Electrochemical oxidation of Catechol derivatives in presence of 4-Hydroxycoumarin
A.R. Khoshroo a, M. Mazloum-Ardakani *a, D. Nematollahi b
Department of Chemistry, Faculty of Science, Yazd University, Yazd 89195-741, Iran
b
Department of Chemistry, Faculty of Science, University of Bu-Ali-Sina, Hamadan 65174, Iran
a
The electrochemical oxidation of catechols has been described and has shown that these compounds can be oxidezed to quinones.
The quinones formed are quite reactive and can be attacked by a variety of nucleophiles. The mechanism is dependent on such
parameters as, nature of nucleophile, electrolysis medium (solvent, acidity or pH…) and catechol type. In this work, the
electrochemical oxidation of 1, 2-diol-4-(1, 3-dithiolan-2-yl) benzene (DITHBD) has been studied in the presence of 4Hydroxycoumarin as nucleophile in water/acetonitrile (80/20) solutions using cyclic voltammetry and controlled-potential
coulometry methods. Monitoring of the electrolysis was carried out by cyclic voltammetry. Cyclic voltammetry of
DITHBD in the buffered solution shows one anodic peak and corresponding cathodic peak which corresponds to the
transformation of diphenolic structure to the corresponding o-quinoneand vice versa within a quasi-reversible two
electron process. But, cyclic voltammograms of DITHBD in the presence of 4-Hydroxycoumarin show one anodic peak
but on the reverse scan the cathodic peak disappears. Effects of some parameters such as nucleophile concentration and
scan rate of potential on the voltammograms were investigated. Also, by using controlled potential coulometry technique,
the number of electrons transferred in the electrochemical oxidation of DITHBD was determined. The cyclic
voltammograms of DITHBD were digitally simulated and kinetic parameters of Michael addition reactions were
estimated.
Reference
[1] D. Nematollahi, M. Rafiee, Green Chem. 7 (2005) 638.
[2] D. Nematollahi, S. M. Golabi, Bull. Electrochem. 14 (1998) 97.
Dispersive Liquid–Liquid Microextraction Combined with Flame Atomic Absorption Spectrometry for preconcentration
and determination of copper (ΙΙ) in water samples and real water samples
Ghadamali Bagherian Dehaghi, Mansour Arab Chamjangali, Hassan Shariaty* Eivari
College of Chemistry, Shahrood University of Technology, I. R. Iran
E-mail: h_shariaty65@shahroodut.ac.ir and h_shariaty65@yahoo.com
A method dispersive liquid-liquid microextraction (DLLME) combined with flame atomic absorption spectrometry (FAAS) for
preconcentration and determination of copper(II) ions in water samples was developed. In this work, the N,N'-bis(salicylidene)-ophenylenediamine (salophen) was used as a selective chelating agent that it forms a stable and hydrophobic complex with
copper(II) ions. The Cu-Salophen complex is extracted from aqueous phase into extraction solvent. The effective parameters on
the extraction recovery were studied and optimized. The mixture of acetone and chloroform was used as disperser solvent and
extraction solvent. 1mL of this mixture by syringe was injected to 10ML solution containing chelating agent and copper ions was
buffered at pH=2. Then solution was centrifuged and 60 μL of enriched phase was diluted with ethanol and aspirated directly into
the flame of AAS. Under optimum conditions, detection limit (three times the standard deviation of the blank values) and the
relative standard deviation (RSD%) of ten replicate determinations of 0.050 μg mL−1 copper(II) were 0.75 ng mL-1 and 2.7%,
respectively. The calibration curve was linear in the range of 3-200 ng.mL-1. This procedure was successfully applied to the
determination of Cu(II) in real water samples.
Reference
[1]- R. Khani, F. Shemirani, B. Majidi, / Desalination 266 (2011) 238–243
[2]- X. Wen et al. / Microchemical Journal 97 (2011) 249–254
[3]- S.Z. Mohammadi, D, Afzali, et al. / Analytica Chimica Acta 653 (2009) 173–177.
[4]- P. Hashemi, S M. Hosseini, J. Chin. Chem. Soc., Vol. 57, No. 1, 2010, 111-117.
Introducing iterative algorithm as a multivariate calibration method in predication of components’ concentration in
detergent washing powder
Mohammadhossein Ahmadi Azghandi*, Mohammadreza Khanmohammadi
Chemistry Department, Faculty of Science, Imam Khomeini International University, Qazvin, Iran, mhahmadia58@gmail.com
The basic principle of Iterative Multivariate Calibration Algorithm was investigated, and used for simultaneous quantitative
determination of Sodium Tripolyphosphate (STPP), Sodium Sulfate (SS) and sodium Carbonate (SC) in commercial washing
powders by ATR-FTIR spectrometry which demonstrates with serious spectral overlapping.There are two main approaches for
determination of a linear equation in the mathematical discipline of linear algebra; one is based up on matrix decomposition [1]
and the other is iterative method [2]. The decomposition method for FTIR was studied earlier by other groups [3-6]. In this
report, the iterative algorithm in multivariate calibration systems with high overlapping is introduced. An iterative method
attempts to solve a problem by finding successive approximations to the solution starting from an initial guess. This approach is
in contrast to direct or decomposition methods (e.g. K-matric, P- matrix, Multi linera regression, Principle component analysis,
...), which attempt to solve the problem by a finite sequence of operations, and in the absence of rounding errors, would deliver
an exact solution. However, iterative methods are often useful for linear problems involving a large number of variables
(sometimes of the order of millions), where decomposition methods would be prohibitively expensive (and in some cases
impossible) even with the best available computing power.
The data were also processed by KM which has been used widely for multivariate calibration in chemometrics[1]. The statistical
parameters for both methods are shown that iterative method is more reliable while it is simple to be performed in comparison
with KM calibration. More reliable results were obtained by this algorithm and the introduction of iterative method will offer a
new field in chemometrics data processing efforts.
Reference
[1]. Y. Ding , T. Mu, Q. Wu, S. Si, Chemometr. Intell. Lab. Sys. 88 (2007) 167–169.
[2]. V. Simoncini, D. B. Szyld, Numer. Linear Algebra Appl. 14 (2007) 1–59.
[3]. M. Yu, Y. Ding, Q. Wu, Y. Gao, X. Liu, X. Bi, J. Iran. Chem. Res. 2 (2009) 23-29.
[4]. Y. Ding, M. Yu, L. Wang Y. Xu, Spectroscopy and spectral analysis 27 (2007) 28-31.
[5]. M. R. Khanmohammadi, A. Ashori, J. Surfact. Deterg. 10 (2007) 81–86.
[6]. M. H. Ahmadi, M. R. Khanmohammadi, Journal of Spectroscopy and Dynamic, 2011, in press.
Investigation of the effect of solvent, surfactant and β-cyclodextrin on the acidity constants of a recently synthesized Schiff
base by spectrophotometry and spectrofluorimetry using rank annihilation factor analysis.
Abbas Afkhami*, Esmail Tammari, Farzad Khajavi, Reza Azadbakht, Esmail Noroozpour
Annihilation of the contribution of one chemical component from the original data matrix is a general method in rank annihilation
factor analysis (RAFA). Theoretically, RAFA can be used for equilibrium study of the acid-base properties of mono-and
polyprotic indicators and organic acids [1]. A two-rank annihilation factor analysis (TRAFA) method has been proposed for
determination of the acidity constants of diprotic acids [2]. In this work, TRAFA was used for determination of the acidity
constants of a new synthesized Schiff base in binary mixtures of solvents of dimethylformamide (DMF) and water with different
volume ratios. After recording the electronic absorbance spectra of the Schiff base solution at different pHs, the results of
principal component analysis (PCA) showed that there were three principal components in the absorbance data matrix. Then the
contributions of both components H2A and A2- were annihilated from the absorbance data simultaneously, which made feasible
the determination of two successive acidity constants. It was found that by increasing in the DMF contents of binary solvents, the
first acidity constant (pK1) is almost fixed and the second acidity constant (pK2) is increased. Flourescence spectra of the Schiff
base solution were also obtained in different pHs and TRAFA was applied for determination of acidity constants of the Schiff
base. In addition, several surfactants (cationic, anionic and neutral) were added to the Schiff base solution in the below and above
of their critical micelle concentration, and RAFA was used to the spectrophotometric studies of the effect of surfactants on the
acidity constants of Schiff base. The results indicated that pK1 is almost fixed and pK2 is increased in the presence of surfactants.
The effect of β-cyclodextrin on the acidity constants of the Schiff base was also investigated and it showed that there is no
significant effect on the acidity constants and the fluorescence intensity of neutral form of the Schiff base is increased by forming
inclusion complex with β-cyclodextrin.
Reference
[1] A. Afkhami, L. Khalafi, Anal. Chim. Acta 569 (2006) 267.
[2] B. Hemmateenejad, A. Abbaspour, H. Maghami, A. Foroumadi, Anal. Chim. Acta 607 (2008) 142.
A new strategy for simultaneous determination of hydroxylamine and phenol using p-aminophenol modified carbon
nanotubes paste electrode
Ali A. Ensafi*, E. Heydari
Department of Chemistry, Isfahan University of Technology, Isfahan 84156–83111, Iran
Hydroxylamine (HX) is a reactive chemical that tends to be explosive, and the nature of the hazard is not entirely understood.
Hydroxylamine is used as a reducing agent in a myriad of organic and inorganic reactions. It can also act as antioxidants for fatty
acids. Some non-chemical uses include removal of hair from animal hides and photography developing solutions[1]. Phenol and
its vapors are corrosive and harmful for eyes, skin, and the respiratory tract Repeated or prolonged skin contact with phenol may
cause dermatitis, or even second and third-degree burns due to phenol's caustic and defatting properties[2]. The electrochemical
methods, using chemically modified electrodes (CMEs) have been widely used as sensitive and selective analytical methods for
the detection of the trace amounts of hazardous compounds. One of the most important properties of CMEs has been their ability
to catalyze the electrode process via significant decreasing of overpotential respect to unmodified electrodes. In this work, a
carbon paste electrode (CPE) chemically modified with multiwall nanoparticles and p-aminophenol (p–AP) was used as a
selective electrochemical sensor for the simultaneous determination of hydroxylamine and phenol. Using square wave
voltammetry (SWV), a highly selective and sensitive determination of HX and phenol has been explored at the modified
electrode. Square wave voltammetric peaks current of HX and phenol increased linearly with their concentrations at the ranges of
0.5 – 180.0 μmol L–1 and 10.0 – 650.0 μmol L–1, respectively with detection limits of 0.15 and 7.1 μmol L–1 for HX and phenol,
respectively. The separation of anodic peaks potential of HX and phenol reached 0.65 V using square wave voltammetry. The
RSD% for ten replicates determination of 1.0 and 5.0 μmol L–1 HX were 1.3% and 1.5%, respectively, whereas for 15.0 and 30.0
μmol L–1 phenol, they were 1.1% and 1.2%, respectively. With good selectivity and sensitivity, the present method provides a
simple method for selective detection of HX and phenol in real samples such as water samples.
Reference
[1] Patnaik, Pradyot, Handbook of Inorganic Chemicals, McGraw Hill, 2003, pp. 385–386.
[2] Budavari, S., The Merck Index: An Encyclopedia of Chemical, Drugs, and Biologicals, Whitehouse Station, NJ: Merck, 1996.
Second-order standard addition for fast determination of seven UV filters in sunscreen products by high-performance
liquid chromatography-diode-array detection and MCR-ALS method
Maryam Vosough, Nahal Rahimdoost*, Seyyed Hamid Ahmadi
Chemistry and Chemical Engineering Research Centre of Iran, P.O. Box 14335-186 Tehran, Iran
Skin cancer accounts for almost half of all cancers in the world. A majority of skin cancer are associated with exposure to
harmful radiation from sun. Sunscreens are topical lotion that disperse UV-absorbing compound in oily base. These compounds
usually contain one or more aromatic cycles as well as conjugated double bonds which enable them to strongly absorb the
electromagnetic (UV) radiation and convert it to the thermal energy through vibration energy levels [1-2]. A fast
chromatographic methodology based on standard addition is presented in this study for simultaneous quantification of seven
organic UV filters (benzophenone-3, 4-methylbenzilidene camphor, octocrylene, 1-(4-tert-butylphenyl)-3-(4-methyoxyphenyl)
1,3-propanedione, ethylhexyl methoxy cinnamate, ethyl hexyl salicylate and homosalate) in three sunscreens samples.
Sunscreens samples were diluted in (50:50, v/v) (methanol : acetonitrile), then separated on an ODS column (15 cm × 0.46 cm, 5
µm) in less than 2.5 min using a non-aqueous mobiles phase consisted methanol–acetonitrile (50:50, v/v) with a flow-rate of 1.5
ml/min. Second-order calibration using multivariate curve resolution-alternating least squares (MCR-ALS) were applied on
three-way data obtained from liquid chromatography with diode array detection (LC-DAD) through standard addition method.
The standard calibration carve were linear for benzophenone-3, 4-methylbenzilidene camphor, octocrylene, 1-(4-tertbutylphenyl)-3-(4-methyoxyphenyl) 1,3-propanedione, ethylhexylmethoxy cinnamate, ethyl hexyl salicylate and homosalate in
the concentration ranges 0.05-50 mg L-1 , 0.05-50 mg L-1 , 0.02-50 mg L-1 , 0.02-100 mg L-1 , 0.02-50 mg L-1 ,0.1-100 mg L-1
and 0.1-100 mg L-1 respectively. Recoveries ranging from 98 to 102 % for all UV filters in sunscreens proved the accuracy of
the proposed method in all samples . Relative standard deviation (RSD%) of the determination of the above compounds were less
than 9.2%. The proposed method was validated and figures of merit were calculated for all analytes. The results showed that
coupling of a fast HPLC-DAD method with powerful algorithms MCR/ALS can be considered as an efficient and environmental
friendly method for quantification of UV filters in sun care formulation.
Reference
[1] .C.G.Smyrniotakis, Helen A. Archontaki, J. chromatogr.A ,1031 (2004) 319-324
[2] . S.C. Rastogi, G.H. Jensen, J. chromatogr.A, 828 (1998) 311–316.
[3] . D. L. Giokas, A. Salvador, A. Chisvert, Trends Anal. Chem. 26 (2007) 360-374.
The direct electron transfer of glucose oxidase and glucose biosensor based on MWCNT/poly 4-Aminothiophenol
/glutaraldehyde
M.A. Kamyabi*, S. Sharifyrad
Department of Chemistry, Zanjan University, P.O. Box 45195-313, Zanjan, Islamic Republic of Iran
The "third generation" of biosensors is truly reagent less and these sensors are based on the direct transfer of electrons between
the enzyme and the electrode. In glucose sensors based on direct electron transfer in glucose oxidase, efficient electron-transfer
pathways between the immobilized glucose oxidase and the electrode surface have to be established so to allow a fast electron
transfer and concomitantly avoiding free-diffusing redox species [1]. In this study, the direct electrochemistry of glucose oxidase
(GOD) adsorbed on an electropolymerized poly 4-aminothiophenol/multiwall carbon nanotubes (MWCNTs) modified glassy
carbon electrode (GCE) was investigated. This GOx modified electrode was used as a biosensing element for determination of
glucose. The effect of various factors such as electropolimerization pH, amount of nanotube and monomer, deposition time,
number of cycle electropolimerization and pH of glucose determination were studied and optimum value for each factor is
suggested. The electrocatalytic ability of biosensor for oxidation of glucose was investigated by currents of GOD in the negative
potential. The immobilized GOD displayed a pair of redox peaks with a formal potential of -0.482 mV in 0.1 M pH 7.0 phosphate
buffer solution. The immobilized GOD could electrocatalyze the reduction of dissolved oxygen and resulted in a great increase of
the reduction peak current. Upon the addition of glucose, the reduction peak current decreased, which could be used for glucose
detection with a high sensitivity of 0.037 µA/µM, detection limit of 4.99 µM at 3σ and a linear range in 5- 150µM .
Furthermore, the apparent Michaelis–Menten constant 6.07 µM, of GOD on the modified GCE exhibits excellent
bioelectrocatalytic activity of immobilized enzyme toward glucose oxidation.
Reference
[1]Y.Liu,M.Wang,F.Zhao,Z.Xu,S.Dong.",Biosensors and Bioelectronics".21(2005)984-988.
The inhibitive effect of some tetrazole derivatives on the corrosion of mild steel in hydrochloric acid solution
a
N. Soltani*,a, A. Teimourib, F. Loghmani
Payame Noor University (PNU), (a: Shahin Shahr Branch and b: Isfahan) , Isfahan, Iran
Iron and its alloys are widely used in industry. Mild steel is one of the important iron containing alloy used in different
applications and is susceptible to corrosion due to its thermodynamic instability especially in aggressive media [1]. To remove
unwanted scale and salt deposits or mill scales formed during manufacture, metals are immersed in acid solutions, which are
known as an acid pickling bath. In order to reduce the degree of metal attack and rate of consumption of the acid, corrosion
inhibitors are added to the pickling solutions. Most of the well known acid inhibitors are organic compounds containing nitrogen,
sulphur and oxygen atoms, which allow an adsorption on the metal surface [2-4]. In this study, the corrosion inhibition of mild
steel in 1.0 M HCl solution by four tetrazole derivatives was investigated using weight loss and electrochemical measurements
(potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) technique,) and quantum chemical calculations.
Potentiodynamic polarization studies clearly reveal that these tetrazoles act essentially as mixed type inhibitors. The adsorption
of these compounds on the mild steel follows Langmuir adsorption isotherm. The effect of temperature on the corrosion was
investigated by the weight loss method and some thermodynamic parameters were calculated. The mechanism of inhibition was
discussed in the light of the chemical structure of the undertaken inhibitors. Quantum chemical calculation based on the density
functional theory (DFT) method was performed. Then, the molecule structural parameters, such as the frontier molecular orbital
energy HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital), the charge distribution
and the fraction of electrons (∆N) transfer from inhibitor to mild steel were calculated and discussed. Quantitative Structure–
Activity Relationship (QSAR) approach has been conducted in attempt to correlate the corrosion inhibition properties of these
inhibitors with their calculated quantum chemical parameters.
Reference
[1] M.K. Pavithra, T.V. Venkatesha, K. Vathsala, K.O. Nayana, Corros. Sci. 52 (2010) 3811–3819.
[2] R. Hasanov, S. Bilge, S. Bilgiç, G. Gece, Z. Kılıç, Corros. Sci. 52 (2010) 984-990.
[3] Y. Tang, X. Yang, W. Yang, R. Wan, Y. Chen, X. Yin, Corros. Sci.. 52 (2010) 1801–1808.
[4] Y. Tang, X. Yang, W. Yang, R. Wan, Y. Chen, X. Yin, Corros. Sci. 52 (2010) 1801–1808.
Cyclic Voltammetric Determination of Epinephrine by Carbon Paste Electrode prepared by a novel graphite and
Modified with a new Derivative of Hydroquinone
Mohammad Mazloum-Ardakani*a, Ali Benvidi a, Afsaneh Dehghani a, Nooshin Rajabzadeh a, Mohammad Ali Sheikh-Mohseni a, Hossein
Naeimib
a
Department of Chemistry, Faculty of Science, Yazd University, Yazd, I.R. Iran
b
Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan, I.R. Iran
Carbon-paste electrodes modified with novel derivative of hydroquinone have been used to study the electrocatalytic oxidation of
epinephrine (EP). In the first part cyclic voltammetry was used to investigate the redox properties of this modified electrode at
various scan rates. The apparent charge transfer rate constant, ks=1.98 s-1, and transfer coefficient, α=0.54, for electron transfer
between modifier and carbon paste electrode were calculated. In the second part, the mediated oxidation of EP at the modified
electrode was described. It has been found that under optimum condition (pH=7.0) in cyclic voltammetry, the oxidation of EP
occurs at apotential about 180 mV less positive than that of an unmodified carbon paste electrode.The values of transfer
coefficients (α=0.47), catalytic rate constant (k=0.199 M-1s-1) and diffusion coefficient (D=5.3×10-6 cm2s-1) were calculated for
EP, using electrochemical approaches [1]. Differential pulse voltammetry (DPV) exhibited two linear dynamic ranges for
different concentrations of EP.
Reference
[1] Bard AJ, Faulkner LR (2001) Electrochemical methods. Fundamentals and applications. Wiley, New York
Silica-coated magnetic nanoparticles modified with sodium dodecyl sulfate (SDS) for extraction of Pyridostigmine
bromide (PB) and Neostigmine methyl sulfate (NEO)
M.Soleimani*, M.Rezaie
Department of Chemistry, Imam Khomeini International University (IKIU), Qazvin, Iran
m-soleimani@hotmail.com
We report here the synthesis of new sorbent comprising silica-coated magnetic nanoparticles (SCMNPs) modified with the
surfactant sodium dodecyl sulfate (SDS) for solid phase extraction of Pyridostigmine bromide (PB) and Neostigmine methyl
sulfate (NEO) from medical sample based on mixed hemimicelles solid-phase extraction (MHSPE). These magnetic
nanoparticles carrying the medical targets could be easily separated from the aqueous solution simply by applying an external
magnetic field, no filtration or centrifugation was necessary. Compared with pure magnetic particles, a thin silica layer would
protect the iron oxide core from leaching out in acidic conditions [1]. SDS–coated Fe3O4/SiO2 NPs system was selected due to
lower elution volume required and more effective of the target compounds [2]. The advantage of this new method still include
easy preparation and regeneration of sorbents, short times of sample pretreatment and high extraction yield. A formation of
superparamagnetic silica-coated (Fe3O4/SiO2 core/shell) nano-particles inspected by using scanning electron microscopy (SEM)
and x-ray diffraction (XRD). Under selected conditions, concentration factor of 143 was achieved for both of them by using this
method to extract 500 mL of different matrices. The detection limits obtained for PB and NEO with UV spectrophotometer was
30.7 and 31.16 ng/L, respectively.
Reference
[1] X. Zhao, Y. Shi, T. Wang, Y. Cai, G. Jiang, J. Chromatogr. A. 1188 (2008) 140-147.
[2] L. Sun, C. Zhang, L. Chen, J. Liu, H. Jin, H. Xu, L. Ding, J. Chromatogr. A. 638 (2009) 162–168.
NICKEL-POLY (O-ANISIDINE)-MODIFIED CARBON IONIC LIQUID ELECTRODE; AN ELECTROCATALYST
FOR METHANOL OXIDATION
Reza Ojania, Jahan-Bakhsh Raoofa, Saeed Zamania
a: Electroanalytical Chemistry Research Laboratory, Faculty of Chemistry, Mazandaran University, Babolsar, Iran. E-mail: fer-o@umz.ac.ir.
There is a growing interest to direct methanol fuel cells (DMFCs) due to elimination of hydrogen storage, high energy density
of methanol, modularity, vibration free and silent operation and its high potential as a power source in portable electronic
applications [1].On the other hand the use of Ni as the catalyst for alcohol electro-oxidation is of interest because it is an
inexpensive metal. Many electrodes that include nickel as a component in their manufacture can be used as catalysts in fuel cells.
Nickel is commonly used as an electrocatalyst for both anodic and cathodic reactions in organic synthesis and water electrolysis
[2]. Recently ionic liquids (ILs) have been used in the electroanalysis due to the advantages such as high conductivity and wide
electrochemical windows [3]. As a new kinds of chemical modified electrode, ionic liquid modified electrode had aroused great
interests, which exhibited the characteristics such as simple preparation procedure, high rates of electron transfer and good antifouling ability [4].
In this study, with respect to advantages of ionic liquids, we decided to use the effect of the1-butyl-3metylimidazolium bis
(trifluorometylsulfonyl) imide ([bmim]NTF2) as an ionic liquids on electrosynthesis of poly(o-anisidine) film. Then, this poly (oanisidine) film which is a new conductive organic matrix was employed for a better dispersion of nickel ions as a low cost
electrocatalyst for electrocatalytic oxidation of methanol at the surface of polymeric electrode. This polymeric modified electrode
can oxidize the methanol with high current density (over 19 mA Cm−2). Thus, this electrode can be a candidate in terms of high
current density as an anode for power sources such as DMFCs.
Reference
[1] S. Celik, D. Mahmut , Int. J. hydrogen energy 35 (2010) 2151.
[2] T.C. Wen, S.M. Lin, J.M. Tsai, J. Appl. Electrochem. 24 (1994) 233.
[3] A. Ciszewski, G. Milczarek, J. Electroanal. Chem. 426 (1997) 125.
[4] N. Maleki, A. Safavi, F. Tajabadi, Anal. Chem. 78 (2006) 3820.
Synthesis of Ammonium Based Task Specific Ionic Liquid:
Modified Approach
a
Ghazaleh Aliakbarzadeha*, Mohammad Reza Milani Hosseinia, Shahab Shariatib
Department of Analytical Chemistry, Iran University of Science and Technology, Tehran, Iran.
b
Department of Chemistry, Rasht Branch, Islamic Azad University, Rasht, Iran
Room-Temperature Ionic Liquids (RTILs) have melting points below the room temperature and are widely employed in
analytical chemistry, due to their unique properties such as negligible volatility, thermal stability and non-flammability. RTILs
generally are consisted of bulky and non-symmetrical organic cations, whereas their anions could be organic or inorganic [1].
Through the incorporation of functional group on either cation or anion of ionic liquids, Task-specific ionic liquids (TSIL) were
synthesized and adjusted for specific applications such as metal extraction and electrochemistry [2,3]. In this study, a Taskspecific ionic liquid (Tricaprylmethylammonium thiosalicylate [A336][TS]) was synthesized for application as a selective
extraction solvent based on modification of the literature method. For this propose, the previous method for synthesis of a
hydrophobic long-chain ammonium based ionic liquid with thiol functional anion [4] was investigated and modified. Briefly, the
target ionic liquid was synthesized through chemical reaction of Tricaprylmethylammonium chloride with thiosalicylic acid as a
Bronsted acid in the presence of proper amounts of sodium hydroxide. After separation and purification of synthesized
tricaprylmethylammonium thiosalicylate ([A336][TS]), its structure was characterized by FT-IR spectrometry. In comparison
with the previous synthesis method, our outcome has shown better results. Finally, the applicability of the synthesized Taskspecific ionic liquid as an extracting solvent for metallic ions in ligandless extraction process was investigated and satisfactory
results were obtained.
Refrence
[1] P. Sun and D. W. Armstrong, "Ionic liquids in analytical chemistry," Analytica Chimica Acta, vol. 661, pp. 1-16.
[2] J. M. Reyna-Gonzalez, A. A. J. Torriero, A. I. Siriwardana, I. M. Burgar, and A. M. Bond, "Extraction of Copper(II) Ions from Aqueous Solutions with a
Methimazole-Based Ionic Liquid," Analytical Chemistry, vol. 82, pp. 7691-7698.
[3] N. Papaiconomou, J.-M. Lee, J. Salminen, M. von Stosch, and J. M. Prausnitz, "Selective Extraction of Copper, Mercury, Silver, and Palladium Ions from Water
Using Hydrophobic Ionic Liquids," Industrial & Engineering Chemistry Research, vol. 47, pp. 5080-5086, 2007.
[4] A. Stojanovic, D. Kogelnig, L. Fischer, S. Hann, M. Galanski, M. Groessl, R. Krachler, B. K. Keppler ,” Phosphonium and Ammonium Ionic Liquids with
Aromatic Anions: Synthesis, Properties, and Platinum Extraction” Aust. J. Chem. 2010, 63, 511.
Fabrication of bulk-modified carbon paste electrode containing [W10O32]4- polyanion supported on modified silica gel:
preparation, electrochemistry and electrocatalysis
Z. Fotoohabadi, E. Shams
*
Department of Chemistry, University of Isfahan, Isfahan, Iran
E-mail: e_shams@chem.ui.ac.ir
Polyoxometalates (POMs) constitute the largest subclass of polyanions, which are of particular interest in catalysis and
electrocatalysis. Although, there is an increasing interest in the electrocatalytic properties of POMs, their application in the
development of chemically modified electrodes (CMEs) is limited. The key reason is the high solubility of POMs in aqueous
solutions. Practical applications of POMs for the preparation of CMEs depend on successful immobilization of these compounds.
There are several methods for the immobilization of POMs on to the electrode surface. A serious drawback of the electrodes
modified by these methods is their poor long-term stability. Moreover, the electrode surfaces cannot be renewed in the event of
leakage, contamination or passivation. In order to overcome this problem, it is desirable to develop a new simple and reliable
procedure for the preparation of bulk POM-modified carbon paste electrodes [1, 2, 3]. In this study, [W10O32]4- polyanions
supported on the surface of 3-aminopropyl(triethoxy)silane (APS) modified silica gel was synthesized and used as a bulk
modifier to fabricate a chemically modified electrode. (APS-W10O32)-modified silica gel was prepared by adding silica gel
derivatized by APS to decatungstate acid [H4W10O32] polyoxometalate solution [4, 5]. The electrochemical behavior of the
modified electrode was characterized by cyclic voltammetry in aqueous 0.5MH2SO4 adjusted to pH1 by concentrated NaOH
solution. The electrode offered attractive properties such as reproducibility, simplicity of electrode preparation, high stability and
a distinct advantage of renewing and simple polishing in the event of surface fouling. Further, due to low solubility of [W10O32]4supported on APS in aqueous solution there was no leaching of the electrode material, hence a single electrode surface can be
used for multiple analytical determination. This electrode showed good electrocatalytic activity toward periodate reduction thus
the performance of this electrode was optimized for the purpose of evaluating its potential as an analytical amperometric sensor
for trace determination of IO4-.
Refrence
[1] Hamidi, H.; Shams, E.; Yadollahi, E; Esfahani, F.K. Talanta 74 (2008) 909–914.
[2] Hamidi, H.; Shams, E.; Yadollahi, E; Esfahani, F.K. Electrochim Acta 54 (2009) 3495–3500.
[3] Wang, X.; Wang, E.; Lan. Y.; Hu. C. Electroanalysis 14(2002) 15.
[4] Paul, S.; Clark, J.H. Green Chem. 5 (2003) 635.
[5] Kumar, A. Catal Commun. 8 (2007) 913-916.
Application of Taguchi Method in The Optimization of electrochemical treatment of the soap and detergent industry
2
wastewaters
P. Moradi* , S. Rowshanzamir1,2, M.H. Eikani3
*
Kurdistan Power Generation Management Company (E-mail: p_moradi@sanandajpowerplant.ir
School of Chemical Engineering, Iran University of Science and Technology, Narmak, Tehran 16846-13114, Iran (Email: rowshanzamir@iust.ac.ir)
3
Department of Chemical Industries, Iranian Research Organization for Science & Technology (IROST), Tehran, Iran
(E-mail: eikani@irost.org)
Water wastage is a serious worldwide problem. The availability of clean water for various human needs in the next decades
seems to become a challenge to take up [1]. Electrochemistry offers promising approaches for the prevention of pollution
problems in the process industry. Attractive advantages of electrochemical processes are generally: versatility, energy efficiency,
amenability to automation, cost effectiveness [2]. EF treatment evaluated in this paper is one of the electrochemical treatment
applications. That includes the combined advantages of electrochemical and Fenton treatment methods, and each of them is a
powerful treatment choice. The hydroxyl radical is one of the most powerful oxidizing which can effectively and non- selectively
react with a wide range of compounds of environmental concern, even leading to their mineralization[3]. Taguchi designs of
experiment (DOE) methods are extensively used to optimize the critical parameters of any process.. In this study, the Taguchi
method is used for COD reduction potential of soap and detergent industry wastewaters by electrochemical processes. The
wastewater samples were taken from Paxan Company in Tehran, Iran. Four parameters at different levels were selected:
temperature (20 and 60°C), pH (1, 2, 3 and 4), hydrogen peroxide concentration (5000, 10000, 20000, and 40000 mg/l) and
current (2, 3, 4, and 5 A). A possible matrix is a sixteen-trial orthogonal array, which is labelled an L16 matrix. In data analysis,
signal-to-noise (S/N) ratios are used to allow the control of the response as well as to reduce the variability about the response.
The use of ANOVA (analysis of variance) is to calculate the statistical confidence associated with the conclusions drawn.
Taguchi method was used and the optimal levels thus determined for the four factors were: temperature 20°C, pH 3, hydrogen
peroxide concentration 40000 mg/l and current 5 A. For these conditions, COD was reduced by 96/36% within 60 min for an
initial COD of 5130 mg/L. The most important result of this research was study of the effective parameters in removing COD by
electro-Fenton reaction and determining the portion of each parameter, so that by analyzing ANOVA it was obtained that among
the experimented parameters, pH with 60.35%, hydrogen peroxide with 23.61%, current with 7.75% and temperature with 6.4%
had greatest effect.
Reference
[1] Amal, L., Oturan, M.A., Oturan, N., Chaouch, M., “Removal of textile from water bye electro-Fenton process”, Environ Chem Lett 5, 35-39(2007)
[2] JÜttner, K., Galla, U and Schmieder, H., “Electrochemical approches to environmental problems in the process industry” Electrochimica Acta, 45, 2575-2594
(2000)
[3] Pozzo A. D., Ferrantelli P., Merli C. and Petrucci E., Oxidation efficiency in the electro-Fenton process, Journal of Applied Electrochemistry 35,
391–398 (2005)
identification of Taxane deterpenoids using semi-preparative SPE-HPLC and LC-MS
Soleymankhani Majid,* Rafati Hassan, Rezadoost Hassan, Joshani Azade
Purification and Department of Phytochemistry, Medicinal Plants and Drugs Research Institute, Shahid Beheshti
University, Evin, Tehran, Iran.
Corresponding Author E-mail: m.soleymankhani@gmail.com
Taxane diterpenoids are the best known compounds of natural origin, which has been employed in the pharmaceutical industry;
they are extracted from different parts of yew trees (Taxaceae), cell cultures, and Taxane-producing endophytic fungi. Paclitaxel
is the most important compound of this group. It kills tumor cells by enhancing the assembly of microtubules and inhibiting their
de-polymerization. It has been widely applied in the clinical treatment of various malignant tumors such as breast cancer, ovarian
carcinomas, skin cancer, and non-small-cell lung cancer. 1 There are many reports in which many kinds of separation and
purification methods for these most demanding compounds are used.2 Although HPLC is mainly used for the determination of
main Taxoids from both plant materials and biological fluids, it is difficult to separate some Taxoids well because of their similar
structures. Therefore, it is necessary to develop a reliable and short-term method for the simultaneous determination of these
compounds.3 LC-MS is a powerful instrument in natural product research in which mass analyses could be used for
determination of known compounds.4In this study, solid phase extraction with C18 stationary phase was used as a clean-up step.
Taxane Purification is carried out using analytical HPLC. Then this procedure scaled up to semi-preparative SPE-HPLC and
analyzed using LC-MS system. Base on this method, four important Taxane including Paclitaxel, Cephalomannine, 10deacetylbaccatin III, baccatin III were determined.
Reference
[1] Schiff, P. B.; Fant, J.; Horwitz , S. B. Nature, 1979, 277, 665.
[2] Sang, H. P.; Ho J. C.; Byung, H. H. Journal of Chromatography, 2006, 1123, 15
[3] Yu, J. F.; Rui, S.; Yuan, G. Z.; Shuang, M. L.; Wei, L.; Thomas, E.; Cheng, B. G.; Lin, Z.; Hao, L. Biomed. Chromatogr. 2009; 23, 63
[4] Edward. H.; Kerns, K. J.; Volk, S. H.; Jounral of Natural Products, 1994, 57, 1391
Zinc hydroxide Nanoparticle loaded on activated carbon efficient application for removal of Arsenazo (III) from aqueous
solution
Ebrahim Shareifpoora, Syamak Nasiri Kokhdanb*
Chemistry Department, Gachsaran Azad University, Gachsaran Branch - Iran,
b
Young Researchers club, Yasooj Branch, Islamic Azad University, Yasooj, Iran
*E-mail: syamak.nasiri@yahoo.com, eb_shareif_prt@yahoo.com
a
Zn(OH)2-NP_AC (solely or loaded on another support) has very interesting physicochemical properties, such as ordered structure
with high aspect ratio, ultra-light weight, high mechanical strength, high electrical conductivity, high thermal conductivity,
metallic or semi-metallic behavior and high surface area. Therefore, they are very useful adsorbent for waste water treatment.
The graphical correlation of various adsorption isotherm models like, Langmuir, Freundlich, Tempkin and Dubinin–
Radushkevich have been carried out for these dyes on this new adsorbents. The adsorption over Arsenazo (III) has been found
endothermic and feasible in nature. Various thermodynamic parameters, such as, Gibb’s free energy, entropy and enthalpy of the
on-going adsorption process have been calculated. The kinetic studies suggest the process following pseudo second order kinetics
and involvement of particle diffusion mechanism. In summary we described a method for efficient removal and recovery of
hazardous dye from wastewater. The method makes use of naked, inexpensive magnetic nanoparticles with surface affinity to the
dye [1, 2].
Reference
[1]. Shahnaz Qadri, Ashley Ganoe and Yousef Haik, Ionic Liquid Mediated Dye Recovery from Aqueous Solution, Nature Precedings : hdl:10101/npre.2008.2111.1 :
Posted 23 Jul 2008
[2]. M. Ghaedi, A. Hassanzadeh, S. Nasiri Kokhdan, chem. Eng. data.56, 2011, 2511-2520.
Determination of silver by differential pulse stripping voltammetry with carbon paste electrode modified by carbon
nanotubes and N, N-bis(2-hydroxybenzylidene)-2,2(aminophenylthio)ethane
Hadi Hassani Nadiki* a, Mohammad Ali Tahera, Iran Sheikhshoaiea
a
Department of Chemistry, Shahid Bahonar University of Kerman
Silver is a metal of commercial importance for use in high strength and corrosion resistance alloys, and jewellery. For example,
because of the marked antibacterial properties of silver,Its compounds and alloys have been widely used in dental and
pharmaceutical preparations, and in implanted prosthesis [1]. Stripping voltammetric analysis is one of the most sensitive
methods for determining ion metals [2]. The application of modified carbon paste electrodes (MCPE) in this analysis has
attracted considerable attention in recent years [3]. MCPEs have several advantages such as non-toxic, low background current,
wide range of used potential, rapid renewal and easy fabrication [4]. Modifier gagent, N, N-bis(2-hydroxybenzylidene)2,2(aminophenylthio)ethane (NBHAE) Was synthesized and purified as described elsewhere [5], and used for Preparation of
MCPE. For differential pulse anodic stripping voltammetric experiments, the MCPE was immersed in a 20mL of sample solution
(pH 9.5) containing a known amount of Ag(I) and the solution was stirred for 10 min. This was followed by replacing the
medium with a 0.1 mol L−1 HCl solution, where the accumulated silver (I) was reduced for 20 s in −0.7 V. Finally the differential
pulse voltammogram was recorded from −0.2 to +0.2V (with 30 mVs −1 scan rate, 100 mV pulse amplitude, and 4 ms pulse
period). The ability of the NBHAE to extract silver(I) into the carbon paste leads to an electrode that is precise and accurate. This
method showed a high selectivity, because of the complexation and the exchange of the medium. The calibration graph of Ag(I)
was shown ideally to be a linear relationship from 1–200 µg L−1 , with a slope factor of 1.172 mA(mgL−1)−1 and correlation factor
of 0.999. The detection limit of silver(I) was 0.107µg L−1. The modified electrode prepared in this study could be used for the
determination of silver in water samples and X-ray photographic films with good results.
Reference
[1] Tahereh Rohani, Mohammad Ali Taher, Talanta 80 (22010) 1827-1831.
[2] J. Wang, Analytical Electrochemistry, John Wiley, New York, 2000.
[3] P. Gonzalez, V.A. Cortynez, C.A. Fontan, Talanta 58 (2002) 679.
[4] Y.H. Li, H.Q. Xie, F.Q. Zhou, Talanta 67 (2005) 28.
[5] I. Sheikhshoaie, A. Kamali, Oriental J.Comput. Sci. Technol. 1 (2008) 25–28.
Synthesis and study application of alkyl ammonium hydrogen sulphate as acidic ionic liquids in lead acid batteries
industry
Ahmad Reza Taghipour Jahromi, Behzad Rezaei*, Ali Asghar Ensafi.
Department of Chemistry, Isfahan University of Technology, Isfahan, 84156-83111 I.R. Iran
The lead-acid battery is an electrochemical device for storing chemical energy until it is released as electrical energy. It is used
extensively as automotive, stationary, and traction batteries throughout the world [1]. In this work, the application ionic liquids
(ILs) hexyl, monocyclo-hexyl, bicyclo-hexyl ammonium hydrogen sulphate (employed in this study were synthesized and
purified in our laboratory) and tetrahexyl ammonium hydrogen sulphate (purchased from Sigma-Aldrich-Switzerland)—as
electrolyte additives in low concentrations (5, 10, 15, 20 ppm) on the electrochemical performance of lead acid batteries is
proposed. The electrochemical behavior of Pb–1.66% Sb–0.24% Sn alloy in sulphuric acid solution is investigated in the
presence of the mentioned ILs with different numbers of alkyl or cycloalkyl chains. Particularly, the hydrogen, oxygen evolution
potential, electrochemical performance and corrosion of lead alloy, in the present of these ILs were studied by using, cyclic
voltammetry, linear sweep voltammetry, impedance spectroscopy (EIS) methods and Tafel plots. The IR and NMR spectra show
clearly synthesis of these ILs. The obtained results indicate that hydrogen evolution overpotential of Pb/Sb/Sn alloy in the
presence of ILs increases. This overpotential mainly depends on the concentration of ILs and the number of alkyl and cycloalkyl
chains on the cations. So that by increasing number of alkyl or cycloalkyl branches in ILs, the corrosion rate of the lead alloy
decreases, whereas inhibition efficiency shows a reverse effect. Hence, the adsorption model of the ILs on the corrosion of lead
alloy surface was proposed.
Reference
[1] Fogiel .M. Handbook of basic electricity. Research and Education Association (2003)
Determination of Ammoniuum Ion in Water by Imagr processing and Analysis of a Stain Detector
M. Pakniat, A. Alaee*
Department of chemistry, Faculty of Basic Sciences, Persian Gulf University, Bushehr 75168, Iran
rezaei@cc.iut.ac.ir
The progress and improvement in many field of science are due to popularity of their methods and instruments for even
unauthorized peoples. For the case of chemistry, today, there are great need for monitoring and screening many chemical
parameters in daily life. The length of stain detectors are an appropriate choice to answere such necessities [1]. Image analysis is
the extraction of meaningful information from images by means of digital image processing techniques. These include many
applications in the fields of medicine, remote sensing, biology, astronomy, defense, materials science , manufacturing, security,
robotics, document processing, and assay plate reading. At the same time different statistical methods for improving image
resolution, noise reduction and clustering the image elements were adopted. There are few applications in different branches of
science in relation with or in chemistry but still much of the potential abilities of imaging technique is unexploited e.g. for data
recording or analysis. Today computers, digital photography based on charge transfer devices, mobile etc. are among the
common facilities of people life. We can exploit devices for daily life to transfer chemical tests out of laboratories. For practical
purposes recording all experimental parameters, especially for an unauthorized person is time consuming and tedious. Recording
information especially by an unauthorized person would be a great advantage and returning much data to laboratories as a
drawback. By appropriate arrangement of equipments and inclusion of experimental data in front of a camera all information
needed such as concentrations, flow rate, time, color, area, volume, temperature etc. could be recorded for further investigations
without any conscious supervision. Also much unnoticed points may be saved for not previously predicted investigations. One of
the important tasks of eco-analytical control and ecological monitoring of water is the observation of the level of compounds of
biogenic elements contained in the water, one of such biogenic elements being ammonium nitrogen, which plays an important
role in the metabolism of animal and plant organisms, which inhabit the water bodies [2]. In mammals, sharks, and amphibians, it
is converted in the urea cycle to urea, because urea is less toxic and can be stored more efficiently. In birds, reptiles, and
terrestrial snails, metabolic ammonium is converted into uric acid, which is solid and can therefore be excreted with minimal
water loss. Ammonium is an important source of nitrogen for many plant species, especially those growing on hypoxic soils.
However, it is also toxic to most crop species and is rarely applied as a sole nitrogen source [3].The Nessler reaction has adapted
successfully to a stain detector for determination of ammonia in natural water samples Ammonia reacts with Nessler's reagent
consisting of mercury (II) iodide and potassium iodide in alkaline solution to form yellow color to a deep brown to chocolate
colloidal precipitate suspension based on its concentration. All exprimental parameters were optimized and the calibration curve
have two linear parts from 0.000028 to 0.0047and from 0.01 to 0.1 The RSD of the method is about 5.60%.
Reference
[1] R. Michalski, I. Kurzyca, Pol. J. Environ. Stud. 1 (2006) 5.
[2] F.R.P. Rocha, B.F. Reis, Anal. Chim. Acta 409 (2002) 227.
[3] A. Padarauskas, V. Paliulionyte, B. Pranaityte, Anal. Chem. 73 (2001) 267.
Preconcentration of benzoic acid from aqueous solutions by maghemite nanoparticles
Abbas Afkhami *, Tayyebeh Madrakian, Samaneh Siavashi
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
Cetyl trimethyl amonium bromide(CTAB) modified maghemite nanoparticles (CTAB–γ-Fe2O3), was used for removal of
benzoic acid (BA) from water samples. Prepared maghemite nanoparticles were characterized by TEM, SEM, XRD, BET and
EDX measurements. The influences including initial pH, dosage of adsorbent, amount of surfactant and contact time have been
investigated in order to find the optimum adsorption conditions. BA became adsorbed at pH 8.5. The adsorbed BA was then
desorbed and determined spectrophotometrically. The experimental data were analyzed by the Langmuir and Freundlich
adsorption models. Equilibrium data fitted very well with the Langmuir model signifying the energetic homogeneity of CTABmaghemite surface adsorption sites. The maximum predicted adsorption capacities for BA was obtained as 62.5 mg g −1. It was
shown that the sorbent can remove 65% of the BA within the first 30 min of contact time. Desorption process of the adsorbed
benzoic acid was also investigated using 2 ml of methanol 70% as an eluent.
Reference
[1]-A. Afkhami, R. Moosavi, J. Hazard . Mater. 174 (2010) 398-403.
[2]- A. Afkhami, R. Moosavi, T. Madrakian, Talanta 82 (2010) 785-789.
[3]-A. Afkhami, M. Saber-Tehrani, H. Bagheri, Desalination 263 (2010) 240-248.
[4]-A. Afkhami, M. Saber-Tehrani, H. Bagheri, J. Hazard . Mater. 181 (2010) 836-844.
[5]-A. Afkhami, R. Norooz-Asl, Colloid. Surface 346 (2009) 52-57.
Effect of sodium dodecyl sulfate micellar media on the determination of nitrite based on its reaction with neutral red
Abbas Afkhami, Tayyebeh Madrakian, Minoosh Rohani*
Faculty of Chemistry, Bu-Ali Sina University, Hamadan, Iran
Effect of surfactants on the determination of nitrite based on its reaction with neutral red in acid media was investigated. The
reaction was monitored spectrophotometrically. A cationic surfactant, cetyltrimethylammonium bromide, a non-ionic surfactant,
Triton X-100, and an anionic surfactant, sodium dodecyl sulfate, were tested. Calibration graphs for the determination of nitrite
were obtained in the presence of sodium dodecyl sulfate by both kinetic and thermodynamic methods. Effects of different
parameters were tested and optimum conditions were established. The analytical parameters obtained in the presence of sodium
dodecyl sulfate were compared with those obtained in the absence of it. Nitrite could be determined in the range of 1.0-1200.0 ng
mL-1. The method was applied to the determination of nitrite in waste water samples
Reference
[1]A. Afkhami, T. Madrakian, A. Maleki, Anal. Biochem. 347 (2005) 162.
[2]A. Afkhami, A.A. Mogharnesband, Anal. Lett. 27 (1994) 991.
[3]F.G. Walz Jr., B. Terenna, D. Rolince, Biopolymers 14 (1975) 825.
Synthesiz and spectrophotometric study of complexation of Cu(II), Zn(II), Ni(II), And Co(II), Ions with 3-Benzoyl-1,1Dibenzylthiourea in Acetonitrile Solution
1
N.Samadi1, F.Narimani*2 , A.Solduzi3
Department of Chemistry, Faculty of science,Urmia University, Urmia, Iran
2
pnu ,Urmia, Iran
3
Azad University, Urmia, Iran
So up to present, a large number of papers have been devoted to the study of complexation reaction between metal ions and
various ligands [1-3].Spectrophotometric methods are in general highly sensitive and as such are suitable for studing chemical
equilibria in solution[4-6]. The complexation reactions between 3-Benzoyl-1, 1-Dibenzylthiourea and Cd+2, Ni+2, Cu+2, Co+2
Ions have been investigated in Acetonitile at room temperature using a spectrophotometric technique.
O
S
N
H
N
Mole ratio plots showed that the complexes have ML stoichiometry. The Kf values were determined to each complex using KINFIT
program (computer fitting of absorbance – mol ratio data). The electronic Absorption spectra of are shown in Fig.2. Presence of
isobestic point in 250 nm clearly showed the simple ML complex formation.
3.5
3
2.5
Abs.
2
1.5
1
0.5
0
200
250
300
350
400
Wavelength
Reference
[1] S. Hulanicki, A. Glab, G. Ackermann, Pure Appl. Chem. 55 (7) (1983) 1137.
[2] J. Zhou, Z.H. Vin, J.X. Qu, H.Y. Shum, Talanta 43 (1996) 1863.
[3] B.J. Colston, V.J. Robinson, Analyst 122 (1997) 1451.
[4] M. Kubista, R. Sjoback, B. Albinsson, Anal. Chem. 65 (1993).
[5] S.M. Hoenigman, C.E. Evans, Anal Chem. 68 (1996)
[6] A. Safavi, H. Abdollahi, talanta 53 (2001) 1001.
QSAR Modeling of Cyclohexene Derivatives as Anti-Sepsis Agents Using Artificial Neural Network with Various
Learning Function
Mehdi Mousavi*, Sudabe Mandani
Department of chemistry,faculty of sciences,shahid bahonar university of kerman, kerman 76169, Iran.
* mmousavi@mail.uk.ac.ir
This study deals with developing a quantitative structure-activity relationship (QSAR) model for describing and predicting the
inhibition activity of a new group of cyclohexene derivatives as anti-sepsis agents. The half maximal inhibitory concentrations
(IC50) of these compounds were taken from reference [1]. Prior to the calculation of the molecular descriptors, 3D structures of
the compounds under study were optimized using Semi-empirical quantum-chemical method of AM1 implemented in hyperchem
computer program. Using Dragon software, a total of 1497 molecular descriptors were calculated for each molecule in the data
set. Stepwise multiple linear regression (MLR) method was used as feature selection method. Then, to consider non-linear antisepsis behavior of the molecules under study, back propagation artificial neural network ( BP-ANN) method was implemented.
The ANN program was encoded in MATLAB 7 in our laboratory. The network was generated using the three descriptors
appearing in the MLR model as inputs and the experimental IC50 of the compounds as outputs. For ANN generation, the data set
was randomly divided into three groups: training, test and prediction sets. In order to evaluate modeling and prediction ability of
the ANN, nine different training functions (i.e. traingda, traingd, traingdx, traingdm, trainscg, trainrp, traincgf, traincgb and
trainlm) were used in optimization process. Then the accuracy of the derived 3-6-1 ANN model was illustrated using mean
square error (MSE), leave-one-out (LOO) cross-validation and Y-randomization methods [2]. Comparison of the MSE values for
training and test sets indicates that trainscg, traincgb and trainlm training function are the most suitable functions. In order to
evaluate prediction ability of ANN while using the training functions, MSE of prediction was used as the criteria for this purpose.
It is concluded that Levenberge-Marquardt algorithm (i.e. LM-ANN) show the minimum error for the prediction set. Therefore it
is the most superior training function in this study. IC50 modeling results comparison for LM-ANN and MLR show superiority
of the ANN over that of linear regression method.
Reference
[1] Masami Yamada,* Takashi Ichikawa, Masayuki Ii, Katsumi Itoh, Norikazu Tamura and Tomoyuki Kitazaki , Bioorganic & Medicinal Chemistry 16 (2008)
3941–3958
[2] M. Jalali-Heravi*, M. Asadollahi-Baboli, P. Shahbazikhah, European Journal of Medicinal Chemistry 43 (2008) 548-556
Ni(II) complex modified glassy carbon electrode for electrocatalytic oxidation of gluose
Ali. Benvidi*, Elahe. Noorbala, Ahmad.A. Dehghani
Department of chemistry, Faculty of science, Yazd university, Yazd, Iran
Corresponding Author E-mail: abenvidi@yazduni.ac.ir*, elahenoorbala@yahoo.com
In this work the catalytic oxidation of glucose was investigated by a N-(pyridine-2-ylmethylene)-2-(2(pyridin-2ylmethyleneamino)ethylthio) aniline nickel(II) modified glassy carbon electrode as a sensitive electrochemical sensor. the
modified electrode has been fabricated by electrodepositing a nano structured of Ni(II) complex on GCE in alkaline solution. The
voltammograms obtained for the modified electrode exhibited a continuous increase of the peak current intensities, indicating a
progressive deposition of the electroactive material on the surface of GCE. This complex exhibits the characteristic of improve
reversibility and enhanced current response of Ni(III)/Ni(II) couple and show good electrocatalytic activity toward the oxidation
of glucose. According to the voltammetric studies, the increase in the anodic peak current and subsequent decrease in the
corresponding cathodic peak current, glucose was oxidized on the electrode surface via an electrocatalytic mechanism. Kinetic
parameters such as electron transfer coefficient, diffusion coefficient and rate constant of the electrocatalytic oxidation reaction
are obtained.
Reference
[1] L. Zeheng, J.Q. Zahang, J. F. Song, Electrochim. Acta 54 (2009) 4565.
[2] V.N. Patange, B.R. Arbad, V.G. Mane, S.D. Salunke, Transit. Met. Chem. 32 (2007) 944. [3] M. Yousef Elahi, M.F. Mousavi, S. Ghasemi, Anal. Chim. Acta 54
(2008) 498.
Combined model of molecular structure and mobile phase composition on the retention behavior of hydroxythioxanthone
derivatives in reversed-phase high-performance liquid chromatography
Ali Asghar Amiri1,*, Raha Zomorrodi2 , Mohammad Reza Ba Ezzat2, Farshad Rasti Jahromi2
Department of chemistry, Shiraz Branch, Islamic Azad University, Shiraz, Iran
Department of chemistry, Firoozabad Branch, Islamic Azad University, Firoozabad, Iran
We study the influences of mobile phase composition and molecular structure on retention behavior of some
hydroxythioxanthone derivatives in reversed-phase high-performance liquid chromatography using ternary mobile phase. The
retention behavior of some hydroxythioxanthone derivatives in reversed-phase high-performance liquid chromatography system
using ternary mobile phase (acetonitrile/ methanol/water) has been studied. The influences of mobile phase composition and
molecular structure on the retention behavior of these hydroxythioxanthone derivatives were investigated. Finally a unified model
was built, which considers the effects of both solute composition and solute chemical structure on the retention times of the
hydroxythioxanthone derivatives. By using the equation, one is able to obtain qualitative information and also to predict the
quantitative of retention time of new or non-tested compound. The effects of both solute composition and solute chemical
structure on the retention times of the hydroxythioxanthone derivatives in reversed-phase high-performance liquid
chromatography system using ternary mobile phase (acetonitrile/methanol/water) were investigated and finally a unified model
was proposed.
Reference
[١] P. Janderal, L. Petranek, M. Kucerova, J. Chromatogr. A 791 (1997) 1.
[2] H. Sharghi, A.R. Salimi Beni, Synthesis 17(2004) 29.
[3] Amiri, Safavi, Salimi, Shamsipur, et al. Anal. 605 (2007)11-19
[۵] Shirai, Matsushima, Hait, et al. European Polymer Journal 4 (2010) 1278-1287.
[۶] Dietliker K, et al. Prog. Org. Coat 2007;58:146-57
[٧] Dietlin C, Lalevee J, Allonas X, et al. Appl. Poly. Sci. 2007;107:246-52.
Coated graphite potentiometric sensors based on methyl2-[2-(2-2-[2(methoxycarbonyl)phenoxy]ethoxyethoxy)ethoxy]benzoate for selective determination of Thallium(I)
M. Chamsaz*, M.R. Salavati, I. Razavipanah, M. Ghanei Motlagh, M. Eftekhari
Electrochemistry Research Laboratory, Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad - Iran
The construction and performance characteristics of coated graphite (CGE),Tl(I) ion selective electrodes based on methyl 2-[2(2-2-[2(methoxycarbonyl) phenoxy] ethoxyethoxy) ethoxy] benzoate is described. The electrode reveals a Nernstian behavior
over a wide thallium ion concentration range of 1.0×10-7 to 3.5×10-2 M with a slope of 58.8±0.4 mV/decade of activity. It has a
response time of <10 s and can be used for at least 3 months without any measurable divergence in potential. The electrode is
highly selective for Tl(I) ions in the presence of a number of cations such as alkali, alkaline earth, and heavy metal ions. The
standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficient of the
electrode. This electrode was used for determination of thallium in real samples.
Reference
[1] M.H. Mashhadizadeh, I. SheikhShoaei, Anal. Bioanal. Chem. 375 (2003) 708.
[2] M. Shamsipur, S. Rouhani, H. Sharghi, M.R. Ganjali, H. Eshghi, Anal. Chem. 71(1999) 4983-4943.
[3] M. Shamsipur, M.Yousefi, M.R. Ganjali, Anal. Chem. 72(2000) 2391-2394.
[4] V.K. Gupta, R.N. Goyal, A.K. Jain, R.A. Sharma, Electrochim. Acta 54 (2009)3218.
Separation and pre-concentration of MnVII/MnII speciation on layered double hydroxides prior to flame atomic
absorption spectrometric determination
H. Abdolmohammad-Zadeh*, G.H. Sadeghi, S. Shabkhizan
Department of Chemistry, Faculty of Sciences, Azarbaijan University of Tarbiat Moallem, P.O. Box 53714-161, Tabriz, Iran
* Corresponding author. Tel.: +98 4124327541 ; Fax: +98 4124327541
E-mail addresses: h.abdol@azaruniv.edu, h_abdol@yahoo.com
Elemental speciation involves the separation and quantification of the different oxidation states. Elemental speciation information
is crucial today because the toxicity and biological activity of many trace elements depend on their oxidation states or chemical
forms as well as their quantities. Most measurement techniques for elemental analysis give the total amount of the trace element
and do not have the ability to provide information on the chemical "form" of the element of interest [1]. Manganese is an
essential micronutrient for organisms and plants. However, it is toxic at higher levels [2]. A novel method for the speciation of
MnVII/MnII on layered double hydroxides (LDHs) prior to flame atomic absorption spectrometric (FAAS) determination has been
developed. For this purpose, Ni–Al (NO3–) layered double hydroxide was synthesized by a co-precipitation method [3] and used
as nano-sorbent for separation and pre-concentration of trace quantities of permanganate ions from aqueous samples. The
adsorption rate of LDH for MnVII was 98% at pH 6, while MnII was not adsorbed. MnVII was eluted from the LDH with 1 mL of
5% (m/v) hydroxyl ammonium chloride (as a reductant) and the produced MnII was then determined by FAAS. In the optimum
experimental conditions, the limit of detection (3s) and enrichment factor were 0.37 ng mL−1 and 100, respectively. The relative
standard deviation (RSD) for six replicate determinations of 30 ng mL−1 MnO4– was 2.4 %. The calibration graph using the preconcentration system was linear in the range of 1−80 ng mL−1 with a correlation coefficient of 0.993. In order to validate the
developed method, a certified reference material (NIST SRM 1566b) was analyzed and the determined values were in good
agreement with the certified values. The proposed method applied successfully to the trace determination of MnVII and MnII in
water, milk and rice samples.
Reference
[1] B. Michalke, V. Nischwitz, Anal. Chim. Acta, 682 (2010 23-36.
[2] United Nation Environment Programme, International Labour Organisation and World Health Organization, Environmental Health Criteria 17, Manganese,
Environmental Science Press, China, 1991.
[3] P.S. Braterman, Z.P. Xu, F.Yarberry, Layered double hydroxides (LDHs), in Handbook of Layered Materials; S.M. Auerbach, K.A. Carrado, P.K. Dutta, (Eds.),
Marcel Dekker, Inc, New York, 2004; pp. 373–474.
Simultaneous determination of tryptophan and uric acid on ionic liquid/carbon nanotube modified carbon-ceramic
electrode
B. Habibi*, M. Dadkhah
Electroanalytical Chemistry Laboratory, Department of Chemistry, Faculty of Sciences, Azarbaijan University of Tarbiat Moallem, Tabriz, Iran
Tryptophan (Trp) is an essential amino acid for human and herbivores but is scarcely present in vegetable products. It is
sometimes deficiency fortifier and to pharmaceutical formulations in order to correct possible dietary deficiencies [1]. Uric acid
(UA) is a primary end product of urine metabolism and abnormal levels of UA exhibit symptoms of several diseases like gout,
hyperuricaemia and Lesch-Nyhan syndrome. The elevated UA concentration in serum causes kidney damage and cardiovascular
disease. Only a few methods have been reported for the simultaneous determination of Trp and UA. Yet, such methods require a
long time for extracting and purifying the active principles before analysis. Electroanalytical methods, with respect to their
sensitivity, accuracy and simplicity, have been more of interest in recent years for Trp and UA analysis and development of
voltammetric sensors for determination of Trp and UA has received considerable interest in recent years. CNTs have attracted
much attention due to their high chemical stability, high surface area, unique electronic properties and relatively high mechanical
properties. Recently room temperature ionic liquids have been utilized in the fields of electrochemistry and electroanalysis due to
their unique physicochemical properties including higher ionic conductivity, wider electrochemical windows and good solubility
[2]. The purpose of this work is to study the voltammetric behavior of the CNTs-IL gel biosensor as well as its electrocatalytic
characteristics. The obtained electrode was evaluated as a sensor for sub-micromolar determination of Trp and UA in aqueous
solutions. The measurements were carried out by application of the DPV and CV method in phosphate buffer solution with pH 7.
CNTs-IL can increase anodic peak currents by adsorption of Trp and UA on electrode surface. The anodic peak currents in DPV
were linear to concentrations in the range of 5×10-7M -3×10-4 M and the detection limit of 0.22 µM and 0.5-50.0 µM and the
detection of limit 0.2 µM for Trp and UA, respectively. This newly exploited method was successfully used to determine Trp and
UA in some pharmaceutical samples.
Reference
[1] G. Chen, J.S. Cheng, J.N. Ye, J. Fresenius, Anal. Chem. 370 (2001) 930.
[2] A. Agazzi, F. De Ponti, and et al Liver Dis. 5 (2003) 590.
Silver nanoparticles immobilized in Zein biopolymer film as a new solid electrode modifier for electrocatalytic processes
Atefeh Pourhossein1 , Khalil Farhadi1, Laya Afrasiabi* 2
1) Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
2) Department of Chemistry, Urmia Paym nour University, Urmia, Iran
In recent years, metallic nanoparticles have attracted much more attention in electroanalysis because of their unusual physical
and chemical properties [1,2]. Metallic nanoparticles, especially noble metal nanoparticles modified electrodes usually exhibit
high electrocatalytic activities towards the compounds which have sluggish redox process at bare electrodes. Concerning
electrodes based on use of silver nanoparticles (Ag NPs), however, there were a limited number of references found in the
literature on electrochemical sensors modified by AgNPs. Very recently, AgNPs, which are easy to synthesize, have attracted
some researchers attention due to their quantum characteristics of small granule diameter and large specific surface area as well
as their ability to quickly transfer photoinduced electrons at the surfaces of colloidal particles [3]. A wide variety of polymeric
matrices such synthetic or biopolymers have been used for packing silver nanoparticles nanoparticles on solid electrodes. We
now report a new biopolymeric medium for the immobilization of silver nanoparticles on glassy carbon electrode. Silver
nanoparticle can be easily incorporated on zein biopolymer film by simple one-step synthesis to produce a stable modifier on
electrode surface. The presence of silver nanoparticles on synthesized modifier was confirmed using cyclic and differential pulse
voltammetric techniques. This silver nanoparticle/zein film was chosen as the excellent mediator in electrocatalysis of some
important biological compounds such as glucose and hydrazine. The effect of several parameters such as the thickness of
modifier film, buffer nature and potential scan rate were studied in electrocatalytic processes.
Reference
[1] E. Katz, I. Willner, J. Wang, Electroanalysis 16 (2004) 19.
[2] L. Zhang, X.U. Jiang, J. Electroanal. Chem. 583 (2005) 292.
[3] T. Liu, J. Zhong, X. Gan, C. Fan, G. Li, N. Matsuda, Chem. Phys. Chem. 4 (2003) 1364.
Prediction of migration factors at 3 different mobile phase compositions and combined modifier
Hoda Shamseddin*, Mohammad Hossein Fatemi
University of mazandaran, babolsar, iran
hodashamseddin@gmail.com
Multiple linear regression (MLR) and artificial neural network (ANN) were used to predict the migration factors of some
aromatic compounds at 3 different mobile phase compositions and combined modifier in MEKC. Some topological and
electronic descriptors were calculated for each solute in the data set, and then the stepwise MLR method was used to select more
significant descriptors and MLR model development. The selected descriptors are: Kier & Hall index (order1), relative negative
charge surface area, HA dependent HDSA-2/TMSA, C component of moment of inertia, Y component of dipole moment and
SDS to decanol ratio in mobile phase. In the next step these descriptors were used as input of an ANN. After optimization and
training of ANN it was used to predict the migration factors of external test set as well as internal and training sets. The root
mean square errors for MLR predicted migration factors at 80/20 SDS to decanol ratio was 0.232 , at 90/10 and 100/0 SDS to
decanol ratio were 0.221 and 0.205, respectively, while this value was 0.198 for combined modifier and then we used ANN
model to predict migration factors for it. The RSME for prediction of migration factor using ANN model was 0.179. Comparison
between these values and other statistical parameters for these models revealed that combined modifier had better result and there
were not any significant differences between ANN and MLR in prediction of solute migration factors for combined modifier in
MEKC.
Reference
[1].Terabe, S., Ostuka, K., Ichikawa, K., Tsuchiya, A., Ando, T., Anal. Chem.. 1984, 56, 113-116.
[2]. Fatemi, M. H., jalali-Heravi, M., Knouze, E., Anal. Chem. Acta. 2003, 486, 101-108.
[3]. Fatemi, M. H., Golmohammadi, H., Electrophoresis. 2005, 26, 3438-3444.
[4]. Fu, S., Lucy, C. A., Anal. Chem. 1998, 70, 173-181.
Preconcentration and Determination of dioxane in shampoo samples using dispersive liquid–liquid microextraction
followed by HPLC–UV
Ali gholami* , Hasan jahangiri
University of Kashan , , Faculty of Chemistry , Department Of Analytical Chemistry
1,4-Dioxane (dioxane) is found in household products such as detergents,shampoos, body lotions, dishwashing soap,
pharmaceuticals and cosmetics.It is a manufacturing by-product of the ethoxylation process in above products. The U.S. Food
and Drug Administration (FDA) has provided guidance to manufacturers about a process called “vacuum stripping” to help
minimize the amount of dioxane in their final product. Manufacturers of personal care products should conduct laboratory
analysis to determine the levels of dioxane in their products, and manufacturers using dioxane in their processes should analyze
their waste streams for possible dioxane content. A fast, simple, and sensitive sample preparation procedure based on dispersive
liquid–liquid microextraction (DLLME) is proposed for the determination of dioxane in shampoo samples using isocratic reverse
phase high performance liquid chromatography (RP-HPLC) and UV detection [1-4]. Complicated matrices like soap, shampoo
and lotions can cause significant analytical problems, making it difficult to obtain accurate and reproducible sample
concentrations, especially at lower limits of detection in the part per billion range. The influence of several important parameters
on extraction efficiency of dioxane was evaluated. Under optimal conditions, dioxane were baseline separated within 5.3 min,
with the minimal limit of detection of 0.5 ng mL-1 and coefficient correlations in the range of 0.9980-0.9995.
Reference
[1] M. Rezaee, Y. Assadi, M.R. Milani Hosseini, E. Aghaee, F.Ahmadi, S. Berijani, J. Chromatogr. A 1116 (2006) 1
[2] P. Hashemi, F. Raeisi, A.R. Ghiasvand, A. Rahimi, Talanta 80 (2010) 1926.
[3] P. Hashemi, S. Beyranvand, R.S. Mansur, A.R. Ghiasvand, Anal. Chim. Acta 655 (2009) 60.
[4] Y. Li, G. Wei, J. Hu, X. Liu, X. Zhao, X. Wang, Anal. Chim. Acta 615 (2008) 96.
Synthesis ZnO-MWCNT nanocomposit and application in photo degradation of Azo dyes
ZnO nanoparticles in pure form or as nanocomposites form are one of the materials are able to be use for degradation of Azo-dies
as industrial pollutants under UV light, but combination of Zno nanocomposites with MWCNT’s as ZnO-MWCNT
nanocomposites can provide better result for this aim. Thus important conditions for coating ZnO on MWCNT, can influence it’s
photo-catalytic properties [1-3]. Mentioned work carried out throughout two steps, first step was done by optimization in
oxidation of MWCNT’s surface and then important agent’s in coating ZnO on MWCNT’s surface. Demonstrating of the result
was studied throughout two ways [4-6]. Initially a simple acid-base back titration was completed to quantify total free acidic
groups on surface’s of MWCNT’s for both of functionalized MWCNT’s and then produced nanocomposites. Amount of used
base for naturalize the compound’s surface is showing the total free acidic groups on surface’s of MWCNT. After these steps
Methyl orange as an Azo-dye was investigated for degradation by this optimized produced compound. For this footstep, made
use of UV-visible spectroscopy headed for poverty of Methyl orange compound in the solution under UV light. Outcomes from
this experiment provide evidence that acid-base back titration can offer a trouble-free method to evaluate competence of such
these synthesize.
Reference
[1] A.R. Khataee, M. Zarei, Desalination 273 (2011) 453–460.
[2] M. Scarselli, P. Castrucci, L. Camilli, S. Del Gobbo, S. Casciardi, F. Tombolini, Nanotechnology, 22 (2011) 110-116
[3] Yipeng Du, ChunCheng Hao, Guizhen Wang, Materials Letters 62 (2008) 30–32
[4] M. Skoumal, C. Arias, P.L. Cabot, F. Centellas, J.A. Garrido, R.M. Rodríguez, E. Brillas, Chemosphere 71 (2008) 1718–1729.
[5]. M. Skoumal, R.M. Rodríguez, P.L. Cabot, F. Centellas, J.A. Garrido, C. Arias, E. Brillas, Electrochim. Acta 54 (2009) 2077–2085.
[6] C. Flox, P.L. Cabot, F. Centellas, J.A. Garrido, R.M. Rodríguez, C. Arias, E. Brillas, Appl. Catal. B Environ. 75 (2007) 17–28
Investigation of effect of temperature and sodium dodecyl sulphate (SDS) on critical micelle concentration (cmc) of Triton
X-100 using the conductometery method.
Shahabaddin mohebbia, siavash baharia*, mehdi ahmadi- sabegha and babak mohammadi aghdama
a
Department of basic science, Ahar Branch, Islamic Azad University, , Ahar,Islamic Republic of Iran
Surfactants are widely used as solubilizers, emulsifiers, and detergents in many household and industrial situation showing to
their unique physicochemical properties. The applications of micellar systems or other organized molecular assemblies have been
recognized for many years, and they have been exploited in different areas including the chemical industry, materials science, the
energy industry, and medicine (1–3). In this paper, the effects of temperature on the physicochemical properties of different
surfactants including, sodium dodecyl sulfate (SDS), and Triton X-100 were studied by conductometery. The experimental
results show that the effect of temperature in the mixed surfactants, which mentioned above caused the increase the cmc of
TritonX-100 and decrease the cmc of SDS.
Reference
[1] N.G. Polikhronidi, I.M. Abdulagatov, J.W. Magee, G.V. Stepanov, Int. J.Thermophys. 22 (2001) 189.
[2] N.G. Polikhronidi, I.M. Abdulagatov, J.W. Magee, G.V. Stepanov, Int. J.Thermophys. 23 (2002) 745.
[3] N.G. Polikhronidi, I.M. Abdulagatov, J.W. Magee, G.V. Stepanov, Int. J.Thermophys. 24 (2003) 405.
Ion Imprinted Polymer Particles for Zink Uptake: Synthesis, Characterization and Solid Phase Extraction
Morteza Aghajanzadeh*, Majid Soleimani, Majid Ghahraman Afshar
Department of Chemistry, Imam Khomeini International University, P.O. Box: 288, Qazvin, Iran
G-mail: afshar.analyst@gmail.com
Ion-imprinted polymer (IIP) materials were used for solid-phase extraction (SPE) of ions in different samples. In this study, an
ion-imprinting polymer was introduced for selective extraction and preconcentration of zinc from aqueous solution. In synthesis
process zinc salt, dithizone, 2-vinylpyridine (VP), ethyleneglycol dimethacrylate (EGDMA) and 2, 2-azobisisobutyronitrile
(AIBN) were used as template, Zn(II) complexing reagent, functional monomer, cross-linker and initiator, respectively. This
polymer has been characterized on the basis of FT-IR and thermal analysis (TGA, DTA & DSC). The polymer block obtained
was ground and sieved (55-75µm) and Zn(II) ions were removed from polymer particles by leaching with 1 M of EDTA for 72 h,
which leaves a cavity in the polymer particles. The ion imprinted particles (IIPs) was applied for the selective extraction of Zn(II)
from water. The maximum adsorption capacity of Zn(II) on IIPs was about 3.4 mg g-1. The effect of pH, type of buffer and flow
rate for quantitative enrichment was also investigated. A detection limit of 5.00×10-3 mg L-1 and a relative standard deviation
4.7% were obtained. The IIP–SPE preconcentration procedure showed a linear calibration curve within concentration range from
0.05 to 10 mg L-1 for Zn(II).
Refrence
[1] M.Tuzen, M. Soylak, L. Elci, Anal. Chim. Acta 548 (2005) 101-105.
[2] T. Maranhao, D. Borges,M. Veiga, A. Curtius, , Spectrochemica Acta Part B 60 (2005) 667-672.
[3] A.G. Mayes, K. Mosbach, Trends Anal, Chem 16 (1997) 6-11.
[4] R. Say,M. Erdem, A. Ers¨oz, H. T¨urk, A. Denizli, Appl. Catal.A 286 (2005) 221-226.
[5] L.O. Leal, O. Elsholz, R. Forteza, V. Cerd`a, Analytica Chimica Act. 573–574 (2006) 399–405
.Electrochemical
allopurinol sensor based on molecular imprinting
recognition sites on multiwall carbon nanotube surface
B. Rezaei, O. Rahmanian*
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 I.R. Iran
Molecular imprinting, first constructed by Wulff [1] and Mosbach [2], is a method for making artificial binding sites in a
polymer. MIPs are facile technique and typically prepared by polymerizing a combination of a target molecule (template),
functional monomers and an excess of cross-linker. Binding sites with molecular recognition properties are formed after
removing template molecules from the polymerized network, leaving behind cavities complementary in size and shape to the
template for the subsequent rebinding process. However, diffusion of the analyte across the MIP and heterogeneous distribution
of the binding sites are the most problem with use of MIPs prepared by conventional methods. Therefore, MIPs need to modify in
order to attain a rapid response and reduce binding time. MWCNTs could be convenient option as a support material to overcome
above problems that encountered with use of the MIPs. Herein, a sensitive electrochemical sensor was fabricated for allopurinol
(AP) based on molecularly imprinted polymer (MIP) immobilized on multiwall carbon nanotube (MWCNT) surface. Thin film of
MIP immobilized on MWCNT surface (MIPCNT) with specific binding sites for AP was cast on glassy carbon electrode (GCE).
The morphology and features of the MIPCNT film was characterized by field emission scanning electron microscopy (FE-SEM),
cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and amperometric measurements (I–t) in detail. The
adsorbed amount of AP approached the equilibrium value upon 9 min adsorption. The modified electrode was used to detect the
concentration of AP with a linear range and detection limit (S/N=3) of 1.0-0.01 µM and 6.88 nM, respectively. The MIPCNT
film displayed excellent selectivity towards AP. Finally, the modified electrode was successfully applied to determination of AP
in the human serum sample and two brand tablet samples.
Reference
[1] G.Wulff, A.Sarhan, K.Zabrocki, Enzyme-analogue built polymers and their use for the resolution of racemates, Tetrahed. Lett.14 (1973) 4329-4332.
[2] G.Vlatakis, L.I.Andersson, R. Müller, K. Mosbach, Drug assay using antibody mimics made by molecular imprinting, Nature,361 (1993) 645-647.
Electrosynthesis and Characterization of Zinc Sulfide Nanoparticles
Morteza Khalilian1,*, Mehdi Rahimi-Nasrabadi1, Ali Akbar Davody1 , Seied Mehdi Pourmortazavi2
1
Department of Chemistry, Imam Hossein University, Tehran, Iran
٢
Faculty of Material and Manufacturing Technologies, Malek Ashtar University of Technology, Tehran, Iran
Electrosynthesis has emerged as a convenient and inexpensive technique for the synthesis of various compounds. In this study, a
simple electrosynthesis process has been proposed to preparation of zinc sulfide nanoparticles at low temperature. ZnS
nanoparticles in different sizes were synthesized on a relatively large scale by electrolysis in sodium sulfide solution with zinc
plate as anode. The results showed that particle size of the product could be tuned by reaction parameters such as electrolysis
voltage and sulfide ion concentration as reactant. The morphological (SEM) characterization analysis was carried out for the
obtained ZnS nanoparticles. Detailed particle size of the compound as a function of electrolysis voltage shows that by increasing
voltage from 16 to 24 V, the particle size of ZnS increased. On the other hand, particle size of produced zinc sulfide at a constant
voltage depended on the concentration of sulfide solution. The result of SEM analysis for the prepared zinc sulfide under the best
condition indicates that average particle size of the product is in the range of about 54 nm.
Reference
[1]. Iraj Kohsari; Seiedeh Somayyeh Hajimirsadeghi," Application of the Taguchi Method for Optimization Experimental Condition of Synthesized Barium Chromate
Nanoparticles by a Precipitation Method", Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 2011, 41, 465–471.
[2]. Seied Mahdi Pourmortazavi, Seiedeh Somayyeh, Hajimirsadeghi, Iraj Kohsari, Reza Fareghi Alamdari, Mehdi Rahimi-Nasrabadi," Determination of the Optimal
Conditions for Synthesis of Silver Oxalate Nanorods", Chem. Eng. Technol., 2008, 10, 1532–1535.
[3]. Pourmortazavi, S.M.; Hajimirsadeghi, S.S.; Kohsari, I.; Hosseini,S.G,". Orthogonal array design for the optimization of super critical carbon dioxide extraction of
different metals from a solid matrix with cyanex 301 as a ligand", J. Chem. Eng. Data 2004, 49, 1530.
[4]. Xi, L.; Qian, D.; Huang, X.; Wang, H,"Fine nanoparticles of Al–SnO2 prepared by a co-precipitation route in water/oil microemulsion",J. Alloy Compd. 2008,
462, 42–46.
Second order advantage obtained from a rank deficient electrochemical data using rank annihilation factor analysis
Marcel Maedera*, Hamid Abdollahi b*, Mojtaba Kooshkib
(a)Department of Chemistry, University of Newcastle, Callaghan, New South Wales 2308, Australia
(b)Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan, Iran.
E-mail: abd@iasbs.ac.ir, marcel.maeder@newcastle.edu.au
Rank annihilation factor analysis with the aim of achieving the electrochemical second order advantage has been applied to
potential-time second-order data. In this work a simple way is used to generation of the instrumental electrochemical secondorder data by differential pulse voltammetry [1]. Differential pulse voltammograms of tryptophan (Trp) were recorded at an
unmodified carbon paste electrode. The effect of pH of solution and composition of electrode and type of buffer on the peak
current of DPV has been investigated. The optimum condition for determination of Trp was the phosphate buffer with pH=7.4
and the optimum electrode composition was 30% silicon oil, 70% graphite. The data of a mixture of two electroactive component
has been simulated using the current equation of DPV, according to this equation; pulse duration profile is independent from
nature of electroactive species and only depends on the pulse duration. Therefore the pulse duration profiles of the two
electroactive components have the same shape. This problem leads to degeneracy or the rank deficiency in the pulse duration
profile matrix. Rank deficiency of the mixture data matrix is broken by dosing aliquot amount of analyte of interest to the
standard sample and mixtures. In this procedure (dosing), some of the analyte of interest is added to the mixture during the course
of the reaction [2]. A mixture of Trp and tyrosine has been investigated as a model to show the ability of method. The oxidation
peak potential of Tyr is very close to the Trp oxidation peak potential. So, Tyr is one of the usual interferences in Trp
determination . Results of RAFA shows that the proposed method could be efficiently used for determination of Trp in the
presence of unexpected interferents in the meat extract.
Reference
[1] H. Abdollahi, M. Kooshki, Electroanalysis, 22 (2010) 2245
[2] M. Amrhein, B. Srinivasan, D. Bonvin, M. M. Schumacher, Chemom. Intell. Lab. Syst. 1996, 33, 17.
[3] G.-P. Jin, X.-Q. Lin, Electrochem.Commun., 6 (2004) 454-60.
[4] F.-H. Wu, G.-C. Zhao, X.-W. Wei, Z.-S. Yang, Microchim. Acta, 144 (2004) 243-7.
Design and construction of a stain detector for determination of gases in the air imploying image processing and analysis
M. Pakniat , A. Majedi*
Department of chemistry, Faculty of Basic Sciences, Persian Gulf University, Bushehr 75168, Iran
Rapid tests for qualitative and quantitative analysis have a high level of acceptance and growing demand for practical
experiments out of laboratories at short time and low expense[1]. The main problems are overwhelming the physical and
chemical obstacles of short assay time and not including the complex instrumental provisions [2]. Safety and portability of are
among the main characteristics of such detectors [3,4]. Image analysis is the extraction of meaningful information from images
by means of digital image processing techniques. These include many applications in the industry, laboratory and home. At the
same time different statistical methods for improving image resolution, noise reduction and clustering the image elements were
adopted. There are few applications in different branches of science in relation with or in chemistry but still much of the potential
abilities of imaging technique is unexploited e.g. for data recording or analysis. For practical purposes recording all experimental
parameters, especially for an unauthorized person is time consuming and tedious. Recording information especially by an
unauthorized person would be a great advantage and returning much data to laboratories as a drawback. By appropriate
arrangement of equipments and inclusion of experimental data in front of a camera all information needed such as concentrations,
flow rate, time, color, area, volume, temperature etc. could be recorded for further investigations without any conscious
supervision. Determination of hazardous gases in connection with the health aspects in indoor air is an important occupation
today. Many types of gas detectors are available today but there is still a great need to employ colored tests adopted for such
needs. In this research the potential ability of stain detectors [ 5,6 ] modified to accommodate gaseous samples is under
investigation. Different types of detectors from trapping and equilibrating with a reagent phase to various designs using a
stationary porous substrates were evaluated to obtain the final design. Carbon dioxide was selected as a representative compound
using a merely alkaline reagent phase containing methyl red indicator in a permanent stain detector. All parameters were
optimized regarding the time and the sensitivity needed for analysis. As low as 0.02% of carbon dioxide in air can be determined
with a RSD about 2.5% Based on the practical limitation of our design a linear calibration up to 2% was obtained. The detector
has established a practical basis extending to other gas analysis exploiting available materials in daily life.
Reference
[1] Epperson. P; Sweedler. J; Bilhorn. G; Sims. G. B; Denton. M. B; Anal. Chem.60,1988,282A.
[2] Zolotov. Y.A; Ivanov. V.M; and Amelin, V.G., Trends Anal. Chem., (2002), 21,4, 302.
[3] . Lev. O; Kuyavskaya. B; Kuselman. I; Anal. Chem. Acta, 1992,256,65.
[4] . National Institute of Occupational Safety and Health;Manual of Analytical Methods,3rded;Washington,D.C,1984.
[5] . American Industrial Hygiene Association; Am. Ind. Hyg. Assoc. J,1971,32,405.
[6] . Pakniat. M; A Safavi ; Anal. Lett
Simultaneous determination of four organophosphorous pesticides in tea using GC/FTD
Mehdi Abdollahi a , Shahram Shoeibi b, c , Hossein Rastegar b, c , Behrouz Janatb,e, Maryam Mansourib,c , Morteza Pirali Hamedanif , Roya
Khosrokhavarb,c, Maryam Amirahmadib,c,*
a
School of Pharmacy, Tehran University of Medical Sciences, Tehran, I. R. Iran
Food and Drug Laboratories Research Center, Ministry of Health and Medical Education, Tehran, I. R. Iran
c
Food and Drug Control Laboratories, Food and Drug Deputy, Ministry of Health and Medical Education, Tehran, I. R. Iran
d
Department of food control , School of Pharmacy, Tehran University of Medical Sciences, Tehran, I. R. Iran
e
Food and Drug Deputy, Ministry of Health and Medical Education, Tehran, I. R. Iran
f
Department of Medicinal Chemistry, School of Pharmacy, Tehran University of Medical Sciences, Tehran, I. R. Iran
*Email: maryamamir2001@yahoo.com
b
Tea is a beverage with antioxidant properties and resultant beneficial effects on human health so called as ‘health beverage’. Such
a beverage should be free from toxic elements such as pesticide residues. Analysis of pesticide residues in food and other
environmental commodities have become essential requirement for consumers, producers, and food quality control authorities.
This study was conducted on tea as a main beverage in Iranian food basket. A reliable, rapid and accurate method based on
spiked calibration curves and modified QuEChERS sample preparation was developed for determination of four
organophosphorous pesticide residues in tea by gas chromatography-FTD detector (GC/FTD). Triphenylphosphate (TPP) is used
as internal standard. FTD detector is a high sensitive detector for chemical substance with N & P groups. The use of spiked
calibration standards for constructing the calibration curve substantially reduced adverse matrix-related effects. The recovery of
pesticides at 3 concentration levels (n=3) was in range of 91.77-104.62%.The method was proved to be repeatable with RSD
lower than 20%. The limits quantification for all pesticides were <10 ng/g. The recoveries and repeatabilities were in accordance
with the criteria set by SANCO Guideline.The validated method with using spiked samples for preparation of calibration curves
is an accurate, precision and simple method for analysis of organophosphorous pesticides in tea.
Reference
[1] - Seenivasan,S., Nair Muraleedharan,N., 2011. Survey on the pesticide residues in tea in south
India, Environ Monit Assess. 176:365–37.
[2] - Hajslova, J., Zrostlikova, J., 2003. Matrix effects in (ultra) trace analysis of pesticide residues
in food and biotic matrices. J. Chromatogr. A. 1000, 181-197.
Biphenyl and biphenyl oxide determination in environmental water samples using Dispersive liquid – liquid
microextraction and gas chromatography -flame ionization detection
Abbas Sabzi Kamasaie a, Mohammad Aghamohammadi *b, Mohammad Rezaee c
Department of Chemistry, Islamic Azad University, Saveh Branch, Saveh, Markazi, Iran
*b
Department of Chemistry, Islamic Azad University, Boroujerd Branch, Boroujerd, Lorestan, Iran
c
Nuclear Fuel Cycle Research School Nuclear Science and Technology Research Institute , AEOI , Tehran , Iran
a
Biphenyls widely used in production of hot prance fluids, plastic, optical brighteners, hydraulic fluids, high temperature lubricant
and in perfumery industries [1-2]. In the present work a simple rapid method has been developed for determination of biphenyl
and biphenyl oxide in water sample using dispersive liquid – liquid micro extraction [3] followed by gas chromatography
detection. In this method 15 mL of chlorobenzene as extracting solvent as well as 1 ml methanol as disperser solvent for the
formation of cloudy solution of 5 ml aqueous sample containing biphenyl and biphenyl oxide were used. After extraction, phase
separation was performed by centrifugation and determination of analytes in sediment phase was done by gas chromatography flame ionization detection (FID). The influence of the various analytical parameters on DLLME procedure, i.e. extracting and
disperser solvents type and their volume, ionic strength and etc. has been evaluated and optimized. At optimum conditions, the
enrichment factor for biphenyl and biphenyl oxide were higher than 600. The calibration graph were linear for biphenyl and
biphenyl oxide in the range 0.01-200 mg.L-1 and 0.1-200 mg.L-1 with a detection limit of 0.007 mg.L-1 and 0.08 mg.L-1
respectively. The DLLME–GC method presents good repeatability (RSDs <5%), simplicity, good sensitivity and short extraction
times. The method was applied for determination of biphenyl and biphenyl oxide in environmental water samples with
satisfactory recovery.
Reference
[1] M . Sitting, handbook of toxic and hazardous chemical and carcinogens, 3ed USA 1991.
[2] USEPA office pollution prevention and toxic chemical facts (accessed, Jun1999).
[3] M . Rezaee, Y. Assadi, M.R. Milani Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, Determination of organic compounds in water using dispersive liquid – liquid
microextraction, J. Chromatogar. A, 2006, 1116, 1.
Direct Electrochemistry of Polyphenol Oxidase
1
Jahan Bakhsh Raoof*1, Abolfazl Kiani2, Reza Ojani1, Roudabeh Valiollahi1
Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, Mazandaran University,
Babolsar, Iran
E-mail: j.raoof@ umz.ac.ir
2
Department of Chemistry, Faculty of Science, University of Isfahan, Isfahan, Iran
Many of the copper-containing redox proteins and enzymes show efficient direct electron transfer [1]. The electrode material may
play a vital role in the production of a bio-electrochemical device able to access the desired information. Therefore, the use of
carbon nanotubes (CNTs) can be an efficient approach to achieve the communication between electrode and electro-active centre
of proteins [2,3]. In this paper the direct electrochemistry of polyphenol oxidase (PPO) into banana and apple tissues on a carbon
paste electrode modified by MWCNTs is presented. MWCNTs were from Nanotab, USA, 95%. Graphite powder (particle
diameter = 0.1 mm) was from Merck. Electrochemical studies were carried out using a computer-controlled
potentiostat/galvanostat (Autolab, The Netherlands). Cyclic voltammetry of a: unmodified CPE, b: CPE-MWCNTs, c: CPEbanana and d: banana-MWCNTs-CPE in phosphate buffer solution (pH = 7.00) was studied and no peak current was seen in
curves a, b, and c but was seen in curve d. Thus, direct electrochemistry of enzyme cannot be observed at the surface of
unmodified carbon paste electrode. To demonstrate that the observed signal at the surface of banana-MWCNTs-CPE is due to
redox behavior of PPO, we performed another experiment as follows: first, a differential pulse voltammogram of bananaMWCNTs-CPE was obtained in phosphate buffer (pH = 7.00), and then various concentrations of PPO were added to the
solution and its electrochemical behavior was studied with differential pulse voltammetry. The influence of various parameters
such as pH, scan rate, and heating on the electrochemical signal was examined. The direct electrochemistry of PPO in fruits
tissues was described for the first time. We have shown that MWCNTs can enhance the direct electron transfer between the
electroactive center of PPO in banana tissues and the underlying electrode. It was found that presence of CNTs is essential to
observe the electrochemical activity of PPO in banana and apple tissues.
Reference
[1]S. Shleev, J. Tkac, A. Christenson, T. Ruzgasa, A.I. Yaropolov, J.W. Whittaker, and L. Gorton, Biosensors and Bioelectronics 20 (2005) 2517.
[2]M.J. Eddowes, and H.A.O. Hill, J. Chem. Soc. Chem. Commun. 21 (1977) 771.
[3]P. Yeh, and T. Kuwama, Chem. Lett. 6 (1977) 1145.
Preparation of a Fiber Coating for Selective Solid-phase Microextraction Based on Molecular Sol-gel Imprinting Process:
Application for GC/MS Determination of Caffeine in Human Serum
a
Afshin Rajabi Khorrami*,a, Amene Rashidpur b
Department of Chemistry, Karaj Branch, Islamic Azad University, Karaj, Iran.
b
Young Research Club, Karaj Branch, Islamic Azad University, Karaj, Iran.
In this work, a sol-gel molecularly imprinting polymerization approach has been introduced to produce fiber coatings for
selective solid phase micro extraction (SPME) of caffeine [1,2]. The polymerization mixture was composed of vinyl
trimethoxysilane and methacrylic acid as vinyl metal oxide precursor and functional monomer, respectively [3]. Caffeine was
used as template molecule during polymerization process. The prepared fiber could be coupled directly to gas
chromatography/mass spectrometry (GC/MS) and used for trace analysis of caffeine in a complicated sample such as human
serum. The parameters influencing extraction such as time, temperature and stirring speed were optimized. The prepared coating
showed good selectivity towards caffeine in the presence of some structurally related compounds. Also, it offered high imprinting
capability in comparison to non imprinted coating. Linear range for caffeine was 5.00–80 μg ml-1 and detection limit was 0.1 μg
ml-1.
Reference
[1] R.G.D. C. Silva, F. Augusto, Sol–gel molecular imprinted ormosil for solid-phase extraction of methylxanthines, Chromatogr. A. 2006, 1114, 216–223.
[2] X. Hu, Y. Hu, G. Li, Development of novel molecularly imprinted solid-phase microextraction fiber and its application for the determination of triazines in
complicated samples coupled with high-performance liquid chromatography, J. Chromatogr. A. 2007, 1147, 1-9.
[3] C.I. Lin, A.K. Joseph, C.K Chang, Y.C. Wang, Y.D. Lee, Synthesis of molecular imprinted organic–inorganic hybrid polymer binding caffeine, Anal. Chim. Acta.
2003, 481, 175–180.
Orthogonal signal correction-partial least squares for simultaneous spectrophotometric determination of Nile Blue and
Safranin in waste water
Niloofar Zamani * and Ali Niazi
E-mail: niloofarzamani89@yahoo.com and ali.niazi@gmail.com
Department of Chemistry, Islamic Azad University-Arak Branch, Arak, Iran
The simultaneous determination of Nile Blue and Safranin mixtures by spectrophotometric method is a difficult problem in
analytical chemistry, due to spectral interferences, by Multivariate calibration methods, such as partial least square (PLS)
regression [1], it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range.
Orthogonal signal correction (OSC) [2, 3] is a preprocessing technique used in the information unrelated to the target variables
based on constrained principal component analysis. OSC is a suitable preprocessing method for partial least squares calibration of
mixtures without loss of prediction capacity using spectrophotometric method. In this study, the calibration model is based on
absorption spectra in the 360-760 nm range for 25 different mixtures of Nile Blue and Safranin calibration matrices were formed
form samples containing 0.05-19.5 and 0.05-11.0 µg mL-1 for Nile Blue and Safranin, respectively. The RMSEP for Nile Blue
and Safranin with OSC-PLS were 0.0189 and 0.0161 µg mL-1. This procedure allows the simultaneous determination of Nile
Blue and Safranin in synthetic and real samples such as waste waters and good reliability of the determination was proved.
Reference
[1] A. Niazi, S. Jameh-Bozorghi, D. Nori-Shargh, J. Hazard. Mat. 151 (2008) 603
[2] A. Niazi, A. Yazdanipour, J. Hazard. Mat., 146 (2007) 421.
[3] A. Niazi, A. Azizi, M. Ramezani, Spectrochim. Acta Part A, 71 (2008) 1172.
A novel, effective and low cost catalyst for formaldehyde oxidation based on nickel ions dispersed onto poly(mtoluidine)/Triton X-100 film at the surface of multi-walled carbon nanotube paste electrode
Jahan-Bakhsh Raoof*, Reza Ojani, Samaneh Abdi and Sayed Reza Hosseini
Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, Mazandaran University, 3rd
Kilometer of Air Force Road, Postal Code: 47416-95447, Babolsar, Iran
First author’s e-mail: j.raoof@umz.ac.ir
The simple molecular structure of formaldehyde (HCHO) has prompted its use as a model to gain insight into the processes of the
electrooxidation of small organic molecules, a subject of long-term interest in the development of fuel cell technology [1].
Although formaldehyde is toxic and not very suitable for fuel cells, the study of its electrochemical oxidation is important for the
full understanding of methanol oxidation, because formaldehyde is produced by partial oxidation of methanol [2,3]. In this work
an aqueous solution of Triton X-100 (TX-100) non-ionic surfactant is used as an additive for electropolymerization of mtoluidine (MT) onto multi-walled carbon nanotube paste electrode (CNTPE), which is investigated as a novel matrix for
dispersion of catalysts. Poly (m-toluidine)/TX-100 films have considerably higher redox current than the normal poly (mtoluidine) film. Apparently, the porous PMT (TX-100) films have higher effective surface areas. The as-prepared substrate is
used as porous matrix for dispersion of transition metal ions of Ni(II) by immersing the modified electrode in a nickel (II) sulfate
solution. The electrochemical characterization of this modified electrode exhibits redox behavior of Ni(III)/Ni(II) couple. It has
been shown that PMT/TX-100 at the surface of CNTPE improves catalytic efficiency of the dispersed nickel ions toward
formaldehyde oxidation. Moreover, the effects of various parameters such as concentration of TX-100, concentration of
formaldehyde, accumulation time, potential scan rate, film thickness and monomer concentration on the electrooxidation of
formaldehyde as well as long-term stability of the Ni/PMT (TX-100)/MCNTPE have also been investigated. This modified
electrode can oxidize the formaldehyde with high current density. Ni(OH)2 species onto the poly (m-toluidine)/Triton X-100 film
shows higher catalytic activity towards formaldehyde oxidation than that the other nickel modified electrodes. The value for the
catalytic rate constant obtained from the chronoamperometric method indicates that the modified electrode can overcome the
kinetic limitation for the formaldehyde oxidation by a catalytic process and can decrease the overpotential for the oxidation
reaction of formaldehyde.
Reference
[1] C. Mai, C. Shue, Y. Yang, L. Yang, S. Yau, K. Itaya, Langmuir 21 (2005) 4964-4970.
[2] G. Samjeske, A. Miki, M. Osawa, J. Phys. Chem. C. 111 (2007) 15074 – 15083.
[3] R.Ojani, J.B.Raoof, S.R. Hosseini, J. Solid State Electrochem. 13 (2009)1605–1611.
Investigation of extraction of abamectin by dispersive liquid liquid microextraction combined with high performance
liquid chromatography
Mohammadreza Hadjmohammadia, Aliasghar Golbabanezhad Azizi*a, Pourya Biparvab
a
Department of Chemistry, University of Mazandaran, Babolsar, Iran
b
Research Department of Chromatography, Iranian Academic Center for Education, Cultur & Research (ACECR), Urmia, Iran
Abamectin is a product which was developed as an insecticide and acaricide with contact and stomach action [1]. It belongs
to the family of avermectins which are macrocyclic lactones produced by the actinomycete Streptomyces avemitilis.
Abamectin is widely used for treatment of orange in northern Iran. In this work, a simple and rapid sample pretreatment
technique, dispersive liquid–liquid microextraction (DLLME) coupled with high performance liquid chromatography-UV
detection (HPLC-UV) was used for extraction and determination of recovery of abamectin from water sample. A mixture of
extraction solvent (carbon tetrachloride, chloroform, dichloromethane) and dispersive solvent (acetone, methanol,
acetonitrile) were rapidly injected into 10.0mL sample solution and a cloudy solution was formed. After centrifugation of the
cloudy solution, the sedimented phase was transferred into a vial by a micro syringe and evaporated with nitrogen stream,
then the residue dissolved in 50 µL methanol and injected into HPLC system. Some important parameters, such as the type
and volume of extraction solvent, dispersive solvent and pH of solution were investigated and optimized. The optimized
parameters were: 75µL carbon tetrachloride, 2mL acetone, solution pH 5.5. The intra-day (R.S.D.), inter day (R.S.D)
precision, recovery and enrichment factor were 0.5%, 0.1%, 73.7±5.6% and 200 respectively.
References:
[1] C. Tamlin, Pesticide Manual, Royal Society of Chemistry, 10th ed., 1994, pp. 3-4
[2] A. Giordano, M. Fernández-Franzón, M. J. Ruiz, G. Font, Y. Picó, Anal Bioanal Chem 379 (2009) 1733
[3] M. Hadjmohammadi, M. Peyrovi, P. Biparva, J. Sep. Sci. 33 (2010) 1044
An electrochemical investigation into the interaction between DNA and olanzapine and its sensory application
Mohammad Bagher Gholivand*, Salman Darabi
Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah, Iran
Olanzapine is a drug used commonly as an Antipsychotic agent against schizophrenia disease in world. DNA was utilized as a
pre-concentration element for the determination of olanzapine based on its interaction with DNA. Initially, the interaction
between olanzapine and DNA in 0.04 M pH 4 Britton–Robinson buffer solution was studied by cyclic voltammetry and
Differential pulse voltammetry. Decreasing peaks was observed for olanzapine with increasing concentration DNA. The results
indicated that olanzapine can bound to DNA. The binding constants K of binding with DNA were obtained by cyclic and
differential pulse voltammetry method . From the voltammetric data changes in limiting current with addition of DNA, the
binding constant (K) of the interaction of olanzapine with DNA was found to be 4.35×104 dm3 mol−1. Finally, sensor designed
for the determination of olanzapine Short reaction times (2 min) was sufficient for determining range from 5×10−7 to 1×10−4
mmol L−1, with a linear correlation of r =0.9977 and a detection limit of 2.47×10−7 mmol L−1.
Reference
[1].Biryol, I. and N. Erk, Voltammetric, spectrophotometric, and high performance liquid chromatographic analysis of olanzapine. Anal. Lett., 2003. 36(11): p. 24972513.
[2].Heli, H., S.Z. Bathaie, and M.F. Mousavi, An electrochemical study of neutral red DNA interaction. Electrochim. Acta, 2005. 51(6): p. 1108.
[3].Boghaei, D.M., S.S. Farvid, and M. Gharagozlou, Interaction of copper(II) complex of compartmental Schiff base ligand N,N '-bis(3hydroxysalicylidene)ethylenediamine with bovine serum albumin. Spectrochim Acta Part A Mol Biomol Spectrosc, 2007. 66(3): p. 650-655.
[4].Carter, M.T., M. Rodriguez, and A.J. Bard, Voltammetric studies of the interaction of metal chelates with DNA. 2. Tris-chelated complexes of cobalt(III) and
iron(II) with 1,10-phenanthroline and 2,2'-bipyridine. J. Am. Chem. Soc, 1989. 111(24): p. 8901-8911.
Electrochemical determination of Homovanillic acid in the glassy carbon electrode
Abdolhamid Hatefi-MehrjerdiÚ , Mohammad Ali Karimi, Somaieh Islami-Ramchahi
Department of Chemistry & Nanoscience and Nanotechnology Research Laboratory (NNRL), Payame Noor University, 19395-4697, Tehran, I.R.
of IRAN
Correspondence: hhatefy@yahoo.com
Homovanillic acid (HVA) is one of the major metabolite of catecholamines. It was found that the excretion of HVA in urine
abnormally increased in patients with neuroblastoma, pheochromocytoma, psychosis and other related diseases. So, HVA is often
tested in urine for the diagnosis of these diseases aforementioned and for monitoring the response to therapy in these diseases.
Several methods for the determination of catecholamines have been described in literature including high performance liquid
chromatography (HPLC), flow injection system and capillary zone electrophoresis, but electrochemical detectors, one of the most
powerful techniques to detect these materials has the advantages such as good accuracy, high sensitivity and low cost. Among the
electrochemical techniques, voltammetry and amperometry methods due to the speed and simplicity are more appropriate to
identify organo-compounds. In this study, the electrochemical behavior of Homovanillic acid is investigated on glassy carbon
electrode (GC) using cyclic voltammetry (CV) and square wave voltammetry (SWV) methods in various potential sweep rates
and frequencies and pHs of the buffer solution. Factors were optimized and optimal condition was pH of 2, frequency of 24 Hz,
step potential of 100 mV, and amplitude of 130 mV. Linear calibration curves were obtained in the concentration range of 100–
1000 M and a detection limit of 9 µM of HVA was achieved.
Reference
[1] X. Li, W. Jin, Q.Weng, Analytica Chimica Acta 461 (2002) 123–130.
[2] T. Selvaraju, R. Ramaraj, Electrochimica Acta 52 (2007) 2998–3005.
[3] R.K. Shervedani, A. Hatefi-Mehrjardi, N. Zamiri, Bioelectrochemistry, 69 (2006) 201-207.
[4] R.K. Shervedani, Z. Hemmatian, A. Hatefi-Mehrjardi, Bioelectrochemistry, 75 (2009) 124-129.
Evaluation of solvent microextraction with back extraction (SME/BE) for the determination of estrogens in water samples
Habib Bagheri*, Hossein Maleki , Ali Es’haghi
Department of Chemistry, Sharif University of Technology, P. O. Box 11365-9516, Tehran, Iran
An important group of new emerging pollutants are those capable of disrupting the endocrine system in both humans and animals
– well known as endocrine disrupting compounds (EDC). Among them, steroid estrogens are the most potent since they show the
highest affinity for the estrogen receptors [1,2]. According to their potential to ionize in different pH, a modified solvent
microextraction with back extraction method (SME/BE) combined with high performance liquid chromatography and UV
detection (HPLC-UV) was developed for the determination of estrogens in water samples [3,4]. Estrogens were first extracted
from 6.3 mL of water sample, modified with hydrochloric acid, into hexane. Back extraction step was then performed into 6 µL
of sodium hydroxide solution (pH 13). The extract was subsequently transferred into a liner-like vial and then injected into the
HPLC system. Important parameters influencing the extraction process were optimized and an extraction time of 25 min at 35 ◦C
and NaCl (4% w/v) in aqueous sample gave maximum peak area. Finally, an enrichment factor of 94 for estrone and 74 for
estriol was obtained with a good sample clean-up.
Reference
[1]. D. Kolpin, E. Furlong, M. Meyer, E.M. Thurman, S. Zaugg, L. Barber, H. Buxton, Environ. Sci. Technol. 36 (2002) 1202.
[2]. M.J. L´opez de Alda, D. Barcel´o, J. Chromatogr. A 892 (2000) 391.
[3]. Z. Fan, X. Liu, J. Chromatogr. A 1180 (2008) 187.
[4]. H. Bagheri, F. Khalilian, E. Babanezhad, A. Es-haghia, M.R. Rouini, Anal. Chim. Acta. 610 ( 2008 ) 211.
Thermal stability investigation and comparison of epoxy resin based on the Diglycidyl Ether of Bisphenol A (DGEBA)
and F (DGEBF) cured by amine curing agent
Abolghasem Moraveji a*, aForuzan Gholamian, aAbdorahim Rahmanian Devin, bRasol Modarresi
Department of Analytical Chemistry, Faculty of Chemistry and Chemical Engineering, Malek Ashtar University of Technology, Tehran, Islamic
Republic of Iran
b
Department of Chemistry, Iran university of science and Technology, Tehran, Islamic Republic of Iran
*
Email address: g.moraveji@gmail.com
a
The investigation of diglycidyl ether of bisphenol A (DGEBA) and F (DGEBF) resins cured with amine curing agent by
thermogravimetry_Differential Thermal Analysis (TG-DTA) and Fourier transform infrared (FT-IR) techniques were used to
determine the thermal stability and degradation, retardant property and char structure. The two resins were analyzed by TG-DTA
at 10°C/min in N2 atmosphere in order to determine various parameters. The FT-IR and TG -DTA results show that by removing
epoxy groups and complete curing of resin, the DGEBA is thermally more stable than DGEBF which leads to DGEBA's higher
degradation and char structure temperatures.
Reference
[1]Baljinder, K. K., Bhaskar, B., Dennis, P., & Richard, H. (2009). Studies on the effect of different levels of toughener and flame retardants on. Polymer Degradation
and Stability , 144-152.
[2]Chuan, S., Ying, L. L., & Yie, C. C. (2002). Thermal stability of epoxy resins containing flame retardant. Polymer Degradation and Stability , 41-48.
[3]Weiyi, X., Ganxin, J., Lei, S., & Xin, W. (2010). Flame retardancy and thermal properties of epoxy acrylate resin/alpha-zirconium. Materials Chemistry and
Physics , 196-201.
[4]Xing, L., Yuxiang, O., & Yanshan, S. (2002). Combustion behavior and thermal degradation properties of. Polymer Degradation and Stability , 383-393.
[5]Zhen, D., Yanfang, L., Shuguang, Y., Ning, Z., Xiaoli, Z., & Jian, X. (2009). Kinetics and thermal properties of epoxy resins based on bisphenol. European
Polymer Journal , 1941-1948.
Removal of methylene blue from aqueous solution by a nut shell as an agricultural waste
Maryam Abrishamkar*, Shahla Elhami, Zahra Zirak
Department of Chemistry, Islamic Azad University, Khozestan Science and Research Branch, Ahvaz, Iran. Email:m.abrishamkar@srbiau.ac.ir
Synthetic dyes like methylene blue are toxic to the aquatic life and may have carcinogenic, teratogenic and/or mutagenic effect
on them [1]. Entering of colored effluents into rivers, upset biological activity, so removal of dyes from waste effluents becomes
environmentally important. Conventional treatment methods for removal of pollutants from aqueous solution, like photochemical
degradation, illogical degradation, coagulation, chemical oxidation and adsorption have been investigated with varying success
[2, 3]. Nut shell, an agricultural waste and low cost products have been successfully used for the removal of methylene blue as a
synthetic dye from aqueous solution. Batch adsorption studies have been made by calculating the effect of contact time, the
amount of adsorbent, pH, sieve size and dye concentrations. Equilibrium investigations were analyzed by Langmuir and
Freundlich isotherms. The adsorption capacity for the adsorption of dye using proposed adsorbent was found to be 208.33 mg/g
by Langmuir isotherm for the particle size of 0.75 mm. The maximum removal of 98.19% was obtained at nature pH 5.5 for an
adsorbent dose of 0.1g/50mL dye concentration.
Reference
[1] V. Ponnusami, V. Gunasekar, S. N. Srivastava, J. Hazard. Mater. 169(2009)119-127.
[2] A. B. des Santos, F.J. Cerantes, J.B. van Lier, Bioresour. Technol. 98 (2007) 2369.
[3] N. Dizge, C. Ayiner, E. Demirbas, M. Kobya, S. Kara, J. Hazard. Mater. 150 (2008) 737–746.
Volatile Constituents of Lippia citriodora H. B. et K. from Iran by
HS-SPME, Hydrodistillation and SFME methods.
Kambiz Larijani1*, Mahsa Ansari1, Mohammad Saber-Tehrani1, Parviz Aberoomand Azar1
1
Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran.
In this comparative study, the volatile compounds of Lippia citriodora from Iran were extracted by headspace solid micro
extraction solvent free microwave extraction and conventional hydrodistillation and analyzed by GC and GC/MS. HS-SPME was
performed using a 75 mm carboxen-PDMS fiber in 80°C. ar-curcumene (17.34%), 1,8-cineole(14.39%) and geranial (9.53%)
were the main constituents. In SFME, geranial (16.96%), neral (13.33%) and 1,8-cineole (12.07%) were identified as major
compounds. Geranial (13.13%), limonene (13.57%)and 1,8-cineole were the main constituents in hydrodistillation method.
Reference
[1] C. Argyropoulou, D. Daferera, P. A. Tarantilis,C. Fasseas, M. Polissiou, Biochem. Syst. Ecol. 35 (2007) 831-837
[2] M.E. Pascual, K. Slowing, E. Carretero, D. S. Mata, A. Villar, J. Ethnopharma. 76 (2001) 201–214
Simultaneous determination of acetaminophen and ascorbic acid using modified carbon paste electrode
N. Soltania,*, N. Tavakkolib, A. H. Ataranc, M. Maseratfarc, F. Davar d
Department of Chemistry, Payame Noor University (PNU) (aIsfahan, Shahin Shahr Branch, bIsfahan and cDelijan)
Acetaminophen (AC), is a widely used nonsteroidal analgesic and antipyretic drug for a wide range of treatments and relatively
safe at therapeutic dosages. However, overdoses of AC cause liver and kidney damage and may lead to death [1]. Thus, the
development of efficient, sensitive, and simple analytical techniques for the determination of acetaminophen is important. On the
other hand, most of the scientific literature reports about the major interferences between AA and AC in a variety of matrices [2].
Therefore, the simultaneous determination of AC and AA is of great importance for the elucidation of their precise physiological
functions. Many analytical methods have been developed for the determination of two compounds, including high performance
liquid chromatography (HPLC) [3], spectrophotometry [4] and electroanalytical methods [1]. In electroanalytical area, the
concept of chemically modified electrodes has been developed gradually instead of conventional electrodes to improve the
reactivity, sensitivity and selectivity of the electrode reactions in many applications. In this work, a highly sensitive
electrochemical sensor based on new composite electrode nano Cu/Schiff base /Carbon paste electrode (Cu/Sb/CPE) for the
simultaneous determination of AC and AA is reported. The electrocatalytic properties of modified carbon paste electrode were
characterized by cyclic voltammetry and differential pulse voltammetry in the presence of AC and AA. Using differential pulse
voltammetry the calibration curves of AC and AA were obtained in the range of 2.5×10−7-3×10−4 M and 1.3×10−4-3×10−3 M
respectively. The detection limit of AC was 3.8×10−8 M in the presence of 1 mM ascorbic acid. The effect of pH and scan rate on
the electrode process was investigated. High sensitivity and selectivity, sub-micro molar detection limit, high reproducibility
together with ease of preparation make the electrode very suitable for the determination of acemanitophen in the presence of
ascorbic acid in pharmaceutical and clinical preparations.
Reference
[1] B. Habibi, M. Jahanbakhshi, M.H. Pournaghi-Azar, Anal. Biochem. 411 (2011) 167–175.
[2] M. Mazloum-Ardakani, H. Beitollahi, M. K. Amini, F. Mirkhalaf, B.F. Mirjalili, Biosens. Bioelectron., 26 (2011) 2102–2106.
[3] M.G. Gioia, P. Andreatta, S. Boschetti, R. Gatti, J. Pharm. Biomed. Anal. 48 (2008) 331–339.
[4] R. Sandulescu, S. Mirel, R. Oprean, J. Pharm. Biomed. Anal. 23 (2000) 77–87.
Electrocatalytic oxidation of methanol on glassy carbon electrode modified by platinum nanoparticles dispersed into
polypyrrole film
G. H. Rounaghi 1*, I. Razavipanah
Electrochemistry Research Laboratory, Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad - Iran
Recently, direct alcohol fuel cells (DAFCs), due to their relatively high specific energy, easy handling, low price and easy
accessibility are considered as among the power sources for both stationary and portable device [1]. Among several alcohols
which can be used in a DAFC, methanol is generally considered as the most appropriate fuel because it is a liquid fuel of
relatively high activity in fuel cell systems [1] and can be nearly completely electrooxidized to the final product of CO2 due to its
simple molecular structure [2]. Platinum-based materials are the best anodic materials that exhibit catalytic properties for the
oxidation process of alcohols to proceed at sufficient rare in fuel cells [3].
In this study, glassy carbon electrode used for the electropolymerization of pyrrole and dispersion of platinum nanoparticles into
the resulting polypyrrole (PPy) film. The resulting Pt nanoparticles were characterized by scanning electron microscopy (SEM).
Pyrrole monomers were polymerized on glassy carbon electrode by cyclic voltammetry between -0.8 and 0.8 V (vs. SCE). Then
its surface potentiostatically was coated with Pt nanoparticles at -0.2 V (vs. SCE) in an aqueous solution of 0.1M HClO4
containing 0.002M H2PtCl6. The electrocataltic oxidation of methanol at this modified electrode (GC/PPy/Pt) has been
investigated by cyclic voltammetry in a 0.5M methanol+0.3M HClO4 solution as supporting electrolyte. The presence of
polypyrrole film significantly enhances the catalytic oxidation of methanol on glassy carbon electrode. The effects of various
parameters such as pyrrole monomer concentration, thickness of the polymer film, amount of platinum loadings concentration of
methanol, working potential limit in anodic direction and potential scan rate on the electrooxidation of methanol were
investigated.
Reference
[1]. H. Razmi, E. Habibi., J Solid State Electrochem. 13 (2009) 1897.
[2]. X.M. Ren, P. Zelenay, S. Thomas, J. Davey, S. Gottesfeld.,J. Power Sources. 86 (2000) 11.
[3]. Z.B. Wang, G.P. Yin, Y.G. Lin., J. Power Sources. 170 (2007) 242.
Highly selective potentiometric determination of lanthanum (III) ions in PVC Matrix
M. Ghanei Motlagh*, M.R. Salavati, I. Razavipanah
Electrochemistry Research Laboratory, Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad – Iran
A new solvent PVC membrane (PME) and coated graphite (CGE) electrodes based on two neutral ionophores, 1-methyl-3pyridine-2-yl-thiourea (M1) and 3-amino-2-mercapto-3H-quinazolin-4-one (M2) were explored for preparing PVC-based
membrane sensors selective to lanthanum ion. The sensors exhibited a Nernstian response for La(III) ion over a wide
concentration range (1.3×10-6 to 1.0×10-1 M for PME and 3.0×10-7 to 1.0×10-1 M for CGE) with a slope of 20.1±0.3 (PME) and
23.4±0.4 (CGE) mV decade-1. The lower detection limits by PME and CGE were 7.9×10-7 and 2.0×10-7 M, respectively. The
potentiometric response of the electrodes was independent of the pH of the test solution in the pH range 3.0–9.0 with a fast
response time (<10 s). The applications of prepared sensors were demonstrated in the determination of lanthanum ions in spiked
water sample, and also utilized for indirect determination of F- ions in some mouthwash solutions.
Reference
[1]. P. Buhlmann, E. Pretsch, E. Bakker, Chem. Rev. 98, 1593 (1998).
[2]. M. Shamsipur, M. Yousefi, M. Hosseini, M. R. Ganjali, Anal. Chem. 74, 5538 (2002).
[3].M. R. Ganjali, L. Naji, T. Poursaberi, M. Shamsipur, S. Haghgoo, Anal. Chim. Acta 475, 59 (2003).
[4].R. Kumar, Y. Joshi, Indian J. Chem. B 49, 84 (2010).
[5].M. R. Ganjali, J. Ravanshad, M. Hosseini, M. Salavati-Niasari, M. R. Pourjavid, M. R. Baezzat, Electroanalysis 16, 1771 (2004).
Solid-phase extraction and pre-concentration of iodate from water and biological samples using layered double
hydroxides as a nano-sorbent
H. Abdolmohammad-Zadeh*, K. Tavarid, G.H. Sadeghi
Department of Chemistry, Faculty of Sciences, Azarbaijan University of Tarbiat Moallem, 35 Km Tabriz-Marageh Road, P.O. Box 53714-161,
Tabriz, Iran
* Corresponding author. Tel.: +98 4124327541, Fax: +98 4124327541.
E-mail addresses: h.abdol@azaruniv.edu, h_abdol@yahoo.com
Layered double hydroxides (LDHs), also known as hydrotalcitelike compounds, are a class of synthetic two dimensional nanostructured inorganic materials that have positively charged layers of metal hydroxides, between which are located anions and, in
general, some water molecules. Recently, the layered double hydroxides have been introduced as novel nano-sorbents for solidphase extraction (SPE) by our group, and applied for the separation and pre-concentration of trace levels of organic and inorganic
ions from biological and environmental samples [1,2]. In this work, an innovative nickel–aluminum-zirconium ternary layered
double hydroxide was synthesized and applied for pre-concentration of iodate ions from aqueous solutions. An indirect method
was used for monitoring of the extracted iodate ions. The method is based on the reaction of the iodate with iodide in acidic
medium to form tri-iodide, which can be spectrophotometrically determined at 352 nm. The effect of several parameters such as
pH, sample flow rate and volume, elution conditions, amount of nano-sorbent and co-existing ions on the extraction efficiency
were investigated. In the optimum experimental conditions, the limit of detection (3s) and enrichment factor were 0.12 µg mL−1
and 40, respectively. The calibration graph using the pre-concentration system was linear in the range of 0.2–2.8 µg mL−1 with a
correlation coefficient of 0.997. In order to validate the presented method, certified reference material (CRMs) were analyzed,
and the determined values were in good agreement with the certified values. The proposed method was successfully applied to
the trace determination of iodate in tap water, seawater and human blood serum samples.
Reference
[1] H. Abdolmohammad-Zadeh, Z. Rezvani, G.H. Sadeghi, E. Zorufi, Analytica Chimica Acta, 685 (2011) 212–219.
[2] H. Abdolmohammad-Zadeh, S. kohansal, G.H. Sadeghi, Talanta, 84 (2011) 368–373.
Simultaneous electrochemical determination of caffeine and acetaminophen on SWCNT modified carbon-ceramic
electrode
B. Habibi*, M. Abazari
Electroanalytical Chemistry Laboratory, Department of Chemistry, Faculty of Sciences, Azarbaijan University of Tarbiat Moallem, Tabriz, Iran,
E-mail: B.Habibi@azaruniv.edu
Caffeine (CF) is a bitter, white crystalline xanthine alkaloid that is a psychoactive stimulant. CF is found in varying quantities in
the seeds, leaves, and fruit of some plants, where it acts as a natural pesticide that paralyzes and kills certain insects feeding on
the plants. In humans, CF acts as a central nervous system stimulant, temporarily warding off drowsiness and restoring alertness
[1]. Acetaminophen (AC) is an antipyretic and analgesic drug widely used, it is an effective and safe analgesic agent used
worldwide for the relief of mild to moderate pain associated with headache, backache, and arthritis pain. It is also used for
reduction of fevers of bacterial or viral origin [2]. Only a few methods have been reported for the simultaneous determination of
AC and CF. Yet, such methods require a long time for extracting and purifying the active principles before analysis.
Electroanalytical methods, with respect to their sensitivity, accuracy and simplicity, have been more of interest in recent years for
CF and AC analysis and development of voltammetric sensors for determination of FC and AC in human fluid, pharmaceuticals,
and clinical analysis has received considerable interest in recent years. However, the voltammetric response of CF and AC are
not satisfactory due to their slow heterogeneous electron transfer rate at the bare electrode surfaces. Therefore application of
modified electrodes to increase the electron transfer rate and also the sensitivity were necessary. In this work SWCNT modified
carbon-ceramic electrode was developed for the individual and simultaneous determination of CF and AC. The electrochemical
behavior of these molecules was investigated employing cyclic and differential pulse voltammetry. These studies revealed that
the oxidation of CF and AC is facilitated at the SWCNT. Under the suitable conditions, the anodic peak currents in DPV were
linear to concentrations in the range of 800nM - 180µM and the detection limit of 48 nM and 1.5-50.0 µM and the detection of
limit 1.0 µM for CF and AC, respectively. This newly exploited method was successfully used to determine CF and AC in some
pharmaceutical samples.
Reference
[1] M.H. Fernstrom, J.D. Fernstrom, Life Sci. 57 (1995) 97.
[2] F.A. Armstrong, H.A.O. Hill, N.J. Walton, Acc. Chem. Res 21 (1988) 407.
Degradation of malachite green in water using ZnO nanoparticles
Fatemeh Rafiei1 , Khalil Farhadi2, Laya Afrasiabi*1
1) Department of Chemistry, Urmia Paym nour University, Urmia, Iran
2) Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
Conventional treatment techniques to remove organic matters in water samples include coagulation, flocculation, precipitation,
oxidation, adsorption, and reverse osmosis [1,2]. However, it is very difficult both to obtain satisfactory treatment efficiency and
to reduce the cost associated with infrastructure construction, energy consumption and frequent use of additional chemicals [3. In
recent the use of semiconductor nanoparticles such as in the degradation of contaminants is very interest. Malachite green has
now become a highly controversial compound due to the risks it poses to the consumers of treated fish including its effects on
the immune system, reproductive system and its genotoxic and carcinogenic properties [4,5]. In the present study, we report the
synthesis of nanostructure ZnO semiconductor using a chemical precipitation method. The resulting nanoparticles were
characterized by X-ray diffraction analysis (XRD), Fourier-transforminfrared (FT-IR) spectroscopy. The optical properties were
investigated by UV–vis technique.The absorption spectra exhibit a maximum pick at 384 nm .The activity of the prepared ZnO
nanoparticles has been investigated for the degradation of malachite green in aqueous solutions. The effects of some
experimental parameters such as the amount of ZnO nanoparticles, pH, ionic strength, time and temperature on the degradation
efficiency of malachite green were studied. The obtained results showed that above 80% of malachite green was decomposed
under optimum conditions. The proposed method is very simple, rapid and very cost. The proposed method was successfully
used for the treatment of different water samples.
Reference
[1] X. Ntampou, A. I. Zouboulis, , P. Samaras, Appropriate combination of physicochemical methods (coagulation/flocculation and ozonation) for the efficient
treatment of landfill leachates. Chemosphere, 63 (2006) 722– 730.
[2] E. Durmusoglu, C. Yilmaz, Evaluation and temporal variation of raw and pre-treated leachate quality from an active solid waste landfill. Water, Air, and Soil
Pollution 171(2006) 359–382.
[3] J. Wiszniowski, D. Robert, J. Surmacz-GorskaMiksch, J.V. Weber , Landfill leachate treatment methods: A review. Environmental Chemistry Letters, 4 (2006)
51–61.
[4] D. J. Alderman, R. S. Clifton-Hadley, Malachite green: a pharmacokinetic study in rainbow trout, Oncorhynchus mykiss (Walbaum). J. Fish Dis. 16 (1993) 297–
311.
[5] C. Fernandes, V.S. Lalitha, V.K. Rao, Enhancing effects of malachite green on the development of hepatic preneoplastic lesions induced by Nnitrosodiethylamine in rats. Carcinogenesis 12 (1991) 839–845.
preconcentration and Determination of ultra trace of lead in aqueous solution by dispersive liquid-liquid microextraction
and optimization of the effective parameters by response surface modeling (RSM)
Saeed Habibollahi*, Hossein salavati, Marziyeh Mehtari
Department of chemistry, Payame Noor University, 19395-4697 Tehran, Z.R. of IRAN
A dispersive liquid-liquid microextraction (DLLME) technique was proposed for preconcentration and Determination by the
graghite furnace atomic absorption spectrometry (GFAAS). In this method a mixture of 750 µL methanol (disperser solvent),
containing 35 µL cholorobenzene (extraction solvent) and 63 µL 1-(2-pyridylazo)-2-naphtol(chelating agent), was rapidly
injected by a syringe into 5 mL aqueous sample containing lead ions (analyte). Thereby, a cloudy solution formed. After
centrifugation, the fine droplets containing the extracted lead complex were sedimented at the bottom of the conical test tube.
Then, 10 µL from the sedimented phase, containing the enriched analyte, was determined by GFAAS. Effects of some
parameters on the extraction, such as extraction and disperser solvent type and volume, extraction time, salt concentration, pH
and concentration of the chelating agent were optimized. The response surface method was used for optimization of the effective
parameters on the extraction recovery (ER%). MINITAB software was used for the calculation according to a central composite
design method. Under the optimum conditions, the enrichment factor of 240 was obtained. The calibration graph was linear in the
range of 0.05-1 µgL-1 with the detection limit of 0.03 µgL-1 and a relative standard deviation (R.S.D.) was 4% (seven replicate, 1
µgL-1 concentration). The method was successfully applied to the determination of lead in some water samples.
Reference
[1] Anthemidis. A.N, Talanta 77 (2008) 541.
[2] Naseri. M.T, Milani Hosseini. M.R, Assadi. Y, Kiani. A, Talanta 75 (2008) 56.
[3] Anthemidis. A.N, I.S.I. Adaam, Anal. Chim. Acta 632 (2009) 216.
[4] Jamali. M.R, Assadi. Y,Shemirani. F, Sep. Sci,Technol. 42 (2007) 3503.
A novel and very simple method for extraction and determination of dioxane in some deterjents’ matrix by HPLC–UV
Ali Gholami*, Hasan Jahangiri
University of Kashan , Faculty of Chemistry, Department Of Analytical Chemistry
1,4-Dioxane (dioxane) is found in household products such as detergents,shampoos, body lotions, dishwashing soap,
pharmaceuticals and cosmetics[1]. The U.S. Food and Drug Administration (FDA) has provided guidance to manufacturers about
a process called “vacuum stripping” to help minimize the amount of dioxane in their final product. Manufacturers of personal
care products should conduct laboratory analysis to determine the levels of dioxane in their products, and manufacturers using
dioxane in their processes should analyze their waste streams for possible dioxane content [2]. The increase of ionic strength often
improves the extraction efficiency due to salting out effect using traditional organic solvent as extraction solvent [3]. The pH
value of sample solution determines the existing form of the analytes (as ions or neutral form), which thereafter could affect
extraction efficiency [4].The influence of several important parameters on extraction efficiency of dioxane was evaluated in this
laboratory exercise; we will distill the shampoo mixed with ethanol and adjust several condition then inject to hplc-uv.
Complicated matrices like shampoo, making it difficult to obtain accurate and reproducible sample concentrations, especially at
lower limits of detection in the part per billion range. Under optimal conditions, dioxane were baseline separated within 5.1 min,
with the minimal limit of detection of 25 ng mL-1 and coefficient correlations in the range of 0.9970-0.9985.
Reference
[1]. Johnstone RT. 1959. Death due to dioxane? AMA Arch. Ind. Health. 20:445-447.
[2]. Pilipyuk ZI, Gorban GM, Solomin GI, and Gorshunova AI. 1977. Toxicology of 1-4-dioxane. Space Biology and Aerospace Medicine. 11:70-74. (translated from
Russian).
[3] . H.-H. Lin, Y.-H. Sung, S.-D. Huang, J. Chromatogr. A 1012 (2003) 57.
[4]M. Rezaee, Y. Assadi,M.-R.M. Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, J. Chrmatogr. A 1116 (2006) 1.
Comparison of immiscible organic solvent hollow fiber liquid three phase microextraction and traditional hollow fiber
liquid three phase microextraction combined with electrospray ionization-ion mobility spectrometry for the
determination of propranolol in biological samples
Mohammad Saraji*, Mohammad Taghi Jafari and Mehrnoush Jalil
Department of Chemistry, Isfahan University of Technology, Isfahan, I. R. Iran
In this research, immiscible organic solvent hollow fiber liquid three phase microextraction (IOS-HF-LPME) and traditional
hollow fiber liquid three phase microextraction (t-HF-LPME) combined with electrospray ionization-ion mobility spectrometry
have been compared for determination of propranolol in biological samples (human plasma and urine). Propranolol is a nonselective beta blocker mainly used in the treatment of hypertension [1]. Different parameters influencing the extraction efficiency
such as organic solvent type, concentration of NaOH as donor solution, concentration of acetic acid as acceptor phase, salt
addition, stirring rate, temperature, and extraction time were investigated and optimized. Furthermore, the effect of type of acid
on ESI-IMS signals was studied. The results showed that both extraction methods exhibited good linearity, precision, enrichment
factor, and detection limit. Under optimal condition, the dynamic ranges were 10-500 μg/L and 5-200 μg/L for t-HFLPME and
IOS-HFLPME, respectively. For t-HFLPME, the intra- and inter-day precisions were 2.5 and 7% respectively; and for IOSHFLPME were 5.2% and 7.1%, respectively. The enrichment factors were 102 and 190 for t-HFLPME and IOS-HFLPME,
respectively. IOS-HFLPME showed better extraction efficiency compared to t-HFLPME which reported by other researchers [2].
Capability of two procedures was investigated in real sample analysis and propranolol was successfully determined in urine and
plasma samples without any significant matrix effect.
Reference
[1] J.V. Okopski, J. Clin. Pharm. Ther. 12 (1987) 369.
[2] M. Saraji. M.T. Jafari, H. Sherafatmand, J. Chromatogr. A 1217 (2010) 5173.
Simultaneous spectrophotometric determination by Doolittle multivariate calibration algorithm
Tahereh Momeni Esfehani 1, Babak Asadi 2, Jahan B. Ghasemi 3 and Ali Niazi *,1
E-mail: ali.niazi@gmail.com
1
Department of Chemistry, Islamic Azad University-Arak Branch, Arak, Iran
2
Department of Mathematics, Islamic Azad University – Arak Branch, Arak, Iran
3
Department of Chemistry, K.N. Toosi University of Technology, Tehran, Iran
Doolittle decomposition algorithm (DDA) is a high accuracy, few computation amounts and stable numerical analysis algorithm.
This algorithm can avoid matrix inverting operation, which is often involved in chemometrics such as the methods of K-matrix,
P-matrix, partial least squares [1], etc., reduce the orders of matrixes, speed up the operation of matrixes, and raise the efficiency
of computation. The basic principle of Doolittle Decomposition Algorithm has also been described clearly by Y. Ding et al. [2].
In this work, Doolittle Decomposition Algorithm in conjugation with spectrophotometric data was used to simultaneous
determination of nitrophenol isomers in synthetic and real samples. The aim of this study is to propose DDA method to resolve
ternary mixtures of nitrophenol isomers in trace levels. The proposed methodology is fast, simple and does not generate
hazardous chemical wastes, thus makes it easily possible to be used in control analysis of nitrophenol in real samples. The
experimental calibration matrix was designed by measuring the absorbance over the range 300–520 nm for 21 samples of 1–20,
1–20 and 1–10 mgml−1 of m-nitrophenol, o-nitrophenol and p-nitrophenol, respectively. The RMSEP for m-nitrophenol, onitrophenol and p-nitrophenol were 0.0561, 0.0428 and 0.0127, respectively.
Reference
[1] Y. Ding, T. Mu, Q. Wu, Sh. Si, Chemomet. Intell. Lab. Syst. 88 (2007) 167-169.
[2] J. Ghasemi, A. Niazi, Microchem. J. 68 (2001) 1-11.
Chemical composition of the essential oil from the aerial parts of Pervoskia abrotanoides karel (Lamiaceae) by using
hydrodistillation combined with GC and GC-MS
S. Yazarloo1*, M. Rahimi2, M. siavoshan2, A. Mazloomifar1, M. Mohammadhosseini2, M. Nekoei2
1) Department of Chemistry, Faculty of Basic Sciences, Shahreray Branch, Islamic Azad University, Shahreray, Iran
2)Department of Chemistry, Faculty of Basic Sciences, Shahrood Branch, Islamic Azad University, Shahrood, Iran
saeedyazarloo@gmail.com
Nowadays, essential oils have attracted a unique compartment in different scientific branches involving traditional medication,
perfumes and fragrance industry as well as pharmceutical formulations. In the present report, water-distilled essential oil from
Pervoskia abrotanoides karel (Lamiaceae) an endemic growing wild plant in Iran, was analyzed by GC (equipped with a SE30
column) and GC/MS (with a HP-5MS) under certain temperature programming. A total of 25 compounds were identified
representing 97.86% of the total aerial parts oil among them camphor (19.42%), 1,8-cineol (18.08%), α-pinene(8.78%), δ-3carene (5.64%) and camphene (5.43%) were found to be the major components. According to the chemical profile,
monoterpenoides, sesquiterpenoides and non-terpenoieds constituted 77.26, 11.71, and 8.89 of the oil composition, respectively.
Reference
[1] M.M. Salehand H. Kating,Gas-chromatographic analysis of the volatile oil of PerovskiaabrotanoidesKarel.Planta.Med., 33(1978) 85.
[2] British Pharmacopoeia HMSO, London. 2(1998)137.
[3] R.P. Adams,Identification of Essential Oils Components by Gas Chromatography/Quadrapole Mass Sectrometry, Allured Publishing Corporation, Illinois,
USA,(2001).
[4] R.P. Adams,Identification of Essential Oil Components by Gas Chromatography/Mass Spectrometry, Allured Pubishing Co., Carol Stream, IL., USA, (2007).
Preconcentration and determination of gold based on floating organic drop microextraction (SFODME) by flame atomic
absorption spectrometry solidified
1
Majid Ramezani, Sajad Shahbazi1*, Maryam Mohammadnia2
Department of Chemistry, Faculty of science, Islamic Azad University-ArakBranch-Arak,Iran
2
Department of chemistry,Payame Noor University,Aleshtar,Khoramabad,Iran
E-mail: m-ramezani@iau-arak.ac.ir and sajad.sh1363@yahoo.com
A procedure for the determination of traces amount of gold by liquid-phase microextraction based on solidification of a floating
organic droplet (LPME-SFO) separation and flame atomic absorption spectrometry (FAAS) has been developed. Dithizon was
used as chelating agent. The main parameters affecting the performance of SFODME, such as pH, concentration of ligand,
extraction time, stirring rate, extraction temperature, sample volume and nature of the solvent were optimized. Under the
optimum experimental conditions, a good relative standard deviation for eight determination of 10 ng mL −1 of Au (III) was 2.3
%. An enrichment factor of 850 and detection limits of 2 ng mL−1 was obtained. The procedure was applied to several water and
gold ore.
Reference
[1]. M. Rezaee, Y. Yamini, A. Khanchi, M. Faraji, A. Saleh; J. Hazard. Mat. 178 (2010) 766.
[2] .C. Arpa Sahin, I. Tokgoz; Anal. Chim. Acta 667 (2010) 83.
[3]. J. Ma , J. Zhang , X. Du , X. Lei, J. Li; Microchim Acta 168 (2010) 153.
Experimental and theoretical studies on corrosion inhibition of mild steel in HCl and H2SO4 solutions by a new Schiff
base
a
N. Soltania,*, N. Tavakkolib, F. Loghmanib, M. R. Jalalib
Department of Chemistry, Payam Noor University, Shahin Shahr Branch, Isfahan
b
Department of Chemistry, Payam Noor University, Isfahan
Corrosion in mineral acids represents a terrible waste of both resources and money [1]. Compounds containing both nitrogen and
sulfur groups generally give rise to satisfying inhibition efficiency in acidic media [2, 3]. The inhibition property of these
compounds is attributed to their molecular structure. The structure and the lone electron pairs in the heteroatoms are important
features that determine the adsorption of these molecules on the metallic surface [4].
In this present study, the corrosion inhibition of mild steel in 0.5 M H2SO4 and 1.0 M HCl by a new Schiff base (2-(1-{6-2(aminocarbothioyl)ethanhy-drazonoyl]-2-pyridyl}ethylidene)-1-hydrazinecarbothioamide) has been studied using weight loss
measurements, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) measurements. The results show
that the inhibition efficiency increases with the increase of Schiff base concentration in both acids and the higher inhibition
efficiency is obtained in 0.5 M H2SO4. Polarization studies showed depression of cathodic and anodic polarization curves in the
presence of Schiff base compounds, indicating mixed type corrosion inhibition of the compounds in both acid solutions. EIS
measurements show an increase of the transfer resistance with increasing the inhibitor concentration. The adsorption of Schiff
base molecules on the steel surface obeys Langmuir adsorption isotherm in both acids, and occurs spontaneously. The value of
activation energy (Ea) for mild steel corrosion and thermodynamic parameters such as adsorption equilibrium constant (Kads), free
energy of adsorption (∆Gads) values in both HCl and H2SO4 solutions were calculated and discussed. Density functional theory
(DFT) study gave further insight into the mechanism of inhibition action of Schiff base.
Refrence
[1]. A. Chetouani, A. Aouniti, B. Hammouti, N. Benchat, T. Benhadda, S. Kertit, Corros. Sci. 45 (2003) 1675–1684.
[2]. R. Solmaz, E. Altunbas, G. Kardas, Mater. Chem. Phys. 125 (2011) 796–801.
[3]. N. Soltani , M. Behpour , S.M. Ghoreishi , H. Naeimi , Corros.Sci. 52 (2010) 1351–1361.
[4]. F. Bentiss, B. Mernari, M. Traisnel, H. Vezin, M. Lagrenée, Corro. Science 53 (2011) 487–495.
Simultaneous determination of epinephrine and acetaminophen by a modified carbon paste electrode with MCM/ZrO2
nanostructure
Mohammad Mazloum-Ardakani*, Ali Benvidi, Afsaneh Dehghani, Nooshin Rajabzadeh, Mohammad Ali Sheikh-Mohseni, Mohammad
Abdollahi-Alibeik
Department of Chemistry, Faculty of Science, Yazd University, Yazd, I.R. Iran
Epinephrine (EP), also called adrenaline, is an important hormone secreted by the medulla of the adrenal glands. As a medical
drug, epinephrine is used to stimulate heartbeat and to treat emphysema, bronchitis, bronchial asthma and other allergic
conditions. Acetaminophen (Ac) is widely used as analgesic and antipyretic agent for treating the symptoms of different painful
processes [1]. Therefore determination of EP and AC by a simple way is interesting.
Cyclic voltammetric determination of epinephrine studied by carbon-paste electrodes modified with new modified nanostructured
mesoporous silica as solid acid catalyst. The modified electrode showed electrocatalytic activity toward EP oxidation with a
decrease of the overpotential and an increase of the peak current. The values of transfer coefficients (α) and diffusion coefficient
(D) were calculated for EP oxidation. The modified electrode showed an excellent activity to resolving DPV peaks of EP and AC
in phosphate buffer solution (pH=7.0). This sensor exhibited a good reproducibility, repeatability and sensitivity for simultaneous
determination of EP and AC.
Reference
[1] M. Mazloum-Ardakani et al. Colloids and Surfaces B: Biointerfaces 76 (2010) 82–87
A multiresidue method for determination of 12 pesticides in melon using gas chromatography mass
spectrometry (GC/MS)
Iman Moazzami Goudarzia, Shahram Shoeibi b, c , Hossein Rastegarb,c,Behrouz Janat b,e, Nafiseh Sadeghi d, Mannan Haji Mahmoudi d,
Maryam Amirahmadi b,c*
a
School of Pharmacy, Tehran University of Medical Sciences, Tehran, I. R. Iran
b
Food and Drug Laboratories Research Center, Ministry of Health and Medical Education, Tehran, I. R. Iran
c
Food and Drug Control Laboratories, Food and Drug Deputy, Ministry of Health and Medical Education, Tehran, I. R. Iran
d
Department of food control, School of Pharmacy, Tehran University of Medical Sciences, Tehran, I. R. Iran
e
Food and Drug Deputy, Ministry of Health and Medical Education, Tehran, I. R. Iran
*Email: maryamamir2001@yahoo.com
Recently, with increasing public awareness of food safety, development of some accurate and rapidly analytical methods is
required for the determination of residual pesticides in agricultural products. This study was conducted on validation of an
accurate and rapid method for multi analysis of pesticides residue in melon as a main fruit in Iranian food basket. A reliable,
rapid and accurate method based on spiked calibration curves and modified QuEChERS sample preparation was developed for
determination of 12 pesticide residues in melon by gas chromatography-mass spectrometry(GC/MS).The interested pesticides
are, diazinon, dimethoate, chlortalonil, pirimicarb, chlorpyrifos-methyl, metalaxyl, alpha-endosulfan, beta endosulfan, permethrin
1,2 and fenvelerate1,2 that are belonged to deferent chemical groups of pesticides. Triphenylmetan (TPM) is used as internal
standard. The use of spiked calibration standards for constructing the calibration curve substantially reduced adverse matrixrelated effects. The recovery of pesticides at 3 concentration levels (n=3) was in range of 80.39-97.05%.The method was proved
to be repeatable with RSD lower than 20%. The limits of quantification for all pesticides were <10 ng/g. The recoveries and
repeatabilities were in accordance with the criteria set by SANCO Guideline.Using spiked samples for preparation of calibration
curves is a sensitive, selective, rugged, rapid and simple method in pesticides analysis.
Reference
[1]- Lehotay, S. J., 2000. Analysis of pesticide residues in mixed fruit and vegetable extracts by direct sample introduction/ gas chromatography/tandem mass
spectrometry. J. AOAC Int. 83(3), 680-697.
[2]- Hajslova, J., Zrostlikova, J., 2003. Matrix effects in (ultra) trace analysis of pesticide residues in food and biotic matrices. J. Chromatogr. A. 1000, 181-197.
Electrochemical behaviour of diclofenac on CNT/IL/nanoscale Cu(OH) 2 modified electrode
M. Arvand*, T.M. Gholizadeh
Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box: 1914, Rasht, Iran
Email: arvand@guilan.ac.ir
Non-steroidal anti-inflammatory drugs usually abbreviated as NSAIDs are the most commonly employed first line drug for the
treatment of several diseases [1]. Diclofenac ([2-[(2, 6-dichlorophenyl) amino] phenyl] acetic acid is a popular NSAID drug
widely used to treat inflammatory and painful diseases of rheumatic and non-rheumatic origin. In addition to its medical
importance, some studies indicated that diclofenac can induce some adverse effects on aquatic life [2]. Carbon nanotubes (CNTs)
have become an attractive material in electrochemistry due to their high surface area and outstanding ability to mediate fast
electron transfer kinetics [3]. Furthermore, ionic liquids (ILs) show many characteristics such as good ionic conductivity and
wide electrochemical window [4]. CNT and ILs composite combine the advantages of both materials [3]. On the other hand,
nanostructured transition metal hydroxides/oxides possess the excellent properties such as high surface area and enhanced
chemical/electrochemical activities [5]. In this work, a novel nanocomposite of multiwalled carbon nanotubes, ionic liquid 1Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) and nanoscale Cu(OH)2 was prepared and used for modification
of glassy carbon electrode (GCE). The CNT/IL/nanoscale Cu(OH)2 modified GCE showed electrocatalytic response toward the
oxidation of diclofenac in phosphate buffer solution (pH 8.22). The oxidation process was found to involve 2e, 2H+ with
oxidation potential 0.57 mV (vs. SCE). Effect of scan rate showed that oxidation of diclofenac on CNT/IL/nanoscale Cu(OH)2
modified GCE was diffusion control.
Reference
[1] R.N. Goyal, S. Chatterjee, B. Agrawal, Sens. Actuators B 145 (2010) 743.
[2] X. Zhao, Y. Hou, H. Liu, Z. Qiang, J. Qu, Electrochim. Acta 54 (2009) 4172.
[3] L.Zheng, J. Zhang, J. Song, Electrochim. Acta 54 (2009) 4559.
[4] F. Xiao, F. Zhao, J. Li, L. Liu, B. Zeng, Electrochim. Acta 53 (2008) 7781.
[5] J. Yan, H. Zhou, P. Yu, L. Su, L. Mao, Electrochem. Commun. 10 (2008) 761.
Electrochemical determination of tryptophan at modified carbon paste
electrode Based on SiO2 nanoparticle
a
J. Tashkhourian*a, S. F.Nami Anab, S. Hashemniab
Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran
b
Department of Chemistry, Persian Gulf University, Bushehr 75169, Iran
Tryptophan (Trp) is an essential amino acid for human and herbivores but is scarcely present in vegetable products. It is
sometimes added to dietary and food products as a food fortifier and to pharmaceutical formulations in order to correct possible
dietary deficiencies. The analysis of Trp is of great importance in the biochemical, pharmaceutical and dietetic fields [1].
Recently the application of the carbon paste electrodes modified with nanostructured materials exhibit considerable
improvements in electrochemical behavior of many important compounds [2]. Chemically modified electrodes involving silica
based materials have attracted much attention in the field of electroanalysis. Silica presents attractive properties which could be
advantageously exploited, for example in the accumulation of electroactive analytes before their electrochemical detection [3]. In
this work carbon paste electrodes (CPE) modified with SiO2 nanoparticles were used for the sensitive electrochemical
determination tryptophan(Trp). The electrode prepared by mixing graphite powder, paraffin oil and SiO2 nanoparticle. The
electrochemical response characteristics of these modified electrodes toward Trp were investigated by cyclic voltammetry and
differential pulse voltammetry. Prior to established the detection method experimental variables were optimized. Under the
optimum experimental conditions the peak current was linearly dependent on the Trp concentration in the range of 7 × 10−7 to 3 ×
10-4 mol L−1. Finally, the method was successfully utilized for determination of Trp in a real samples.
Reference
[1] G. Chen, J. S. Cheng, J. N. Ye, J. Fresenius, Anal. Chem. 370 (2001) 930.
[2] A. Antiochia, I. Lavagnini, F. Magno, F. Valentini, G. Palleschi, Electroanalysis 16 (2004) 1451.
[3] H. Zejli, P. Sharrock, J.L. Cisneros, I. Naranjo-Rodriguez, K. R. Temsamani, Talanta, 68 (2005) 79.
Statistical optimization of synthesis of manganese carbonates nanoparticles by precipitation methods
Ali Akbar Davody1,*, Morteza Khalilian Shalamzari1, Mehdi Rahimi-Nasrabadi1, Seied Mehdi Pourmortazavi2
1
Department of Chemistry, Imam Hossein University, Tehran, Iran
٢
Faculty of Material and Manufacturing Technologies, Malek Ashtar University of Technology, Tehran, Iran
In this study, an orthogonal array design (OAD), OA9, was employed as a statistical experimental method for the controllable,
simple and fast synthesis of manganese carbonate nanoparticle. Ultrafine manganese carbonate nanoparticles were synthesized by
a precipitation method involving the addition of manganese ion solution to the carbonate reagent. The effects of reaction
conditions, i.e., manganese and carbonate concentrations, flow rate of reagent addition and temperature, on the diameter of the
synthesized manganese carbonate nanoparticle were investigated. The effects of these factors on the width of the manganese
carbonate nanoparticle were quantitatively evaluated by the analysis of variance (ANOVA). The results showed that manganese
carbonate nanoparticle can be synthesized by controlling the manganese concentration, flow rate and temperature. Finally, the
optimum conditions for the synthesis of manganese carbonate nanoparticle by this simple and fast method were proposed. The
results of ANOVA showed that 0.001 mol/L manganese ion and carbonate reagents concentrations, 2.5 mL/min flow rate for the
addition of the manganese reagent to the carbonate solution and 0 °C temperature are the optimum conditions for producing
manganese carbonate nanoparticle with 75 ± 15 nm width.
Electrochemical and ATR-FTIR Spectroscopic Characterization of Nanostructures Formed by Immobilization of Citrate
on Au-MPA-M(IV) {M: Hf(IV) or Zr(IV) Ions}
Reza Karimi Shervedani*, Mostafa Torabi
Department of Chemistry, University of Isfahan, Isfahan 81746-73441, I.R. Iran
E-mail: rkarimi@sci.ui.ac.ir
Application of metal ions as a mediation glue for immobilization of inorganic and biological species on gold self-assembled
monolayers modified electrodes has been recently reported by us [1]. In this report, electrochemical and spectroscopic
characterization of citrate immobilized on Au-MPA-M(IV), where M(IV) could be Hf(IV) or Zr (IV) are metal ion glues, is
described. The Au-MPA SAM [2] is modified by immobilization of Hf(IV) or Zr(IV) under open-circuit potential through
immersion of the Au–MPA SAM electrode into a stirring solution of 1.0×10−3 M Hf(IV) or Zr(IV), respectively, to form Au–
MPA–Hf(IV) or Au-MPA-Zr(IV) electrode. Accumulation of citrate is performed under optimized conditions by incubation in
citrate solution. Characterization of the modified surface is carried out by voltammetry and electrochemical impedance
spectroscopy in the presence of an appropriate redox probe. Further, the modified surfaces are characterized by means of Fourier
Transform Infrared (FTIR) spectroscopy with the Attenuated Total Reflection (ATR) method. The experimental results will be
presented and described in this congress.
Reference
[1].R.K. Shervedani, S. Poubeyram, Biosens. Bioelectro. 24 (2009) 2199-2204.
[2].R.K. Shervedani, Z. Akrami, H. Sabzyan, J. Phys. Chem. C 115 (2011) 8042-8055.
Cadmium Selenide nano particle loaded on activated carbon as adsorbents for kinetic and equilibrium study of removal
of Arsenazo (III)
Ebrahim Shareifpoora, Mehrorang Ghaedib*, Syamak Nasiri Kokhdanc
Chemistry Department, Gachsaran Azad University, Gachsaran Branch - Iran,
b
Chemistry Department Yasouj University Yasouj 75914-35, Iran
c
Young Researchers club, Yasooj Branch, Islamic Azad University, Yasooj, Iran
*E-mail: m_ghaedi@mail.yu.ac.ir, eb_shareif_prt@yahoo.com
a
Nanoparticles have very interesting physicochemical properties, such as ordered structure with high aspect ratio, ultra-light
weight, high mechanical strength, high electrical conductivity, high thermal conductivity, metallic or semi-metallic behavior and
high surface area. It is a common behavior that nanoparticles would easily aggregate because of the magnetic property of
nanoparticles themselves, so most of the particles exist in chain-like aggregates [1, 2].
In this research Cadmium Selenide nanoparticle loaded on activated carbon has been used as adsorbent for the removal and
recovery of Arsenazo (III) from wastewater. The batch studies have been carried by observing the effects of pH, temperature,
concentration of the dye, amount of adsorbents, sieve size of adsorbent, contact time, etc. The graphical correlation of various
adsorption isotherm models like, Langmuir, Freundlich, Tempkin and Dubinin–Radushkevich have been carried out for this
adsorbent. The adsorption over alizarin red s has been found endothermic and feasible in nature. Various thermodynamic
parameters, such as, Gibb’s free energy, entropy and enthalpy of the on-going adsorption process have been calculated. The
kinetic studies suggest the process following pseudo second order kinetics and involvement of particle diffusion mechanism.
Reference
[1]. Jing Fan, Yanhui Guo, JianjiWang, Maohong Fan, Rapid decolorization of azo dye methyl orange in aqueous solution by nanoscale zerovalent iron particles,
Journal of Hazardous Materials 166 (2009) 904–910.
[2]. A.D. Bokare, R.C. Chikate, C.V. Rode, K.M. Paknikar, Iron-nickel bimetallic
nanoparticles for reductive degradation of azo dye Orange G in aqueous solution,
Appl. Catal. B: Environ. 79 (2008) 270–278.
Determination of valproic acid in biological fluids by dispersive liquid-liquid microextraction gas chromatography-flame
ionization detection without prior derivatization
Rana fazeli bakhtiyaria, Abolghasem Jouyban*b, Vahid Panahi Azara , Mohammad Hossein Sorouraddinc
a
Liver and Gastrointestinal Diseases Research Center, Tabriz University of Medical Sciences
b
Drug Applied Research Center and Faculty of Pharmacy, Tabriz University of Medical Sciences
c
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz
Valproic acid (2-propylpentanoic acid, VPA) is widely used in the control of a variety of seizure types as a major antiepileptic
drug. Determination of antiepileptic drugs in body fluids on a routine basis is important to clarify and control their therapeutic
and toxic effects[1]. The analytical methods reported for the determination of VPA include gas chromatography (GC), high
performance liquid chromatography (HPLC) and capillary electrophoresis (CE) [2]. The combination of advanced instruments
with novel sample preparation methods leads analysts to the access of trace amounts of the analytes with higher accuracy. VPA is
concentrated by a new technique called dispersive liquid - liquid microextraction (DLLME) technique. In this method, a mixture
of a suitable extraction solvent (40 μL chloroform) and a dispersive solvent (1 mL acetone) is injected quickly into the sample by
syringe and a cloudy solution is formed. After centrifuging, 1 μL of organic phase is collected at the bottom of conical test tube,
is removed by microsyringe and injected into gas chromatograph - flame ionization detector. Some important parameters such as
extraction and dispersive solvents and their volume are investigated. Under optimum conditions, linear range of calibration
curves was between 0.3 -50 μg mL-1. Relative standard deviations (RSD %) were 4.5, 1.8 and 0.5 % at concentrations of 0.5, 5
and 40 μgmL-1 (n=6), respectively. Thus proposed method has been successfully utilized for the VPA in human plasma and
saliva samples.
Reference
[1] R. Ahmadkhaniha, N. Rastkari, F. Kobarfard, H. Pakdaman, O. Ahmadkhaniha, A. Kebriaeezadeh,
IJPS, 3(2007)37.
[2] G. K. Belin, S. Krähenbühl, P. C. Hauser, J. Chromatogr. B, 847 (2007) 205.
Computational design and synthesis of a high selective molecularly imprinted polymer for voltammetric sensing of
propazine in food samples
Mohammad Bagher Gholivand*, Nashmil Karimian, Ghodratollah Malekzadeh
Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah, Iran
The design and construction of a high selective voltammetric sensor for propazine by using a molecularly imprinted polymer
(MIP) as recognition element were introduced. In order to study the intermolecular interactions in the pre-polymerization mixture
and to find a suitable functional monomer in MIP preparation, a computational approach was developed [1-3]. It was based on
the comparison of the binding energy of the complexes between the template and functional monomers. Having confirmed the
results of computational method, two MIPs were synthesized with functional monomers MAA and AAM, and the result indicated
that acrylamide (AAM) is the best candidate to prepare MIPs. The carbon paste electrode modified with molecularly imprinted
polymer (MIP-CPE) [4-6] was applied for propazine determination using cathodic stripping voltammetric method. Some
parameters affecting the sensor response were optimized and then the calibration curve was plotted. Two dynamic linear ranges
of 0.01 – 1.0 µM and 1.0 – 55.0 µM were obtained. The detection limit of the sensor was calculated as 0.001µM. This sensor was
used successfully for propazine determination in food samples.
Reference
[1] Gholivand, M. B., Khodadadian, M., & Ahmadi, F., Analytica Chimica Acta, 658, 2010, 225–232.
[2]Li, Y., Li,X., Li, Y., Dong, C., Jin, P., & Qi, J., Biomaterials 30,2009, 3205-3211.
[3] Azenha, M., Kathirvel, P., Nogueira, P., & Fernando-Silva, A., Biosensors and Bioelectronics, 23, 2008, 1843-1849.
[4] Alizadeh, T., Analytica Chimica Acta, 623, 2008, 101-108.
[5] Li, C., Wang, C., Wang, C., & Hu, S., Analytica Chimica Acta, 545 ,2005, 122-128.
[6] Yeh, W. M., & Ho, K. C., Analytica Chimica Acta, 542, 2005, 76-82.
Separation/preconcentration of phosphate in water samples on immobilized iron oxide magnetite nanoparticles prior to
determination by molybdenum blue method and UV-Vis spectrometry
Mohammad Ali Karimi , Adolhamid Hatefi-Mehrjardi*, Havva Mahmoodian, Asghar Askarpour Kabir , Shahla Nezhad Khorasani
Department of Chemistry & Nanoscience and Nanotechnology Research Laboratory (NNRL), Payame Noor University, 19395-4697, Tehran, I.R.
of IRAN hhatefy@yahoo.com
Phosphorus is the eleventh most abundant element on the surface of the earth and is most commonly found as phosphate. It plays
an important role in biochemical processes and is a key factor in the eutrophication of surface water [1]. The often employed
spectrophotometric method for the determination of phosphorus is based on an ammonium molybdate reaction, followed by
stannous chloride reduction of the complex in acidic medium, which is catalyzed by phosphate ion producing a complex known
as molybdenum blue [2]. In this work, a simple, selective and rapid method for solid phase extraction and spectrophotometric
determination of phosphate Using magnetic nanoparticles of iron oxide has been developed. After preparing nanoparticles,
determine the nature and effect of the size and morphology and the presence of magnetism by coating machines were studied by
VSM, XRD, SEM and FT-IR. Various parameters affecting the adsorption of phosphate such as pH of the solution, type, volume
and concentration of desorbing reagent, amount of adsorbent, amount of eluting agent and interference effects were investigated
and were optimized. The preconcentration factor under the optimal experimental conditions was 200 ml. Also, relative standard
deviation (RSD) 1.51% for 5 and 10 mg.ml -1 was obtained. Detection limit of measurement was 0.038 ppm phosphate ion.
Reference
Mahadevaiah, M.S. Yogendrakumar, M.S. Abdul Galil, M.A. Sathish, M.S. Suresha, G. Nagendrappa, E.J. Chemistry, 4 (2007) 467.
Leprevost, Química Analítica dos Minerais, Livros Técnicos e Científicos Editora S.A., Rio de Janeiro, Brazil, (1975).
Electrosynthesis and Characterization of Zinc Tungestate Nanoparticles
Mehdi Rahimi-Nasrabadi1,*, Morteza Khalilian1, Seied Mehdi Pourmortazavi2
1
Department of Chemistry, Imam Hossein University, Tehran, Iran
٢
Faculty of Material and Manufacturing Technologies, Malek Ashtar University of Technology, Tehran, Iran
Electrosynthesis has emerged as a convenient and inexpensive technique for the synthesis of various compounds. In this study, a
simple electrosynthesis process has been proposed to preparation of zinc tungestate nanoparticles at low temperature. Zinc
tungestate nanoparticles in different sizes were synthesized on a relatively large scale by electrolysis in sodium tungestate
solution with zinc plate as anode. The optimal conditions were determined using the Taguchi method [1,2]. The results showed
that particle size of the product could be tuned by reaction parameters such as electrolysis voltage and tungestate ion
concentration as reactant. The morphological (SEM) characterization analysis was carried out for the obtained ZnWO4
nanoparticles. Finally, the optimum conditions for the synthesis of zinc tungestate nanoparticles by this simple and fast method
were proposed. The results of ANOVA showed that 0.01 mol/L tungestate ion concentration, electrolysis voltage of 8 V and 0 °C
temperature are the optimum conditions for producing zinc tungestate nanoparticles with 58 ± 10 nm widths.
Reference
[1] G. Taguchi, System of Experimental Design, Kraus, White Plains, N.Y, 1987.
[2] S. M. Pourmortazavi, I. Kohsari, S. S. Hajimirsadeghi, Central European Journal of Chemistry 7 (2009) 74–78.
Development of a cloud point extraction and preconcentration method for zinc ion prior to UV-Vis spectrophotometry
determination
Fatemeh Abbasitabar1*, Soheila Shahryari2, Vali Zare-Shahabadi3
1
2
Department of Chemistry, Marvdasht Branch, Islamic Azad University, Marvdasht, Iran
Department of Chemistry, Firouzabad Branch, Islamic Azad University, Firouzabad, Iran
3
Department of Chemistry, Mahshahr Branch, Islamic Azad University, Mahshahr, Iran
. E-mail: fabbasitabar@gmail.com
Dithizone (diphenyl thiocarbazone) was used as a complexing agent in cloud point extraction [1-3] for the first time and applied
for selective preconcentration of trace amounts of zinc ion. The analyte in the initial aqueous solution was acidified with
phosphoric buffer (pH =4) and Triton X-114 was then added as a surfactant. After phase separation, based on the cloud point
separation of the mixture, the surfactant rich phase was diluted with ethanol and the analyte determined in the enriched solution
by UV-Vis spectrophotometer. After optimization of the complexation and extraction conditions, a preconcentration factor of 50
was obtained for only 10 ml of sample. The analytical curve was linear in the range of 1.0×10-7-5.0×10-5 mol L−1 and the limit of
detection was found to be 6.0×10-8 mol L −1. The proposed method was applied to the determination of zinc in water samples.
Reference
[1]. J.L. Manzoori, A. Bavili-Tabrizi, Microchim. Acta, 141 (2003), 201.
[2]. A. Shokrollahi, M. Ghaedi, O. Hossaini, N. Khanjari, M. Soylak, J. Hazard. Materials, 160 (2008), 435.
[3] T.M. Florence, Talanta 29 (1982) 345.
An investigation on the curing behavior of epoxy resin based on bisphenol F (DGEBF), in the presence of nanofillers
Abolghasem moraveji *, Foruzan Gholamian, Farideh Bataghva, Sara Ghariban
Department of Analytical Chemistry, Faculty of Chemistry and Chemical Engineering, Malek Ashtar University of Technology, Tehran, Islamic
Republic of Iran
*
Email address: g.moraveji@gmail.com
In this study, the cure process of epoxy resin based on bisphenol F (DGEBF) with poly amine hardener in the presence of
nanosilica investigated through Differential Scanning Calorimetry (DSC) and Fourier transform infrared (FT-IR). The total
reaction enthalpy (the maximum produced heat of reaction during curing) and glass Transition (Tg) was measured by DSC scans
from 25 to 250 °C at rate of 10°C/min. All results were compared to those of bare epoxy resin and a decrease in ΔH and slight
increase in Tg were observed. In curing process, the reaction occurs between amine active hydrogens and epoxy groups.
Reduction in total reaction enthalpy in presence of nanosilica indicates lower degree of cure. Therefore, some of epoxy rings
residue in the matrix and FT-IR spectra shows epoxy ring peak (the band at 914 cm-1). These results indicate that some amine
active hydrogens covered with nanoparticles. As a matter of fact Tg depends on crosslinking and increases with higher
crosslinking. DSC curves show slight increase of Tg upon addition of nanosilica. This increase happens because of large surface
area that enhances the crosslinking.
Reference
[1]Baller, G., Thomassey, M., Ziehmer, M., & Sanctuary, R. (2010). The catalytic influence of alumina nanoparticles on epoxy curing. Thermochimica Acta, 34-39.
[2]Branda, F., & Tescione, F. (2010). A new extra situ sol–gel route to silica/epoxy (DGEBA). original paper .
[3]Hong, S., & Tasi, G. (2001). The adsorption and curing behaviors of the epoxy/amidoamine system in the presence of metal oxides. Journal of Thermal Analysis
and Calorimetry, 31-64.
[4]Zhen, D., Yanfang, L., Shuguang, Y., Ning, Z., Xiaoli, Z., & Jian, X. (2009). Kinetics and thermal properties of epoxy resins based on bisphenol fluorene structure.
European Polymer Journal, 1941-1948
[5] R. Durairaj • Lam Wai Man. (2011). Effect of epoxy and filler concentrations on curing behaviour
of isotropic conductive adhesives. J Therm Anal Calorim.
[6] Suzana Samarzˇija-Jovanovic´• Vojislav Jovanovic´• Sandra Konstantinovic´• Gordana Markovic´•
Milena Marinovic´-Cincovic´. (2010). Thermal behavior of modified urea–formaldehyde resins. J Therm Anal Calorim.
Using Multivariate Curve Resolution for determination of H 2O2 with flow injection system and Electrochemical detector
Hamid Abdollahia* ,Behzad Haghighi b*, Seyed Taher Seyyedinb
Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan, Iran.
E-mail: abd@iasbs.ac.ir, haghighi@iasbs.ac.ir
etermination of analyte of interest in the presence of unexpected interferences is very important. The ability of quantification in
the presence of unknown interference is called second order advantage.Usually this advantage is achieved from second order
data.[1]Although there are several approaches for obtaining second order data ,electrochemical second order data is relatively
rare compared with spectroscopy. The proposed approach is recommended for obtaining second order data from flow injection
system with voltammetric detection. The selected voltammetric technique for analyte detection was Linear Sweep Voltammetry
(LSV), which provides richer multivariate information than the more widespread employed univariate amperometric detection.
Use of other voltammetric detection techniques was also attempted but they gave much poorer results because of instrumental
and software limitations concerning data acquisition times. Determination of hydrogen peroxide (H2O2) with high selectivity and
sensitivity is of great importance, because H2O2 is a product of several biological, enzyme-catalyzed reactions.Ascorbic acid is
one of the interferences for determination of H2O2 so minimizing effects of this is important. A novel application of Multivariate
Curve Resolution (MCR) method for the resolution and quantitation of coeluted analyte mixtures in flow injection system with
voltammetric detection(VD) is presented. The method is tested in the resolution and quantitation of mixtures of hydrogen
peroxide and ascorbic acid in a carbon ionic liquid electrode(CILE). The optimum condition for determination of H2O2 was the
phosphate buffer with pH=6.8 and the optimum electrode composition was 45% ionic liquid, 55% graphite. Experimental
parameters optimized included scan rate and electrochemical potential range and flow rate. Finally scan rate was set at 1 scan /s,
or 0.4 V/s since potential range was always 400 mV.flow rate was 15 rpm. Rank deficiency of the mixture data matrix is broken
by augmentation data matrix of analyte of interest to the standard sample and mixture.[3] The results show that VD-MCR
provides accurate quantification with minimal effort (a single injection of the sample and each standard). Also,It is a good way
for fast initial screening of optimal potential when amperometric detection is preferred.[4]
Reference
[1].H. Abdollahi, M. Kooshki, Electroanalysis, 22 (2010) 2245
[2].Berbel,F.; Kapoya,E.; DÌaz-Cruz,J.M.; Arin ˜o,C.; Esteban,M.; Tauler,R. Electroanalysis .2003. 15. 5 6
[3].Esteban,M.; Arin ˜o,C.; Dı ´az-Cruz,J.M. Trends in Analytical Chemistry .2006.25.1
[4].González-García,O.Ariño,C.; DÌaz-Cruz,J.M.; Esteban,M. Chemometrics and Intelligent Laboratory Systems.2008. 93. 49
Kinetic- Spectrophotometric Determination of 1,1-dimethylhydrazine and a new method for its colorimetric monitoring
Akbar afshar asl*, Reza Ghiaee, Davod Heydari, Vahid Oroojpour
Iranian Aerospace Organization. Tehran post box no. 16585-111
1,1-dimethylhydrazine is a highly toxic substance, so special care needs to be taken to its use. A method for the rapid and
accurate determination of trace quantities of 1,1-dimethylhydrazine based on its inhibition effect in the reaction between bromate
and hydrochloric acid is developed. The decolorization of methyl orange by the reaction products was used to monitor the
reaction spectrophotometrically at 525 nm. The method allows the determination of 1,1-dimethylhydrazine in the range 2.00×107
_ 5.00×10-4 M. The relative standard deviation for determination of 8.65×10-7 and 2.25×10-6 M 1,1-dimethylhydrazine is 2.3%
and 1.3% respectively. The detection limit of the method is 1.83×10-7 M. As human's eyes are not able to distinguish a slight
change in the color, therefore 1,1-dimethylhydrazine colorimetric sensor, designed and built by simple and cheap equipment and
operated for permanent use. This simple, accurate, cheap and rapid sensor has been used for monitoring and determining of 1,1dimethylhydrazine in the range of 1.25×10-5 _ 5.00×10-6 M in the industry.
Reference
[1]. Abbas Afkham, Akbar Afshar Asl, Kinetic-spectrophotometric determination of hydrazine by the inhibition bromat-hydrochloric acid reaction. Analytica Chimica
Acta,419 (2000) 101-106
[2]. P. Linares, M. D. Lugue de Castro and M. Valcarcel. Analyst, 1986, 111, 1405.
[3]. Arthur I. Vogel, A Text-Book of Quantitative Inorganic Analysis, Third Edition, Longman, London, 1961, 384.
[4]. G. C. Miller, G. N. Miller, Translated by S. M. Gollaby, statistics for Chemical Analyses, Tabriz, 1373
[5]. Vogel’s Text-Book of Quantitative Chemical Analysis, Sixth Edition, J. Mendham, C. Denney, J. D. Barnes, M. J. K. Thomas, Page154-155.
[6]. Chemical Analysis, Second Edition, HERBERT A. LAITINEN, WALTER E. HARRIS, McGraw-HILL, Page 540.
The inhibitive effect of two Schiff bases on corrosion behaviour of 304 stainless steel in sulphuric acid solution
a
N. Soltani*a, N. Rasoulib, M. Maseratfara
Payame Noor University (PNU), aShahin Shahr Branch, bKoohpayeh Branch) Isfahan, Iran
The corrosion of stainless steel (SS) in acidic solutions is a fundamental academic and industrial concern that has received a
considerable amount of attention [1]. Various types of inhibitors are injected into solution in order to reduce the corrosion rate to
safe level [2]. Many research works have been developed in order to correlate the substituent effect and the inhibition efficiency
of organic molecules. Furthermore, the adsorption depends on the electronic structure of inhibiting molecules, steric factor,
aromaticity and electron density at donor site, presence of functional group such as -C=O, -HC=N-, -N=N-, R-OH, etc.,
molecular area, molecular weight of the molecule, temperature and electrochemical potential at the metal/solution interface [3, 4].
Schiff base, an organic compound having general formula R-C=N-R´ where R and R´ are aryl, alkyl or cycloalkyl or heterocyclic
groups formed by the condensation of an amine and a carbonyl group, is a potential inhibitor. The greatest advantage of many
Schiff base compounds is that they can be conveniently and easily synthesized from relatively cheap material In this work, the
corrosion inhibition characteristics of two synthesized Schiff bases, namely 2-[(1E)-2-(3-{3-[(1E)-2-(2-hydroxyphenyl)-1azavinyl]phenyl}phenyl)-2-azavinyl]phe-nol (PBP) and 2-[(1Z)-2-(4-{4-[(1Z)-2-(2-hydroxy-5-nitrophenyl)-2-azavinyl]phenyl}phenyl)-2-azavinyl]-4-nitrophenol (NPBPN) on the 304 stainless steel corrosion in 1 M sulphuric acid have been investigated
by weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. Effect of
temperature on the mechanism and also on the efficiency of the corrosion inhibition process was studied using the Arrhenius
approximation of the rate law. Polarization experiments were performed at different solution temperatures. Thermodynamic
parameters for the corrosion process were obtained and interpreted. The adsorption of the inhibitor, on the steel surface in the
acid medium (1 M H2SO4) obeyed the Langmuir adsorption isotherm. Moreover, in this study, the behaviour and the relation
between molecular structure and the inhibitive effects of these substances on the corrosion inhibition of steel in hydrochloric acid
solution are investigated.
Reference
[1] M. Abdallah, Mater. Chem. Phys. 82 (2003) 786–792.
[2] M. Behpour, S.M. Ghoreishi, N. Soltani, M. Salavati-Niasari, Corros. Sci. 51 (2009) 1073–1082.
[3] X. Li, Sh. Deng, H. Fu, Corros. Sci. 52 (2010) 3413–3420.
[4] S.M.A. Hosseini, M. Salari, E. Jamalizadeh, S. Khezripoor, M. Seifi, Mater. Chem. Phys.119 (2010) 100–105.
The effect of magnetic field on the stability of (kryptofix 22DD)
complexes with yttrium ion
M. Gholizadeh, G. H. Rounaghi 1*, I. Razavipanah, M.R. Salavati
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran.
Crown compound are ligands with selectivity for metal ions. In order to understand the interactions between ligand, ion and
solvent we resorting to study of magnetic field effect on ion-macrocyclic complexes. Therefore, we studied the complexation
between kryptofix 22DD and Yttrium ion in methanol through the conductometry technique at the different temperature by a
nonlinear least-square program (Genplot) under magnetic field. We observed that stability constants of complexes in the presence
of the magnetic field were decreased. Like-wise, we observed that, magnetic field influenced on ion, solvent and ligand one by
one.
Reference
[1]. Eshaghi, Z., Gholizadeh. M., Talanta. 64 (2004) 121.
[2]. Cai, R., Yang, H., He, J., Zhu, W., J. Mol. Struct. 938 (2009)15.
[3]. Ansari Fard, M., Rounaghi, G. H., Chamsaz, M., Taheri, K., J. Incl. Phenom. Macrocycl. Chem. 64 (2009) 49.
Application of glassy carbon electrode modified with multi-walled carbon nanotube (MWCNTs) and Nickel hydroxide
nano-particles (NHNPs) composite as a novel sensor for simultaneous determination of Dopamine and Tramadol
Ali rezaei , Ali Babaei* , Majid Amini khah , Ali Reza Taheri
Department of Chemistry, Faculty of Sciences, Arak University, Arak, Iran
Dopamine (DA) is one of the most significant catecholamine’s and belongs to the family of inhibitory neurotransmitters that
plays a significant role in the functioning of central nervous, renal and hormonal systems as well as in drug addition and
Parkinson’s disease[1].Tramadol (TRA) is a centrally acting analgesic that has an analgesic efficacy and potency that ranges
between weak opioids and morphine. TRA is the only clinically available non-scheduled opioid that available as drops, capsules
and sustained- release formulations for oral use, suppositories for rectal use and solution for intramuscular, intravenous and
subcutaneous injection. The drug acts as an opiate agonist, by selective activity at the la- opioid receptor. Since DA is a
compound which play a potential role in humanmetabolism and TRA act as an opiate agonist, by effect on la-opioid receptor and
central nervous system. It is significant to fabricate sensitive and simple Sensors for the determination of DA and TRA. In the
present work, we outline the use of a multi-walled carbon nanotube (MWCNTs) and nickel hydroxide nano-particles (NHNPs)
composite modified glassy carbon electrode as a sensor for simultaneous determination of DA and TRA. The electroanalytical
determination of DA and TRA was studied by cyclic voltammetry(CV) and differential pulse voltammetry (DPV) methods.
Several parameters were studied for the optimization of the sensor such as electrode composition, pH effect, time effect, potential
scan rate and interferences in potential. Our study has led to a novel sensor with useful characteristics as low limit of detection
(LOD < 1μmol L-1) and good reproducibility (RSD ≤ 2%) and wide linear dynamic range (LDR). The obtained linear range was
in the range of 0.5×10-6 to 280×10-6 M for DA and 2×10-6 to 350×10-6 M for TRA with DPV measurements .Therefore, to
confirm its usefulness, the analytical performance of our sensor for determination of DA and TRA in human serum and human urine.
Reference
[1] Hong-Yuan Chen, Electroanalysis 18, 2006, No. 3, 282 – 290
[2] M.A- Campanero, Chromatographia 48, 1998 No. 7/8, 555 – 560
Solid phase extraction based on layered double hydroxides as potential nano-sorbents for the pre-concentration and
determination of phosphate in natural waters
H. Abdolmohammad-Zadeh*, A.A. Khatami, G.H. Sadeghi
Department of Chemistry, Faculty of Sciences, Azarbaijan University of Tarbiat Moallem, P.O. Box 53714-161, Tabriz, Iran
* Corresponding author. Tel.: +98 4124327541 ; Fax: +98 4124327541.
E-mail: h.abdol@azaruniv.edu, h_abdol@yahoo.com
Layered double hydroxides (LDHs) are micellar mixed hydroxides containing positively charged main layers and undergoing
anion exchang chemistry [1]. In recent years many studies have been devoted to investigation the ability of LDHs to remove
harmful oxyanions such as phosphate, chromate, arsenate and etc from contaminated waters [2]. In this work, we have
successfully synthesized Ni-Al layered double hydroxides by co-precipitation method and applied as nano-sorbent in solid phase
extraction of phosphate anions. Several parameters affecting on extraction efficiency such as pH, sample loading volume, sample
loading flow rate, concentration of eluent (NaOH) and volume of eluent were investigated and optimized. We have found that
layered double hydroxides as nano-sorbents in solid phase extraction have more efficiency for pre-concentration over the 98% of
phosphate anions and elimination of interfering ions. In the last year’s, determination of phosphate by spectrophotometric method
based on formation hetero poly acids followed with combination of phosphate with molybdate in acidic medium were the most
common used method. The basic problem in this method was tolerance of interfering ions such as silicate, arsenate, etc. that leads
to lack of selectivity. Another problem was time consuming and the cost of pre-concentration step. Overcoming to accurate and
rapid and lower limit of detection in proposed method was accessible by focusing on potential efficiency of oxyanion adsorption
and elimination of interfering ions by LDHs. In the optimum conditions, the detection limit and pre-concentration factor of
presented method were 0.1 ng mL−1 and 70, respectively. The presented method was successfully applied for the determination of
phosphate ions in natural water samples.
Reference
[1] F. Cavani, F.Trifiro, A. Vaccari, Catalysis Today, 11 (1991) 173–301..
[2] K. H. Goh, T.T. Lim, Z. Dong. Water Research, 42 (2008) 1343–1368.
Syntheses, structural and solution studies of Hg (II) complex with 1 - (4-Chlorophenyl)-3-(4-Ethoxyphenyl) Triazene
Mohammad Kazem Rofouei*, Samira M. Sharifkhani, Salameh Azimi
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
Email: s.sharifkhani@yahoo.com
The synthesis of 1-(4-Chlorophenyl)-3-(4-Ethoxyphenyl) Triazen (CET), [HL], and the reaction of CET with Hg (No3)2 in
acetonitrile as solvent, resulted in the formation of [HgL2] and [HgL], are reported in this article. This compound was
characterized by means of NMR, FT-IR, UV spectroscopy and CHN analysis. The resulting absorbance against [Hg2+]/[Hl] mole
ratio plot, reveals distinct inflection points at a metal-to-ligand molar ratio of about 0.5 and 1 emphasizing the formation of a 1:2
and 1:1 complexes. 1-(4-Chlorophenyl)-3-(4-Ethoxyphenyl) Triazen (CET) used as ligand and its structure is shown in Fig. 1. It
was synthesized as follows: A 2000 ml flask was charged with ice and water and then cooled to 0 ºC in an ice-bath. After that
6.38 g of 4-chloroaniline and 10 ml of hydrochloric acid (d = 1.18 g ml-1) were added to the mixture, and then a solution of
NaNO2 containing 3.45 g in 25 ml of water was added during 15 min under stirring solution. Afterwards, a solution containing
6.47ml of 4-Ethoxyaniline in 25 ml of methanol was added drop wise with vigorous stirring for a period of 30 min to this
mixture. Finally, pH was adjusted to 7-8 with the solution of sodium acetate 18% and stirred for 2 hours. The brown residue was
filtered and dissolved in diethyl ether, after evaporation of diethyl ether, a purified yellow powder was obtained, which has a
melting point of 117 - 119 ºC. In a typical procedure, the absorbance of 2.0 ml of ligand was measured by UV spectrophotometer.
Then a known amount of the concentrated solution of Mercurry (II) nitrate solution was added in a stepwise manner using a 5µl
Hamilton syringe. The mole ratio data obtained by the physicochemical method employed were fitted by using a non-linear leastsquares curve fitting program KINFIT. The resulting absorbance against [Hg2+]/[HL] mole ratio plot, reveals distinct inflection
points at a metal-to-ligand molar ratio of about 0.5 and 1 emphasizing the formation of a 1:2 and 1:1 complexes. The conditional
formation constants were evaluated as log K1 = 4.56 ± 0.001 and log K2 = 4.96 ± 0.001
Fig1. The 1-(4-Chlorophenyl)-3-(4-Ethoxyphenyl) Triazen (CET)
Reference
1.M.K.Rofouei, M.Hematyar, V.Ghoulipour and J.A.Gharmaleki,Inorg. Chim. Acta 362(2009)3777.
Attenuated total reflaction infrared spectroscopy (ATR-IR) for determination of amlodipine besylate
E.Konoz∗,A.H.Mohsen sarrafi,Z.Mazaheri
1) Department of Chemistry, Islamic Azad University, Faculty of science, Central Tehran Branch, Tehran, Iran
Konozelaheh@gmail.com
Attenuated total reflection Fourier transform infrared spectroscopy is one of the most powerful methods for recording infrared
spectra of biological materials in general, and of biological membranes in particular. ATR-IR system was found to have good
sensitivity and can analyze samples as low as 0.1 mg/ml. The quantification of amlodipine through infrared spectroscopy was
developed and validated for pharmaceuticals in tablet form. The method involves the extraction of the active ingredient with
direct determination in the extract through band area measurement in the 1191 and 1212 cm-1.The linearity , detection limits,
precision and accuracy of the calibration curve, amlodipine extraction,infrared analysis and data manipulation were determined
in order to validate the method. Moreover,the statistical results were compared with the quantification of amlodipine through
ATR-IR detection.The recovery values obtained in the analysis of pharmaceutical are within the 96-98% rangeThe
calibration.The value of LOD and LOQ obtained in this band area. Model was developed based on simple Beer’s law using the
FT-IR carbonyl region (C O) from 1191 to1212cm−1. The excellent coefficient of determination (R2) was achieved (0.9992)
with 0.01mg standard error of calibration. This work clearly revealed the capability of the transmission FT-IR spectroscopy.
Reference
[1] S J.S.Basha , S A.Naveed , N.K.Tiwari. Journal of Chromatography B, 853 (2007) 88–96
[2] (a) J.J. Dressman, J.K. Kramer (Eds.), Pharmaceutical Dissolution Testing, Taylor and Francis, Boca Raton, FL, 2005;
[3] Aftab, Kandhro, Sherazi, S. T. H., Mahesar, S. A., Bhanger, M. I., Talpur, M., Younis, M.,& Rauf, Abdul (2008).
[4] Beullens, K., Kirsanov, D., Irudayaraj, J., Rudnitskaya, A., Legin, A., Nicolaï, B., et al.(2006).
Electrochemical behavior of L-DOPA as an important biological molecule: Experimental and theoretical studies
Marzieh Eslami*, Hamid R. Zare, Mansoor Namazian
Department of Chemistry, Yazd University, Yazd, 89195-741, Iran
Fax: +98 351 8210991 Tel.: +98 351 8122669
E-mail: Eslami_marzieh@yahoo.com; hrzare@yazduni.ac.ir
Historically, l-dihydroxyphenylalanine (L-DOPA) is considered as a prodrug to increase dopamine levels for the treatment of
Parkinson’s disease. This compound is able to cross the blood–brain barrier whereas dopamine itself cannot [1-3]. In this study,
electrochemical oxidation of L-DOPA, as important biological molecule, has been studied in 0.1 M phosphate buffer solution,
using cyclic voltammetry, as well as quantum chemical calculations. The effect of different parameters such as pH, L-DOPA
concentration, temperature and time window of the chosen electrochemical method has been studied for understanding the
oxidation mechanism of L-DOPA. The results show that the oxidation mechanism of L-DOPA is an ErCiEr mechanism. Also, the
experimental data indicate that, in acidic pHs, the rate of the subsequent chemical reaction is less than neutral and basic pHs. It is
supposed that the subsequent chemical reaction of dimerization is more likely for the oxidation form of L-DOPA. The transfer
coefficient, a, and exchange current density, j0, for oxidation of L-DOPA at the glassy carbon electrode are determined in
different pHs. Also, the acidic dissociation constant and the standard redox potential, E0¢, of L-DOPA were determined. Finally,
The standard potentials and the acidic dissociation constant of L-DOPA have been also calculated using standard ab initio
calculations at the G3MP2 level of theory, in conjunction with a continuum solvation model.
Reference
[1] Barnes, H.V., 1988. Clinical Medicine.Year Book Medical Publisher,NewYork, pp. 745–750.
[2] Misu, Y., Goshima, Y.,Miyamae, T., 2002. Trends Pharmacol. Sci. 23, 262–268.
[3] Misu, Y., Goshima, Y., 1993. Trends Pharmacol. Sci. 14, 119–123.
Application of Doolittle Multivariate Calibration Algorithm (LU decomposition) for infrared spectrometric
determination of some ingredients in high overlapping systems
Mohammadhossein Ahmadi Azghandi*, Mohammadreza Khanmohammadi
Chemistry Department, Faculty of Science, Imam Khomeini International University, Qazvin, Iran
mhahmadia58@gmail.com
There are some conventional analytical methods for analysis of a washing powder samples e.g. extraction by ethanol or classical
wet chemistry methods [1]. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectrometry has been
introduced as an efficient technique with high signal-to-noise ratio for quantitative determination of ingredients of washing
powder samples [2-3]. There are several multivariate calibration methods to extract the spectral data for each compound in a
mixture with similar spectral characteristics. Partial least-squares (PLS) are a usual tool for multivariate calibration because of the
quality of the obtained calibration models, the ease of its application and the availability of software. Doolittle Decomposition
Algorithm (DDA) is a very simple, accurate and stable numerical analysis algorithm with an easy computational procedure. This
algorithm can avoid matrix inverting operation, which is often involved in chemometrics such as K-Matrix (KM), P-Matrix (PM)
and partial least squares (PLS) methods, reduce the orders of matrixes, speed up the operation of matrixes, and raise the
efficiency of computation. [4-5]. In this paper, Doolittle algorithm has been developed for simultaneous determination of sodium
Sulfate (SS), sodium Carbonate (SC) and Sodium Tripolyphosphate (STPP) in a commercial detergent powder samples by using
ATR-FTIR spectroscopy and evaluating the results obtained by multivariate K-Matrix and DDA.
Reference
[1]. ASTM Method D501–89, Standard test method for sampling and chemical analysis of alkaline detergents. American Society for Testing and Material,
Philadelphia.
[2]. M. Khanmohammadi, A. Ashori, K. Kargosha, A. Bagheri Garmarudi, J Surfact Deterg 10:81–86 (2007).
[3]. M. H. Ahmadi, M. R. Khanmohammadi, Journal of Spectroscopy and Dynamic, (2011), in press.
[4]. Y.P. Ding, Analytical Sciences 21 (2005) 327.
[5]. N.Y. Chen, Y.P. Ding,G.Z. Li, C.Z. Ye, Q.S. Wu, Computers and Applied Chemistry19 (2002) 717.
Direct electrochemistry of adenine on multi-walled carbon nanotubes modified carbon ionic liquid electrode
M. Arvanda,*, A. Niazib, R. Motaghed Mazhabib, P. Biparvac
Department of Chemistry, Faculty of science, University of Guilan, P.O. Box: 1914, Rasht, Iran
b
Deparment of Chemistry, Islamic Azad University, Arak Branch, Iran
c
Research Department of Chromatography, Iranian Academic Center for Education, Culture & Research (ACECR), Urmia, Iran
Email: arvand@guilan.ac.ir
a
Deoxyribonucleic acid (DNA) is an important substance which plays significant role in biological heritage, information storage
and in protein biosynthesis. Adenine is an important purine base existed in DNA, which participates in processes as distinct as
energy transduction, metabolic cofactors and cell signaling. In recent years ionic liquids (ILs) have received great attention due to
their specific characteristics such as good chemical and thermal stability, high ionic conductivity, negligible vapor pressure and
wide electrochemical windows. Carbon nanotubes (CNTs) with single or multiple walls have attracted considerable attention of
the researchers. With their unique advantages such as high conductivity, high chemical stability, extremely high mechanical
strength and modulus, CNTs modified electrodes were successfully applied to study and determine many biological and organic
molecules. In the present study, a novel and reliable electrochemical sensor based on CNT, ionic liquid 1-etyl-3methylimidazolium hexafluorophosphate (EMIMPF6) composite film modified carbon paste electrode (MWNT-IL/CPE) was
proposed for determination of adenine. The adenine oxidation responses were monitored by differential pulse voltammetric
measurement. Compared with the carbon paste electrode and the ionic liquid modified carbon paste electrode not only
significantly enhanced the oxidation peak currents of adenine, but also lowered its oxidation overpotential, suggesting that the
synergistic effect of MWNT and IL could dramatically improve the determining sensitivity of adenine. The MWNT-IL/CPE
showed good stability, high accumulation efficiency and enhanced electrocatalytic ability for the detection of adenine. The
proposed method for the measurement of adenine in urine and milk powder was successfully applied with satisfactory results.
Reference
[1] Q. Shen, X. Wang, J. Electeroanal. Chem. 632 (2009) 149–153.
[2] C. Tang, U. Yogeswaran, S.M. Chen, Anal. Chim. Acta 636 (2009) 19–27.
[3] W. Sun, X. Li, Y. Wang, R. Zhao, K. Jiao, 54 (2009) 4141–4148.
[4] W. Sun, Y. Duan, Y. Li, H. Gao, K. Jiao, Talanta 78 (2009) 695–699.
Solid Phase Microextraction of Phthalates in Water Using Polyphosphate-Doped Polypyrrole Coated on Steel Fiber
A. Mollahosseini*1, M. Abdollahi2, R. Shirazi2 and N. Baghbadrani2
1. Department of Chemistry, Iran University of Science and Technology, Tehran, Iran
2. Faculty of Technical and Engineering, Islamic Azad University, Saveh Branch, Saveh, Iran
Phthalate esters (PEs), commonly known as phthalates, are a class of chemical compounds primarily used as plasticizers.
Phthalate esters are widely used as additives in the manufacturing of plastics to make them flexible. Extensive use of these
chemicals resulted in their presence in various environmental matrices such as water, soil and food. Certain phthalates and/or
their metabolites are suspected to be human endocrine disruptors and carcinogens, and due to their potential risks for human
health and the environment, some of them have been included among priority pollutants. The most popular methods for
analyzing phthalates are chromatographic techniques, such as GC or HPLC [1]. But, due to the low sensitivity of such methods, a
sample preparation technique is usually necessary prior to the analysis of these compounds. Solid-phase microextraction (SPME),
due to its simple, fast and solvent-free features and high concentration factor has received growing interest for many areas,
including its applications in phthalate analysis. In the present work, a steel fiber coated with polyphosphate-doped polypyrrole
was used to extract a group of PEs. The coating was carried out from an aqueous solution containing pyrrole and polyphosphate,
using constant potential coulometry (CPC). The extraction behavior of the coated fiber towards dibutylphthalate (DBP), diisobutylphthalate (DIBP), benzylbutylphthalate (BBP), and bis-(2-ethylhexyl) phthalate (DEHP) was examined.
The effects of various parameters, including extraction time and temperature, salting-out effect, desorption time and temperature
were studied. At optimum conditions, intra and inter-day repeatability of the method was between 6.1-7.1 and 5.4-7.6%
respectively. Linear ranges were in the range of 0.1-25 μg/mL and detection limits were between 0.1-0.2 ng/mL. Recoveries were
found in the range of 91-96%. As real samples, various mineral waters and were studied.
Reference
[1]. J.-F., Jen and T.-C., Liu, J. Chromatogr. A 1130 (2006) 28-33.
Separation, qualitative and quantitive analyse of volatile constituents in Pulicaria gnaphalodes (vent) Boiss (Asteraceae)
Leaf parts by GC and GC-MS
S. Yazarloo1*, M. Rahimi2, M. siavoshan2, M. Mohammadhosseini2, A. Mazloomifar1, M. Nekoei2
1) Department of Chemistry, Faculty of Basic Sciences, Shahreray Branch, Islamic Azad University, Shahreray, Iran
2)Department of Chemistry, Faculty of Basic Sciences, Shahrood Branch, Islamic Azad University, Shahrood, Iran
saeedyazarloo@gmail.com
The present report deals with identification and quantification of essential oil obtained from Leafparts of Pulicaria gnaphalodes
(vent) Boiss (Asteraceae)as a growing wild in Semnan province (Iran). Essential oils have attracted a unique compartment in
different scientific branches involving traditional medication, perfumes and fragrance industry as well as pharmceutical
formulations. In the present report, water-distilled essential oil from Pulicaria gnaphalodes (vent) Boiss (Asteraceae) an endemic
growing wild plant in Iran, was analyzed by GC (equipped with a SE30 column) and GC-MS (with a HP-5MS) under certain
temperature programming. A total of 27 compounds were identified representing 92.63% of the total aerial parts oil among them
1,8-cineol (20.19%), α-terpineol (6.79%), cadinol epi-alpha (6.71%) and chrysanthenol (6.07%) were found to be the major
components. According to the chemical profile, monoterpenoides, sesquiterpenoides and non-terpenoieds constituted 75.03, 9.91,
and 7.69 of the oil composition, respectively.
Reference
[1] M. Jahangir, Chemical and Biological Studies on Some Members of Asteraceae Family and PseudocalymmaElegans,A Native of Brazil, H.E.J. Research Institute
of Chemistry/ University of Karachi, (2001) 212.
[2] K.A. Eshbakova andA.I. Saidkhodzhaev, Chemistry of Natural Compounds, 37(2001)2.
[3] British Pharmacopoeia HMSO, London. 2(1998)137.
[4] R.P. Adams,Identification of Essential Oils Components by Gas Chromatography/Quadrapole Mass Sectrometry, Allured Publishing Corporation, Illinois,
USA,(2001).
[5] R.P. Adams,Identification of Essential Oil Components by Gas Chromatography/Mass Spectrometry, Allured Pubishing Co., Carol Stream, IL., USA, (2007).
Preparation and photo-catalytic activity of Ag–TiO2 thin films prepared by sol–gel dip coating
Mohsen Behpour*, Maryam Chakeri
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, I. R. Iran
E-mail: m.behpour@kashanu.ac.ir
Semiconductor photocatalysts have been of considerable interest in the past decades owing to their application in both oxidations
of organic compounds for purpose of environmental purification and solar energy conversion. Among the multitudinous
photocatalysts, TiO2 appears to be the most promising and suitable material due to its superior properties, such as stability, low
cost and non-toxicity [1]. Photo-oxidation by using TiO2 photo-catalyst is being widely studied as a relatively new technique of
pollution abatement [2]. But TiO2 has been applied in UV-light photocatalysis. Nevertheless visible-light photocatalytic activity
would make this material more attractive for applications [3]. Most of the metal ion doped entered TiO2 lattice resulting the shift
in optical absorption edge towards visible side. Addition of polyethylene glycol (PEG) alters the surface morphology and
structure of the films. Many researchers have paid attention in developing modified TiO2 powder catalyst but using the powder
catalyst has the disadvantages like stirring during the reaction and separation of catalyst after each run. The preparation of thin
film catalyst will overcome these problems. In this work thin films of silver (Ag) doped titanium dioxide (Ag–TiO2) were
prepared on a glass substrates by using sol–gel dip coating method. The surface structure of the film was modified by adding
different concentrations of PEG into the TiO2 sol. The increase in concentration of PEG increases the number and size of the
pores on surface of the film by decomposition of PEG when the films are subjected to heat treatment. Photo-catalytic properties
of the surface modified and Ag ion doped TiO2 catalyst was investigated by degradation of methyl orange in visible light.
Reference
[1] P. Huo, Y. Yan, S. Li, H. Li, W.Huang, Desalination, 2010, 256, 196–200
[2] R.S. Sonawane, B.B. Kale, M.K. Dongare, Mate. Chem. Phys, 2004, 85, 52–57
[3] E. Camps, L. Escobar-Alarcon, M. A. Camacho-Lopez, D. A. S. Casados, Mate. Sci. Eng. B, 2010, 174, 80–83
The inhibition of stainless steel corrosion in 0.5 M H2SO4 solutions by a new Schiff base
N. Tavakkoli*,a, N. Soltanib, F. Loghmania, M.R. Jalali
Department of Chemistry, Payam Noor University, Isfahan
b
Department of Chemistry, Payam Noor University, Shahin Shahr Branch, Isfahan
a
The study of organic compounds as acid corrosion inhibitors is a subject of immense interest due to their usefulness in several
industrial applications such as pickling of metals, cleaning of boilers and acidification of oil wells [1]. Schiff base compounds
due to the presence of the –C=N– group, electronegative nitrogen, sulphur and/or oxygen atoms in the molecule, have been
reported to be effective inhibitors for the corrosion of steel in acid media by several authors [2-4]. In the present work, the
inhibition effect of a new Schiff base (2,6-bis{[2-(4-nitrophenyl)-1-diazenyl] methyl}pyridine) on the corrosion of stainless steel
in 0.5 M H2SO4 has been studied by weight loss, electrochemical impedance spectroscopy (EIS), polarization measurements and
UV–visible spectrophotometric. The obtained results show that the inhibition efficiency compound Schiff base is 99.7% at 1×10-3
M additive concentration. All measurements show that inhibition efficiencies increase with increase in inhibitor concentration.
This reveals that inhibitive actions of inhibitors were mainly due to adsorption on mild steel surface. Polarization curves
indicated that the inhibitors behave mainly as mixed type inhibitor. The inhibitor was adsorbed on the steel surface according to
the Langmuir adsorption isotherm model. From the adsorption isotherm, some thermodynamic data for the adsorption process
were calculated and discussed. Effect of temperature on the mechanism and also on the efficiency of the corrosion inhibition
process was studied using the Arrhenius approximation of the rate law. The UV–visible absorption spectra of the solution
containing the inhibitor after the immersion of steel specimen indicate the formation of a Schiff base Fe complex which may be
responsible for the observed inhibition. Inhibition efficiency values increase with the inhibitor concentration but decrease with
rise in temperature suggesting physical adsorption mechanism. Quantum chemical calculations were further applied to reveal the
adsorption structure and explain the experimental results.
Reference
[1] I.B. Obot, N.O. Obi-Egbedi, N.W. Odozi, Corros. Sci., 52 (2010) 923–926.
[2] M. Behpour, S.M. Ghoreishi, N. Mohammadi, N. Soltani, M. Salavati-Niasari, Corros. Sci., 52 (2010)
4046–4057.
[3] Nabel A. Negm, Mohamed F. Zaki, Colloids and Surfaces A: Physicochem. Eng. Aspects 322 (2008) 97–102.
[4] M.G. Hosseini, M. Ehteshamzadeh, T. Shahrabi, Electrochim. Acta, 52 (2007) 3680–3685.
A voltammetric sensor for the simultaneous determination of L-cysteine and tryptophan using a p-aminophenol-multiwall
carbon nanotube paste electrode
Ali A. Ensafi*, Samira Dadkhah-Tehrani, Hassan Karimi-Maleh
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
Amino acids, which are of great importance in biochemistry, are molecules composed of one amine group, a carboxylic acid
group, and one of a series of side chains that vary among different amino acids. Amino acids play central roles both as building
blocks for proteins and as intermediates in metabolism [1]. Cysteine plays an important role in stabilizing extracellular proteins.
It can also react with itself to form an oxidized dimer by forming a disulfide bond. The thiol residue of cysteine is readily
oxidized in electrochemical reactions at the surface of various thiol-sensitive electrodes. Tryptophan, an essential amino acid, is
the largest of amino acids in size. It is also a derivative of alanine, having an indole substituent on the β carbon. The indole
nitrogen can donate hydrogen bonds, as a result of which tryptophan, or at least the nitrogen in it, is often in contact with the
solvent in folded proteins [2]. In this work, two amino acids, L-cysteine and tryptophan, could be simultaneously determined in
an aqueous solution (pH=6.0) using a carbon nanotube paste electrode (CNPE) modified with p-aminophenol as a mediator. The
results indicate that the electrode is efficient in terms of its electrocatalytic activity for the oxidation of L-cysteine, leading to an
overpotential reduced by more than 550 mV. Using differential pulse voltammetry, we could measure L-cysteine and tryptophan
in one mixture independently from each other by a potential difference of about 600 mV. Electrochemical techniques are used to
determine the diffusion coefficients, kinetic parameters such as electron transfer coefficient, and the rates of electro-oxidation of
L-cysteine at the surface of the p-aminophenol-modified CNPE. The peak current is found to depend linearly on L-cysteine and
tryptophan concentrations within the ranges of 0.5 – 100 μmol L–1 L-cysteine and 10.0 – 300 μmol L–1 tryptophan. The detection
limits for L-cysteine and tryptophan are found to be 0.3 and 5.7 μmol L–1, respectively. The proposed method is also used for the
determination of L-cysteine and tryptophan in urine, river water, blood plasma, and serum samples using standard addition
methods.
Reference
[1] W. Sakami, H. Harrington, Ann. Rev. Biochem. 32 (1963) 355-398.
[2] V.R. Young, J. Nutr. 124 (1994) 1517S–1523S.
Synthesis and characterization of sulfur nanoparticles and comparison between micro and nano sulfur as solid phase
extractors for nickel removal from different water samples
M. Soleimani*, F. Aflatouni
Department of Chemistry, Imam Khomeini International University (IKIU), Qazvin, IRAN,
E-mail: m-soleimani@hotmail.com
Nickel is a toxic heavy metal [1]. Direct determination of trace nickel ions by flame atomic absorption spectrometry (FAAS) is
limited due to their low concentrations in real samples and matrix interferences [2]. Solid phase extraction (SPE) is the most
common technique for preconcentration of analytes in water samples [3]. Recently, sulfur's micro and nano particles used to
remove heavy metals. Orthorhombic and monoclinic sulfur are the most stable forms with crown-shaped molecules. The
interaction between these molecules and Mn+ is similar to host-guest interaction such as those occurring between crown ethers
and metal ions. In SPE, size of the sorbent is a critical factor which affects its efficiency. In this paper, sulfur nanoparticles were
synthesized via novel water in oil (W/O) microemulsion system containing cyclohexane as oil phase, Triton X-100 as surfactant,
butanol as co-surfactant and sodium polysulfide or hydrochloric acid solution as aqueous phase, respectively. Then nanoparticles
were characterized by XRD, SEM, EDS and FTIR methods. The results showed that the prepared sulfur nanoparticles have
monoclinic structure, spherical shape, high purity and average size of about 22nm. Finally, a comparison study was performed
between synthesized sulfur nanoparticles and sulfur micro particles (particle size<40µm and purity>99% bought from Merck,
Darmstadt, Germany) for extraction and preconcentration of nickel ions from different water samples prior to determinations by
FAAS. The effects of the analytical parameters including sample pH, elution, sample flow rate, sample volume and interfering
ions were investigated for each adsorbent. Under the optimum experimental conditions, preconcentration factor, analytical
detection limit, adsorption capacity and reusability of the sorbent were obtained for micro sulfur as 100, 0.0018 µg/mL,
15.75µg/g, 10 cycles, respectively. Whether, using sulfur nano particles these amounts were obtained as 166.67, 0.00108 µg/ml,
30.08 µg/g, and >70 cycles, respectively. These results show that, sulfur nano particles adsorbent will cause to higher
preconcentration factor, lower detection limit, higher adsorption capacity and more reusability of the sorbent.
Reference
[1] M.K. Amini, M. Kabiri, Journal of the Iranian Chemical Society, 2(1) (2005)32-39.
[2] J. Minczenski, J. Chwastowska, R. Dybezynski, Ellis Horwood, Chichester, 1982.
[3] M. Ghaedi, B. Karami, Sh. Ehsani, F. Marahel, M. Soylak, Journal of Hazardous Materials, 172 (2009) 802–808.
Electrochemical and quantum chemical study of 2-{[(2)-1-(4-methylphenyl)methylide]amino}-1-benzenthiol as corrosion
inhibitors for copper in HCl media
N. Mohammadi, M. Behpour*
E-mail: n.mohammadi@grad.kashanu.ac.ir
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, I. R. Iran
Copper due to its high electrical and good mechanical workability, is widely used in pipelines for domestic and industrial water
utilities [1]. Scale and corrosion products have a negative effect on heat transfer, causing a decrease in heating efficiencies of the
equipment, which is why periodic de-scaling and cleaning in hydrochloric acid pickling solutions are necessary. It is accepted
that anodic dissolution of copper in chloride environments is influenced by the chloride concentration and the acidity of the
medium. At chloride concentrations lower than 1 M, the dissolution of copper occurs through formation of CuCl and CuCl -2 . On
the other hand, at concentrations higher than 1 M, higher cuprous complexes such as CuCl 23 - and CuCl 34- are formed [2]. Schiff
bases due to the presence of the –C=N– group, electronegative nitrogen, sulphur atoms, have been reported as effective inhibitors
for the corrosion of metal in acid media [3-6]. At this work corrosion inhibition of new compound as corrosion inhibitor for
copper in 15% HCl has been investigated by electrochemical and quantum methods. Electrochemical measurements indicate that
the Schiff base has inhibiting properties about 98% at 5 mM concentration of inhibitor. Potentiodynamic polarization results
show that corrosion potential shift toward a more positive potential region in the presence of Schiff base than that of blank
solution. Adsorption of inhibitor on copper surface follows Langmuir adsorption isotherm. The negative value of ΔGºads about 36 Kj mol-1, indicate inhibitor strongly adsorbed on the copper surface. Results from Arrhenius plots show that the inhibition
efficiency decrease with increasing temperature and the activation energy is greater in presence of inhibitor. The increase in Ea in
the presence of inhibitor may be interpreted as physical adsorption. Quantum chemical calculations are further applied to explain
experimental results and reveal adsorption structure.
Reference
[1] El-Sayed M. Sherif, R.M. Erasmus, Coll. Inter. Sci. 309 (2007) 470.
[2] E.M. Sherif, Su-Moon Park, Electrochim. Acta. 51 (2006) 4665.
[3] K.C. Emregül, O. Atakol, Mater. Chem. Phys. 82 (2003) 188.
[4] A. Asan, M. Kabasakaloğlu, Corros. Sci. 47 (6) (2005) 1534.
[5] K. Stanly Jacob, G. Parameswaran, Corros. Sci. 52 (2010) 224.
[6] M. Behpour, S. M. Ghoreishi, J. Mater. Sci. 44 (2009) 2444.
Enantioseparation of phosphinothricin and effect of enantiomers on catechin biosynthesis in wheat
a
Mohammad Khodadadya1, Alireza Ghasempoura, Mohammad Kazem Ramezani b
Medicinal Plants and Drugs Research Institute, Shahid Beheshti University, Evin, Tehran, Iran
b
Pesticides Research Department, Plant Protection Research Institute, Tehran, Iran
Phosphinpthricin or Glufosinate- ammonium (GL) is a chiral herbicide. The mode of action of this herbicide is based on
inhibition of amino acid biosynthesis and photosynthesis inhibition [1, 2]. The previous reports showed that L- glufosinate is
more active than D- glufosinate[3]. In this study, the first report for investigation of the enantiomeric separation of GL has been
reported. Also, the effect of these enantiomers on catechin biosynthesis and growth inhibition in wheat plant was studied. The
best enantioseparation of GL was achieved by using high performance liquid chromatography (HPLC) on a Eurocel 01 column.
The optical rotation of separated enantiomers was confirmed the purity of each isomers. The effect of enantiomers on wheat
growth was measured 6 days after treatment with individual enantiomers in the different concentrations on wheat. These results
confirmed that (+) L –GL is more toxic than (-) D-GL and dry weight of shoots and roots of wheat species were differenced by
different concentrations of each enantiomer. In the last report, we showed that catechin concentration changed after wheat
cultivar-Puccinia triticina infection [4]. Thus, after treatment of wheat by each enantiomer, the measurement of catechin had
done. It demonstrated the effect of enantioselectivity of GL on catechin biosynthesis in wheat shoots was clear, while effect of
enantioselectivity of GL in catechin content in wheat roots was not very distinct.
Reference
[1]-Yao et al, 2008, Environmental Toxicology (2009) 24: 148–156
[2]-Zhou et al, J. Agric. Food Chem (2009) 57: 1624-1631
[3]-S. Tan, R. Evans, Amino Acids (2006) 30: 195-204
[4]-Ghasempour et al, Food Chemistry (2011) 125: 1287-1290
An alignment independent 3D-QSAR and qualitative pharmacophore study of antitumor activity of β-carboline
derivatives
Valentin Davoudian, and Jahan B.Ghasemi
Chemistry Department, Faculty of Sciences, K. N. Toosi University of Technology, Tehran, Iran
Jahan.ghasemi@gmail.com
Alignment-free, three dimensional structure-activity relationship (3D QSAR) analysis have been performed on a series of βcarboline derivatives as antitumor potent agents toward HepG2 human tumor cell lines[1]. A highly descriptive and predictive 3D
QSAR model were obtained through the calculation of alignment-independent descriptors (GRIND descriptors)[2]. The
procedure for computing the descriptors involves two step, in the first step the fields are simplified, and in the second one, the
results are encodedinto alignment-independent variables using a particular type of autocorrelation transform. Themolecular
descriptors so obtained can be used to obtain graphical diagrams called “correlograms”and applied in different chemometric
analyses, such as principal component analysis(PCA) orpartial least-squares(PLS). For a training set of 30 compounds, PLS
analyse results in a three-component model which displays a correlation coefficient (r2) of 0.957 and a standard deviation of the
error of calculation (SDEC) of 0.116. Validation of this model was performed using leave one out; with q2of 0.846. This model
gives a remarkably high r2 (0.658) for the test set of 10 compounds.The results of 3D QSAR was verifiedby a qualitative
pharmacophore [3] generated by HipHop algorithm in Catalyst software package. Based on pharmacophore feature analysis, the
dominant feature group in the training set molecules are hydrophobic aromatic groups. The results of the 3D QSAR model which
can be interpreted easily are in agreement with the results of qualitative pharmacophore model.
Reference
[1] R.Cao, X.Guan, B.Shi, Z.Chen, Z.Ren, W.Peng, H.Song, Design, synthesis and 3D-QSAR of β-carboline derivatives as potent antitumor agents. Eur.J.Med.Chem.
45(2010) 2503-2515
[2] M. Pastor, G. Cruciani,I. McLay, S. Pickett, S. Clementi, GRid-INdependent descriptors (GRIND): A. a novel class of alignment-independent three-dimensional
molecular descriptors. J. Med. Chem. 43 (2000) 3233–3243.
[3] Guner, O.F., Ed.pharmacophore Perception, Development and Use in Drug Design; International University Line: La Jolla, CA,200
Statistical optimization of synthesis of manganese carbonates nanoparticles by precipitation methods
Ali Akbar Davoudi1,*, Mehdi Rahimi-Nasrabadi1, morteza khalilian1, Seied Mehdi Pourmortazavi2
1
Department of Chemistry, Imam Hossein University, Tehran, Iran
٢
Faculty of Material and Manufacturing Technologies, Malek Ashtar University of Technology, Tehran, Iran
Copper oxalate nanoparticles were synthesized by simple and fast direct chemical precipitation method. Taguchi analysis was
used in this study to optimize experimental conditions of precipitation process [1,2]. CuC2O4 nanoparticles in different sizes
were synthesized on a relatively large scale in aqueous media using addition of copper ion solution to the oxalate reagent. The
effect of reaction conditions such as: copper and oxalate concentrations, flow rate of reagent addition and temperature of the
reactor on the diameter of synthesized copper oxalate particles were investigated. The efficiency and participitation of these
variables in size control of copper oxalate particles were quantitavely evaluated by the analysis of variance (ANOVA). The
results showed that copper oxalate nanoparticles can be synthesized by controlling copper concentration, oxalate concentration,
and flow rate of reagent addition. Finally, the optimum conditions for synthesis of copper oxalate nanoparticles by this cost
effective chemical technique were proposed. The results of ANOVA showed that 0.25 mol/L copper ion and oxalate reagents
concentrations, 2.5 mL/min flow rate for the addition of the manganese reagent to the carbonate solution and 30 °C temperature
are the optimum conditions for producing manganese carbonate nanoparticle with 61 ± 15 nm width.
Reference
[1] G. Taguchi, System of Experimental Design, Kraus, White Plains, N.Y, 1987.
[2] S. M. Pourmortazavi, S. S. Hajimirsadeghi, M. Rahimi-Nasrabadi, I. Kohsari, Chem. Eng. Comm. 198 (2011)1182–1188.
Coating of silica sol-gel on copper wire modified by self assembled monolayer as a novel technique for preparation of
SPME fibers and its application through extraction of eucalyptus volatile organic compounds
P. Abroomand-azarã , S. Mohammadi-azar, J. Norooz-haghi, M. Saber-tehrani
Islamic Azad University, Department of Chemistry, Science and Research Branch, Tehran, Iran
Solid-phase microextraction (SPME) is based on distribution of the analytes between the sample (or its headspace) and the
stationary phase coated on a solid support (fiber). Notwithstanding various advantages of commercially available SPME fibers,
this method encounter with many drawbacks such as [1]: a) low recommended operation temperature; b) instability in organic
solvents; c) stripping of coating; d) short lifetime and finally, e) their high cost. The reasons of these disadvantages are the lack of
the proper chemical bonding of stationary phase coating with the fiber surface, and the relatively high thickness of the
conventional fibers [2]. In this study silica sol-gel films prepared by dip-coating on modified copper wire was presented as a
novel technique for preparation of solid-phase microextraction fibers. The application of this fiber was evaluated through the
extraction of some volatile organic compounds (VOCs) of Eucalyptus leaf in headspace mode and parameters affecting the
extraction efficiency such as sample amount, extraction temperature and extraction time were optimized. Extracted compounds
were analyzed by gas chromatography-mass spectrometry (GC-MS) instrument. The results obtained indicated that prepared
fibers have some advantages relative to previously prepared SPME fibers: a) chemical bonding of stationary phase to the wire
surface by using an intermediate layer that bind to the surface and, to the stationary phase, in another hand; b) the stationary
phase thickness are tunable; c) prepared fibers are unbreakable and finally, d) their cost is low. Also results showed that SPME is
a fast, simple and sensitive technique for sampling and sample introduction of Eucalyptus VOCs and need a little sample amounts
(0.2 gr).
Reference
[1]. Kumar A., Gaurav, Malik A. K., Tewary D. K., Singha B., Anal. Chim. Acta 610 (2008) 1–14.
[2]. Sarafraz-Yazdi A., Sepehr S., Es’haghi Z., Piri Moghadam H., chromatographia, 72 (2010) 923–931.
Kinetics and isotherms of removal Arsenazo (III) on Zinc sulphur nano particle loaded on activated carbon as adsorbents
Ebrahim Shareifpoora, Syamak Nasiri Kokhdanb*
Chemistry Department, Gachsaran Azad University, Gachsaran Branch - Iran,
b
Young Researchers club, Yasooj Branch, Islamic Azad University, Yasooj, Iran
*E-mail: eb_shareif_prt@yahoo.com , syamak.nasiri@yahoo.com
a
The Zinc sulphur nano particle loaded on activated carbon was used for the sorption of Arsenazo (III) from aqueous solutions.
The effect of solution pH, initial dye concentration, and temperature and sorption time on dye removal was studied [1]. The
equilibrium sorption isotherms have been analyzed by the linear, Freundlich, Langmuir, Temkin and Dubinin - Radushekevich
models. The Langmuir isotherms have the highest correlation coefficients. The apparent thermodynamic parameters were
calculated and the obtained values support the conclusion that the dye molecules sorbs by entropy-driven, endothermic process.
The kinetic of the sorption was analysed using the pseudo-first order, pseudo-second and intraparticle diffusion order kinetic
models. The data showed that the second-order equation was the more appropriate, which indicate that the intraparticle diffusion
is the rate limiting factor [2]. The use of low-cost, easy obtained, high efficiency and eco-friendly adsorbent has been investigated
as an ideal alternative to the current expensive methods of removing dyes from wastewater [3].
Reference
[1]. M.Husseien, A.A.Amer, Azza El-Maghraby, Nahla.A.Taha, Utilization of Barley Straw as a Source of a Activated Carbon for Removal of Methylene Blue from
Aqueous Solution, Journal of Applied Sciences Research, 3(11): 1352-1358, 2007
[2]. Daniela Suteu and Doina Bilba, Equilibrium and Kinetic Study of Reactive Dye Brilliant Red HE-3B Adsorption by Activated Charcoal, Acta Chim. Slov. 2005,
52, 73–79.
[3]. Ahmed El Nemr, Ola Abdelwahab, Amany El-Sikaily, Azza Khaled, Removal of direct blue-86 from aqueous solution by new activated carbon developed from
orange peel, Journal of Hazardous Materials 161 (2009) 102–110.
Determination of Sulfite Ion in Water by Imagr processing and Analysis of the display part of a Stain Detector
M. Pakniat, E. Kamyab*
Department of chemistry, Faculty of Basic Sciences, Persian Gulf University, Bushehr 75168, Iran
The progress and improvement in many field of science are due to popularity of their methods and instruments for even
unauthorized peoples. For the case of chemistry, today, there are great need for monitoring and screening many chemical
parameters in daily life. The length of stain detectors are an appropriate choice to answere such necessities[1]. Image analysis is
the extraction of meaningful information from images by means of digital image processing techniques. These include many
applications in the fields of medicine, microscopy , remote sensing, intracellular analysis, biology , astronomy, defense, materials
science , manufacturing, security, robotics, document processing, and assay plate reading. At the same time different statistical
methods for improving image resolution, noise reduction and clustering the image elements were adopted. There are few
applications in different branches of science in relation with or in chemistry but still much of the potential abilities of imaging
technique is unexploited e.g. for data recording or analysis. To day computers, digital photography based on charge transfer
devices, mobile etc. are among the common facilities of people life. We can exploit devices for daily life to transfer chemical
tests out of laboratories[2]. For practical purposes recording all experimental parameters, especially for an unauthorized person is
time consuming and tedious. Recording information especially by an unauthorized person would be a great advantage and
returning much data to laboratories as a drawback. By appropriate arrangement of equipments and inclusion of experimental data
in front of a camera all information needed such as concentrations, flow rate, time, color, area, volume, temperature etc. could be
recorded for further investigations without any conscious supervision. Also much unnoticed points may be saved for not
previously predicted investigations[3]. In this study the iodometric determination of sulfite ion was adopted with a permanent
length of stain detector. Sulfite ion is used in food and pharmacological industries as an antioxidant. Injection of a sample
containing the sulfite ion in the reducing iodine reagent containing starch indicator in the detector generates a pale stain at the
display part of the detector. The length, area and the intensity of the stains increase with the concentration of the sulfite ion in the
samples. All of steps were recorded with a CCD camera and the analytical responses were extracted from the processed images
selected from them. All exprimental parameters were optimized and the calibration curve have two linear parts from10^-7 to10^4
M and from10^-4 to 0.1M The RSD of the method is about 5.8%.
Reference
[1] A. Safavi, M. Pakniat, Anal. Chim. Acta, 355, 227 (1996)
[2] D. Noble, Anal. Chem., 65, 1037 (1993)
[3] I. Kusclman, B. I. Kuyavskaya, D. Lev, Anal. Chim. Acta, 256,65 (1992)
Sensitive spectrophotometric determinatiom of trace amounts of vanadium(V) in foodstuff and water samples
T.MADRAKIAN*, R.SIRI
Faculty of Chemistry, Bu- Ali Sina University, Hamedan, Iran
A cloud-point extraction process using micelle of the cationic surfactant CTAB to extract Vanadium(V) from aqueous solutions
was investigated. The method is based on the color reaction of vanadium with bromopyrogallol red in the presence of potassium
iodide at pH 4.0 acetate buffer media and micelle-mediated extraction of complex. The optimal extraction and reaction conditions
(e.g., surfactant concentration, reagent concentration and effect of time) were studied and the analytical characteristics of the
method (e.g., limit of detection, linear range, preconcentration and improvement factors) were obtained. Linearity was obeyed in
the range of 0.03–50.00 ng mL−1 of vanadium(V) ion and the detection limit of the method was 0.015 ng mL−1. The relative
standard deviation (R.S.D.) and relative error for five replicate measurements of 32.00 ng mL−1 V(V) were 1.62% and 2.48%,
respectively. The interference effect of some anions and cations was also tested. The method was applied to the determination of
Vanadium(V) in foodstuff (tomato, carrot, tea, potato,cabbage and fish) and water samples.
Reference
[1] K. Pyrzynska, T. Wierzbicki (2004) Determination of vanadium species in environmental samples. Talanta, 64, 823.
[2] K. G. Fernandes, A. R. A. Nogueira, J. A. Gomes Neto, J. A. Nobrega (2004) Determination of vanadium in urine by electrothermal atomic absorption
spectrometry using hot injection and preconcentration into the graphite tube. J. Braz. Chem. Soc, 15, 676.
[3] S. L. Narayana , K. J. Reddy , S. A. N. Reddy, Y. Sarala, A. V. Reddy (2008) A highly sensitive spectrophotometric determination of micro amounts of
vanadium(V) in environmental and alloy samples by using 3, 4-dihydroxybenzaldehydeisonicotinoylhydrazone (3,4-DHBINH). Environ Monit Assess, 144, 341.
[4] B. Patel, G.E. Henderson, S.J. Haswell, R. Grzeskowiak (1990) Analyst, 115, 1063.
[5] J. Wei, N. Teshima, T. Sakai (2008) Flow Injection Analysis for Oxidation State Speciation of Vanadium(IV) and Vanadium(V) in Natural Water. Anal. Sci., 24,
371.
[6] I. O. Królicka, H. Podsiadly, K. Bukietynska, M. Z. Zboch, D. Nowak, K. S. Lukaniuk, M. M. Blaszkiewicz (2004) J. Inorg. Biochem., 98, 2087.
[7] A. A. Ensafi, T. Khayamian, S. S. Khaloo (2008) Simultaneous determination of trace amounts of vanadium and molybdenum in water and foodstuff samples
using adsorptive cathodic stripping voltammetry., Int. J. Food Sci. Technol., 43, 416.
[8] R. R. Greenberg, H. M. Kingston (1983) Trace element analysis of natural water samples by neutron activation analysis with chelating agent. Anal. Chem., 55,
1160
3D-QSAR and Docking studies of a series of sulfonamides derivatives as carbonic anhydrase I inhibitors
Nastaran Meftahi and Jahan B. Ghasemi*
Department of chemistry, faculty of sciences, K.N.Toosi University of Technology, Tehran, Iran
Jahan.ghasemi@gmail.com
3D-QSAR methods, CoMFA region focusing (CoMFA-RF) and CoMSIA[1] with docking studies were applied for investigating
32 carbonic anhydrase I inhibitors. These inhibitors have been studied for the development of antiglaucoma, antitumor,
antiobesity or anticonvulsant drugs[2]. Docking analysis by GOLD [3] scores provide conformations which have been realigned
in CoMFA and CoMSIA models. The CoMFA–RF and CoMSIA models using 24 docking conformations in training set give
q2Loo values of 0.615 and 0.637, r2nv values of 0.701 and 0.713, respectively. These results of CoMFA-RF and CoMSIA with and
without docking conformations were compared. The ability of prediction and robustness of the models were validated by using
test set, cross validation (leave one out and leave ten out), bootstrapping, and progressive scrambling. The all-orientation search
(AOS) was used to achieve the best orientation and minimize the effect of initial orientation of the structures. The docking results
confirmed CoMFA and CoMSIA contour maps. The effect of different subtituents were presented and discussed according to 3D
contour map of CoMFA and CoMSIA.
Reference
[1] R.D. cramer, D.E.Patterson, J.D.Bunce, Comparative Molecular Field Analysis (CoMFA). 1. Effect of shape on binding of steroids to carrier proteins
J.Am.Chem.Soc.110 (1988) 5959-5967
[2] V. Dudutienė, L. Baranauskienė and D. Matulis. Benzimidazo[1,2-c][1,2,3]thiadiazole-7-sulfonamides as inhibitors of carbonic anhydrase , Bioorg. Med.Chem.
17 (2007) 3335-3338
[3] A. Politi, S. Durdagi, P. Moutevelis-Minakakis, , G. Kokotos, T. Mavromoustakos, Development of accurate binding affinity predictions of novel renin inhibitors
through molecular docking studies. J. Mol. Graphics Modell. 29 (2010) 425-435
QSAR study and predicted values of compounds of non-nucleoside inhibitors (pIC90) on the growth of a severe type of
virus HIV-1, describe
the structure by using chemometrics methods PLS and OSC– PLS
Simin Zebarjadi* , Majid Ramezani , Ali Niazi, Hamideh Zeinali
Department of chemistry,Islamic Azad University, Arak Branch,Arak,Iran
E-mail: Mramezani44@gmail.com, Ali.niazi@gmail.com
A quantitative structure-activity relationships (QSAR) study is suggested for the prediction of some non-nucleoside derivatives
inhibitors (pIC90) as a function of molecular structures and using chemometrics methods such as PLS and ODC-PLS [1,2]. The
subset of descriptors, which resulted in the low prediction error, was selected by PLS. This model was applied for the prediction
of the pIC90 of some non-nucleoside derivatives, which were not in the modeling procedure. The errors of prediction low were
obtained by using PLS and ODC-PLS method. The resulted model showed high prediction ability with RMSEP of 0.430 and
0.368 for PLS and ODC-PLS models, respectively.
Reference
[1]. Jonckheere, H.; Anne´, J.; De Clercq, E. Med. Res. Rev.2000, 20, 129.
[2 ]. Stazewski, S.; Morales-Ramirez, J.; Tashiima, K. T.;Rachlis, A.; Siest, D.; Stanford, J.; Stryker, R.; Johnson,P.; Labriola, D. F.; Farina, D.; Marnion, D. J.;
Ruiz, N.M. N. Engl. J. Med. 1999, 34, 1865.
Influence of electrolyte flow rate and current density on the copper deposition for a electrorefining cell in Sarcheshmeh
copper complex
Mohsen Daman afshan*,Ataollah soltani Goharrizi,Amir Sarafi,Fereshteh Bakhtiari
Department of Chemical Engineering, Shahid Bahonar University, Kerman, Iran
The copper electrolysis process is used to produce pure copper in industrial scale in large electrolysis cell groups. Pure copper is
needed for example in conductors, where even small amounts of impurities decrease the electrical conductivity. Electrorefining
entails: (a) electrochemically dissolving copper from impure copper anodes into electrolyte. (b) Selectively electroplating pure
copper from this electrolyte without the anode impurities. In this paper the influence of electrolyte flow rate and current density
on the copper deposition rate during copper Electrorefining were investigated. The electrolyte composition and deposition rate of
copper in a refining cell of sarcheshmeh copper complex were determined experimentally. It shows that High current densities
give rapid copper plating but Excessive current densities may cause anodes to passivate by producing Cu2+ ions at the anode
surface faster than they can come away. This problem reduces the current efficiency, so current density should be keep near the
passivation point. The results also indicate that by increasing the flow rate, passivation will be reduced.
Reference
[1]. Y. Konishi, Y. Nakamura, Y. Fukunaka, K. Tsukada, K. Hanasaki, Anodic dissolution phenomena accompanying supersaturation of copper sulfate along a
vertical plane copper anode, Electrochimica Acta 48 (2003) 2615_/2624.
[2]. M.A. Pasquale, S.L. Marchiano, A.J. Arvia, Non-isothermal ionic mass transfer at vertical parallel plate electrodes under natural convection. Comparison and
validity range of dimensionless correlations, Electrochimica Acta 48 (2002) 153_/163.
[3]. Y. Konishi, Y. Tanaka,Y. Kondo, Y. Fukunaka, Copper dissolution phenomena along a vertical plane anode in CuSO4 solution, Electrochimica Acta 46 (2000)
681–690.
[4]. A. A. Wargg, Free convection mass transfer at mesh electrodes, Int. J. Heat Mass transfer. Vol. II, pp. 979-984. Pergmon Press 1968. Printed in Great Britain.
[5]. A. Eklund, F. Alawoon, D. Simonsson, R. I. Karlsson and F. H. Bark, THEORETICAL AND EXPERIMENTAL STUDIES OF FREE CONVECTION AND
STRATIFICATION OF ELECTROLYTE IN A COPPER REFINING CELL, Electrochimica Acta, Vol. 36, No. 8, pp. 1345-1354,1 991, Printed in Great Britain.
[6]. Zigler,D.and Evans,j. Mathematical modeling of electrolyte circulation in cells whit planar vertical electrodes- part I. electrorefining cell, journal of the
electrochemical society,1989
[7]. W.G. DAVENPORT, M, KING, M. SCHLESINGER ,A.K. BISW
Quantitative structure-activity relationship (QSAR) study of antipsychotic activities of some drugs compounds using
linear and nonlinear methods
Nasser Goudarzi, M. Arab Chamjangali, Y. Ebrahimi*
College of chemistry, Shahrood University of Technology, Shahrood, Iran
Ebrahimi.yalda10@gmail.com
One of the most important compounds series that used as σ receptor is arylalkoxyphenylalkylamine. These compounds can be
used as antipsychotic drugs. In the present work an artificial neural network (ANN) was used to create a model of antipsychotic
activities for a data set including 49 arylalkoxyphenylalkylamine derivatives. Multiple linear regression (MLR) model of the
same data was developed for comparison. The QSAR models were validated by cross-validation as well as application of the
models for prediction of anti-HIV activities of external set of compounds which did not contribute to model development steps.
The determination coefficients and mean squared error (MSE) for MLR and ANN models are 0.909, 0.927, 0.1045 and 0.0507
respectively. The obtained results show the superiority of ANN than MLR model for prediction of antipsychotic activities of
these compounds.
Reference
[1] Goudarzi, N., Goodarzi, M., Molecular Physics 2009, 106, 1495-1503.
[2] Goudarzi, N., Goodarzi, M., Araujo, M. C. U., J. Agric. Food Chem. 2009, 57, 7153-7158.
[3] Goudarzi, N., Fatemi, M. H., Samadi. A., Spectroscopy Letters 2009, 42, 186-193.
Development of a New Quantum Chemical Descriptor for Corrosion Inhibition study of Benzimidazole and Aniline
Derivatives on Iron
a
Mehdi Mousavi*a, Hossein Safarizadeh
Department of Chemistry, Faculty of Sciences, Shahid Bahonar University of Kerman, P.O.Box
76175-133, Kerman, Iran
*mmousavi@mail.uk.ac.ir
Interaction energies (Eint) of benzimidazole and aniline derivatives on iron surface were determined using cluster model and
quantum chemical calculations at density functional theory level. To fulfill this aim, the structures of inhibitor molecules and iron
unit cell were optimized using B3LYP/LANL1MB methods at density functional theory (DFT). The calculated interaction
energies and many other quantum chemical descriptors such as energy of the highest occupied molecular orbital (EHOMO), surface
area (SAA), volume and polarizability of the molecules were considered in linear and non-linear regression modeling procedures.
It is shown that the newly proposed descriptor (Eint) is the most effective descriptor in describing the corrosion inhibition
behavior of the molecules and the results obtained are in good agreement with experimental evidence. In the present work, the
quantum chemical study is focused on the calculation of interaction energies between the inhibitor molecules and the iron atom
unit cell, upon which the adsorption is directly tacking place. Interaction energy between the inhibitor molecule and the metal
surface, Eint, can be calculated based on cluster model [1,2] using Eq. (1):
Eint = E inhibitor-cluster – (E cluster + E inhibitor)
(1)
where, E inhibitor, E cluster and E inhibitor-cluster are electronic energies of the inhibitor molecule, the iron cluster and of the inhibitoriron system, respectively. Linear and non-linear regression methods were used to choose the most informative descriptors from a
pool of 1060 descriptors. It is concluded that a combination of Eint, polarizability and volume of inhibitor molecules are
satisfactorily described the corrosion inhibition phenomena (r= 0.988). It is concluded that the newly proposed descriptor, Eint,
successfully described the corrosion inhibition behavior of the aniline and the benzoimidazole derivatives on iron in acidic media.
This may be due to the facts that, in contrast to many QSAR studies, in the cluster model all participants of a chemical reaction
are taken into account. Also, in the DFT method applied here, it is possible to calculate energy of the system more accurately and
more precisely.
Reference
[1].R.M.Issa,M.K.Awad,F.M.Atlam,Appl.Surf.Sci.255(2008)2433.
[2]M.R.Arshadi,M.Lashgari,GH.A.Parsafar,Material chemistry and Physics 86(2004)311-314
Molecularly imprinted solid-phase extraction for the selective determination of Cefuroxime Sodium in human serum and
urine with high performance liquid chromatography
*
Zohre Sadat Hosseinifard*, Homayon Ahmad Panahi
Department of Chemistry, Islamic Azad University, Central Tehran Branch, Tehran, Iran
sample cleanup technique combined with high performance liquid chromatography In Sodium in biological fluids using
molecularly imprinted solid-phase extraction as the this work, a novel method is described for the determination of Cefuroxime
(HPLC). The molecularly imprinted polymers (MIPs) were prepared using methacrylic acid and Allyl glycidil ether/
iminodiacetic acid as the functional monomer and N, N-methylene diacrylamid as the cross-linker in methanol solution using
cefuroxime sodium as the template molecule and 2,2-azobis-isobutyronitrile as the initiator. The novel imprinted polymer was
used as a solid-phase extraction sorbent for the extraction of cefuroxime sodium from human serum and urine. Various
parameters affecting the extraction efficiency of the polymer have been evaluated. The optimal conditions for molecularly
imprinted solid-phase extraction (MISPE) consisted of conditioning 1mL methanol and 1mL of deionizedwater at neutral pH,
loading of 5mL of the water sample (25_gL−1) at pH 4.0, washing using 2mL acetonitrile/acetone (1/4, v/v) and elution with 3×
1mL methanol/acetic acid (10/0.01, v/v). The MIP selectivity was evaluated by checking several substances with similar
molecular structures to that of cefuroxime sodium. Results from the HPLC analyses showed that the calibration curve of
cefuroxime sodium using MIP from human serum and urine is linear in the ranges of 0.5-100 and 1.5–100_gL−1 with good
precisions (3.7% and 3.1% for 5.0_gL−1), respectively. The recoveries for serum and urine samples were higher than 92%.
Reference
[1] Y. Pic´o, V. Andreu, Anal. Bioanal. Chem. 387 (2007) 1287.
[2] F.G. Tamayo, E. Turiel, A. Mart´ın-Esteban, J. Chromatogr. A 1152 (2007) 32.
[3] E. Turiel, G. Bordin, A.R. Rodr´ıguez, J. Sep. Sci. 28 (2005) 257.
[4] M. Turchan, P. Jara-Ulloa, S. Bollo, L.J. Nunez-Vergara, J.A. Squella, A. Alvarez[5] N. Masque, R.M. Marce, F. Borrull, Trends Anal. Chem. 20 (2001) 477.Lueje, Talanta 73 (2007) 913.
Study the different characteristics of Iranian Pistacia atlantica Desf exudates
Savedoroudi P*, Mirzajani F, Ghassempour A
Department of Phytochemistry, Medicinal Plants and Drugs Research Institute, Shahid Beheshti University,G.C. Evin, Tehran, Iran, P.O.Box:
19835-389
Pistacia atlantica Desf. belonging to the genus Pistacia of the family Anacardiacea, is one of the main oleoresin producing
species with economic and pharmaceutical importance[1]. In Iran, oleoresin of this plant has been used in making chewing gum.
One of the critical points affecting the quality of final products in chewing gum industries is the process of preliminary
preparation. In order to monitor this factor, the final physical properties of cooked exudates were evaluated by using the glass
transition variations so the thermal gravimetric method, (TG) and differential scanning calorimetry, (DSC) were used. Moreover,
In order to evaluate the influence of variation of the different geographical area where the raw materials were collected, the
essential oil from the oleoresin, collected from six different locations in Iran, was obtained and its chemical composition was
determined with GC and GC-MS. The yield range of essential oil was 17-22% (w/w), and the major compound is α-pinene,
(92%). According to the various traditional medicinal usage of Pistacia atlantica, for example in the treatment of peptic ulcer[2],
antimicrobial activity of essential oil was investigated against variety of respiratory and gastrointestinal microorganisms.
Furthermore, as it was mentioned previously, the oleoresin contains a water soluble carbohydrate fraction[3] which is subjected
for further analysis. The monosaccharides constituted of extracted polysaccharides were studied. The results demonstrate that the
major constitutions were arabinose and galactose.
Reference
[ 1]. V. P. Papageorgiou, M. M. Bakola-Christianopoulou, K. K. Apazidou, and E. E. Psarros, J. Chromatogr. A, 769, 263 (1997).
[2]. H. Y. Abdel-Rahman and A. M. Youssef, J. Am. Oil Chem. Soc., 52, 423 (1975)
[3]. F. Kottakis, F. Lamari, Ch. Matragkou, G. Zachariadis, N. Karamanos, and T. Choli-Papadopoulou, Amino Acids, 34, 413–420 (2008)
QSPR-based estimation of the depuration half-lives for Polychlorinated biphenyls congeners
Mohammad Hossein Fatemi, Zohreh Gharehchahi*
Faculty of Chemistry, University of Mazandaran, Babolsar, Iran.
E-mail: Gharehchahi.z@gmail.com
Polychlorinated biphenyls (PCBs) belong to a class of hazardous and environmental pollutants, which have been produced
commercially since 1929. Thermal stability and high resistance of these compounds, making them useful in a wide variety of
applications, such as dielectric fluids in transformers and capacitors, heat transfer fluids, flame retardants, pesticide extenders and
lubricants [1]. These contaminants do not readily break down and therefore may remain for a long period in the environment,
transported long distances and distributed in air, water, and soil by reason of their persistence, hydrophobicity and inertness
properties [2,3]. Quantitative structure-property relationship (QSPR) is one of the most promising in silico methods, which
explore a pattern in data by using descriptors derived from molecular structure to predict the property of new and untested
chemicals possessing similar molecular features. In this work, a QSPR model was developed to estimate depuration half-lives (log
(t1/ 2 ) ) of 62 PCBs in juvenile rainbow trout.Three linear and nonlinear learning approaches, namely (i) multiple linear regression
(MLR), (ii) artificial neural network (ANN) and (iii) support vector machine (SVM), were used for correlating the structure of
PCBs to half-lives. Statistical results confirm the superiority of ANN over MLR and SVM techniques. The most informative
descriptors were; BEHm3 (highest eigenvalue n.3 of Burden matrix/weighted by atomic masses), JGI1 (mean topological charge
index of order 1), Lop (lopping centric index) and GATs 8 e (Geary autocorrelation lag-8/weighted by atomic Sanderson
electronegativities). The results of ANN model revealed high correlation between the observed and predicted values of log
(t1/ 2 )
with the square correlation coefficients of 0.908, 0.917 and 0.874 for training, internal and external test sets, respectively.
Assessing the model was evaluated by using leave-one-out cross validation which produce Q2=0.86 and y-scrambling procedure
(R2=0.44). The results of this study revealed the robustness of ANN model to estimate PCBs congener's half-lives.
Reference
[1] E. Bentzen, D. Mackay, B.E. Hickie, D.R.S. Lean, Environ. Rev. 7 (1999) 203-223.
[2] F. Wania and D. Mackay, Total Environ., 160-161 (1995) 211-232.
[3] R. Van der Oost, J. Beyer, N.P.E. Vermeulen, Environ. Toxicol. Pharmacol., 13 (2003) 57.
quantitative structure-activity relationships (QSAR) study and predicted max values of 1-4 Naphthoquinone and
derivatives , describethe nodal structure by using chemometrics methods PLS and ODC– PLS
Samira hashemi*, Ali Niazi, Hamideh Zeinali
Department of chemistry,Islamic Azad University, Arak Branch,Arak,Iran
E-mail: ali.niazi@gmail.com
A quantitative structure-activity relationships (QSAR) study is suggested for the prediction of λmax as a function of molecular
structures and using chemometrics methods such as PLS and ODC-PLS[1]. The subset of descriptors, which resulted in the low
prediction error, was selected by PLS. This model was applied for the prediction of the λmax of 1-4 Naphthoquinone and
derivatives, which were not in the modeling procedure. The errors of prediction low were obtained by using PLS and ODC-PLS
method. The resulted model showed high prediction ability with RMSEP of 11.86 and 2.708 for PLS and ODC-PLS models,
respectively.
Reference
[1]. Analytica Chimica Acta, Volume 663, Issue 1, 17 March 2010,
Deposition of Pt nanoparticles in a mesoporous metal organic framework (MIL-101) modified carbon paste electrode:
Application for direct methanol fuel cell
a
J.B. Raoof *a, F. Chekinb, R. Ojania, S. bararia
Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, Mazandaran University,
Babolsar, Iran
b
Department of Chemistry, Islamic Azad University, Ayatollah Amoli Branch, Amol, Iran
Direct methanol fuel cells (DMFCs) are potential alternative energy sources for portable electronic devices because of their high
energy-conversion efficiency, low pollution emission, and safe fuel handling. However, the electrooxidation of methanol is a
very complex reaction, during which many intermediates and poisoning species are involved [1]. In an acidic medium, the most
efficient catalyst for this reaction is platinum and its alloys [2,3]. The electrocatalytic activity of platinum particles for methanol
oxidation is dependent on many factors [4,5]. Of these, the supporting materials and their surface conditions are essential for the
Pt catalyst to produce high catalytic activity [6]. Thus, the development of advanced and more stable supporting materials is
highly advantageous. In recent years increased attention has focused on metal– organic frameworks (MOFs) [7] as new porous
materials. These materials, which containing nanometric pores and channels, currently receive a considerable amount of attention
due to their potential applications in a number of industrially important areas, such as gas storage, separation and catalysis areas
[8,9]. In this work, a mesoporous metal organic framework was synthesized and its structure and morphology was characterized
by XRD, BET and SEM techniques that have shown nanometric pore size and large surface area. This synthesized structure was
utilized as platinum catalyst support, in the matrix of carbon paste electrode (Pt/MIL-101/CPE). We have deposited the Pt
nanoparticles in the pores of this substrate by an electrochemical method. Also, presence of Pt particles in pore of structure was
confirmed with SEM. Then the electrooxidation of methanol on modified electrode was evaluated by cyclic voltammetry method,
which showed potential catalytic ability of the platinum particles for methanol oxidation reaction. Finally, we have investigated
the effect of some parameters such as potential sweep rate and methanol concentration on the methanol oxidation reaction.
Reference
[1] H. Wang, T. Loffler, H. Baltruschat, J. Appl. Electrochem. 31 (2001) 759.
[2] D. Pan, J. Chen, W. Tao, L. Nie, S. Yao, Langmuir 22 (2006) 5872.
[3] F.S. Hoor, C.N. Tharamani, M.F. Ahmed, S.M. Mayanna, J. Power Sources 167 (2007) 18.
[4] A. Kabbabi, F. Gloaguen, F. Andolfatto, R. Durand, J. Electroanal. Chem. 373 (1994) 251.
[5] A. Gamez, D. Richard, P. Gallezot, F. Gloaguen, R. Faure, R. Durand, Electrochim. Acta 41(1996) 307.
[6] J.S. Yu, S. Kang, S.B. Yoon, G. Chai, J. Am. Chem. Soc. 124 (2002) 9382.
[7] H.l. Li, M. Eddaoudi, M. O’Keeffe, O.M. Yaghi, Nature 402 (1999) 276.
[8] G. Férey, Chem. Mater. 13 (2001) 3084.
[9] M.J. Rosseinsky, Micropor. Mesopor. Mater. 73 (2004) 15.
Homology Modeling and Docking Study to Investigate Serotonin Binding Sites on Polymorphic Proteins
F. Keshavarz, T. Khayamian*, S. Gharaghani
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran.
Some experimental and statistical studies have revealed that gene polymorphism can result some variations in biological
functions. Since serotonin is a very essential neurotransmitter which plays roles in regulation, vascular function and disease and
treatment of many psychiatric disorders, it was chosen as the key ligand to investigate the effect of polymorphic genes and hence
polymorphic proteins on the binding of serotonin to four protein sets of 1MO-B, a serotonin receptor which included 2C7515,
human monoamine oxidase B, and 2VRL16, human MAO-B and a pair of dSERT protein types, serotonin receptor; 1GXW17,
Thermolysin (Tln), and 3FXS18, Metal exchange in thermolysin, SLC6A4, solute carrier family 6 member 4 in Homo sapiens,
and BAG35984.1, unnamed protein product in Homo sapiens, and AAA36029.1, serotonin receptor in Homo sapiens, and
BAA94457.1, 5-hydroxytryptamine (serotonin) receptor 1B in Gorilla gorilla. Previous studies had demonstrated the importance
of such polymorphisms in some diseases and alternative functions. Thus, it is tried to study serotonin delivery changes due to
polymorphism by the means of sequence alignment, docking, homology modeling and binding site analysis, for the first time.
Sequence identity of all the four pairs was more than %99 and the lowest coverage between templates and query sequences was
also %71. Though the sequence identity among polymorphic protein sets was high, the results indicated that the number of Hbond and hydrophobic interactions, the binding site residues, binding affinity and ligand energy differed, significantly. But the
binding sites of each set were positioned on the same chain. The best binding site coverage referred to 1GXW and 3FXS set. It
was also revealed that serotonin tends to bind its receptors (1GXW and 3FXS) more strongly and it binds weakly to its
transporters(SLC6A4 and BAG35984.1).
Reference
[1]. Murphy,D. L., Fox,M. A., Timpano,K. R., Moya,P. R., Ren-Patterson,R., Andrews,A. M., Holmes,A., Lesch,K. and Wendland,J. R. (2008). How the serotonin
story is being rewritten by new gene-based discoveries principally related to SLC6A4, the serotonin transporter gene, which functions to influence all cellular
serotonin systems. Neuropharmacology, 55(6), 932-960.
[2]. Vanhoutte, P. M. and Cohen, R. A. (1983). The elusory role of serotonin in vascular function and disease. Biochemical Pharmacology, 32(24), 3671-3674.
[3]. Gershon, M. D., and Tack, J. (2007). The Serotonin Signaling System: From Basic Understanding To Drug Development for Functional GI Disorders.
Gastroenterology, 132(1), 397-414.
A sensitive method for determination of Ni (II) based on
atomic absorption spectrometry in combination with dispersive
liquid–liquid microextraction
Nasser Dalali*, Atefeh Azizi, Fereidoon Rahmani
Phase separation & FIA-Lab., Department of Chemistry, Faculty of Sciences, Zanjan University, Zanjan, 45195-313, Iran.
E-mail:Nasser_zn@yahoo.com
Nickel is known to be either essential or toxic at trace levels to human, animals and plants for metabolic processes depending on
its concentration range. It is clear that the determination of trace amounts of Ni in environmental and food samples is of great
significance from the public health and environmental point of view [1, 2]. Dispersive liquid–liquid microextraction (DLLME)
has become a very popular environmentally benign sample-preparation technique, because it is fast, inexpensive, easy to operate
with a high enrichment factor and consumes low volume of organic solvent [3]. In present work 5 mL solution containing 0.5 µg
mL−1 Ni(II) was adjusted to pH 8 with an appropriate phosphate buffer solution and 100 µL of 1-Nitroso-2-Naphthol 2.1×10-3 M
were added to a test tube with conical bottom. By using a syringe, 1.0 mL ethanol (disperser solvent) containing100 µL CCl4
(extraction solvent) was injected to the above solution, the mixture was immediately centrifuged for 5 min at 3000 rpm. The
volume of the sedimented phase was determined. The sedimented phase was quantitatively transferred into another small tube
and allowed to evaporate at room temperature. Finally the residue was dissolved in 1.0 mL 0.1 M nitric acid and the nickel
content was determined by flame atomic absorption spectrometry. Some effective parameters on extraction and complex
formation, such as, pH, extraction and disperser solvent type and their volumes, extraction time, salt effect and concentration of
the chelating agent have been optimized. Under optimum conditions, the calibration graph was linear in the range of 25-1000 µg
L−1 and the detection limit was 1.5 µgL−1 (3Sb/m, n = 6). The relative standard deviation was also obtained as ±1.8 % (n = 6, C =
0.4 μg mL-1). The results show that dispersive liquid-liquid microextraction combined with flame atomic absorption spectrometry
(FAAS) is a rapid, simple, sensitive and efficient analytical method for the separation and determination of trace amount of Ni
(II) ions.
Reference
[1] A. Safavi, N. Iranpoor, N. Saghir, S. Momeni, Anal. Chim. Acta 569 (2006)139.
[2] A. Safavi, H. Abdollahi, M.R.H. Nezhad, R. Kamali, Spectrochim. Acta 60A (2004) 2897.
[3] M. Rezaee, Y. Yamini, M. Faraji, J. Chromatogr. A 1217 (2010) 2342.
Solid Phase Extraction as tool for Determination and preconcentration of trace amount of copper and iron ions in
water samples by1,5- diphenyl carbazone loaded on sulfur
Maria fori1*
1)Chemistry Department, Gachsaran Azad University, Gachsaran, Iran
E-mail:maria.fori@yahoo.com
In this paper ability absorption of some heavy metals ions have been studied by some of water sample s. for this work 1,5diphenel carbazone modified sulfur have been used for the solid phase extraction of copper and iron prior to their flame atomic
absorption spectrometric determinations. The influences of the various analytical parameters including pH, amounts of reagent,
sample volume and eluent type etc. on the recovery efficiencies of copper and iron ions were in water. The detection limits by
three sigma for analyte ions were 1.2 ng ml-1, 1.5 ng ml-1 using 1,5-diphenel carbazone for copper and iron ions ,respectively.
The presented procedure was applied to the determination of analytes in water samples with successfully results (recoveries
greater than 94 %, R.S.D. lower than 1.2% for n=3). The determination of trace metals in the environmental samples including
water samples has been continuously in order to designate the level of pollution as the number of ecological and health problems
associated with environmentaln contamination continue to rise.Direct instrumental analysis of these samples is difficult because
of complex formation and significant matrices,which invariably influence normal instrumental analysis.In addition,some metals
have low concentrations,which are near or below the limit of detection of the instrument. Preconcentration can slove the above
two problems and leads to simplified heavy metals determination. Solid phase extraction is preferred on account of the
fast,simple and direct application in micro litre volume without any sample loss, higher preconcentration factor, rapid phase
separation ,time and cost saving [1-4]. The purpose of this work is to investigate a Preconcentration- separation procedure for
Cu2+ and Fe2+ in some in water samples on1,5-diphenel carbazone modified with sulfur.
Reference
[1] M.Ghaedi, M.R.Fathi, A.Shokrollahi, F.Shajarat.Lett.39(2006)1171-1185.
[2] E.M.Soliman, M.B.Saleh, S.A.Ahmed, Anal.Chem.Acta 523(2004)133-140
[3] J.Posta, A.Alimonti, F.petruci, S.Caroli, Anal.Chem.Acta 325 (1996)185-193
[4] J.P.Chen, M.Lin, Carbon 39(2001) 1491-1504
Construction of Chromium Potentiometric Sensor by Using 6picTUBenzo as an Excellent Ionophore
Leila Hajiaghababaei, Neda Mohamadi*, Forogh Adhami
Department of Chemistry, Islamic Azad University, Shahre Rey Branch, Tehran, Iran
E-mail: lhajiaghababaei@yahoo.com , mohamadineda10@yahoo.com
The increasing use of ion sensors in the field of environmental, agriculture, industrial and medicinal analysis is putting more and
more pressure on analytical chemists to develop new sensors for the fast, accurate, reproducible, selective and cheap
determination of various species. On the other hands, chromium is a highly toxic pollutant generated from many industrial
processes such as electroplating, metal finishing, leather tanning, pigments, nuclear power plants, textile industries, chromate
preparation, etc [1,2]. Therefore, in this work, we report a novel potentiometric sensor to chromium determination by using a new
ligand (Fig.1) [N-banzoyl-N′ (6 methyl-2-pyridyl) thiourea] as an excellent ionophore.
O
S
C
H3C
N
N
H
C
N
H
Fig.1. the structure of ligand
Different amounts of the ionophore along with appropriate amounts of PVC, plasticizer and additive were dissolved in
tetrahydrofuran (THF), and the solution was mixed well. The solvent was evaporated slowly until an oily concentrated mixture
was obtained. A Pyrex tube was dipped into the mixture for about 10 s so that a transparent membrane of about 0.3 mm thickness
was formed. The tube was then pulled out from the mixture and kept at room temperature for about 10 h. The tube was then filled
with an internal filling solution. The electrode was finally conditioned for 24 h by soaking in a chromium solution. The effects of
some factors such as response time, pH, life time, selectivity and internal solution were investigated. Finally, it was used for
direct determination of chromium and as an indicator electrode in potentiometric titration of chromium ion.
Reference
[1] P.A. Brown, S.A. Gill, S.J. Allen, Water Res. 34(2000) 3907.
[2] K, K, Wong, C.K, Lee, K. Low, M.J. Haron, Chemosphere 50 (2003) 23.
[3] H.A.Zamani, G.Rajabzadeh, M.R.Ganjali, Sens.ActuatorsB119 (2006)41–46.
[4] M.R.Ganjali, N.Khoshdan, O.R.Hashemi, S.A.S.Sajjadi, Pol.J.Chem.74 (2000)1389 –1398.
Transport of Cu2+ ion across a bulk liquid membrane containing a new Schiff base as carrier
Mehdi Taghdiria, Mohammad Hossein Mashhadizadehb, Mahnaz Falahati a, Hadi Kargara
a
Department of Chemistry, Payame Noor University, Ardakan, Yazd, Iran
b
Department of Chemistry, Tarbiat Moalem University, Tehran, Iran
The transport of Cu2+ through a chloroform bulk liquid membrane containing Schiff base, 6,6´-Diethoxy-2,2´-[2,2-dimethyl
propane-1,3-diylbis(nitrilomethylidyne)]-diphenol [1] as a specific ion carrier was studied. The liquid membrane (25ml of
CHCl3) contained Schiff base. The aqueous source phase (5ml) contained Cu2+ ion, buffered at distinct pH with ammonium
buffer. The receiving phase (10ml) contained different acids and substances. The effect of parameters influencing the transport
efficiency such as type and concentration of the stripping agent used as the receiving phase, time, type copper salt and the
addition of synergistic agents has been investigated. Optimum conditions of transport are Schiff base concentration (1× 10-4M) in
the liquid membrane. The source phase comprised of a solution of Cu(NO3)2.3H2o (1×10-5M), buffered at pH=7 with ammonium
buffer, and a solution of 0.1M nitric acid and 1×10-3M sodium dodecyle sulfate (SDS) and 1×10-3M 1,10-Phenanthroline
monohydrate served as the receiving phase. Under optimum conditions the extent of Cu2+ transport across the liquid membrane
was about 79% after 2h. The selectivity of the method was assessed by performing the single Cu2+, Pb2+, Cd2+ and Ni2+ ions. This
transport is very selective to copper over other ions.
Reference
[1] Fun, H-K; H. Kargar; R. Kia; A. Jamshidvand. Acta. Cryst. (2009) E 65, O 707.
[2] A. Rouhollahi, E. Zolfonoun, M. Salavati-Niasari/ Separation and Purification Technology 54 (2007) 28–33.
[3] M.R. Yaftian, A.A. Zamani, S. Rostamnia/ Separation and Purification Technology 49 (2006) 71–75.
Development of novel sensor for electrochemical determination of diazepam on the basis of bismuth-modified pencil
graphite electrode
Esmaeel alipoura,*, Shahram Ebrahimyb , Mohammad taghi Vardini b
Electroanalytical Chemistry Laboratory, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
b
Department of Applied Chemistry, Faculty of Chemistry, Islamic Azad University-Tabriz Branch, Tabriz, Iran
E-mail: i-alipour@tabrizu.ac.ir
a
Diazepam,7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one is the most commonly benzodiazepine drug
used as hypnotic, tranquilizer, anticonvulsant and muscle relaxant [1-2]. It is also an abused drug in which sudden with drawal,
particularly from high dosage, carries the risk of epileptic seizures. Determination of diazepam using bismuth modified pencil
graphite electrode (PGE) is described. The influences of electrochemical pretreatment of PGE on the ability of the electrode in
bismuth immobilization, including activation potential and time, were studied and optimum conditions were suggested.
Accordingly, the electrochemical pretreatment of the polished PGE by electrostatic procedure at -1.5 V for 5 min in 0.50M
acetate buffer solution of pH 4.8 is proposed as the optimum pre-treatment procedure. Several parameters affecting bismuth
immobilization on the pre-treated PGE were investigated and optimum conditions were suggested. The bismuth modified PGE
was used for determination of low concentrations of diazepam using differential pulse voltammetric (DPV) analysis. DPVs were
obtained in acetate buffer solution (pH 4.8) containing diazepam showed a cathodic peak about -0.8 V versus SCE. This sensor
was successfully used for determination of diazepam in pharmaceutical tablets.
Reference
[1] C.M. Smith, A.M. Reynard, Essentials of Pharmacology, W. B. Saunders Company, Philadelphia, 1995, p. 226.
[2] P.L. Munson, R.A. Mueller, G.R. Breese, Principles of Pharmacology, Chapman & Hall, U.S.A., 1996, p. 243.
Optimization of a novel method of microwave assisted extraction for extracting of Taxol from Taxus Baccata L. of Iran
using central composite design
Joshani Azade, Ghassempour Alireza, Rezadoost Hassan, Mirzajani Fateme
Department of Phytochemistry, Medicinal Plants and Drugs Research Institute, Shahid Beheshti University, Evin, Tehran, Iran
*Email: Joshani.azade@gmail.com
This work describes an innovative process for the Taxol extraction from needles of Taxus Baccata L. of Iran. The main
advantage of this method compared to domestic closed-vessel MAE is the increase extraction efficiency, higher extraction
safety, less labor-intensive. The efficiency of continues wave (CW), open vessel/atmospheric pressure microwave assisted
extraction, (MAE), of Taxol were optimized by means of a central composite design, (CCD), over the influence of four different
independent variables including the power of the microwave, the irradiation time, the solvent volume to the 1 g of the sample
powder and the percentage of the Ethanol in the extraction solvent, using Design-Expert 6.0.10 software. LC-MS confirmed
presence of Taxol in the sample. The method of high-performance- liquid chromatography assay was validated and applied for
the quantification of each experiment. The effects with the F-probability lower than 0.0001 are considered to be statistically
significant. The values of R2 and adjusted R2 were 0.9944 and 0.9983, respectively. The standard error of the estimate showed a
3.99×10-3 value for the standard deviation of the residuals. The results demonstrates that not only the net effect of irradiation and
the ethanol percentage; but also their two factor interactions with each other and also the power and the volume of solvent are
influenced on the recovery of Taxol extraction. Moreover the three factor interactions of power and the time of irradiation with
the rest of parameters ate influential. The optimized conditions were established to be 20 min for extraction time, 53-60 W for
extraction power, 14 ml for extraction solvent volume, and the 74% (v/w) of ethanol.
Au-Pt alloy nanoparticles based chemiresistor for detection of alcohols
a
H. Jamalabadia, Mohammad Reza Milani Hosseini a*, M. Najafib
Department of Analytical Chemistry, Faculty of Chemistry, Iran University of Science and Technology, Tehran, Iran
b
Department of Chemistry, Faculty of Science, Imam HossienUniversity, Tehran, Iran
Metal nanoparticle based chemiresistor is a chemical sensor in which a thin film of nanoparticle material is cast onto the
interdigital microelectrode. In these sensors electrical resistance change is related to vapour concentration of sample. These
sensors have some advantages such as low temperature operation, sensitivity to a wide range of volatile organic compounds,
capability of miniaturization without loss of sensitivity [1-3]. The detection and measurement of alcohols are important for many
purpose including medical and clinical applications, food industries, ethanol production and etc. Various types of sensors with
different construction, sensitivity and selectivity such as metal oxides semiconductors, conductive polymer composites and
carbon nanotubes based sensors have been proposed to detect and measure alcohols. Among which the chemiresistors that can
detect and measure the alcohols through their vapour is the most significant effort. In this study the three different chemiresistors
based on Au, Pt and Au-Pt alloy nanoparticles stabilized with 11-mercaptoundecanoic acid were developed and effect of metal
compositions on the sensitivity and selectivity for some small organic molecules was investigated. The responses toward ethanol,
methanol, 2-propanol , butanol, acetone and ethyl acetate were compared.The chemiresistor based on Au-Pt alloy nanoparticles
(Au:Pt with 1:2 molar concentration ratio) showed more selectivity and sensitivity than others over methanol in ranges below 50
ppm. Above this range the sensitivity of all compositions were nearly the same. The limit of detection for methanol were 10,5,2
mgL-1 for Au, Pt and Au-Pt nanoparticle, respectively. The response and recovery times were obtained by measuring the time to
reach 90% of the plateau value. The metal nanoparticle -based chemiresistors had acceptable response in a 2–200 mgL-1 range
with response time among 5-7s and recovery time among 50-70s in this range
Reference
[1] B.Raguse, C.Barton, K.Muller, E.Chow, L.Wieczorek,''Gold nanoparticle chemiresistor sensors in aqueos solution:comparison of hydroghobic and hydrophilic
nanoparticle vol.113,no.34,2009,pp.15390-15397
[2] M.G.Ancona, A.W.Snow, E.F.Foos,W.Kruppa, R.Bass,"Scaling Property of Gold Nanocluster Chemiresistor Sensor,"IEEE Sensors
jornal,vol.9,no.6,2006,pp.1403-1414.
[3] F. J. Ibañez, F. P. Zamborini," Chemiresistive Sensing of Volatile Organic Compounds with Films of Surfactant-Stabilized Gold and Gold−Silver Alloy
Nanoparticles," ACS Nano, vol.2, no.8,2008, pp. 1543-1552
A Novel Capacitive Sensor for Ephedrine Based on Electropolymerized Molecularly Imprinted Polymer
a
Elahe Ramezanipoor a, Mohammad Reza MilaniHosseini a*, Mostafa Najafi b
Department of Analytical Chemistry, Faculty of Chemistry, Iran University of Science and Technology, Tehran, Iran
b
Department of Chemistry, Faculty of Science, Imam Hossien University, Tehran, Iran
Drug abuse has increased dramatically during the past three decades. Ephedrine has been characterized as a prohibited compound
by the International Olympic Committee [1]. Athletes tested positive for ephedrine often claim to have received it while using
products without indication, due to the fact that ephedrine is an ingredient of common anti-cold preparations and of various
nutritional supplements. Therefore, the determination of ephedrine in biological and pharmaceutical samples via a simple, fast,
inexpensive, reliable and sensitive method is of great interest. The different procedures developed for the detection and
determination of ephedrine in plasma and urine such as gas-liquid chromatography, radioimmunoassay, membrane electrode
methods, liquid chromatography and capillary electrophoresis involve laborious, intensive, and expensive procedures [2]. The
capacitive sensing method has attracted considerable attention in modern analytical chemistry because of their sensitivities and
specificities. Moreover it provides simple and inexpensive detection of analyte–receptor binding without using additional
reagents or labels. Capacitance transducer is based on the electrical double layer theory. Any adsorption or binding of reagents
onto the dielectric layer changes its thickness and/or dielectric behavior, which can be detected by measuring the capacitance of
the system [3]. In this study, we developed a capacitive chemical sensor based on an electropolymerized molecularly imprinted
polymer for ephedrine detection. Electrochemical impedance spectroscopy was applied for rapid and sensitive estimation of
ephedrine levels. The sensor´s linear response range was between 1-15 µM, with a detection limit of 0.4 µM. selectivity and
reproducibility and repeatability of the sensor were all found to be satisfactory.
Reference
[1] E. V. Piletska, M. Romero-Guerra, I. Chianella, K. Karim, A. P. F. Turner, and S. A. Piletsky, "Towards the development of multisensor for drugs of abuse based
on molecular imprinted polymers," Analytica Chimica Acta, vol. 542, pp. 111-117, 2005.
[2] E. G. Cookeas and C. E. Efstathiou, "Flow injection-pulse amperometric detection of ephedrine at a cobalt phthalocyanine modified carbon paste electrode,"
Analyst, vol. 125, pp. 1147-1150, 2000.
[3] A. Aghaei, M. R. Milani Hosseini, and M. Najafi, "A novel capacitive biosensor for cholesterol assay that uses an electropolymerized molecularly imprinted
polymer," Electrochimica Acta, vol. 55, pp. 1503-1508.
Electrochemically controlled solid-phase microextraction (EC-SPME) based on nanostructure conducting polypyrrole for
spectrophotometery determination of benzoate ion
Ahmad Manbohi and Naader Alizadeh*
Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
Food preservatives are usually used during the production and storage of the foods for controlling the growth of undesirable
microorganisms. Among food preservatives, benzoate is the main antiseptic additives in fluid foods. The appropriate amount of
preservatives appears to be safe, but large amount of preservatives is harmful to human health [1,2]. Therefore, a fast, simple and
accurate method of analyzing food preservatives is necessary and important. The preparation of a new nano-structure fiber based
on conductive polypyrrole synthesized by electrochemically method and using for electrochemically controlled solid-phase
microextraction (EC-SPME) of benzoate ion (Bz-) was invastigated. The fiber made by electrodeposition of pyrrole in the
presence of Bz- ion on the stainless steel wire and characterized using spectrophotometery analysis. The effect of polymerization
conditions and type of dopant on the extraction characteristics of the fibers was investigated. The polymer morphology was
investigated using scanning electron microscopy (SEM). The Bz- ion uptake to fiber is enhanced if a positive potential is applied
to the conducting fiber. Accumulated benzoate ion is released rapidly from the fiber if the applied potential is switched to a
negative value. The effects of uptake and release potential, uptake and release time, and pH of uptake and release solution on the
extraction behavior of the fiber are studied. The calibration graphs were linear in the range of between 1.1×10-5-5.5×10-4 mol L-1
and detection limits were 5.2×10-6 mol L-1. The fiber-to-fiber reproducibility was also investigated. A satisfactory reproducibility
of fibers with R.S.D. < 6% were obtained. The EC-SPME was prepared by doping of Bz- ion in polypyrrole (PPy-Bz) and was
used for selective extraction of Bz- ion in the presence of some organic and inorganic anions. The results of the present study
point to the possibility of developing a selective extraction process for Bz- ion using a nanostructured PPy-Bz film through an
electrically switched anion exchange. The EC-SPME has been successfully applied to benzoate determination in soft drinking
samples.
Reference
[1] China Food Additive Production & Application Industry Association, Handbook of Food Additives, China Light Industry Press, Beijing, 1996.
[2] H.M. Pylypiw Jr., M.T. Grether, J. Chromatogr. A 883 (2000) 299–304.
Enhancement of chemiluminescence of KMnO4-HCHO by gold/silver nanoalloys and its application in amino acids
determination
Mohammad Amjadi*, Jamshid L. Manzoori, Javad Hassanzadeh
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
In this work the catalytic effect of Au/Ag alloy nanoparticles, synthesized by chemical reduction method, on the
chemiluminescence (CL) reaction of permanganate-formaldehyde in the presence of sodium dodecyl sulfate (SDS) micelles was
investigated. According to the results bimetallic nanoparticles enhance this CL reaction intensely and exhibit better catalytic
properties than their monometallic counterparts. Transmission electron microscopy (TEM), energy dispersion X-ray spectrometry
(EDS) and UV-Vis spectra were used to characterize the alloy nanoparticles. It was found that trace amounts of some amino
acids alter CL signal. Based on this phenomenon KMnO4-HCHO-Au/Ag nanoparticles CL system was used for the determination
of these amino acids in the concentration range of 0.01 - 64 µg mL-1 with detection limits in the range of 2-25 ng mL-1. On the
basis of UV-Vis and CL spectra, a mechanism has been proposed for CL enhancement.
Reference
[1] Adcock JL, Francis PS, Barnett NW (2007) Acidic potassium permanganate as a chemiluminescence reagent: A review. Anal Chim Acta 601: 36.
[2] Li SF, Zhang XM, Yao ZJ, Yu R, Huang F, Wei XW (2009) Enhanced chemiluminescence of the rhodamine 6G-cerium(IV) system by Au–Ag alloy
nanoparticles. J Phys Chem C 113:15586.
[3] Li S, Tao S, Wang F, Hong J, Wei X (2010) Chemiluminescence reactions of luminol system catalyzed by nanoparticles of a gold/silver alloy. Microchim Acta
169:73.
The effect of Ni and Cu underlayers on electrochemical activity of Pd for Methanol Oxidation Reaction (MOR) based on
DFT theory
Abolfazl kiani*, Rezvan Kazemi
Department of Chemistry, University of Isfahan, 81746-73441, Isfahan, Iran, E-mail: a.kiani@chem.ui.ac.ir
Pd is an attractive replacement for Pt in Direct methanol fuel cells (DMFCs) due to its high electrocatalytic activity , more
abundance and lower price than Pt [1]. However, in spite of recent advances, inadequate efficiency and high loading of precious
metal (M) are still two major obstacles of the available electrocatalysts. The combination of M with other metals is a common
way to resolve these problems [2]. The effect of underlayer metal could be interpreted by d-bond center (εd) shift predicted by
DFT theory [3]. One of powerful strategies for creating bimetallic electrocatalyst is galvanic repleacement (GR) [4]. In present
work, electrodeposition of Cu and Ni on nanoprous gold film (NPGF) following by partial and complete GR of underlayer metal
by Pd was carried out to prepared Pd(Cu)/NPGF, Pd(Ni)/NPGF and Pd/NPGF, respectively. SEM was used to characterize the
morphology of the electrodes. The electrocatalytic activity and stability of electrodes were investigated by CV and
chronoamperometeric tests.
Table 1: voltammetric and amperometric responses of fabricated electrodes in 1M MeOH +1M KOH solution.
Current(mA)
ip
il(stability current)
Pd(Cu)/NPGF
8.75
0.67
Pd(Ni)/NPGF
6.10
0.31
Pd/NPGF
5.15
0.13
Pd
6.44
0.51
Based on DFT theory, the higher this center locates, the stronger is the affinity of the metal to the adsorbates like CO. As table 1
shows, for Pd/NPGF, εd up-shift increases CO adsorption and reduces the electrocatalytic activity of Pd/NPGF compared to Pd.
While, Pd(Cu)/NPGF exhibits the best performance among others,despite of more εd down-shift for Pd(Ni)/NPGF than
Pd(Cu)NPGF. It seems that severe εd lowering for Pd(Ni)/NPGF not only results in reduction of CO adsorption (second step of
MOR), but also leads to an significantly low methanol chemisorption (first step of MOR). Thus, the moderate down-shift of εd for
Pd(Cu)NPGF causes to Pd(Cu)/NPGF superior behavior [5].
Reference
[1]Bianchini, C.; Shen, P. K. Chem. Rev. 2009, 109, 4183.
[2]Modibedi, R. M.; Masombuka, T.; Mathe, M. K. Int. J. Hydrogen Energy 2011, 36, 4664.
[3]Kitchin JR, N. J., Barteau MA, Chen JG. J. Chem. Phys. 2004, 120, 10240.
[4]Cobley, C. M.; Xia, Y. Mater. Sci. Eng., R: 2010, 70, 44.
[5]Papadimitriou, S.; Armyanov, S.; Valova, E.; Hubin, A.; Steenhaut, O. J. Phys. Chem. C 2010, 114, 5217.
Simultaneous Voltammetric Determination of Dopamine and Ascorbic Acid Using the Carbon Paste Electrode Modified
withSchiff Base Complex of Cobalt and Cationic Surfactant
Hamid Reza Zare-Mehrjardi*, Naghmeh Hassanzadeh
Chemistry Department, Payame Noor University, Tehran 19395-4697, Islamic Republic of Iran
Dopamine (DA) and ascorbic acid (AA) are two compounds of great biomedical interests, playing determining roles in human
metabolism [1]. It is also present in mammalian brain along with several neurotransmitter amines [2,3]. At traditional solid
electrodes, AA is oxidized at potential close to that of DA, resulting in an overlapped voltammetric response [4]. In this work a
carbon-paste electrode (CPE) is modified by incorporating Schiff base complex of cobalt (N,N'-bis(3-ethoxysalicylidene)-4,5
dimethyle-1,2-phenylenediamin-cobalt(II)) and tetraoctylammonium bromide (TOAB). The electrochemical bihavior of DA and
AA on the surface of the modified electrode containing various percents of TOAB is thoroughly investigated by cyclic and
differential pulse voltammetry (CV and DPV). Results of these studies showed that by increasing the weight percent of TOAB in
the matrix of the modified CPE, ∆EP for oxidation of AA and DA is increased, which makes it suitable for simultaneous
voltammetric detection of AA and DA. The modified electrode showed efficient electrocatalytic activity in lowering the anodic
overpotentials and enhancement of the anodic currents. The effects of potential sweep rate and pH of the buffer solution on the
response of the electrodes, and the peak resolution is thoroughly investigated by cyclic and differential pulse voltammetry. The
best peak resolution for these compounds using the modified electrode is obtained in solutions with pH 4.0. Peak potential
separation nearly 469 mV is resulted for two compounds. The preparation of the modified electrode is very easy and renewed by
simple polishing. This electrode has very good reproducibility (R.S.D.≤3%), high stability in its voltammetric response (more
than two month without any considerable change in response), wide linear dynamic range and low detection limit (submicromolar) for both AA and DA. The prepared electrode is successfully applied for the voltammetric detection of AA and DA
in pharmaceutical preparations.
Reference
[1]. X.Liu, Y.Penga, X.Qua, Sh.Ai, R.Han, X.Zhu , Journal of Electroanalytical Chemistry 654 (2011) 72–78
[2]. Z. Nasri, E. Shams, Electrochimica Acta 54 (2009) 7416–7421
[3]. S. Thiagarajan, S.-M. Chen, Talanta 74 (2007) 212–222
[4]. S. Shahrokhian, H.R. Zare-Mehrjardi, Electrochimica Acta 52 (2007) 6310–6317
Silver nanoparticles plasmon resonance-based method for the determination of nicotinamide adenine dinucleotide
(NADH)
Mohammad Amjadi* and Elahe Rahimpour
Faculty of Chemistry, University of Tabriz, Tabriz, Iran
Corresponding Author E-mail: amjadi@tabrizu.ac.ir
The reduced form of Nicotinamide Adenine Dinucleotide (NADH) is an important coenzyme found in living cells. It participates
in various biosynthetic reactions especially in enzymatic catalysis of many dehydrogenases. Therefore, its determination at trace
levels is very important in enzyme assays [1,2,3]. In this work a very simple and sensitive method was developed for the
determination of NADH. The method is based on the redox reaction between silver nitrate and NADH in alkaline solution at
70ºC. The formation of silver nanoparticles as result of this reaction leads to a color change of solution from colorless to yellow.
The absorbance of solution was monitored at 420 nm, which results from plasmon resonance of silver nanoparticles. Various
experimental factors affecting the absorbance signal including the concentration of sodium hydroxide, ammonia and silver
nitrate, the presence of various surfactant, time and temperature were studied and optimized. Under the optimum conditions, the
calibration graph was linear in the range of 0.5 – 25 µM with a detection limit of 0.15 µM. The standard deviation of six replicate
determination of 10 µM NADH was 3.2%. The effect of some potentially interfering species was also studied. The proposed
method can be applied to various enzymatic assays.
Reference
[1]. G. Ambartsoumian, R. Dari, R.T. Lin, E.B. Newman, Microbiology 140 (1994) 1737–1744.
[2]. U.C. Sauer, F. Canonaco,S. Heri, A. Perrenoud, E. Fischer, J. Biol. Chem. 279 (2004) 6613–6619.
[3]. H. Freeman, K. Shimomura, E. Horner, R.D. Cox, F.M Ashcroft, Cell Metab. 3 (2006) 35–45.
Mixed hemimicelle solid-phase extraction based on sodium dodecyl sulphate -coated Fe3O4/SiO2 NPs for extraction of
cadmium and lead in water samples and their determination by FAAS
Malihe davudabadi farahani, farzaneh Shemirani*
School of Analytical Chemistry, University College of Science, University of Tehran, Tehran, Iran
shemiran@khayam.ut.ac.ir
Magnetically driven separation technology has received considerable attention in the recent decade for its great potential
application .In this study, we investigate the application of silica-coated magnetite nanoparticles (SCMNPs) modified with an
anionic surfactant as adsorbent for micro extraction and determination of trace amounts of Cd (II) and Pb (II) from various water
samples. The synthesized silica-coated MNPs in combination with sodium dodecyl sulphate (SDS) have the ability to
adsolubilize the metal ions after complexation with 1-(2-pyridylazo)-2-naphthol (PAN).The NPs bearing the target metals are
easily separated from the aqueous solution by applying an external magnetic field and the complexed metals were desorbed using
nitric acid. The desorbed analytes are introduced into the flame atomic absorption spectrometer. The effect of pH, complexing
agent, kind and concentration of eluant, micro extraction time, amount and capacity of adsorbent, desorption conditions, sample
volume, ionic strength and interfering ions on the recovery of the analyte were investigated and optimized. Under the optimized
condition, with 500.0mL sample an enrichment factor of 245 was obtained.The proposed method has been applied to the
determination of these metal ions at trace levels in certified reference materials and real samples with satisfactory results.
Reference
[1] C. Huang, B. Hu, Spectrochimica Acta Part B 63 (2008) 437–444.
[2] J. S. Suleiman, B. Hu, H. Peng, C. Huang, Talanta 77 (2009) 1579–1583.
[3] M. Faraji, Y. Yamini, M. Rezaee, Talanta 81 (2010) 831–836.
[4] X . Zhao , Y . S hi, Y . C ai , S . Mou, Environ. Sci. Technol. (2008), 42, 1201–1206.
Electrocatalytic Oxidation of Captopril on Glassy Carbon Electrode Using Chlorpromazine as a Homogeneous Mediator
Fahimeh Jalali* and Hossein Bahramipur
Department of Chemistry, Razi University, Kermanshah, Iran
Captopril, 1-[(2S)-3-mercapto-2-methylpropionyl]-L-proline (CAP), is a verbal drug and has been widely used as
antihypertensive drug and to moderate heart failure . Several methods have been applied to the determination of captopril,
including high performance liquid chromatography spectrophotometry and electrochemical methods
In this work, the anodic oxidation of captopril (CAP) has been studied on a glassy carbon electrode. It was shown that
chlorpromazine (CPZ) can catalyze the oxidation of CAP in an aqueous buffer solution (pH 4.0) to produce a sharp oxidation
peak current at about +0.70 V versus Ag/AgCl. In order to evaluate the catalytic rate constant for oxidation of CAP (kcat) static
chronoamperometry was used. The values of diffusion coefficient (D), and kcat were 5.64×10-6 cm2 s-1 and 6.346 ×102 M-1 sec-1,
respectively. The transfer coefficient, α, was also estimated to be 0.34 using Tafel equation. The catalytic peak currents of linear
sweep voltammograms were linearly dependent on CAP concentration in the range of 10–250 μM, and the detection limit was
calculated to be 3.65 μM for a S/N = 3. This method was used in the determination of low concentrations of CAP in
pharmaceutical preparations as well as urine samples successfully.
Reference
[1] K. Fiorey, Analytical Profiles of Drugs Substances, Academic Press, New Yor 1982, 11, 81.
[2] A. Khedr, Biomed. Chromatogr 1998, 12, 57-60.
[3] J. Russell, J. A. M., C. Hensman, W.E. Smith, J. Reglinski, J. Pharm.Biomed. Ana 1997, 15, 1757-1763.
[4] H. T. Askal, , Talanta 1991, 38, 1219.
[5] R.I. Stefan, J. K. v. S., H.Y. Aboul-Enein, Biosens. Bioelec 2000, 15 1.
[6] A.A. Ensafi, J. Braz. , Chem. Soc 2008, 19, 405.
[7] X. Ioannides, A. E., A. Voulgaropoulos, , J. Pharm. Biomed. Anal 2003, 33, 309.
Electrocatalytic oxidation of L_cysteine at carbon paste electrode in presence of chlorpromazine as a mediator
F. Jalali*and S. Ranjbar
Department of Chemistry, Razi University, Kermanshah, Iran.
Detection of L-cysteine (Cys) is of great importance since it plays crucial roles in biological systems. It provides a modality for
the intramolecular crosslinking of proteins through disulfide bonds to support their secondary structures and functions. L-cysteine
requires positive overpotential at most conventional electrodes to undergo the process of electrochemical oxidation. Thus, several
chemically modified electrodes have been designed and characterized for the electroactive oxidation of cysteine [1-4].In the
present work we propose a new approach to the electrochemical detection of L-cysteine in pH 6.00 by using chlorpromazine
(CPZ) as a mediator on carbon paste electrode. In our experimental work, direct electro-oxidation of Cys at a carbon paste
electrode was very slow in phosphate buffer solution. However, in the presence of a small amount of CPZ the anodic peak
current was remarkably enhanced. Effect of buffer pH solution on the oxidation of Cys was studied and results show that
catalytic oxidation is more favored at pH 6.00. Also influence of CPZ concentration on the peak currents was studied, and 0.05
mM CPZ was selected as optimum concentration for mediator. Linear sweep voltammetry experiments of 0.05 mM of CPZ were
performed in phosphate buffer solution containing various concentrations of Cys. The electrocatalytic peak current of CPZ
oxidation was linearly dependent on Cys concentration. The calibration plot was linear in the range 2.6 - 241µM with a limit of
detection of 0.95µM, and standard deviation (R.S.D.%) of 4.2%. The method was validated by using in the determination of
small amounts of Cys in water samples. The accuracy and precision of the results were quite satisfactory.
Reference
[1] M. Santhiago, P.R. Lima, W. J.R. Santos, L.T. Kubota, Sensors and Actuators B 146 (2010) 213–220.
[2] Y. H . Bai, J.J. Xu, H.Y. Chen, Biosensors and Bioelectronics 24 (2009) 2985–2990.
[3] H. Razmi, H. Heidari, Analytical Biochemistry 388 (2009) 15–22.
[4] Q. L .Sheng, H. Yu, J.B. Zheng, Solid State Electrochem 12 (2008)1077–1084.
Voltammetric Determination Of Methimazole Using a Oxovanadium(Iv) Schiff Base Complex Modified Carbon-Paste
Electrode
F. jalali* . L. miri
Department of Chemistry, Razi University, Kermanshah, Iran
Methimazole, 2-mercapto-1-methylimidazole, (MMI) is used in the treatment of hyperthyroid by the production of thyroxin, a
hormone excreted by the thyroid gland, inhibits the formation of thyroid hormones. Methimazole is adsorbed by the
gastrointestinal tract and concentrated in the thyroid gland. Several analytical procedures have been described for the
determination of methimazole including spectrophotometry , and HPLC [3]. Schiff base complexes of transition metal ions are
efficient catalysts both in homogeneous and heterogeneous reactions and the activity of these complexes varied with the type of
ligands, coordination sites and metal ions [4]. In this paper the electrochemical behavior of methimazole (MMI), as an antithyroid
agent, is investigated on the surface of a carbon-paste electrode modified with a newly synthesized oxovanadium(IV) as a Schiff
base complex ([VO(SB)]). The prepared modified electrode showed an efficient catalytic role in the electrochemical oxidation of
MMI, leading to enhancement of the kinetics of the electrode reaction. The mechanism of the electrocatalytic process on the
surface of the modified electrode is analyzed by obtaining the cyclic voltammograms in various potential sweep rates and pH
values of the buffer solutions. The differential pulse voltammetry is applied for the determination of submicromolar amounts of
MMI. A linear dynamic range of 9 × 10–7 M - 4 × 10–4 M with a detection limit of 8 × 10–7 M is resulted for MMI. The diffusion
coefficient (D) and catalytic rate constant (k') was estimated by chronoamperometry. The relative standard deviation for 20 μM of
MMI was found to be 1.7% . In order to further validate its possible applications, the method was used for the quantification of
MMI in pharmaceutical formulations.
Reference
[1] Aslanoglu, M. and N. Peker, J. Pharm. and Biomed. Anal, 33(5) (2003) 1143.
[2] Dong, C.H., et al., J. Anal. Chem., 65(7) (2010) 707.
[3] K. Kusmierek, E. Bald, Talanta 71 (2007) 2121.
[4] K.C. Gupta, A. K. Sutar. Coord. Chem. Rev., 252 (2008) 1420.
Bismuth hexacyanoferrate modified disposable pencil-lead electrode for electrocatalysis and determination of ascorbic
acid
Karim Asadpour-zeynali*, Parvaneh Mohammadhosseinpour
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 5166616471, Iran
Modification of electrode surfaces with various electroactive materials is an intresting area of research in designing
electrochemical sensors. To date various materials have been used to make modified electrodes. Among them metal
hexacyanoferrates have attracted much attention due to their intresting properties such as ability to mediate electrochemical
reactions, so they are known as useful electrocatalysts in electrochemical processes and are suitable as electrode modifiers[1-2].
In this work we report the preparation of pencil lead electrode (PLE) modified with bismuth hexacyanoferrate by electrochemical
method. In this way the mixture of bismuth and hexacyanooferrate was electrodeposited on the bare PLE by cyclic voltammetry
method. The electrochemical behavior of bismuth hexacyanooferrate modified PLE was investigated. In addition, the present
modified electrode exhibited the advantageous of simple preparation, fast response and good stability. The modified electrode
used for determination of ascorbic acid in drug formulation and fruit juices by cyclic voltammetry and amperometery techniques.
Reference
[1] J. Zheng, Q. Sheng, L. Li, Y.Shen, J. Electroanal. Chem. 611 (2007) 155-161
[2] M. R. Majidi, K. Asadpour-Zeynali, K. Shahmoradi, Y. Shivaeefar, J. Chin. Chem. Soc., 57, (2010) 391-398
Presentation of generalized net analyte signal standard addition method for simultaneouse determination of some
pesticides with spectrophotometric technique
Karim Asadpour-Zeynali*, Elhameh Saeb, Javad Vallipour
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 5166616471, Iran
Use of net analyte signal as a powerful tool for quantitative purposes in analysis of multivariate data firstly has been proposed by
Lorber in 1997. Net analyte signal is defined as a part of a signal that is orthogonal to the contribution of other coexisting
constituents. Generalized net analyte signal standard addition method (GNASSAM) is the same as net analyte signal standard
addition (NASSAM) but there are some differences between them such as simultaneously increasing a mixture of standards in
GNASSAM instead of adding of standard solution of each component separately in NASSAM. In this paper we have developed
an analytical method for the simultaneous determination of three nicotinoid pesticides residues (i.e. acetamiprid (ACT),
imidacloprid (ICL), and thiamethoxam (TMX)) in some synthetic mixtures. In this way, simultaneous measurements of binary
and ternary mixture of pesticides are presented. At first the simultaneous standard addition of a binary mixture was performed
and the concentrations of both chemical species were obtained. For a triplet mixture of analytes standard addition procedure was
done only in one step by standard addition of a triplet mixture of standards of analytes and then the concentration of each analyte
was calculated. Results show that suggested method can be used for measuring the concentration of chemical species which have
relatively strong spectral overlapping. The statistical analysis of results shows that the accuracy and precision of proposed
method are comparable to the other multivariate calibration methods.
Reference
[1] A. Lorber, K. Faber, B. R. Kowalski, J. Anal. Chem. 69 (1997) 1620- 1626
[2] S. Seccia, P. Fidente, D. Montesano, P. Morrica, J. Chromatogr. A. 1214 (2008) 115–120
[3] Q. Zhou, Y. Ding, J. Xiao, J. Anal. Bioanal. Chem. 385 (2006) 1520–1525
Kinetic-spectrophotometric determination of bromate in mixtures of iodate-bromate and periodate-bromate using net
analyte signal standard addition method
Karim Asadpour-Zeynali*, Sanaz Ranjdar
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz 5166616471, Iran
A kinetic spectrophotometric method for determination of bromate in the presence of iodate and periodate was proposed. The
method is established on the different kinetic behavior of the analyte which react with iodide in acidic media. The kinetic data
were collected at 352 nm, within a time range of 50-350 s at 1 s interval, and the absorbance increased linearly with the
concentration of bromate. Kinetic data were processed by net analyte signal standard addition method (NASSAM). The proposed
method was successfully applied to the determination of bromate in binary mixture of iodate-bromate and periodate-bromate.
Reference
[1] K. Asadpour-Zeynali, M. Bastami, Spectrochim Acta Part A 75(2010) 589-597.
[2]A. Afkhami, A.R. Zarei. Talanta 60 (2003) 63-71.
[3]Y. Ni, Y. Wang, Microchem J 86 (2007) 216-226.
Growth of metalic nanostructures at gold electrode by electrochemical deposition in the absence of supporting electrolyte
N. Abbasi, A. Kiani*
Department of chemistry, Faculty of science, University of Isfahan , Iran
E-mail: a.kiani@chem.ui.ac.ir
Nanometer scale metals have attracted attention due to their use in nanodevices. These nanostructured materials have been
synthesized by different techniques, in one aspect the method of fabrication is classified into template (hard or soft) and nontemplate processes. Templates are employed for the exclusive growth of nanostructures in the direction normal to the substrate
surface. However, the removal of the template is difficult. Thus, the design of a template free procedure is of great importance
[1]. In this work, we present a novel and simple electrochemical method for fabrication of silver nanostructures by template free
electrodeposition in the absence of any supporting electrolyte [2].
The growth of silver nanostructures was carried out in an electrochemical cell contains a small of recordable disks (CD-R) made
of gold as the working electrode. For the electrodeposition, a chronopotentiometry mode was applied. The behavior of silver
electrodeposition at different times, different applied currents, and in the present of L-cysteine was studied. The product was
characterized by scanning electron microscopy (SEM) fitted with an energy dispersive X-ray (EDX) spectrometer. In summary,
silver nanostructures were deposited on the electrode without use of the template. In this procedure, the absence of the supporting
electrolyte plays a key role. When a potential is applied to the working electrode, most of the potential drop occurs in the region
of double layer. Because of the low concentration of electrolyte, the double layer becomes thick and the potential drop is in a
large scale. Therefore mass transfer in solution occurs mostly by migration. The electric field gradients near the tip (primary
formed nucleuses at the electrode surface) is larger than that of smooth area, thus, the ions like to diffuse toward the tip on the
electrode and consequently resulted in a rough nanostructure surface.
Reference
[1] Zheng, X.-J.; Jiang, Z.-Y.; Xie, Z.-X.; Zhang, S.-H.; Mao, B.-W.; Zheng, L.-S. Electrochemistry Communicatication. 2007, 9, 629-632.
[2] Jiang, Z.-Y.; Xie, Z.-X.; Zhang, S.-H.; Zheng, L.-S.; Xie, S.-Y.; Huang, R.B. Chemical Physics Letters. 2003, 347, 645-649.
Spectrophotometric determination of acidity constants of nitroso – R - salt in binary methanol , dioxan and DMSO-water
mixtures by chemometrics methods
Maryam saki* and Ali Niazi
Department of Chemistry, Islamic Azad University – Arak Branch, Arak, Iran
(E-mail: maryam_saki@ymail.com and ali.niazi@gmail.com)
The acidity constants of nitroso – R – salt (Figure 1) in binary mixtures of methanol , dioxan, and DMSO-water at 25 °C and an
ionic strength of 0.1 M (KNO3) in pure water and aqueous media containing percentages (10-50% w/v), have been determined
spectrophotometrically.
Figure 1. Chemical structure of nitroso – R – salt
DATA ANalysis (DATAN) program is applied for determination of acidity constants. The absorption spectra of nitroso– R – Salt
in binary solvent mixtures of at various pH values in 330-500 nm intervals were recorded. Sample spectra of nitroso – R - salt in
water with pH values ranging from 1.0 to 12.0 at 0.1 M KNO3 is shown in Figure 2.
WATER PH
ABSORPTION
1
0.8
0.6
0.4
0.2
0
330
380
430
480
530
WAVELENGHT
Figure 2. Spectra of nitroso – R – salt in pure water at 0.1 M KNO3 at different pH values.
The obtained results indicated that acidity constants decrease as the content of an organic solvent in the medium increases. The
acidity constants of all related equilibria are estimated using the whole spectral fitting of the collected data. The DATAN
program [1-3] was applied for determination of acidity constants. The effect of solvent properties on acid-base behavior is
discussed. This indicates that the acid ionization constants of nitroso –R – salt obtained in various percentages of different
solvent-water mixtures are governed by electrostatic effects. The amounts of pKa1 is obtained 7.09.
Reference
[1] A. Niazi, M. Ghalie, A. Yazdanipour, J. Ghasemi, Spectrochim. Acta Part A 64 (2006) 660-664.
[2] A. Niazi, A. Yazdanipour, J. Ghasemi, M. Kubista, Coolect. Czech. Chem. Commun. 71 (2006) 1-14.
[3] A. Niazi, A. Yazdanipour, J. Ghasemi, M. Kubista, Spectrochim. Acta Part A 65 (2006) 73-78.
Extraction and Simultaneous Determination ions Copper and Cobalt by Spectrophotometric and Chemometrics Methods
R. Moradi1,2*, S. Jameh-Bozorghi3, A. Niazi4
young researchers club, Islamic Azad University, Touyserkan Branch, Touyserkan, Iran
(Email: reza.moradi_bi@yahoo.com)
2
Department of Applied Chemistry, Faculty of science, Islamic Azad University, North Tehran Branch,Tehran,Iran
3
Department of Chemistry, Faculty of sciences, Islamic Azad University, Touyserkan Branch, Touyserkan, Iran
4
Department of Chemistry, Faculty of Science, Islamic Azad University, Arak Branch, Arak, Iran
1
The extraction and simultaneous determination of metal cation mixtures by using spectrophotometric method is a difficult
problem in analytical chemistry, due to spectral interferences. By multivariate calibration methods, such as partial least squares
(PLS) regression, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration
range. Orthogonal signal correction (OSC) is a preprocessing technique used for removes the information unrelated to the target
variables based on constrained principal component analysis. Liquid- liquid extraction methods for the separation and
determination of copper and cobalt are limited[1]. In this study, a mixture of 25 different concentration of copper and cobalt has
been prepared and their absorption spectra in the wavelength range between 350-750 nm was recorded. Simultaneous
determination of copper (II) and cobalt (II) was accomplished based on reaction of these cations and ligand 1-(2-Thiazolyl azo)2-naphthol(TAN)[2]. RMSEP value for copper with the OSC and without OSC respectively, 0.7317 and 8.2738 and the Cobalt
with the OSC and without OSC respectively in 0.1884 and 5.2563 was. Dynamic linear range for copper is 1-300 ng ml-1 and for
cobalt is 1-200 ng ml-1. This method was used to simultaneously measurement of mentioned cations in synthetic and real
samples.
Determination of the optimal, in a 50 mL volumetric flask, 0.2 mL 1-(2-Thiazolyl azo)-2-naphthol, 2mL buffer pH=10 was
poured and then distilled twice with distilled water was brought to volume. The metal injection syringe was Hamiltonian. Then,
solutions were transferred to a separator funnel 4mL of the extraction solvent dichloromethane to the solution was added. The
solution for 5 minutes, then the separator funnel and shake were two phases were allowed to be separated completely. When the
organic phase containing the above ligand would be contacted with aqueous phase containing copper(II) and cobalt (II), complex
formation is occurred between ligand with copper(II) and cobalt(II) and simultaneously they are brought to the organic phase.
Quantitative measurements have been done based on absorption read in the organic phase. Spectrum in the wavelength range
350-750nm will be reviewed.
Refrence
[1] J. Ghasemi, A. Nikrahi, A. Niazi, Turk J Chem. 29 (2005) 669-678.
[2] A. Niazi, A. Yazdanipour, Chinese Chemical Letters. 19 (2008) 860-864.
Application of response surface design to dispersive liquid – liquid microextraction method: Preconcentration of trace
amount of copper ion
Zahra Heidari, GholamhassanAzimi*
Department of Chemistry, Faculty of Sciences, Arak University, Arak, Iran
Dispersive liquid-liquid microextraction (DLLME) and flame atomic absorption spectrometry techniques were used in order to
extraction and determination of copper ion. Dithizone was employed as a chelating agent. Carbon tetrachloride and acetonitrile
were used as extraction and dispersive solvent, respectively. Some operative parameters on the extraction efficiency such as
extraction and dispersive solvents types and their volumes, the extraction time, the salt effect, pH and the concentration of
chelating agent have been examined.The effects of screened factors on the extraction recovery have been studied by one at the
time and response surface design (Box-Behnken) methods. Analysis of effects revealed that the recovery has a nonlinear relation
to the pH and there is a considerable interaction between pH and the volume of extractant solvent. Using the optimum conditions
recommended by response surface design method, an enrichment factor of 154 was achieved for 10 mL of water sample. The
calibration curve was linear in the range of 0.20-0.90 µg mL-1 with detection limit of 0.094 µg mL-1. The relative standard
deviation for ten replicated measurements of a solution containing 0.30 µg mL-1 of copper was 4.6%. The relative recoveries of
copper in tap and mineral water samples at spiking level of 0.30 and 0.40 µgmL-1 were 97.3, 95, 96.7 and 98%, respectively.
Reference
[1] P. Liang, H. Sang, Anal. Biochem, 380(2008) 21-25.
[2] A.N. Anthemidis, K.I.G. oannou, Talanta, 79(2009) 86 – 91.
[3] M.T. Naseri, P. Hemmatkhah, M.R. MilaniHosseini, Y. Assadi, Anal. Chem. Acta, 610 (2008) 135-141.
[4]P.X. Baliza, L.S.G. Teixeira, V.A. Lemos, Microchem. J, 93 (2009) 220 -224.
[5] N. M.Najafi, H. Tavakoli, R. Alizadeh, S. Seidi, Anal. Chim.Acta, 670 (2010) 18-23.
Spectrophotometric study of complexation of Cd2+, Ni2+and Mn2+ ions with 1,2-bis[O-(N-methylidenamino-2-thiol-1,3,4thiadiazole-5- yl)phenoxy]ethane
Zahra Heidari, GholamhassanAzimi*, Sattar Ebrahimi
Department of Chemistry, Faculty of Science, Arak University, Arak, Iran
The complexation of Cd2+, Ni2+ and Mn2+ ions with 1,2-bis [O -(N- methylidenamino-2- thiol-1,3,4-thiadiazole-5yl)phenoxy]ethane as ligand (scheme1) has been investigated in acetonitrile solvent. The stoichiometry and stability constants of
complexes were specified by UV-visible spectrophotometry. A hard modeling method is used in order to accomplish data
processing. The outcomes of these processes are spectral profiles, concentration profiles of different species, residual errors and
good estimation of conditional formation constants. The calculations shows that the complexes with 1:2 and 2:1 stoichiometric
are more possible for Cd2+ , Ni2+ ions and 1:1 and 1:2 for Mn2+ ions in acetonitrile solvent. The stability of the complexes with
Mn(II) is bigger than Cd(II) and Cd(II) bigger than Ni(II).
Scheme1: structure of 1,2-bis [O-(N-methylidenamino-2-thiol-1,3,4-thiadiazole-5-yl)phenoxy]ethane
Reference
[1] M. Vosough, M. Maeder, M. Jalali-Heravi , S.E. Norman, Spectrochim. Acta. A, 70(2008)674-681.
[2] M. Asadi, M. SetoodehKhah, J. Iran. Chem. Soc, 7(2010)875-882.
[3] H. Abdollahi, S. Zeinali, Talanta, 62(2004)151-163.
[4] N. Alizadeh, M.A. Zanjanchi, H. Sharghi, R. Khalifeh, M.Shamsipur, J. Iran. Chem. Soc, 5(2008)610-616.
Potentiometric Cr (VI) selective electrode based on novel Surfactant modified- zeolite PVC membranes
Alireza Nezamzadeh-Ejhieh*and Mehri Shahanshahi
Department of Chemistry, Islamic Azad University, Shahreza Branch
Chromium is one of the most abundant elements on Earth and can be found in sewage of chemical industries. The mentioned ion
is absorbed by body easily and can cause cancer in lungs, larynx and stomach. The goal of this study is therefore, constructing the
membrane electrode containing nano-clinoptilolite modified with Hexadecylpyrdinium bromide (HDPBr) surfactant. The results
of potentiometric determination of dichromate showed that modified electrode have higher affinities toward dichromate than
those to unmodified electrode. The electrode exhibits linear response of the dichromate ions in the concentration range of
2.5×10−5 to 1.0×10−1 M with 4.2×10−7 M detection limit at pH=5 and a Nernstian slope of 29.9±0.9 mV per decade of dichromate
concentration. The electrode has a response time about 15–20 s and it can be used at least for 2 months with good reproducibility
and repeatability. The proposed method has a good responses in direct and indirect potentiometry.
Reference
[1] R. Ansari "Application of polyaniline and its composites for adsorption/recovery of chromium (VI) from aqueous solutions" Acta Chim. Slov. 53 (2006) 88-94.
[2] A. Nezamzadeh-Ejhieh, N. Masoudipour; "Application of a new potentiometric method for determination of phosphate base of on a surfactant-modified zeolite
carbon-paste electrode (SMZ-CPE)", Anal. Chim. Acta 658 (2010) 68-74.
[3] A. Nezamzadeh-Ejhieh, E. Mirzaeyan; "Oxalate membrane-selective electrode based on surfactant-modified zeolite" Electrochim. Acta. (2010) DOI:10.1016/
j.electacta.2011.02.069.
Synthesis of molecularly imprinted polymer as sorbent for selective extraction of olanzapine
Atefeh Tamaddona*, Leyla Karimkhania, Samaneh Keyvanfara, Behrouz Akbari-aderganib
a
Department of Chemistry, Central Tehran Branch, Islamic Azad University, Tehran, Iran
b
Food & Drug Laboratory Research Center, Food & Drug Department, Ministry of Health and Medical Education, Tehran, Iran
Olanzapine is one of the most commonly used drugs for atypical antipsychotics. Olanzapine has been approved by the FDA for
the treatment of schizophrenia, acute mania in bipolar disorder, agitation associated with schizophrenia and bipolar disorder, and
as maintenance treatment in bipolar disorder and psychotic depression. In this study, a novel method is described for the
determination of olanzapine using molecularly imprinted solid-phase extraction (MISPE) combined with high-performance liquid
chromatography (HPLC). The water-compatible molecularly imprinted polymers (MIPs) were prepared using methacrylic acid as
functional monomer, ethylene glycol dimethacrylate (EGDMA) as cross-linker, 2,2’-Azobis(isobutyronitrile) or AIBN as a
commonly used initiator with the presence of chloroform as porogen solvent and olanzapine as template molecule. The novel
imprinted polymer was used as a sorbent for the extraction and determination of olanzapine in pharmaceuticals. Various
parameters affecting the extraction efficiency of the polymer have been evaluated. The MIP selectivity was evaluated by
checking substances with similar molecular structures to that of olanzapine.
Reference
1- Karsten Haupt, Analyst, , 126 ( 2001) 747–756
2- H. Yan, K. H. Rowa, G. Yang, Talanta 75 (2008) 227–232
3- A. Beltran, R.M. Marcé, P.A.G. Cormack, F. Borrull, Journal of Chromatography A, 1216 (2009) 2248–2253
Novel PVC-membrane sensors based on a newly synthesized ionophore and chromoionophoreI for Hg (II) ion
Z. Moradia, A. R. Firooz*a, Z. Hajianiª, A. R. Khosro pourª
a
Department of Chemistry, University of Isfahan, Isfahan 81746-73441, Iran
E-mail: a.firooz@sci.ui.ac.ir
The designe of sensitive and discriminating optical sensors remains as an emerging frontier in analytical chemistry and has
gained scientific interests mainly due to the need for fast, easy and economical monitoring of enviromental samples especially
for heavy metal ions in a reasonable time. Generally, optodes include a sensing membrane as the selection device. The spectral
change in absorption (or emission) caused by either the analyte itself, or the analyte reacting with a specific indicator, gives a
more or less direct measure of the analyte concentration. No further samplings, addition of reagents or dilutions are normally
required [1-5]. In addition, the determination of heavy metals in the aquatic environment is of tremendous interest due to their
hazardous effects on the ecosystem and the human health depending on their dose and toxicity. In this work an optical sensor is
introduced for the determination of mercury ions. The sensor is based on the interaction of Hg(II) with newly synthesized 5-(4Cholorophenyl)-4,5-dihydro-3-phenylpyrazole-1-carbothioamide as ionophore in plasticized polyvinyl chloride (PVC)
membrane incorporating chromoionophoreI as proton-selective indicator and sodium tetraphenylborate (NaTPB) as lipophilic
anionic sites. The membranes were cast onto glass substrates and used for the determination of mercury ions in aqueous
solutions. The PVC membrane composition plus the other experimental variables being optimized, the detection limit is
7×10⁻¹⁰ M Hg(II) , with a widely linear range 1×10⁻⁹ to 1×10⁻⁵ M and a response time = 8min. The sensor can be easily and
completely regenerated by dilute EDTA solution.
Reference
[1] O.S. Wolfbeis, Fibre Optic Chemical Sensors and Biosensors, CRC Press, Boca Raton, FL,1991.
[2] W.R. Seitz, CRC critical review. Chemical sensors based on immobilized indicators and fiber optics, Anal. Chem. 19, 1988, 135.
[3] O.S. Wolfbeis, Fiber optic chemical sensors and biosensors, Anal. Chem. 72, 2000, 81.
[4] J. Homola, Model of a chemo-optical sensor based on plasmon excitation in thin silver films, Sens. Actuators B, 11,1993, 481.
[5] K.M. Wang, Theories and Methods of Optical Chemical Sensors, Hunan Education press,Changsha, 1995.
Development of a highly sensitive and selective bulk optode for determination
of Hg (II) based on a synthesized ionophore and chromoionophoreV
a
b
Z. Hajiania, A. R. Firooz*a, H. Sharghi b
Department of Chemistry, University of Isfahan, Isfahan 81746-73441, Iran
Department of Chemistry, Faculty of Sciences, Shiraz University, Shiraz 71454, Iran
E-mail: a.firooz@sci.ui.ac.ir
Today, measuring small amounts of organic and inorganic species, especially ions of heavy metals is very important in various
environmental [1] and other fields, so different methods have been introduced. Among a wide range of methods, optical sensors
(optodes) have highly been regarded in the analytical chemistry [2-5]. Optodes enjoy several advantages such as good
selectivity, high sensitivity, relatively fast resp-onse time, large response range, long life, low cost, small size, method of
preparation and easy work that are influenced by the technique the membrane were stabilized reagent [6]. In this work, an
optode is producted to determine the mercury ions. The optode is based on the interaction mercury ion with synthetic ligand
1,15-diaza-3,4,1,13-dibenzo -5,11-dithia-8-oxa-1,15-(2,6-pyrido)cycloocta-decane-2,14-dione [7] as ionophore in membrane
polyvinyl choloride (PVC) in the presence chromoionophoreV as proton-selective indicator, Sodium tetraphenyl borate(NaTPB) as anionic salts and o-NPOE as plasticizer. Membrane solution is placed on a glass surface with dimensions
of 5Cm x 90Cm and in order to determine the mercury ion that this membrane is placed in contact with the aqueous
solution. Membrane composition optimized and detection limit is 7.0×10⁻¹¹ M Hg(II) , with a widely linear range 1.0×10⁻¹⁰1.0×10⁻⁵M and response time < 45s.The optode is used to determine mercury ions in water samples. Today many optodes are
producted to determine mercury ions[5,8,9] optode is producted than optodes is reported is high sensitive.
Reference
[1]Huber, C.; Klimant, I.; Krause, C.; Wolfbeis, O. S. Anal. Chem. 2001, 73, 2097 .
[2]Ortuno, J.A.; Albero, M.I.; Garacia, M.S.; SanchezPedreno, C.; Garcia, M.I.;Exposito, R. Talanta, 2003, 60, 563.
[3]Safavi, A.; Sadeghi, M. Talanta, 2007, 71, 339.
[4]Gonzalez, G. P.; Hernando, P. F.; Algeria, J. S. D. Anal. Chim. Acta, 2009, 638, 209.
[5]Ensafi, A. A.; Fouladgar, M. Sens. Actuators, B, 2009, 136, 326.
[6]Rosatzin, T.; Holy, P.;Seiler, K.;Rusterholz, B.; Simon, W. Anal. Chem., 1992, 64, 2029.
[7]Sharghi, H.; Paziraee, Z. Synthesis. 2004, 4, 600.
[8]Safavi, A.; Bagheri, M. Sens. Actuators, B, 2004, 99, 608.
[9]Yari, A.; Papi, F. Sens. Actuators, B, 2009, 138, 467.
A Quasi 4D QSAR and docking study on potent Gram-negative specific LpxC inhibitors using molecular dynamic
Reihaneh Safavi, Jahan B. Ghasemi*
Chemistry Department, Faculty of Sciences, K.N. Toosi University of Technology, Tehran, Iran
E-mail address: Jahan.ghasemi@gmail.com
A quasi 4D-QSAR has been carried out on a series (43 compounds) of potent Gram-negative LpxC inhibitors [1]. This approach
makes use of the molecular dynamics (MD) trajectories and topology information retrieved from the GROMACS package [2].
This new methodology is based on the generation of a conformational ensemble profile, CEP, for each compound instead of only
one conformation, followed by the calculation intermolecular interaction energies at each grid point considering probes and all
aligned conformations resulting from MD simulations. These interaction energies are the independent variables employed in a
QSAR analysis. The comparison of the proposed methodology to Comparative Molecular Field Analysis (CoMFA) formalisms
was performed. This methodology explores jointly the main features of CoMFA and 4D-QSAR models. Stepwise multi linear
regression was used for the selection of the most informative variables and PLS regressions were applied to find the best
predictive model. Leave-N-out cross validation (LNO) and y-randomization were performed in order to confirm the robustness of
the model in addition to analysis of the independent test set [3]. PLS model provided the following statistics: r2 = 0.94, q2 =0.82,
r2pred =0.78. To verify the results, a molecular docking study was performed with CDOCKER algorithm. Visualization of the
descriptors of the best model help us to interpret the model from the chemical point of view, supporting the applicability of this
new approach in rational drug design.
Reference
[1] U. Faruk Mansoor, Dilrukshi Vitharana, Panduranga Adulla Reddy, Dayna L. Daubaras, Paul McNicholas, Peter Orth, Todd Black, M. Arshad Siddiqui.
Bioorganic & Medicinal Chemistry Letters. 2011,21, 1155-1161
[2] Jo o Paulo A. Martins, Euz ́ bio G. Barbosa, Kerly F. M. Pasqualoto, M ́ rcia M. C. Ferreira. J. Chem. Inf. Model. 2009, 49, 1428-1436
[3] Rudolf Kiralj; Márcia M. C. Ferreira. J. Braz. Chem. Soc. 2009, 20, 770-787.
Simultaneous determination of catechin and gallic acid in Green Tea extract by an electrochemical sensor based on a
carbon paste electrode modified with gold nanoparticle
Zohreh Hadadi, Mohsen Behpour*, Sayed mehdi Ghoreishi, Maryam Khayatkashani
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, 87317-51167, I. R. Iran
E-mail address: m.behpour@kashanu.ac.ir
Green tea is derived from the fresh tea leaves of Camellia sinensis L. Phenolic compounds including are assumed to be
responsible for the potential benefits of green tea. Specifically, health benefits of tea have been attributed to the antioxidant
activity of phenolic compounds [1-5]. In this study, we report a novel and sensitive electrochemical method for the simultaneous
determination of catechin and gallic acid in extract of green tea. A voltammetric determination of catechin and gallic acid was
conducted with a novel sensor based on a modified carbon paste electrode with gold nanoparticle. The electrochemical behavior
of catechin and gallic acid at the modified sensor was characterized by cyclic voltammetry, chronocuolometry, linear sweep
voltammetry, differential pulse voltammetry and rotating disk electrode voltammetry. Electrochemical parameters such as the
diffusion coefficient (D), electron transfer coefficient (α), electron transfer rate constant (k) and ionic exchange current density
(i0) were determined for catechin and gallic acid. Satisfactory dynamic ranges and low detection limits were obtained for both
compounds. The results revealed that the modified electrode showed an electrocatalytic activity toward anodic oxidation of
catechin and gallic acid, and an enhanced current response in buffered solutions at a pH of 2.0. This method was successfully
applied to the determination of catechin and gallic acid in extract.
Reference
1. Wang, H.; Helliwell, K.; You, X. Food Chem. 2000, 68, 115–121.
2. Rice-Evans, C. A.; Miller, N. J.; Paganga, G Free Radic. Biol. Med. 1996, 20, 933–956.
3. Furuno, K.; Akasako, T.; Sugihara, N. Biol. Pharm. Bull. 2002, 25, 19–23.
4. Romani, A.; Minunni, M.; Mulinacci, N.; Pinelli, P.; Vincieri, F. J. Agric. Food Chem. 2000, 48, 1197–1203.
5. Paul, A.; Kilmartin Chyong, F. Food Chem. 2003, 82, 501–512.
Effect of acid treatment and pillaring on natural layered material, characterization and catalytic evaluation of modified
clay as a solid acid catalyst and separation and determination of products
Hossein Faghihiana*, Mohammad Hadi Mohammadia, Zahra Nasr Isfahani b, Mahmood Beigib
a
Department of Chemistry, University of Isfahan, Isfahan, Iran. 81746-73441
b
R & D Department, Iran Chemical Industries Investment Company (I.C.I.I.C.), Isfahan, Iran
Linear alkylbenzenes (LABs) have been prepared in high yields from detergent-range linear olefins via regioselective benzene
alkylation. Acid-activated pillared natural montmorillonite clays provide enhanced shape-selective alkylation performance when
employ as heterogeneous catalysts. In the work natural montmorillonit was prepared from Sejzi deposits located in the East of
Isfahan, Iran. After treating natural samples by 2M sulfuric acid, Al-polyhydroxocation was employed to pillaring it. A mixture
of a clay diluted suspension (2%) was treated with the pillaring solution. The modified solids were characterized by TG, DTG,
XRD, BET, TPD techniques and elemental analysis. The specific surface area and thermal stability of the modified clay was
increased as a result of the pillaring process. The catalytic activity of the catalyst was assessed for benzene alkylation in a batch
liquid phase and the reaction conditions were optimized. The results showed that under optimized conditions of B/O=15 at 418 K
after 270 minutes the conversion of 98.91% was obtained. The selectivity of 34.74 % was also obtained for 2-phenyle isomers.
The products were analyzed by GC-FID. Deactivation of catalysts is essentially due to the formation and trapping of heavy
secondary products (coke) within the pores. The amount of coke precursors in the catalyst was calculated by TGA method as the
difference between the sample mass after drying at 473 K under N2 atmosphere and switching from nitrogen to air at 873 K. The
amount of formed coke was less than 2% W.
Reference
[1] Z. Da et al.Catalysis Letters, 61 (1999) 203–206.
[2] C. Berger et al. Microporous and Mesoporous Materials, 83 (2005) 333–344.
[3] Steven L. Suib et al. Studies in Surface Science and Catalysis, vol.149 (2004) 341-353.
[4] S. R. Guerra e t al. Catalysis Today 133–135 (2008) 223–230
[5] M. Guisnet et al., Journal of Molecular Catalysis A: Chemical 305 (2009) 69–83.
Analysis of non-isothermal chemical equilibria measurements; Determination of thermodynamic parameters of
complexation equilibria
1
1
Fattahi A., 2 Abdollahi H., 1Azimi G.*, 1Houdgar S.
Department of Chemistry, Faculty of Sciences, Arak University, Arak
2
Department of Chemistry, Institute for advanced Studies in Basic Sciences, Zanjan, Iran
So far the chemical equilibria were the center of attention in many scientific and industrial points of view. Among the different
parameters which usually are investigated by researcher, conditional and thermodynamic equilibrium constants seems to be most
important criteria in this subject. In conventional method of determination of equilibrium constant, the concerned reactions were
allowed to reach equilibrium at a fixed temperature. Then the concentrations of different species involved in the reaction are
determined by various methods in order to calculate the equilibrium constants. Mole ratio titration in combination with
spectrophotometric methods are one the most popular and precise methods which used by chemists in order to study different
chemical equilibria such protonation and complexation equilibria. In conventional mole–ratio method, the temperature from start
to the end of experiments should be kept constant in order to achieve reliable results. In this research, we introduced nonisothermal mole–ratio titration measurements for determination stability constant of different complexation equilibria based on
chemometrics (hard modeling) method. The purposed method is based on the calculation of thermodynamic parameters (standard
enthalpy change and standard entropy change) instead of stability constant (K). The ability of purposed method was firstly
proved by a set of different mole-ratio simulated data. The spectral changes through mole-ratio experiments were simulated
against the amount of titrant while temperature changed as a predefined profile. Finally different model of complexation reaction
were examined practically. The spectrophotometric mole-ratio data in combination of temperature profile were fitted to
appropriate models. The values of thermodynamic parameters for each of equilibria systems were computed with a high degree
of precision and accuracy. Furthermore the calculated stability constant by using Van’t Hoff equation were compared by values
which directly determined by regular mole-ratio method at fixed temperature. The results indicated that the purposed method
could be safely applying for determination of stability constant from nonisothermal measurements.
Reference
[1]. D. J. Leggett (editor), Computational Methods for the Determination of Formation Constants, Plenum Press, 1985.
[2] A.E. Martell and R.J. Motekaitis, The Determination and Use of Stability Constants, Wiley-VCH, 1992.
[3]. M.maeder, Y. M. Neuhold, " Practical Data Analysis in Chemistry ", Newcastle, Australia September (2006).
Determination and Pre-concentration of Samarium (II) ions in Environmental Samples by Chemical Modification of
Yeast Cells
*
Farahnaz Zoriasatein, Homayon Ahmad Panahi, Nika Shakerin, Elham Moniri1
*
Department of Chemistry, Islamic Azad University, Central Tehran Branch, Iran
1
Department of Chemistry, Islamic Azad University, Varamin (Pishva) Branch, Iran
A method is reported for surface modification of Yeast cells. The yeast cell wall was modified by Procion red a known regent for
affinity chromatography. The resulting sorbent has been characterized by FT-IR, elemental analysis, thermogravimetric analysis
(TGA) and studied for the pre-concentration and determination of trace Sm(II) ions from environmental water samples. The
concentration of the metal ion in the sample after pre-concentration was determined by inductively coupled plasma atomic
emission spectroscopy (ICP-AES), The sorption capacity of functionalized resin was 6.5 mg.g−1. A recovery of 96% was
obtained for the metal ion with EDTA 0.1 M as eluting agent. The profile of Samarium uptake on the sorbent reflects good
accessibility of chelating sites in the modified yeast cells. The equilibrium adsorption data of Sm(II) on modified resin were
analyzed by Langmuir, Freundlich, Temkin and Redlich–Peterson models. The method was successfully applied for
determination of Samarium ions in sea water sample.
Reference
[1] Valko, M., Rhodes, C. J., Moncol, J., Chem. Biol. Interact. 2006, 160(1), 1–40.
[2] Lison, D., De Boeck, M., Verougstraete, V., Occup. Environ. Med. 2001, 58(10), 619–625.
[3] Yaman, M., Curr. Med. Chem. 2006, 13(21), 2513–2525.
[4] International Agency for Research on Cancer (IARC), Monographs on the evaluation of carcinogenic risks to humans, International Agency for Research on
Cancer, Lyon, 1991, 52, 363.
Spectrophotometric Determination of 3-Phenoxybenzaldehyde using2, 4- Dinitrophenylhydrazine
Zeinab Yazdani* and Mahboubeh Saeidi
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, Iran
There is increasing interest in pesticide transformation products, because they can be present at higher level than the parent
pesticide itself [1]. 3-phenoxybenzaldehyde is the transformation product of Fenvalerate. Fenvalerate is a synthetic pyrethroid
insecticide that is used to control flying and crawling insects in public health situations and animal houses. In addition to a high
insecticidal activity, it has a moderately long persistence in plants. It is rapidly hydrolyzed in alkaline media and one of the
products is 3- phenoxybenzaldehyde [2, 3]. In this work, a simple spectrophotometric method for determination 3phenoxybenzaldehyde is described. This method is based on the formation of yellow color compound between 3phenxybenzaldehyde and 2, 4-dinitrophenyl hydrazine. The maximum absorbance observed for this compound was at 437 nm.
Operational parameters such as concentration and volume of reagent, ionic strength and time of formation colored compound has
been studied. The optimized conditions developed were utilized for the determination of 3- phenoxy benzaldehyde. The detection
limit (for S/N=3) was 0.014 μg.mL-1 and the calibration curve was linear from 1 to 40 μg.mL-1 (r2=0.9986) .Relative standard
deviation of replicates analysis of 10μg.mL-1 3- phenxy benzaldehyde was 0.1%. The molar absorptivity of 5544 L.mol-1.cm-1and
Sandell,s sensitivity of 0.13μg.cm-2 were calculated. The applicability of the method was demonstrated by determining 3phenoxy benzaldehyde in Tap water.
Reference
[1] V. Andreu, Y. Pico′, Trends in Anal. Chem. 23(2004) 772
[2] R. Raghava naiad and R. v. Prabhakara Raju, Pestic. Sci. 44(1995) 163-166
[3] B. L. Swaroop, etal. J. Anal. Chem. 61(2006) 755-759
Kinetic-spectrophotometric determination of Osmium
Ehsan Mirparizi*, Abbas fazli nia, Nasim shams
Department of Chemistry, , Islamic Azad University, Neyriz Branch, P.O. Box 74915-311, Shiraz, Iran.
Corresponding Author E-mail: Ehsanmirparizi@yahoo.com
A simple, rapid and sensitive method is described for determination of trace amount of Osmium based on its catalytic on the
reduction of Methylene blue with ascorbic acid and oxidation of janus green with bromate. The reaction was monitored
spectrophotomtrically by measuring the decrease in absorbance of methylene blue at 665 nm and janus green at 618 nm .
Osmium (4-20 ppm and 20-220 ppm) was determine in the presence of methylene blue and ascorbic acid. The detection limit
was 0.9 ppm and relative standard deviation for ten replicate determination of 4, 20 and 180 ppm Osmium were1.9%, 2.4% and
2.9%, respectively. The influence of several foreign ions were studied and it was applied to determination of Osmium in natural
water. Osmium was determined in the presence of janus green and Potassium bromate in the rang of 0.5-5.0 ppm too. The
detection limit was 0.15 ppm and relative standard deviation for ten replicate determination of 1 and 5 ppm Osmium were 1.6%
and 2.9% , respectively.
Conductance study of complexation ability of Li +, Na+ , K+ and NH4+ cations with 15-Crown-5 in Acetonitrile-Methanol
binary solutions
G. H. Rounaghi*, E. Razavipanah, B. Deiminiat, F. Razghandi
Department of Chemistry, Faculty of sciences, Ferdowsi University of Mashhad, Mashhad - Iran
Since Pedersen’s discovery of crown ethers and their abilities to bind strongly with metal ions in 1967 [1], the study of crown
ethers has grown at an incredible rate. The syntheses of many different types of crown ethers have been documented in the
literature and their binding properties such as binding selectivity and strength toward a wide range of metal ions, nonmetal ions,
and neutral molecules have been investigated [2-4]. In this paper, complexation reactions of 15-crown-5 with Li+, Na+, K+ and
NH4+ cations in acetonitrile-methanol (AN-MeOH) binary mixtures were studied at different temperatures using conductometric
method to investigate how the selectivity and thermodynamics of complexation ractions between the alkali cations and the
macrocyclic ligand are affected by the nature of cations, ligands and also by the composition of acetonitrile-methanol binary
solution. The stability constants of the resulting 1:1 complexes were calculated from the computer fitting of the molar
conductance-mole ratio data at various temperatures. The results show that the selectivity order of 15C5 for the metal cations in
AN-MeOH binary system (mol% AN=50) at 25˚C is: Na+ > NH4+ ~ K+ > Li+. The values of thermodynamic parameters (DH°c
and DS°c) for formation of complexes were obtained from temperature dependence of stability constants of complexes using the
van’t Hoff plots. It was found that in most cases complexation reactions between Li+, Na+ , K+ and NH4+ cations with 15C5 are
enthalpy and entropy stabilized and these parameters are influenced by the nature and composition of the mixed solvents. The
enthalpy versus entropy plot of all thermodynamic data shows a fairly good linear correlation indicating the existence of
enthalpy-entropy compensation in the complexation reactions.
Refrence
[1] Pedersen, C.J., J. Am. Chem. Soc. 89 (1967) 7017.
[2] Liu, Y.C., Kuo, M.C., Lee, C.W., Liang, Y.R., Lee. G.H., Peng, S.M., Yeh, C.Y., Tetrahedron Lett. 49 (2008) 7223.
[3] Kawai, H., Kusuda, A., Mizuta, S., Nakamura, S., Funahashi, Y., Masuda, H., Shibata, N., J. Fluorine Chem. 130 (2009) 762.
[4] Coppola, C., Simeone, L., Trotta, R., De Napoli, L., Randazzo, A., Montesarchio, D., Tetrahedron 66 (2010) 6769.
Adsorptive stripping voltammetric determination of methyldopa on a multiwalled carbon nanotubes modified GCE
Behzad Rezaei*, Neda Askarpour
Department of Chemistry, Isfahan University of Technology, Isfahan 84156–83111, I.R. Iran
Methyldopa (MTD), chemically known as α-methyl-3,4-dihydroxyphenylalanine, is a catechol derivative (catecholamine).
Catecholamines are aromatic vic-diols and can be oxidized electrochemically to o-quinones. MTD is converted to a
methyldopamine and
α-methylnorepinephrine and widely used as an antihypertensive agent. MTD is a centrally acting αadrenoreceptor agonist, which reduces sympathetic tone and produces a fall in blood pressure. Various methods like
spectrophotometry, gas chromatography and chemiluminescence has been described in literature for determination of MTD [1,
2]. Electrochemical sensing based on carbon nanotubes (CNTs) is now a developed research field. The extraordinary
electrochemical features of CNTs make them suitable for use in Faradaic processes (e.g., the fast electrontransfer kinetics of
CNTs, due to the presence of edge plane graphite sites within the walls and at the ends of CNTs) or in non-Faradaic processes
(e.g., the large changes in conductance when CNTs can accept or withdraw charges from or to molecules in their nearest
chemical environment) [3]. So far, various papers based on modified electrode with CNTs are reported to enhance the electron
transfer rate. But, the objective of this research is to develop a MTD sensor using CNTs based on a strong adsorption of MTD on
the surface of CNT that can serve as a preconcentration step for highly sensitive adsorptive stripping measurement. In this study a
CNTs modified glassy carbon electrode (CNT-GCE) was developed to determine MTD. The study of electrochemical behavior
of MTD was investigated employing cyclic voltammetry, chronocoulometry, electrochemical impedance spectroscopy and
adsorptive differential pulse voltammetry. At the MWCNTs coated GCE, the remarkable peak current enhancement and negative
shift of peak potential occurred for MTD oxidation, compared with that of a bare GCE. As a result, MWCNTs strongly enhanced
the electron transfer rate of oxidation of MTD and the determination sensitivity of MTD was significantly improved. After
optimization of analytical conditions, this modified electrode was used as a sensor for determination of MTD in different real
samples with satisfactory results.
Reference
[1] T.E. Young, B.W. Babbitt, and L.A. Wolfe, J. Org. Chem. 1980, 45, 2899–2902.
[2] A. Afkhami, D. Nematollahi, T. Madrakian, L. Khalafi, Electrochim. Acta 2005, 50, 5633–5640.
[3] P.Yanez-Sedeno, J. Riu, J.M. Pingarron, F. Xavier Rius, Trends in Anal. Chem. 2010, 29, 939–953.
Electrochemical synthesis of pyrimido [2,1-b] [1,3] benzothiazol-2-ones using catechol derivatives and methylthiouracil
M.Arab Cham jangalia, M.bakherada, M.Ameria*
a: Faculty of Science College of Chemistry, Shahrood University of Technology, Shahrood, Iran
In recent years it has been proved that electro-synthesis is an efficient reagent-free method for selective synthesis of biological
and pharmaceutical compounds [1]. On the other hand, Michael addition reaction, as one of the effective organic reactions, has
been shown its importance during last years [2]. Herein, following on the previous works on electrochemical generation of
quinones in the presence of various nucleophiles [3], we report the electrochemically oxidation of catechol in the presence of
methylthiouracil as a possible nucleophile.the catechol derivatives react with through Michael addition reaction by applying
controlled potential coulometery at (0.15 M, PH=7) water/acetonitrile (90/10) solution using cyclic voltammetry and controlledpotential coulometry. The results indicate the formed heterocyclic product was identified by IR, HNMR and TLC and melting
point.
O
H3C
N
H
CH3
OH
NH
S
OH
OH
N
+
O
N
H
OH
S
Reference
[1].T. Hvdlicky, D. A. Frey, E. Larry, Green Chem. 1 (1999) 57
[2].D. Nematollahi, A. Amani, E. Tammari, J. Org. Chem.72 (2007) 3646
[3].D. Nematollahi, E. Tammari, J. Org. Chem. 70 (2005) 7769.
.
Headspace solid-phase microextraction of Alkanes from aqueous media by electrochemically deposited carbon
nanotube/polypyrrole composite on a tungsten fiber
V.Shahinfard*, M.R.Vardast, N.Samadi
Department of chemistry Faculty of science Urmia University Urmia,Iran
v.shahinfard@gmail.com
A novel headspace solid-phase microextraction (HS-SPME) method using a tungsten wire electrochemically coated with
oxidized multiwalled carbon nanotubes–polypyrrole composite (MWCNTs–PPy) was used in the gas chromatographic (GC)
determination of Alkanes in aqueous samples. The composite coating did not swell in organic solvents nor did it strip off from
the substrate. It was also highly stable and extremely adherent to the surface of the tungsten fiber. The effects of various
parameters on the efficiency of SPME process such as extraction time, extraction temperature, desorption time, stirring speed,
and desorption temperature were studied. Under optimized conditions, the detection limits for the Alkanes varied between 0.01
and 0.2 ngmL−1. relative standard deviations for various Alkanes at 50 ngmL−1 concentration level (N= 6) using a single fiber
were 1.94-4.43% . The fiber-to fiber RSD% (N= 3) was 3.51-6.73% at 50 ngmL−1. The linear ranges varied between 0.05 and
500 ngmL−1.
Reference
[1] P. Olszowy, M. Szultka, T. Ligor, J. Nowaczyk, B. Buszewski J. chromatog. B 878 (2010) 2226-2234.
[2] A. Mohammadi, Y. Yamini, N. Alizadeh, J. chromatog. A 1063 (2005) 1.
[3] A. Mohammadi, A. Ameli, N. Alizadeh, Talanta. 78 (2009) 1107-1114.
[4] N. Alizadeh, H.Zarabadipour, A. Mohammadi. A. Chimica Acta 605 (2007) 159-165.
[5] [A. Mollahosseini, E. Noroozian A. Chimica Acta 638 (2009) 169-174] .
[6] [L. Chen, W. Chen, C. Ma, D. Du, X. Chen Talanta 84(2011) 104-108].
[7] [B.J.G. Silva, F.M. Lancas, M.E.C. Queiroz J. Chromatog. A 1216 (2009) 8590-8597].
[8] [A. Karimi, N. Alizadeh, Talanta 79 (2009) 479-485].
Investigation of contaminant potential and neutralization methods of waste water associated with hydrometallurgy plant
of Sarcheshmeh copper complex, in order to find suitable methods for pollution prevention
1
Jaber Saeed1,2, Mohammad Mirzaei1,*, Reza Naseh2, Ali Esmaeilnejad2
Department of Chemistry, Faculty of Science, Shahid Bahonar University, Kerman, I.R.Iran
2
R & D Division of Sarcheshmeh Cupper Complex, Sarcheshmeh, Kerman, I.R.Iran
E-mail: m_mirzaei@mail.uk.ac.ir
According to the volume of fluid supply tanks, in heavy rainfalls time, the excess fluid of hydrometallurgy operations which has
been entered in system during rainfall is released into the Shoor river of Sarcheshmeh copper complex. The excess fluid has a
high acidity and contains heavy metals. In addition to environmental dangers, the releasing of this fluid into the river decreases
the pH of river’s water severely. It causes a decrease in the efficiency of the Sarcheshmeh copper complex refinery. Also, due to
acidic condition of water, it may ruin the dam reversal water equipments. In this project, three methods of industrial water
refinement have been investigated in four various pH values. These three methods were using of the lime, using of the caustic
soda, and using of caustic soda and lime combination[1]. The pH values were 7, 8, 9, and 10. Also, alongside these three
methods, the effects of covering agents and clotting materials have been studied. After refinement steps, because of determination
of the water type, refined water was characterized by ICP analysis for elemental analysis and anions analysis. In addition to
adjustment of pH value, we decreased the concentration of the most of poisonous elements until below allowed limit in drinking
water in the three applied methods. Also, we could separate the released valuable metals by sedimentation process. They can be
recycled from the sediments. Based on the results, the best and the most economical method was the using of lime in the pH
value of 8.
Reference
[1] H. Chen, X. Ma, H. Dai, Cement and Concrete Composites, 32 (2010) 436-439.
Determination of Mo(VI) in the presence of calcon by using of differential pulse voltammetry in real samples
S. M. Ghoreishi*, S. Mazaheri
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, I. R. Iran
E-mail: s.m.ghoreishi@kashanu.ac.ir
Molybdenum is an essential trace for both plants and animals, including humans. In animals, it is a component of xanthin oxidase
and other redox enzymes [1]. In plants, this element is necessary for the fixation of atmospheric nitrogen by bacteria at the start
of protein synthesis [2]. Pure Mo finds important applications as a catalyst in a variety of petrochemical processes [3]. It appears
to be toxic when its concentration in plants is higher than 5µgg-1. In human serum Mo(VI) concentration was reported lower than
1µgL-1 [4]. Azo dyes contain one or more azo groups (–N=N–), and each one of them is attached to at least one aromatic group
are among the most widely used synthetic dyes [5]. 1- (2- hydroxy-l-naphthylazo)-2-naphthol-4-sulphonic acid namely calcon is
one of the azo dyes that we used as a chelate to form complex for determination of Mo(VI). In this work a very sensitive and
selective metode for the determination of Mo(VI) by differential pulse voltammetry is described. This metod is based on the
formation of Mo(VI) electroactive complex with calcon. The optimum operating conditions are the following: buffer solution
(pH 2.0) as the supporting electrolyte, a ligand concentration of 2x10-6 M, scan rate 0.05 Vs-1, accumulation time, (120 S), pulse
height (0.05 V), pulse width (0.06 S) are optimized. The oxidation peak of the complex is proportional to the Mo(VI)
concentration in the range of 1.6x10-9 to 2.2x10-4 M. The DPvoltammograms of Mo(VI) complex show three linear relations
between peak current and concentration of ligand-Mo(VI). The detection limit of Mo(VI) is 3.4x10-10 M. The influence of foreign
ions on the Mo(VI) determination is also studied. The results are shown more stability of Mo(VI) to some of the metals. This
method is tested on artificial solution and also used it for the determination of Mo(VI) in real samples.
Reference
[1] R.Garg, M.K.Saini, N. Fahmi, R.V. Singh, Transit. Metal chem.. 31(2006)363
[2] C.Neunhauserer, M.Berreck, H.Insam, Water Air soil Pollut. 128(2001)85
[3] S.Goldberg, S.M.Lesch, D.l.Suarez, soil Sci. Soc. Am. J. 66(2002)1836
[4] P.Schramel, I.Wendler, Fresenius J.Anal. Chem. 351(1995)567
[5] C. Regina Costa, F. Montilla, E. Morall ◌n, P. livi ,Electrochim. Acta 54 (2009) 7048–7055
Selective and sensitive detection of dopamine in the presence of uric acid and ascorbic acid by CdS-nanoparticles
modified carbon paste electrode
N. Soltania, , N. Tavakkolib, N. Ziaieb*, F. Davarc
Department of Chemistry, Payam Noor University, Shahin Shahr Branch, Isfahan
Department of Chemistry, Payam Noor University, Isfahan,
Nasrin_soltani2056@yahoo.com
Dopamine (DA), uric acid (UA), and Ascorbic acid (AA) are of great biomedical interest in playing determining roles in human
metabolism as well as the central nervous and renal systems [1]. DA coexists with ascorbic acid and uric acid in the extra cellular
fluids of central nervous system and serum in mammals. The concentrations of AA and UA are much higher (100–1000 times)
than that of DA in body fluids. It would cause the overlapped voltammetric responses and difficultly discriminating signal in
electrochemical analysis. Therefore, the sensitivity and selectivity are very important consideration as determining DA in the
presence of AA. Various electrochemically and chemically modified electrodes have been fabricated to resolve the voltammetric
peaks of UA, DA and AA [2]. Modification of carbon paste electrodes using nano-materials, can greatly improve the physical
characteristics of the fabricated sensors, such as their sensitivity, abrasion resistance and causticity resistance with respect to nonmodified carbon paste electrodes [3]. In this study, a CdS modified carbon paste electrode was created to simultaneously
characterize ascorbic acid (AA), dopamine (DA), and uric acid (UA) levels via cyclic voltammetry (CV) and differential pulse
voltammetry (DPV). In the simultaneous detection of the three aforementioned analytes using DPV, the electrochemical potential
differences among the three detected peaks were 180 mV (AA to DA), 110 mV (DA to UA), and 290 mV (AA and UA),
respectively. The calibration curves for DA, UA and AA were obtained in the range of 2.5 ×10-5 -.1.0 ×10-4 M, 1.0 ×10-6 -.1.0
×10-4 M and 5.0 ×10-6 5.0 ×10-3 M, respectively. The lowest detection limits (S/N = 3) were 2.35 ×10-7 , 4.28 ×10-7 and , 7.06
×10-7 M for DA, UA and AA, respectively. Method was applied to the determination of DA, UA and AA in real samples.
Reference
[1] M. R. Moghadam, Sh. Dadfarnia, A. M. Haji Shabani, P. Shahbazikhah, Anal. Biochem. 410 (2011) 289–295.
[2] H.R. Zare, N. Rajabzadeh, N. Nasirizadeh, M.M. Ardakani, J. Electroanal. Chem. 589 (2006) 60–69.
[3] M. Pandurangachar, B. E. Kumara Swamy, B. N. Chandrashekar , O. Gilbert, B. S. Sherigara, Journal of Molecular Liquids 158 (2011) 13–17.
The effects of sulfonate anion dopants on the conductivity and response behavior of nanostructure polypyrrole gas
sensors
Sajad Pirsa and Naader Alizadeh *
Department of Chemistry, Factually of Science, Tarbiat Modares University, P.O.Box, 14115-175, Tehran, Iran
E-mail:aliazden@modares.ac.ir
Five sulfonate anions, including HSO3-, para toluene sulfonate (PTS), dodecyl benzene sulfonate (DBS), dodecyl sulfonate (DS)
and 5-sulfo salicylate (SS) were used to dope polypyrrole film. Sulfonated doped polypyrrole (PPy-S) gas sensor have been
prepared by polymerization of pyrrole on surfaces of the polystyrene fibers in the presence of an oxidizing agent. The presence of
the dopants in the conducting polymer matrix was verified by FTIR spectroscopy and morphology of the resulting PPy-S was
analyzed by scanning electron microscopy (SEM). The effects of the dopant type and concentrations on the conductivity and
response patterns of the PPy-S sensors to the different gas were studied. The PPy-S gas sensors had demonstrated fast response
time (<1s). The sensitivity of the PPy-S gas sensors for various molecules was also reported [1, 2].
Reference
[1] S.Pirsa, N. Alizadeh “Design and fabrication of gas sensor based on nanostructure conductive polypyrrole for determination of volatile organic solvents” Sensors
and Actuators B 147 (2010) 461–466
[2] S.Pirsa, N. Alizadeh “Dodecylsulfate-Doped Conducting Nano porous Polypyrrole Gas Sensor Coupled to a Gas Chromatograph for Speciation and
Determination of Some Aromatic Hydrocarbons in Water Using Dispersive Liquid–Liquid Microextraction Method” IEEE sensor accepted for publication 2011
Development of a novel and simple ionic-liquid microextraction method for sensitive determination of terazosin in
pharmaceutical and biological samples
Kourosh motevalli*
Department of Applied Chemistry, Faculty of Technical & Engineering, Islamic Azad University - South Tehran Branch, Tehran, Iran, P. O. Box:
11365-4435.
The present work describes a novel, efficient and environmentally friendly sample preparation method based on the application
of pyridinium ionic liquid (IL) as a microextraction solvent. Hydrophobic 1-Hexylpyridinium hexafluorophosphate [Hpy][PF6]
ionic liquid was used as the extractor and terazosin as the model compound. [Hpy][PF6] was employed as the extraction solvent
due to some physicochemical properties like high hydrophobicity, water immiscibility and quite viscosity. The performance of
the microextraction method was improved by introducing a common ion of pyridinium IL into the sample solution. Due to the
presence of the common ion, the solubility of IL was increased and the volume of the settled IL-phase was not influenced by
variations in the ionic strength (up to 30% w/v). After preconcentration step, the enriched phase was introduced to the
spectrofluorimeter for the determination of terazosin. The obtained results revealed that this system did not suffer from the
limitations of that in conventional ionic-liquid microextraction. Under optimum experimental conditions, the proposed method
provided a limit of detection (LOD) of 0.027 µg L-1 and a relative standard deviation (R.S.D.) of 2.4%. The present method was
successfully applied to terazosin determination in actual pharmaceutical formulations and biological samples. Considering the
large variety of ionic liquids, the proposed microextraction method earns many merits, and will present a wide application in the
future.
Reference
[1] R. Mudiyala, A. Ahmed, J Am Geriatr Soc, 51 (2003) 424-426.
[2] H. Lepor, K. Jones, W. Williford, J Urology, 163 (2000) 1134-1137.
[3] H.H. Abdine, F.A. El-Yazbi, S.M. Blaih, R.A. Shaalan, Spectrosc Lett, 31 (1998) 969-980.
[4] C.Q. Jiang, M.X. Gao, J.X. He, Anal Chim Acta, 452 (2002) 185-189.
[5] R.A. Silva, A.N. Masi, X-Ray Spectrom, 36 (2007) 279-283.
[6] P.Y. Cheah, K.H. Yuen, M.L. Liong, J Chromatogr B, 745 (2000) 439-443.
[7] A.P. Zavitsanos, T. Alebic-Kolbah, J Chromatogr A, 794 (1998) 45-56.
Quantitative Structure–activity relationship study of new anti-tuberculosis agents derived from oxazoline benzyl esters
Zahra Garkani-Nejad*, Mahboobeh Jabbari
Chemistry Department, Faculty of Science, Vali-e-Asr University, Rafsanjan, Iran
E-mail:garakani@vru.ac.ir
At the present work, QSAR analysis for modeling the anti- tuberculosis activity screening of a series of oxazoline benzyl ester
derivatives were carried out using Chemometrics methods. First, a large number of descriptors were calculated using Hyperchem
[1], Mopac [2] and Dragon [3] softwares. Then, the SPSS/PC [4] software package was used for the model generation and a
suitable number of descriptors were selected using multiple linear regression (MLR) technique. It is clear that many MLR models
will result using stepwise multiple regression procedure. Among them, we have to choose the best one. It is common to consider
statistical parameters for this purpose. These parameters are the number of descriptors, correlation coefficient (R) for training and
prediction sets, Standard error (SE) for training and prediction sets and F statistic. A reliable MLR model is one that has high R
and F values, low SE and least number of descriptors. In addition to these, the model should have a high predictive ability. In the
best selected models for two GAST and GAS media, correlation coefficient (R) for training set was 0.833 and 0.824, and for
prediction set was 0.932 and 0.935, respectively. Obtained results indicate ability of our models for prediction of antituberculosis activity of oxazoline benzyl ester derivatives. Also, selected descriptors in the models show that topological
parameters are the most parameters that affect on anti- tuberculosis activity.
Reference
[1] HYPERCHEM pro 8.0.5. www.softarchive.net.
[2] WINMOPAC 7.21, (1990).
[3] DRAGON software, version 3, Todeschini R., consonni V., pavan M. (2003).
[4] SPSS, version 16 (2008), www.spsscience.com.
Spectrophotometric study of the interaction between Cd(II)- Schiff base complex with anions in non-aqueous media and
their application in optical sensors
Sorab ershad*, Saharnaz Mehrkia
Chemistry Department, Payame Noor University, 19395-4697, Tehran, I. R. of Iran.
* Email: s_ershad@pnu.ac.ir
New optode membranes for the sensitive and selective determination of iodid ion based on a change in the absorption spectrum
of a polymer film is proposed. Interaction between new Schiff-base metal complex (Cd L) with various anions such as Br-,Cl-, F-,
SO42-, NO2-, PO43-, SCN-, NO3-,I- and CO32- in acetonitrile solution was studied by spectrophotometric method. The results have
exhibited formation of new and selective products between Schiff-base complexes and iodide ion. Membranes composed of
plasticized poly vinyl chloride (PVC), Cd (II)-Schiff-base complex as a chromoionophore and plasticizers were prepared on the
glass slide. The influence of some parameters such as pH, time, nature plasticizers and membrane composition on the response of
sensors were investigated and membranes with optimum composition were selective. A linear reponse was attained in the Iconcentration range and calculated limit of detection. Optical sensors based on Cd(II)-Schiff base complex (Cd L) showed a
reproducible result with relative standard deviation (RSD) of 4.0 % and response time of ~ 5 Min. The optode membrane has
been successfully applied to determine the iodid ion in real sample.
Reference
[1] X. Liu, Y.Qin, Anal. Sci., 2008, 24, 1151.
[2] S. Ershad, L. A. Sagathfroush, G. Karim-Nezhad, Anal. Sci ., 2009 , 25, 665.
[3] A. A. Ensafi, M. Bakhshi, Sens. Actuators B., 2003, 96, 435.
[4] N. Ye, K. Wygladacz, E. Bakker, Anal. Chim. Acta., 2007 , 596, 195.
[5] S. M. Marxer, M. H. Schoenfisch, Anal.Chem., 2005, 77, 848.
[6] J. Janata, M. Josowicz, Anal.Chem., 1998, 70, 179R.
Tm3+ PVC membrane sensor based on N,N'-bis(pyridine-2-carboxamido)-2-aminobenzylamine as ionophore
Somayeh Harimi*, Hassan Ali Zamani
Department of Applied Chemistry, Quchan Branch, Islamic Azad University, Quchan, Iran
A Tm(III) ion-selective membrane sensor based on N, N'-bis(pyridine-2-carboxamido)-2-aminobenzylamine(BPCA) as
ionophore in membrane composition was prepared. The influences of different parameters like the membrane composition and
pH of the sample solution on the potentiometric response of the sensor were also studied. Interestingly, the electrode performance
provided a very good response for Tm3+ in a wide concentration range (from 1.0×10-6 to 1.0×10-2 mol L-1) with a detection limit
of 6.3 × 10-7 mol L-1[1] and a slope of 20.4 ± 0.3 mV per decade of Tm3+ concentration. The optimum responses were found with
membrane composition of 30% PVC, 66% nitrobenzene (NB) as solvent mediator, 2% BPCA and 2% sodium tetraphenyl borate
(NaTPB). In addition, it possessed a fast response time of about 5 s and it functioned in the pH range of 2.8-8.3 with a usage of at
least 2 months without observing any deviations. The proposed electrode showed an excellent selectivity[2] for Tm3+ over a
broad variety of alkali, alkaline earth, transition and heavy metal ions. In order to investigate the sensors analytical applicability,
it was tested as an indicator electrode in potentiometric titration of Tm(III) with standard EDTA.
Reference
[1] E. Bakker, P. Bühlamnn, E. Pretsch, Chem. Rev. 97 (1997) 3083.
[2] Y. Umezawa, K. Umezawa, H. Sato, Pure Appl. Chem. 67 (1995) 507.
Effect of Hydrogen Peroxide on the Electrochemical Behaviors of Lead Dioxide Nanoparticles
Hassan Karami1,2*, Farzaneh Firoozi1
Department of Chemistry, Payame Noor University, 19395-4697, Tehran, I.R. of Iran
2
Nano Research Laboratory, Department of Chemistry, Payame Noor University, Abhar, I.R. of Iran
1
This works deals with investigations about synthesis of lead dioxide nanoparticles and the effect of hydrogen peroxide on their
electrochemical behaviors. Based on the previous reports, cyclic voltammetry method can be used as a synthesis technique and a
powerfull method to study the effect of additives on the electrochemical behaviors of eelectroactive materials [1,2]. In the present
method, lead dioxide nanoparticles were synthesized by direct oxidation of lead substratye as working electrode in 1 M sulfuric
acid by cyclic voltammetry method. To find the optimized condeitions of the synthesis, the amounts of potential scan rate and
sulfuric acid concentration were varied and the morphology and particles sizes of the samples were studied by sacnning electron
microscopy (SEM). The experimental results showed that the optimized potential scan rate and sulfuric acid concentration are 70
mV.s-1 and 1 M, respectively. The effect of hydrogen peroxide on the electrochemical behaviors of the synthesized lead dioxide
nanoparticles was investigated in sodium hydroxide and sodium sulfate electrolytes. Initial studies showed that the lead dioxide
nanoparticles have more reversibility in sodium sulfate electrolyte so that, this electrolyte was selected for next studies. The
effect of hydrogen peroxide concentration was inevtigated on electrochemical parameters of lead dioxide nanoparticles including
anodic peak current ( I pa ), cathodic peak current ( I cp ), anodic peak potential ( E pa ) and cathodic peak potential ( E cp ). Hydrogen
peroxide makes more reversibility for lead dioxide redox peaks and also, it cause to shift cathodic and anodic potentials toward
positive and negative potentials, respectively. These concepts mean that hydrogen peroxide makes easier reduction of lead
dioxide and oxidation of lead sulfate. On the other hands, anodic and cathodic peak currents are decreased when hydrogen
peroxide concentration is increased. Based on this result, hydrogen peroxide acts as inhibitor for redox reaction of lead dioxide
nanoparticles. Finally, the effects of solution temperature and potential scan rate were investigated on the electrodegradation of
hydrogen peroxide. Based on the obtained results, use of high temperatures causes to increase degradation rate of hydrogen
peroxide. At 70ºC and more, hydrogen peroxide is completely decomposed during one cycle of cyclic voltammetry. Based on the
obtaied results, hydrogen peroxide concentration can be determined based on decreasing lead dioxide redeox peaks. Therefore,
Lead dioxide nanostructured electrode was used as amerometric sensor for the determination of hydrogen peroxide in aquas
solutions. Based on the obtained results, cyclic voltammetry can be used as a simple and reliable method to synthesize lead
dioxide nanoparticles. Hydrogen peroxide affect considerably on the redox propeties of lead dioxide nanoparticles. Therefore,
lead dioxide nanoparticles can be used as sensing agent of hydrogen peroxide in aquas solutions.
Reference
[1] H. Karami, A. Yaghoobi and A. Ramazani, Int. J. Electrochem. Sci. 5 (2010) 1046.
[2] H. Karami and A. Yaghoobi, J. Clust. Sci. 21 (2010) 725.
Electrochemical sensor for high sensitive determination of hydrogen peroxide based on Prussian blue film modified
nanoporous gold electrode
Seyran Ghaderi, Masoud Ayatollahi Mehrgardi*
Department of Chemistry, University of Isfahan, Isfahan81746-73441, Iran
E-mail: m.mehrgardi@chem.ui.ac.ir
Development of high sensitive, selective, accurate and rapid method for hydrogen peroxide (H2O2) determination is a very
important analytical task, because it is a byproduct of several oxidase catalyzed reactions and an essential mediator in industrial,
clinical, pharmaceutical and many other fields[1]. Electrochemical sensors have been shown to be the most convenient, sensitive
and selective tools for H2O2 monitoring. Most of the modified electrodes for determination of H 2O2 are based on enzymes but
there are some practical problems related to the use of enzyme in these analytical devices[2]. During recent years, there has been
growing interest in using nonenzymatic modified electrodes[3]. Nanotechnology has recently become one of the most exciting
forefronts in analytical chemistry. The nanoporous gold (NPG) is an emerging material for use invarious applications, due to its
unique properties: high surface-to-volume reaction, high stability, excellent conductivity and biocompatibility[4]. In this study, a
sensor for determination of hydrogen peroxide based on its electrocatalytic reduction on Prussian blue (PB) modified NPG
electrode has been investigated. The NPG was prepared in two steps; in the first step, the gold substrate is anodized in phosphate
buffer (pH 7.4). Afterwards, ascorbic acid is used as a reducing agent to reduce gold oxide to metallic gold. Then prussian blue
film electrodeposited onto NPG electrode. The redox peaks related to the PB modified electrode were changed by the addition of
H2O2; increasing of cathodic peak current and decreasing of anodic compartment is indicative of the electrocatalytic reduction of
H2O2. The cyclic voltammograms of modified electrode in the KCl solution is directly proportional to the scan rate; suggesting
that the PB is adsorbed on the surface of electrode. This electrode exhibited sufficient electrochemical stability, high sensitivity
and selectivity in detecting hydrogen peroxide in the presence of oxygen and other interferents in compare with other PB based
H2O2 sensors.
Reference
[1] H. Notsu, T. Tatsuma, A. Fujishima, J. Electroanal. Chem. 2002, 523, 86.
[2] V. G. Gavalas, N. A. Chaniotakis, Anal. Chim.Acta 2001, 427, 271.
[3] J. Zhang, J. Li, F. Yang, B. Zhang, X. Yang, J. Electroanal. Chem. 2010, 638, 173.
[4] X. L. Luo, A. Morrin, A. J. Killard, M. R. Smyth, Electroanalysis 2006, 4, 319.
Prediction of retention times for some pesticides in liquid chromatography by using linear and nonlinear chemometric
methods
Saeid Khodadoust*
Young Researchers Club, Branch Dehdasht, Islmic Azad University, Dehdasht, Iran
*E-mail: saeid.kh64@gmail.com
Pesticides are substances with high toxic effects and persistence in the environment have been widely used in agriculture
throughout the world [1]. The quantitative structure–retention relationships (QSRR) [2] method is employed to predict the
retention times (RTs) of pesticides by molecular descriptors which were calculated by Dragon software. After the calculation
molecular descriptors for all molecules, a suitable set of molecular descriptors were selected by using genetic algorithm (GA) and
then the data set was randomly divided into training and prediction set. The selected five descriptors were used to build QSRR
models with multi-linear regression (MLR) and artificial neural network (ANN) modeling techniques [3,4]. The ANN models
(including multilayer perceptrons (MLP) and generalized regression neural network (GRNN)) were build and optimized with
intelligent problem solver (IPS) in Statistica 7.1software. Both linear and nonlinear models show good predictive ability, of
which GA-GRNN model demonstrated a better performance than that of the GA-MLR and GA-MLP models. The root mean
square error of cross validation (RMSECV) of the training and the prediction set for the GA-GRNN model was 1.345 and 2.810,
and the correlation coefficients (R) were 0.955 and 0.927 respectively, while the square correlation coefficient of the cross
validation (
) on the GA-GRNN model was 0.951, revealing the reliability of this model. The resulting data indicated that
GA-GRNN could be used as a powerful modeling tool for the QSRR studies.
Reference
[1] W.H.O. (World Health Organization), Environ. Health Criteria, 63, Geneva 1986.
[2] R. Kaliszan, Structure and Retention in Chromatography. A Chemometric Approach, Harwood Academic Publishers, Amsterdam, 1997.
[3] S. Riahi, M.R. Ganjali, E. Pourbasheer, P. Norouzi, Chromatographia 67 (2008) 917–922.
[4] J. Zupan, J. Gasteiger, Neural Networks in Chemistry and Drug Design, Wiley-VCH Verlag, Weinheim, 1999.
Quantitative structure activity relationship (QSAR) studies of some phthalimide analogues as HIV-1 integrase inhibitors
Saeid Khodadoust*, Azarmidokht sheini, Fereshteh Zarghampour, Zahra Andikaey
Department of Chemistry, Yasouj University, Yasouj. Iran
*E-mail: saeid.kh64@gmail.com
Human immunodeficiency virus type 1 (HIV-1) integrase (IN) is a potential target for anti–HIV therapy, it is essential enzyme
required for replication of acquired immunodeficiency syndrome (AIDS) virus [1]. Phthalimide derivatives act against HIV-IN
and thus have the potential to become a part of an anti-HIV drug regimen. Thus a quantitative structure activity relationship
(QSAR) was performed on these phthalimide analogues based inhibitors of HIV-IN to understand the structural features
influencing the affinity of these inhibitors towards the enzyme. In the present study, QSAR analysis for selected phthalimide
analogues [2] was carried out by means of different software. Then stepwise multiple linear regression (MLR) was applied to
modeling and prediction of the potential inhibitory activity of tricyclic phthalimide derivatives as inhibitors of HIV-1-IN. These
compounds were randomly divided into training and test sets, that each of them consisting of 31 and 8 molecules respectively. In
the next step the MLR method was employed to screening descriptors and construction of a QSAR model for training set. Then
the prediction power of obtained models was evaluated by test set. Among all possible multiple combination of descriptors
parameters obtained for modeling HIV-1-IN inhibitory activity of these compounds, the best selected model consisting of five
descriptors. The statistical parameters of obtained model were R=0.94, F=36.34, SE=0.213 for training set and R=0.92, F=32.46,
SE=0.231 for the test set respectively. To further validate the model, cross-validation test and SPRESS were used to the credibility
of obtained model. The obtained results indicate the suitability of this model in prediction phthalimide analogues as anti HIV-1
activities.
Reference
[1] Barre-Sinoussi, F.; Chermann, J.C.; Rey, F.; Nugeyre, M.T.; Chemaret, S.; Gruest, J.; Daugust, C.; Axler-blin, C.; Byun-Vezinet, F.; Rouzioux, C,; Rozenbaum,
W.; Montagnier, L. Science 1983, 220, 868.
[2] Verschueren, W. G.; Dierynck,I.; Amssoms,K.I.E.; Hu,L; Boonants,P.M.J.G.; Pille,G.M.E.; Daeyaert,F.F.D.; Hertogs,K.; Surleranx, D.L.N.G.; Wigerinck,
P.B.T.P.J. Med. Chem 2005, 48, 1930.
Determination of N-methylcarbamate insecticides in water samples using dispersive liquid–liquid microextraction and
HPLC with the aid of experimental design and desirability function
Saeid Khodadoust*, Mohammadreza Hadjmohammadi
Department of Chemistry, University of Mazandaran, Babolsar, Iran.
*E-mail address: saeid.kh64@gmail.com
Pesticides having different structures and biological activities are widely used for agricultural and non-agricultural purposes
throughout the world. Due to their widespread use, pesticides need to be determined in various environmental, such as soil, water
and air [1]. A rapid and simple method for the extraction and preconcentration of N-methylcarbamates (NMCs) (carbofuran,
carbaryl and promecarb) in water samples using dispersive liquid–liquid microextraction (DLLME) [2,3] using chemometrics
was developed. Influence variables such as volume of extracting (CHCl3) and dispersing solvents (ACN), pH and ionic strength,
extraction time and centrifugation time and speed were screened in a 27–4 Plackett–Burman (P-B) design was investigated. The
significant variables were optimized by using a central composite design (CCD) combined with desirability function (DF)
[4]. At optimum conditions values of variables set as 126 µL chloroform, 1.5 mL acetonitrile, 1 min extraction time, 10 min
centrifugation at 4000 rpm min-1, natural pH, 4.7 % (w/v) NaCl, the separation was reached in less than 14 min using a C18
column and an isocratic binary mobile phase (acetonitrile: water (50:50 v/v)) with flow rate of 1.0 mL min−1. At optimum
conditions method has linear response over 0.001-10 µgmL-1 with detection limit between 0.0001-0.0005 µgmL-1 with relative
standard deviations (RSDs) in the range 2.18-5.06 % (n=6).
Reference
[1] W.H.O. (World Health Organization), Environ. Health Criteria, 63, Geneva 1986.
[2] M. Fernández, Y. Pico´, J. Mañes, J. Chromatogr. A 871 (2000) 43-56.
[3] M. Rezaee, Y. Assadi, M.R. Milani Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, J. Chromatogr. A 1116 (2006) 1-9.
[4] E.C. Harrington, The desirability function, Ind. Qual. Control 21(1965) 494-498.
Reductive determination of sulfite at electroless plated bi-metallic copper-palladium electrocatalyst modified aluminum
electrode (Cu/Pd-Al)
H. Dastangoo*, R. Rahmati
Electroanalytical Chemistry Laboratory, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
Sulfite is one of the oldest and most widespread preservative, antibacterial and antioxidant compound and controller agent of
enzymatic reactions during production and storage, present naturally or as additive in food and beverages. Sulfite occurrence in
the food chain is not without effect on the human health. For example, the bioavailability of some vitamins is reduced in the
presence of sulfite in food; therefore it is important that sensitive and accurate methods be available for the determination of
sulfite ion. The reported analytical methods for sulfite assay mainly include spectrophotometry [1], chemiluminescence [2],
chromatography [3] and enzymatic techniques [4]. However, the majority of these methods need extensive sample pretreatment
and reagent preparation. In this sense, the development of electrochemical methods has been of considerable interest, because
their use involves several advantages such as rapid response, high selectivity and low cost. In this work, electroless modification
of the palladized aluminum electrode (Pd-Al) with metallic copper particles via a chemical process was carried out effectively by
immersing of the Pd-Al surface in cupric solution. The electrocatalytic reduction of sulfite by using Cu/Pd-Al modified electrode
was investigated by cyclic voltammetry; note that commonly electroanalytical methods rely on the oxidation of sulfite at
polarized electrodes. As analytical application of the Cu/Pd-Al modified electrode, differential pulse voltammetry (DPV) method
was used for the determination of sulfite. The optimum conditions of Cu/Pd-Al electrode responses for electroreduction of sulfite
including amount of palladium loading, copper coverage, type of supporting electrolyte and its pH were determined. Under the
optimized conditions, DPV responses exhibited a linear dependency on the concentration of sulfite in range of 10-1000 mM. This
modified electrode possesses advantages such as high sensitivity, good repeatability, wide range of linear response, good
chemical and mechanical stability, and simple fabrication.
Reference
[1] L.Q. Yin, D.X. Yuan, M. Zhang, Chin. Chem. Lett. 21 (2010) 1457.
[2] M.V. Navarrro, M.R. Payán, M.A.B. López, R. Fernández-Torres, M.C. Mochón, Talanta 82 (2010) 2003. [3] S. Theisen, R. Hänsch, L. Kothe, U. Leist, R.
Galensa, Biosen. Bioelectron 26 (2010) 175.
[4] M.K. Sezgintürk, E. Dinçkaya, Talanta 65 (2005) 998.
A novel solid-phase microextraction using coated fiber based sol–gel technique using poly(ethylene glycol) grafted multiwalled carbon nanotubes for determination of BTEX in water samples with gas chromatography–flam ionization detector
Ali Sarafraz-Yazdi*, Amirhassan Amiri, Gholamhossein Rounaghi, Hossein Eshtiagh Hosseini
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Iran
In this study, poly(ethylene glycol) (PEG) grafted multi-walled carbon nanotubes (PEG-g-MWCNTs) were synthesized by the
covalent functionalization of MWCNTs with hydroxyl-terminated PEG chains. For the first time, functionalized product PEG-gMWCNTs used as selective stationary phase to prepare the sol–gel solid-phase microextraction (SPME) fiber in combination
with gas chromatography-flame ionization detector (GC–FID) for the determination of ultra-trace levels of Benzene, Toluene,
Ethylbenzene and O-Xylene (BTEX) in real water samples. The PEG-g-MWCNTs were characterized by Fourier transform
infrared spectra and also Thermo-gravimetric analysis, which verified that PEG chains were grafted onto the surface of the
MWCNTs. The scanning electron micrographs of the fiber surface revealed a highly porous structure which greatly increases the
surface area for PEG-g-MWCNTs sol–gel coating. This fiber demonstrated many inherent advantages, the main being the strong
anchoring of the coating to the fused silica resulting from chemical bonding with the silanol groups on the fused-silica fiber
surface. The new PEG-g-MWCNTs sol–gel fiber is simple to prepare, robust, has high thermal stability and long lifetime, up to
200 extractions. Important parameters influencing the extraction efficiency such as desorption temperature and time, extraction
temperature, extraction time, stirring speed and salt effect were investigated and optimized. Under the optimal conditions, the
method detection limits (S/N=3) were in the range of 0.6–3 pg mL–1 and the limits of quantification (S/N=10) between 2–10 pg
mL–1. The relative standard deviations (RSDs) for one fiber (Repeatability) (n=5) were obtained from 4.40 up to 5.75% and
between fibers or batch to batch (n=3) (Reproducibility) in the range of 4.31–6.55%. The developed method was successfully
applied to real water samples while the relative recovery percentages obtained for the spiked water samples at 20 pg mL–1 were
from 90.21 to 101.90%.
Reference
[1] R.P. Belardi, J.B. Pawliszyn, Water Pollut. Res. J. Can. 24 (1989) 179.
[2] C.L. Arthur, J. Pawliszyn, Anal. Chem. 62 (1990) 2145.
[3] A. Sarafraz-Yazdi, A. Amiri, Trends Anal. Chem. 29 (2010) 1.
[4] S.L. Chong, D.X. Wang, J.D. Hayes, B.W. Wilhite, A. Malik, Anal. Chem. 69 (1997) 3889.
Spectrophotometric determination of acidity constants of Hydroxy Naphthol Blue in binary Acetonitrile, Dioxane and
DMF-water mixtures using chemometrics methods
Shadi Bozorgzad Fahadan* , Ali Niazi
Department of Chemistry, Islamic Azad University – Arak Branch, Arak, Iran
E-mail: shadi_bozorgzad@yahoo.com and ali.niazi@gmail.com
A new procedure was use for estimating acidity constants of Hydroxyl Naphthol Blue (Figure 1) by using the spectrophotometric
method at 25 °C and at the constant ionic strength 0.1 M (KNO3) in pure water as well as in aqueous media containing variable
percentages (10–50% w/v) of organic solvents. The used organic solvents were Acetonitrile, Dioxane and DMF.
OH
SO3
HO
SO3
N N
SO3
Figure 1. Chemical structure of Hydroxy Naphthol Blue.
The absorption spectra of hydroxyl naphthol blue in binary solvent mixtures at various pH values in 400-750 nm intervals were
recorded. Sample spectra of Hydroxyl Naphthol Blue in water with pH values ranging from 1.0 to 12.0 at 0.1 M KNO3 is shown
in Figure 2.
Absorbance
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
400
500
600
Wavelength (nm)
700
Figure 2. Spectra of Hydroxy Naphthol Blue in water at 0.1 M KNO3 at different pH values.
The obtained results indicated that acidity constants decrease as the content of an organic solvent in the medium increases. The
DATAN program [1-3] was applied for determination of acidity constants. This indicates that the acid ionization constants of
Hydroxyl Naphthol Blue obtained in various percentages of different solvent-water mixtures are governed by electrostatic effects.
The amounts of pKa1 and pKa2 are obtained 6.53 and 11.02.
Reference
[1] A. Niazi, M. Ghalie, A. Yazdanipour, J. Ghasemi, Spectrochim. Acta Part A 64 (2006) 660-664.
[2] A. Niazi, A. Yazdanipour, J. Ghasemi, M. Kubista, Spectrochim. Acta Part A 65 (2006) 73-78.
[3] A. Niazi, A. Yazdanipour, J. Ghasemi, A. Amini, Sh. Bozorgzad, M. Kubista, Chem. Eng. Comm. 195 (2008) 1257-1268.
Fabrication of an electrochemical sensor using nickel nitroprusside nanostructures for determination of ascorbic acid
a
F. Mousavi a , R.E. Sabzi *,b , A. Salehi a
Department of chemistry, faculty of science, Paymnoor Urmia university, I.R. Iran
b
Department of Chemistry, Faculty of science, Urmia University, I.R. Iran
During the past few years, materials of nanometer-scale have attracted much more interest because of their unusual properties
compared to the bulk counterparts. In recent years, Ni-based nanomaterials are of great interest for researchers from a wide range
of disciplines [1-2]. Typically, the metallic Ni nanomaterials have an important application in catalytic reaction for its high
reactivity and an excellent example is in the Fischer–Tropsch synthesis. Different salt of Ni nanostructures also was used as a
biosensor [3]. This work describes an approach for fabrication of ordered nanostructure of nickel nitroprusside (NiNP) as
nanoparticle, nanotube and naorod. For this purpose, the template method, especially those based on porous anodic aluminum
oxide (AAO) membrane, was used as a simple and effective strategy for synthesis of one-dimensional nanostructures. Nickel
nanowires and nanotubes were fabricated in a conventional three-electrode electrochemical cell. After removing alumina partially
using 0.5M NaOH solution, potentiodynamic derivatization of Ni nanorods by sweepping the electrode potential between 0 and 1
V for about 40 cycles with a scan rate of 50 mV s-1 yields a good modifier layer on Ni nanorods. The NiNP films on Ni
nanostructures show an excellent electrocatalytic activity toward the oxidation of ascorbic acid (AA) in 0.5 M BPS with pH 7 as
supporting electrolyte. The concentration of AA was determined in some real samples.
Reference
[1] X.W. Wang, Z.H. Yuan, S.Q. Sun, Y. Q. Duan, L. J. Bie Mater. Chem. Phys. 112 (2008) 329.
[2] R.E. Sabzi, K. Kant, D. Losic Electrochim. Acta 55 (2010) 1829.
[3] M.Y. Jiang, Y. Lu, Y. He, G. Shen, R. Yu, Biomaterials 28 (2007) 3408.
Cobalt nitroprusside nanostructures as a sensor for determination of dopamine
a
A. Mehmannavaz a , R.E. Sabzi *,b , L. Lotfzad pak a , A. Salehi a
Department of chemistry, faculty of science, Paymnoor Urmia university, I.R. Iran
b
Department of Chemistry, Faculty of science, Urmia University, I.R. Iran
In the last few years the interest towards nano-structures fabrication has grown enormously, thanks to their physical properties
and to the possibility of obtaining nano-devices. For this purpose, template fabrication is the preferred technique [1], because of
the possibility to tailor the geometry of nanowires or nanotubes: with this method the material is synthesized within the
cylindrical pores of a membrane having uniform diameters, in order to obtain an array of dense-packed (near) identical nanostructures. Cobalt nitroprusside (CoNP) as a modifier has been used by many scientist [2-3]. In this work we used anodic alumina
oxide (AAO) as a template for fabrication of cobalt nitroprusside (CoNP) nanowire and nanotubes. Nanoparticles of CoNP also
synthesized using chemical methods. The method is based on the conversion of Co into CoNP nanostructures by electrochemical
oxidation in the presence of nitroprusside ions. After removing alumina partially using 0.5 M NaOH solution, potentiodynamic
derivatization of Ni nanorods by sweepping the electrode potential between 0 and 1 V for about 40 cycles with a scan rate of 50
mV s-1 yields a good modifier layer on Ni nanorods.The prepared nanostructures were used for fabrication of modified electrode.
The effects of supporting electrolytes, solution pH and other parameters were studied on the electrochemical behavior of the
modified electrode. The CoNP electrode were found to be active for the electrocatalytic oxidation of dopamine (DA). The
electrochemical oxidation of DA in 0.5 M H2SO4 was studied.
Reference
[1] C.R. Martin, Chem. Mater. 8 (1996) 1739.
[2] M.H. Pournaghi-Azar, R. Sabzi J. Electroanal. Chem. 543 (2003) 115.
[3] M. H. Pournaghi-Azar, R. E. Sabzi Electroanalysis 16 (2004) 860.
Preparation of Iron nitroprusside nanostructures for determination of ascorbic acid
L. Lotfzad pak a , R.E. Sabzi *, b , A. Mehmannavaz a , A. Salehi a
a
Department of chemistry, faculty of science, Paymnoor Urmia university, I.R. Iran
b
Department of Chemistry, Faculty of science, Urmia University, I.R. Iran
Transition metal nitroprusside as a modifier have been used on different electrodes [1-4]. Iron nitroprusside (FeNP) have
attracted extensive attention because of their outstanding properties including, electrocatalysis, and molecular magnetism. This
paper describes an approach for fabrication of ordered nanoarrays of FeNP nanostructures with different morphologies such as
particles, rods and tubes in order to advance their properties and applications. The method is based on the conversion of Fe into
FeNP nanostructures by electrochemical oxidation in the presence of nitroprusside ions, using nanoporous anodic alumina oxide
(AAO) as a template. The structure and morphology of formed Fe and FeNP nanoarrays were confirmed by scanning electron
microscopy (SEM), showing agreement with the pore structures of the AAO template. The FeNP nanostructure modified
electrode showed a well-defined redox couple due to [FeIII/II]system. The effects of supporting electrolytes, solution pH and
other parameters were studied on the electrochemical behavior of the modified electrode. The electrocatalytic activity of FeNP
nanorod array electrodes showed high catalytic properties for the detection of ascorbic acid and the potential to be used as a
direct sensing application. In this respect ascorbic acid was determined in some fruit juice using hydrodynamic amperometric
method.
Reference
[1] M. H. Pournaghi-Azar, R. E. Sabzi Electroanalysis 16 (2004) 860.
[2] M.H. Pournaghi-Azar, H. Dastangoo J. Electroanal. Chem. 567 (2004) 211.
[3] H. Razmi, H. Heidari J. Electroanal. Chem. 625 (2009) 101.
[4] H. Razmi, Es. Habibi Anal. Biochem. 392 (2009) 126.
Synthesis and characterization of Al (III)-ion imprinted polymer as a new sorbent for separation and preconcentration
of aluminium
Negin Yazdanian*1,Mohamad Rabani1,Homayon Ahmad Panahi2,Elham Moniri3
1
Department of chemistry,North Tehran Branch,Islamic Azad Univercity,Tehran,Iran
2
Department of chemistry,Central Tehran Branch,Islamic Azad Univercity,Tehran,Iran
3
Department of chemistry,Varamin(Pishva)Branch,Islamic Azad Univercity,Tehran,Iran
The selective removal of aluminium ions has been extensively investigated by applying several techniques. Among them, the use
of specific polymeric adsorbents has been considered one of the most promising techniques[1]. Ion imprinted polymers(IIPs)are
recently identified nano-porous polymeric materials which on leaching the imprint ion can rebind, sense or transport (when cast
as membranes) selectively the target analyte in presence of closely related inorganic ions. The IIPs find interesting applications in
solid phase extraction, sensors and membrane separations of inorganics[2]. In this study ,we have prepared a novel ion imprinted
polymer(IIP) to removal aluminium ions in solution samples.The imprinted polymer was prepared by copolymerization of allyl
glycidyl ether/iminodiacetic acid (AGE/IDA) as functional monomers in the presence of N,N'-Methylenebisacrylamide as
crosslinker. The polymerization was carried out in bulk with free radical initiation using 2,2'-azobisisobutyronitrile(AIBN). The
polymer particles were characterized by Fourier transform inferared (FT-IR),scanning electron microscopy(SEM)and elemental
analysis. The effect of various experimental conditions ,eg.pH,adsorption and desorption time and volume of eluent on the
extraction efficiency were investigated and optimized. The optimum pH for quantitative aluminium retention was 5,while elution
was completed with 5 mL of 0.5 M nitric acid. The influence of various cationic interferences on percent recovery of complex
was studied. The results clear revealed that the Al(III) content was retained completely by the IIP ,even in the presence of the
diverse ions. The total capacity of IIP was found to be 62.4 mg g ¹in 20 C. The method was applied to the recovery and
determination of aluminium in different real samples. The imprinted polymers exhibited good characteristics for adsorption and
preconcentration of target aluminium. Finally, the IIP beads can be used many times without decreasing their adsorption
capacities significantly.
Reference
[1]M.Andaç,E. özyapɪ ,S. ŞeneΙ,R.Say,A.Denizli,Ion-selective imprinted beads for aluminum removal from aqueous solutions,Ind.Eng.Chem.Res.45(2006)1780-1786.
[2]T.Prasada Rao,R.kala,S.Daniel,Metal ion-imprinted polymers-Novel materials for selective recognition of inorganics,Analytica chimica Acta 578(2006)105-116.
Simultaneous spectrophotometric determination of New Fuchin and Victoria Blue in waste textile water by Dolittle
multivariate calibration
Arezoo Bashiri Far * and Ali Niazi
Department of Chemistry, Faculty of Sciences, Islamic Azad University-Arak Branch, Arak, Iran
E-mail: a.bashiri_1@yahoo.com and ali.niazi@gmail.com
A simple, novel and sensitive spectrophotometric method was described for simultaneous determination of New Fuchin and
Victoria Blue dyes in waste water samples. All factors affecting on the sensitivity were optimized and the linear dynamic range
for determination of dyes were found. The simultaneous determination of these dyes by using spectrophotometric methods is a
difficult problem, due to the spectral interferences. Dolittle Multivariate Calibration (DMCA) was investigated and the
chromogenic system of dyes with overlapping absorption peaks was analyzed by DMCA. The basic principle of Dolittle
Decomposition Algorithm is discussed in several papers [1]. Dolittle Decomposition Algorithm is a high accuray, few
computation amounts and stable numerical analysis algorithm. This algorithm can avoid matrix inverting operation, which is
often involved in chemometrics such as the methods of K-matrix, P-matrix, PLS, etc., reduce the orders of matrixes, speed up the
operation of matrixes, and raise the efficiency of computation. The partial least squares modeling was used for the multivariate
calibration of the spectrophotometric data. The experimental calibration matrix was designed by measuring the absorbance over
the range ٤٠٠-٧٠٠ nm for 25 samples of ٠.٧٥-٧.٥ µg mL-1 and ١.٥-١٨ µg mL-1 of New Fuchin and Victoria Blue, respectively.
The RMSEP for New Fuchin and Victoria Blue with DMCA and PLS were 0.1536, 0.1281 and 0.1368, 0.1159, respectively. The
proposed method was successfully applied for the determination of New Fuchin and Victoria Blue in synthetic and real samples
such as waste textile water.
Reference
[1] Y. Ding, T. Mu, Q. Wu, Sh. Si, Chemom. Intell. Lab. Syst. 88 (2007) 167.
[2] A. Niazi, J. Ghasemi, A. Yazdanipour, Anal. Lett. 38 (2005) 2377.
[3] A. Niazi, J. Ghasemi, A. Yazdanipour, Spectrochim. Acta Part A 68 (2007) 523..
Electrocatalytic activity of nanoporous Ag and Pd foam towards hydrogen evolution reaction and H 2O2 reduction
Paria Shahbazi, Abolfazl Kiani*
Department of Chemistry, Faculty of Science, University of Isfahan, Isfahan, Iran.
E-mail: a.kiani@chem.ui.ac.ir
A simple and rapid method for fabrication of nanoporous metals (Ag, Pd) foam using electrochemically deposited nanoporous
copper foam were presented. Ideally direct electrochemical formation of (Ag, Pd) foam structures without any additive reagent
does not lead to a desire result, however indirect fabrication starting from electrochemically fabricated Cu foam seems promising
[1-3]. High-purity copper sheets were cleaned by immersing in acetone and dilute HCl through a period of sonication. The cu
sheet was cut into smaller pieces and served as substrate for deposition of copper foam. The Pd and Ag foam were prepared in
two steps. Step one consisted of electrodeposition of copper foam by applying constant current to electrochemical cell, containing
acidic aqueous CuSO4 solution (without stirring or N2 bubbling). Electrochemically fabricated highly porous copper at a copper
sheet plays two roles; as a hard template and a redox inducer deposition of Ag or Pd. The redox induced replacement of copper
foam with Ag or Pd was done via simply immersion of as-fabricated nanoporous copper foam in cation aqueous solutions of Ag
or Pd. The copper was oxidized by cations which were reduced and deposited because of more positive redox potential
comparing to that of copper. The surface morphology of the as-fabricated foams were characterized by the scanning electron
microscopy (SEM), EDX and X-ray diffraction. From SEM images of typical 3-D foam structure of palladium or silver can be
seen that the foam on the copper sheet as substrate, exhibiting intresting porous structures and its walls are composed of
numerous small ramified deposits. Two redox reaction, hydrogen evolution reaction and H2O2 reduction were investigated as an
example to demonstrate the electrocatlytic ability of as-fabricated foams. The silver and palladium foam electrodes exhibit
remarkable electrocatalytic activity toward hydrogen evolution reaction and reduction of hydrogen peroxide.
Reference
[1] Shin, H. C.; Dong, J.; Liu, M. Adv. Mater. 2003, 15, 1610.
[2] Raoof, J. B.; Ojani, R.; Kiani, A.; Rashid-Nadimi, S. Int. J. Hydrogen Energy. 2010, 35, 452.
[3] Cherevko, S.; Chung, C. H. Electrochem. Commun. 2011, 13, 16.
Surface characterization and catalytic evaluation of copper promoted MCM-41
Sh.Sohrabnezhad*ª¸A.Valipour b
ªDemartment of chemistry,Faculty of Science,University of Mohaghegh Ardabili,Ardabil,Iran
b
Department of Chemistry,Faculty of Science,Payam_e Noor Univrsity,Ardabil,Iran
The discovery of highly ordered mesoporous materials (MCM-41) has drawn considerable attention due to their structure
characteristics such as uniform pone-size distribution, highly specific surface area, and pore volume. These materials are
important for potential application in the field of large organic molecule adsorptions and catalytic transformations of bulky
molecules [1]. The Mobil composition of Matter No.41(MCM-41)Containing Cu varying from 1to5 Wt% of Cu was synthesized
under ion exchange and impregnation conditions. The samples were characterized by X-ray powder diffraction (XRD),Fourier
transform infrared spectroscopy (FTIR),UV-Vis diffuse reflectance spectroscopy (UV-Vis DRS)and Transmission electron
microscopy (TEM).X-ray diffraction potterns indicate that the modified materials retain the standard MCM-41 structure. FT-IR
show that Cu2+located into pores of mesoporous materials. Diffuse reflectance spectra reveal Formation of octahedral Copper in
MCM-41.Nano catalyst is used for photo degradation of methylene blue.
Reference
[1] M. ch.Dalconi,G,Cruciani,A.Alberti,P. Ciambelli, Micropor.Mesopor.Mater 94(2006).
Preconcentration and separation of 5-hydroxy indol 3-acetic acid using iron oxide nanoparticles and its HPLC
determination
Zahra Ramezani1, Sahar Farsimadan
Nanotechnology Rresearch Center, Faculty of Pharmacy, Jundishapur University of Medical Sciences, Ahvaz, Iran
College of Sciences, Chemistry Department, Payamenoor University, Shiraz, Iran
5-hydroxy indol-3-acetic acid (5HIAA) is one of the serotonin metabolite that plays an important role in forensic sciences. It is
one of the biological markers used in detection of alcoholism. Different analytical methods for separation and preconcentration of
this marker from urine samples are reported. (1-5) In this study 5-HIAA is preconcentrated and separated from aqueous solution
using magnetic iron oxide nanoparticles. Effect of different parameters such as type of modifier, pH, volume and kind of buffer,
weight of nano iron oxide, contact time, kind and volume of eluents were investigated. Two evaluate the results 10 µl of samples
were injected on XDB C18 (150 × 4.6mm ) 5µm column and the signals were detected at278 nm. Mobile phase were a mixture
of Methanol and 15mM acetate buffer (pH 4.5) containing 1 mM octansulfuric acid and acetonitrile (65:35). Calibration at
optimum conditions for 5-HIAA were linear in the range of 10-150 ng mL-1. This range is more sensitive than ordinary
calibration of the system. It was also showed that trace amount of this compound in urine samples can be determined. The limit
of detection was 10ppb . Within days and between days reproducibility confirmed the precision of the method. Effect of different
constituent presented in Urine were investigated for the preconcentration and determination of 5-HIAA in these kind of samples.
Finally the method was applied for the determination of 5-HIAA in urine samples.
Reference
[1].Goldfrank, L.R., Flomenbaum, N.A., Howland,M.A. Hoffman,R.S.,Nelson ,L.S.goldfrank`s Toxicologic Emergencies, 7 th ed. McGrow-Hill Inc., New york, 2002
[2]. Adrian G. Millera,∗, Heather Brownb, Tim Deggc, Keith Allenc, Brian G. Keevil,journal of chromatography B 878(2010), 695-699
[3]. Wilhelmina H.A. de Jonga, Kendon S. Grahamb, Elisabeth G.E. de Vriesc, Ido P. Kema.journal of chromatography B 878(2008), 28-33
[4]. Juha Rainio a,b,*, Fabio De Giorgio a, Federica Bortolotti c, Franco Tagliaro. Legal Medicine 10 (2008) 229–235
Electrically-enhanced microextraction for highly selective transport of three β-blocker drugs
Yadollah Yamini, Shahram Seidi, Maryam Rezazadeh
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
Adrenoceptor antagonists briefly called as beta-blockers are drugs mainly used for treatment of hypertension [1]. Measurement of
β-blockers in bio-fluids is important not only in controlling the therapy compliance of the patients or intoxication but also in the
field of doping control. In this work, facilitated transport of three β-blocker drugs including atenolol (ATE), betaxolol (BET) and
propranolol (PRO) was investigated under electrical field across a supported liquid membrane (SLM) using phosphoric acid
derivatives as selective ion carriers, dissolved in 2-nitro phenyl octyl ether (NPOE). In the presence of di-(2-ethylhexyl)
phosphate (DEHP) and tris-(2-ethylhexyl) phosphate (TEHP) in the membrane phase, the three β-blockers showed completely
different transport behaviors which enabled highly selective separation of these drugs based on these observations. Each βblocker migrated from 3 mL of sample solutions, through a thin layer of specific organic solvent immobilized in the pores of a
porous hollow fiber, and into a 15 µL acidic aqueous acceptor solution present inside the lumen of the fiber. The influences of
fundamental parameters affecting the transport of target drugs including type of ion carrier for selective separation of each drug
and its concentration in the membrane phase, extraction voltage, time of transport, pH of donor and acceptor phases, stirring
speed of donor phase and salt effect were studied. After microextraction process, the extracts were analyzed by HPLC-UV.
Under optimal conditions, ATE was selectively extracted from different saliva samples with extraction recovery of 37%. A good
linearity was achieved for calibration curve with a coefficient of estimation higher than 0.997. Detection limits and intra-day
precision (n = 3) were less than 2 µg L-1 and 8.8%, respectively. Regarding short extraction time, satisfactory LODs and RSDs,
EME may have a strong potential as a future sample preparation technique.
Reference
[1] K. Parfitt (Ed.), Martindale: The Complete Drug Reference, 32nd Ed., Pharmaceutical Press, London, 1990.
Electrochemical Study of Catechols in presence of 2-Acetyl-γ- butyrolactone by cyclic voltamogram
a
M.Arab Cham jangalia, M.bakherada, M.Ameria*
Faculty of Science College of Chemistry, Shahrood University of Technology, Shahrood, Iran
Electrochemistry has emerged as a powerful tool for the synthesis of complex organic molecules [1]. The investigation of electrooxidation of catechol and its derivative show that the formed o-quinones are quite reactive. O-quinones can be attacked as the
Michael acceptors by solvent, supporting electrolyte and additives to producing various compounds through the 1,4-addition
Michael reaction. In this direction, the electro-oxidation of catechol has been studied in the presence of 2-Acetyl-γ-butyrolactone
at pH 7.0 (0.15 M phosphate buffer) and in the presence of water:ethanol (90:10) as solvent. The results indicate that catechol and
its derivatives react with 2-Acetyl-Gama-butyrolacton under EC mechanism and give products. The cyclic voltammetry and
controlled potential coulometry were selected as methods for electrochemical studies and synthesis. The product has been
characterized by IR, HNMR, and TLC and melting point.
OH
O
O
O
OH
O
OH
CH3
+
O
OH
O
H 3C
Reference
[1] J. B. Sperry, D. L. Wright, Chem. Soc. Rev. 35 (2006) 605.
[2] D.Nematollahi, S.M. Golabi,J.Electroanal. Chem.481 (2000) 208.
[3] D.Nematollahi, A. Ariapad,M.Rafiee, J. Electroanal.Chem.602 (2007) 37.
[4] D.Nematollahi, E.Tammari,H.Karbasi,Int.J.Electrochem.Soc.2 (2009) 986.
Thermodynamics of ZrO 2+ Cation Complexation with Dibenzo-18-Crown-6 in Mixed Nonaqueous Solvents
G.H. Rounaghi*, B. Deiminiat, S. Tarahomi
Department of Chemistry, Faculty of sciences, Ferdowsi University of Mashhad, Mashhad - Iran
Since the time Pedersen published the first report on crown compounds in 1967, [1] these compounds have been considered for a
wide range of applications including enzyme models, biophysics, and medicine [2]. The binding ability and selectivity of crown
ethers to metal ions depend on several factors: such as the size of the crown ether cavity, metal ion radius, type of donor atom,
conformation of the crown ether, the nature of the solvent and etc. Solvent plays a crucial role in the binding selectivity of the
crown ethers for metal ions [3, 4]. In this paper, the complexation reaction of dibenzo-18-crown-6 (DB18C6) with ZrO 2+ cation
was studied in some binary solvent solutions of acetonitrile (AN), 1,2dichloroethane (DCE), nitromethane (NM) and ethylacetate
(EtOAc) with methanol (MeOH), at different temperatures by conductometry method to investigate how the selectivity and
thermodynamics of this reaction are affected by the nature and composition of binary solutions. The stability constant of the
resulting 1:1 complex at each temperature was determined using a computer fitting conductance-mole ratio data. The results
revealed that, the (DB18C6.ZrO)2+ complex is more stable in the EtOAc-MeOH binary mixed solvents compared with the other
binary mixed solvent solutions. A nonlinear relationship was observed for changes of log Kf of (DB18C6.ZrO)2+ complex versus
the composition of the binary mixed solvents. The corresponding standard thermodynamic parameters (DH°c, DS°c) were obtained
from temperature dependence of the stability constant. The results show that the (DB18C6.ZrO)2+ complex is enthalpy
destabilized but entropy stabilized and the values along with the sign of these parameters are influenced by the nature and
composition of the mixed solvents.
Reference
[1] Pedersen, C.J., J. Am. Chem. Soc. 89 (1967) 7017.
[2] Glendening, E.D., Feller, D., Thompson, M.A., J. Am. Chem. Soc. 116 (1994) 10657.
[3] Agnihotri, P., Suresh, E., Ganguly, B., Paul, P., Ghosh, P.K., Polyhedron. 24 (2005) 1023.
[4] Rounaghi, G.H., Heydari, S., Russ. J. Coord. Chem. 34 (2008) 836.
Spectrophotometric Determination of Transformation Product of Carbaryl, 1-naphthol Using 2, 4-dimethyl aniline
Shahab.Parang* and Mahboubeh Saeidi
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, Iran
There is increasing interest in pesticide transformation products, because they can be present at higher level than the parent
pesticide itself [1]. Carbaryl is the common name for the carbamic acid derivative, 1- naphthyl N- methyl carbamate. Carbaryl is
a carbamate insecticide that is used for the control of chewing and sucking insect .It is also used to control earth-worms in turf
and used as a growth regulator for fruit thinning of apples and an animal ectoparasticide. the carbaryl is easily hydrolysed to 1naphthol in alkaline media [2]. In this work, a simple, rapid and sensitive spectrophotometric method is proposed to
determination of transformation product of carbamate pesticide, carbaryl (1-naphtol). The method is based on the coupling of 1naphtol with new coupling agent 2, 4-dimethyl aniline. The maximum absorbance observed for this coloured complex was at
418nm. Operational parameters such as concentrations and volumes of: Reagent, HCl, NaNO2, NaCl, NaOH, and the time of
formation colored compound has been studied and the optimized conditions developed were utilized for the determination of 1naphthol. The proposed method had a detection limit of 3.8 ng.mL-1(for S/N=3) and a linear response (r2> 0.9992) over the
concentration range of 0.01-40μg.mL-1.Under the optimum experimental conditions, the described method present a good
repeatability, with a relative standard deviation (RSD) of 0.06% (for a level of 10 μg.mL-1, n=5). The molar absorptivity of 10656
L.mol-1.cm-1was calculated. The applicability of the method was demonstrated by determining 1-naphthol in Tap water.
Reference
[1] V. Andreu, Y. Pico′, Trends in Anal. Chem. 23(2004) 772
[2] L. Jacqueline, etal. J. Agri. Food Chem. 52(2004)8066-8073
[3] C.S.P.Sastry, D.Vijaya and D.S.Mangala, Analyst, 1987, 112, 75-78
[4] C.S.P.Sastry, D.Vijaya and K.Ekambreswara Rao, Food Chemistry, Volume 20, Issue 2, 1986, Pages 157-162
Development of a New Quantum Chemical Descriptor for Corrosion Inhibition study of Benzimidazole and Aniline
Derivatives on Iron
a
Mehdi Mousavi*a, Hossein Safarizadeh
Department of Chemistry, Faculty of Sciences, Shahid Bahonar University of Kerman, P.O.Box
76175-133, Kerman, Iran
*mmousavi@mail.uk.ac.ir
Interaction energies (Eint) of benzimidazole and aniline derivatives on iron surface were determined using cluster model and
quantum chemical calculations at density functional theory level. To fulfill this aim, the structures of inhibitor molecules and iron
unit cell were optimized using B3LYP/LANL1MB methods at density functional theory (DFT). The calculated interaction
energies and many other quantum chemical descriptors such as energy of the highest occupied molecular orbital (EHOMO), surface
area (SAA), volume and polarizability of the molecules were considered in linear and non-linear regression modeling procedures.
It is shown that the newly proposed descriptor (Eint) is the most effective descriptor in describing the corrosion inhibition
behavior of the molecules and the results obtained are in good agreement with experimental evidence. In the present work, the
quantum chemical study is focused on the calculation of interaction energies between the inhibitor molecules and the iron atom
unit cell, upon which the adsorption is directly tacking place. Interaction energy between the inhibitor molecule and the metal
surface, Eint, can be calculated based on cluster model [1,2] using Eq. (1):
Eint = E inhibitor-cluster – (E cluster + E inhibitor)
(1)
where, E inhibitor, E cluster and E inhibitor-cluster are electronic energies of the inhibitor molecule, the iron cluster and of the inhibitoriron system, respectively. Linear and non-linear regression methods were used to choose the most informative descriptors from a
pool of 1060 descriptors. It is concluded that a combination of Eint, polarizability and volume of inhibitor molecules are
satisfactorily described the corrosion inhibition phenomena (r= 0.988). It is concluded that the newly proposed descriptor, Eint,
successfully described the corrosion inhibition behavior of the aniline and the benzoimidazole derivatives on iron in acidic media.
This may be due to the facts that, in contrast to many QSAR studies, in the cluster model all participants of a chemical reaction
are taken into account. Also, in the DFT method applied here, it is possible to calculate energy of the system more accurately and
more precisely.
Reference
[1].R.M.Issa,M.K.Awad,F.M.Atlam,Appl.Surf.Sci.255(2008)2433.
[2]M.R.Arshadi,M.Lashgari,GH.A.Parsafar,Material chemistry and Physics 86(2004)311-314
Determination of uranium in ultra trace amount by dispersive liquid-liquid microextraction coupled with the
spectrophotometer
a
M. Chakani a, Mohammad Reza Milani Hosseini a*, M. Najafi b
Department of Analytical Chemistry, Faculty of Chemistry, Iran University of Science and Technology, Tehran, Iran
b
Department of Chemistry, Faculty of Science, Imam Hossien University, Tehran, Iran
Uranium, a radioactive and toxic metal is mobile element in a surface environment and exists in water, soil, and rocks. Therefore
determination and measurement of Uranium in water samples is very important [1]. Several methods have been reported on
preconcentration and determination trace amount of uranium which were not capable of ultra trace determination, such as
electrochemical methods, cloud point extraction, and solid phase extraction . Dispersive liquid-liquid microextraction (DLLME)
has good ability to measure ultra trace amount (the microgram values) of uranium in water samples.The advantages of DLLME
method are simplicity, rapidity, low cost, high recovery, high enrichment factors and being an environmental benignity [3]. In
this paper, DLLME coupled with spectrophotometer is used for determination of uranium in the water samples. One variable at a
time method was used to optimize extraction and disperser solvents; as a result, the carbon tetrachloride and ethanol were
selected as the most efficient extraction and disperser solvents respectively. Furthermore, orthogonal array design with an OA 16
(45) matrix was applied to optimizing the extraction conditions. pH: 9; ligand to metal mole ratio: 40; volume of extraction
solvent: 70 μL; volume of disperser solvent: 1 mL and without salt addition were parameters that obtained from this step.The
figures of merit were obtained from the optimized condition. Dynamic linear rang and LOD (LOD=3Sb⁄m) were 0.5-30 µgL-1 and
0.19 µgL-1 respectively. The relative standard deviation (RSD) for 6 replicated measurements was 2.8%. The enhancement factor
was 102. The method applied for several real samples and the results obtained are very satisfactory and will be reported in the
original text.
Reference
[1] B. Khadro and N. Jaffrezic-Renault, "A miniaturized system for ultratrace uranium analysis in waters," Procedia Engineering, vol. 5, 2010, pp. 1212-1215.
[2]C. Jie, L.Ming, "Spectrophotometric determination of ultra trace uranium(VI) in seawater after extractive preconcentration with ionic liquid and
dimethyphenylazosalicylfluorone," Intern. J. Environ. Anal. Chem., vol. 88, 2008, pp. 583-590.
[3] M. Rezaee, Y. Yamini, and M. Faraji, "Evolution of dispersive liquid-liquid microextraction method," Journal of Chromatography A, vol. 1217, 2010, pp. 23422357.
Development of novel sensor for electrochemical determination of Morphine in real samples
a
Esmaeel Alipoura,* and Sima Gasemlob
Electroanalytical Chemistry Laboratory, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
b
Faculty of Sciences, Islamic Azad University-Ahar Branch, Ahar, Iran
E-mail: i-alipour@tabrizu.ac.ir
As a major component in opium, morphine is often used to relieve severe pain in patients, especially those undergoing a surgical
procedure. It is recommended by the World Health Organization (WHO) for the relief of moderate cancer-related pain. However,
it is toxic in excess and when abused. Different methods have been used for the determination of morphine in plasma, urine, and
opium samples, such as high-performance liquid chromatography (1), gas chromatography (2), capillary electrophoresis (3) and
chemiluminescence (4). However, these methods are expensive, and not suitable for the in situ measurement. In contrast, the
electroanalytical techniques have many attractive features, such as favorable portability, easy operation procedures and high
sensitivity. Therefore, they are popular in the determination of morphine (5-8). Here, development of novel sensor for
electrochemical determination of Morphine in real samples is described. Several parameters affecting determination of Morphine
on the pre-treated pencil graphite electrode (PGE) such as PGE activation potential and time, pH and kind of PGE activation
buffer solution, pH and kind of morphine determination solution were investigated and optimum conditions were suggested. This
sensor was successfully used for determination of low concentrations of morphine in real samples using differential pulse
voltammetric (DPV) method. DPVs were obtained in phosphate buffer solution (pH 7) containing morphine showed an anodic
peak about 0.4 V versus SCE.
Reference
[1] Berga, T., Lundanes, E., Christophersen, A.S., Strand, D.H., 2009. J. Chromatogr. B 877 (4), 421–432.
[2] Hofmann, U., Seefried, S., Schweizer, E., Ebner, T., Mikus, G., Eichelbaum,M., 1999. J.Chromatogr. B 727 (1–2), 81–88.
[3] Zhang, Q.L., Xu, J.J., Li, X.Y., Lian, H.Z., Chen, H.Y., 2007. J. Pharm. Biomed. Anal. 43(1), 237–242.
[4] Francisa, P.S., Adcock, J.L., Costin, J., Purcell, S.D., Pfeffer, F.M., Barnett, N., 2008. J.Pharm. Biomed. Anal. 48 (3), 508–518.
[5] Niazi, A., Ghasemi, J., Zendehdel, M., 2007. Talanta 74 (2), 247–254.
[6] Norouzi, P., Ganjali, M.R., Moosavi-movahedi, A.A., Larijani, B., 2007. Talanta 73 (1), 54–61.
[7] Pournaghi-Azar, M.H., Saadatirad, A., 2008. J. Electroanal. Chem. 624 (1–2), 293–298.
[8] Salimi, A., Hallaj, R., Khayatian, G.R., 2005. Electroanalysis 17 (10), 873–879.
Equilibrium and thermodynamic study of waste tea as biosorbent for removal copper from waste water
Fatemeh Shahhoseini* , Zahra Darabi , Ali Niazi,
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Arak Branch, Arak, Iran
(email: shahhoseini_fatemeh@yahoo.com)
Heavy metal ions are nowadays among the most important pollutants in surface and ground water. They are often discharged by a
number of industries, such as metal plating facilities [1-3]. The biosorption of Cu(II) ions on the dried yeast biomass was
investigated in batch biosorption equilibrium experiments. The effect of the initial metal ion concentration, contact time,
temperature, biosorbent dose and pH on the biosorption rate and capacity was studied. The effect of contact time and initial metal
ion concentration on the biosorption was studied), with varying metal ion concentrations (ranging from 5 to 10000 mgl-1). A
weighted sample of biosorbent as 100 mg was mixed with a 10 ml of metal ion solution of known initial concentration at 150 rpm
for 60 min. For the other adsorption experiments, 10 ml of metal solution of known initial concentration was shaker with
adsorbent (10 mg) at the desired temperature (10 , 15 , 20, 30 , 35, 40, 45,50 and 60 °C), for 60 min at the end of the period, after
centrifugation, it was analyzed by using Atomic Absorption Spectrophotometer. The waste Tea were gathered from twigs in to
clean plastic bags, washed with ion-free distilled water and then dried at 80° C for 24 h. Dried biomass was powdered by using
mortar and pastel. The powdered biomass was sieved to 40–50 mesh, For sorbent the most effective pH was found to be 7. Metal
ion biosorption increased as the ratio of metal solution to the biomass quantity decreased. Biosorption/g biosorbent decreased as
the quantity of biomass increased. The biosorption of metal ion increased as the initial metal concentration increased.The
equilibrium data for copper best fit the Longmuir adsorption isotherm model. Kinetic studies showed that the biosorption rates
could be described by a second-order expression.The sorbent could be regenerated using 0.01 HCl and 0.02 HNO3 during
repeated biosorption–desorption cycles.The results from these studies show a novel way of using waste Tea to remove Coppr
from metal-polluted water.
Reference
[1] Bulut, Y.;Tez, Z.; Hazard. Mater. 2007, 35, 41
[2] Schiewer, S.; Environmental Microbe-Metal Interactions, ASM Press, 2000.
[3] Akhtar, N.; Hazard. Mater. 108, 2004, 85.
Synthesis of Poly[5-(4-benzylacrylicamide)-10,15,20-tris(4-benzylamin)porphyrin and its Efficient Application as Neutral
Carrier for Preparation of New Copper Selective Electrode: Investigation of Influence of Multiwalled Carbon Nanotubes
on Its Response
M.Behfar*a, M.Ghaedia, R. Behfar b, K.Mortazavic, Z. Andikaeya, M.Nejatia
a)
Chemistry Department, Yasouj University Yasouj Iran 75914-353.
b)
Chemical Engineering Department, Arak University, Arak, Iran.
c)
Chemistry Department, Gachsaran Azad University, Gachsaran, Iran.
*Email: mina_behfar_65@yahoo.com
In the first new polymer of porphyrin was synthesized and characterized then its new materials has been used for construction
new copper carbon paste electrode (CPE). The influence of variables including carbon paste composition, sodium
tetraphenylborate (NaTPB), ionophore, MWCNT and Nujol on the electrode response was studied and optimized. The optimum
conditions were set as following, carbon: NaTPB: Nujol: Carrier: MWCNT in the emount of 150:3:30:7:20 mg respectively. At
optimum values of all variables, electrode response was linear over the 1.0 × 10-8 to 1.0 × 10-1 mol L-1 for by a Nernstian slope
of 29.84 ±1.00 mV per decade of a Cu2+ ion concentration. The proposed electrode show good charestristic performance viz.
low detection limit (8.5× 10-9 mol L-1 (0.272 ng m L-1)), wide applicable pH range (2.5-5.5) with short response time (<2 s),
and adequate life time (3 months). The calculated potentiometric selectivity coefficients of these proposed electrode by fixed
interference method (FIM) and separate solution method (SSM) indicate its selective response toward Cu2+ ions over various
interfering ions.Finally, the electrode has been successfully applied for the determination of Cu2+ ions content in various real
samples. Carbon paste electrode, Copper-selective electrode, Potentiometric sensors, poly[5-(4-benzylacrylicamid)-10,15,20tris(4-benzylamin)pophyrin]
Reference
[1] M.J. Gismera, J. R. Procopio, M. T. Sevilla, and L. Hernandez, 17512Copper(II) ion-selective electrodes based on dithiosalicylic and thiosalicylic acids,
Electroanalysis., 15 (2003) 126-132.
[2] L. P. Singh, and J. M. Bhatnagar, 17511Copper(II) selective electrochemical sensor based on Schiff Base complexes, Talanta, 64 (2004) 313-319.
[3] K. Ren, A liquid state copper(II) ion-selective electrode containing a complex of Cu(I)) with salicylaniline, Talanta, 36 (1989) 767-771.
Comparative Study by Electrochemical Impedance Spectroscopy (EIS) On Corrosion Resistance of Different Painted
Galvanized Steel Systems
a
S.Moradi a, M.Peikari *a, M.A.Golozar b
Technical Inspection Engineering Department, Petroleum University of Technology, Abadan
Email: peikari@put.ac.ir , somayemoradi@ait.put.ac.ir
b
Department of Materials Engineering, Isfahan University of Technology, Isfahan, Iran
Organic coating in combination with sacrificial metal coating is the most popular method of protecting steel against corrosion in
marine and atmosphere environments. The excellent corrosion resistance of such systems has been attributed to the synergy
between the cathodic protection provided by the sacrificial metallic coating and the combined barrier resistance of the metal and
organic coatings. Traditionally continuously hot dip zinc-coated steels are used for such applications. This is not only due to cost
reasons but also mainly to the fact that the Zn based layer is electrochemically more active than the substrate, therefore, it
offering cathodic protection to steel. In this work the corrosion resistance of five different coating systems including galvanized
steel, galvanized steel covered with an organic layer, phosphated and chromated galvanized steels covered with an organic layer
and bare carbon steel panels were assessed by electrochemical impedance spectroscopy (EIS) that is a very important
electrochemical method of corrosion monitoring to study the effect of galvanizing, organic coating and conversion coatings on
corrosion resistance of carbon steel. EIS tests were performed by exposing the coupons to a 5.0 wt.% NaCl aqueous solution in a
three-electrode cell and the impedance data were analyzed and results were compared with each other. On the basis of all the
electrochemical impedance spectroscopy results it could be concluded that conversion coatings in combination with organic
coating on HDG steel improve the corrosion resistance of the coating system more than an organic coating alone.
Reference
[1]- S. González, M.A. Gil, J.O. Hernández, V. Fox, R.M. Souto, Resistance to corrosion of galvanized steel covered with an epoxy-polyamide primer coating,
Progress in Organic Coatings 41 (2001) 167–170
[2]- B. del Amoa, L. Vélevab, A.R. Di Sarli , C.I. Elsner, Performance of coated steel systems exposed to different media-Part I. Painted galvanized steel, Progress in
Organic Coatings 50 (2004) 179–192
[3]- J.B. Bajat, V.B. Miˇskovic´ -Stankovi ´ca, J.P. Popi´c, D.M. Draˇzic´, Adhesion characteristics and corrosion stability of epoxy coatings electrodeposited on
phosphated hot-dip galvanized steel, Progress in Organic Coatings 63 (2008) 201–208
[4]- B. Ramezanzadeh, M.M. Attar, M. Farzam, Corrosion performance of a hot-dip galvanized steel treated by different kinds of conversion coatings, Surface &
Coatings Technology 205 (2010) 874–884
[5]- S. Palraj, M. Selvaraj, P. Jayakrishnan, Effect of phosphate coatings on the performance of epoxy polyamide red oxide primer on galvanized steel, Progress in
Organic Coatings 54 (2005) 5–9
[6]- P. Puomi, H.M. Fagerholm, J.B. Rosenholm , K. Jyrka¨s, Comparison of different commercial pretreatment methods for hot-dip galvanized and Galfan coated
steel, Surface and Coatings Technology 115 (1999) 70–78
[7]- K. Raeissi, M.R. Toroghinejad, The effect of chromated and organic layers on corrosion resistance of galvanized steel sheets, Progress in Organic Coatings 62
(2008) 61–64
[8]- S. Le Manchet, J. Landoulsi, C. Richard, D. Verchère, Study of a chromium-free treatment on Hot-Dip Galvanized steel: Electrochemical behaviour and
performance in a saline medium, Surface & Coatings Technology 205 (2010) 475–482
[9]- J.B. Bajat, V.B. Miˇskovic´-Stankovic´, N. Bibic´, D.M. Draˇzic´, The influence of zinc surface pretreatment on the adhesion of epoxy coating electrodeposited on
hot-dip galvanized steel, Progress in Organic Coatings 58 (2007) 323–330
[10]- T.S.N. Sankara Narayanan, SURFACE PRETREATMENT BY PHOSPHATE CONVERSION COATINGS: A REVIEW, Rev.Adv.Mater.Sci. 9 (2005) 130177
A New Device for Semi-automated Cloud Point Extraction-Solid Phase Extraction (CPE-SPE) of Phenazopyridine in
Human Serum
Payman Hashemi,* Fariba Nazari Serenjeh, Mehdi Safdarian, Ali Reza Ghiasvand
Department of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran
E-mail: payman_hashemi@yahoo.com
Phenazopyridine hydrochloride is an azo dye that has been used for long time in conjunction with antibacterial agents for the
treatment of urinary-tract infections [1,2]. During the past years, cloud point extraction (CPE) has become one of the most
preferred preconcentration methodologies to enhance the sensitivity in determination of both inorganic and organic samples [3,4].
In this work, a new simple device was developed for cloud point extraction (CPE) coupled solid-phase extraction (SPE) of
phenazopyridine in human serum (Fig. 1). The nonionic surfactant Triton x-100 was used as the surfactant-mediated extractant.
For CPE, 1 mL Triton x-100 (2%, v/v) was added to 4 mL aqueous solution of phenazopyridine (pH=8) and the mixture was
heated (to 90 °C) for 5 min. After this step, the turbid solution was passed through a cold preconcentration column packed with
C18 sorbent. The surfactant rich phase was retained by preconcentration column (at 0 °C) and eluted with ethanol (at 30°C). The
analytical parameters were investigated such as pH, surfactant concentration and incubation temperature and time were optimized
by a central composite design (response surface) method. Six replicated analysis at the optimized conditions, resulted in a
recovery of 99.73% and an RSD of 2.45.
Reference
[1] B. Nickerson., S. Scypinski, H. Sokoloff, S. Sahota, J. Liq. Chromatogr. 1995, 18, 3847.
[2] Y. Yamini, J. Arab, M. Asqhari-Khiavi, J. Pharm. Biomed. Anal. 2003, 32, 181.
[3] M.A. Bezerra, A.R.A. Nogueira, L.A. Sergio, L.C. Ferreira, Int. J. Environ. Anal. Chem. 2008, 88, 131.
[4] V.A. Lemos, R.S. da Franca, Moreira, Sep. Purif. Technol. 2007, 54, 349.
Application 1,5- diphenyl carbazid loaded on sulfur For Determenation and preconcentration of pb2+ and zn2+ ions in
Fruit Samples by FAAS
*
Maryam.Eslami
1)Chemistry Department, Islamic Azad University, Gachsaran Branch, Gachsaran, Iran
Email:Maryameslami79@yahoo.com
A simple and sensitive method for the simultaneous preconcentration of nutritionally important minerals in Fruit samples has
been reported. The method is based on the adsorption of zn2+ and pb2+ ions on 1,5- diphenyl carbazid loaded on sulfur. The ions
are eluted using 4 mL 2 mol L-1 HCl in water. Flame atomic absorption spectrometry was used for measurements. The influences
of the analytical parameters including pH, sulfur and ligand amount, concentration and type of eluent, flow rate of sample and
eluent, sample volume were investigated. The effects of matrix ions on the recoveries of analyte ions were also investigated. The
recoveries of analytes were generally higher than 94 %. The detection limits for pb2+ and zn2+ were 0.15 ng ml-1 and 1.5 ng ml-1
respectively. The method has been successfully applied for these metals content evaluation in Fruit samples.
Reference
[1] M. Ghaedi , H. Tavallali, A. Shokrollahi, Journal of Hazardous Materials 166 (2009) 1441–1448
[2] M. Ghaedi, A. Shokrollahi, A.H. Kianfara, Journal of Hazardous Materials 162 (2009) 1408–1414
Removal of Direct Red 12B from aqueous solution by zinc oxide nanoparticle loaded on activated carbon Shahdokht
Shamsaldini, Mehrorang Ghaedi*
Chemistry Department, Islamic Azad University,Ghachsaran Branch,Ghachsaran,Iran
The removal of dyes from industrial waste before they discharged in to the water bodies is very important from health and
hygiene point of view and for environmental protection.In this work, efficiency and performance of zinc oxide nano particle
loaded on activated carbon adsorbent for the removal and recovery of Direct Red 12B from wastewater.The maximum removal
was 99% for 30mg L–1 of Direct Red 12B concentration on 0.01g L–1 carbon concentration.Acidic pH was favorable for the
adsorption of direct red 12B . The influence of variables including pH, concentration of the dye, amount of adsorbent, contact
time and temperature on the dye removal has been investigated in batch method by one at a time optimization method. The
graphical correlation of various adsorption isotherm models like, Langmuir, Freundlich and Tempkin have been carried out for
this adsorbent. Calculation of various thermodynamic parameters such as, Gibb’s free energy, entropy and enthalpy of the ongoing adsorption process indicate feasibility and endothermic nature of Direct Red 12B adsorption on all adsorbents.
Reference
[1] F. D. Ardejani, K. H. Badii, N. Y. Limaee, N. M. Mahmoodi, M. Arami, S.Z. Shafaei, A. R. Mirhabibi, Numerical modeling and laboratory studies on the removal
of Direct Red 23 and Direct Red 80 dyes from textile effluents using orange peel, a low-cost adsorbent, Dye Pigm. 2007, 73(2), 178.
[2]Alessio, B., Maximilian, D., Pierandrea, L. N., & Piero, B. (2007). Synthesis and characterization of zinc oxidenanoparticles: application to textiles as UVabsorbers. J Nanopart Res.[3] R. Sivaraj, C. Namasivayam, K. Kadirvelu, Orange peel as an adsorbent in the removal of Acid violet 17 (acid dye) from aqueous
solutions,Waste Manage.2001, 21(1), 105.
[4] B.H. Hameed, A.A. Ahmad, N. Aziz, Isotherms, kinetics and thermodynamics of acid dye adsorption on activated palm ash, Chem. Eng. J. 2007, 133(1-3),195.
Removal and recovery of Cd from waste waters using salix.L tree leaves
Saeed Reza Hadizadeh * and Ali Niazi
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Arak Branch, Arak, Iran
(E-mail: hadizadehsaeed@yahoo.com
and
ali.niazi@gmail.com)
Heavy metal ions are nowadays among the most important pollutants in surface and ground water. They are often discharged by a
number of industries, such as metal plating facilities, mining operations and tanneries, which can lead to the contamination of
fresh water and marine environment. Heavy metal ions are extremely toxic and harmful even at low concentrations, which can
seriously affect plants and animals and have been involved in causing a large number of afflictions. Therefore, the limitation of
these metals from waste waters is important to protect public health. The objective of this study was to investigate the biosorption
potential of salix.L tree leaves to tree Waste waters contaminated with Cd. The metal loading capacity of yeast biomass was
determined as a function of the initial metal ion concentration, contact time, temperature, biosorbent dose and pH. The
biosorption data were analyzed by Freundlich and Langmuir isotherm models. Thermodynamic parameters ∆H°, ∆S° and ∆G°
were estimated, these parameters show that adsorption is endothermic, favorable and spontaneous. Another advantage of using
this new sorbent is high capacity for removal of heavy metals from medium acidic aqueous solutions.
Reference
[1] Y. Bulut, Z. Tez, J. Hazard. Mat., 35 (2007) 41.
[2] A. Cabuk, T. Akar, S. Tunal, O. Tabak, J. Hazard. Mat., 33 (2006) 317.
Adsorption of Folic acid, Riboflavin and Ascorbic acid from Aqueous Samples by Fe3O4 Magnetic Nanoparticles using
Ionic Liquids as Modifier
Mozaffar Asadi, Ghodratollah Absalan*, and Sedigheh Kamran
Professor Masoumi Laboratory, Department of Chemistry, College of Sciences, Shiraz University, 71454, Shiraz, Iran
Nanoparticles of Fe3O4 as well as its binary mixtures with ionic liquids (IL-Fe3O4) were prepared and used for adsorption of folic
acid, riboflavin and ascorbic acid. The mean size and the surface morphology of both nanoparticles were characterized by TEM,
DLS, XRD, FTIR and TGA techniques. The pH of the point of zero charge (pHpzc) values of both Fe3O4 and IL-Fe3O4 were
obtained based on the experimental curves corresponding to the immersion technique. Experimental results were obtained under
optimum experimental conditions of: nanoparticle dosage of 40 mg and a contact time of 10 minutes when initial concentration
of each vitamin was 20 mg L−1. The isotherm evaluations revealed that the Freundlich model attained better fits to the
equilibrium data than the Langmuir model. The maximum adsorption capacities were 22.5, 4.8 and 6.9 mg folic acid, riboflavin
and ascorbic acid per gram adsorbent, respectively. The adsorption capacities of the vitamins were found to depend on their
chemical structures, pH of the solution and temperature. The applicability of two kinetic models including pseudo-first order and
pseudo-second order models was estimated on the basis of comparative analysis of the corresponding rate parameters,
equilibrium adsorption capacity and correlation coefficients. Furthermore, both adsorption processes of folic acid and ascorbic
acid were endothermic and they could be desorbed from IL-Fe3O4 nanoparticles by using NaCl solution at pH 3.0.
Reference
[1]M. Miyahara, A. Vinu, K. Ariga, Matter Sci. Eng. C Biol. Sci. 27 (2007) 232-236.
[2]D.K. Kim, Y. Zhang, W. Voit, K.V. Rao, M. Muhammed, J. Magn. Magn. Mater. 225 (2001) 30- 36.
[3]B. M. Borah, B. Saha, S. K. Dey, G. Das, Journal of Colloid and Interface Science 349 (2010)114 -121.
[4] W. Shen, H. Wang, R. Guan ,Z. Li, Colloids and Surfaces A: Physicochem. Eng. Aspects 331 (2008)263 –267.
Development of a Cobalt PVC Membrane Optode Based on a
New Schiff Base as Ionophore
Ghodratollah Absalan*, Mohammad Hassan Ghasvari Jahromi, Sedigheh Kamran, and Mozaffar Asadi
Professor Masoumi Laboratory, Department of Chemistry, College of Sciences, Shiraz University, 71454, Shiraz, Iran
A plasticized PVC membrane optode incorporated with N, N´ bis(salicyliden)-2,3-diaminopyridine, as ionophore, and dioctyl
sebacate was used as a reversible sensing device for the direct optical determination of cobalt (II). The reduction in the
absorbance of the optode at the wavelength of 325 nm was related to cobalt ion concentration in aqueous samples. Under the
optimum experimental conditions, the linear measuring range of cobalt (II) was found to be 1.0×10−5 - 1.1×10−3 M with a
detection limit of 2.5×10−6 M cobalt (II) (n=10). Typical response time of membrane was 3-4 min. The optode was reversible and
could readily be regenerated with ethylene diamine tetraacetic acid. The optode was applied for determination of cobalt (II) in
mineral and tap water samples.
Reference
[1] M. Asadi, A. Kianfar, S. Torabi, K. Mohammadi, J. Chem. Thermodyn. 40 (2008) 523.
[2] M. Shamsipur, T. Poursaberi, A. R. Karimi, M. Hosseini, A. Momeni, N. Alizadeh, M. Yousefi, M. R. Ganjali, Anal. Chim. Acta, 501 (2004) 55.
[3] H. Karimi, M. F. Mousavi, M. Shamsipur, Anal. Chim. Acta, 481 (2003) 213.
[4] M. A. Barmchi, Sh. Sohrabnezhad, M. F. Mousavi, M. Shamsipur, M. A. Zanjanchi, Anal. Chim. Acta, 491 (2003) 193.
Removal of phenol from aqueous solutions by surfactant-modified beta zeolite
Hossein.faghihian*and Nafiseh.poorbasirat
Islamic azad university, Shahreza branche, Shahreza, Iran
Phenols and related compound are toxic to humans and aquatic life, causing oxygen demand in receiving waters. Waste water
containing phenolic compounds must be treated before being discharged to receiving media [1]. There are various technologies
for the removal of phenol, biological, chemical and physical. Among them, physical method, in Phenols and related compounds
are toxic to humans and aquatic life, causing oxygen demand in receiving waters. Waste water containing phenolic compounds
must be treated particular adsorption process is generally considered the best. zeolites have been widely used as adsorbents, thay
are an important class of hydrated aluminosilicates and possess cage-like structures with internal and external surface areas of up
to several hundred square meters per gram [2].In this study the removal of phenol from aqueous solutions using surfactantmodified synthetic beta zeolite (SMZ) was investigated. Zeolite Beta were prepared by hydrothermal method and were modified
with N-cetylpridinium bromide (CPDBr). The samples were characterized by XRD, UV/Vis and FTIR spectroscopy. The phenol
removal was determined in a batch system taking into consideration the different quantities of surfactants (0.05 and 0.1 mol/l),
contact time, initial phenol concentration and adsorbent dosage [3]. The results showed that the (SMZ) possessed good
adsorption capacity to phenol. Increase in the initial phenol concentration, adsorbent dosage and time could effectively increase
the phenol adsorption capacity. The calibration plot of absorbance versus concentration for phenol showed a linear renge to 10-50
mg/L. Phenol concentration was determined in the aqueous solutions by UV/Vis spectroscopy [4].
Reference
[1] S. Rengaraj, S.H. Moon, R. Sivabalan, B. Arabindoo, J. Waste Manage. 22 (2002) 543–548
[3] M. C. Diaz-Nava, M. T. Olgun, M. Solache- Ros, M. T. Alarcon-Herrera, A. Aguilar-Elguezabal, J. Isncl. Phenom. Macro. Chem. 51 (2010) 231-240
[4] A. Kuleyin, J. Hazard. Mater. 144 (2007) 307–315
Desulfurization of dibenzothiophene by Titanium dioxide/natural zeolite Composite
H.Faghihian*, Sh.Naimie
Department of Chemistry Shahreza Branch, Islamic Azad University, Shahreza/Iran
E-mail address: Faghihian@ iaush.ac.ir
Naeimi_sh@yahoo.com
In this research desulfurization of dibenzothiophene (DBT) in n-hexan solution by using TiO2/clinoptilolite as photocatalyst
under ultraviolet irradiation has been studied. Firstly nanocrystalline titanium dioxide prepared by sol-gel process by using
titanium (IV) isopropoxide and was immobilized on clinoptilolite by solid state dispersion method (SSD). The photocatalyst was
characterized by XRD, TEM, FTIR and SEM techniques. The effect of experimental parameters such as irradiation time, amount
of photocatalyst, TiO2 content and initial pollutants concentration were studied and optimized. Dibenzothiophene concentration
was measured by HPLC (Agilent 1200 model) with column of zorbax, Eclipse XDB-C18 .The results showed that the kinetics of
reaction is first order. In order to investigate the reusability of the catalyst, desulfurization experiments were performed under
similar conditions for four cycles. It was concluded that after 4 cycle 73% of desulfurization was occurred.The results show that
DBT can successfully be oxidized under experimental conditions. At the optimized conditions, 92% desulfurization was
obtained.The results show that TiO2/clinoptilolite is an active photocatalyst for desulfurization of sulfur pollutants.
Reference
[1] Jua Z, Dishun Z, Liyan Y and Yongbo Li. "Photocatalytic oxidation of dibenzothiophene using TS-1 " J. Chemical Engineering Journal 156 (2010) 528-531.
[2] Habib M.H and Vosooghian H. "Photocatalytic degradation of some organic sulfides as environmental pollutants using titanium dioxide suspension" J.
Photochemistry and Photobiology 174 (2005) 45-52.
[3] Su C, Hong B-Y and Tseng C-M. " Sol- gel preparation and photocatalysis of titanium dioxide" J. Catalysis Today 96 (2004) 119-126.
Optimization of matrix solid phase dispersion followed by gas chromatography for extraction and determination of
organochlorine pesticides and degradation products
Amir Salemia, Maryam Vosough*b, Elham Shafieic
Environmental Sciences Research Institute, Shahid Beheshti University, Tehran, Iran.
b
Chemistry and Chemical Engineering Research Center of Iran, Tehran, Iran.
c
Department of Chemistry, Faculty of Science, Payam-e-nour University, Ardabil, Iran
.
a
Matrix solid phase dispersion, MSPD has been applied for extraction and preparation of soil samples for gas chromatographicelectron capture detection determination of organochlorine pesticides and some of their natural degradation products (16
analytes). Sample preparation procedure was as follows; soil sample was dried and sieved to obtain particles smaller than 2 mm.
1-2 g of the soil was mixed thoroughly with a predetermined amount of dispersing phase and also with reversed phase solid
sorbents, if necessary. The mixture was transferred to an extraction cartridge, containing 1 g of sodium sulfate and finally specific
portions of proper solvent were passed through the cartridge to extract the analyte and carry them to gathering vial. This solution
was ready to be injected to the GC. Type and weight of the solid phase materials and also their ration to the taken sample, as well
as type and volume of the extraction solvent are the most important factors which affect the extraction efficiency. The proposed
method benefits from speed and simplicity of the procedure and instrumentation, consumption of low volumes of organic
solvents and applicability on little amounts of solid and semi-solid samples. Factorial design was used to study and screen the
most important factors followed by a Box-Behnken response surface methodology (based on global desirability function) to
obtain the factor levels leading to the highest extraction efficiency for all of the analytes. Calibration curve was obtained at the
optimum point, using spiked soil samples at 6 concentrations, and showed to be linear for at least 2 orders of magnitude.
Repeatability of the entire method was less than 12% and LODs were ranged from 0.1 up to 2.0 ngg-1.
Reference
[1] S.A. Barker, J. Chromatogr. A, 885 (2000) 115.
[2] X.-G. Chu, X.-Z. Hu, H.-Y. Yao, J. Chromatogr. A, 1063 (2005) 201.
[3] J.L. G´omez-Ariza, M. Bujalance, I. Gir´aldez, A. Velasco, E. Morales, J. Chromatogr. A, 946 (2002) 209.
[4] M. Fernandez, Y. Pico, J. Manes, J. Chromatogr. A, 871 (2000) 43.
Chemometric tools for monitoring Iranian yogurt drink (Doogh) during storage by excitation-emission matrix
fluorescence spectroscopy
Maryam Vosough*, Marzieh Khaksar, Reza Zadmard
Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186 Tehran, Iran
Analysis of dairy products as an important class of food commodities has been performed during the last decade using
fluorescence spectroscopy. This technique is fast, selective, sensitive and non-destructive. The potential of using fluorescence in
food research has increased recently with the propagated assisting of chemometrics and with technical and optical developments
of spectrofluorometers [1-2]. Front-face florescence spectroscopy has been used for measuring light induced oxidation in various
dairy products such as cheese and yogurt [2-3]. Yogurt drink or Doogh as one of the most favourite drinks in Iran was explored in
the present study using spectrofluorescence in the right angel mode for the first time. Here, multivariate data analysis of principal
component analysis (PCA), unfold principal component analysis (U-PCA) and parallel factor analysis (PARAFAC) were used for
exploratory analysis of Iranian yogurt drink during storage. These methods were applied to the excitation-emission matrices
(EEM) of fresh samples, stored at 4˚C in the refrigerator and the samples stored in clear glass vials for three weeks and exposed
to light at 25˚C, respectively. EEMs were recorded every 5 nm over the ranges λem= 310-750 nm and λex= 220-300 nm. A
pronounced decrease of fluorescence intensity in the emission region of riboflavin (525nm) was observed in samples exposed to
light as compared to fresh ones. Data matrices were pre-processed (column mean-centred) before analysis. PCA and U-PCA of
two and three-way data arrays revealed clear exploration of samples according to storage conditions. Then a three-component
PARAFAC model under non-negativity constraint in all modes and with explained variance of 99.3% was found to be optimal
for interpreting the discrimination between the groups (scaled data). With the proposed model and removing outlier samples,
successful classification of Doogh samples (more than 94%) under different storage conditions was accomplished which
confirmed the results obtained using exploratory analysis through PCA.
Reference
[1]. E.M. Becker, J. Christensen, C.S. Frederiksen, V.K. Hauggard, J. Dairy Sci. 86 (2003) 2508.
[2]. C.M. Andersen, G. Mortensen, J. Agric. Food Chem., 56 (2008) 720.
[3]. J. Christensen, E.M. Becker, C.S. Frederiksen, Chem. Intell. Lab. Syst., 75 (2005) 201.
Liquid–liquid microextraction based on room temperature ionic liquid coupled to flame atomic absorption
spectrometry for determination of cobalt in real samples.
Mahmoud Chamsaza, Mina Adibib, AtefeAtarodia*, Mohammad Eftekharia, SaeidAsadpoura
a
Department of Chemistry, Faculty of sciences, Ferdowsi university of Mashhad, Mashhad, Iran
b
Department of Specialty Chemical, Division of Chemical and Petrochemical, Research Institute of Petroleum Industry (RIPI), Tehran, Iran
Cobalt is a naturally occurring element found in rocks, soil, water, plants, and animals. It is an essential micronutrient required
for the growth of both plants and animals. Cobalt can be beneficial for humans because it is a part of Vitamin B12 [1,2].Room
temperature ionic liquid (RTIL) is a kind of burgeoning green solvent. Recently RTILs with unique properties such as negligible
vapor pressure, water stability, favorable viscosity and density characteristics, good thermal stability, non-volatility and good
selective solubility have been used as alternative solvents for separation purposes[3]. Extractions of metal ions using room
temperature ionic liquids (RTILs) combined with suitable complexing agents have been recently developed in
analyticalchemistry, thus allowing extraction of low polar compounds from aqueous solution[4, 5].In this work, A
preconcentration method based on liquid liquidmicroextraction (LLME) employing room temperature ionic liquids (RTILs)
coupled to flame atomic absorption spectrometry (FAAS) was developed for cobalt determination in real samples. The
methodology is based on the complexation of Co with sodium diethyldithiocarbamatetrihydrate reagent (NaDDTC.3H2O)
followed by extraction of the resulting complex by the RTIL 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim][PF6]).
After phase separation, the enriched analyte in the final solution was determined by flame atomic absorption spectrometry
(FAAS).Under the optimum experimental conditions, the limit of detection (based on 3Sb/m)and the enhancement factor were 9.2
µgL−1 and 38, respectively. The relative standard deviation for ten replicated analysis of 210 µg L−1 Co2+ was calculated to be
3.9%. Validation of the methodology was performed by standard addition method and the method was successfully applied to the
determination of cobalt in vitamin B12 capsule, spring and tap water samples. The accuracy of the developed procedure was
evaluated by analysis of the certified reference material NCS DC 73301.
Reference
[1] E.J. Underwood, Trace Elements in Human and animal Nutrition, 4th ed., Academic Press, New York,
1977.
[2] D. Purves, Trace Element Contamination of the Environments, Elsevier Science Publishers BV,
Netherlands, 1985.
[3] J.L. Anderson, D.W. Armstrong, G.T. Wei, Anal. Chem., 2006, 78, 2892.
[4] P. Berton, R. Wuilloud, Anal.Chim.Acta, 2010, 662, 155.
[5] M. Gharehbaghi, F. Shemirani, M. Farahani, J. Hazard.Mater., 2009, 165, 1049.
Cloud point extraction of Fe3+and Cd2+ ions using a new binuclear Schiff base following spectrophotometric study and
determinationbyAAS
A.Shokrollahi *a ,A.H.Kianfara, Z.Kavehpishghadamb,Z.AzamiArdekania,S.Eslamib
a
Department of Chemistry, Yasouj University, Yasouj,75918-74831, Iran
b
Department of chemistry,Firoozabad branch, Islamic Azad University, Firoozabad,Fars, Iran
Email: ashokrollahi@mail.yu.ac.ir
Cloud point extraction by phases of nonionic surfactants (NS) is a high- performance, selective, and ecologically safe method for
microcomponent separation and preconcentration [1]. In this work,a simple, sensitive and selective cloud point extraction method
is described for the preconcentration and atomic absorption spectrometric determination of Fe +3and Cd2+in watersamples[1].
Primarily the interaction between the cited ions with (E)-1-(2,4-di hydroxyl-5-(1-(2-hydroxy phenyl imino) ethyl) phenyl)
ethanone (DHHPIEPE)was investigated spectrophotometrically.Thus,the cloud point extraction methodology was developed for
precocentration anddetermination ofFe+3and Cd2+. After complexation with DHHPIEPE in basic medium, analyte ions are
quantitatively extracted to therich phase of Triton X-114 following centrifugation. The chemical variables affecting the
preconcentration process were optimized. A typical cloud point experiment required the following steps: an aliquot of 15 ml of a
solution containing 66.6μg L-1 Fe3+and 133/3 μg L-1 Cd2+ions, 0.16% (w/v) Triton X-114 andDHHPIEPE(0.16mM ) was adjusted
to pH 10 by addition of NaOH. The mixture was shaken for 1 min and left to stand in a thermo-stated bath at 60°C, for 20 min.
Separation of the phases was achieved by centrifugation at 3500 rpm for 15 min. The whole system was cooled in an icebath for
5 min that the surfactant rich phase would regain its viscosity. In this way, the bulk aqueous phase was easily decanted. The
remaining micellar phase was dissolved to 0.5 mL in 1.0 M HNO3 in methanol and the Fe+3 and Cd2+ and ions content was
readily evaluated by FAAS. The proposed method offers a simple, rapid,inexpensive,and environmentally being methodology for
preconcentration and separation of trace metal ions in aqueous solutions. It was applied to the analysis of natural and waste water
samples.
Reference
[1]. E. Pramauro, E. Pelezetti, Surfactants in Analytical Chemistry, Elsevier, Amsterdam, 1996
Study of quantitative structure– retention indices relationship of the mono methyl alkanes in fossil fuels by multiple linear
regression and support vector machines
Aboozar fallahzadeh1, Aiyoub parchehbaf jadid 2
1. Department of Chemistry, Payame Noor University of Ardabil, Ardabil, Iran
2. Department of Applied Chemistry, Islamic Azad University-Ardabil Brunch, Ardabil, Iran
A Support vector machine (SVM) model in quantitative structure property relationship (QSPR) was developed for predicting
retention indices of 122 mono methyl alkanes of fuel .The total number of descriptors were calculated with Dragon software and
a subset of calculated descriptors was selected from 18 classes of Dragon descriptors with a stepwise multiple linear regression
(MLR) as a feature selection technique by SPSS 18 Software. For evaluation of retention indices by SVM method STATISTICA
software was used. One descriptor, SRW06 (Self Returning Walk) was selected as the most feasible descriptor. The data was
randomly divided to the training, prediction sets. The predictive ability of the model was evaluated using cross validation
method. The root mean squares error (RMSE) of MLR and SVM model was 10.227, 24.955 for the validation data set. The
performance of the MLR model was also compared with support vector machine (SVM) model and the results showed the
superiority of the MLR over SVM model.
Reference
[1] Kissin, Y.V. and G.P. Feulmer, Gas-Chromatographic Analysis of Alkyl-Substituted Paraffins.
Journal of Chromatographic Science, 1986. 24(2): p. 53-59.
[2] Phillips, M., K. Gleeson, J.M. Hughes, J. Greenberg, R.N. Cataneo, L. Baker, and W.P. McVay,Volatile organic compounds in breath as markers of lung cancer: a
cross-sectional study.Lancet, 1999. 353(9168): p. 1930-3.
[3] Zarei, K. and M. Atabati, Zh Anal Khim, 2005. 60: p. 825 - 831.
[4] Du, Y. and Y. Liang, Data mining for seeking accurate quantitative relationship between
molecular structure and GC retention indices of aklanes by projection pursuit. Comput BiolChem, 2003. 27: p. 339 - 353.
Ultrasound–assisted emulsification solidified floating organic drop microextraction of trace amount of tellurium prior to
graphite furnace atomic absorption spectrometry
Fariba Fathi* a,b, Maryam Ghanbariana,b, Daryoush Afzalib, Ali Mostafavia
a
Department of Chemistry, Shahid Bahonar University of Kerman
b
Environment Department, International Center for Science, High Technology & Environmental Sciences, Kerman
E-mail: Fathirad.Fariba@gmail.com
A novel method of ultrasound-assisted emulsification solidified floating organic drop microextraction (USAE-SFODME) was
developed for preconcentration of trace amount of tellurium before graphite furnace atomic absorption spectrometry
determination. Several variable factors that influence the complex formation and extraction of Te, such as pH, concentration of
APDC, type and volume of the extracting solvent, sonication and centrifuging time, were optimized. Under the optimum
conditions, the calibration graph was linear in the range of 0.01-0.5 ng mL-1 with limit of detection of 0.004 ng mL-1. Relative
standard deviation was ±4.2% (C=2.0 ng mL-1 n=10).Tellurium is regarded as rare, non-essential element and known to be toxic
to living biological [1]. Tellurium usually occurs at low concentration levels, therefore separation and preconcentration procedure
is necessary prior to determination of it [2]. For this procedure, 14.0 mL sample solution containing 0.08 ng of Te and 2 µL of
ammonium pyrrolidinedithiocarbamate (APDC) 0.001% was adjusted to pH 1.5 and placed in a 15 mL screw cap glass test tube
and then, 40.0 µL of 1-Undecanol were added to it and sonicated for 3 min. A cloudy solution was formed in the test tube. In this
step, the complex of Te-APDC was extracted into the fine droplets of 1-Undecanol. The solution was centrifuged at 2500 rpm for
6 min and the extraction solvent floated on the surface of aqueous solution. Then it was solidified and transferred into a conical
vial and melted quickly at room temperature. The sample solution was injected into the GFAAS for analysis. The proposed
method was applied for preconcentration and determination tellurium in different samples and the recoveries of spiked samples
were shown good accuracy.This method has been developed for the sensitive determination of Te in water samples. The
procedure is simple, sensitive, rapid and inexpensive and low toxicity since only very small amount of extraction solvent is used
without affecting the sensitivity of the method.
Reference
[1] Z.F. Chai, H.M. Zhu, Atomic Energy Press, Peking, China, 1994, pp. 201–204.
[2] A. Taylor, Biochemistry of tellurium, Biol. Trace Elem. Res. 55 (1996) 231–239
Pre-concentration and determination of ultra trace of methadone in water samples and body liquids using dispersive
liquid-liquid microextraction by gas chromatography-mass spectrometrometry
Saeed Habibollahi* , Nahid Tavakoli, Zeinab Tofighi Zavareh
Department of Analitical Chemistry Isfahan University Of Payame noor, Iran
E-mail:tofighi_zavare@yahoo.com
Methadone is a potent analgesic and sedative. It is widely used in the treatment of heroin addiction and is often encountered in
forensic specimens[1]. In this work dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry
(GC/MS) was applied for preconcentration and determination of methadone from water sample, blood, salivia and urin. In
electron impact ionization/ selective ion monitoring (EI/SIM) gas chromatography/mass spectrometry (GC/MS) mode,
methadone produces, predominantly a m/z 72 ion.For the extraction, 1.0ml dispersive solvent (isopropanol) and 50.0µl extraction
solvent (chloroform) was inject rapidly into a glass tube with conical bottem containing aqueos solution of methadone. this
injection led to a cloudy water solution, coused by the final droplets dispertion of the immiscible extraction solvent (chloroform)
in aqueous sample. The final step of the microextraction procedure was centrifugation to coolect the dispersed tinny chloroform
droplets in the bottem of conical test tube. Then 1µl of sedimented phase was inject into the GC/MS and methadone determind.
Some effective parameters on extraction such as: extraction and dispersive solvent type and volume, salt addition, time of
extraction, pH and effect of ultra sonic wave were studid and optimized. consequently enrichment factors and limits of detection
(LOD), were ranged 800 and 0.01ng/ml, respectively. Also relatively standardard deviation (R.S.D) and correlation coefficient
were in the rang of <10% (n=5) and 0.995 respectivly. As a result, the proposed method successfully was used for analysis of real
samples such as tap water, Isfahan zayande rood ( river water), saliva, urin and plasma. The methode proved suitable for the preconcentration and determination of methadone in water samples and bod
Reference
[1] C. Moore, F. Guzaldo, M.J. Hussain, D. Lewis, J. chromatogr. B 867 (2008) 219-225
[2]Panagiota D. Nikolaou, Ioannis I. Papoutsis, Julia Atta-Politou, Sotiris A. Athanaselis,
Chara A. Spiliopoulou, Antony C. Calokerinos, Constantinos P. Maravelias, Forensic Science International 119 (2001) 155-160
Central composite design for Optimization of dispersive liquid-liquid microextraction followed by HPLC-DAD
determination of Cr+3 and Co+2 based on the complexation reaction with MDTC
Amir Chehrehghani*, Naser Samadi, Mohammad Reza Vardast
Department of Chemistry, Faculty of Science, Urmia University Urmia, Iran
The aquatic environmental pollution caused by heavy metals has become a subject of considerable public and scientific concern
due to their toxicity to human health and biological systems [1]. Assadi and co-workers has developed a simple and rapid
preconcentration and microextraction method, called dispersive liquid–liquid microextraction (DLLME), as a highly promising
environmentally friendly sample preparation technique with target analytical potential [2,3]. The effects of various experimental
parameters in extraction were investigated using two optimization method, one variable at a time and central composite design.
The experimental design was done at five levels of operating parameters. In this study, a dispersive liquid-liquid microextraction
(DLLME) method was used for preconcentration of Cr (III) and Co (II) cations in water samples. Morpholin -4-carodithioate
(MDTC) was used as chelating agent prior to extraction. High-performance liquid chromatography-diode array detection (HPLCDAD) was used for quantification of the analytes after preconcentration. The effects of extraction, nature and volume of disperser
solvent, pH value of sample solution, extraction time and extraction temperature were investigated. Under the optimum
conditions, the calibration graphs were linear in the range of (10-4000μg L-1) and (5-4000 μgL-1) with detection limits of 3 μg L-1
and 3 μg L -1 for Co(II) and Cr(III) respectively. Recoveries and enrichment factures for Cobalt and Chromium were obtained
(90%, 63.69) and (84%, 58.42), respectively. The DLLMEHPLC-DAD method was successfully applied to the analysis of Cr
(III) and Co (II) in aqueous samples.In conclusion,We now report the DLLME application, as a separation and preconcentration
technique, for the rapid determination of Cobalt and Chromium amounts in water samples using the Morpholin -4-carodithioate
(MDTC) as chelating agent. Eventually, High-performance liquid chromatography-diode array detection (HPLC-DAD) was used
for detection.
Reference
[1] V. Gómez, M.P. Callao, Chromium determination and speciation since 2000, Trend. Anal. Chem. 25 (2006) 1006–1015.
[2] Rezaee M, Assadi Y, Milani Hosseini MR, Aghaee E, Ahmadi F, Berijani S (2006) J Chromatogr A 1116:1–9
[10]Rahnama Kozani R, Assadi Y, Shemirani F, Milani Hosseini MR, Jamali MR (2007) Talanta 72:387–393
[4] M. A. Neouze and U. Schubert, Monatsh. Chem., 139(2008)183–195.
Flame atomic absorption spectrometric determination of Bi(III) after solid phase extraction on MWCNT modified with 1buthyl 3-methyl immidazolium hexa flouro phosphate supported on sawdust
N. Pourreza*, K. Sheikh-Najdi
Department of Chemistry, College of Science, Shahid Chamran University, Ahvaz
Email: npourreza@yahoo.com
Bismuth is present in seawater at concentration of about 10-10 M(ca. 20 ng dm-3) and also is used in medicine due to its anti acid
action and mildly astringent action in gastrointestinal disorders .Although the absorption of Bi(III) in the human organism is
generally low, several cases of nephrotoxic, neurotoxic, and kidney damage symptoms attributable to the use of Bi(III) - containing
pharmaceutical formulations have been reported . Bismuth and its compounds are also used in semiconductors, cosmetic
preparations, alloys and metallurgical additives, and in the preparation and recycling of uranium nuclear fuels. A novel solid -phase
extraction method for the determination of Bi(III) by atomic absorption spectrometry is described. Multiwalled carbon nanotubes
(MWCNT) modified with 1-buthyl 3-methyl immidazolium hexaflouro phosphate (MWCNT-[BMIM]PF6) and supported on
sawdust was used as an adsorbent for preconcentration of trace amount of bismuth. In this method, Bi(III) ions are retained on
(MWCNT--[BMIM]PF 6) adsorbent in a column after formation of negative complex with iodide. The adsorbed complex is eluted
from the column with a solution of nitric acid (3 mol L-1) and determined by flame atomic absorption spectrometry. The recovery of
metal ions adsorbed on the column was calculated from the amounts of Bi(III) ions in the starting sample and the amounts eluted
from the column. The effect of various analytical parameters, such as pH, sample volume, concentration and volume of nitric acid
as eluent, iodide concentration in sample solution and interfering ions was investigated in order to achieve highest sensitivity and
selectivity. The calibration graph was linear in the range of 4-300 ng mL- 1 of Bi(III) in the initial solution. The detection limit based
on 3Sb was 2.3 ng mL- 1 and relative standard deviation (RSD) for 20 ng mL-1 of Bi(III) ions was 2.3%. The method was applied to
the determination of Bi(III) ions in water and pharmaceutical samples.
Referance
[1] T. Shamspur, A. Mostafavi .J Hazard. Mater., 2009, 168 ,1548.
[2] J. Wang, H. Chu, Y. Li, ACS Nano, 2008, 2, 2540.
[3] Katsyuba, J. Phys. Chem. A 2007, 111, 352.
Sensitive determination of Sunset Yellow and Tartrazine in food samples by using sol-gel electrode modified with
carbon nanotube-ionic liquid (CNT-IL) nanocomposite
M. R. Majidi *, R. Fadakar bajeh baj, A. Naseri
Electroanalytical Chemistry Laboratory, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
* E-Mail: sr.majidi@gmail.com
Sunset Yellow and Tartrazine are synthetic organic food dyes that can be found in common food products such as beverages,
candies, dairly products and bakery products. The presence and content of these dyes must be controlled due to their potential
harmfulness to human beings [1]. Therefore simultaneous and sensitive determination of Sunset Yellow and Tartrazine in
food samples is neccesary. To best of our knowledge, various methods such as high-performance liquid chromatography
(HPLC) [2], spectrophotometry [3] for the determination of Sunset Yellow and Tartrazine were presented. Because of
electroactivity of Sunset Yellow and Tartrazine, electrochemical methods have been used for their determination [1, 4].
Carbon nanotubes have excellent electrocatalytic properties for the redox reaction of different electroactive species. Ionic
liquids (ILs) are organic salts which melt below 100 °C, often even at room temperature. ILs have a number of valubale
properties such as high ionic conductivity, electrochemical and thermal stability, ion-exchange properties, extraction and
catalytic activity, etc. Due to their nature ILs are non-flammable, non-volatile and , therefore, non-hazardous witch make
them attractive as ˝green˝ solvents for many chemical processes both of industrial and laboratory scales [5]. In the present
work Sunset Yellow and Tartrazine were sensitively determined on the sol-gel electrode modified with carbon nanotubeionic liquid (CNT-IL) nanocomposite. Based on electrocatalytic and surface enhanced effect of carbon nanotube-ionic liquid
(CNT-IL) nanocomposite; sensitivity of the modified electrode for the determination of Sunset Yellow and Tartrazine were
improved. Therefore determination of low levels of Sunset Yellow and Tartrazine in food samples were possible. This
method succesfully was used for the detrmination of Sunset Yellow and Tartrazine in differnt soft drinks.
Reference
[1] W. Zhang, T. Liu, X. Zhang, W. Huang, C. Wan, Colloids and Surfaces B: Biointerfaces 74(2009) 28
[2] M. Poul, G. Jarry, M.O. Elhkim, J.M. Poul, Food Chem. Toxicol. 47 (2009) 443
[3] E. Dinc, E. Baydan, M. Kanbur, F. Onur, Talanta 58 (2002) 579
[4] J.J.B. Nevado, J.R. Flores, M.J.V. Llerena, Talanta 44 (1997) 467
[5] V. Carrera, E. Sabater, E. Vilanova, M.A. Sogorb, J. Chromatogr. B 847 (2007) 88
Preconcentration procedure using ionic liquid based liquid liquid microextraction (IL-LLME) for determination of
cadmium at trace levels by flame atomic absorption spectrometry.
Mahmoud Chamsaz, Mohammad Eftekhari*, AtefeAtarodi, Saeid Asadpour
Department of Chemistry, Faculty of Sciences, Ferdowsi university of Mashhad, Mashhad, Iran.
Because of the toxicity of cadmium even at low concentration to plants and humans, the quantification of cadmium is very
important. It can be cause of diseases as: hypertension, arteriosclerosis, cancer, etc [1]. For many years flame atomic absorption
spectrometry (FAAS) has been a standard analytical tool for determination of metals in various matrices owing to its wide
application range, simplicity in operation and low cost of analysis [2].In order to achieve accurate, sensitive and reliable results at
trace levels; preconcentration and separation steps are needed prior to analyte determination by FAAS.Ionic liquids (ILs) can be
defined as organic salts that are liquid at or near room temperature. The immiscibility of some ILs with water (which allows
formation of biphasic systems) and their negligible vapor pressure as well as the high solubility of organic species in them makes
ILs suitable solvents for conventional liquid-liquid extraction [3].n this research, a method was developed for the determination
of cadmium at trace levels with using ionic liquid based liquid liquid microextraction (IL-LLME) method followed by flame
atomic absorption spectrometry (FAAS). In this method, cadmium was complexed with ammonium pyrrolidinedithiocarbamate
(APDC) and extracted into an ionic liquid phase. IL-LLME is a simple and rapid method for extraction and preconcentration of
metal ions from real samples, and this method is much safer in comparison with the organic solvent extraction.Some effective
factors that influence the extraction efficiency such as, pH, ligand concentration, amount of IL, extraction time, and ionic strength
effect were completely investigated and optimized. The limit of detection (LOD) obtained under the optimum condition was 1.1
µg L -1and relative standard deviation for ten replicate determinations of 100 μgL-1 was 3.4%. The proposed method was
successfully applied for determination of cadmium in water samples and spinach leaves.
Reference
[1] M. Stoeppler, Hazardous Metals in the Environment. Techniques and Instrumentation in Analytical Chemistry, Elsevier, Amsterdam, 1992.
[2] C.R.T. Tarley, A.F. Barbosa, M.G. Segatelli, E.C. Figueiredo, P.O. Lucas, J. Anal. At.Spectrom.,2006, 21, 1305.
[3] J.L. Anderson, D.W. Armstrong, G.T. Wei, Anal. Chem., 2006, 78, 2892.
Investigation of Inclusion Complex of b-Cyclodextrin with MycophenolateMofetil
a
LidaKhalafi* a, Mohammad Rafieeb, FatemehMahdiuna
Department of Chemistry, Faculty of Science, Islamic Azad University, Shahr-e-Qods Branch, Tehran, Iran
b
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan Iran
* Email: l_khalafi@yahoo.com
Nowadays Cyclodextrins known as the most successful group of macrocyclic compounds within the field of supramolecular
chemistry [1]. They have a unique ability to form inclusion complexes with wide variety of molecules. The complexation of the
guest molecule can effectively change its chemical or physical properties [2, 3]. Mycophenolatemofetil (MMF) is a promising
drug for immune-mediated skin diseases. It is currently approved for the prevention of organ rejection. MMF inhibits de
novopurine synthesis, which leads to decreased proliferation of activated lymphocytes, thus resulting in reduction of antibody
production, changes in the recruitment and induction of apoptosis [4]. In this work the acid-base equilibrium of MMF is studied
in the absence and presence of β-cyclodextrin (β -CD).
Structure of MycophenolateMofetil
The conditional acidity constants are obtained by rank annihilation factor analysis (RAFA) as a function of β-CD
concentrations.Also the formation constants for inclusion complexes of β-CD with both acidic and basic forms are calculated by
nonlinear least-squares fitting. The calculated stability constants show that the acidic form of MMF forms more stable inclusion
complex than its basic anionic form.Preferential inclusion of the acidic form causes a decrease in the conditional acidity constants
in the presence of β-CD.
Reference
[1] L. Khalafi, Res. J. Chem. Environ. 12 (2008) 102.
[2] A. Afkhami, L. Khalafi, Anal. Chim.Acta, 569, (2006), 267-274.
[3] A. Afkhami, L. Khalafi, Anal. Chim.Acta, 599, (2007) 241-248.
[4] C.N. Pisoni, M.J. Cuadrado, M.A. Khamashta, G.R. Hughes, D.P. D’Cruz, Rheumatology (Oxford), 46, (2007),516–8.
Study of Complex Formation between Cerium Cation and Dicyclohexyl-18-Crown-6 in Some Aqueous and None aqueous
Binary Mixtures
Sh. Yari, M. Ansari Fard*, K. Taheri, M. davardoost Manesh
Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, Zahedan, Iran
*E-mail address: mansari@hamoon.usb.ac.ir
The complexation reaction between Ce3+ cation with Dicyclohexyl-18-Crown-6 ligand was studied in water-acetonitrile(H2O-AN),
dimethylformamide-methanol(DMF-MeOH), dimethylformamid-acetonitrile(DMF-AN) and methanol-ethanol(MeOH-EtOH) binary
mixtures using conductometric method. The stability constants of crown ether complexes have been determined by using of different
techniques[1-3]. Among these various methods, the conductometric technique is a sensitive and inexpensive method with a simple
experimental arrangement for such investigation. The stability constants of crown ether complexe were calculated from variation of
molar conductance as a function of ligand / cation mole ratios using a GENPLOT computer program [4]. The conductance data show
that the stoichiometry of complexe in all of studied solvent systems is 1:1. The values of stability constants show that the stability of
complexe is affected by nature and composition of the mixed solvents [5,6] and a non linear behavior was observed for the variation
of the logarithm of stability constant (Log K f) of the complexe versus the composition of mixed solvent. This behavior may be due to
some kind of solvent-solvent interactions and changing the structure of solvent system when they are mixed and these changes
influence the slovation events and also conformation of the crown ether ligand [7]. The changes in the standard enthalpy (ΔH°c) for
complexation reaction was determined in the usual manner from the slope of the Van't Hoff plots assuming that (ΔCP) is equal to
zero over the entire temperature range investigated. The changes in standard entropy (ΔS°c) were calculated from the relationship
ΔG°298.15= ΔH°c
-298.15ΔS°c. The values of ΔHºc and ΔSºc show that in the most cases the formation of
(DH18C6.Ce3+) complex are enthropy stabilized and enthalpy destabilized.
Reference
[1]- K.Taheri, M.Chamsaz, G.H.Rounaghi and M.AnsariFard, Journal of Inclusion Phenomena and Macrocyclic Chemistry, 63, 43-52 (2009).
[2]- G. H. Rounaghi and R.Sanavi, Polish J. Chem., 80, 719 (2006).
[3]- K. Taheri, G.H. Rounaghi, M.Chamsaz, M.Ansari, Asian J.Chem.(in press, 2008).
[4]- Genplot, Computer. Graphic. Service, USA (1989).
[5]- P.Fux, J.Lagrange and P.Lagrange, J.Am. Chem. Soc.,107,5927(1985).
[6]- B.L.Haymore, J.D. Lamb, R.K. Izatt, R.M. Izatt and J.J. Christensen, J.Inorg. Chem.,21, 1598(1982).
[7]- K. Izutsu, Electrochemistry in nonaqueous solutions. WILEY-VCH, Verlag GmbH D-69496, (2002).
Solvent effect on stability and thermodynamic behavior of complex of 18-Crown-6 with Hydroxyl Ammonium Cation (
HONH3+ )
M. Davardoost Manesh , K. Taheri*, M. Ansari Fard ,Sh. Yari
Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, Zahedan, Iran
E-mail address: Taheri38kh@hamoon.usb.ac.ir
Many applications of crown ether compounds are based on their complexant strength with various cations, and hence the stability
constants of their complexes and follow the factors which affect their stability are important in many procedures such as
separation, extraction, ion transport, chromatography and improvement the selectivity of analytical method[1-2]. In this study, the
complexation reaction between HONH3+ cation with 18-Crown-6 (18C6) ligand have been studied in (DMF-MeOH), (H2OMeOH) and (H2O-DMSO) binary mixtures using conductometric method.The stability constants of crown ether complexes were
calculated from variation of molar conductance (Λm) as a function of ligand / cation mole ratios using a GENPLOT computer
program. The changes in the standard enthalpy (ΔH°c) for complexation reactions were determined in the usual manner from the
slope of the Van't Hoff plots assuming that (ΔCP) is equal to zero over the entire temperature range investigated. The changes in
standard entropy (ΔS°c) were calculated from the relationship
ΔG°298.15= ΔH°c
-298.15ΔS°c[3]. The conductance
data show that the stoichiometry of complex in all of studied solvent systems is 1:1 and the stability and thermodynamic
parameters of complex is affected by nature and composition of the mixed solvents and a non linear behavior was observed for
the variation of the logarithm of stability constant (Log Kf) of the complex versus the composition of mixed solvent[4] .In
addition, the results indicate that the complex are entropy stabilized but enthalpy destabilized and in general both thermodynamic
parameters (∆Sº, ∆Hº) vary to more positive values with increasing MeOH or DMSO concentration in solutions and due to more
change of T∆SºC , the stability of complexes increases.
Reference
[1].Jeng, J., Shin, J.S.Analyst (Lond.)109, 641–643 (1984).
[2].Cronin, L. Annu. Rep. Prog. Chem., Sect. A:Inorg. Chem. 100, 323–383 (2004)
[3].M. Ansari Fard.,G. H. Rounaghi, J. Incl. Phenom. Macrocycl. Chem., 52, 39-44 (2005).
[4].G. H. Rounaghi , M. H. Arbab Zavar , K. Badiee , F. Boosaidi and M. S. Kazemi, J. Incl. Phenom. Macrocycl. Chem., 59,363-369(2007).
Study of Complex Formation Between Dicyclo-18-Crown-6 with La3+ Cation in Some Binary Mixed Solvents
M. Davardoost Manesh , K. Taheri* , M. Ansarifard
Department of Chemistry, Faculty of Sciences, University of Sistan and Baluchestan, Zahedan, Iran
E-mail address: Taheri38kh@hamoon.usb.ac.ir
The complexation reaction between La3+ cation with macrocyclic ligand,Dicyclo-18-crown-6 ,was studied in MeOH-DMF,
MeOH-EtOH, and AN-EtOH binary solutions at different temperatures using the conductometric method. The changes of molar
conductance (Λm) versus the ligand to metal mole ratios , for complexation of La3+with Dicyclo-18C6 in various binary mixed
solvents were studied. [L]t and [M]t are the total concentrations of the crown ether and the metal ion respectively [1]. stability
constants of crown ether complex were calculated from variation of molar conductance as a function of ligand/cation mole ratios
using a GENPLOT computer program[2].The conductance data show that the stoichiometry of complex in all of studied solvent
systems is 1:1.It was found in all cases ,a non-linear behavior was observed for the variation of logkf of the complex versus the
composition of the mixed solvents[3].The thermodynamic parameters (ΔH°cand ΔS°c) for complexation reaction between
Dicyclo-18C6 with La3+ cation in MeOH-DMF were obtained from temperature dependence of the stability constants of complex
using the vanʼt Hoff plot[4]. The obtained results show that the values of ΔH°c and ΔS°c for formation of complex are quite
sensitive to the nature and composition of the mixed solvent[5].The experimental values of ΔH°c and ΔS°c show that in most cases
, the complexation reaction between Dicyclo-18C6 with La3+ in MeOH-DMF binary solution is enthalpy destabilized but entropy
stabilized, therefore the entropy of complexation reaction is the principal driving force for formation of complex.
Reference
[1].M. Ansari Fard , G. H. Rounaghi , M. Chamsaz and K. Taheri , J. Incl. Phenom. Macrocycl. Chem., 64, 49-56(2009).
[2].Genplot, Computer. Graphic. Service, USA (1989).
[3]. De Boer, J.A.A., Reinhoudt, D.N., Harkema, S., Van
Hummel,G.J., De Jong, F, J. Am. Chem. Soc., 104, 4073–4076 (1982).
[4].G. H. Rounaghi , E. Razavipanah , J Incl Phenom Macrocycl Chem ., 61,313–318(2008).
[5].G. H. Rounaghi ,S. Tarahomi, M. Mohajeri. J Incl Phenom Macrocycl Chem ., 63,319–325(2009).
Stability of Dibenzo-18-Crown-6 Complexes with Ce3+, Y3+, UO22+ and Sr2+ Cations in Acetonitrile–Dimethylformamide
Binary Solutions
Gholam Hossein Rounaghi a , Somayeh Tarahomi a* and Roya Rahmanian b
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran
b
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Mashhad Branch, Mashhad, Iran
a
Crown ethers are noted for their remarkable selectivity towards specific cations, making them excellent choices for the separation
of desired ions from mixtures by solvent extraction and membrane transport [1,2]. Among several factors influencing the
formation of macrocyclic complexes, the ability of solvent molecules to solvate metal ions and, thus, to compete with the
donating groups of the ligands for the coordination sites of the central cation plays a fundamental role [3,4].The goal of this
investigation is to study the effect of the nature of the cation and also the composition of the mixed solvents on selectivity and
thermodynamic of complexation reactions of dibenzo-18-crown-6 (DB18C6) with Ce3+, Y3+, UO22+ and Sr2+ metal cations in
acetonitrile (AN)- dimethylformamide (DMF) binary systems using the conductometric technique.The stability constants of the
resulting 1:1 complexes were calculated from computer fitting of the molar conductance-mole ratio data. A non–linear
relationship was observed between the stability constants (logKf) of these complexes with the composition of AN–DMF binary
solutions, which was explained on the basis of changes occurring in the structure of the mixed solvents and also the preferential
solvation of the cations, ligand and the resulting complexes in solutions. The results show that the selectivity order of DB18C6
for the metal ions in pure DMF at 25C is: UO22+> Sr2+> Ce3+> Y3+, but this selectivity order is changed with the composition of
the mixed solvents. The corresponding thermodynamic parameters (Hc, Sc) were obtained from temperature dependence of the
stability constants using the van’t Hoff plots. The results show that both parameters are affected by the nature and composition of
the solvent systems.
Reference
[1]. Izatt, R.M., Pawlak, K., and Bradshaw, J.S., Chem. Rev., 91 (1991) 1721.
[2]. Izatt, R.M., Bradshaw, J.S., Nielsen, S.A., Lamb, J.D., Chem. Rev., 85 (1985) 271.
[3]. Agnihotri, P., Suresh, E., Ganguly, B., Paul, P., and Ghosh, P.K., Polyhedron., 24 (2005) 1023.
[4]. Rounaghi, G.H., Mohajeri, M., Tarahomi, S., Rahmanian, R., J. Solut. Chem. 40 (2010) 377.
Complexation of 4'-nitrobenzo-15-crown-5 with Zn2+, Mn2+, Cr3+ and Sn4+ cations in acetonitrile–ethanol binary mixtures
Gholam Hossein Rounaghi a*, Somayeh Tarahomi a and Fatemeh Hesami b
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran
b
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Mashhad Branch, Mashhad, Iran
a
Macrocyclic crown ethers [1] are widely used as a promising separating agent [2] because of their excellent ability as a neutral
host for selective charged metal ions (guest) in its narrow cavity in various non aqueous solvents. Studies of crown ether
complexes in various solvents show that the thermodynamic and kinetic parameters for complexation processes and even the
stiochiometry of crown ether complexes are affected by the nature and composition of the solvent system [3,4].The goal of this
investigation is to study the effect of the nature and composition of the mixed solvents on selectivity and thermodynamic of
complexation reactions of 4'-Nitrobenzo-15-Crown-5 with Zn2+, Mn2+, Cr3+ and Sn4+ metal cations in acetonitrile (AN)-ethanol
(EtOH) binary systems using the conductometric technique.
The stability constants of the resulting 1:1 complexes were determined from computer fitting conductance-mole ratio data. The
results show that the selectivity order of 4'NB15C5 for the metal cations in AN–EtOH (mol%AN=76) binary solution at 298.15
K is: Cr3+> Mn2+ ≈ Zn2+> Sn4+, but the selectivity order is changed with the composition of the mixed solvents. A non–linear
relationship was observed between the stability constants (logKf) of these complexes with the composition of AN–EtOH binary
solutions. The corresponding thermodynamic parameters (Hc, Sc) were obtained from temperature dependence of the stability
constants using the van’t Hoff plots. The results show that the values and also the sign of these parameters are influenced by the
nature and composition of the mixed solvents.
Reference
[1]. Pedersen, C.J., J. Am. Chem. Soc. 89, 7017–7036 (1967).
[2]. Izatt, R.M., Bradshaw, J.S., Nielsen, S.A., Lamb, J.D., Chem. Rev. 85, 271–339 (1985).
[3]. G. H. Rounaghi, R. Sanavi, Polish J. Chem., 80, 719-727 (2006).
[4]. M. Chamsaz, G. H. Rounaghi, M. R. Sovizi, Russian J. of Inorg. Chem., 50, 413-417 (2005).
A novel optical sensor for determination of Aluminum
Safiyeh Bahmanzadeh*
University of payamenoor. Bandarabbas, Iran
Aluminum compounds are used in several fields including medicals and industrial, so, determination and measurement of it is
very important. various methods have been used for the determination of Aluminum[1,2,3,4]. In this paper, an optical chemical
sensor for determination of Aluminum based on immobilization of Eriochrome Cyanide R on triacetylcellulose membrane is
described. The immobilized reagent on triacetylcellulose was prepared according to the following procedure [5].The transparent
triacetylcellulose membranes were produced from waste photographic film tapes that were previously treated with commercial
sodium hypochlorite for several seconds in order to remove colored gelatinous layers. The films were treated with a clear solution
of Eriochrome Cyanide R in ethylene diamine (10 mg in 10 ml of ethylenediamine) for 2 min at ambient temperature. Then they
were washed with water for removing ethylene diamine and loosely trapped dyes. The absorbance of membranes were finally
investigated in a universal buffer at pH 6. The absorption spectra of Eriochrome Cyanide R in immobilized forms on hydrolyzed
cellulose acetate at different concentration of Al(III) were recorded. The spectral characteristic of this sensor showed a maxima at
535 nm. This wavelength was selected for further studies because of higher selectivity and sensitivity at this wavelength. The plot
of the absorbance difference against the concentration difference exhibits a linear range between 0.12-21 µmolL-1(2-500µg L-1)
with a detection limit of 0.2 µmol L-1 Al(III). The response time was tested by recording the absorbance change from a pure
buffer (pH 6) to a buffered Aluminum solution of 15 µmol L-1. The membrane was found to reach 95% of the final signal at 3–6
min depending on the concentration of Al3+. [6]. Ions such as Ag+,Mn2+,Cr3+,Cr6+ Mg2+, Ca2+, Fe3+,Ba2+, Zn2+, Ni2+, Co3+, Mn2+,
Bi3+ and Cu2+ show no interference on the determination of Al3+.
Reference
[1] V. N. Bulut, D. Arslan, Journal of Hazardous Materials 182 (2010) 331.
[2] O. Y. Nadzhafova, O.A. Zaporozhets, Talanta 67 (2005) 767.
[3] D. Kara, A.Fisher, S. J. Hill Analytica Chimica Acta 611 (2008) 62.
[4] S. L. Zhou, S. J. Liu, X. Y. Jiang,, Microchemical Journal 96 (2010) 412.
[5] A. Safavi, M. Bagheri, Sensors and Actuators B 90 (2003) 143.
[6] A. Safavi, M. Bagheri, Sensors and Actuators B 107 (2005) 53
A New Stable Cobalt Optode Based On Immobilization Of Nitroso-R On Cellulose Acetate membrane
Safiyeh Bahmanzadeh*
University of payamenoor. Bandarabbas, Iran
Cobalt is an essential trace element, however, it can be toxic at higher concentrations. So, it often requires methods capable of
quantitatively monitoring its presence at trace levels [1–5]. In this paper an optical chemical sensor for determination of Cobalt
based on immobilization of Nitroso-R(sodium 1-nitroso-2-hydroxynaphthalene-3,6-disulfonic acid) on triacetylcellulose
membrane is described. For preparation of this optode, [6] waste photographic film tapes that were previously treated with
commercial sodium hypochlorite, were used. The films were treated with a clear solution of Nitroso-R in ethylene diamine (6 mg
in 10 ml of ethylenediamine) for 2 min at ambient temperature. Then they were washed with water for removing ethylene
diamine and loosely trapped dyes. The absorbance of membranes were finally investigated in a universal buffer at pH 5.5. The
absorption spectra of Nitroso-R in immobilized forms on hydrolyzed cellulose acetate at different concentration of Co(II) were
recorded. The spectral characteristic of this sensor showed a maxima at 430 nm. This wavelength was selected for further studies
because of higher selectivity and sensitivity at this wavelength. The plot of the absorbance difference aganst the concentration
difference exhibits a linear range between 0.4-1.7 nmolL-1(0.7-30µg L-1) with a detection limit of 0.2 µmol L-1 Co(II). The
response time was tested by recording the absorbance change from a pure buffer (pH 5.5) to a buffered Cobalt solution of 1 nmol
L-1. The membrane was found to reach 95% of the final Signal at 4–6 min depending on the concentration of Co2+. [7]. Ions such
as Ag+,Mn2+,Sb2+, Mg2+, Ca2+, Ba2+, Zn2+, Ni2+, Al3+, Mn2+, Bi3+ and Cu2+ show no interference on the determinan of Co2+.
Reference
[1]. M. Haij, S. Dadfarnia, and K. Dehghan, Talanta 59 (2003) 719.
[2] B. Welz, M. Sperling, Atomic absorption spectrometry, 3rd ed., VCH,Weinheim, 1999, pp. 499.
[3] A. Carlosena, M. Gallego, M. Valca´rcel, , J. Anal. At. Spectrom. 12 (1997) 479– 486.
[4] F. Baruthio, F. Pierre, Biol. Trace Elem. Res.39 (1993) 21– 31.
[5] E.D. Caldas, M.F. Gine-Rosias, J.G. Dorea, Anal. Chim. Acta 254 (1991) 113.
[6] A. Safavi, M. Bagheri, Sensors and Actuators B 90 (2003) 143.
[7] A. Safavi, M. Bagheri, Sensors and Actuators B 107 (2005) 53
Simultaneous spectrophotometric determination of trace amounts of chlorine and bromate ion in water samples after
micelle-mediated extraction
Hayedeh Bagheri Sadeghi1 , Ali Reza Zarei2, Maryam Shahverdi1*
Islamic Azad University, Central Tehran Branch, Basic Sciences, Department of Chemistry
2
Department of Chemistry and chemical Engineering, Malek Ashtar University of Technology ,Tehran, Iran
Maryamshahverdi7@gmail.com
1
Chlorine is a commonly used household cleaner and disinfectant. With addition of chlorine to water, some of the chlorine reacts
first with organic materials and metal ions in the water and is not available for disinfection that is called the chlorine demand of
the water [1]. Bromate is a by-product formed when drinking water is disinfected to kill bacteria the disinfection process is called
ozonation. Studies of very low dose in animals showed bromate to be cancer and mutagenic (causing a change in a gene or
chromosome)[2]. A cloud point extraction process using the nonionic surfactant Triton X-114 for extraction and preconcentration
of chlorine and bromate ion from aqueous solution was investigated. The method is based on the extraction of triiodide ion, the
colored product of the reaction of chlorine and bromate with iodide in acidic media. The triiodide was concentrated in surfactant
rich phase and then determined spectrophotometrically at 358 nm. For the determination of chlorine and bromate in mixture, two
sets of conditions were established. In one set of conditions only periodate reacted with iodide but in the other set both ions
reacted with iodide. The data were evaluated by the method of proportional equations. Under the optimized conditions, the
method allowed the determination of chlorine and bromate at concentrations between 1.0 and 2000 ng/mL, respectively. The
proposed method was successfully applied to the determination of chlorine and bromate in water samples
Reference
[1]American conference of Governmental industrial Hygienists (ACGIH).2003Guide to Occupational Exposure Values , Cincinnati ,OH
[2]. Agency for Toxic Substances and Disease Registry Division of Toxicology and Environmental Medicine1600 Clifton Road NE, Mailstop F- 62
Investigation of the interaction of amoxicillin (antibiotic drug) with Mn (II) ions in aqueous solution by Spectroscopic and
conductometric methods
R.S.Khoshnood, Donya Arefi*, Fatemeh Zahra Maknoni, Reza Arefi , H.Behmadi, GH.H.Rounaghi
Department of Chemistry, Faculty of Science, Islamic Azad University, Mashhad Branch, Mashhad, Iran
Rskhoshnood@yahoo.com
Β-lactam antibiotics (e.g., amoxicillin) are traditionally used for the treatment of common bacterial infections in both human and
food-producing animals[1,2]. Manganes is so-called biometal since it inters into the composition of some metalloenzemes
necessary for the normal course of biochemical processes. Small amount of copper should be constantly taken in by the human
body with food[3-5]. Spectroscopic methods were used for the determination of Amoxicillin using complex formation with Mn
(II). The complexation of reaction between Mn2+ metal cations with amoxicillin were studied in aqueous solution at different
temperatures using the conductometric method.The value of log kf calculated from the absorption spectra and conductivity
measurement for Mn-amoxicillin complex at 25˚C. Enthalpy and entropy of complexation were determinate from the temperature
dependence of the complextion Constance[6,7]. The interaction of amoxicillin with Mn (II) ions has been found to form one
complex with metal to ligand composition of 1:1.The results show that the complexation formation is affected by the nature of
solvents, time, PH, temperature.
Reference
[1] Alfonso Ferandez-Gonzalez,Rosana Badia,Marta Elenapiaz-Gavcia Analytical Biochemistry 341(2005) 113-121
[2] B.shaik,W.A.Moats,Liquid chromatographic analysis of antibacterial drug residues in food products of animal origin,j,chromatogr.643(1993)369-378
[3] V.G.alekseew and L.V.Demeskaya,Koovd.Khim.33(3),211(2007)[Russ.j.cood .chem33(3),203(2007)].
[4] V.G.alekseew and V.G.Zanislov,Koovd.Khim.52(5),763(2007) [Russ.j.Inorg.chem 52(5),698(2007)]
[5] V.G.alekseem.V.J.Lyam tseva and I.S.Samuilova,Zh.Neory.Khim52(3),433(2007) [Russ.j.Inorg.chem 52(3),328(2007)]
[6] GH.H.Rounaghi,A.Soleamani and R. k.Sanavi:journal of inclusion phenomena and macrocyclic chemistry(2007)58:43-48
[7] GH.H.Rounaghi and M.Ansarifard: journal of inclusion phenomena and macrocyclic chemistry 52,39(2005)
Potentiometric study of acridine/dipicolonic acid Proton-Transfer system and its complexation with UO22+ ion in
dioxane/H2O solvent
Ardeshir Shokrollahi* and Roghayyeh Aghaei
Chemistry Department, Yasouj University, Yasouj 75918-79831, Iran
Email: ashokrollahi@mail.yu.ac.ir
Potentiometry is not limited to aqueous solutions, even with the use of the glass electrode. For all practical purposes these
alcohol-water or dioxane- water solvents can be treated just like aqueous solutions for potentiometric purposes [1].In this work
the protonation constants of acridine (Acr), and dipicolonic acid (pydcH2) as the building blocks of the proton-transfer systems
(AcrH)2(pydc), and the stability constants of these system were determined by potentiometric studies in a dioxane/H2O (1:1 v/v)
mixture. The choice of the solvent mixture was dictated by the low solubility of Acr in pure water at neutral and alkaline pH
values. The stoichiometry and the formation stability constants of complexes formed on reacting pydcH2/Acr 1:1 molar mixtures
with the UO22+ ion in dioxane/H2O (1:1 v/v) were investigated by potentiometric pH titration methods. The stoichiometries of the
complex species formed in solution were compared with those observed for the crystalline metal ion complexes. Ligand
protonation constants and stability constants of proton-transfer systems and their complexes with uranyl cation were evaluated
using the program BEST described by Martell and Motekaitis [2] The value of the autoprotolysis constant for dioxane/H2O (1:1
v/v) solution (Ks = [H+][OH-]) was calculated according to the literature[2]. For pydc(L), Acr (Q)– UO2 binary systems, the most
likely species are: UO2L, UO2LH2, UO2L2 and UO2Q2. For the pydc-Acr-UO2 ternary system the predominant species are:
UO2LQH and UO2L2Q2H3. The results of solution study was compared with the obtained of solid state.
Reference
[1] V. Uitert, L. G. Fernelius, W. C. J. Am.Chem. Soc. 1953, 75, 451
[2] A. E. Martell, R. J. Motekaitis, “Determination and Use of Stability Constants”, 2nd ed., VCH, New York. 1992.
Rapid determination of trace amounts of Dimethylamine in water and biological samples by dispersive liquid-liquid
microextraction combined with spectrophotometric analysis
Ali Reza Zarei*, Kobra Mardi, Soheila Chalavi , Hossein Dehghani
Department of Chemistry, Faculty of Materials, Malek Ashtar University of Technology, Tehran,Iran.
E-mail: zarei1349@gmail.com
Dimethylamine (DMA) is a aliphatic amine that used in, vulcanization accelerators for sulfucured rubber, lubricants, textile
waterproofing agent, pharmaceuticals, and as a component of rocket propellants, as an anti knock agent in other fuels [1]. But it
is very toxic because it is an irritant of the eyes, skin, mucous membranes [2]. DMA has been reported to have unspecified
effects on tumour cells in culture [ 3], to inhibit succinate oxidation in brain tissue [4] and to cause a dose –dependent dcrease in
overall size, nucleic acid and protein content of cultured mouse embryos. It is of particular interest, however, as it has the ability
to undergo nitrosation to dimethylnitrosamine, a potent carcinogen [5]. DMA can be found in human urine and is also present in
other body fluids, including blood and gastric fluid [6]. Therefore determination of trace amounts of DMA is important in water
and blood samples to evaluating the toxicity of it in these samples. In this paper, we developed a novel method for
preconcentration and spectrophotometric determination of trace amounts of dimethylamine in water and blood samples by using
dispersive liquid-liquid microextraction (DLLME) technique. The method is based on derivatization of dimethylamine with
Folin,s reagent (1,2-naphthoquione-4-sulphonic acid), and extraction of product using DLLME technique. Some important
parameters, such as reaction conditions and the kind and volume of solvents and concentration of reagent were optimized. the
calibration graphs were linear for this method in the range of 50-800 with detection limit 20 ng ml1. Average recoveries for
spiked samples were determined to be between 97.5-105%. The proposed method was applied for determination of
dimethylamine in water and human serum samples.
Reference
[1] "Occupational health Guidelines for chemical Hazards " ,NIOSH/OSHA, , DHHS (NIOSH) Publication No. 81-123, 1981.
[2] Hathaway GJ, Proctor NH, Hughes JP, and Fischman ML Proctor and Hughes' chemical hazards of the workplace. 3rd ed. New York, NY: Van Nostrand
Reinhold, 1991.
[3] A.Q. Zhang, S.C. Mitchell, R.L. Smith, Dimethylamine in hyman urin, Clinica Chemica Acta, 233 (1995) 81-88.
[4] I. Guest, D.R. Varma, Developmental toxicity of methylamines in mice, J. Toxicol. Environ. Health 32, 319, 1991.
[5] S.C. Mitchell, A.Q. Zhang, R.L. Smith ,Dimethylamine and diet, foodchemtox, 46 (2008) 1734-1738.
[6] K.Chobanyan, A.Mitschke, F.M. Gutzki, D. Stichtenoth, D.Tsikas, Accurate quantification of dimethylamine in human plasma and serum by GC-tandem MS as
pentafluorobenzamid derivative in the positive-ion chemical ionization mode, J.chromatogar B, 851 (2007) 240-249.
A selective optical sensor for nickel determination based on incorporating of (1-pyridylazo)-2- naphtol in a poly (vinyl
chloride) membrane
Saeed Babaee, Akram sadat Nabavi, Shahram Ghanbari Pakdehi
*Faculty of Materials, Malek Ashtar University of Technology, P. O. BOX 15875-1774, Tehran, Iran.
The pollution by heavy metals from natural waters is a great concern nowadays due to their potentially toxic effects on
environmental organisms [1]. According to EPA regulations, the recommended water quality criterion for nickel is set below
0.6ppm for human consumption [2]. Over the past two decades, an interest has been increased on the development of optical
chemical sensors for the determination of various metals [3]. The choice of matrix for the membrane optode is governed by the
parameters such as permeability for the analyte, relatively low cost, good mechanical properties and etc. [4].In this work a new
optical sensor was fabricated for determination of Nickel ions . The optode membrane was prepared by incorporation of 1pyridylazo 2-naphthol (PAN) and sodium tetraphenylborate (NaTPB) in a plasticized poly (vinyl chloride) membrane containing
Dioctyl adipate (DOA) as a plasticizer. Color of the sensing membrane in contact with Ni2+ ions at pH 6, was changed from
orange to red. The different variables affecting uptake efficiency were evaluated and optimized. Under the optimum conditions
(i.e. 25.64% PVC, 64.10% DOA, 6.41% PAN, 3.84% NaTPB and response time of 10 min.), the proposed sensor displayed a
linear range of 0.2–10 µg mL-1 with a detection limit of 0.05 µg mL-1. Also the precision (RSD%) was better than 1.55% for 5
replicate determinations of 1 µg mL-1 Ni 2+ in various membranes. The interfering effect of some cations and anions was also
studied and the results showed that the sensor was high selective in the presence of EDTA (1.1×10-3 M) as a masking agent .
Finally, the fabricated optical sensor was successfully applied to the monitoring of Ni+2 in real water samples.
Reference
[1] E. Luiz Silva, P. Santos Roldan, M. Fernanda Gine, J. Hazard. Mater. 171 (2009) 1133–1138.
[2] http://www.epa.gov/safewater/dwh/c-ioc/ nickel.html.
[3] M.R. Ganjali, M. Hosseini, M. Hariri, F. Faridbod, P. Norouzi, Sens. Actuators B 142 (2009) 90–96.
[4] Y. Kalyan, A.K. Pandey, P.R. Bhagat, R. Acharya, V. Natarajan, G.R.K. Naidu, A.V.R. Reddy, J. Hazard. Mater. 166 (2009) 377–382.
An optical sensor based on incorporating of (1-pyridylazo)-2- naphtol in a poly (vinyl chloride) membrane for determination
of cadmium in water samples
Saeed Babaee, Akram sadat Nabavi, Shahram Ghanbari Pakdehi
*Faculty of Materials, Malek Ashtar University of Technology, P. O. BOX 15875-1774, Tehran, Iran.
Cadmium has a limited number of applications but is used for a variety of consumer and industrial materials. It's principal uses
include: protective plating for steel, stabilizers for polyvinyl chloride, pigments in plastics and glasses, electrode material in
nickel-cadmium batteries [1]. EPA has also established an interim Maximum Contaminant Level (MCL) of 0.01 mg/L for
cadmium in drinking water [2]. Over the past two decades, an interest has been increased on the development of optical chemical
sensors for the determination of various metals [3]. The choice of matrix for the membrane optode is governed by the parameters
such as permeability for the analyte, relatively low cost, good mechanical properties [4].In this work a new optical sensor was
fabricated for determination of Cadmium ions. The optode membrane was prepared by incorporation of 1-pyridylazo 2-naphthol
(PAN) and sodium tetraphenylborate (NaTPB) in a plasticized poly (vinyl chloride) membrane containing ortho-nitrophenyl octyl
ether (o-NPOE) as a plasticizer. PAN can react with Cd+2 in pH=8 to form water-insoluble colored complex. The different
variables affecting uptake efficiency were evaluated and optimized. Under the optimum conditions (i.e. 26.14% PVC, 63.17%
o-NPOE, 5.91% PAN, 4.78% NaTPB and response time of 10 min.), the proposed sensor displayed a linear range of 0.2–8 µg
mL-1 with a detection limit of 0.04 µg mL-1. Also the precision (RSD%) was better than 2.31% for 5 replicate determinations of
1 µg mL-1 Cd+2 in various membranes. The interfering effect of some cations and anions was also studied and that the sensor
was high selective in the presence of EDTA as a masking agent. Finally, the fabricated optical sensor was successfully applied to
the monitoring of Cd+2 in mineral water samples.
Reference
[1]. Friberg, L., Elinder, C.G., and Kjellstrom, T. IPCS, Environmental Health Criteria 134. Cadmium. World Health Organization, Geneva, 1992.
[2]. http://www.epa.gov/safewater/dwh/c-ioc/ Cadmium.html.
[3] .M.R. Ganjali, M. Hosseini, M. Hariri, F. Faridbod, P. Norouzi, Sens. Actuators B 142 (2009) 90–96.
[4]. Y. Kalyan, A.K. Pandey, P.R. Bhagat, R. Acharya, V. Natarajan, G.R.K. Naidu, A.V.R. Reddy, J. Hazard. Mater. 166 (2009) 377–382.
A selective optical sensor for Zirconium determination based on incorporating of 4-(5-bromo-2-pyridylazo)-5(diethylamino)-phenol in a poly (vinyl chloride) membrane
Saeed Babaee, Akram sadat Nabavi, Shahram Ghanbari Pakdehi
* Faculty of Materials,Malek Ashtar University of Technology, P. O. BOX 15875-1774, Tehran, Iran.
Zirconium is extensively used in chemical industries where corrosive agents are employed [1]. According to EPA regulations, the
recommended water quality criterion for Zirconium is set below 17µg/l for human consumption [2]. Recent years ,we have seen
an increasing interest in the development and construction of optical chemical sensors for heavy metal ions[3].They have been
accepted as analytical chemistry advantageous because they can be miniaturized and can be manufactured in low cost [4].In this
work a new optical sensor was fabricated for determination of Zirconium ions. The optode membrane was prepared by
incorporation of 4-(5-bromo-2-pyridylazo)-5-(diethylamino)-phenol (Br-PADAP) and sodium tetraphenylborate (NaTPB) in a
plasticized poly (vinyl chloride) membrane containing dioctyl adipate (DOA) as a plasticizer. Color of the sensing membrane in
contact with Zr4+ ions at pH 11, was changed from yellow to Reddish orange. The different variables affecting uptake efficiency
were evaluated and optimized. Under the optimum conditions (i.e. 25.641% PVC, 64.102% DOA, 6.41% Br-PADAP, 3.846%
NaTPB and response time of 8 min.), the proposed sensor displayed a linear range of 0.2–10 µg mL-1 with a detection limit of
0.05 µg mL-1. Also the precision (RSD%) was better than 1.55% for 5 replicate determinations of 0.6 µg mL-1 Zr4+ in various
membranes. The interfering effect of some cations and anions was also studied and the results showed that the sensor was high
selective in the presence of EDTA (1.1×10-3 M) as a masking agent. Finally, the fabricated optical sensor was successfully
applied to the monitoring of Zr4+in real water samples.
Reference
[1]. A.Abbaspour, L. Baramakeh, Sens. Actuators B 114 (2006) 950–956.
[2]. http://www.epa.gov/safewater/dwh/c-ioc/ Zirconium.html.
[3].A.Yari, H. A. Abdoli, J. Hazard. Mater 178 (2010) 713–717.
[4].H. Faghihian , M. Kabiri-Tadi ,Microchim Acta (2010) 168:147–152.
Investigation of complex formation between Sr2+ ion and piperazine -dipicolonic acid proton transfer system in aqueous
solution
Jeiran karami Arekhloo1 , Ardeshir Shokrollahi*2 , Mohammad Ghadermazi3
1. Department of Chemistry, Islamic Azad University of Gachsaran, Gachsaran, Iran
2. Department of Chemistry, University of Yasouj, Yasouj, Iran, 75918-79831
3. Department of Chemistry, Faculty of Science, University of Kurdistan, Sanandaj, Iran
E-mail: ashokrollahi@mail.yu.ac.ir
In recent years the complexation of many transition and heavy metal ions with several proton transfer systems including pyridine2,6-diamine, melamine, creatinine, 2-aminopyrimidine / dipicolonic acid(pydc)[1-4] were studied in solid state and solution, but
the interaction of this proton transfer system with alkaline earth wasn't attended. In this work the complexation constants and
stoichiometry of piperazine-dipicolonic acid system with Sr2+ ion in aqueous solution at 25.0 ± 0.1°C and ionic strength of 0.1M
supported by NaNO3 were investigated by potentiometric pH titrations. The overall stability constant, logarithm of β-values, of
all species present were evaluated by computer refinement of pH-volume data using the BEST computer program[5].Distribution
diagrams depicted using Hyss2009 program[6]. The observed species of pydc(L)-Sr and piperazine(Q)-Sr, binary species are:
SrL, SrL2, SrLH, SrQ2 and SrQH. It was seen for the pydc-piperazin-Sr, ternary species are: SrLQH2, SrLQH3 and SrLQ2H. The
stoichiometry of one of the most abundant complexes species in solution was found to be similar to the crystalline strontium
complex.
Reference
[1]. M.A. Sharif, H. Aghabozorg, A. Shokrollahi, G. Kickelbick, A. Moghimi, M. Shamsipur, Polish J. Chem. 80 (2006) 847.
[2]. A. Moghimi, M.A. Sharif, A. Shokrollahi, M. Shamsipur, H. Aghabozorg, Z. Anorg, Allg. Chem. 631(2005) 902.
[3]. H. Aghabozorg, M. Ghadermazi, F. Ramezanipour, Acta Crystallogr. E62 (2006) o1143.
[4]. Hossein Eshtiagh-Hosseini a, Zakieh Yousefi, Masoud Mirzaei, Ya-Guang Chen, S. Ali Beyramabadi, Ardeshir Shokrollahi, Roghayyeh Aghaei , Inorganica
chimica Acta 370 (2011) 141
[5]. A. E. Martell, R. J. Motekaitis, Determination and Use of Stability Constants, 2nd ed.,VCH, NewYork, 1992.
[6]. L. Alderighi, P. Gans, A. Ienco, D. Peters, A. Sabantini, A. Vacca, Coord Chem. Rev., 184, (1999), 311
Ion pair based liquid phase microextraction: A new strategy for ligandless metal extraction
Morteza Moradi, Yadollah Yamini
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
Palladium can be found as a free metal associated with platinum and other platinum group metals (PGMs), as well as with nickel
and copper deposits. In the last few years, palladium was used as a component of three-way catalyst of automobile exhaust
fumes Some of palladium compounds have been reported as potential health risks to humans, causing asthma, allergy, rhino
conjunctivitis and other serious health problems [1]. Recently, surfactant assisted dispersive liquid–liquid microextraction (SADLLME), which uses microliter volume of extraction solvent along with a few milliliters of ultra-pure water containing ionic
surfactant (emulsifier agent) such as CTAB, TTAB or SDS, was developed [2]. A novel method for the determination of
palladium as a model was developed by ion pair based liquid phase microextraction and inductively coupled plasma-optical
detection. In this methodology, cationic surfactant has two fundamental functions; (1) the formation of an emulsified phase and
(2) the ion pair formation with Pd (II) in the presence of iodide ions and making it extractable into organic phase. The effective
parameters on the extraction efficiency such as the extraction solvent type and its volume, type of the surfactant and its
concentration, KI amount and HCl concentration of the sample were optimized. In the proposed approach, tetradecyl trimethyl
ammonium bromide (TTAB) was used as emulsifier and ion pairing agent, and 1-octanol was selected as extraction solvent.
Under the optimum conditions, the enhancement factor of this method for palladium reached at 146. The detection limit for
palladium was 0.09 μg L-1, and the relative standard deviation (RSD) was 4.1% (n = 5, C = 10.0 μg L-1). The proposed method
was applied for extraction and determination of palladium in different environmental sample.
Reference
[1] R. Merget, G. Rosner, Sci. Total Environ. 270 (2001) 165.
[2] M. Moradi, Y. Yamini, A. Esrafili, S. Seidi, Talanta 82 (2010) 1864.
Atmospheric pressure gas-phase ammonium/ alkylammonium exchange studies of some crown ether complexes using ion
mobility spectrometry: A thermodynamic investigation and collision cross section measurements
a
Parvin Shahdousti a, Naader Alizadeh * a, Mahmoud Tabrizchi b
Department of Chemistry, Faculty of Science, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
b
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
Study of host-guest complexation in the gas phase leads to understand the nature of the intrinsic binding interactions involved in
molecular recognition [1]. Crown ethers are particularly useful in modeling biologically relevant ion transport processes,
antibody–antigen association and enzyme catalysis. The complexing of ammonium ions with crown ethers serves as a model for
the interactions of ions with biological membranes, as well as with the interior of enzymes [2]. In the present work, a systematic
evaluation of the intermolecular binding forces responsible for the association of crown ethers (hosts) with alkylamines (guests)
is presented by exchanging the ammonium and alkylammonium in the ion source of atmospheric pressure ion mobility
spectrometry (IMS). The hydrogen-bonding interactions of crown ether/alkylammonium ion complexes is examined with respect
to macrocyclic size effects of five crown ethers (12-crown-4, 15-crown-5, benzo-15-crown-5, 18-crown-6 and aza-18-crown-6)
and the gas-phase basicities of five homologous series of alkylamines. Our approach is based on a formalism assuming an
equilibrium: [host + NH4]+ + [guest + H]+ ↔ [host + guestH]+ + [NH4]+. The exchange equlibrium constant for this process was
calculated using the relative peak intensities of the corresponding species in the IMS spectra. Determination of the equilibrium
constants at different temperature via Van’t Hoff plots led to the standard molar enthalpy change DH˚ that is equivalent to the
guest-exchange affinity of different crown ethers. The collision cross-sections are measured for the formation of complexes ions
and different alkylammonium ions which are produced. Complexes of 15C5 with two different normal and iso-alkylamine
showed a gas phase selectivity binding to normal alkylamines relative to iso-alkylamines.
Reference
[1] C. A. Schalley, Supramolecular chemistry goes gas phase: the mass spectrometric examination of noncovalent interactions in host– guest chemistry and molecular
recognition, Int. J. Mass Spectrom. 194 (2000) 11–39.
[2] D. J. Cram, J. M. Cram, Design of complexes between synthetic hosts and organic guests, Acc. Chem. Res. 11 (1978) 8-14.
Synthesis of Ion Imprinted Polymers for uptake of Cobalt(II) from invironmental samples.
Sahar Afzali Borujeni *, Alireza Feizbakhsh, Homayon Ahmad Panahi, Samira Kamalroosta, Fateme Dadjoo, Rozita Abdollahifard
Department of Chemistry, Central Tehran Brench, Islamic Azad University, Tehran, Iran
E-mail: sahar.afzali2011 @gmail.com
Ion imprinted (IIPs) were prepared from Allyl glycidil ether/iminodiacetic acid (AGE-IDA) as the functional monomer and N,N
methylen-diacrylamid as the cross-linker in ethanol solution using Co(II) as the template ion and 2,2-azo-bis-isobutyronitrile
(AIBN) as the initiator. The polymer was characterized by elemental analysis, Fourier Transform Infrared (FT-IR) and
thermogravimetric analysis (TGA) and studied for preconcentration and determination of Co(II) using flame atomic absorption
spectroscopy. Optimum pH value for sorption of the metal ion was 5. The sorption capacity the fanctionalized polymer was 39. A
recovery of 101% was obtained for the metal ion. The effect of ,ions investigated to evaluate the sensivity. The synthesized
polymer was successfully applied for metal ion determination in environmental samples.
Reference
[1] K. Dhal, in: B. Sellergren (Ed.), Molecularly Imprinted Polymers: Man-Made Mimics of Antibodies and Their Applications in Analytical Chemistry, Elsevier,
Amsterdam, 2003, p. 185.
[2] M. Tada, Y. Iwasawa, J. Mol. Catal., A 199 (2003) 115.
[3] L. Ye, P.A.G. Cormack, K. Mosbach, Anal. Commun. 36 (1999)35.
[4] Wang, Shijie: Cobalt- Its recovery, recycling, and application, Journal of the Minerals, Metals, and Materials Society 58(10), 47-50, 2006.
[5] Y.S.Kim, G.In, C.W. Han, J.M.Choi, Microchem.J.80, 151, 2005.
[6] K. Mosbach, Trends in Biochemical Sciences 19 (1994) 9.
[7] P.K. Dhal, F.H. Arnold, Macromolecules 25 (1992) 7051.
New molecularly imprinted polymer for extraction, preconcentration and determination of Nalidixic acid
Somayeh Ashrafi Mahabadi* 1, Homayon Ahmad Panahi1, Afshin Rajabi Khorrami2
1
Department of Chemistry, Central Tehran Branch, Islamic Azad University, Tehran, Iran
2
Department of Chemistry, Karaj Branch, Islamic Azad University, Karaj, Iran
E-mail: somayeh.ashrafi26@gmail.com
Nalidixic acid imprinted polymer has a hig application in cilinical purposes. Molecularly imprinted polymers (MIPs) has been
prepared using nalidixic acid as the template molecule. The polymer was synthesized in a non-covalent approach with N,NDimethylacrilamid (DMAA) and Allyl glycidil ether / imino diacetic acid (AGE/IDA) as the functional monomer, N,N
methylene diacrylamid as the cross-linker in the methanol solution and 2,2'-azobis-isobutyronitril (AIBN) as the initiator. The
polymerization was performed via a free radical. The synthesized MIP was identified by Fourier transform infrared (FT-IR) and
thermo gravimetric analysis (TGA). The effect of various parameters like pH, adsorption time, amount of adsorbent and
adsorption capacity of adsorbent at optimum conditions were considerd and followed by HPLC-UV analysis. Non-imprinted
polymer (NIP) was also synthesized in the absence of the template compound. Batch adsorption experiments were used to
evaluate the binding affinity of the imprinted polymer. It was confirmed that the binding ability of the prepared MIP for nalidixic
acid was essentially sufficient in the presence of the other compounds coexisting in serum sample. It was demonstrated that this
MIP could be applied to direct enrichment and determination of nalidixic acid from tablet matrix and human plasma.
Reference
[1] Xingliang Song , Jinhua Li , Jiangtao Wang , Lingxin Chen , Talanta 80 (2009) 694-702.
[2] Peter A. G. Cormack , Amaia Zurutuza Elora , Journal of Chromatography B , 804 (2004) 173-182.
[3] Qin-Zhong Feng , Li-Xia Zhao , Wei Yan , Jin-Ming Lin , Zhi-Xia Zheng , Journal of Hazardous Materials 167 (2009) 282-288
QSRR Study on the Retention Times of Poly Chlorinated Biphenyls by Artificial Neural Network
Mohammad Danandeh-Jenagharad1, Moosa Norouzi2, Morsal Khozuei3
1
The Holy Prophet Higher Education Complex, Ardabil, I. R.Iran.
2
Department of Applied Chemistry, Islamic Azad University, Ardabil Branch, Iran.
3
Department of Chemistry, Payame Noor University (PNU), Ardabil, Iran
Email: danandeh@gmail.com
Polychlorinated Biphenyls are among the most studied group of organic compounds with environmental significance [1].
Toxicological effects of exposure to polychlorinated biphenyl include hepatotoxicity, immunotoxicity and reproductive problems,
as well as respiratory, mutagenic and carcinogenic effects [2].A quantitative structure-retention relationship (QSRR) was
developed to predict the retention time (tr) of 125 PCBs. A suitable set of molecular descriptors was calculated and the bestfitting descriptors were selected by using ANN. An ANN with 1-2-1 architecture was generated using one molecular descriptor
that appears in the multi parameter linear regression (MLR) model. The R2v is input and its output is retention time. It was found
that a properly selected and trained neural network with 125 PCBs could represent the dependence of the retention time on
molecular descriptors fairly well. For evaluation of the predictive power of the ANN, an optimized network was used to predict
the tr of 42 compounds in the prediction set, which were not used in the optimization procedure. Statistical results are shown in
Table 1.
Training
R2
RMSE
0.983 1.341
Validation
R2
RMSE
0.985 0.657
Prediction
R2
RMSE
0.984 0.599
Reference
[1] Sanchez, E.; Fernandez, S.M.; Lopez-Aparicio, P.;Recio, M.N.; Perez-Albarsanz, M.A. Chem. Biol. Interact, 125 ,2000, 117.
[2] Safe, S. Crit. Rev. Toxicol, 21 ,1990, 51.
An optical uranyl- selective sensor based on a newly synthesized
Lignd, bis (2-hydroxy-1-naphthaldehydene)-1, 2-Phenylendiamin
M. Ghaedia*, A. Amiri Pebdania, B. Sadeghiana, M. Nejati Biyareha, J. Tashkhourianb, M. Montazerozohorizohorya
a
Chemistry Department, Yasouj University Yasouj 75914-35, Iran
b
Chemistry Department, Shiraz University, Shiraz, Iran
Email m_ghaedi@mail.yu.ac.ir, Arezooamiri84@yahoo.com
The characterization of an optical sensor membrane is described for the determination of uranyl based on the immobilization of
bis (2-hydroxy-1-naphthaldehydene)-1, 2-Phenylendiamin on a PVC membrane. Recent decades have seen an increase in the
development of optical chemical sensors (optodes) as viable alternatives to other types of sensors. The great activity seen in the
field of ion-sensitive optical fiber devices and their application to trace analysis of heavy metal ions has given rise to several
sensing schemes, new indicator dyes and highly diversified methods of immobilization. Both the method of immobilization and
the class of matrix exert a significant effect on the performance of ion-sensitive layers[1,2].In this work the absorption spectra of
free and immobilized ligand were obtained after being equilibrated in buffer solution (pH 3) containing different concentrations
of uranyl. The spectral change is a result of the addition of UO22+ ions and the complex formation. The absorbance maxima of the
immobilized bis (2-hydroxy-1-naphthaldehydene)-1, 2-Phenylendiamin are located at 383 nm. This optode has a linear range of
2×10-6–7.3×10-5 mol L−1 for UO22+ ions with a limit of detection of 2×10-6mol L−1 at a wavelength of 383 nm. The response time
of optode is within 5–7 min depending on the concentration of UO22+ ions. The selectivity of the optode to UO22+ ion in the
presence of other metal ions including Mg2+, Ca2+, Ba2+, Zn2+, Ni2+, Co3+, Mn2+, Cd2+, Bi3+ and Al3+ is high, with the exception of
Th+4,Cu2+ ions as the main interference.
Reference
[1] G.J. Moody, B.B. Saad, J.D.R. Thomas, The development of polymer matrix membranes for ion selective electrodes, Sel. Electrode Rev. 10 (1988) 71–78.
[2] A. Safavi, M. Bagheri, Design of a copper (II) optode based on immobilization of dithizone on a triacetylcellulose membrane,Sensors and Actuators B 107 (2005)
53–58.
Determination of valproic acid in human serum by headspace solid-phase microextraction-GC method
Asghar Razmizadeh a , Reza E. Sabzi a,b , Mohammad Reza Vardast a, *
a. Department of Chemistry, Faculty of Science, Urmia University, I.R. Iran
b. Institute of Biotechnology, Urmia University, Urmia, I.R. Iran
E-mail:mrvardast@gmail.com
Valproic acid (2–propylpentanoic acid, VPA) is a broad-spectrum antiepileptic drug with unique anticonvulsant properties and
used in the treatment of epilepsy and mood disorders. Therapeutic use of VPA has been associated with a rare, but severe and
often fatal hepatotoxicity characterized by steatosis with or without necrosis of the liver [1]. Several methods for quantification
of VPA in plasma have been described, and most of them have been based on immunological methods [2] and gas
chromatographic procedures with the flame ionization detector (FID) [3-4] or mass spectrometric (MS) detection [5]. In this
study a polyaniline (PAN)-MWCNT composite which was electrochemically coated on a platinum wire was employed to extract
valproic acid from human serum and pharmaceutical formulations system. Experimental parameters consisting of adsorption
temperature, adsorption time, stirring rate, salt concentration and headspace volume were evaluated and optimized by means of
an experimental design method. The experimental results indicated that adsorption temperature and salt concentration were the
most significant factors in the analysis procedure. The optimized conditions were as follows: 70 oC of adsorption temperature, a
constant stirring speed of 700 rpm and 10 min of extraction carried out in 12 mL of water samples with NaCl, 4M. The proposed
method was linear approximately three orders (20–10000 gL-1) of magnitude for the tested compounds, with linear correlation
coefficients (R2) greater than 0.998.
Reference
[1] J.R. Stephens, R.H. Levy, Pharm. Weekbl. Sci. 14 (1992) 118.
[2] W. Ehrenthal, M. Rochel. Arzneim-Forsch. 32 (1982) 449.
[3] A.S. Wohler, A. Poklis, J. Anal. Toxicol. 21 (1997) 306.
[4] M.A. Farajzadeh, K. Farhadi, A.A. Matin, P. Hashemi, A. Jouyban Anal. Sci. 25 (2009) 875.
[5] G. Nagai, S. Ono, N. Yasui-Furukori, A. Nakamura, K. Mihara, T. Kondo, Ther. Drug Monit. 31 (2009) 592.
Polyaniline-MWCNT composite based fiber for headspace solid-phase microextraction of alkane samples
Asghar Razmizadeh a , Reza E. Sabzi a,b , Mohammad Reza Vardast a, *
a. Department of Chemistry, Faculty of Science, Urmia University, I.R. Iran
b. Institute of Biotechnology, Urmia University, Urmia, I.R. Iran
E-mail:mrvardast@gmail.com
Conducting polymers are unique because they show physical and chemical property changes after chemical or electrochemical
treatment. These changes can be used in different applications. Recently, the potential use of these polymers in trace analysis [1],
especially in solid-phase microextraction (SPME), has raised considerable interest [2, 3]. SPME is a relatively new extraction
technique, which combines sampling and preconcentration in one step. It requires no solvents or complicated apparatus and
provides good results over a wide range of analyte concentrations. In this study a polyaniline (PAN)-MWCNT composite which
was electrochemically coated on a platinum wire was employed to extract the some alkanes (C10-C18) from aqueous system. It
was found that the coating was porous and had large specific area and adsorption capacity;in the composite MWCNTs and
polyaniline interacted with each other and the film kept stable up to 300 ◦C. The as-made fiber was used for the headspace solidphase microextraction (HS-SPME) of some alkane compounds. Experimental parameters consisting of adsorption temperature,
adsorption time, stirring rate, salt concentration and headspace volume were evaluated and optimized by means of an
experimental design method. The experimental results indicated that adsorption temperature and salt concentration were the most
significant factors in the analysis procedure. The optimized conditions were as follows: 35 oC of adsorption temperature, a
constant stirring speed of 700 rpm and 10 min of extraction carried out in 12 mL of water samples with NaCl, 0.1 M. The
proposed method was linear approximately three orders (0.01–100 gL-1) of magnitude for the tested compounds, with linear
correlation coefficients (R2) greater than 0.997. In addition, the fiber also presented advantages of easy preparation and low cost.
Therefore, it is a promising SPME fiber.
Reference
[1] M. Trojanowicz Microchim. Acta 143 (2003) 75.
[2] J. Wu, Z. Mester, J. Pawliszyn Anal. Chim. Acta 424 (2000) 211.
[3] B.J. Yates, K.R. Temsamani, O. Ceylan, S. Otemiz, T.P. Gbatu, R. LaRue, U. Tamer, Talanta 58 ( 2002) 739.
Adsorption of lead and Strontium from aqueous solutionsby polymeric Al/Fe modified bentonite
H.Faghihian * and E.Bahramian
Department of Chemistry, Islamic Azad University, ShahrezaBranchc, Iran
Faghihian@iaush.ac.ir , Elham_bahramian@yahoo.com
Adsorption of lead and strontium from aqueous solutions by polymeric Al/Fe modified bentonite was studied. Batch adsorption
studies were carried out as a function of contact time, pH, adsorbent dose and initial metal concentration. Fourier transform
infrared spectrometry (FT-IR) and scanning electron microscopy (SEM) were respectively used to analyze the functional groups
and surface morphology of the bentonite or polymeric Al/Fe modified bentonite,.SEM images show that modification with
polymeric Al/Fe species reduces the clay particle size and aggregation. The results indicate that the maximum adsorption of
polymeric Al/Fe modified bentonite was obtained in the pH range 3.0–6.0 for lead and strontium.The adsorption data was
analyzed by both Freundlich and Langmuir isotherm models and the data was well fitted by the Freundlich isotherm model.
Kinetic data correlated well with the pseudo-second-order kinetic model, suggesting that the adsorption process might be
chemical sorption. Thermodynamic studies showed that the adsorption process was endothermic and spontaneous in nature.
Reference
[1] W.R. Cullen, K.J. Reimer, Arsenic speciation in the environment, Chem. Rev. 89 (1989) 713–764.
[2] J.Q. Jiang, Removing arsenic from groundwater for the developing world—a review, Water Sci. Technol. 44 (2001) 89–98.
[3] S.L. Chen, S.R. Dzeng, M.H. Yang, K.H. Chiu, G.M. Shieh, C.M. Wai, Arsenic species in groundwaters of the blackfoot disease area, Taiwan, Env. Sci. Technol.
28 (1994) 877–881.
Sliver nanoparticles-based resonance light scattering method for the determination of rifampin in pharmaceutical and
biological samples
Mohammad Amjadi*, Amin Zahedi
Faculty of Chemistry, University of Tabriz, Tabriz, Iran
Email: amjadi@tabrizu.ac.ir
Silver nanoparticles (Ag NPs) have many interesting physicochemical characteristics, which have led to their wide applications
in various areas of chemistry [1]. One of the well-established properties of Ag NPs is surface plasmon resonance absorption
which has widely been utilized for chemical sensing of various substances [2]. Most of these procedures use a change in
extinction intensity of Ag NPs for optical detection. However, a much more useful and sensitive property of NPs, which can be
used for sensing purposes, is their ability to efficiently scatter light. In the present work, rifampin, an important antituberclusis
drug, was determined by using resonance light scattering (RLS) propertiy of Ag NPs. Rifampin, due to its reducing property can
react with silver nitrate to form Ag NPs in the presence of polyvinyl alcohol as a stabilizer. Upon formation of Ag NPs a marked
enhancement in RLS intensity at 400 nm is observed. The RLS intensity is proportional to drug concentration. Various
experimental factors affecting the RLS signal including the concentration of sodium hydroxide, ammonia and silver nitrate, the
presence of various surfactant, time and temperature were studied and optimized. Under the optimum conditions, the calibration
graph was linear in the range of 1.5×10-7M - 1×10-8 M with a detection limit of 5×10-9 M. The standard deviation of six replicate
determination of 7×10-8 M rifampin was 1.1%. The effect of some potentially interfering species was also studied and the method
was applied to the determination of rifampin in pharmaceutical and biological samples.
Reference
[1] K. Shrivas, H. F. Wu, Anal. Chem. 80 (2008) 2583-2589
[2] H. Zhoua, X. Wua, F. Menga, J. Yang, M. Wang, Specrochim. Acta Part A 78 (2011) 681–686
Synthesis of a New Molecularly Imprinted Polymer and its Application for Extraction, Preconcentration and
Determination of Theophylline
Mahsa oskouei* , Hayedeh Bagheri Sadeghi, Homayon Ahmad Panahi, Mahsa Mahabadi.
Department of Chemistry, Central Tehran Branch, Islamic Azad University, Tehran, Iran.
E-mail:mahsa.oskouei@gmail.com
Theophylline has been introduced in the therapy of chronic airway disease since several decades ago. Determination of trace
amounts of theophylline in tablets and biological fluids is of great interest.In this work a new molecularly imprinted polymers
(MIPs) has been synthesized by N,N-dimethyl-acrilamid(DMAA) and allyl glycidil ether/imino diacetic acid(AGE/IDA) as the
functional monomer ,N,N methylen diacrylamid as the crosslinker in the methanol solution using theophylline as the template
molecule and 2,2’-azobis-isobutyronitril (AIBN) as the initiator. The polymerization was performed in presence of Cu2+ which
can coordinate with the drug and retain it in the polymer. The polymer was characterized by, elemental analysis, FT-IR, and
thermo gravimetric analysis(TGA).The effect of various parameters like pH, adsorption time, amount of adsorbent and adsorption
capacity of adsorbent at optimum conditions were examined. The synthesized polymer was successfully applied for
preconcentration and subsequent determination of theophylline from tablet matrix.
Reference
[1] Ramakrishna V.S. Nirogi, Vishwottam N. Kandikere, Manoj Shukla, KoteshWara Mudigonda, Devender R. Ajjala, Journal of Chromatography B,848 (2007) 271276.
[2] Peter A. G. Cormack, Amaia Zurutuza Elora, Journal of Chromatography B, 804 (2004) 173-182.
Removal of nickel from surface waters and determination by flame atomic absorption spectrometry
a
Fatemeh Sabermahani *,a, Mahboubeh Saeidi b, Vajihe Sharif zade a,
Department of Chemistry, Payame Noor University of Kerman, Kerman, Iran
b
Department of Chemistry, Vali-e-asr University of Rafsanjan, Kerman, Iran
Nickel is essential constituent in plant urease. Urease-rich legumes such as jack beans and soybeans generally contain high nickel
concentrations [1]. Compared with other transition metals, nickel is a moderately toxic element. However, it is known that
inhalation of nickel and its compounds can lead to serious problems, including cancer of the respiratory system [2]. Moreover,
nickel can cause a skin disorder known as nickel-eczema [3].Nickel can be entered into waters from industrial processes and
waste disposal, beside; it enters environmental samples from dissolution of soils and street dust. Therefore, it is necessary and
important to develop sensitive methods for determining nickel in environmental samples.In this work, a new sorbent, alumina
coated with 5-Br-PADAP was prepared for removal and preconcentration trace amounts of Ni(II) in surface water samples. The
procedure is based on retention of the analyte on the alumina load with 5-Br-PADAP at pH~6. The separation/preconcentration
conditions for the quantitative recovery were investigated. The limit of detection (LOD) based on three times the standard
deviation of the blank, was 0.187 ng mL-1 for nickel. Obtained sorption capacity for 1 g sorbent was 6.0 mg Ni. The linearity was
maintained in the concentration range of 0.625 to 6.0 ng mL-1 in the original solution. Eight replicate determinations of a mixture
containing 2.0 µg mL-1 of the element in the final solution gave relative standard deviation 0.82. The accuracy of the results was
verified by analyzing the spike water samples. The good precision and high tolerance to interferences from matrix ions are other
advantages. The proposed method was successfully applied to the determination trace amounts of Ni in the surface waters.
Reference
[1] E. Merian, M. Anke, M. Ihnat, M. Stoeppler, Elements and Their Compounds in the Environment, Vol. 2, 2rd edn. Wiley/VCH, Weinheim, 2004.
[2] D. Templeton, Biological Monitoring of Chemical Exposure in the Workplace. Word Health Organization, Geneva 1990.
[3] J. Kristiansen, J.M. Kristiansen, T. Henriksen, N.H. Nielsen, et al. Anal. Chim. Acta 403 (2000) 265-272.
Preconcentration of trace amounts of cadmium from plant samples with rubeanic acid on alumina
a
Fatemeh Sabermahani a,* Malihe Zamani b
Department of Chemistry, Payame Noor University of Kerman, Kerman, Iran
b
Department of Chemistry, Azad University of Kerman, Kerman, Iran
Cadmium (II) is listed as the sixth most poisonous substance jeopardizing human health. Exposure to lower amounts of cadmium
may cause gastrointestinal irritation, vomiting, abdominal pain and diarrhea. Acute exposure may affect kidneys resulting in
tubular proteinosis and some times fatality [1]. Cd enters the organism primarily via the alimentary and/or respiratory tract. The
sources of this metal are food, drinking water and air [2]. Due to that, trace and ultra-trace determinations of Cd in environmental
and biological samples have become of increasing interest [3].Solid phase extraction (SPE) is an attractive method that reduces
consumption of and exposure to solvent, disposal costs and extraction time. The nature and the properties of the sorbent materials
are of prime importance for effective retention of materials in SPE. This work is devoted to the examination of rubeanic acid as a
complexing agent with Cd(II), and the feasibility of alumina as a solid phase extractor was investigated. The results showed that
the cadmium ions were easily retained in the form of metal-rubeanic acid complex on alumina from aqueous solution. The
linearity was maintained in the concentration range of 0.02-2.0 µg mL-1 in the final solution or 0.25-25.0 ng mL-1 in the original
solution. LOD of cadmium based on three times standard deviations of the blank on a sample volume 400 mL was 0.03 ng mL-1.
Eight replicate determinations a mixture of 1.0 µg mL-1 of cadmium in the final solution, gives a mean absorbance of 0.4047 with
relative standard deviation ±2.1%. The complex formation between cadmium and rubeanic acid was very fast. The use of organic
solvents in the proposed method was eliminated. The proposed method was successfully applied to the analysis of various plant
samples.
Reference
[1] K. Parsad, P. Gopikrishna, R. Kala, T.P. Rao, G.R.K. Naidu, Talanta (2006) 938.
[2] J.L. Manzoori, G. Karim-Nezhad, Anal. Chim. Acta 521 (2004) 173-177.
[3] L. Li, B. Hu, L. Xia, Z. Jiang, Talanta 70 (2006) 468-473.
Simultaneous electrocatalytic determination of epinephrine, uric acid and folic acid on the carbon nanotube paste
electrode modified with a new synthesized mediator
1
Hadi Beitollahi1, Alireza Mohadesi2,3,*, Saideh Khalilizadeh3,Mohammad Ali Karimi2
Environmental Department, Research Institute of Environmental Sciences, International Center for Sciences, High Technology and
Environmental Sciences, Kerman, Iran
2
Department of Chemistry, PayameNoorUniversity, Tehran19395-4697,Iran
3
Department of Chemistry, PayameNoorUniversity (PNU), P.O. Box 76175-559, Kerman, Iran
E-Mail: mohadesi_a@yahoo.com
Application of carbon nanotube paste electrodes in the electrochemical determinations has been widely considered as a sensitive
and selective analytical method for the detection of trace amounts of biologically important compounds. One of the most
important properties of carbon nanotube paste electrode,in comparison to other chemically modified electrodes, has been better
selectivity and sensitivity and also their ability to simultaneous determinations. With respect to relatively selective interaction of
the electron mediator with the target analyte in a coordination fashion, Modified carbon nanotube paste electrode capable to
considerably enhance the selectivity in the electroanalytical methods [1-3].In this study, the electro-oxidation of epinephrine
(EP), uric acid (UA), folic acid (FA), and their mixture has been studied by carbon nanotube paste electrode modified with a new
synthesized mediator using cyclic voltammetry, chronoamperometry and differential pulse voltammetry. This modified electrode
exhibited potent and persistent electron mediating behavior followed by well-separated oxidation peaks towards EP,UA and FA
with activation overpotential in phosphate buffer pH=7.0. The anodic overpotential of epinephrine is deceases about 200 mV by
this modified electrode. Thus, for the ternary mixture containing EP, UA and FA the three compounds can be well separated from
each other at the scan rate of 50 mV/s. The obtained catalytic peak current was linearly dependent on the EP, UA and FA
concentrations in the range of 0.5-1000, 30-900 and 10-500 µM, respectively. The detection limits for EP,UA and FA were 0.1,
20 and 5 µM,respectively. The modified electrode showed good sensitivity, selectivity and stability, and was employed for the
determination of EP, UA and FA in the real samples.
Reference
[1] P. Xiao, F. Zhao, B. Zeng,.Microchem. J. 85 (2007) 244-249.
[2] M. Boopathi, M. Won, Y. Shim, Anal. Chim.Acta 512 (2004) 191–197.
[3] W. Ren, H. QunLuo, N.B. Li, Biosens. Bioelectron. 21 (2006) 1086–1092.
Determination of Cytochrome C in Chicken Liver Tissue with Polyethylene Oxide Modified Carbon – Ionic Liquid
Electrode
a,b
Khosrow. Zare Farashbandib ,Mohammad-Reza Milani Hosseini*a
Department of Analytical Chemistry, Faculty of Chemistry, Iran University of Science and Technology, Tehran, Iran.
A Carbon Ionic Liquid Electrode (CILE) was modified by Polyethylene Oxide (PEO) for electrochemical measurement of
Cytochrome C in complex biological matrixes. The base CILE was fabricated using Graphite powder and BMIMPF6 with the
ratio of 60/40 (w/w). Two CILEs were created by filling a fraction of the paste at the end of a glass tube and inserting a copper
wire from the other end. One of the CILEs was heated in an oven at 70°C for one hour. Afterwards, few drops of a 600 ppm
solution of PEO in deionized water were placed on the surface of the electrode, and the electrode was placed upside down inside
an airtight plastic container for the water to evaporate slowly. The modified and unmodified CILEs were used to determine the
Cytochrome C content of chicken liver tissue using cyclic voltammetery. The accuracy of the results was determined using
standard addition method. The cyclic voltammetery procedure was designed similar to the other works done with CILEs and
proteins [1-3]. The liver tissue was suspended in 100ml of phosphate buffer solution (pH = 8.5) and was homogenized using a
sterilized blender in Order to extract the Cytochrome C of chicken liver tissue into an aqueous solution. The resulting suspension
was then subjected to differential centrifuge to separate the mitochondria[4]. The resulting mitochondrial pellet was then
resuspended in buffer solution, homogenized and left alone for one hour at 4°C before analysis. The modified electrode showed
greater electrochemical sensitivity than normal carbon paste electrode and greater selectivity and sensitivity in a complex matrix
compare to unmodified CILE. Under optimal conditions, this electrode can be used in the concentration range of 750 ppb to 1000
ppm and also has a detection limit of 370ppb (3σ).
Reference
[1] A. Safavi, N. Maleki, O. Moradlou, M. Sorouri, Electrochemistry Communications, 10 (2008) 420-423.
[2] X. Shangguan, H. Zhang, J. Zheng, Electrochemistry Communications, 10 (2008) 1140-1143.
[3] W. Sun, X. Li, Z. Zhai, K. Jiao, Electroanalysis, 20 (2008) 2649-2654.
[4] M. Ott, J.D. Robertson, V. Gogvadze, B. Zhivotovsky, S. Orrenius, Proceedings of the National Academy of Sciences of the United States of America, 99 (2002)
1259-1263.
Colorimetric Biosensing of Mercury (II) Ion in Water Media Using Unmodified Silver Nanoparticles
a
a
Mehrdad Forough, bSalahaddin Hajizadeh, a Aysan Rafipour, bKhalil Farhadi
Department of Chemistry, Faculty of Science, Payame Noor University, Khoy, Iran
b
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
Among various heavy metals, mercury is considered as one of the most dangerous metal ions for environment and most
commonly encountered toxic risks, because it is widely distributed in air, water and soil [1, 2]. Therefore, it is critical to be able
to detect and measuring the level of Hg2+ in both environmental and biological samples under aqueous conditions. Thus, we
employed the green synthesized Ag NPs as a selective and sensitive colorimetric sensor to probe Hg2+ in water media without
interference of other transition-metal ions, alkali metal ions and alkaline earth metal ions. It is well known that biologically
synthesized Ag NPs exhibit a yellowish-brown color due to SPR band in Ag NPs solution [3]. After addition of Hg2+ solution to
freshly prepared silver nanoparticles, the color of Ag NPs solution changes from yellowish-brown to pale yellow and its color
decreases gradually with increasing concentration of Hg2+ and finally changes immediately to colorless after addition of a known
concentration of mercury (II). The color change was monitored using UV-Vis spectrometry and naked eye. Our proposed
mechanism demonstrates that an oxidation reaction between silver and mercury ions would be occurred [4]. Thus we suggest that
the green synthesized Ag NPs can be used for the colorimetric detection of Hg2+ with the limit of detection (LOD) 2.2 × 10-6 M.
In conclusion, a simple, label free, cost effective, selective and sensitive detection method has been developed using unmodified
and biologically prepared Ag NPs as a colorimetric probe that allows rapid and real time detection of Hg2+. The facile synthesis,
high stability, and water solubility of the biologically prepared Ag nanoparticles probes allow a reliable assay performed in
aqueous environments without requirement to any temperature control unit, and DNA engineering and etc.
Reference
[1]. A.P. de Silva, D.B. Fox, A.J.M. Huxley, T.S. Moody, J. Coord. Chem. Rev. 205 (2000) 41-57.
[2]. A.P. de Silva, H.Q.N. Gunaratne, T. Gunnlaugsson, A.J.M. Huxley, C.P. McCoy, J.T. Rademacher, T.E. Rice, J. Chem. Rev. 97 (1997) 1515.
[3]. M. Forough, K. Farhadi, Turkish J. Eng. Env. Sci.34 (2010) 281 – 287.
[4]. A. Fan, Y. Ling, C. Lau, J. Talanta.82 (2010) 687.
A new carbon nanotube-paste electrode modified with a new synthesized ferrocene derivative for electrocatalytic
determination of N –acetylcysteine
Ashraf Salmanipour1,*,Hadi Beitollahi2, Mohammad Ali Taher1, Rahman Hosseinzadeh3
Department of Chemistry, ShahidBahonar University of Kerman, P.O. Box 76175-133, Kerman, Iran.
2
Environmental Department, Research Institute of Environmental Sciences, International Center for Sciences, High Technology and
Environmental Sciences, Kerman, Iran
3
Department of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
*
Email: a_salmanipour_k@yahoo.com
1
N -Acetyl-L–cysteine (NAC), as an acetyl derivative and also one of the homologues of the L -cysteine, a sulfur containing
amino acid R-SH,is a very important amino acid.This compound has shown to exert cancer-protective mechanisms and effects in
experimental models. With respect to its relatively large oxidation overpotential, the corresponding voltammetric signals on the
surface of unmodified electrodes are usually weak [1, 2]. In order to decrease the undesirable anodic overpotential in the
electrochemical oxidation of NAC, various chemically modified electrodes have been constructed. Carbon nanotubes are a kind
of porous nanostructure material with properties such as high electrical conductivity and high mechanical strength. The subtle
electronic properties of carbon nanotubes suggests that they have the ability to promote electron transfer reaction when used as
the electrode material in electrochemical reaction, which provides a new way in the electrode surface modification for designing
new electrochemical sensors [3].In the present paper, a sensitive and selective electrochemical method for the determination of
NAC was developed using a novel carbon paste electrode modified by a new ferrocene derivative and carbon nanotubes.In a
phosphate buffer solution (pH 5.0) the peak potential for the oxidation of NAC was lowered by at least 450 mV compared with
that obtained for an unmodified CPE.The values of electron transfer coefficients, diffusion coefficient and catalytic rate constant
were calculated for NAC, using electrochemical approaches. Differential pulse voltammetry exhibited a wide linear dynamic
ranges and a sub-micro molar detection. Also, the modified electrode was employed for the determination of NAC in the real
samples such as NAC tablet.
Reference
[1] I.S. da Silva, M.F. AntãoAraújo, H.A. Ferreira, J.J. Gomes Varela Jr., S.M.C.N. Tanaka, A. A. Tanaka, L. Angnes, Talanta 83 (2011) 1701-1706.
[2]J. B. Raoof, R. Ojani, M. Amiri-Aref, F. Chekin, J. Appl. Electrochem. 40 (2010) 1357–1363.
[3]S. Suresh, A.K. Gupta, V.K. Rao, Om kumar, R. Vijayaraghavan, Talanta 81 (2010) 703-708.
Removal of fluoride from aqueous solutions by using Zein/H2SO4 as a bio-polymer composite
S. Mottaghizadeh1, K. Farhadi1, M. Bahram1, J. Behmanesh*2
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
2
Department of water engineering, Faculty of agriculture Urmia University, Urmia, Iran
1
Fluoride has been known for centuries as a toxic element. The main source of fluoride in aqueous solution is fluoride-rich rocks
through which the water has percolated. Fluoride may also be derived from mining or industrial activity in some areas [1].
According to the World Health Organization (WHO) guidelines, the upper limit of fluoride concentration in drinking water is 1.5
mg/L [2]. Concentration higher than this can lead to fluorosis, which causes a serious health problem for the population [3]. In
this study removal of fluoride ions was examined in aqueous sodium fluoride solutions using the bio-polymer composite
adsorbents. Zein /H2SO4 as an adsorbent were investigated to removal of fluoride ions from aqueous solutions. The determination
method is SPADNS method which shows a color change in the visible region on addition of water containing fluoride to reagent
solution. The system variables studied include initial concentration of the fluoride, agitation time, adsorbent dose, pH with
Central Composite Design (CCD) and the optimal experimental conditions were evaluated. The highest adsorption of Zein
/H2SO4 occurs at pH 4.5-6 at 30 min and amounts of fluoride ions adsorbed per unit mass of the adsorbents were found to be 0.70
mg/g at ambient temperature from 5 mg L-1 fluoride solution. The effect of co-ions was investigated in this study. The adsorption
data were investigated by Langmuir and Freundlich isotherms.
Reference
[1] V.A. Stanley, K.S. Pillai, Pollut. Res. 18 (1975) 305.
[2] WHO, Guidelines for Drinking Water Quality, 45, World Health Organization,Geneva(1993)
[3] M.Karthikeyan, K.K.Satheesh kumar, K.P.Elango Batch sorption studies on the removal of fluoride ions from water using eco-friendly conducting polymer/biopolymer composites. Desalination (2010)
[4] H.Parham, N.Rahbar Solid phase extraction-spectrophotometric determination of fluoride in water samples using magnetic iron oxide nanoparticles Talanta80
(2009) 664-669.
[5] X.Zhao,J.Wang, F.Wu, T.Wang, Y.Shi, G.Jiang, Removal of fluoride from aqueous media by Fe 3 O4 &Al(OH) 3 magnetic nanoparticles, J.Hazard.Mater 173(2010)
102-109.
[6 ]T.Wajima,Y.Umeta,S.Narita,K.Sugawara, Adsorption behavior of fluoride ions using a titanium hydroxide-derived adsorbent, Desalination 249 (2009) 323-330.
A QSPR model for prediction of selectivity coefficients of a venlafaxine-selective electrode using MLR and LS-SVR
Azadeh Khanmohammadi*, Amir Hossein Ghandi
Department of Analytical Chemistry, Islamic Azad University,Gachsaran branch,Iran
E-Mail:A.khanmohammadi@iaug.ac.ir
A least squares support vector regression (LS-SVR) was applied for prediction of selectivity coefficients of venlafaxine-selective
electrode for some drugs and organic compounds [1]. In this way a quantitative structure-property relationship (QSPR) model
was constructed based on calculated molecular descriptors [2]. In the first step molecular descriptor were calculated. Then the
stepwise multiple linear regression method was used to select most important descriptors which responsible for the selectivity
coefficient of venlafaxine-selective electrode for interfering compounds. Seven molecular descriptors selected by stepwise
multiple linear regression method were used as inputs to perform LS-SVR model. The root-mean-square errors of LS-SVR
calculated selectivity coefficients for training and test set are 0.101, 0.221 and the correlation coefficients are 0.996 and 0.953,
respectively. Also the Q2 = 0.86 which revealed the reliability of this model. The results of this study reveal that LS-SVR
technique can be used as a powerful tool for prediction of selectivity coefficient.
Reference
[1] Suykens J.A.K., Gestel T.V., Brabanter J.D., Moor B.D., Vandewalle J. Least Squares Support Vector Machines, World Scientifics, Singapore, (2002).
[2] Ensafi, Ali A.; Faridfar, R.; Allafchian, Ali R. A Novel Selective Coated-Wire Potentiometric Sensor for Venlafaxine Determination in Pharmaceutical
Compounds, Plasma and Urine: nSensor Letters, (2011) 9, 479-484.
Preconcentration and determination of trace amount of Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) by flame atomic
absorption spectrometry
Jalal Derakhshankhah, Hassan Zavvar Mousavi*
Chemistry Department, College of Science, Semnan University, Semnan, Iran
hzmousavi@semnan.ac.ir
Sensitive and accurate determination of heavymetal ions at trace levels in the water samples are very important part of
environmental and publichealth studies [1–3]. For this purpose, flame atomic absorption spectrometry (FAAS) has been
continuously used. However the relatively lower element concentrations than detection limits of atomic absorption spectrometry
and the interfere effects sourced from the matrix of the real samples are two main difficulties in these determinations. These
difficulties could generally be prevented by using preconcentration and separation methods. A method for preconcentration and
determination of trace amount of Pb(II), Cd(II), Cu(II), Ni(II) and Zn(II) ions has been described. The method based on the
collection of analyte metal ions on a column of Artemisia Siberi plantand determination of analytes by flame atomic absorption
spectrometry (FAAS). The method was optimized for several parameters including of pH, matrix effects and sample volume. The
effect of foreign ions on the recovery of heavy metal ions has also been studied. The limit of detection of the proposed method
+
-
+
+
+
+
for Ni2 , Cd2 , Pb2 , Zn2 and Cu2 was found to be 2.37, 1.23, 4.74, 3.95 and 2.10 µg L 1, respectively. The proposed method
has been successfully applied to the determination of heavy metal ions in different water samples. The recoveries of analytes
were generally in the range of 93–100%.
Reference
[1] U. Divrikli, A. A. Kartal, M. Soylak, L. Elci, J. Hazard.Mater. 145 (2007) 459.
[1] M. Ghaedi, E. Asadpour, A. Vafaie, Bull. Chem. Soc. Jpn. 79 (2006) 432.
[3] Y. Guo, B. Din, Y. Liu, X. Chang, S. Meng, J. Liu, Talanta, 62 ( 2004) 207.
Multiwalled carbon nanotubes modified with 2-(4,5-Diphenyl-1-H-Imidazol-2-yle)4-Nitrophenol as efficient adsorbent for
solid phase extraction and preconcentration of some metal ions in food samples
a
M. Jamshidia, M. Ghaedi*b, K. Mortazavia, M. Roostab
Chemistry Department, Islamic Azad University, Gachsaran Branch, Gachsaran, Iran
b
Chemistry Department, Yasouj University, Yasouj, Iran
Email: jamshidi_mozhdeh@yahoo.com
Generally in trace metal determination, preconcentration and separation procedure is necessary to improve sensitivity and
selectivity of determination. Solid phase extraction (SPE) is a powerful tool for separation/enrichment of heavy metal ions [1-3].
Among various SPE materials MWCNTs have shown high adsorption efficiency towards metal ions which can be exploited to
develop preconcentration systems for trace analysis [4, 5]. In this work, a new procedure is proposed for the enrichment of trace
amount of understudy metal ions subsequent their determination by FAAS was based on the sorption of analyte metal ions on the
modified multiwalled carbon nanotubes (MMWCNTs) as a new, sensitive, easily prepared and stable solid sorbent.The proposed
method is based on utilization of multiwalled carbon nanotubes modified with 2-(4,5-Diphenyl-1-H-Imidazol-2-yle)4Nitrophenol as chelating reagent. The separation parameters for effective adsorption of understudy metal ions including effects of
pH, amount of ligand and carbon, condition of eluent, concentration of metal ions were examined. The optimum pH value for the
separation of understudy metal ions on the new sorbent was 5.0. The detection limit of Cu2+,Co2+, Ni2+, Pb2+ and Zn2+ ions was
0.69, 0.48,0.72, 3.94 and 0.25 ng mL-1 while respective preconcentration factor for Ni2+, Cu2+ ions was 80 and for Ni2+, Pb2+ and
Zn2+ ion was 20, 30 and 60 respectively with RSD between 2.25-4.35. The proposed procedure was applied to the analysis of
various real samples. The validity of the proposed method using certified reference material proved its application. The
separation occurred efficiently, resulting in good enrichment factor and low LOD. The presented method can be successfully
applied to the preconcentration and determination of analyte ions in different real samples.
Reference
[1] M.B. Arain, T.G. Kazi, M.K. Jamali, H.I. Afridi, N. Jalbani, J.A. Baig, J. Hazard. Mater, 154 (2008) 998.
[2] M. Karve, R.V. Rajgor, J. Hazard. Mater, 141(2007) 607-613.
[3] M. Ghaedi, M. R. Fathi, F. Marahel, F. Ahmadi, Fres. Environ. Bull, 14 (2005) 1158-1163.
[4] W. Hong, W. Hongyu, B. Han, B. Du, J. Lu, Microchim Acta, 166 (2009) 41-46.
[5] Y.H. Li, S.G. Wang, Z.K. Luan, J. Ding, C.L. Xu, D.H. Wu, Carbon, 41 (2003) 1057-1062.
Application of amino-functionalized magnetite nanoparticle for extraction of parabens from cosmetic and enviromental
samples and determination by gas chromatography-photo ionization detector (GC-PID)
Maryam abbasghorbani1, Mohammad Saraji2, Abdolmohammad Attaran3, Mahmood Payehghadr4
1
Department of Chemistry, Payame Noor University (PNU), Mashhad, Iran
2
Department of Chemistry, Isfahan University of Technology, Isfahan, Iran
3
Department of Chemistry, Payame Noor University (PNU), Delijan, Iran
4
Department of Chemistry, Payame Noor University (PNU), Karaj, Iran
Recently use of nanometer-sized particles for sample extraction in chemical analysis is gaining research interest [1,2]. In this
study, amino-functionalized magnetite nanoparticle (AF-MNs) has been successfully synthesized and applied for extraction of
some parabens (methyl paraben, ethyl paraben, i-propyl paraben, n-propyl paraben and butyl paraben) from cosmetic and
environmental samples. The amount of 5 mg synthesized magnetite nanoparticles was added to the sample. The mixture was
stirred by ultrasonic bath for 5 min. AF-MNs were been deposited at the bottom of the vial from their suspension by an Nd–Fe–B
strong magnet and analytes were desorbed by a few microliter of an organic solvent. Extracted compounds were monitored by
gas chromatography-photo ionization detector after derivatization with acetic anhydride. Main factors affecting the extraction and
derivatization of parabens such as the amount of magnetite, pH value, desorption solvent and amount of acetic anhydride were
optimized. Under optimized conditions, enrichment factors and recoveries of the studied compounds were obtained in the range
of 110–256 and 25–72%, respectively. Dynamic ranges of the calibration curves were between 1 and 50 for methyl- and 0.5 and
20 ngmL−1 for ethyl-, i-propyl-, n-propyl- and butyl parabens respectively. Limit of detection for methyl paraben was 0.3 ngmL−1
and those of ethyl-, i-propyl-, n-propyl- and butyl parabens were between 0.05 and 0.1 ngmL−1. Relative standard deviations
(RSDs %) for five repeated measurements were between 6 and 8. Compared with conventional extraction methods, the
advantages of proposed method still include easy preparation and regeneration of sorbents, short times of sample pretreatment,
high extraction yields and consuming low volume of toxic and expensive organic solvent. The feasibility of the method for the
determination of analytes in real samples was checked in river water and mouthwash solution.
Reference
[1]. P.C. Lin, M.C. Tseng, A.K. Su, Y.J. Chen, C.C. Lin, Anal. Chem. 79 (2007) 3401.
[2]. S.Y. Chang, N.Y. Zheng, C.S. Chen, C.D. Chen, Y.Y. Chen, C.R.C. Wang, J. Am. Soc. Mass Spectrom. 18 (2007) 910.
Investigation of the capability of positive and negative electrospray ionization ion mobility spectrometry for
determination of pioglitazone
M. Kamfiroozi, M.T. Jafari*, Z. Badihi
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
Pioglitazone hydrochloride ((±)-5-{ρ-[2-(5-ethyl-2- pyridyl) ethoxy] benzyl}-2, 4-thiazolidinedione hydrochloride) [1] is a
thiazolidinedione antidiabetic agent used in the treatment of type 2 diabetes. This drug decreases insulin resistance in the
periphery and liver, that results in increased insulin-dependent glucose disposal and decreased hepatic glucose output.
Pioglitazone has also been used to treat non-alcoholic steatohepatitis (fatty liver), but this use is presently considered
experimental. In the other studies pioglitazone was analyzed by UV–second derivative spectrophotometric and colorimetric
methods [2], high-performance liquid chromatography (HPLC) [1] and square-wave adsorptive cathodic stripping voltammetry
[3]. However, these methods are time consuming and expensive in addition to their need to skilled operator.In this work,
application of ion mobility spectrometry (IMS) as a detection technique for determination and validation of pioglitazone was
investigated and evaluated for the first time. Portability, speed, low cost, ease of maintenance, and low detection limits (~ppb) are
the main advantages of IMS [4]. In this regard, pioglitazone was analyzed by IMS in both positive and negative modes. The
results of this study demonstrate the linear dynamic range of 0.02-2.00 μg/mL and 0.05-20.00 μg/mL for negative and positive
modes of IMS, respectively. The obtained low detection limits for negative and positive IMS was 0.008 and 0.02 μg/mL for the
determination of pioglitazone.
Reference
[1] R.T. Sane, S.N. Menon, S. Inamdar, M. Mote, G. Gundi, (2004). Chromatographia, 59, 451–453.
[2] S.T. Ulu, F.T. Elmalı, (2009). Analytical Letters, 42, 2254–2270.
[3] N.A. Al-Arfaj, E.A. Al-Abdulkareem, F.A. Aly, (2008) International Journal of Biomedical Science, 4, 310–318.
[4] M.T. Jafari, B. Rezaei, M. Javaheri, (2011) Food Chemistry, 126, 1964–1970.
Separation and preconcentration of Cd(II) by solid-phase extraction using carbon active modified with multiwall carbon
nanotubes and new disulfide compound
Ail A. Ensafi*, M. Jokar
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
Cadmium is considered to be of as highly toxic as probably carcinogenic for humans [1]. Cadmium(II) is listed as the sixth most
poisonous substance jeopardizing human health. Exposure to lower amounts of cadmium may cause gastrointestinal irritation,
vomiting, abdominal pain and diarrhea. Acute exposure may affect kidneys resulting in tubular proteinosis and sometimes fatality
[2]. Different analytical techniques have been reported to determine cadmium ions in water samples including atomic absorption
spectrometry, inductively coupled plasma (ICP)-atomic emission spectrometry and ICP-mass spectrometry, anodic stripping
voltammetry, differential pulse stripping voltammetry, potentiometric stripping analysis, ion chromatography,
spectrophotometry, electrochemiluminescence, and molecular fluorescence spectroscopy. Therefore, in this study, we describe
application of new disulfide compound and multiwall carbon nanotubes as absorbance in preconcentration and determination of
Cd(II) using flame atomic absorption spectrometry. The method is based on adsorption of cadmium ions onto the activated
carbon modified with multiwall carbon nanotubes and a new disulfide compound. Then, the adsorbed ions were washed using
0.05M HNO3 and the eluent was used to determine the Cd(II) ions using flame atomic absorption spectrometry. The results
obtained show that the modified activated carbon has the greatest adsorption capacity of 50 µg of Cd(II) per 1.0 g of the solid
phase. The optimal pH value for the quantitative preconcentration was 7.0 and full desorption is achieved by using 0.05M HNO3
solution. It is established that the solid phase can be used repeatedly without a considerable adsorption capacity loss. The
detection limit was less than 2 ngmL−1 Cd(II), with an enrichment factor of 330. The developed method has been applied to the
determination of trace cadmium (II) in water and waste water samples. The accuracy was assessed through recovery experiments.
Reference
[1] International Agency for Research on Cancer, IARC Monographs on the Evaluation of Carcinogenic Risk of Chemicals to Humans, IARC, Lyon, 1979, pp. 1–20,
27.
[2] K. Prasad, P. Gopikrishna, R. Kala, T.P. Rao, G.R.K. Naidu, Solid phase extraction vis-a-vis coprecipitation preconcentration of cadmium and lead from soils onto
5,7-dibromoquinoline-8-ol embedded benzophenone anddetermination by FAAS, Talanta 69 (2006) 938–945.
Determination of Lead(II) in water and wastewater samples by flame atomic absorption spectrometry using multiwall
carbon nanotubes and new disulfide absorbance
Ail A. Ensafi*, M. Jokar
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
The determination of trace amounts of lead in environmental samples is currently of great importance due to their high toxicity,
accumulative and persistent character in the environment and living organisms. Thus, there is great interest concerning the
implementation of a reliable preconcentration system for lead(II) for analytical determinations. Now, one of the most used matrix
removal preconcentration methods is the on-line retention of the analyte on an adequate solid support by using microcolumns in a
flow system, based on mass transfer between a liquid phase and a solid one.1 These preconcentration systems can be on-line
coupled to several atomic detection techniques. Flame atomic absorption spectrometry (FAAS) is a simple and very available
technique for the determination of heavy metals in water samples. However, the main problem is a low sensitivity for trace metal
at the ng/ml level. This limitation can be overcome by using a preconcentration procedure. Solid-phase extraction (SPE)
techniques have found increasing applications for the preconcentration of trace metal ions and the elimination of matrix
interference prior to an AAS analysis. Therefore, in this study we describe application of new nano-particles disulfide compound
and multiwall carbon nanotubes as absorbance in preconcentration and determination of lead(II) using flame atomic absorption
spectrometry. After the preconcentration step, the metal ions are eluted automatically by 2.0 ml of 0.05 M nitric acid solution and
the lead ions contents was determined by flame atomic absorption spectrometry. The influence of chemicals, pH and flow
variables were studied as well as effect of potential interfering ions. Under the optimum conditions, the lead ions in aqueous
samples were concentrated about 500 fold by the column. The detection limit was 4.0 μg L–1. The recovery percent of spliced
lead(II) was in the range of 99% – 102% . Finally, this method was use as a simple and powerful technique for determination of
lead (II) in real samples such as water and wastewater samples.
Reference
[1]. I. Rodunshkin and T. Ruth, J. Anal. At. Spectrom., 1997, 12, 1181.
Using ziziphus nummularia as a new, natural and low cost adsorbent for removal of dyes, application: Removal of bromo
cresol green from aqueous solution and kinetic and thermodynamic study of process
A. Shokrollahi*, A. Alizade, A. Najibi
Department of Chemistry, Yasouj University 75918-74821, Iran
E-mail address: ashokrollahi@mail.yu.ac.ir
In this study ziziphus nummularia (ZPN) is used for the removal of bromocresol green (BCG), from several water solution. The
effect of various parameters such as: pH, dye concentration, amounts of adsorbents, size of adsorbent particles, and contact time
on removal processing was investigated. Parameters of kinetic models including lagerggren, pseudo second order, particle
diffusion, film diffusion, and elovich were calculated. Adsorption isothermal data could be interpreted by the Langmuir,
Freundlich, Tempkin and D-R isotherm models. SEM micrographs using a scanning electron microscope were studied. An FT-IR
analysis for ZPN was performed [1]. Protonation constants of BCG were evaluated using the BEST program [2]. For equilibrium
adsorption studies, a known amount of adsorbent was equilibrated with dye solution of desired at room temperature for definite
time periods. At the end of the pre-determined time intervals, the adsorbent was removed by simple filtration. The filtrate was
analyzed for the residual BCG, spectrophotometrically. ZPN with the special characteristics such as: availability,
inexpensiveness, large area, and the desired pores were used for removal of dyes. The experimental data correlated reasonably
well by the Tempkin, Freundlich and Langmuir models. The surface morphology studies using SEM proves that, it contains
move pores which lead to develop more adsorption sites. Adsorption process is dependent on pH and temperature and follows
pseudo- second- order kinetics model. The values of ΔH°, ΔS° and ΔG° results show that the adsorbent employed has a
considerable potential as an adsorbent.
Reference
[1] G. Sreelatha, V. Ageetha, J. Parmar, and P. Padmaja, J. Chem. Eng. 56, 2011 25.
[2] A. Shokrollahi,, M. Ghaedi, H. R, Rajabi, M. S. Niband, Spectrochim. Acta Part A, 2008, 71, 655–662.
A new method for determination of traces Co 2+ with Single Drop Micro Extraction Technique (SDME)
Maryam gharbi afshar*, Ali mazloomifar, Allah gholi ghasri
Islamic Azad University,Shahr-eRey Branch,Faculty of Science,Department of Chemistry,Tehran, Iran
Email: mazloomifar@yahoo.com , maryam.afshar17@yahoo.com
Single drop micro extraction (SDME) combined with graphite furnace atomic absorption spectrometry (GFAAS) was proposed
for simultaneous separation/enrichment and determination of trace amounts of Cobalt in surface water. In this method 1-(2pyridylazo)-2 naphthol (PAN) was used as chelating agent. A certain amount of cobalt solution was adjusted at the optimum pH
and treated with special volume of PAN that was transferred to a vial. Then, a non-polar non-ionic complex was formed. The
solution was stirred by magnetic stirrer at an optimum speed. The amount of organic solvent was taken by the Hamilton syringe
and its needle was used to pierce the vial septum. The syringe plunger was depressed to expose the drop. After the extraction, the
microdrop was retracted and directly injected into the graphite the furnace atomic absorption and, the special signal was
observed.Some effective parameters on extraction such as pH of solution, sample volume, stirring rate, concentration ligand, time
and temperature of complex formation, sampling temperature, type and volume of organic solvent, time of extraction,
temperature of atomization, were optimized. One of the most important advantages of (SDME) is its low cost; moreover, due to
its trivial usage of organic solvent, it helps protect the environment.
Reference
[1]. s. nazari, determination of trace amounts of cadmium by modified graphite furnace atomic absorption spectrometry after liquid phase microextraction, Micro
chemical journal 90 (2008) 107 -112
[2]. Eva Aguilera –Herrador, Rafael Lucena, Soledad Cárdenas, Miguel Válcarcel, The roles of ionic liquids in sorptive microextraction techniques Trends in
Analytical chemistry, Vol.29, No.7, 2010
[3]. M. shirani bidabadi,Sh.dadfarnia,A.M haji shabani,Solidified floting organic drop microextraction (SFODME) for simultaneous separation/preconcentration and
determination of cobalt and nikel by graphite furnace atomic absorption spectrometry.jornal of Hazardous Materials 166 (2009) 291-296
Complexing ability of kryptofix5 with Cd 2+ cation in some binary mixed non-aqueous solvents
Gholam Hossein Rounaghi*, Azar Hosseinzadeh Attar
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran
Cryptands (trade name Kryptofix) are cyclic or polycyclic molecules which contain three or more binding sites held together
by covalent bonds [1,2]. Due to the similarities of open-chain polyethylene glycols, there has been a growing interest in the
coordination chemistry of these ligands and their metal ion complexes [3].In the present study, we report the results of the
complexation study between kryptofix5 and Cd 2+ cation in mixed non-aqueous solvents by conductometry method.The
complexation reaction of 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (kryptofix5) with Cd 2+ cation was studied in
acetonitrile-ethylacetate (AN-EtOAc), acetonitrile-dimethylformamide (AN-DMF), methanol-acetonitrile (MeOH-AN) and
dimethylformamide - ethylacetate (DMSO-EtOAc) binary mixed solvent solutions at various temperatures. The stoichiometry
and the stability of the (kryptofix5-Cd) 2+ complex were determined conductometrically. The conductance data show that in all
of the solvent systems, the stoichiometry of the complex formed between the ligand and Cd 2+ cation is 1:1 (ML). The stability
of (kryptofix5-Cd) 2+complex is sensitive to the solvent composition and temperature. The results revealed that, the stability
constant of (kryptofix5-Cd) 2+complex in the binary mixed solvents varies in the order: AN–EtOAc>AN–MeOH>AN–
DMF>EtOAc-DMF. In the case of the pure organic solvents, the sequence of the stability of the complex changes as:
ANEtOAcMeOHDMF. Addition of kryptofix5 to Cd2+ cation solution in all of the binary solvent systems at different
temperatures results in an increase in molar conductivity which indicates that the (kryptofix5-Cd) 2+ complex is more mobile
than free solvated Cd2+ cation. The values of standard thermodynamic parameters (∆H0c , ∆S0c) which were obtained from the
temperature dependence of the stability constant using van’t Hoff plots, show that in most cases, the complex is enthalpy and
also entropy stabilized. In some of the binary solutions, the changes in standard enthalpy for the complexation reactions is
negligible, therefore, it seems that the complexation process in these solvent systems are probably athermic. But in other
binary mixed solvent solutions, the complexation reaction is exothermic or endothermic.
Reference
[1]. M. Kazem Rofouei, A. Ahmadalinezhad, M. Taghdiri, J. Incl. Phenom. 58, 377–382 (2007).
[2]. G.H. Rounaghi, E. Razavipanah, F. Kaveh, J. Incl. Phenom. 68, 245–252 (2010).
[3].M.Payehghadr, A.Zamani, A.R.Salehi Sadaghiani, M.Taghdiri. J. Incl. Phenom 62, 255–261 (2008).
Vinylferrocene modified multiwall carbon nanotubes paste electrode for determination of glutathione in blood samples
Ail A. Ensafi*, M. Monsef
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
Glutathione (GSH) is a tripeptide that contains an unusual peptide linkage between the amine group of cysteine and the carboxyl
group of the glutamate side chain. An antioxidant, GSH protects cells against such toxins as free radicals [1]. Thiol groups are
kept in a reduced state at a concentration of approximately ∼5 mM in animal cells. GSH reduces any disulfide bond formed
within cytoplasmic proteins to cysteines by acting as an electron donor. In the process, GSH is converted to its oxidized form,
glutathione disulfide. GSH is found almost exclusively in its reduced form since the enzyme reverting it from its oxidized form,
glutathione reductase, is constitutively active and inducible upon oxidative stress. In fact, the ratio of reduced GSH to oxidized
GSH within cells is often used scientifically as a measure of cellular toxicity [2]. Therefore, suggestion of new voltammetric
sensor for determination of this biological compound in blood sample is very important for physiological and medical
investigation. In this work, we propose vinylferrocene as a new mediator for the rapid, sensitive, and highly selective
voltammetric determination of glutathione using multiwall carbon nanotubes paste electrode. The experimental results showed
that the carbon nanotubes paste electrode has a highly electrocatalytic activity for the oxidation of GSH in the presence of
vinylferrocene as a mediator. Cyclic voltammetry, double potential step chronoamperometry, and differential pulse voltammetry
(DPV) are used to investigate the suitability of this modified electrode for the electrocatalytic oxidation of GSH in aqueous
solutions. It is shown that vinylferrocene can catalyze the oxidation of GSH in an aqueous buffer solution to produce a sharp
oxidation peak current at about +0.4 V. Kinetic parameters such as electron transfer coefficient and catalytic reaction rate
constant, k/h, are also determined. Using DPV and under the optimum conditions at pH 8.0, the electrocatalytic oxidation peak
current of GSH shows a linear dependence on GSH concentration in the GSH concentration range of 0.1 to 100.0 μM. The
proposed method may, thus, also be used as a novel, selective, simple, and precise method for the voltammetric determination of
GSH in such real samples as hemolyzed erythrocyte.
Reference
[1]. Pompella A, Visvikis A, Paolicchi A, De Tata V, Casini AF (2003) Biochem Pharmacol 66:1499
[2]. Pastore A, Piemonte F, Locatelli M, Lo Russo A, Gaeta LM, Tozzi G, Federici G (2003) Clin Chem 47:1467
Extraction of azole antifungal drugs from milk and biological fluids using Hollow fiber based on two immiscible organic
solvent and analysis by gas chromatograph equipped with FID
Behnam Ebrahimpour, Yadollah Yamini, Ali Esrafili
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
Azole antifungal agents are the most rapidly expanding group of antifungal drugs. Azole antifungal drugs are known to have
caused anaphylaxis if they are not used properly. Clotrimazole (CZ) and miconazole (MZ) are drugs belonging to these azole
drugs [1]. In the present work, the new three-phase HF-LPME followed by GC instrument with flame ionization detector (FID)
was applied for the extraction and determination of trace amount of two mentioned drugs as model azole antifungal agent in milk,
urine and plasma samples. Three-phase HF-LPME was used to extract the analytes from 24.0 mL sample solution adjusted at pH
8.0, through an organic phase (dodecane) as supported liquid membrane (SLM) into an organic acceptor phase (acetonitrile),
located inside the lumen of hollow fiber. The effective parameters, such as fiber length, sample volume, extraction time, pH in
sample solution and stirring rate were studied using one at a time method. Under optimal conditions, the limit of detections
(LODs) as low as 0.3 ng mL-1, linear dynamic range of 1-400 ng mL-1, the relative standard deviations < 5 % and extraction
recoveries of 58% and 45% were obtained for CZ and MZ, respectively, which corresponded to preconcentration factors of 639
for CZ and 496 for MZ. Finally it was applied for analysis of drugs in urine, plasma and milk samples and satisfactory results
were obtained.
Reference
[1] A. Arranz, C. Echevarria, J. M. Moreda, A. Cid, J. F. Arranz, J. Chromatogr. A 871 (2000) 399.
Complexing ability of kryptofix 22DD with La+3 cation in some binary mixed non-aqueous solvents
Gholam Hossein Rounaghi*, Azadeh Shafaie Bejestani
Department of Chemistry, Faculty of Science, Ferdowsi university of Mashhad, Mashhad, Iran
Lehn discovered macrobicyclic compounds called the cryptands [1]. Cryptands (trade name kryptofix) molecules are three
dimensional analogues of crown ethers. Some kryptofixes are used to produce 18F-Pharmaceuticals [2]. Studies of crown ether
complexes in various solvents show that the thermodynamic and kinetic parameters for complexation processes and even the
stiochiometry of the crown ether complexes are affected by the nature and composition of the solvent system [3,4].The aim of
this investigation is to study the effect of the nature and composition of the mixed organic solvents on stoichiometry, stability and
thermodynamics of complexation reaction of kryptofix 22DD with La+3 cation in some binary mixed non-aqueous solvents.The
complexation process between La+3cation with kryptofix 22DD was studied in acetonitrile-ethylacetate (AN-EtOAc), acetonitrilemethanol (AN-MeOH), acetonitrile-dimethylformamide (AN-DMF) and acetonitrile-ethanol (AN-EtOH) binary mixtures at
different temperatures by conductometric method. The conductance data show that in all cases, the stoichiometry of the complex is
1:1 [ML]. The stability constant of the resulting 1:1 complex at each temperature was calculated from computer fitting of the
molar conductance-mole ratio data.The results revealed that, the stability constant of (kryptofix 22DD.La)+3 complex in the pure
organic solvents at 25ºC varies in the order:EtOAc>EtOH>MeOH>AN>DMF. The values of thermodynamic parameters (∆Hcº and
∆Scº) for formation of (kryptofix 22DD.La)+3 complex were obtained from temperature dependence of the stability constant using the
van’t Hoff plots.The results show the sign and also the values of standard thermodynamic quantities are influenced by the nature and
composition of the mixed solvents.
Reference
[1]. J. M. Lehn, 16 (1973) 1.
[2]. W. Chen, T. Cloughesy, N. Kamdar, J. Nucl. Med. 46 (2005) 945.
[3]. G.H. Rounaghi et al, J. Incl. Phenom. 67 (2010) 443.
[4]. G.H. Rounaghi, E. Razavipanah, F. Kaveh, J. Incl. Phenom. 68 (2010) 245.
Optimization of Controlling Aspect Ratio of Silver Nanorods
Using Response Surface Methodology
M. Reza Hormozi Nezhad*1,2, Hossein Robatjazi1, Mehdi Jalali-Heravi1, Heshmatollah Ebrahimi-Najafabadi1
1
. Chemistry Department, Sharif University of Technology, Tehran, Iran
2
. Institute for Nanoscience and Nanotechnology, Sharif University of Technology, Tehran, Iran
The properties of metallic nonorads vary due to changes in their composition, size and shape, all which depend on the aspect ratio
of the nonorads. This work focuses on the optimization of the silver nanorads’ aspect ratio using response surface methodology
(RSM). Seed-mediated synthesis, which is the newest method with less difficulty, has been used for the synthesis of silver
nonorads. Silver ions were, first, reduced with sodium borohydride in the presence of sodium citrate dehydrate, as stabilizer.
Then, the prepared seeds were added to a solution containing more metal salt, a weak reducing agent (ascorbic acid) and a rodlike
micellar template (cetyltrimethylammonium bromide, CTAB). Three factors of ratio of metal seed to metal salt, amount of
ascorbic acid and the concentration of CTAB were selected as main factors affecting the aspect ratio and their values were
optimized using RSM. Mathematical models were proposed for the prediction of transverse and longitudinal Plasmon band
wavelength and the optimized condition was obtained for the synthesis of the silver nanorods with highest aspect ratio. It is found
that the ratio of metal seeds to metal salt is the most important factor controlling the aspect ratio of the silver nanorads. The
optimum values for the factors were found to be 0.06 mL of seed, 7.2 × 10-3 M of ascorbic acid and 0.05 M of the CTAB in the
final solution. The optimum predicted value for the longitudinal plasmon band is 653.9 nm, which is in agreement with the
experimental value of 655.0 nm.
Study of Complexation of kryptofix5 with cation in some binary mixed non- aqueous solvents
Gholam Hossein Rounaghi*. Razieh Bahmani
Department of Chemistry, Faculty of Sciences, Ferdowsi university of Mashhad, Mashhad, Iran.
Cryptands (trade name kryptofix) are cyclic or polycyclic molecules which contain three or more binding sites held together by
covalent bonds. These molecules are three dimensional analogues of crown ethers. The properties of cryptands as complexing
agents are well known and have been largely investigated in the past years [1-3]. The purpose of this investigation is study of the
effect of the nature and composition of the mixed solvents on complexation reaction between cation with the macrocyclic ligand,
1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane (kryptofix5) in binary mixed non-aqueous solvents. The complexation
reaction between cation with kryptofix5 was studied in ethylacetate (EtOAc)- acetonitrile (AN), ethylacetate (EtOAc) dimethylformamide (DMF), ethylacetate (EtOAc)-dimethylsulfoxide (DMSO) and ethylacetate (EtOAc)-methanol (MeOH)
binary solutions at different temperatures using the conductometric method. The changes of molar conductance (Λm) versus the
ligand to the cation molar ratios ([L]t/[M]t) for complexation of kryptofix5 with cation in these solvent systems were studied at
different temperatures. The conductance data show that the stoichiometry of complex formed in all cases is 1:1(ML). Addition of
kryptofix5 to cation in all systems at different temperatures results an increase in molar conductivity. This indicates that the
(kryptofix5-in these solvent systems, is more mobile than free solvated cation. A non-linear behavior was observed for the
change of logKf of (kryptofix5-complex versus the composition of the binary solvent systems. The stability order of the complex
in the binary solutions at 25oC was found to be: EtOAC-AN > EtOAC-MeOH > EtOAC-DMF > EtOAC-DMSO. The values of
thermodynamic parameters (Δ, Δ) were obtained from temperature dependence of the stability constant of (kryptofix5-using vant
t Hoff plots and the results show that in most cases ,the complex is enthalpy and entropy stabilized and the thermodynamics of
complexation reaction is affected by the nature and composition of the mixed solvents.
Reference
[1]. G. H. Rounaghi, M. H. Soorgi, M.S. Kazemi, J. Inorganic Chemistry., 55, 3 (2010).
[ 2]. KHALID M. TAWARAH, MOHAMMAD A. KHASAWNEH, SHEHADEH A, J Inclusion Phenomena and Macrocyclic Chemistry., 51, 143–148, (2005).
[3]. G.H. Rounaghi, S. Tarahomi, M. Mohajeri. J. Inclusion Phenom. Macrocyclic Chem., 63, 319 (2009).
Synthesis of new aluminum ion imprinted polymer for solid phase extraction and preconcentration of Al(III) from
different matrices
F. Shakerian, S. Dadfarnia*, A. M. Hajishabani
Department of Chemistry, Faculty of Sciences, Yazd University, Yazd, 89195-741, Iran
Email: sdadfarnia@yazduni.ac.ir
During the last few decades aluminum and its distribution in the environment has been the subject of interest of many scientists.
The concentrations of its dissolved species in most natural waters are below the µg L-1 level due to its relatively low solubility. A
variety of analytical techniques including atomic absorption spectrometry [1], inductively coupled plasma-atomic emission
spectrometry (ICP-AES) and spectrofluorimetry have been used for the determination of Al(III) in environmental samples [2].
However, trace determination of aluminum by these techniques required a separation/enrichment step prior to analysis. The
widely used techniques for the separation and preconcentration of aluminum include liquid–liquid extraction [3], ion exchange
[4], solid-phase extraction (SPE) [5] and cloud point extraction (CPE) [6]. In this study a new Al(III)-imprinted polymer (IIP) has
been synthesized by using styrene and ethyleneglycoldimethacrylate (EGDMA) as a monomer and cross linker respectively, in
the presence of Al(III)-8-hydroxyquinoline (oxine) complex. The imprinted Al(III) ions were completely removed by leaching
the IIP with HCl (50% v/v) and characterized by FT-IR and SEM. The maximum sorption capacity for Al(III) ions was found to
be 3.11 mg g-1 at pH 7.0. Variables affecting the IIP solid phase extraction were optimized by univariable methods. A sample
volume of 400 mL resulted in preconcentration factor 194. Precision (n=7) at 125 µg L-1 level were 3.42. With preconcentration
of 400 mL of sample detection limit of 1.6 µg L-1 was determined. The method was applied to the determination of aluminum in
various samples. The accuracy was assessed through recovery experiments, independent analysis by furnace atomic absorption
and analysis of certified references alloy and ore samples.
Reference
[1] L. Zhu, K. Li, S. Zhou, Q. Hu, G. Yang, Z. Huang, J. Chen, Asian J. Chem. 20 (2008)4433.
[2] B. Bocca, A. Alimonti, F. Petrucci, N. Violante, G. Sancesario, G. Forte, O. Senofonte,Spectrochim. Acta B 59 (2004) 559.
[3] J. Komarek, R. Cervenka, T. Ruzicka, V. Kuban, J. Pharm. Biomed. Anal. 45 (2007)504.
[4] S.B. Erdemoglu, K. Pyrzyniska, S. Gucer, Anal. Chim. Acta 411 (2000) 81.
[5] M.B. Luo, S.P. Bi, J. Inorg. Biochem. 97 (2003) 173.
[6] A.B. Tabrizi, Food Chem. 100 (2007) 1698.
Flow Injection Kinetic Spectrophotometric Method for theDetermination of Trace Amounts of Bromide and Iodide
SiavashNouroozi*,Zahra Koohbour
Department of Chemistry, Faculty of Science, Zanjan University, Zanjan, 45195-313
Bromine and Iodine exist in environmental samples (water, soils) mainly in halide form. Control over bromide and iodide
contents in drinking water, underground and sea water also in drugs is of great importance [1].Iodine is an essential nutrient
found in seawater, seafood, and iodine-enriched food, such as iodized table salt. The most common forms of iodine in diet are
iodide and iodate. Iodine deficiency affects thyroid hormone production and leads to developmental diseases, goiter, and
paralysis [2]. Because iodide is an essential source of iodine, there is need to determine iodide in a variety of
matrices.Development of aflow injection kinetic-spectrophotometric method for the determination of trace amounts of bromide
and iodide based on the catalytic effect of these ions on the redox reaction between sulfonazo III and bromate in acidic media is
proposed.Several chemical (pH, reagents concentrations) and FIA manifold (flow rate, reaction coil length, volume of sample
injected and temperature) factors are affect in the sensitivity in this determination and all of them were studied and optimized. In
the optimum conditions, calibration curves were obtained in the range from 4.0 to 600.0 µM for both of analyt. The calibration
curve for bromide and iodide was linear over the concentration range from 6.0to 75.0µMwith r 2 =0.995.Detection limit of 3.0 and
3.5µM was obtained for bromide and iodide, respectively.relative standard deviations (n = 10) are 2.34% for 60.0µM bromide
and 1.6% for 40.0µM iodide.The effects of several interferences of cations and anions on the determination of bromide and
iodide were investigated. The analytical system was applied for the determination of bromide and iodide in table salt, obtaining
ananalyte recovery ranging from 99.4 to 99.9 % for the bromide and 98.8 to 99.9 for the iodide.The present method allows for the
precise and speed determination and safety analysis of the FIA technique.
Reference
[1] J. J. Mutic, S. D. Nikolic-Mandic, A. Dj. Lolic, and D. D. Manojlovic, J. Anal. Chem., 63(9), 2008, 907.
[2] B. de Benoist, M. Anderson, I. Egli, B. Takkouche, H. Allen.,Iodine StatusWorldwide: WHO Global Database on Iodine Deficiency. Department of Nutrition for
Health and Development. World Health Organization, Geneva, 2004.
Determination of Hg (II) in Environmental Water Samples by Dispersive Liquid-liquid Microextraction Prior to GC-FID
1
Ali SarafrazYazdi1,*, Maryam AbediOstad1, FaridehMofazzeli2
Department of chemistry, Faculty of sciences, Ferdowsi University of Mashhad, Mashhad, Iran.
2
Department of Chemistry, Islamic Azad University-Quchan branch, Quchan, Iran.
Mercury exists in two forms in the environmental samples, i.e. inorganic salts and organic compounds. Determination of mercury
in these samples is very important, due to its health effects.In the present study, diphenylation of mercury using phenylboronic
acid as a derivatization reagent was used for the determination of Hg (II) in water samples [1].The present work describes the
possibility of using a method of LLME in extraction of mercuric compounds from water samples prior to GC-FID by utilizing a
simple, rapid and cheap extraction device.The pH of the feed solution was kept in pH 5 with acetate buffer solution thus, the
optimized conditions are: derivatization time, 10 min; extraction solvent, 16μL Carbon tetrachloride; disperser solvent, 1 mL
ethanol; sample volume, 5 ml and also ionic strength of the aqueous feed solution were optimized. Under the optimal conditions,
the enrichment factor for diphenylmercury was 931 and the limit of detection (LOD), calculated on the basis of five replicates
was 0.005 μg mL-1. The repeatability of the method, expresses as relative standard deviation (RSD) was 5.1 (n=6). The linear
range was between 0.01-10 μg mL-1. The proposed method was applied to the determination of mercury in different water
samples such as tap and well water. The results show that the contents of mercury in the two samples are all under the detection
limits; therefore, separate samples were spiked with 0.02 μg mL-1 of the target compound. The obtained relative recoveries (RR
%) for diphenylmercury were 108.88 and 92.57 % for tap and well water, respectively.The proposed method can be compared
with the other microextraction techniques such as SDME. The data show that the proposed method presents a lower limit of
detection and higher recovery and enrichment factor values and it requires very lower extraction time [2].
Reference
[1] A.Sarafraz-Yazdi, M.Y.Khuhawar, P.C.Uden. J. Chromatogr, 1992, 594, 395-399
[2] A.Sarafraz-Yazdi, S.Banihashemi, Z.Es'haghi. J.Chromatographia, 2010, 71, 1049-1054
Solid phase extraction and determination of trace amounts of Cu(II) using modified magnetite nanoparticles and flame
atomic adsorption spectrometric method
Mohammad Ali Karimi*, Abdolhamid Hatefi-Mehrjardi, Laila Azh, Asghar Askarpour Kabir, Javad Yarahmadi
Department of Chemistry & Nanoscience and Nanotechnology Research Laboratory (NNRL), Payame Noor University, Sirjan, Iran.
Email: ma_karimi43@yahoo.com
It is well known that trace elements play an important biochemical and physiological role in the regulation of metabolism and
influence human growth, development, health and disease. Copper is essential trace element, having a complex role in many
body functions, and has a great influence on arterial strength [1]. The determinations of heavy metals are usually carried out by
both atomic spectrometry including flame or graphite furnace atomic absorption spectrometry and inductively coupled plasmamass spectrometry [2,3]. Among the various analytical techniques, flame atomic absorption spectrometry (FAAS) has been used
more than other and for more selectivity, sensitivity and improves the detection limit has been used by researchers. In this work,
we have adapted solid phase extraction (SPE) with FAAS. The inherent assist of SPE is the selectivity and preconcenteration
factor that could be attained [4].We have used a fast and simple method using alumina coated magnetite nanoparticles
(ACMNPs) modified by the sodium dodecyl sulfate (SDS) and immobilized by ammonium pyrrolidine dithiocarbamate
(APDC/SDS-ACMNPs) for extraction and preconcentration of Cu(II) ions in water samples and determination by FAAS.
Magnetite nanoparticles synthesized and characterized by vibrating sample magnetometery (VSM), scanning electron
microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectrometry (FTIR). Copper ions are adsorbed on
APDC/SDS-ACMNPs were isolated by an external magnet and the adsorbed analyte was eluted with 0.3 M HNO3 solution and
quantified using FAAS. The separation/preconcentration conditions, such as pH, reagents concentrations, the standing time, the
sample volume, the elution condition and the interfering ions were investigated and optimized. At the pH range of 3-5.5, the
maximum adsorption of Cu(II) ions onto the APDC/SDS-ACMNPs were above 94%. The detection limit and relative standard
deviation of this method were 0.017 µg mL−1 and 2.7% (n = 7, C=5 µg mL−1), respectively. The prepared sorbent was applied for
the preconcentration of trace amounts of Cu(II) in different real samples with satisfactory results.
Reference
[1] A. Ramesh, B.A. Devi, H. Hasegawa, T. Maki, K. Ueda., Microchem. J. 86 (2007) 124.
[2] M. Ghaedi, A. Shokrollahi, A.H. Kianfar, A. Pourfarokhi, N. Khanjari, A.S. Mirsadeghi, M. Soylak, J. Hazard. Mater. 162 (2009) 1408.
[3] N. Rajesh, B. Deepthi, A. Subramaniam, J.Hazard. Mater. 144 (2007) 464.
[4] L. Sun, C. Zhang, L. Chen, J. Liu, H. Jin, H. Xu, L. Ding, Anal. Chim. Acta 638 (2009) 162.
Separation/preconcentration of arsenate in water samples with modified magnetite nanoparticles prior to its
determination by molecular spectrophotometry technique
Mohammad Ali Karimi*, Abdolhamid Hatefi-Mehrjardi, Azadeh Khayrkhah, Javad Yarahmadi, Asghar Askarpour Kabir
Department of Chemistry & Nanoscience and Nanotechnology Research Laboratory (NNRL), Payame Noor University, Sirjan, Iran.
Email: ma_karimi43@yahoo.com
Arsenic (As) is a known Group A human carcinogen. The association between cancer and other diseases (e.g., hypertension,
diabetes) with As levels in drinking water has been the subject of numerous reports [1]. The main sources of As are volcanoes,
arsenic-containing minerals and industrial, solid residues from mining extraction and agrochemicals. The principal sources of
human exposure to As consist of food and drinking water, where arsenic is present in both organic and in inorganic forms [1-3].
Magnetic solid-phase extraction (MSPE) technique with nanometer-sized solid phase particles is a new, simple, direct, efficient
and inexpensive method for preconcentration and separation of materials at trace and ultra-trace levels in environmental samples
[4].In this work, a MSPE method with nanosize magnetite adsorbents has been used for simple and rapid preconcentration of
arsenate ions in water samples. Alumina coated magnetite nanoparticles (ACMNPs) synthesized and then modified by
cetyltrimethyl ammonium bromide (CTAB) as surfactant for separation and preconcenteration trace amounts of AsO43- prior to
its determination by molecular spectrophotometry technique using molybdenum blue method. MNPs and ACMNPs synthesized
according and characterized by vibrating sample magnetometery (VSM), scanning electron microscopy (SEM), X-ray diffraction
(XRD) and Fourier transform infrared spectrometry (FTIR). Optimal experimental conditions including amount of reagents, pH
value, standing time, sample volume, type, volume and concentration of eluent and co-existing ions have been studied and
established. Under the optimal experimental conditions, the preconcentration factor, detection limit, linear range and relative
standard deviation (RSD) of AsO43- ion were 250 (for 500 mL of sample solution), 0.033 mg L−1, 0.2-12 mg L−1 and 1.04% (for
1 mg L-1, n=5), respectively. The presented procedure was successfully applied for determination of arsenic content in different
water samples.
Reference
[1] J.V.S. Smith, J. Jankowski, J. Sammut, Appl. Geochem. 18 (2003) 1479.
[2] T. Hayakawa, Y. Kobayashi, X. Cui, S. Hirano, Arch. Toxicol. 79 (2005) 183.
[3] G. Jiang, et al., Chem. Res. Toxicol. 16 (2003) 873.
[4] X. Zhao, Y. Shi, T. Wang, Y. Cai, G. Jiang, J. Chrom. A 1188 (2008) 140.
Differential Pulse anodic Voltammetric Determination of Pantoprazole in Pharmaceutical Dosage forms and Human
Plasma using Paramagnetic MgFe2O4 Ferrite Nanoparticles Multiwalled Carbon Nanotube Modified Electrode
Aliasghar Ensafi*, Alireza Allafchian
Isfahan University of Technology, Chem. Dept., 84156-83111, Isfahan, Iran
E-Mail:allafchian@yahoo.com
Pantoprazole is used as an anti-ulcer drug through inhibition of H+, K+-adenosine 5′-triphosphatase in gastric parietal cells. It
reduces the gastric acid secretion regardless of the nature of stimulation. The use of differential pulse voltammetry for the
determination of pantoprazole in pharmaceutical dosage forms and human plasma using a glassy carbon electrode has been
examined. In this work, MWCNTs were decorated with MgFe2O4 nanoparticles to modify a glassy carbon electrode to develop a
sensitive, selective, and fast method for the determination of pantaprazole at trace levels. This method is based on the different
properties of the mediators plus nanoparticles such as strong adsorptive ability, huge specific area, subtle electronic properties,
and excellent electrocatalytic activity [3,4]. Five milliliters of the buffer solution (pH 5.0) was transferred into an electrochemical
cell using a three-electrode system containing the modified electrode as a working electrode. Then, the cyclic voltammogram
(CV) was recorded with a scan rate of 20 mV s–1 and a pulse amplitude of 50.0 mV.. The peak current was measured and
recorded as a blank signal (Ib). Once the background voltammogram was obtained, aliquots of the sample solution containing 5
mL of the buffer solution, pH 5.0, plus a sufficient amount of pantaprazole solution were introduced into the cell. The peak
current was measured and recorded as a sample signal (Is). The difference in the current (Ips – Ipb) was considered as a net signal
(∆Ip) for each of the experiments. A calibration graph was prepared by plotting the net peak currents vs. pantaprazole
concentrations in the solutions.The electrochemical results discussed above demonstrate the electrochemical response of
pantaprazole on the MgFe2O4–MWCNTs modified electrode. It was shown that the proposed method outperforms the other
reported electrochemical methods in analyzing pantaprazole with a satisfactory sensitivity, a linear dynamic range and with a low
experimental detection limit of 0.01 μmol L–1. Based on our findings, this modified electrode can properly be used for the
determination of pantaprazole in pharmaceutical and urine samples with satisfactory results.
Reference
[1] McMillan, A., Young, H., Int J STD AIDS 18 (2007): 253–4
[2] Adam, D., Hostalek, U., Troster, K., Infection 23 (1995) 83–6
[3] Rezaei, B., Damiri, S., Sensors and Actuators B. 134 (2008) 324–331.
[4] Cai, Y., Zhang, Y., Su, Sh., Li, Sh., Ni, Y., Frontiers in Bioscience 12 (2007) 1946-1954.
Voltammetric sensor based on Gold Nanoparticles Decorating of Multiwalled Carbon Nanotubesas to Detection of
Clarithromycin in Pharmaceutical Samples
Behzad Rezaei*, Zohreh Mirahmadi-Zare
Isfahan University of Technology, Chem. Dept., 84156-83111, Isfahan, Iran
E-Mail:Mirahmadi_zare@yahoo.com
The electrochemical behavior of clarithromycin hydrochloride as an antibiotic was studied in the multiwalled carbon nanotubes
(MWCNTs), decorated with Au nanoparticles (GNMWCNTs) and used for the modification of the glassy carbon electrode
(GCE), through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Even though clarithromycin has a
high oxidation potential on the GCE, it can be oxidized much better on the GNMWCNTs due to electrocatalytic effect of nano
gold decorated on MWCNTs modified electrode. Under optimized conditions, the oxidation peak current was dependent on the
clarithromycin concentration and was linear in the ranges of 0.10 – 1000 μmol L-1 with a detection limit of 0.01 μmol L-1 (3
Sb/N). Nowadays, clarithromycin is a macrolide antibiotic used to treat pharyngitis, tonsillitis, acute maxillary sinusitis, acute
bacterial exacerbation of chronic bronchitis, pneumonia skin and skin structure infections. In addition, it is sometimes used to
treat legionellosis, helicobacter pylori, and lyme disease [1-3]. Therefore, selective, sensitive and simple determination of
clarithromycin in biological samples is very important. As mentioned before, the electrochemical response of clarithromycin on
the GNMWCNTs modified electrode is enhanced by using gold nanoparticles due to its catalytic effect on the electro-oxidation
of clarithromycin. It was also shown that the proposed sensor is a leading electrochemical method in analyzing clarithromycin
with a satisfactory sensitivity and determination range and with a low experimental detection limit of 0.01 μmol L-1. Based on our
findings, this modified electrode can be satisfactorily used for the determination of clarithromycin in pharmaceutical and urine
samples
Reference
[1] Choi,S. J., Kim,S. B., Lee, H., Na, D. H., Yoon, Y. S., Lee, S. S., Kim, J. H., Lee, K. Ch., Lee, H. S., Talanta 54 (2001) 377–382.
[2] Taninaka, C., Ohtani, H., Hanada, E., Kotaki, H., Sato, H., Iga, T., J. Chromatogr. B. Biomed. Sci. Appl. 738 (2000) 405.
[3] Wilms, E., Trumpie, H., Veenendaal, W., Touw, D., J. Chromatogr. B. Anal. Technol. Biomed. Life Sci. 814 (2005) 37.
Surface redox induced polymerization of aniline via electrooxidized gold surface
Abolfazl Kiani*, Iman Baghaei
Department of Chemistry, University of Isfahan, Isfahan 81746-73441, I. R. Iran
a.kiani@chem.ui.ac.ir
Synthesizing nanostructured polyaniline (PANI) has recently attracted a great deal of interest and growing attention[1]. PANI
nanostructures is obtained by oxidative polymerization of aniline in aqueous acidic solution either by electrochemical or chemical
methods[2]. Here we report a simple approach to synthesize nanostructured PANI in an aqueous solution via electrooxidized gold
surface. In this present method the polymerization of aniline occurred as a spontaneous redox process in which oxidized gold
surface was reduced by aniline, which were oxidized and simultaneously polymerized. A typical nanoporous gold film (NPGF)
electrode was prepared using the method published in literature with small of recordable disks (CD-R) made of gold as working
electrode by anodization of the gold substrate in a solution of phosphate (pH 7.4) for 3min via applying a step potential from
open circuit potential (OCP) to 4V vs. Ag/AgCl[3] . Then aniline was used as reducing agent to reduce gold oxide (Au 3+) to
metallic Au. Reduction Au3+ by aniline yielding its cation radical simultaneously that these species trigger the polymerization.
Various methods such as cyclic voltammetry (CV), Atomic force microscopy (AFM), Infrared spectrum (IR) were used to
investigate and characterize fabricated nanostructured PANI. In summary, a facile method was developed for the synthesis of
nanoscaled PANI via surface redox induced polymerization by electrochemical oxidized gold surface in which in situ generated
Au3+ was used as oxidant for oxidative polymerization of aniline.
Reference
[1].Wang , Y.; Tran, H. D.; Kaner, R. B., Applications of Oligomers for Nanostructured Conducting Polymers. Macromolecular Rapid Communications 2011, 32, (1),
35-49.
[2].Huang, J.; Kaner, R. B., Nanofiber Formation in the Chemical Polymerization of Aniline: A Mechanistic Study. Angewandte Chemie 2004, 116, (43), 5941-5945.
[3].Kiani, A.; Fard, E. N., Fabrication of palladium coated nanoporous gold film electrode via underpotential deposition and spontaneous metal replacement: A low
palladium loading electrode with electrocatalytic activity. Electrochimica Acta 2009, 54, (28), 7254-7259.
Modification of MCM-41 with Cobalt Phthalocyanine and its use for photochemical degradation
M.A. Vahedi, M.A. Zanjanchi*, M. Arvand, A. Fallah-Shojaei
Department of Chemistry, Faculty of Science, University of Guilan, Rasht, Iran
The confinement of photoactive species into the structure of mesoporous materials is an attractive area of investigation [1]. A
structural model MCM-41 is a fascinating choice. Metallophthalocyanines of iron, manganese and cobalt have been successfully
anchored onto surface of mesoporous and amorphous silica and have been used as catalysts in the liquid-phase oxidation of
aromatic compound. These compounds can be used for the removal of toxic organic contaminants. Heterogeneous photocatalysis
is one of the most promising techniques in the past 20 years for elimination of pollutants [2].In the present work, we have
immobilized CoPcS in MCM-41 using 3-(aminopropyl)-trimethoxysilane (APTMS) as functional reagent. XRD patterns of
MCM-41(a), APTMS-MCM-41(b) and CoPcS-APTMS-MCM-41(c) are shown in Fig 1. This figure demonstrate that highly
ordered photocatalyst was prepared. BET data showed a decrease in specific surface area of mesoporous which has been
modified with the functional group APTMS and doped phthalocyanine. Our IR studies showed that our immobilization was
successful and the modifier was immobilized on the walls of mesoporous. The photocatalytic properties of the samples were
investigated by degradation of 2, 4-dichlorophenol in aqueous solute under UV light. The effect of different amounts of catalyst
and different irradiation time for the degradation of 2, 4-dichlorophenol are shown in Fig 2.
Fig 1
Fig 2
The results showed that almost complete degradation of the pollutant took place within 3.5h using 30 mg of the photocatalyst.
Reference
[1] P. Karandikar, M. Agashe, K. Vijayamohanan, A.J. Chandwadkar, Applied Catalysis A: General 254 (2004) 133-143.
[2] M.A. Zanjanchi, A. Ebrahimian, M. Arvand, Journal of Hazardous Materials 175 (2010) 992-1000.
Kinetic Spectrophotometric study of the reaction between a synthetic phosphoraneligand with 2,3 dichloro5, 6dicyanobezoquinonein some nonaqueous solvents
ABBAS AFKHAMI *, TAYYEBEH MADRAKIAN, MOSAYEB REZAEI
Faculty of Chemistry, Bu-AliSinaUniversity,Hamedan, 6517838683, IRAN
Kinetic complex formation reaction of nitro benzoyl diphenylmethylenephosphorane (NBDMP) with 2,3dichlrodicyanobenzoquinone (DDQ) has been investigated spectrophotometrically at various temperatures in chloroform
,dichloromethane, nitro methane and acetonitrile solutions. The results indicated the formation of the charge transfer complex and
subsequent formation of DDO- in solution were related to the fast transformation of the initially formed DDQ- ion and
consumption of DDQ- radical ion [1]. The Pseudo-first order rate constants at various temperatures for the formation of theionic
intermediate, and the final product have been evaluated by computer fitting of theabsorbance time data to appropriate
equations.The activation parameters of the complexes have been determined from the temperature dependence of kinetic
constants by Eyring equation. The influence of solvent properties on the kinetics of the resulting charge-transfer complexes is
discussed [2].
Reference
[1] H. Skurai, A. Izuoka, T. Sugawara,Preparation and Property of Ionic Ct Complex of DimethylaminoNitronylNitroxide with DDQ, Mol. Cryst. Liquid Cryst. Sci.
Techol., Sect. A. 306 (1997) , pp. 415-421.
[2]T. Madrakian, M. Torabbeigi, M. A. Zolfigol, “Spectrophotomtric Study of Charge Transfer Complexes of Tetraethyleneglycol-bis-(8-quinolyl)ether with ICl 3 in
Some Nonaqueous Solvents”, J. Incl. Phenom., 53(3),(2005), 177-181.
Simultaneous spectrophotometric determination of phenolic acids in aqueous media using the partial least squares
method
Rouhollah Khani, Farzaneh Shemirani*, Sayede Maryam Sajjadi
School of Analytical Chemistry, University College of Science, University of Tehran, Tehran Iran
E-mail: shemiran@khayam.ut.ac.ir
Phenolic acids are hydroxylated derivatives of benzoic and cinnamic acids. Recent interest in phenolic acid stems has increased
because of their potential protective role, through ingestion of fruits and vegetables, against oxidative damage diseases (coronary
heart disease, stroke and cancers). In the current study, a direct spectrophotometric method for simultaneous determination of
three phenolic acids (p-hydroxybenzoic acid, vanillic acid and caffeic acid) in aqueous media is proposed. The resolution of a
ternary mixture of the phenolic acids by the application of partial least squares method was performed. Calibration graphs were
linear in the range of 1.0–5.0, 2.0–10.0 and 2.0–10.0 μg mL−1 for p-hydroxybenzoic acid, vanillic acid and caffeic acid,
respectively. The experimental calibration matrix was designed with 25 mixtures of these chemicals. Absorbance data were taken
between 235 and 315 nm. The root mean square error of prediction (RMSEP) for p-hydroxybenzoic acid, vanillic acid and caffeic
acid were 0.2246, 0.4465 and 0.4148, respectively. This procedure allows simultaneous determination of phenolic acids in
synthetic matrix samples and aqueous media and good reliability of the determination was proved.
Reference
[1] A. Safavi, G. Absalan, S. Maseum, Anal. Chim. Acta 432 (2001) 229-233.
[2] M.R. Khoshayand, H. Abdullahi, M. Shariatpanahi, A. Saadatfard, A. Mohammadi, SpectrochimiActa Part A 70 (2008) 491–499.
[3] A. Safavi, H. Abdollahi, M. R. Hormozi Nezhad, Talanta 59 (2003) 515- 523.
[4] C.F. Monica, A. Ferraro, M. Patricia, A. Castellano, S. Teodoro, A.B. Kaufman, J. Pharm. Biomed. Anal. 26 (2001) 443-45.
Design of experiments to develop an efficient electromembrane extraction for salbutamol and terbutaline from
pharmaceutical formulations and water samples
Maryam Rezazadeh, Yadollah Yamini, Shahram Seidi
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
Salbutamol (SB) and terbutaline (TB) are two selective β2-receptor agonists wildly used in sort as bronchodilators to prevent
exercise induced asthma [1]. Electromembrane extraction (EME) followed by high performance liquid chromatography (HPLC)
coupled with ultraviolet (UV) detection was developed and validated for determination and quantification of salbutamol and
terbutaline. A 200 V electrical field was applied to extract the analytes from 3.0 mL sample solution adjusted at pH 3.0, through
an organic phase which consists of 80% 2-nitrophenyl octyl ether (NPOE) and 10% di-(2-ethylhexyl) phosphate (DEHP) and
10% tris-(2-ethylhexyl) phosphate (TEHP) as supported liquid membrane (SLM) into an acidic acceptor solution which adjusted
at pH 1.0, located inside the lumen of hollow fiber. To achieve the best extraction conditions the SLM was optimized separately
and other parameters, such as extraction time, applied voltage and pH in sample solution and acceptor phase was studied using
experimental design. Under optimal conditions extraction recoveries of 53% and 43% were obtained for salbutamol and
terbutaline, respectively, which corresponded to preconcentration factors of 89 for salbutamol and 72 for terbutaline. The method
offers acceptable linearity with estimation of coefficient higher than 0.9947 and relative standard deviation less than 4.7%.
Finally it was applied for analysis of drugs in aqueous samples.
Reference
[1] J.M. Weiler, Allergic and Respiratory Disease in Sports Medicine, Marcel Dekker, New York, 1997.
Centeral composite design for the optimization of Mo(VI) removal from water samples using layered double
hydroxides(LDHs)
Mehdi Aghaei ; Morteza Bahram ; Behruz Azizi ; Khalil Farhadi*
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
The Layered double hydroxides (LDHs), known as anionic clays, have received great attention in the last decades because of
their high anion exchange capacities. The structure of LDHs is based on positively charged brucite -like sheets and the positive
charges are balanced by intercalation of anions in the hydrated interlayer regions [1]. Molybdenum has long been known as one
of the biologically active transition elements [2]. Molybdenum deficiency has often been reported, but at large concentrations,
molybdenum may be toxic as it leads to secondary copper deficiency [3]. Therefore removal of this ion from water samples is of
significant importance from an environmental point of view. In this study ZnAl-NO3 and MgAl-NO3 LDHs was synthesized by
a co-precipitation method [4]. Optimum experimental conditions for removal of Mo(VI) by LDH was obtained by Centeral
composite design (CCD). Batch adsorption studies have been carried out to determine the effect of the contact time , pH and the
amount of adsorbent on the adsorption process. The Langmuir and Freundlich adsorption isotherms were used to model the
adsorption behavior [5]. The kinetics were fitted with the pseudo-first order and pseudo-second order models. The constructed
model showed that adsorbent weight significantly affect the adsorption process and contact time has significant interaction with
pH and adsorbent weight. The experimental data match well with Langmuir isotherm with a correlation coefficient of 0.9693 and
0.9936 respectively for ZnAl-NO3 and MgAl-NO3 and adsorption kinetics follows a pseudo-second-order kinetic model.
Reference
[1] A. Violante, M. Pucci, V. Cozzolino, J. Zhu, M. Pigna, Sorption/desorption of arsenate on/from Mg–Al layered double hydroxides: Influence of phosphate, J.
Colloid Interf. Sci 333 (2009) 63–70.
[2] A. Afkhami, R. Norooz-Asl, Removal, preconcentration and determination of Mo(VI) from water and wastewater samples using maghemite nanoparticles,
Colloids. Surf., A 346 (2009) 52–57.
[3] A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry, 6th ed., Wiley Interscience, 1999, pp. 920–922.
[4] L. Lv, P. Sun, Z. Gu, H. Du, Removal of chloride ion from aqueous by ZnAl-NO3 layered double hydroxide as anion-exchanger, J. Hazard. Mater 161 (2009)
1444–1449.
[5] Q. Chang, L. Zhu, Z. Luo, M. Lei, S. Zhang, H. Tang, Sono-assisted preparation of magnetic magnesium aluminum layered double hydroxides and their
application for removing fluoride, Ultrason. Sonochem 18 (2011) 553–561.
Electrooxidation of methanol on (Ni - Al – LDH) modified carbon paste electrode
Khalil Farhadi *, Robab Abbasi
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
khalil.farhadi@yahoo.com ; kh.farhadi@urmia.ac.ir
There is an increasing interest in the development of the direct methanol fuel cell (DMFC) due to its possible use in electric
vehicles [l-2]. The performance of DMFC has improved markedly in the past years. Despite many efforts devoted to the
DMFC development, there still remain problems to be overcome in terms of efficiency and power density. One of the reasons
is the relatively slow kinetics of methanol oxidation reaction at the anode. In this study the electrochemical behavior of Ni(II)
– Al(III) – LDH (Layered Double Hydroxide) as carbon paste electrode (CPE) towards methanol oxidation has been studied
in alkaline solution using cyclic voltammetery (CV) and chronoamperometry (CA) techniques. In CV studies, in the presence
of methanol, modified electrode shows a significantly higher response for methanol oxidation. The peak current of the
oxidation of nickel hydroxide increase is followed by a decrease in the corresponding cathodic current in presense of
methanol. The effect of scan rate, amount of modifier and concentration of methanol, on the activity of the electrode has been
examined. Moreover, the anodic currents show linear dependence on the concentration of methanol. The modified electrode
for methanol determination is of the property of simple preparation, good stability and fast response.
Reference
[1] WITHAM C K, CHUN W, VALDEZ T I, NARAYANAN S R. Performance of direct methanol fuel cells with sputter-deposited anode catalyst layers [J].
Electrochem Solid State Lett, 3 (2003) 497-500.
[2] CHEN C Y, YANG P. Performance of an air-breathing direct methanol fuel cell [J]. J Power Sources, 123 (2003) 37-42.
Determination of fuberidazole by using admicelle-enhanced synchronous fluorescence spectrometry
M. Amjadi*, P. Ghandforoushan
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Iran.
E-mail: amjadi@tabrizu.ac.ir
Fuberidazole [2-(2'-furyl)benzimidazole] is a fungicide widely used in agriculture as the principal active substance of various
commercial formulations. Therefore, its determination at low levels in environmental samples is of high importance.In the
present work, a simple and highly sensitive method for the determination of fuberidazole in river and underground water was
developed. Fuberidazole in water samples was concentrated into sodium dodecyl sulfate (SDS)-alumina admicelles. The
collection was performed by adding SDS and alumina particles into the sample solution at appropriate pH. After gentle mixing,
the resulting suspension was passed through a membrane filter to collect the SDS admicelles containing highly concentrated
pesticide. Adsolubilization of analytes occurred through hydrophobic and electrostatic interactions. The filter was placed on a
slide glass and then covered with a fused silica glass plate before setting in a fluorescence spectrometer. Fuberidazole was
selectively determined by the synchronous fluorescence scan (SFS) analysis with keeping wavelength intervals between
excitation and emission to 30 nm. Calibration graph was linear in the range of 0.01-4 ng mL-1 with a detection limit of 7.7 pg
mL−1. The relative standard deviation (n = 5) was 1.18% for 2 ng mL-1 of fuberidazole. The recovery results for several real
samples were satisfactory.
Reference
[1] Moral, A. Dolores Silia, M., Rubio, S, Perez Bendito, D. 2006, Anal.Chim. Acta., Vol. 569: 132-138.
[2] Saitoh, T., Itoh, H. and Hiraide, M., 2009, Talanta, Vol. 79(2):177-182.
Sight into reaction of Azithromycin antibiotic with Zn2+ ion in non aqueous solution by Conductometric and
Spectrophotometric Method
Toktam laal Zakaria1,*, Razieh Sanavi Khoshnood1, Maasome Adine Mohmmadzade1
And Zarin Eshaghi2
1. Department of Chemistry, Faculty of Science, Islamic Azad University of Mashhad, Mashhad, Iran
2. Department of chemistry, Payame Noor University (PNU), Mashhad, Iran
* E-mail: toktamzakaria@yahoo.com
Azithromycin is a novel of the family of 15- membered macrolide antibiotics named azalides [1,2]. Clinical work showed that
the concurrent ingestion of antibiotic with drugs containing multivalent cations could reduce the bioavailability by up to 90% [3,
4]. First of all the interaction of the antibiotic azithromycin with Zn (NO3)2.6H2O in methanol solvent has been investigated by
Conductometric method to determine the number of complexes formed. After that, the interaction of the antibiotic with Zn2+
cation was studied by Spectrophotometric method under equilibrium conditions. The interaction of azithromycin with Zn2+ salt
has been founded to form one complex with metal to ligand composition of 1:4. The spectra were analyzed to determine the
coordination number of the complexes formed and to calculate their formation constants. The value of (Kf = 6.0× 105 M-4) was
calculated from the absorption spectra for Zn2+- azithromycin complex at room temperature. Spectrophotometric method was
developed and used to determine azithromycin- Zinc at a λmax of 375(nm). The influence of pH, time, temperature and
interferences has been tested. The experiments show that formation of complex is influenced by pH and temperature. The reason
of complex absorbance in acid media is that macrolides are stable in neutral solution, but their glycoside relations are hydrolysed,
hence it will be more possible to form complex with multivalent ions also the increasing of temperature helps it.
Reference
[1]. M. Rachidi, J.Elharti, Analytical Lettrs, 2007, 40, 53
[2]. B. Nigovic, B. Smimunic, Journal of Pharmaceuticalans Biomedical Analysis, 2003, 32,197.
[3]. A.W. El-Rjoob, J. Al-Mustafa, Z. Taha, M.Abous, Jordan Journal of Chemistry, 2008, 3,199.
[4]. R.Gandhi, O.Pillai, R.Thilagavathi, B. Gopalakrishnan, C.Lal Kaul, R.Panchagnula. European Journal of Pharmaceutical Sciences, 2002, 16,175
Determination of BTEX in sea water of Persian Gulf by headspace SPME-GC-FID
Masood Shokria, Ebrahim Abouzari-Lotfa,*, Ahmadreza Ebrahimipoora, Hossein Moeinb, Asieh Ahmadalinezhadc, Azadeh Asadollahia,
Nemat Allah Jaafarzadeh Haghighid, Hossein Delshabb, Ali Javadia
a
Iranian Academic Center for Education, Culture and Research, Tarbiat Moallem Branch, Moffateh Ave, No. 49, Tehran, Iran. bDepartment of
Environment of Bushehr Province, Ashuri St. Postal Code: 7515877473 Bushehr Iran. cDepartment of Chemistry, Lakehead University, Thunder
Bay, Ontario, Canada P7B 5E1, dDepartment of Environmental Health, Ahvaz Jondishapour Medical Sciences University, Ahvaz, Iran.
Levels of benzene, toluene, ethylbenzene and the xylenes (BTEX) in the 11 different harbors in Persian Gulf were investigated.
Samples were taken between Dylam and Asaluyeh over a 625 km trajectory [1], and extracted by solid phase microextraction
(SPME) and quantified by gas chromatography coupled with flame ionization detection (GC-FID). The chromatographic analysis
was performed using an Agilent 6820 gas chromatograph equipped with a flame ionization detector and a fused silica HP-5
capillary column. The oven temperature program was as follows: 40 °C held 3 min, rate 5 °C min-1 to 50°C. (held 2 min), rate 10
°C min-1 to 80 °C (held 1 min), rate 25 °C min-1 to 220°C, (held 2 min). An injector temperature was maintained at 250 °C. Three
commercially available SPME fiber coatings, with different polarity and inner structure were tested for efficiency of headspace
SPME extraction of BTEX. the responses achieved with PDMS 100 μm fibers were the best; In HS-SPME, the exposure time of
the fiber in the headspace is important because analysis with very short times may reduce significantly the response[2]. The fiber
was exposed directly to the headspace above the sample for 5, 10, 15, 20 and 30 min, under the same conditions. In regard of
reasonable extraction efficiency and appropriate analysis time, 10 minute was ultimately chosen as the preferred extraction time.
After analyzing all experimental results, the following conditions have been selected to evaluate the performance of the method:
300 rpm stirring rate, 10 min extraction time, 3 min desorption time, 250 °C desorption temperature, 20% (w/v) salt and 35 °C
extraction temperature.The relative standard deviation (R.S.D.) for the procedure varied in the range of 3-8%. The method
detection limits (MDLs) were found between 0.08 (ethylbenzene and o-xylene) and 0.5 ng/ml (benzene).
Reference
[1] Nadim, F., Bagtzoglou, A.C., Iranmahboob, J., 2008. 51, 556-565.
[2] Pawliszyn, J., 1997.Solid Phase-Microextraction: Theory and Practice, Wiley-VCH, New York.
Electrochemical study of bi-metallic nanoelectrocatalyst of
CNT-g-PCA-Pt-M (M: Co, Ni) in methanol fuel cells electrodes
Nahid Sarlak1,2, Mohammad Amin Farahmand Nejad1,2*, Saeed Shakhesi2, Keyvan Shabani2
1-Department of Chemistry, Faculty of Science, Lorestan University, Khorram Abad, I.R.Iran
2-Department of Nano Technology & Nano Science, Engineering Research Institute, Tehran, I.R.Iran
Email:m_farahmand22@yahoo.com
In this work, first we opened MWCNT and then polymerized it using citric acid and synthesized CNT-g-PCA[1]. The reaction of
Nickel and Cobalt ions with CNT-g-PCA was studied using UV-Vis spectroscopy. The effective parameters on this reaction such
as sonication time, pH and time of reaction were optimized. Then TEM analysis was carried out for confirm the encapsulation of
nanoparticles. Based on the optimum conditions CNT-g-PCA-Pt-M, (M: Ni, Co) were synthesized [2-4] and then NaBH4 as a
reducing agent was added to the solution for reducing metal ions to the nanoparticles. CNT-g-PCA-Pt-M (M: Co, Ni) were
deposited on the surface of a cupper wire as a working electrode by using the electrospray technique[5-6] and then the modified
electrode characterized with SEM analysis. Cyclic voltametery was employed to study the electrochemical properties of bi-metal
nanoelectrocatalysts in oxidation of methanol. Based on electrochemical data, bi-metal nanoelectrocatalysts caused a
considerable increase in the current, compared to the Platinum nanoelectrocatalysts.
Reference
[1] M. Adeli, A. Bahari, H. Hekmatara, J. Nano:Brief Reports and Reviews, 3 (2008) 37.
[2] E.I. Santiago, L.C. Varanda, H.M. Villullas, J. Phys. Chem. C 111 (2007) 3146.
[3] J.R.C. Salgado, E. Antolini, E.R. Gonzalez, J. Phys. Chem., B 108 (2004) 17767.
[4] T. Lopes, E. Antolini, F.R. Gonzalez, J. Power Sources, 164 (2007) 111.
[5] J.H. Kim, K.W. Nam, S.B. Ma, K.B. Kim, J. Carbon, 44 (2006) 1963.
[6] A. Jaworek, J. Mater. Sci., 42 (2007) 266.
A new inside-needle extraction method based on molecularly imprinted polymer to solid-phase dynamic extraction and
pre-concentration of methamphetamine followed by gas chromatography analysis
Djavanshir Djozan*1, Saeed Mohammad Sorouraddin1, Mir Ali Farajzadeh1 and Tahmineh Baheri2
1) Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
2) The Research Center of Antinarcotics Police, Tehran, Iran
E-mail: djozan@tabrizu.ac.ir
In the past decades, modern sample preparation methods such as solid-phase micro-extraction (SPME), membrane-assisted
solvent extraction (MASE) and stir-bar sorptive extraction (SBSE) [1] have been developed. In recent years, inside-needle
capillary adsorption trap (INCAT) technique has been developed as a solvent-free sample preparation approach [2]. Molecular
imprinting polymer (MIP) is a technology to produce polymers programmed to recognize a target or a class of target molecules
[3]. A novel inside-needle extraction method was developed through thermal polymerization of methamphetamine (MAMP)-MIP
on the interior surface of a 1 mm i.d. stainless steel tube. 1.9 mmol MAMP and 30 mmol methacrylic acid were dissolved in 30
mL acetonitrile (porogen). Then, 120 mmol ethylene glycol dimethacrylate and 280 mg of AIBN (initiator) were added. The
stainless steel tube with a flexible steel wire (10cm×0.2mm o.d.) in the middle was filled with the prepared pre-polymer solution
and was sealed with septum. The polymerization was carried out at 50°C for 14 h. After completion of the polymerization, the
wire was withdrawn. The coated stainless steel tube could be mounted on a glass syringe and used as an extraction device
(extraction needle). It was directly coupled with GC systems. The parameters being effective on extraction processes, namely
sample volume, flow rate, pH and ionic strength of the sample were investigated and optimized. The fabricated needle coating
(MAMP-MIP layer) was durable and showed very good chemical and thermal stability. The extraction needle showed high
selectivity as well as great extraction capacity for MAMP. The extraction of MAMP, amphetamine (AMP) and 3,4methylenedioxymethamphetamine (MDMA, Ecstasy) was performed using the fabricated extraction needle followed by GC
analysis. The fabricated needle was proved to be applicable to the analysis of real samples by comparing the results obtained for
non-spiked and spiked samples of urine.
Reference
[1] E. Rodriguez, R.J. Barrio, A. Goicolea, Z. Gomez de Balugera, Anal. Chim. Acta 384 (1999) 63.
[2] F. Musshoff, D.W. Lachenmeier, L. Kroener, Forensic Sci. Int. 133 (2003) 32.
[3] Dj. Djozan, M.A. Farajzadeh, S.M. Sorouraddin and T. Baheri, Chromatographia, 73 (2011) 975.
Development of Sorbentless Cryogenic Needle Trap device for the extraction of BTEX from soil samples
Dj. Djozan*, J. Norouzi, M.S. Sorouraddin, M.A. Farajzadeh
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran.
E-mail: djozan@tabrizu.ac.ir
Sample preparation procedure has a capital role in modern analytical. A lot of methods were developed during last decades [1].
In the last few years, several microextraction methods using a needle extraction device have also been developed based on
different extraction media [2]. In these approaches partitioning between sample matrix and needle or capillary coating is achieved
during the sampling. The needle trap device was first introduced in late 1970s as a Tenax-filled needle [3].In this study a new
simple, rapid, solvent and sorbentless needle trap device (SCNTD) for the extraction of benzene, toluene, ethylbenzene and
xylene from soil and other solid samples has been developed. The system has been designed using a 2 mL glass syringe as
extractor. The gaseous sample or the components in headspace of the solid sample are circulated through the syringe needle
where a flow of liquid nitrogen is passed into outer jacket of needle. The analytes are trapped on the inner surface of needle due
to very low temperature of needle. Once the total extraction is achieved, the needle is removed and placed in the GC injector
valve. Trapped analytes are thermally desorbed and analysed by GC. The effect of some experimental factors such as trapping
time and temperature, sample temperature, desorption time and flow rate of sample headspace were investigated and the optimum
conditions were achieved. The overall sampling and analysis times were less than 20 min. Using the proposed method at the
optimum conditions, an excellent extraction efficiency (>85%) of BTEX present in the soil sample was obtained. Due to the
absence of sorbents in the trapping needle, complete desorption of trapped compounds is very fast and carry-over was less than
1% after 30 seconds desorption at 200 ºC. The GC analysis of extracted compounds was performed with the good analytical
characteristics. Relative standard deviation values are below 10% .The limits of detection ranges from 2.23 to 5.32 ng g -1.
Reference
[1] A. Wang, F. Fang, J. Pawliszyn, J. Chromatogr. A 1072 (2005) 127.
[2] N. Jakubowska, B. Zygmunt, J. Chromatogr. A 1216 (2009) 422.
[3] F. Raschdorf, Chimia, 32 (1978) 478-483
Antioxidant activity of Scutellaria luteo-coerulea in the DPPH, β-carotene/linoleic acid and FRAP assay by UV-Vis
spectrophotometer
Mohammad Nik Bin1*, Nasrin Kazemipour2, Jafar valizadeh2, Malek Taher Maghsoodlou1, Amene Davarimanesh1, Mohammad Ansari
Moghadam1
1
Department of Chemistry, Faculty of Science, University of Sistan & Baluchestan, I. R. Iran
2
Department of Biology, Faculty of Science, University of Sistan & Baluchestan, I. R. Iran
E-mail: m.nikbin17@gmail.com
In the recent years, the importance of antioxidants in the protection of organisms or tissues, or of nonliving systems against
oxidative stress has become evident [1]. The aerial parts of scutellaria luteo-coerulea were extracted with different solvents and
antioxidant activities were evaluated by DPPH, β-carotene/linoleic acid and FRAP assay. All absorbances of them were measured
by UV-Vis spectrophotometer. Their IC50 values were calculated and results were compared with BHT and Ascorbic acid as
standard [2]. In DPPH and FRAP assay, the ethanol extract was the most potent radical scavenger. IC50 value of ethanol extract in
DPPH assay was 81.37 µg/ml. In FRAP assay value of antioxidant activity was 6.7 mmol Fe2+/mg sample. In β-carotene/linoleic
acid assay, the ethyl acetate extract was the most potent radical scavenger and its IC50 value was 829.7 µg/ml.
Reference
[1] Luís M. Magalhães et. al, Flow injection based methods for fast screening of antioxidant capacity, Talanta 77 (2009) 1559–1566
[2] Anis Ben Hsouna et al, Antioxidant constituents from Lawsonia inermis leaves: Isolation, structure elucidation and antioxidative capacity, Food Chemistry 125
(2011) 193–200
Comparison of antioxidant activity and determination mineral element of Calotropis procera from two different regions
Mohammad Nik Bin1*, Nasrin Kazemipour2, Jafar Valizadeh2, Malek Taher Maghsoodlou1, Amene Davarimanesh1, Mohammad Ansari
Moghadam1
1
Department of Chemistry, Faculty of Science, University of Sistan & Baluchestan, I. R. Iran
2
Department of Biology, Faculty of Science, University of Sistan & Baluchestan, I. R. Iran
E-mail: m.nikbin17@gmail.com
Calotropis procera a wild growing tropical plant possesses various medicinal properties [1]. Presence of some essential and trace
elements C. procera can result in the toxicity of the plant and hence change of leaves colour, inhibition to the germination and
growth of seeds or even death of the plant may be evident [2]. Calotropis procera were collected from Qeshm Island in
Hormozgan province and Iranshahr in Sistan & Baluchestan province. Dried and powdered leaves of C. procera were extracted
with different solvents and antioxidant activities of them were evaluated by DPPH method. The absorbance was read at 517 nm
with UV–Vis spectrophotometer [3]. The results showed that the ethanol extract of C. procera of Iranshahr was the most potent
radical scavenger. On the other hand, mineral element of C. procera was measured by dring ash method and the absorption of
element was measured by atomic absorption spectroscopy (AAS). Results showed high levels of calcium and sodium in both
plant. Abundance arrangement of elements in this plant is as follows: Ca>Na>K>Mg>Fe>Mn>Cr
Reference
[1] S. Roy, R. Sehgal, B.M. Padhy, V.L. Kumar, Antioxidant and protective effect of latex of Calotropis procera against alloxan-induced diabetes in rats, Journal of
Ethnopharmacology 102 (2005) 470–473.
[2] Samina Kabir Khanzada et al, Analysis of fatty acid, elemental and total protein of Calotropis procera medicinal plant from Sindh, Pakistan, Pak. J. Bot., 40(5):
1913-1921, 2008.
[3] Ahmed Akrout et al, Antioxidant and antitumor activities of Artemisia campestris and Thymelaea hirsuta from southern Tunisia, Food and Chemical Toxicology,
2010
Microextraction by packed sorbent for determination of rozmarinic acid followed by high performance liquid
chromatography
Akram Rahimi, Payman Hashemi*
Department of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran
Email:payman_hashemi@yahoo.com
In cases when the analytes of interest are present in a complex matrix, the sample preparation is of crucial importance for the
analysis. The purpose of sample-preparation is to remove interfering substances and also enrichment of the analytes [1].
Microextraction by packed sorbent (MEPS) is a new technique for sample preparation. The new method is very promising, easy
to use, of low cost and rapid in comparison with previously used methods [2]. In this study, a carbon based nanoporous material
(CMK-3) was used for the microextraction of rozmarinic acid by MEPS technique.Two milligrams of CMK-3 Nanoporous
carbon material was inserted into the needle part of a 1 ml syringe as a plug with a filter from both sides and fitted manually into
the syringe. The packed syringe was conditioned before being used for the first time. The rozmarinic acid sample (250 µl) was
drawn through the syringe up and down by a designed device equipped with a stepper motor. The analytes were eluted with 100
µl of acetonitril. The eluate was injected into the HPLC system. After each extraction, the sorbent was cleaned and conditioned
by water followed by methanol. The same packing bed could be used for at least 80 extractions without significant change in its
properties. For optimization of factors affecting the extraction efficiency, a central composite (response surface) design using
Minitab statistical software[3] was used. Under the optimized conditions (i.e. number of absorption 14 times, number of elution
10 times and volume of elution 100 µl) an extraction recovery of 90 (±4.5)% (for n = 5) was obtained. The method was
successfully applied to the determination of rozmarinic acid in rozmary plants samples.
Reference
[1] M. Abd el-Rehim, Journal of Chromatography B 801 (2004) 317–32178.
[2] I. G. Marinoa, J. B. Quintanaa, I. R. odrigueza, S. Schraderb, M. Moederb, Analytica Chimica Acta 684 (2011) 50–57.
[3] Inc. Minitab, Minitab Statistical Software, Release 15 for Windows, State College, Pennsylvania, 2006.
Peroxyoxalate Chemiluminescence of 7-Amino-4-methylcoumarin in presence of Brij 35 as a micellar reagent and
quenching effect of vitamin D3 on it
M. J. Chaichi , S.N. Azizi and M. Heidarpour*
Faculty of Chemistry, Mazandaran University, Babolsar, I.R. Iran
E-mail: jchaichi@yahoo.com
The brilliant chemiluminescence emission resulting from the reaction of some oxalic acid derivatives is one of the most
outstanding branches of chemiluminescence. This group of chemiluminescence reactions, called peroxyoxalate
chemiluminescence (PO–CL), are well-known powerful analytical tools of detecting a wide variety of fluorescent compounds.
These are based on the reaction of hydrogen peroxide with an activated oxalate which results in the formation of one or more
energy-rich intermediates. These intermediates are capable of exciting a large number of fluorophores through the chemically
initiated electron exchange luminescence mechanism [1, 2]. Coumarin derivatives are widely distributed in plants, some of them
being physiologically active [3] and some possessing antimicrobial properties [4, 5]. The active non-ionic surface agent, Brij35,
can produce micellar media in solution. Diffusion the fluoreser to the micelle, provide a rigid media and therefore produce an
enhancing effect of the fluorescence and or chemiluminescence intensity of the coumarin derivative. It is found that the
chemiluminescence (CL) intensity of 7-Amino-4-methyl coumarin can be greatly quenched by vitamin D3 in Brij35 micellar
media. Under optimum conditions, the quenched chemiluminescence intensity is in proportion to the concentration of vitamin D3
in the range of 3×10-3 – 1.6 × 10−2 M. The chemiluminescence signal showed a linear decay while vitamin D3 was added to the
peroxyoxalate (PO-CL) system. The reaction resulted in a Stern–Volmer plot with a Kq value of 82.50 M−1. The PO-CL
parameters were estimated by computer fitting of the experimental CL intensity to proper models.
Reference
[1] M.M. Rauhut, Acc. Chem. Res. 2 (1969) 80
[2] A.G. Mohan, N.J. Turro, J. Chem. Edu. 51 (1974) 528
[3] W.C. Meuly, in: Kirk-Othmer Encyclopedia of Chemical Technology, Wiley/Intersceince, New York, 1988
[4] L. Jurd, A.D. King, K. Mihara, Phytochemistry 10 (1971) 2965
[5] L. Jurd, A.D. King, H. Bayne, K. Mihara, Phytochemistry 10 (1971) 2971
Synthesis and application of silver nanoparticles in reaction of luminol–OCl- system
S. N. Azizi1,2 ,M. J. Chaichi , M. Heidarpour* and S. Ranjbar,1
1- Analytical Division of Chemistry, University of Mazandaran, azizi@umz.ac.ir
2-Nano and Biotechnology Reseach Group, University of Mazandaran, Basbolsar, Iran
Metallic nano particles have been extensively investigated in recent years due to their unusual physical and chemical properties,
which largely differ from their bulk properties. Nanomaterial possesses quantum size effect, volume effect, surface effect and
macroscopic quantum tunneling effect that traditional solid material does not have [1]. Chemiluminescence (CL) is the
phenomenon when vibronically excited product of an exoergic reaction relaxes back to its ground state with emission of photons
[2]. CL detection has many advantages, such as high sensitivity, wide calibration range, relatively inexpensive instrument, rapid
analysis, and suitable for automation. Silver nanoparticles (AgNPs) were synthesized by a simple wet chemical route method and
characterized by using UV–Vis spectra, scanning electron microscopy, X-Ray differaction and FTIR. CL intensity in luminol–
OCl- system obviously decreased in the presence of AgNPs comparing with that in the absence of AgNPs, proving that AgNPs
catalyzed luminol-H2O2 CL reaction [3] but AgNPs can’t catalyzed in luminol–OCl- system. Therefore AgNPs could quench CL
reaction of luminol.Silver nano particle of the size 40-80 nm are formed in the process of oxidation of glucose to gluconic acid by
amine in the presence of silver nitrate and the gluconic caps the nano silver particle. The presence of gluconic acid on the surface
of nano silver particles was confirmed by FTIR studies. We have found that increasing the AgNPs opposite to the luminol-H2O2
system could decrease the chemiluminesence (CL) intensity of luminol-ClO- system. The effects of pH and concentration of
reactants CL intensity in this system are investigated.
Reference
[1] Hao Chen, Feng Gao , Rong He, Daxiang Cui Journal of Colloid and Interface Science 315 (2007) 158.
[2] R. Janardhanan, M.Kaurppaiah, N. Hebalkar, T. Narsinga Rao, “Polyhedron” 28 (2009) 2522
[3] S.L.-C. Hsu, R.-T, Wu, “Mater. Lett’’ 61 (2007) 3719
Electrocatalytic determination of isuprel using multiwall carbon nanotubes as a sensor and N-(3,4-dihydroxy phenethyl)3,5-dinitrobenzamide as a mediator
Ail A. Ensafi*, H. Bahrami
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
4-[1-Hhydroxy-2-[(1-methylethyl)-amino]ethyl]-1,2-benzenediol named isuprel is a catecholamine drug. That is widely used in
the treatment of allergic emergencies such as styptic, bronchial asthma, status asthmatic, cardiac arrest, glaucoma, and ventricular
bradycardia [1]. The cardiovascular effects of isoprenaline compare with epinephrine and norepinephrine, which can relax almost
every kind of smooth musculature that contains adrenergic nerves. However, this effect is pronounced in the musculature of
bronchus and also in the gastrointestinal tract [2]. Therefore, determination of this drug is very important. Thus, in this study we
describe application of N-(3,4-dihydroxy phenethyl)-3,5-dinitrobenzamide in multiwall carbon nanotubes paste matrix as a new
voltammetric sensor for determination of isuprel in aqueous buffer solution. Cyclic voltammetric, chronoamperometric, and
electrochemical impedance spectroscopic methods have used to investigate the suitability of N-(3,4-dihydroxy phenethyl)-3,5dinitrobenzamide as a mediator for the electrocatalytic oxidation of isuprel at pH= 7.0. It was found that in the presence of N(3,4-dihydroxy phenethyl)-3,5-dinitrobenzamide at pH 7.0, the catalytic oxidation peak current of isuprel is high and the
overpotential of isuprel oxidation decreases about 150 mV. Based on the obtained results a mechanism for electrooxidation of
isuprel in the presence of N-(3,4-dihydroxy phenethyl)-3,5-dinitrobenzamide was proposed. The experimental results showed that
the mediated oxidation peak current of isuprel is linearly dependent on the concentration of isuprel in the ranges of 3.0 × 10–7 M
– 1.25 ×10–4 M with differential pulse voltemmetric method. Finally, this modified electrode was used for determination of some
real samples such as drug and urine.
Reference
[1] L.S. Goodman, A. Gilman, The Pharmacological Basis of Therapeutics, 9th ed., McGraw-Hill, New York, 1996, pp. 105–109.
[2] V.G. Bonifacio, H. Luiz, J. Macolino, F.S.M. Teixeira, O.F. Filho, Microchem. J. 78 (2004) 55.
Determination of diclofenac using ionic-liquid multiwall carbon nanotubes paste electrode in patient human urine
Ail A. Ensafi*, M. Izadi
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
Diclofenac sodium (DFNa) (sodium [o-(2,6-dichloroanilino)phenyl] acetate), is a non-steroidal anti-inflammatory drug (NSAID)
with strong anti-pyretic, analgesic and anti-inflammatory properties [1]. It is widely used in clinical medicine for the treatment of
inflammatory conditions such as rheumatoid arthritis, osteoarthritis and ankylosing spondilytis [2,3]. The efficacy of diclofenac
equals that of many newer and established NSAIDs. Therefore, determination of this compound is very important. To date,
several methods for determination of diclofenac have been reported. These include potentiometry, capillary zone electrophoresis
(CZE), high performance liquid chromatography (HPLC), high-performance liquid chromatography-mass spectrometry (HPLCMS), spectrophotometric, thin layer chromatography, gas chromatography and polarographic techniques. To the best of our
knowledge, very little has been reported on voltammetric determination of diclofenac sodium, because the electrooxidation of
diclofenac sodium proceeds very slowly and almost no current response was observed at the usual electrode. Thus in this study,
the direct electrochemistry of diclofenac on modified multiwall carbon nanotubes using carbon ionic liquid (i.e., 1-hexyl-3methylimidazolium hexafluorophosphate was studied. It was found that the electrode showed sensitive voltammetric response to
diclofenac. The experimental results suggested that the modified electrode promoted electron transfer reaction for the oxidation
of diclofenac. The electron transfer coefficient and charge transfer resistant (Rct) of diclofenac at the modified electrode were
calculated. Under the optimized conditions at pH 7.0, the peak current was linear to diclofenac concentrations over the
concentration range of 0.5–350 μmol L−1, using differential pulse voltammetry. The detection limit was 0.31 μmol L−1. The
proposed method was successfully applied to the determination of diclofenac in both ampoules and patient human urine samples.
Reference
[1]. Iliescu, T.; Baia, M.; Miclăuş, V. A Eur. J. Pharm. Sci. 2004, 22, 487-495.
[2]. Gostick, N.; James, I.G.; Khong, T.K.; Roy, P.; Shepherd, P.R.; Miller, A.J. Curr. Med. Res. Opin. 1990, 12, 135-142.
[3]. Crowley, B.; Hamill, J.J.; Lyndon, S.; Mckellican, J.F.; Williams, P.; Miller, A.J. Curr. Med. Res. Opin. 1990, 12, 143-150.
Amperometric determination of hydrogen peroxide by using the palladized aluminum electrode modified with
electroactivated iron-pentacyanonitrosylferrate
H. Dastangoo*, F. Poureshghi
Electroanalytical Chemistry Laboratory, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
Hydrogen peroxide (H2O2) has a significant role in the chemical, pharmaceutical and food industries as an oxidizing, bleaching
and sterilizing agent, and its detection is an important topic in industrial analysis. Moreover hydrogen peroxide determination
plays a fundamental role in the development of biosensors, as it is a by-product of the reaction catalyzed by oxidase enzymes
which is often used to quantify enzymatic substrates. Many spectroscopic and electrochemical methods have been developed for
the detection of H2O2 [1-5]. Among the electrochemical methods, the amperometric sensing based ones are especially promising
due to their simplicity, sensitivity and selectivity, and the modification of working electrode surfaces has contributed to the
improvement of the selectivity and sensitivity of these electroanalytical methods. Metal-cyanoferrates are polynuclear mixed-
valence compounds, well known for their electrocatalytic activity toward hydrogen peroxide reduction.In the present, an
amperometric sensor based on palladized aluminum (Pd-Al) electrode modified with iron pentacyanonitrosylferrate (FePCNF/PdAl) was developed for the determination of hydrogen peroxide. The simple and rapid electroless preparation of FePCNF film on
the Pd-Al electrode was carried out by immersing the Pd-Al electrode in a solution containing ferric cation and nitroprusside
anion. Owing to oxidizing ability of solution, FePCNF is deposited on the Pd-Al electrode. Our investigations showed that
inherently FePCNF/Pd-Al modified electrodes have no defined electroactivity. Further investigations revealed that exerting
negative potential is prerequisite for FePCNF modifier film to become electroactive. The electrocatalytic activity of the
electroactivated modified electrodes toward the reduction of hydrogen peroxide was studied by cyclic voltammetry and
chronoamperometry. A linear calibration curve was obtained over the H2O2 concentration range of 10-300 µM using the
hydrodynamic amperometric technique. The limit of detection (for a signal-to-noise ratio of 3) was found to be 1.88 µM.
Furthermore, the diffusion coefficient of hydrogen peroxide (D) and catalytic rate constant (kcat) were calculated.
Reference
[1] J. Li, P.K. Dasgupta, G.A. Tarver, Anal. Chem. 75 (2003) 1203.
[2] T. Moreno, M.A. Morán López, I.H. Illera, C.M. Piqueras, A.S. Arranz, J.G. Serna, M.J. Cocero, Chem. Eng. J. 66 (2011) 1061.
[3] S. He, W. Shi, X. Zhang, J. Li, Y. Huang, Talanta 82 (2010) 377.
[4] Z.H. Li, D.H. Li, K. Oshita, S. Motomizu, Talanta, 82 (2010) 1225.
[5] J.-M. You, Y. N. Jeong, M.S. Ahmed, S.K. Kim, H.C. Choi, S. Jeon, Biosens. Bioelectron. 26 (2011) 2287.
Presentation an optimum method for determination Dimethylamine(DMA), unsymetrical
dimethylhydrazine(UDMH) and N-nitroso dimethylamine(NDMA) in industrial waste waters
K.Tabar Heydar*, S.H. Ahmadi, A. Shokri, M. Soltannezhad
Chemistry and Chemical Engineering Research Center of Iran, P.O.Box: 14335-186, Tehran
Email: ktabarh@ccerci.ac.ir
The aim of this research is the presentation of a method for the preconcentration and determination of analytes containing aminogroup such as Dimethylamine(DMA), unsymetrical dimethylhydrazine(UDMH) and N-nitroso dimethylamine(NDMA). The
developed method is favorable because of shortening sample preparation time and increasing simplicity. In addition, low cost and
less environmentally problems are of importance of this method. Gas chromatography (GC) has been widely used for amine
analysis because of its inherent advantages of simplicity, high resolving power, high sensitivity, fast analysis and low cost.In this
work, 2-nitrobenzaldehyde and benzensulfonyl chloride derivative agents were used for derivating UDMH and DMA
respectively. Derivation perform to decrease polarity and volatility of this compounds and to improve GC properties.The effects
of some experimental variables were studied on the extraction efficiency. Kind of derivative agent, time of reaction, type and
volume of the extraction solvent, pH and solt addition were also optimized. Type of GC column and the separation program were
also optimized. Under optimum condition, the LOD, LOQ and RSD for DMA 0.36 ng/ml, 1.2ng/ml and %3.4, UDMH 3ng/ml, 9
ng/ml and %6.96, and NDMA 5 ng/ml, 30 ng/ml and %6.64 was obtained respectively. Also CP-Sil 8CB (25m, 0.53mm and
5µm) was selected as the most efficient column.
derivated DMA chromatogram
derivated UDMH chromatogram
Reference
[1] Sotnikov, E. E.; Moskovkin, A.S. J. Anal. Chem. 2006, 61, 129.
[2] Holtzclaw, J. R.; Rose, S. L.; Wyatt, J. R.; Rounbehler, D. P.; Fine, D. H. Anal. Chem. 1984, 56, 2952.
[3]Kataoka, H. J. Chromatogr. A 1996, 733, 19.
[4]Sacher, F.; Lenz, S,; Brauch, H. J. Chromatogr. A 1997, 764, 85.
[5]Kataoka, H.; Shindoh, S.; Makita, M. J. Chromatogr. A 1996, 723, 93.
Calculation of thermodynamic parametrs of solutes using invers gas chromatography
withdicationic ILs as new stationary phase
K.TabarHeydar*, A.Sharifi ,M. Nazifi , M. Mirzaei
Chemistry and chemical Engineering Research center of Iran, P.O.Box:14335-186, Tehran
E-mail: ktabarh@ccerci.ac.ir
The measurements of activity coefficients at infinite dilution of 20 compounds were determinedin four room temperature
dicationic ionic liquids, with the stationary phases loading between 10 and 20% and carried out at different temperatures between
323.15 and 473.15 K. Four new ILs,C12(methylmorpholine)2(NTf2)2, C9(methylmorpholine)2(NTf2)2,C9(ethylmorpholine)2
(NTf2)2 and C12(ethylmorpholine)2(NTf2)2were investigated because of their higher viscosity and thermal stability than their
monocationic one's. The obtained results showed that Invers gas chromatography (IGC) is a useful method for examination of
physiochemical properties of various materials.Inverse gas chromatography (IGC) is a highly sensitive and versatile gas phase to
study the surface and bulk properties of particulate and fibrous materials using retention data.Gas chromatography experiments
were carried out using a Varian CP-3800 gas chromatograph equipped with a heated by 1041 injector and a thermal conductivity
detector(TCD). The injector and detector temperatures were kept at 473K during all experiments. Helium flowratewas adjusted to
obtain adequate retention times.From the following expression can be calculatethe activity coefficient at infinite dilution of solute
“1” in the stationary phase “2” (RTIL):
Where n2is the mole number of the stationary phase component in the column, R is the ideal gas constant, T is the temperature of
the oven, B11 the second virial coefficient of the solute in the gaseous state at temperature T, B13 the mutual virial coefficient
between the solute 1and the carrier gas helium 3 and P01 is the probe vapor pressure at temperatureT.
Reference
[1]Hiraoka, M., Crown Compounds: Their Characteristics and Applications, Elsevier, Amsterdam, 1982.
[2]Lindoy, L. F., The Chemistry of Macrocyclic Ligand Complexes, Cambridge University Press, Cambridge, 1992.
Simultaneous spectrophotometric determination of Cadmium and Zinc in water and biological samples by Dolittle
multivariate calibration
M.H.Moussavi *, A.Niazi and M.heydari
Department of Chemistry, Faculty of Sciences, Islamic Azad University – Arak Branch, Arak, Iran
ali.niazi@gmail.com)
(E-mail: mir.hossein.g@gmail.com and
A simple, novel and sensitive spectrophotometric method was described for simultaneous determination of cadmium and Zinc
according complexation by 4-(2-pyridylazo) Resorcinol in water and biological samples. All factors affecting on the sensitivity
were optimized and the linear dynamic range for determination of Cadmium and Zinc were found. The experimental calibration
matrix was designed by measuring the absorbance over the range 330-570 nm for 25 samples of 0.05-0.70 g ML-1 and 0.05-0.75
g ML-1 of Cadmium and Zinc, respectively. The simultaneous determination of these by using spectrophotometric methods is a
difficult problem, due to the spectral interferences. Dolittle Multivariate Calibration (DMCA) was investigated and the
chromogenic system of dyes with overlapping absorption peaks analyzed by DMCA. The basic principle of Dolittle
Decomposition Algorithm is discussed in several papers [1] Dolittle Decomposition Algorithm is high accuracy, few computation
amounts and stable numerical analysis algorithm. This algorithm can avoid matrix inverting operation which is often involves in
chemometrics such as methods of k-matrix, p-matrix, PLS, etc., reduce the orders of matrixes, speed up the operation of matrixes,
and raise the efficiency of computation. The RMSEP for Cadmium and Zinc with DMCA was 0.1203 and 0.1629, respectively.
The proposed method was successfully applied for the determination of Cadmium and Zinc in synthetic and real samples such as
water and biological samples.
Reference
[1] Y.Ding. T.Mu, Q.Wu, sh. Si, Chemom. Intell. Lab. Syst.88 (2007) 167.
[2] A.Niazi, J.Ghasemi, A. Yazdanipour, Anal, Lett.38 (2005) 2377.
[3] A.Niazi. J Ghasemi, A.yazdanipour, Spectrochim. Acta part A68 (2007) 523.
Corrosion inhibition of 304 stainless steel in 6 M hydrochloric acid solution by Capsicum annum extractas a green
inhibitor
M. Behpour*,M. Arandashti-Arani, M. Khayat-Kashani
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan,I.R. Iran
Acid solutions are commonly used for the removal of undesirable scale and rust in metal finishing industry [1]. Use of inhibitors
is one of the most practical methods for protection against corrosion especially in acid solutions to prevent unexpected metal
dissolution and acid consumption [2]. The known hazardous effects of most synthetic organic inhibitors and restrictive
environmental regulations have now made researchers to focus on the need to develop cheap, non-toxic and environmentally
benign natural products as corrosion inhibitors[3, 4].Corrosion inhibition effect of capsicum annum extract on 304 stainless steel
in 6 M HCl medium has been investigated by weight loss measurements, potentiodynamic polarization and electrochmical
impedance spectroscopy (EIS) methods. Maximum inhibition efficiency (94.13% in 6 M HCl) is obtained at 0.8 g/l Capsicum
annum extract at 25ᵒ C. The polarization studies showed that capsicum annum extract acts as anodic type inhibitor.
Electrochemical impedance spectroscopy was used to investigate the mechanism of corrosion inhibition. The Nyquist plots show
an increase of the transfer resistance with increasing the inhibitor concentration and decreases double layer capacitance. The
temperature effect on the corrosion behavior of mild steel in 6 M HCl without and with the inhibitors was studied in the
temperature range from 25 to 65ᵒ C. The inhibition action of the extract was discussed in view of langmuir adsorption isotherm.
AFM confirmed the adsorption of capsicum annum on mild steel surface. Finally, capsicum annum extract act as a good
corrosion inhibitor for304 stainless steel in 6 M HCl medium. capsicum annum extract being a natural and environmentally
benign product it can be used as an alternative for toxic chemical inhibitors in acidization and acid pickling of mild steel.
Reference
[1] J.M. Sykes, Br. Corros. J. 25 (1990) 175.
[2]H.A. Sorkhabi, D. Seifzadeh, M.G. Hosseini, Corros. Sci. 50 (2008) 3363.
[3]A.K. Satapathy, G. Gunasekaran, S.C. Sahoo, Kumar Amit, P.V. Rodrigues, Corros. Sci 51 (2009) 2848.
[4] M. Behpour, S.M. Ghoreishi, M. KhayatKashani , N. Soltani , 3Materials and Corrosion, 60 (2009) 895.
Direct Electrosynthesize of Poly(o- anisidine)- TiO2 Nanocomposite Coating on Aluminum Alloy 3004 and Its Corrosion
Protection Performance
S.M. Ghoreishi*, M. Shabani- Nooshabadi, Y. Jafari
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, I.R. Iran
Electropolymerized polymer coatings on aluminum alloy 3004 (AA 3004) can replace for the carcinogenic chromate coating [1].
In this work, poly(o-anisidine)- TiO2 nanocomposite coatings were electrochemically synthesized on AA3004 from an aqueous
solution containing 0.5 M oxalic acid with 0.2 M o- anisidine and 1 g/1 of dispersed TiO2 nanoparticles of 10 nm size by using
the galvanostatic method [2,3]. The synthesized coatings were characterized by fourier transform infrared spectroscopy (FTIR),
scanning electron microscopy (SEM) and atomic force microscopy (AFM). Optical absorption spectroscopy reveals the
formation of the emeraldine form of poly(o-anisidine)- TiO2 nanocomposite [4]. The corrosion performances of poly(oanisidine)- TiO2 nanocomposite coatings were investigated in 3.5% NaCl solution by the potentiodynamic polarization technique
and electrochemical impedance spectroscopy (EIS). The current corrosion decreases significantly from 8.7 µA cm−2 for uncoated
AA 3004 to for 0.2 µA cm-2 for poly(o-anisidine)- TiO2 nanocomposite coated on surface AA 3004 . The corrosion rate of the
poly(o- anisidine)- TiO2 nancomposite coated AA 3004 found to be 1.2×10−5 mmyear−1 which is ∼ 267 time lower than observed
for bare AA 3004. The potential corrosion increases from −0.84 V versus SCE for uncoated AA 3004 to -0.69 V versus SCE for
poly(o- anisidine)- TiO2 nanocomposite coated AA 3004 electrodes. The positive shift in potential corrosion (anodic protection)
indicates the protection of the AA 3004 surface by the poly(o- anisidine)- TiO2 nanocomposite coatings. The EIS results are in
good agreement with the potentiodynamic polarization measurements. This study reveals that the poly(o-anisidine)- TiO2
nanocomposite coating has excellent corrosion protection properties and can be considered a potential coating material to protect
AA 3004 against corrosion in aqueous 3.5 % NaCl.
Reference
[1] V. Karpagam, S. Sathiyanarayanan, G. Venkatachari, Curr. Appl. Phys, 8 (2008) 93.
[2] R. Rajagopalan, J.O. Iroh, appl. Surf. Sci, 218 (2003) 58.
[3] O. Zubillaga, F.J. Cano, I. Azkarate, I.S. Molchan, G.E. Thompson, A.M. Cabral, P.J. Morais, Surf. Coat. Technol, 202 (2008) 5936.
[4] M. Shabani-Nooshabadi, S.M. Ghoreishi, M. Behpour, Electrochim. Acta, 54 (2009) 6989.
Determination of acidity constants of Rosolic Acid in binary ethanol-water mixtures by spectrophotometric and
chemometrics methods
Elnaz Kousha* and Ali Niazi
Department of Chemistry, Islamic Azad University – Arak Branch, Arak, Iran
(E-mail: elnazkousha@yahoo.com & ali.niazi@gmail.com)
The acidity constants of Rosolic Acid (Figure 1) in binary mixtures of ethanol–water at 25 C and an ionic strength of 0.1 mol L-1
have been determined by spectrophotometric and chemometrics methods.
Figure 1. Chemical structure of Rosolic Acid.
The spectra of Rosolic Acid in binary solvent mixtures at various pH values in 380-600 nm intervals were recorded (Figure2).
Figure 2. Absorption spectra of Rosolic Acid in water at 0.1 M KNO3 at different pH values.
As the percent of ethanol increases in solvent mixtures the pKa constants increased as well. There is linear relationship between
acidity constants and the mole fraction of ethanol in the solvent mixtures. The effect of solvent composition on acidity constants
and pure spectrum of each component are also discussed. DATAN program was applied for determination of acidity constants.
The output of DATAN program is pKa values, number of principal components, projection vectors (loadings), concentration
distribution diagrams and pure spectrum of each assumed species [1-2]. The amounts of pKa1 and pKa2 are obtained 1.65 and
10.32.
Reference
[1] A. Niazi, M. Ghalie, A. Yazdanipour, J. Ghasemi, Spectrochim. Acta Part A 64 (2006) 660-664.
[2] A. Niazi, A. Yazdanipour, J. Ghasemi, M. Kubista, Spectrochim. Acta Part A 65 (2006) 73-78.
Ion imprinted polymer based new ion-selective electrode for the trace determination of Nickel (II) ions
Mohammad Hossein Arbab Zavvar*a, Mahmoud chamsaza,Gholamhosein Zohoria , Abolfazl Darroudib,a, Ahmad Rezvania
a
Department of Analytical Chemistry, Faculty of Science, University of Ferdowsi, Mashhad.Iran.
b
Department of Analytical Chemistry, Faculty of technical Samen, Mashhad,Iran
The need for nickel monitoring is important due to its toxic nature [1].Imprinted polymers are biomimetic materials used for the
sensitive and selective detection of analyte molecules. Through host guest interactions, imprinted polymers often display
recognition capabilities comparable to those of antibody–antigen systems. The Nickel (II) ion imprinted polymer particles(IIP)
were synthesized via single pot method by dissolving preformed binary complex of Nickel(II) with 5,7-dichloroquinoline-8-ol
(DCQ) and 4-vinylpyridine (VP) in acetonitrile (porogen) and copolymerized thermally after addition of MMA(monomer) and
EGDMA (crosslinking monomer) in the presence of 2,2-azobisisobutyronitrile (initiator) according to literature through the wellknown [2]. A graphite disk electrode was fabricated from a graphite rod with a 4 mm diameter housed and glued into a Teflon
holder. The exposed surface of the disk electrode was polished to a shiny finish with SiC paper. The electrode was rinsed with
water and allowed to dry. The chemically modified disk graphite electrodes were prepared by thorough mixing PVC, NPOE,
NaTPB and Nickel (II) IIP particles (30–60µm size) in proportions of 27, 5, 53 and 15% (w/w), respectively that were dissolved
in 2.5 ml of tetrahydrofuran (THF). After the mixture homogenized in a sonicator and then poured into a beaker. The THF
solvent was allowed to evaporate at room temperature to obtain a concentrated mixture, then covered carefully graphite disk with
concentration mixture. The solvent allowed evaporating to thin PVC film formed on the graphite electrode surface. The potential
response obtained with the electrodes prepared with nickel(II) IIP membrane .The plot obtained for the sensor with nickel (II) IIP
particles showed a slope of 29.32mV per decade over a wider concentration range of 2×10−7 to 1×10−2M of nickel (II) is the
expected Nernstian slope for the divalent cations. The limit of detection was 1×10−7M calculated based on the IUPAC definition.
Potentiometric selectivity coefficients, describing the preference of the nickel(II) IIP based ISE for nickel(A) relative to an
interfering ion( B) were determined by the matched potential method(MPM), recommended by IUPAC. Selectivity parameter
data for various ions are presented in Table 2.
Table 2- Selectivity coefficients, KNi,M pot , of various interfering ions (Mn+)
Mn+
Na+
K+
Cu2+
Mg2+
Ca2+
Ag+
Zn2+
KNi,M pot
4.0×10−4
5.0×10−4
1.0×10−3
6.0×10−4
1.0×10−3
2.0×10−4
4.0×10−3
Reference
[1] Jacobo Otero-Romaní, Antonio Moreda-Pin˜ eiro, Pilar Bermejo-Barrera, Antonio Martin-Esteban, analytica chimica acta 6 3 0 ( 2 0 0 8 ) 1–9.
[2] Coogan T P, Latta D M, Snow E T, Costa M (1989) CRC Crit Rev Toxicol 19: 341
Ion imprinted polymer particles of Thallium (I): synthesis, characterization and as new sorbent for preconcentration and
separation of thallium (I)
Mohammad Hossein Arbab Zavvara, Mahmoud chamsaza,Gholamhosein Zohoria , Abolfazl Darroodi*b,a
a
Department of Analytical Chemistry, Faculty of Science, University of Ferdowsi, Mashhad.Iran.
b
Department of Analytical Chemistry, Faculty of technical Samen, Mashhad.Iran
Thallium is a heavy metallic element which exists in environment mainly combined with other elements (primarily oxygen,
sulfur and the halogens) in inorganic compounds. Thallium can be found in nature as Tl (I) and Tl (III) ions but its monovalent
state has higher stability, whereas its trivalent state forms complexes of greater stability. Each oxidation state of the element
exhibits different bioavailability and toxicity property [1] and hence thallium speciation in environment is important. As the total
concentration of thallium in aquatic environment is very low, an analytical technique featuring high sensitivity and low detection
limit is required [2].During the last years ion-imprinted polymers (IIPs), as selective sorbents for a particular chemical form of
the given element, have received much attention. The high selectivity of IIPs can be explained by the polymer memory effects
towards the metal ion interaction with a specific ligand, coordination geometry, metal ion coordination number, charge and size
[3].In this study, a thallium (I) ion-imprinted polymer as a new sorbent has been synthesized for the first time. This sorbent was
used for SPE and preconcentration of Tl (I) ions from aqueous solutions.Thallium (I) ion-imprinted polymer (IIP) particles were
synthesized by preparing the ternary complex of thallium (I) ions with 5, 7-dichloroquinoline-8-ol (DCQ) and 4-vinylpyridine
(VP). Thermal copolymerization with methyl methacrylate (functional monomer, MMA) and ethyleneglycoldimethacrylate
(cross-linking monomer, EGDMA) was then performed in the presence of acetonitrile (porogen) and 2, 2-azobisisobutyronitrile
(initiator, AIBN). The imprinted ion was removed from polymer by stirring of the above particles with 1M HNO 3 to obtain the
leached IIP particles. Moreover, control polymer (CP) particles were similarly prepared without the thallium (I) ions. The
unleached and leached IIP particles were characterized by surface area analysis (BET), X-ray diffraction (XRD), Fourier
transform infra-red spectroscopy (FT-IR) and scanning electron microscopy (SEM).The preconcentration of the thallium (I)
traces was studied during rebinding with the leached IIP particles as a function of pH, the weight of the polymer material, the
preconcentration and the uptake times, the uptake volume and the aqueous phase volume. Electrothermal atomic absorption
spectrometry (ETAAS) was employed for determination of thallium in aqueous solution. The limit for detection of the method
was 0.02ngmL−1, while the relative standard deviation for five replicates was 2.5%.
Reference
[1] C.H. Lan, T.S. Lin,Ecotox. Environ. Safe. 61 (2005) 432–435.
[2] M. Chamsaz, M. H. Arbab-Zavar, A. Darroudi, T. Salehi,,j.hazadous materials, 167 (2009)
597–601.
[3] Mohammad Hossien Arbab-Zavar,Mahmoud Chamsaz, Golamhossien Zohuri, Abolfazl Darroudi, j.hazadous materials, 185 (2011) 38-43.
Optimization of process variables for removal of Na-dimethyl dithiocarbamate pesticide by a natural zeolite using BoxBehnken design
Seyed Naser Azizi& Neda Asemi
Analytical division, Faculty of chemistry, University of Mazandaran, Babolsar, Iran, Po Box: 47 416 – 95447
E-mail: azizi@umz.ac.ir
The scope of this study was adsorption of Na-dimethyl dithiocarbamate pesticide from aqueous solution onto clinoptilolite (a
natural zeolite) using Response surface methodology (RSM) based on Box-Behnken design. Box-Behnken was employed to
investigate the effects of different operating conditions on pesticide removal efficiency in aqueous solution. Based on our
previous work from pesticide Vapam removal process by Coresta N°1 method [3], the main operational parameters and their
levels were selected in order: initial pH of solution ranging from 2 to 12, contact time from 2 to 24 h and dosage of adsorbent
from (0.25 to 0.75 g/L) and were consecutively coded as X1, X2 and X3. Initial pesticide concentration, C0= 1.6 mg/L was a fixed
input parameter. A second order polynomial equation was then derived to predict responses (maximum adsorption %). The
significance of independent variables and their interactions were tested by means of the analysis of variance (ANOVA) with 95%
confidence limits. The optimum values of selected variables were obtained by solving the quadratic regression model, as well as
by analyzing the response surface counter plots. The experimental conditions at optimum point with maximum adsorption of
pesticide were determined to be pH=2.5, contact time= 8 h and dosage of adsorbent= 0.75 g/L.
Reference
[1] D. F. Goldsmoth, j. Environ. Pathol. Toxicol. Oncol. 19 (2000) 171-175.
[2] G. Guo, Y. Long, Sep. Purif. Technol. 24 (2001) 507-518.
[3] S.N. Azizi, N. Asemi, J. Environ. Sci. Health B. 45 (2010) 800-807.
Template effect on analcime zeolite adsorption ability
S.N. Azizi *, Salma Ehsani tilami
Analytical Division, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran Email: azizi@umz.ac.ir, P.O.Box: 47416-95447
Amino acids are industrially important as supplements to stock feed and in the improvement of protein quality in food technology
[1]. The interactions of amino acids with silica alumina compounds and zeolite have aroused the interest of researchers since
these materials show the potential to play an important role in prebiotic chemical evolution [2, 3].In this work, to evaluate the
effect of template on physicochemical properties of synthesized zeolite, their ability to adsorb methonine was studied. Different
zeolites were prepared according to the reported procedures [4]. All of these zeolites have an equal Si/Al ratio in their
synthesized gels composition; meanwhile, introducing the methonine as a template has changed their physicochemical properties.
As a first step of the typical experiment 0.1 g zeolite, deionized water and HCl or NaOH were mixed. Then, methionine was
added and stirred overnight at room temperature. After equilibration, the residual solute concentrations in liquid phase were
analyzed by fluorescence spectroscopy.In order to examine the influence of zeolite structure as a function of template effect on
the adsorption process, the adsorption of methionine on three types of zeolites such as methionine-templated analcime, free
template analcime and methionine-template zeolite P was investigated. For the analysis of the adsorption isotherms, we tried to
fit the experimental isotherm by Freundlich and Langmuir equations. Although the adsorption isotherm deviated from Langmuir
equation, they accorded with the Freundlich equation.The results indicated that the adsorption of aminoacid is not only depends
on zeolites surface area but also to their pore size for capturing this material. The existence of template in zeolite synthesis could
help enlarging the pore size and enhancing the adsorption ability.
Reference
[1] Munsch, S.;Hartmann,M.; Ernst, S. Chem. Commun. 2001, 1978.
[2] Rao, M.; Odom, D.G.; Oro, J.J. Mol. Evol. 1980, 317.
[3] Orgel, L. E.; Origines Life Evol. Biosphere. 1998, 227.
[4] Azizi, S. N.; Ehsani Tilami, S. Z. Anorg. Allg. Chem. 2009, 635
Biotechnological synthesis of Gold Nanoparticles (Green-Gold) Using Leaf Extract of Urtica dioica
1
Rahim Molaie , Reza Emamali Sabzi1, Khalil Farhadi1
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
Biosynthesis of nanoparticles has arisen as a promising alternative to conventional synthetic methodologies owing to its ecofriendly advantages, and the involved bioprotocol still needs further clarification. Low cost of synthesis and non toxicity are main
features making it more attractive potential option for biomedical field and elsewhere. Here, we studied the fast and simple
Biological synthesis of gold nanoparticles using Urtica dioica plant leaf extract as the reducing and stabilizing agent. The
synthesis of the gold nanoparticles was monitored by UV-visible spectroscopy. UV–visible spectrum of the aqueous medium
containing gold nanoparticles showed a peak around 530 nm. Different pH and molar concentration ratios of HAuCl4 were
studied for the synthesis of gold nanoparticles. The nanoparticles formed were characterised by scanning electron microscopy
(SEM), Fourier transform infrared (FTIR), UV-Vis spectroscopy and X-ray diffraction (XRD). This method allowed the
synthesis of gold nanoparticles in the absence of a surfactant or polymer to direct nanoparticle growth.
Reference
[1] M. Sastry, A. Ahmad, M. Khan, R. Kumar, Curr. Sci. 85. (2003). 162.
[2] A. Ahmad, P. Mukherjee, S. Senapati, D. Mandal, M.I. Khan, R. Kumar, M. Sastry, Colloids Surf. B 28. ( 2003). 313.
[3] M. M. Kemp, A. Kumar, N.Kubotera, S.Mousa, S. A. Mousa, T. J. Park, R. J. Linhardt P. Ajayan, Biomacromolecules 10. (2009). 589.
[4] A. Absar, S. Satyajyoti, M. I. Khan, K. Rajiv, M. Sastry, J. Biomedical Nanotechnnology, 1. (2005). 47.
[5] A. B. Bazylinski, B. R. Frankel, , Nature reviews – Microbiology, 2.(2004). 213.
[6] K. B. Narayanan, N. Sakthivel, Adv Colloid Interface Sci 156. (2010). 1.
Trace analysis of chlorobenzenes in water samples: A new approach to automation of dynamic hollow fiber liquidphase microextraction
Ali Esrafili, Yadollah Yamini*, Mahnaz Ghambarian, Morteza Moradi, Shahram Seidi
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University,
P.O. Box: 14115-175, Tehran, Iran
Chlorobenzenes (CBs) are a class of environmental pollutants used as industrial solvents, pesticides, dielectric fluids, deodorant
and chemical intermediates. They can enter into the environment at trace level and may be detected in surface and ground waters
and in some biological tissues [1,2].In this work, a dynamic hollow fiber liquid-phase microextraction (DHF-LPME) technique
combined with gas chromatography/electron capture detector (GC-ECD) was described for the extraction and determination of
five chlorobenzenes in water samples using an automated dynamic extraction device, called TT-tube extractor, consists of a
polypropylene hollow fiber mounted inside a stainless steel tube by means of two tee-connectors in flow system. Toluene was
used as extraction solvent which fills the lumen and the pores of the hydrophobic fiber dynamically using programmable syringe
pump and 20 mL sample was pumped continually along the cut side of the fiber. The factors affecting the DHF-LPME of target
analytes such as type of organic solvent, ionic strength, TT-tube diameter, sample volume, extraction and dwelling times were
investigated and the optimal extraction conditions were established. In the optimum conditions, limits of detection (LODs) as low
as 0.01 µg L-1, linear dynamic range in the range of 0.2-100 µg L-1 and the relative standard deviations (RSD %, n = 5) < 7 %
were obtained. The developed method was provided perconcentration factors as large as 973. To evaluate the practical
applicability of the designed extractor, chlorobenzenes were extracted from environmental aqueous samples and appeared good
analytical results. A hollow fiber membrane can be used at least 20 times without loss in the efficiency and carry-over of the
analytes between runs. The system is cheap and convenient and requires minimal manual handling.
Reference
[1] M.N. Sarrion, F.J. Santos, M.T. Galceran, Rapid Commun. Mass Spectrom. 14 (2000) 2271.
[2] U.S. EPA, U.S. Environmental Protection Agency. Chlorinated benzenes; Final Test Rule. 40 CFR Part 799. Fed. Reg. 51 (1986) 24657.
Synthesis of Nanocrystals NaA Zeolite from stems of grain sorghum ash: Parameter Optimization Using Taguchi Robust
Design
Seyed Naser Azizi*& Narjes Bakhshandeh Sorkhcolaei
aAnalytical Division, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran,
E- Mail: Azizi@umz.ac.ir
The Taguchi method of experimental design is very well suited to improving the production process of synthetic nanoparticles[1].
The effects of Na2O/SiO2, SiO2/Al2O3 ratios, temprature and time in the initial synthetic mixture on the crystallization of
nanoparticles of NaA zeolite under atmospheric pressure were studied. Applying the Taguchi method significantly reduced the
time and cost for optimization [2].The obtained products were characterized by scanning electron microscopy, X-ray diffraction
and FT-IR spectroscopy. In this work, Stems of sorghum ash was successfully used as a silica source for the synthesis of zeolite
Linde type A in sodium form (NaA).The Stems of sorghum was collected from north of Iran after ashing analyzed with XRF to
determine elemental composition. Then Kalapathy et al. method [3] was used for extraction of silica from SSA. The XRF of SSA
shows more than 80% of hydrated silica (SiO2). The template free nanozeolite NaA was synthesized by mixing silicate solution
with freshly prepared aluminate soulution. In the current study, a Taguchi L9 design was used as a statistical tool in order to
investigate the effects experimental parameters in the initial synthetic mixture of the crystal size of NaA zeolite. A Taguchi
orthogonal experimental design with three levels of the above mentioned parameters was used to optimize the experiment
parameters by the analysis of variances (ANOVA).On the basis of the result it was concluded that optimum factors for synthesis
of nanocrystals NaA are Na2O/SiO2= 7, SiO2/Al2O3= 1.5, temperature= 50 oc, Time= 18 h.
Reference
[1]. Abrishamkar, M., Azizi, S.N., Kazemian, H., Z. Anorg. Allg. Chem. 637, 154-159, 2011.
[2]. Wang,X.J., Yan,C.L., Inorg.Mater. 46, 517-521, 2010.
[3]. Kalapathy, U., Proctor, A., Shultz J Bioresource Technol. 73, 257-262, 2000.
The Electrochemical Synthesis of Nano-Cu/Multi-Walled Carbon Nanotubes Modified Composite Graphite Electrode for
Electrocatalytic Application
1
Parisa Ansari1, Ramin M.A.Tehrani1, Mohammad Jafarzadeh2
Department of Chemistry, Shahre Rey Branch, Islamic Azad University, Tehran, Iran
2
Faculty of Chemistry, Razi University, Kermanshah, Iran
E-mail: Rmt@iausr.ac.ir
Nowadays, nanomaterials have found much attention due to unique properties and controllably design in their fabrication.
Electrodeposition of metals and alloys is a much interested approach with great abilities in electrosynthesis of metallic
nanoparticles (NPs) [1-3]. In this work, copper nanoparticles (Cu -NPs) have been electrochemically synthesized and uniformly
dispersed onto multi-walled carbon nanotubes modified coated composite graphite electrode (MWCNTs/CG). Cyclic
voltammetry, scanning electron microscopy (SEM), transmission electron microscope (TEM) and energy dispersive x-ray
analysis (EDX) were utilized for investigation of electrochemical properties, morphology of nanocomposite and presence of Cu
on the modified electrode. The TEM analysis indicated that the Cu-NPs with an average particle size of 70 nm have been
obtained. The nano-Cu- MWCNTs/CG electrode was employed for the electrocatalytic reduction of nitrite ion (NO2-) in acidic
media. A high cathodic current was obtained at peak potential of -100 mV vs Ag/AgCl. The results revealed that electrochemical
parameters, amount of MWCNT, scan rate and the nitrite concentration affected the morphology of modified electrode and its
application to the reduction of NO2-.
Reference
[1] L. Huang, E.S. Lee and K.B. Kim, Colloid Surf. A-Physicochem. Eng. Asp. 262 (2005) 125-131.
[2] S. Arai, T. Saito and M. Endo, J. Electrochem. Soc. 157 (2010) D147-D153.
[3] S. Yang, X. Zeng, X. Liu, W. Wei, S. Luo, Y. Liu and Y. Liu, J. Electroanal. Chem. 639 (2010) 181-186.
New ion selective carbon paste electrode for potentiometric determination of chloropheniramin maleate
Ahmad Soleymanpour*, Homeira sadat mirfakhraee
School of Chemistry, Damghan University, Damghan, Iran
Performance characteristics of a novel potentiometric carbon paste electrode (CPE) responsive to the chloropheniramin maleate
(CPM) drug for the fast, easy avd selective determination of the drug described. Chlorphenamine maleate is a first-generation
alkylamine antihistamine used in the prevention of the symptoms of allergic conditions such as rhinitis and urticaria [1].
chlorpheramine is an antihistamine used to relieve symptoms of allerge, hay fever, and the common cold. These symptoms
include rash, watery eyes, itchy eyes/ nose/ skin, cough, runny nose, and sneezing [2,3]. The constructed potentiometric sensor
for this drug is based on the use of the β-cyclodextrin as a good ionophore in the carbon paste matrix. The most advantages of
CPEs are ease of preparation, modification and regeneration and specially low cost [4]. The proposed CPE exhibits fast, stable
and repeatable response for the chloropheniramin maleate cation over concentration range from 3.010-6 to 2.310-3 M in the pH
range 4.0-7.5. No interferences are observed by many inorganic and organic species sucs as amino acids, glocose, urea,
phosphate, bicarbonate, chloride, sodium and potassium ions. Potentiometric determination of chloropheniramin maleate in
different pharmaceutical and biological samples such as chloropheniramine maleate tablets and blood serum samples showed
good recoveries of chloropheniramin maleate. Potentiometric titration of chloropheniramin maleate solution with
tetraphenylborate as a titrant has been monitored with the proposed selective CPE as an indicator electrode.
Reference
[1] A. Carlsson, M. Lindqvist, J. Pharm. Pharmacol., 21 (1969) 460.
[2] E. Hellbom, Med. Hypotheses, 66 (2006) 689.
[3] V. Andronis, M. Mesiha, F. plakogiannjs, Pharm. Acta Helv., 70 (1995) 301.
[4] R. Stefan, J.Van-staden, H. Aboul-Enein, Talanta, 48 (1999) 1139.
Simultaneous determination of pesticides at trace levels in water using
Functionalized multiwalled carbon nanotubes as solid-phase extractant and partial least squers(PLS) method
Nahid sarlak*, Asghar taherifar
Department of Analytical Chemistry, Faculty of Chemistry, University of lorestan, khoramabad, I.R. Iran
E-mail: sarlak.n@gmail.com
In this work, the application of solid-phase extraction with functionalized multivariate calibration for simultaneous determination
of Mancozeb and Pymetrozin in tap water was presented. Functionalized multiwalled carbon nanotubes (opened MWCNTs)
adsorbent showed a perfect extraction/preconcentration of pesticides present at trace levels. Functionalization of the surface of
MWCNTs can be realized by chemical oxidation treatment using different reagents such as HNO3/H2SO4 mixture and MWCNTs
were opened according to reported procedures in literatures [1]. Mancozeb is used to protect many fruit, vegetable, nut and field
crops against a wide spectrum of fungal diseases. Dithiocarbamates (DTC) form an important class of pesticides for broadspectrum control of a variety of fungal diseases on growing crops [2]. Pymetrozine first registered in 1999 by EPA has a unique
mode of action that is not fully understood and Pymetrozine is in class of pyridine azomethine. Although the pesticides can be
accurately quantified by SPE and liquid chromatography[3,4], SPE–PLS-1 method was found simpler and operated at lower
running costs. The experimental factors that affect pesticides extraction by opened MWCNTs adsorbent such as elution, eluent
volume, solution pH, and extraction flow rate were studied and optimized. The figures of merit of the proposed method were:
limits of detection 10 and 3 (µg.L-1), linear ranges10-600 and 3-87 (µg.L-1) for pymetrozin, mancozeb respectively and RSD%
method was less than 2% for mancozeb and 3.2% and for pymetrozin .
Reference
[1] M. Adeli, A. Bahari and H. Hekmatara, NANO: Brief Rep. Rev. 3 (2008) 37-44.
[2] Y. shimamura, N. tomiyama, M. murakoshi, H. kobayashi and O. matano, J. pesticide Sci. 23 (1998) 241-249.
[3] X. Yang, H. Zhang, Y. Liu, J. Wang, Y.C. Zhang, A.J. Dong, H.T. Zhao, C.H. Sun and J. Cui, J. Food Chemistry, 127(2011)855-865.
[4] Gouri Satpathy, Yogesh Kumar Tyagi and Rajinder Kumar Gupta, J. Food Chemistry, 127(2011)1300-1308.
Robust ionic liquid-based dispersive liquid–liquid microextraction against high concentration of salt for preconcentration
and determination of Cr (VI) in various samples and FAAS determination
Mohsen Taziki, Farzaneh Shemirani*, Behrooz Majidi
School of Chemistry, University College of Science, University of Tehran,Tehran, Iran
A new Ionic liquid-based dispersive liquid–liquid microextraction method was developed for preconcentration and determination
of compounds in aqueous samples containing very high salt concentrations. This method can solve the problems associated with
the limited application of the conventional IL-based DLLME in these samples. This is believed to arise from dissolving of the
ionic liquids in aqueous samples with high salt content. In this method, the robustness of microextraction system against high salt
concentration (up to 40%, w/v) is increased by introducing a common ion of the ionic liquid into the sample solution. The
proposed method was applied satisfactorily to the preconcentration of Chromium in saline samples. In this procedure, the
hydrophobic chelate of chromium with ammonium pyrrolidinedithiocarbamate (APDC) was extracted into the fine droplets of 1hexyl-3-methylimidazolium hexafluorophosphate ([Hmim][PF6]), which was dispersed into the aqueous sample solution. Several
variables such as the volume of [Hmim][PF6], salt content, sample pH, concentration of APDC, and extraction time were
investigated in detail. Under optimum conditions a linear calibration graph in the range of 1–70 μg L−1 of Cr in the initial solution
with r = 0.9998 (n = 10) was obtained. Detection limit based on three times the standard deviation of the blank (3Sb) was 0.26 μg
L−1 (n = 10) and the relative standard deviation (R.S.D.) for 20 μg L−1 of Cr was 2.68% (n = 10), respectively. The method was
successfully applied to the determination of trace amount of Chromium in sea water and food additive salt .
Reference
[1] Liang, P., Sang, H.B., 2008. Speciation of chromium in water samples with cloud point extraction separation and preconcentration and determination by graphite
furnace atomic absorption spectrometry. Journal of Hazardous Materials 154, 1115-1119.
[2] Kotas, J., Stasicka, Z., 2000. Chromium occurrence in the environment and methods of its speciation. Environmental Pollution 107, 263-283.
[3] Myers, C.R., Myers, J.M., B.P., Carstens, Antholine, W.E., 2000. Reduction of chromium (VI) to chromium (V) by human microsomal enzymes: effects of iron
and quinines. Toxic Subst. Mech. 19, 25-51
[4] Tuzen, M., Soylak, M., 2007. Multiwalled carbon nanotubes for speciation of chromium in environmental samples. Journal of Hazardous Materials 147, 219-225.
Application of nano-clinoptilolite modified with dimetyglyoxime (DMG) for removal of Ni(II) from aqueous solutions
Alireza Nezamzadeh-Ejhieh*, Mehdi Kabiri-Samani
Department of Chemistry, Islamic Azad University, Shahreza Branch
DMG supported on clinoptilolite as a selective sorbent of Ni(II) from aqueous solutions. In this work an Iranian natural
clinoptilolite zeolite was converted to the nano particles by mechanical method and then it was modified by
dimethylglyoxime(DMG). The modified compound was investigated by FT-IR spectroscopy. Removal of Ni(II) by modified and
unmodified natural zeolite was investigated in batch procedure. It was found that modified zeolite has higher absorption capacity
for removal of Ni(II). The effects of analytical parameters such as pH, dose of DMG, concentration of nickel solution,
equilibrium time and selectivity were studied. The results of selectivity experiments showed that the modified zeolite has a good
selectivity for nickel in the presence of different mono and multivalent cations.
Refrence
[1] F. Fu, Q. Wang," Removal of heavy metal ions from wastewaters: A review" J. Environ. Manage. 30 (2010) 1-12.
[2] M.E. Argun. "Use of clinoptilolite for theremoval of nickel" J. Hazard. Mater 150 (2008) 587-595.
[3] N. Rajic, D. Stojacovic, M. Jovanovic, N.Z. Logar, M. Mazaj, V. Caucic,"Removal of Nickel (II) from aqueous solution using the natural clinoptilolite" Appl.
Surf. Sci 257 (2010) 1524-1532.
Electrodeposition of nano –structured lead dioxide at a graphite electrode by FFT continues cyclic voltammetry
a
Eslam Salahifara, Parviz Norouzi*a, Mohammad Reza Ganjalia
Center of excellence in electrochemistry, department of chemistry, Tehran university ,Tehran , Iran
A new electrodeposition method was used for the preparation of nano-structured PbO2 at a graphite electrode at room
temperature by FFT continuous cyclic voltammetry. The nano-structured PbO2 films have been widely used as positive electrode
in the lead-acid batteries and for waste water treatment. It was showed that structure stability and cathodic current of the formed
films was significantly improved compared with reported results by other classic method. The deposition of the film consists of
two stages ; a potential step(1650mV for 165.s), and then, a potential ramp (with scan rates 1 and 5 V/s). In this procedure,
potential waveform was continually applied on the electrode (at least for 1000 cycles). The PbO2 nano–structured was
characterized by scanning electron microscopy (SEM). Under optimized experimental condition , PbO2 particles formed has
dimension of 80-90 nm, as shown by SEM. Analysis by electrochemical impedance spectroscopy (EIS) revealed that the charge
transfer resistance of the electrodeposited film obtained by FFTCCV method decreased in comparison with the constant current
method. The result of linear polarization measurements confirm suitability of electrode for wastewater treatment.
Reference
[1] Polarco AM,Palams S,Renoldi F, Mascia M. on the performance of Ti/SnO2 and Ti/PbO2 anodes in electrochemical degradation of 2-cholorophenol for wastewater
management.JAppl electrochem1999;29:147-51.
[2]JohansonDC, FengJ,Houk LL. Direct electrochemical degradation of organic wastes in aqueous media. ElectrochimActa 2000;46:323-30
[3]Velayuthan D, Noel M. preparation of the polypyrrole- lead dioxide composite electrode for electrochemical applications. Talanta 1992;39:481-6.
[4]Stucki S, Theis G, KolzR,DevantayH,christen HJ. Ozone in water using a membrelelectrolyzer. J ElectrochemSoc 1985;132:367-71
[5] D.C. Johnson, J. Feng, L.L. Houk, Electrochim. Acta 46 (2000) 323
Separation and recovery of vanillic acid from caffeic and other phenolic acids in honey through a bulk liquid membrane
and its determination using HPLC
Shahriar Shadabi1,*, Ali Reza Ghiasvand1.2, Payman Hashemi1,2
1
Department of Chemistry, Lorestan University, Khoramabad, Iran
2
Razi Herbal Medicines Research Center, Lorestan University of Medical Sciences, Khoramabad, Iran
Most of the phenolic acids exist in honey extracts possess significant antioxidant activity. Vanillic (Va) and caffeic acid (Ca) are
two of them that have beneficial antioxidant and medicinal effect. Therefore, development of new effective separation and
purification methods for these antioxidants has attracted a great deal of attention [1-3]. The purpose of this study is selective
transport and separation of vanillic and caffeic acids in honey samples using a bulk liquid membrane (BLM) method. A 20 mL
portion of dichloromethane was placed at the bottom of a 50 mL hand-made transport vial consists of two co-axes pyrex
cylinders (two end open inner tube with a 20 mm I.D. hold by a 30 mm I.D. as outer cylinder). 5 mL aqueous sample solution
(donor phase, pH=2.0) containing the analytes and 2.5 mL distilled deionized water (receiving phase, pH=9.0) were placed on top
of this organic phase. The two water phases were separated by inner cylindrical tube. The effects of pH of the source phase and
receiving phase, nature and volume of organic solvent of liquid membrane, stirring rate, transport time and ionic strength were
investigated.Caffeic and vanillic acids were analyzed by RP-HPLC-UV using acetonitrile and ammonium acetate buffer (pH=5,
0.01M) gradient elution. The recoveries of Va and Ca were 91.75 and 16.52, respectively. Limit of detections (LODs) were found
to be 0.14 µg.mL-1 for Va and 0.72 µg.mL-1 for Ca. Relative standard deviations (RSD%) of 2.56, 5.83 were obtained for Va
and Ca, respectively. The proposed BLM-HPLC-UV method was successfully applied for separation and determination of
vanillic acid in the presence of caffeic acid and other compounds in different high quality samples of honey from Lorestan
province.
Reference
[1] J. Hayes, P. Allen, N. Brunton, M. O'Grady, J. Kerry, Food Chem. 126 (2010) 948-955.
[2] Z. Fang, Y. Hu, D. Liu, J. Chen, X. Ye, Food Chem. 108 (2008) 811-817.
[3] T.R. Reddy, J. Ramkumar, S. Chandramouleeswaran, A. Reddy, J. Mem. Sci. 351 (2010) 11-15.
An investigation on the interfacial interaction and filler reinforcement of RDX with Neutral Polymeric Bonding Agent via
FT-IR spectroscopy
Forouzan Gholamian, Mahdi Ansari, Sara Ghariban, Farideh Bataghva*
Department of chemistry, Analytical chemistry group, Malek- Ashtar University of Technology, Tehran, Iran
Email: fbataghva@yahoo.com
Composite propellants (CPs) are the most important class of solid rocket propellants [1]. Solid rocket propellants are energetic
polymer composites filled with finely divided solid particles called fillers. Often as much as 80 weight percent of the propellant is
oxidizer along with about 10 weight percent of a metal fuel, thus, giving a solid loading of around 90 weight percent of the total
composition [2]. Addition of oxidizers such as AP, HMX and RDX to those propellants increases energy and performance but
some difficulties such as dewetting and poor mechanical properties were resulted [3]. Addition of bonding agent is a key
technique to solve these problems [4]. Therefore Composite propellants require certain interaction between polymer and filler in
order to prevent separation around a particle of filler and obtaining desired mechanical properties [5]. As the mater of fact, in this
paper, the interfacial interaction of RDX containing NPBA or coated filler in order to improve propellants mechanical and other
desired properties, via FT-IR spectroscopy illustrated and discussed.
Reference
[1] Sunil Jain, Mehilal, S. Nandagopal, P.P. Singh, K.K. Radhakrishnan, and B. Bhattacharya. Size and Shape of Ammonium Perchlorate and their Influence on
Properties of Composite Propellant. High Energy Materials Research Laboratory, Pune-411 021 -2009, Defence Science Journal, Vol. 59, No. 3, May 2009, pp. 294299
[2] GORDANA S. MOHAMED M. ZREIGH. Investigation of the interfacial bonding in composite propellants.1,3,5-Trisubstituted isocyanurates as universal bonding
agents . J. Serb. Chem. Soc. 2006, 71(5): 445–458
[3] Kim, Hyoun-Soo. Improvement of mechanical properties of plastic bonded explosive using neutral polymeric bonding agent. Propellants, Explos, Pyrotech,
1999,24(2): 96-98
[4] Wu Wenhui, Yao Weishang, Zheng Bin. Surface and interfacial properties of polymeric bonding agents and nitramine crystal fillers. Theory Pract Energ Mater,
2nd, 1997. 350-355
[5] Jelena Petković, Amhamed Wali, Dušan Mijin, Gordana Ušćumlić. The Influence of Bonding Agents in Improving Interactions in Composite Propellants,
Determined Using the FTIR Spectra. Scientific Technical Review,Vol. LIX, No.3-4, 2009
Synthesis of titania-silica composite by the sol-gel-hydrothermal method for photodegradation of 2,4-dichlorophenol in
aqueous solution
H.Faghihian* and N. Ghorbani shahkuchaki
Department of Chemistry, Islamic azad university, Shahreza branch, Shahreza, Iran
Organic contaminants present in industrial wastewater are of major concern with respect to the health of the general public[1].
Chlorophenols constitute an important class of soil and water pollutants arising from their wide use as pesticides, herbicides and
as wood preservatives[2]. Heterogeneous photocatalysis has been widely investigated as a method for depollution of waste
streams. The photochemical activity of titania is modified by promoting or suppressing the recombination of electron and hole
pairs which are formed by UV light excitation. One of methods to improve the photocatalytic activity of titania is attachment to
silica[3]. In this research, titania–silica composite was prepared by sol-gel-hydrothermal method. The structure of the composite
was characterized by XRD and FT-IR techniques [4]. The synthesized photocatalyst was used for degradation of 2,4dichlorophenol. The experimental condition were optimized.
Reference
[1] Ruiyuan. Yang, Min. Wang, Zhongqun. Shen, Wenfeng. Wang, Hongjuan. Ma, Jianzhong. Gu, Radiat. Phys. Chem. 76 (2007) 1122–1125.
[2] Satoshi. Horikoshi, Atsushi. Tokunaga, Natsuko. Watanabe, Hisao. Hidaka, Nick. Serpone, J. Photochem. Photobiol. A: Chem. 177 (2006) 129–143.
[3] Hadi. Nur, Mater. Sci. Eng. B. 133 (2006) 49–54.
[4] Zhijie. Li, Bo. Hou, Yao. Xu, Dong. Wu, Yuhan. Sun,Wei. Hu, Feng. Deng, J. Solid State Chem. 178 (2005) 1395–1405
.
Selective response of dopamine in the presence of ascorbic acid on carbon paste electrode modified with multi-walled
carbon nanotube by differential puls stripping voltammetry
Mahboubeh Masrournia ,Maryam abdoljavadi*,Mohsen abdoljavadi
Department of Chemistry, Faculty of Science, Mashhad Branch ,Islamic Azad University,Mashhad,Iran
E-mail: masrournia@yahoo.com
Dopamine (DA) and ascorbic acid (AA) are compounds of great biomedical interest, playing significant roles in the functioning
of the human metabolism, central nervous and renal systems [1]. Since these two species usually coexist in real biological
matrixes, the development of a selective and sensitive method for simultaneous determination of DA and AA is highly desirable
for analytical application and diagnostic research [2]. In recent years, voltammetric techniques for the detection of DA and AA
have attracted considerable interest due to their fast response and high sensitivity.Among many methods for determination of DA
in the presence of ascorbic acid in biological samples, MWCNT-modified electrodes have shown to be a powerful tool. the
modified electrode is applied as a selective and sensitive voltammetric sensor for simultaneous detection of AA and DA. All
solutions were prepared with distilled water. The modified-CPE was prepared by mixing 0.015g of MWCNT, 0.15g of graphite
powder and 0.06mL paraffin liquid a mortar by hand until a homogeneous paste was obtained[3].The modified electrode offers
an excellent and stable response for the determination of DA in the presence of AA. The results of cyclic and differential pulse
voltammetric investigations show that the modified electrode possesses an efficient electrocatalytic activity for the
electrochemical oxidation of DA and AA. The effective electrocatalytic property, excellent peak resolution and ability for
masking the voltammetric responses of the other biologically reducing agents, make the modified electrode suitable for
simultaneous and sensitive voltammetric detection of sub-micromolar amounts of AA and DA. The modified electrode shows
good selectivity, sensitivity, reproducibility and high stability. In general CPE are popular because CPE are easily obtainable at
minimal costs. CPE is highly selective sensors for inorganic and organic electrochemistry.
Reference
[1]H.R. Zare, N. Rajabzadeh, N. Nasirizadeh, M.M. Ardakani, J. Electroanal. Chem.589 (2006) 60.
[2] J. Tashkhourian, M.R. Hormozi Nezhad J. Khodavesi, S. Javadi , Journal of Electroanalytical Chemistry 633 (2009) 85–91
[3] J. Zheng, Y. Zhang, P.Yang . Talanta 73 (2007) 920–925
A Sensitive Simultaneous Determination of Acetaminophen and Adrenalin on a Glassy Carbon Electrode Coated with a
Film of Chitosan/Room Temperature Ionic Liquid/Single-Walled Carbon Nanotubes Nanocomposite
Mohammad Afrasiabia*, Ali Babaeia, Mitra Babazadeha, SHokat Kianipourb
a Department of Chemistry, Faculty of Science, Arak University, Arak, Iran
b Department of Chemistry, Faculty of Science, Semnan University, Semnan, Iran
Remarkable attention has been paid on carbon nanotubes (CNTs) in recent years. sensors based on CNTs illustrate lower
overvoltages and higher peak currents in the voltammetric response of several compounds of clinical, biological and
environmental interest.1-3 The applications of RTILs in electrochemistry to prepare of the modified electrode have been
extensively increased because of their unique chemical and physical properties such as high chemical and thermal stability, low
toxicity, high ionic conductivity, wide electrochemical potential window and increasing the sensitivity of response.4,5 The
present work demonstrates that simultaneous determination of acetaminophen (ACT) and adrenalin (AD) can be performed on
single-walled carbon nanotube/Chitosan/Ionic liquid modified glassy carbon electrode (SWCNT-CHIT-IL/GCE). The electrooxidation of ACT and AD were investigated with cyclic voltammetry (CV), differential pulse voltammetry (DPV) and also
chronoamperometry (CA) methods. DPV experiments showed that the oxidation peak currents of AD and ACT are proportional
to the corresponding concentrations over the 1 - 580 μmol/L and 0.5 – 400 μmol/L ranges, respectively. Moreover, the modified
electrode acts as an efficient amperometric sensor. The R.S.D. at a concentration level of 15 μmol/L AD and 15 μmol/L ACT
were 1.69 % and 1.82 %, respectively. Finally the sensor was used for simultaneous determination of AD and ACT in real
samples with satisfactory results.
Reference
[1] Sanchez, S.; Pumera, M.; Cabruja, E.; Fabregas, E. Analyst 2007, 132, 142.
[2] Rivas, G. A.; Rubianes, M. D.; Rodriguez, M. C.; Ferreyra, N. F.; Luque , G. L.; Pedano, M. L.; Miscoria, S. A.; Parrado, C. Talanta 2007, 74, 291 Review.
[3] Rubianes, M. D.; Arribas, A. S.; Bermejo, E.; Chicharro, M.; Zapardiel A.; Rivas, G. Sen. Actuators: B 2010, 144, 274.
[4] Lu, X. B.; Hu, J. Q.; Yao, X.; Wang, Z. P.; Li, J. H. Biomacromolecules 2006, 7, 975.
[5] Zhao, G. C.; Xu, M. Q.; Ma, J.; Wei, X. W. Electrochem. Commun. 2007, 9, 920.
Develop a Glassy Carbon Electrode Coated with a Film of Chitosan/ Room Temperature Ionic Liquid/Single-Walled
Carbon Nanotubes for Sensitive Simultaneous Determination of Pracetamol and L-dopa
Mohammad Afrasiabia*, Ali Babaeia, Mitra Babazadeha, SHokat Kianipourb
a Department of Chemistry, Faculty of Science, Arak University, Arak, P.O. Box 38156-879, Iran
b Department of Chemistry, Faculty of Science, Semnan University, Semnan, Iran
In the last years, carbon nanotubes (CNTs) have been used as a very attractive material for a wide range of applications due to
their unique structural, electronic, mechanical, geometric and chemical properties. They have received enormous attention for the
development of electrochemical sensors.1 Room temperature ionic liquids (RTILs) have been extensively used as a material for
preparation of the modified electrode because of their interesting properties such as low toxicity, wide electrochemical potential
window, high ionic conductivity and increasing the sensitivity of response.2,3 A natural-polymer, Chitosan is an attractive
biocompatible, high mechanical strength, high hydrophilicity, low cost, chemical inertness; good adhesion that exhibits excellent
membrane-forming ability, thus, CNTs could be uniformly distributed in the Chitosan film.4,5 Recently, preparation of the
modified electrodes with room-temperature ionic liquids and carbon nanotubes composite have gained increasing attention for
combining their desirable benefits to develop the performances of electrochemical sensing. The electro-oxidation of paracetamol
(PAR) and 3, 4-dihydroxyphenylalanine (L-dopa) has been investigated by application of single-walled carbon
nanotube/Chitosan/Ionic liquid modified glassy carbon electrode (SWCNT-CHIT-IL/GCE) using cyclic voltammetry (CV),
differential pulse voltammetry (DPV) and chronoamperometry (CA) methods. The DPV data showed that the obtained anodic
peak currents were linearly dependent on the L-dopa and PAR concentrations in the range of 2-450 μmol L-1 and 1-420 μmol L1, respectively. The fabricated sensor revealed some advantages such as convenient preparation, high sensitivity, good
repeatability and stability. The experimental results revealed that SWCNT-CHITIL/GCE could be successfully employed as an
electrochemical sensor for simultaneously determination of PAR and L-dopa in human serum and urine.
Reference
[1] Babaei, A.; Afrasiabi, M.; Mirzakhani, S.; Taheri, A. R.; J. Braz. Chem. Soc. 2011, 22, 334.
[2] Zhao, F.; Wu, X. E.; Wang, M. K.; Liu, Y.; Gao, L. X.; Dong, S. J.; Anal. Chem. 2004, 76, 4960.
[3] Du, P.; Liu, S.; Wu, P.; Cai, C.; Electrochim. Acta. 2007, 52, 6534.
[4] Zhang, M. G.; Smith, A.; Gorski, W.; Anal. Chem. 2004, 76, 5045.
[5] Qian, L.; Yang, X. R.; Talanta 2006, 68, 721.
Determination of rate constants for alkaline hydrolysis of dimethyl phthalate in different solvents using MCR-ALS
K. Zarei*, M. Atabati, Z. Salehabadi
School of Chemistry, Damghan University, Damghan, Iran
When chemical species have overlapping response, soft modeling chemometrics methods may be used to isolate the individual
species-dependent responses. Chemometrics techniques such as multivariate curve resolution- alternative least square (MCRALS) are very flexible and let the operator apply constraints that prevent the calculation from converging to a chemically invalid
solution [1]. But in order to determine the kinetic parameters of the chemical system, the kinetic profiles resolved by this
technique have to be fit to a chemical model separately [2].In this work, alkaline hydrolysis of dimethyl phthalate as a real system
was studied by the proposed method. This reaction is a two-step pseudo first-order consecutive reaction [3,4]. In order to
investigation of this procedure, the changes of absorption spectra were measured in the range of 255 to 300 nm at time interval of
30 sec for time period of 50 min. Then MCR-ALS was applied to resolve the two-way kinetic-spectral data measured from UVVis instrument and finally the rate constants in water were calculated as K1=0.004 0.001 and K2=0.0005 0.0001. The rate
constant in mixtures of water with some other solvents were also determined. The results are in agreement with other reports.
Reference
[1] R. Gargallo, R. Tauler, F. Cuesta Sanchez, D.L. Massart, Trends Anal. Chem., 15 (1996) 279–286.
[2] Y. Tan, J.H. Jiang, H.L. Wu, H. Cui, R.Q. Yu, Anal. Chim. Acta 412 (2000) 195–202.
[3] M. Bahram, Anal. Chim. Acta 603 (2007) 13-19.
[4] Z.L. Zhu, J. Xia, J. Zhang, T.H. Li, Anal. Chim. Acta 454 (2002) 21-30.
Prediction of solubility of pesticides in water using multivariate adaptive spline (MARS) and adaptive neuro-fuzzy
inference system (ANFIS)
K. Zarei*, M. Atabati, Z. Eftekhari
School of Chemistry, Damghan University, Damghan, Iran
Pesticides are necessary and essential in agricultural production. However, the risk of residues in the food consumed is present,
which are damaged to human. Therefore detection of pesticides residues in agricultural production is very important. [1]. It is
important to develop a model to predict the solubility of pesticides in water because empirical strategy for determination of
solubility has great disadvantages in terms of time and costs. MARS is a local modeling technique, dividing the data space in
several possibly overlapping region and fitting truncated spline functions in each region. A truncated spline function consists of a
left-sided and a right-sided segment, separated by a so called knot location [2].The synergism of fuzzy logic (FL) systems and
neural networks (NN) has produced a functional system capable of learning, high level thinking, and reasoning [3]. The network
structure that implements FL is referred to as an adaptive neuro-fuzzy inference system (ANFIS). The goal of ANFIS is to find a
model or mapping that will correctly associate the inputs (descriptors) with the target (property) [4]. In this work, a quantitative
structure-solubility relationship was developed to predict the solubility of some pesticides. A set of 1497 zero-to threedimensional descriptors were used for each molecule in the data set. Multivariate adaptive spline was successfully used as a
descriptor selection method. Three descriptors were selected and used as inputs for adaptive neuro-fuzzy inference system
(ANFIS). The root mean square errors for the calibration, prediction and validation sets were 0.47, 0.60 and 0.60, respectively.
The results were compared with those obtained from three other models. In one model multivariate adaptive regression spline
(MARS) was used as a descriptor selection method and also as a mapping model. In the other model multiple linear regression
(MLR) was applied for descriptor selection and also modeling and in last model classification and regression tree (CART) was
used for descriptor selection and modeling. The results showed MARS-ANFIS can be used as a powerful model for prediction of
solubility of pesticides.
Reference
[1] X. Li, F. Luan, H. Si, Z. Hu, M. Liu, Toxicol. Lett. 175 (2007) 136-144.
[2] M. Jalali-Heravi, M. Asadollahi-Baboli, A. Mani-Varnosfaderani, J. Pharm. Biomed. Anal. 50 (2009) 853-860.
[3] L.A. Zadeh, Infom. Control 8 (1965) 338-353.
[4] M. Jalali-Heravi, P. Shahbazikhah, Electrophoresis 29 (2008) 363-374.
A new method for removal monitoring and simultaneous determination of three textile dyes in contaminated water
Abdolhossein Naseri a,* , Ali R. Khataee b, Leila Moradkhannejhad b
a Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, , Tabriz, Iran
b Department of Applied Chemistry, Faculty of Chemistry, University of Tabriz, , Tabriz, Iran
There are numerous types of synthetic dyes like nitro, indigo and azo which are widely used for different purposes in industries.
The effluents from these industries cause the water bodies not only to become colored, but also cause an environmental damage
to the living organisms [1]. It is, therefore, essential to remove these dyes from water bodies or treat them in such a way so as to
minimize the damage to the environment and also decolorize the water [2]. To investigate the efficiency of treatment, it is
necessary to develop an effective and reliable analytical method to monitor the dye's concentrations. Nowadays, the
spectrophotometric techniques remain largely used in this field. In spite of the spectrophotometric method is rapid, cheap and
simple, the direct spectrometric measurements show lack of specificity because the spectra are strongly overlapped. In such cases
the chemometric techniques become an indispensable tool to overcome these problems[3,4]. A new direct UV–Vis
spectrophotometric method for simultaneous determination of three textile dyes (C.I. Basic Blue 3, C.I. Basic Red 46 and
Malachite Green) in the aqueous mixture has been proposed. The spectra of the samples, standard solutions and synthetic
mixtures were disposed in a column-wise augmented data matrix. This kind of data structure, analyzed by multivariate curve
resolution-alternating least squares (MCR-ALS) made it possible to exploit the so called ‘second order advantage’. MCR-ALS
algorithm was applied to the experimental data under the non-negativity and equality constraints. As a result, the concentration of
each dye in the in the aqueous mixture of three dyes and their corresponding pure spectra were obtained. The results were
validated using an HPLC method. Our findings revealed that the accurate results could be obtained even in the presence of
interferences using second order advantage.
Reference
[1]. H. Zollinger, Color Chemistry. Synthesis, Properties and Applications of Organic Dyes and Pigments, 3 ed: Wiley - VCH, New york, 1991.
[2]. Khataee, V. Vatanpour, A. R. Amani Ghadim, J. Hazar. Mater. 2009, 161 (2-3), 1225.
[3]. H. C. Goicoechea, A. C. Olivieri, R. Tauler, Analyst, 2010, 135 (3), 636.
[4]. A. Naseri, H. Abdollahi, Anal. Methods, 2011, 3 (2), 429.
QSPR Correlation of the Melting Point for Pyridinium Bromides Ionic Liquids Using MARS
K. Zarei*, M. Atabati, K. Kor
School of Chemistry, Damghan University, Damghan, Iran
Ionic liquids (ILs) are a class of novel compounds that are composed entirely of ions, melt at relatively low temperatures, and
may be thought to resemble molten metallic ionic melts such as NaCl at 800 oC. In contrast to the molten salts, certain ILs are
moisture stable, have miniscule volatility, and are water immiscible, all characteristics of a unique class of potentially
environmentally benign solvents [1]. Solubility, polarity, viscosity and melting points are thus of utmost importance, and their
estimation from the chemical structure is highly desired to focus synthetic efforts on ILs with the best chances of exhibiting the
required characteristics [2].Multivariate adaptive regression spline (MARS) is a local modeling technique, dividing the dataspace
in several possibly overlapping region and fitting truncated spline functions in each region. A truncated spline function consists
of a left-sided, and a right-sided, separated by a so called knot location [3,4].The known experimental melting point values of the
126 ILs were taken from the literature [1]. The 3-D structures of these compounds were optimized using HyperChem software
with semiempirical AM1 optimization method. After optimization a total of 1497 0-, 1-, 2-, and 3-D descriptors were generated
using Dragon software. In this work shuffling cross-validation technique was used for feature selection. To this purpose the data
set was divided into twelve subsets, and variable selection process was performed for different combinations of these subsets by
MARS. Then the most frequent descriptors in the models (5 descriptors, complementary information content, 3D-Morse-signal /
weighted by atomic masses, mean atomic van der waals volume, local dipole index and geary autocorrelation-lag 4 / weighted by
atomic Sanderson electronegativities) were selected as the most important variables describing the melting point. The selected
descriptors were then used for construction of MARS equation. Finally this model was applied to predict melting point of ILs.
Squared correlation coefficient was obtained as 0.8023. The results showed MARS can be used as a powerful model for
prediction of the melting point of ILs.
Reference
[1].A R. Katritzky, A. Lomaka, R. Petrukhin, R. Jain, M. Karelson, A. E. Visser, R. D. Rogers, J. Chem. Inf. Comput. Sci. 42 (2002) 71-74.
[2] G. Carrera, J. Aires-de-Sousa, Green Chem. 7 (2005) 20-27
[3] J. H. Friedman, Ann. Stat. 1991, 19 (1991) 1-67.
[4] M. Jalali-Heravi, M. Asadollahi-Baboli, A. Mani-Varnosfaderani, J. Pharm. Biomed. Anal. 50 (2009) 853-860.
Sulfur as a new adsorbent for solid phase extraction of nickel from standard and river water samples
M. Soleimani, F. Aflatouni*
Department of Chemistry, Imam Khomeini International University (IKIU), Qazvin, IRAN
E-mail: fatemeaflatouni@yahoo.com
Heavy metals are toxic and harmful, even at low concentrations to aquatic life, human beings and the environment [1]. One of
them is nickel which is toxic and carcinogenic. Flame atomic absorption spectrometry (FAAS) has been widely used for the
determination of trace metal ions. However, direct determination of metal ions at trace levels by FAAS is limited due to their low
concentrations and matrix interferences. So using a preconcentration method is necessary, before determination by FAAS [2].
Solid phase extraction (SPE) is the most common technique used for preconcentration of analytes in water samples [3]. In SPE
procedure the choice of appropriate adsorbent is a critical factor to obtain full recovery and high enrichment factor. In this
research work a new method based on adsorption of nickel ions on sulfur is described for preconcentration of Ni (II) followed by
flame atomic absorption spectrometric determinations. The effects of the analytical parameters including pH of the sample
solution, eluting solution conditions, flow rate of sample solution, sample volume and interfering ions for the column solid phase
extraction were investigated. Under the optimum experimental conditions, preconcentration factor, analytical detection limit,
adsorption capacity and reusability of the sorbent were determined. Under the optimum experimental conditions,
preconcentration factor and analytical detection limit were determined as 100 and 0.0018µg mL-1, respectively. The adsorption
capacity was obtained as 15.75µg g-1.The proposed method was applied for the determination of nickel in river water samples.
Reference
[1] P.E.Warwick, I.W. Croudace, A.G. Howard, Anal. Chem. 72 (2000) 3960
[2] J. Minczenski, J. Chwastowska, R. Dybezynski, Ellis Horwood, Chichester, 1982.
[3] A. Mostafavi, D. Afzali, M.A. Taher, Anal. Sci. 22 (2006) 849–853.
Extraction of Neostigmine methyl sulfate by synthesized (Fe3O4 /SiO2) nano – particles sorbents modified with
surfactant
Majid Soleimani Marzie Rezaie*
Department of Chemistry, Imam Khomeini International University (IKIU), Qazvin, IRAN
E-mail: Mr.medicen@yahoo.com
In this study , a new type of superparamagnetic silica-coated ( Fe3O4/SiO2 core/shell ) nano - particles modified by the
surfactant sodium dodecyl sulfate (SDS) has been successfully synthesized and applied for extraction of Neostigmine methyl
sulfate (NEO) from medical sample based on mixed hemimicelles solid-phase extraction (MHSPE). Compared with pure
magnetic particles, a thin silica layer would protect the iron oxide core from leaching out in acidic conditions [1]. SDS – coated
Fe3O4/SiO2 NPs system was selected due to lower elution volume required and more effective of the target compounds [2]. The
advantage of this new method still include easy preparation and regeneration of sorbents, short times of sample pretreatment and
high extraction yield. A formation of superparamagnetic silica- coated (Fe3O4 /SiO2 core/shell) nano- Particles inspected by
using scanning electron microscopy (SEM) and x-ray diffraction (XRD). Under selected conditions, concentration factor of 143
was achieved by using this method to extract 500 mL of different matrices. The detection limit obtained for NEO with UV
spectrophotometer was 31.16 ng/mL.
Reference
[1] X. Zhao, Y. Shi, T. Wang, Y. Cai, G. Jiang, J. Chromatogr. A. 1188 (2008) 140-147.
[2] L. Sun, C. Zhang, L. Chen, J. Liu, H. Jin, H. Xu, L. Ding, J. Chromatogr. A. 638 (2009) 162–168.
Polymer grafting on nano graphite support using imino diacetic acid-allyl glycidyl ether for preconcentration and
sorption of enrofloxacin
Atefeh Alimadadi a,∗, Homayon Ahmad Panahia a, Faramarz Afashar Taromi b, Neda Veisi a
a Department of Chemistry, Islamic Azad University, Central Tehran Branch, Iran
b Department of Polymer Engineering, Amirkabir University of Technology, Tehran, Iran
A method is reported for surface grafting of polymer containing a functional monomer, poly[1-(N,N-bis-carboxymethyl)amino-3allylglycerol-co-dimethylacrylamide] (poly(AGE/IDA-co- DMAA) onto nano graphie using cyanuric chloride as a linking agent.
Monomer 1-(N,N-bis-carboxymethyl)amino-3-allylglycerol (AGE/IDA) was synthesized by reaction of allyl glycidyl ether with
iminodiacetic acid. The resulting sorbent has been characterized by Fourier transforms infrared spectroscopy (FT-IR), elemental
analysis, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and evaluated for the preconcentration and
sorption of Enrofloxacin. Enrofloxacin is a fluoroquinolone antibiotic sold by the Bayer Corporation under the trade name
Baytril. Enrofloxacin is currently FDA-approved for treatment of individual pets and domestic animals in the United States. The
effects of various parameters like reaction pH, the best eluent, the best time of enrofloxacin sorption and etc were considered.
The optimum pH value for sorption of the enrofloxacin was 6. The sorbent can be reused for 15 cycles of sorption–desorption
without any significant change in sorption capacity. The profile of compound uptake by the sorbent reflects good accessibility of
the active sites in the poly(AGE/IDA-co-DMAA)-grafted nano graphite. Scatchard analysis revealed that the homogeneous
binding sites were formed in the polymers. The equilibrium adsorption data of compound by modified resin were analyzed by
Langmuir, Freundlich, Temkin and Redlich–Peterson models.
Reference
[1] L.V.A. Gurgel, L.F. Gil, Carbohydr. Polym. 77 (2009) 142.
[2] Yang, j.; Xu, T.; Lu, A.; Zhang, Q.; Fu, Q J. Appl. Polym. Sci. 2008,109, 720.
[3] M. Jahanshahi, H. Ahmad Panahi, S. Hajizadeh, E. Moniri, Chromatographia 68(2008) 41.
[4] Y. Ho, A.E. Ofomaja, Biochem. Eng. J. 30 (2006) 117.
Development of dispersive liquid-liquid microextraction combined with gas chromatography as a simple, rapid, sensitive
and efficient method for the simultaneous determination of class 1 residual solvents in pharmaceutical samples
Mir Ali Farajzadeh, Leila Goushjuii*
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
Organic volatile residuals (OVRs) in pharmaceuticals are defined as organic volatile chemicals that are used or produced in the
manufacture of drug substances, or in the preparation of drug products. The International Conference on Harmonisation of
Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH) [1] and the Pharmacopoeias [2] provide limits
and offer analytical methods, which in most cases are static headspace sampling coupled to gas chromatography (HS-GC).
Besides, headspace solid phase microextraction (HS-SPME) sample preparation is often applied, and nowadays various full
evaporation techniques are also popular [3, 4]. But each of them has some disadvantages and limitations. In this study, a novel,
simple, sensitive, and environmentally friendly approach has been presented for the simultaneous determination of class 1
residual solvents (RSs) (1, 1-dichloroethene, 1, 2-dichloroethane, 1, 1, 1- trichloroethane, carbon tetrachloride and benzene) in
pharmaceutical products using dispersive liquid-liquid microextraction (DLLME) combined with gas chromatography-flame
ionization detector (GC-FID). Sample preparation step was carefully evaluated. Under the final working condition, 100 µL of N,
N-dimethylformamide containing 25 µL 1, 2-dibromoethane was dispersed into 5 mL of aqueous solution of pharmaceuticals
without salt addition. The mixture was centrifuged at 3000 rpm (3 min) to allow phase separation. An aliquot of the settled
extract was injected into the GC-FID system. Analytical parameters of the proposed method were investigated and a good
linearity and a broad linear range (50-160000 µg L-1 for CCl4, 10–32000 µg L-1 for 1, 1-dichloroethene, 1, 2-dichloroethane,
and 1, 1, 1-trichloroethane, and 2–6400 µg L-1 for benzene) were obtained. The method exhibited enrichment factors, ranging
from 133 to 353. Finally the proposed method was successfully utilized for preconcentration and determination of class 1 RSs in
different pharmaceutical samples and satisfactory results. The satisfactory results obtained prove that this method can be a
suitable alternative to previously reported methods.
Reference
[1] Proceedings of International Conference on Harmonisation of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH), Tripartite
harmonised guideline Q3C Impurities, Residual Solvents, 1997.
[2] Residual Solvents (5.4), European Pharmacopoeia, Supplement (4.6), Directorate for the Quality of Medicines of the Council of Europe, trasbourg, 4th ed., 2004,
p. 3911.
[3] C. Witschi, E. Doelker, Eur. J. Pharm. Biopharm. 43 (1997) 215–242.
[4] C. Camarasu, C. Madichie, R. Williams, Trends Anal. Chem. 25 (2006) 768– 777.
TiO2-functionalized Fe3O4@SiO2 as an adsorbent for aqueous cadmium(ІІ) removal
Esmaeil Shams*, Fateme Yarmohammadian
Department of Chemistry, University of Isfahan
Email: e_shams@chem.ui.ac.ir
Heavy metals have been put much more attention nowadays because the toxic effect of them at low concentration has been
found[1]. Cadmium has been classified by U.S. Environmental Agency as a probable human carcinogene[2]. Therefore, it is of
great interest to explore ways to effectively remove these heavy metals ion from the wastewater [3]. Magnetite silica core@shell
nanoparticles (Fe3O4@SiO2) were prepared by combining coprecipitation and sol-gel methods[4] and functionalized with TiO2,
aiming to remove Cd(ІІ) ion from aqueous media. Nanoparticles were characterized by XRD, XRF and FT-IR. The adsorption of
Cd(II) ions was examined by batch equilibrium technique. The effects of temperature, pH, initial Cd(II) concentration and contact
time on the efficiency of Cd(II) removal were studied. The equilibrium data, analyzed by using Langmuir and Freundlich
isotherm models, showed better agreement with the former model.The adsorption of Cd2+ ions was studied in aqueous solutions
in the concentration range of 2-50 mg/L. The maximum adsorption capacity (qmax) for Cd2+ ions under the optimal conditions
(pH=6 , equilibrium time=1h, temp=50°C) was estimated to be 76.32mg/g. The metal loaded Fe3O4@SiO2-TiO2 nanoparticles
could be recovered easily from aqueous solution by magnetic separation and regenerated by acid treatment.
Reference
[1] Zhou, Q.; Zhao X.; Xiao, J. Talanta 2009, 77, 1774-1783.
[2] Bayramoglu, G.; Arica, M. Y. Chem. Engs. J. 2008, 143, 133-140.
[3] El-Shafey, E.I.; J. Hazard. Material. 2010, 175, 319-327.
[4] Mahmoudi, M.; Sant, S.; Wang, B.; Laurent, S.; Sen, T. Adv. Drug Delivery Rev. 2011 Jan-Feb;63(1-2):24-46. Epub 2010 May 26..
A new carbon paste selective electrode for sensitive and selective determination of carvedilol
A. Soleymanpour*, M. Ghasemian
School Of Chemistry, Damghan University, Damghan, Iran
Carvedilol is a nonselective β-blocking agent with vasodilating properties with are attributed mainly to its blocking activity at
receptors [1]. It has been confirmed that carvedilol shows a far greater antioxidant activity than other commonly used betablockers. Carvedilol is used in the treatment of mild to moderate hypertension and angina pectoris, congestive heart failure (CHF)
and is often used in combination with other drugs [2]. Different analytical methods have been developed for the determination of
carvedilol and its metabolities including chromatography, spectrophotometry and voltammetry [3,4], thus for easy, fast and
selective determination of carvedilol, in this work a new carbon paste electrode based on the use of ion association complex of
carvedilol cation whit phosphotangestate is construeted. The most advantages of CPEs are ease of preparation, modification and
regeneration and specially low cost. The proposed electrode exhibits a Nernstian slope of 58.6 mV per decade for carvedilol over
a wide concentration range of 7.44×10-7 - 5.6×10-2 M, with a low detection limit of 9.0×10-7 M. The electrode has a relatively
fast response time (less than 9 s), satisfactory reproducibility and good life time (more than 2 months). The potentiometric
response is independent of the pH of the test solution in the pH range 4-7. Potentiometric titration of carvedilol solution with
tetraphenylborate as a titrant has been monitored with the proposed sensor as an indicator electrode. The electrode was
successfully applied to determine carvedilol in carvedilol tablet and also blood serum samples. The inclusion complex formation
between α- and β-cyclodextrine and carvedilol was studied potentiometrically and equilibrium constant of these complexes were
calculated.
Reference
[1] S. Chakraborty, D. Shukla, D. Mishra, S. Singh, informa. Healthcare, 6 (2010) 237.
[2] B. Michael, M. B. Fowler, am. J. cardiol., 93 (2004) 35.
[3] G. Dutu, C. Cristea, B. Ede, V. Harceaga, A. Saponar, E. Popovici, R. Sandulescu, farmacia, 58 (2010) 430.
[4] B. Dogan, S. A. Ozkan, electroanalysis, 22 (2005) 2074.
Spectrophotometric investigation of the interaction of erythromycin with Manganes (II) Ion
Razieh Sanavi Khoshnood1, Hillsa Bidkhori1*,Zarin Eshaghi2
1. Department of Chemistry, Faculty of Science,Mashhad branch, Islamic Azad University of Mashhad Mashhad ,Iran
2. Department of chemistry,Mashhad branch, Payame Noor University (PNU) ,Mashhad, Iran
* E-mail: hillsa.bidkhori@yahoo.com
Erythromycin is a macrolid antibiotic consisting of a 14-membered macrocyclic lactone ring attached to two sugar moieties [1].
the drug targets at the ribosome and inhibits the protein synthesis of Gram positive bacteria [2].This work aimed to study of
interaction between erythromycin ligand and Mn2+cation in methanol solvent and determination ofcomplex by
spectrophotometric methode
under equilibrium conditions.methode of continuous variation (Job’s methode)was
employed.measurment on complex was done at wavelength of 250 nm and the influence of pH ,time and interferences has been
tested The interaction of erythromycin with Mn2+ has been founded to form one complex withMetal to ligand composition of 1:2
and the value of formation constant was obtained to indicate the complex is stable.
Reference
[1]. I . Kanfer, M F. Skinner, R B. Walker, Journal of chromatography A, 812 (1998) 255-286.
[2]. A. Kucers, N. Mck Bennet. The use of Antibiotics, William Heienemann Medical Books Ltd. London (1979).
Photoinduced Electron Transfer between Triphenylpyrylium Ion (TPP+) and certain amines
A. Samadi-Maybodi*a, S. Masoomeh Pouralia, A.R. Khodabandeha, M.J. Chaichia, P. Biparvab
a Division of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
b Research Department of Chromatography, Iranian Academic Center for Education, Culture and Research (ACECR), Urmia, Iran
E-mail: samadi@umz.ac.ir
Photoinduced electron transfer (PET) processes have attracted growing interest in the last decades [1,2]. In such a process,
amines are excellent electron donors because of their low ionization potentials. The lone pair electrons on the nitrogen atom lead
to facial electron transfer reactions of amines in a number of processes. 2,4,6-triphenylpyrilium hydrogen sulfate (TPPHSO4) is a
very strong oxidant in both the singlet and triplet excited states, able to oxidize several organic donors (D) to the corresponding
radical cations (D•+) with concomitant formation of the triphenylpyranyl radical, TPP• [3]. The photoinduced interaction
between TPP+ and certain aromatic and aliphatic amines were studied in aqueous medium by using absorption and fluorescence
spectroscopic methods. Linear Stern-Volmer plots were obtained from measurements.TPP and all amines were obtained from
Sigma and Merck, respectively. The fluorescence quenching measurements were carried out in Perkin Elmer LS3 Luminescence
Spectrometer. Absorption spectra were recorded using T 90+ UV/VIS spectrometer. Samples were prepared by dissolving TPP
(100 ppm) in water and administering the appropriate amounts of amines with sampler.To study the PET reactions in the excited
state, it is very important to know the type of ground state interaction of fluorophore-quencher molecules. Investigating the effect
of amines on the absorption spectrum of TPP+, the results indicates that the addition of amines neither gives peak shift nor new
peak formation; there is no change in the absorption spectrum of TPP+. This precludes the possibility of ground state complex
formation between TPP+ and amines.Comparing two categories of amines, it is worth noting that aromatic amines possess higher
kq than aliphatic amines, because the former may donate electrons from their aromatic rings (π-donors), while later act as pure
“n-donors”. The quenching constant increases with decreasing of ionization potential values, which supports the above trend [4].
Reference
[1] J. Mattay, Angew. Chem., Int. Ed. Engl. 26 (1987) 825.
[2] M.A. Fox, Adv. Photochem. 13 (1986) 237.
[3] B. Branchi, M. Bietti, G. Ercolani, M.A. Izquierdo, M.A. Miranda, and L. Stella, J. Org. chem. 69 (2004) 8874.
[4] D. Rehm and A. Weller, Ber. Bunsen-Ges. Phys. Chem. 73 (1969) 834.
Central composite design applied to optimization of Lead (ІІ) ion membrane electrode based on N,N′-bis(3-etoxy
salicyliden)-2,2-dimethyl-1,3-propane diamine
Mohammad Mazloum-Ardakani*a, Saeed Masoumb, Azimeh Ali Mandegaric,d
aDepartment of Chemistry, Faculty of Science, Yazd University, Yazd, Iran
bDepartment of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Iran
cDepartment of Chemistry, Payam Noor University (PNU), Ardakan center, Iran
dDepartment of Chemistry, Payam Noor University (PNU), Shiraz center, Iran
A design of experiment was used to evaluate the effects of significant parameters and to obtain the optimum value of important
variables in composition of membrane.Central composite design (CCD) under Response Surface Methodology (RSM) was
applied to modeling and optimization the influence of some variables such as PVC, plasticizer, ionophore, additive amounts and
pH value, on the performance of PVC membrane Lead (ІІ) ion-selective electrode [1]. RSM is a collection of mathematical and
statistical techniques which is useful for modeling and problem analysis purposes [2]. RSM was used to describe the individual
and interactive effects of these five variables at five levels, combined according to a Central Composite Design [3]. In order to
gain a better understanding of these variables effects on electrode performance, the models were presented as 3-D response
surface graphs [1].The electrode is prepared by dissolving appropriate amount of PVC, ionophore (N,N′-bis(3-etoxy salicyliden)2,2-dimethyl-1,3-propane diamine), plasticizer (DOP) and additive (NaTPB) in about 5 mL THF. The electrode exhibits a linear
Nernstian response over the range of (1×10-1 M to 1×10-4 M) of Lead (ІІ) ion, with a slope of 28.5 mV per decade. The
electrode could be used over a wide pH range 3.5-5.0.
Reference
[1] K. Farhadi, M. Bahram, D. Shokatynia, F. Salehiyan. Talanta 76 (2008) 320–326.
[2] A. Z. Abdullah, H. Abdullah, S. Bhatia, B. Salamatinia and N. Razali. IIUM Engineering Journal, 11 (2010) 106-122.
[3] Guaracho VV, Kaminari NM, Ponte MJ, Ponte HA. Journal of Hazardous Materials, 172 (2009) 1087-1092.
Electrochemical Detection of Different Single Base Mismatches Using Morin as a Molecular Reporter
Maedeh Esnaashari Isfahani, Masoud Ayatollahi Mehrgardi*
Department of chemistry, University of Isfahan, Isfahan, 81746-73441, Iran
:
DNA hybridization biosensors play an important role for pharmaceutical, clinical and forensic applications. The surveys of drugDNA interactions would offer new compounds to be tested for an effect on a biochemical target, and also to be utilized as
promising hybridization indicators for the DNA biosensors [1-3]. In this research, an electrochemical DNA biosensor has been
developed based on the mediated charge transfer through double-stranded DNA (ds-DNA) to oxidize Morin as a molecular
reporter. The recognition layer has been formed by immobilization of an amino-labeled 20-mer single-stranded deoxyribonucleic
acid (ss-DNA) on mercaptopropionic acid modified gold electrode (AuE) using N hydroxy sulfosuccinimide (NHS) and N-(3dimethylamino) propyl-N'-ethylcarbodiimide hydrochloride (EDC) chemistry. The covalently immobilized capture probe could
be selectively hybridized with its complementary target DNA to form ds-DNA on AuE surface. The hybridization and formation
of double helix structure can be transduced using differential pulse voltammetric (DPV) experiments. When the double helix
structure is perfect and the target is completely matched to the probe, the charge will transfer through the p-stack of DNA and a
well-defined peak for Morin is observed. Surprisingly, the presence of even a single base mismatch in the structure causes
diminish in the charge transfer and the peak current of Morin is decreased significantly. The peak current of Morin was found to
decrease in the following order: complementary modified AuE, mismatch hybrid-modified AuE, non-complementary modified
AuE.
Reference
[1]. Erdem, A.; Ozsoz, M., Electroanalysis 2002, 14 (14), 965-974.
[2]. Tiwari, S.; Pitre, K. S., Voltammetric DNA biosensor for the study of mechanism of action of anticancer drug-adriamycin. CSIR: 2008.
[3]. Gao, Z.; Tansil, N., Anal. Chim. Acta 2009, 636 (1), 77-82.
Chemometrics Analysis of sound-solvent interactions using solvent structural information
Bahram Hemmateenejad*, Poorandokht Ilani kashkooli
Chemistry Departmen, Shiraz University, Shiraz, Iran
Email:Hemmatb@sums.ac.ir
Ultrasound is a type of energy which can help analytical chemists in almost all their laboratory tasks, from cleaning to detection.
Ultrasonic technique has been employed to investigate the properties of any substance to understand the nature of molecular
interactions in pure liquid [ ], liquid mixtures [ - ] and ionic interactions in electrolytic solutions [ , ]. Also Measurements of
ultrasonic velocity in liquids [ - ] give information about physico-chemical behavior of liquid mixtures such as molecular
association and dissociation. There are also some literature reports concerning the prediction of sound velocity in solvents using
physically derived models. However, the derived models are limited to specified solvent systems and in some instances they are
highly complicated. Thus, there is a need to generate simple models, which are able to predict the sound velocity in a broad range
of solvents, even different solvent mixtures. Mixed solvents are interesting, because two solvents mixed together produce a
solvent with quite different properties, both, physically (dielectric, density and viscosity) and chemically (acid–base and donor–
acceptor properties).The speed of sound in binary solvents has been investigated extensively. Whilst in some binary solvent
system the sound velocity changes linearly with mole fraction, in some other mixed solvents nonlinear behavior can be observed.
Thus, the dependency of sound velocity on mole fraction in binary solvents is highly dependent on the chemical structure of the
individual solvents and the solvents composition.The individual experimental ultrasonic velocity of liquid mixtures and pure
liquids were taken from the literature [ ]. For this study, ultrasonic velocity of 15 pure solvent and 55 binary solvents (with
different molar fraction) at 298ºK were used .The molecular structures of all components were drawn into Hyperchem software (
HyperChem) and optimized using the AM1 molecular mechanics force field. There after, by Dragon software, molecular
descriptors were calculated using these optimized molecular structures. After calculating molecular descriptors of all components
available in data set, the problem is to find a linear equation that can predict the desired property with the least number of
variables as well as highest accuracy. The stepwise selection based multi-linear regression (MLR) algorithm is used to find the
best model.We used this solvent structural information for predict sound-solvent interactions. The square of the correlation
coefficient (R2), the cross-validated squared correlation coefficient (R2cv), root mean square error of model (RMSE), the crossvalidated root mean square error (RMSE cv), were used as criteria for stability and robustness of the models. A small difference
between R2 and R2cv denotes high predictive ability of the model. The best model found was a four- descriptor model. An R
value of 0.975 was given by the final model. This multivariate linear model has four parameters. This equation isU=52.024 +
123.063 ΔG (6A°) + 150.325 ATS3e - 270.280 Mor28m + 68.984 C-040R2 = 0.975, R2 cv = 0.966, RMSE=29.97, RMSE
cv=35.131
Reference
[ 1]. L. Palaniappan, V. Karthikeyan, Indian J. Phys., 79 (2005) 155.
[2 ]. S. Nithiyanantham, L. Palaniappan, Acta Ciencia. Indica, 36 (2005) 533.
[ 3]. S. Nithiyanantham, L. Palaniappan, Acta Ciencia Indica, 37 (2006) 382.
[ 4]. R. Nithya, S. Mullainathan, S. Nithiyanantham, R. Rajasekaran R, E-J. Chem, 6 (2009) 138.
[ 5]. S. Nithiyanantham, L. Palaniappan, Met. Mater. Processes, 20 (2008) 203.
[ 6]. M. Satya Narayanamurthy, Curr. Sci., 33 (1964) 364.
[7 ]. V.S. Soitkar, S.N. Jajoo, Acoust. Lett., 7 (1984) 1991.
[8 ]. M. G. Sheshagiri Rao, Indian J Pure Appl Phys, 9 (1971) 169.
[ 9]. A. Nithya, S. Nithyanandham, S. Mullainathan and Rajasekaran M, E-Journal ofChemistry, 6(1) (2009) 138.
A novel glucose biosensor based on a glassy carbon electrode modified with GOx/TTF-TCNQ/MWCNT
M.A. Kamyabi*, M. Moharramnejad
Department of Chemistry, Zanjan University, P.O. Box 45195-313, Zanjan, Islamic Republic of Iran
Novel biosensors based on redox enzymes have been the subject of considerable recent interest. In general, these biosensors
achieve specificity for the substrate of interest via the enzyme, which is immobilized on the electrode surface. The current which
results from the enzyme mediated reaction is measured and is proportional to the substrate concentration. In this study, a novel
glucose biosensor was constructed based on the immobilization of glucose oxidase (GOx) with cross-linking by glutaraldehyde
on a glassy carbon electrode, (GCE), which was modified with tetrathiafulvalene–tetracyanoquinodimethane, (TTF-TCNQ), by
dropping on multiwall carbon nanotubes. The GOx modified electrode was mounted as a working electrode into a conventional
three-electrode cell. The experimental conditions were studied and optimized for hydrogen peroxide as a model compound. The
enzyme electrode can sensitively determine glucose at a low working potential, mainly based on the oxidation of H2O2. The
incorporated TTF-TCNQ can significantly improve the oxidation of H2O2 on the electrode, although a part of the TTF-TCNQ
functions as a mediator [1]. Compared with the same electrode prepared without TTF-TCNQ incorporated, the TTFTCNQ/MWCNT modified electrode had better performance characteristics at a working potential of 200 mV (versus Ag/AgCl).
The biosensor exhibited excellent performances for glucose with a high sensitivity (0.0381μA/μM), a low detection limit
(9.8μM), a wide linear range (10-140μM), and good reproducibility, stability, and selectivity. Finally, the results of these¬
experiments demonstrate that the catalytic ability of TTF-TCNQ in enzyme-base electrochemical sensor is quite general, and
also, it has been demonstrated that this sensor can be well used for the assay of glucose in serum samples.
Reference
[1] M. Cano , J. L. Avila, M. Mayen, M. L. Mena , J. Pingarron, R . Rodriguez-Amaro, "Journal of Electroanal Chem", 615 (2008) 69–74.
Controlled release of Imatinib Mesylate by amino benzene functionalized nanoporous SBA-15 as a novel carrier
Leila Hajiaghababaei1, Mahtab Eslambolipour1*, Alireza Badiei2
1Department of Chemistry, Islamic Azad University, Shahre Rey Branch, Tehran, Iran
2Department of Chemistry, University of Tehran, Tehran, Iran, 3 Osvah pharma. Co. As supporter
Drug delivery is the new strategies for the delivery of biologically active compounds at the Right dose, at the Right time and at
the Right Place. Novel drug delivery systems are designed with polymers, liposome, micelles and nanoporous compounds.
Modified nanoporous compounds, with the desired functional groups that are attached to the walls of the pores, are ideal for
absorption and release of variety of compounds. They are nontoxic and biocompatible and have large surface, adjustable pore
size, thermal and chemical stability and controllable degration rates.Therefore, in this study, amino benzene functionalized
mesoporous SBA-15 molecular sieve was prepared to evaluate its application as imatinib mesylate drug delivery system. Imatinib
mesylate is a drug used to treat certain types of cancer (chronic myelogenous leukemia, gastrointestinal stormal tumors). This
drug was doped inside the pores of the SBA-15 by contacting a solution of the imatinib mesylate in an appropriate solvent with
the porous solid, and the drug release process from the matrix into a simulated body fluid (SBF) solution and phosphate buffers
has been studied. The effect of several variables such as (amount of adsorbent, concentration of drug, stirring time and pH) has
been studied. The best loading of the imatinib mesylate was done at pH 5 after stirring for 60 minutes. The results showed that
the release effect of imatinib mesylate in the prepared samples was made in a slow release pattern thus the SBA-15 fits to be used
as a carrier for controlled release of imatinib mesylate.
Reference
[1]Functionalized mesoporous silica nanopartical based drug delivery system to rescue acrolinen –mediated cell death " nanomedicine 3(4) 507-519 (2008).
[2].Confinement & controlled release of bisphosphonate on ordered mesoporous Silica-based material “J.Am.chem soc.128, 8116-8117 (2006).
[3].Watching silica nanoparticle glow in biological world “Anal. chem.” 78 (3), 646-654 (2006).
Study the effect of body size (Total length and total weight) on the degree of the aggregation of Cd in Mudskipper
Periophthalmus waltoni in region of Persian Golf
Kooseg, N1, Rahmani, A.2, Kamrani, E.3, Taherizadeh, M. R.4
1Department of Fisheries, Faculty of Natural Resources, Hormozgan University, Hormozgan, Bandar Abbas.
2Department of Chemistry, Hormozgan University, Bandar Abbas.
3Department of Fisheries, Hormozgan University, Bandar Abbas.
4Department of Biology, Hormozgan University, Bandar Abbas.
Email of Corresponding Author: Naserkooseg@yahoo.com
Heavy metals are dangerous pollution in sea ecosystem.1 They have bad effects on fish.2 In this research the study of body size
effect (total length and total weight) on the degree of the aggregation of the concentration of cadmium in Mudskipper
Periophthalmus waltoni in the regions of Khamir Port, Dargahan and Golshahr (Persian Golf) was performed. 180 samples of
Mudskipper waltoni (in every station and in each season separately n= 30) in each region was sampled during the seasons of
summer and winter randomly, which after the biometry in laboratory, the muscle tissue was separated and the cadmium metal
was extracted by chemical digestion method, and its concentration was determined by Atomic Absorption Spectrometry (AAS).3
The results showed significant correlation between the degree of cadmium aggregationin muscle tissue of Mudskipper waltoni
and body size (total length and total weight) (p<0.05). It means that by increasing that total length and total weight, the
aggregation of cadmium in fish body is increased. According to the results, cadmium concentration in muscle tissue of
Mudskipper waltoni was significantly different in the regions and also between two seasons of summer and winter in these three
regions (p<0.05 in both cases). In both summer and winter seasons, Khamir port region had the highest concentration of cadmium
with respect to Dargahan and Golshahr. There was no significant difference between the concentration of cadmium in male and
female of Mudskipper waltoni at the studied regions (p>0.05) with regard to the results of this research, we can say that the
contamination of petroleum, industrial and municipal activities in these regions of Persian Gulf during the different seasons affect
the aggregation of cadmium in Mudskipper waltoni, while this contamination is less than the limitation of global standard.
Reference
[1]Al-Yousef, M. H.; Ei-shahawi, M. S.; Al-Ghais, S. M. Science Total Environment 2000, 256, 87-94.
[2]Agbozu, I. E.; Ekweozor, I. K. E.; Opuene, K. Environmental science Technology 2007, 4, 93-97.
[3].MOOPAM, Manual of oceanographic observations and pollutant analysis methods. 3rd ed, 1989-1999, Kuwait, p 321.
Determination of mercury in real water samples using in situ derivatization followed by solid-phase microextraction and
gas chromatography-flame ionization detector
Ali Sarafraz-Yazdi*, Elham Fatehyan, Amirhassan Amiri
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Iran
The in situ derivatization and solid-phase microextraction (SPME) method based on sol-gel technology coupled with gas
chromatography-flame ionization detector (GC-FID) was proposed for the determination of mercury at trace levels in water
samples. The method is based on the diphenylation using phenyl boronic acid, subsequent extraction of diphenylmercury onto a
fiber sol-gel coating. In this study poly(ethylene glycol) modified with multi-walled carbon nanotubes (PEG/CNTs) coating fiber
were used for determination of mercury. The scanning electron micrographs of the fiber surface revealed a highly porous
structure which greatly increases the surface area of PEG/CNTs sol–gel coating. This fiber demonstrated many inherent
advantages, the main being the strong anchoring of the coating to the fused silica resulting from chemical bonding with the
silanol groups on the fused-silica fiber surface. The new PEG/CNTs sol–gel fiber is simple to prepare, robust, has high thermal
stability and long lifetime. The pH of the feed solution was kept in pH 5 with acetate buffer solution. Then, the optimized
conditions are: derivatization time, 10 min; extraction time, 60 min; extraction temperature, 40 ºC; stirring rate, 1000 rpm;
sample volume, 5 mL. After extraction, the fiber is directly injected into the injector port of GC for desorption, separation and
quantification. Under the optimal conditions, the method detection limits (S/N=3) and the limits of quantification (S/N=10) were
obtained. Also, the relative standard deviations (RSDs) for one fiber (Repeatability) (n=5) and between fibers or batch to batch
(n=3) (Reproducibility) were obtained. The developed method was successfully applied to real water samples.
Reference
[1] R.P. Belardi, J.B. Pawliszyn, Water Pollut. Res. J. Can. 24 (1989) 179.
[2] C.L. Arthur, J. Pawliszyn, Anal. Chem. 62 (1990) 2145.
[3] S.L. Chong, D.X. Wang, J.D. Hayes, B.W. Wilhite, A. Malik, Anal. Chem. 69 (1997) 3889.
Fabrication and characterization of a novel electrocatalyst film containing MWCNT-g-PCA-(M: Pt &Pd &Pt/Pd) by
electrospray deposition method for DMFCs
Nahid Sarlak* a,b, Akram dourani b
a Department of Analytical Chemistry, Faculty of Chemistry, University of Lorestann, khorram Abad, I.R.Iran
b Engineering Research Institute (Iranian Space Agency), Department of Nano Technology & Nanoscience, Tehran, I.R.Iran
E-mail: sarlak.n@gmail.com
In this work we describe the development and application of a novel carbon nanotube /polycitric acid (MWCNT-g-PCA)
nanocomposite as an efficient nanocatalyst for methanol fuel cell. Modifying CNT surface with desired functional groups by
chemicaltreatments is a common strategy to get well-dispersed metal nanoparticles on CNTs. The modifications with polymers
improved the adhesion of the Pt, Pd and Pt/ Pd nanoparticles on MWCNT surface. With this method electrocatalysts with a
narrow particle-size distribution and good dispersion have been produced. Carbon nanotube (CNT) film electrodes were
fabricated by a novel process involving the electrostatic spray deposition (ESD) of a CNT solution. The CNT film electrodes
showed well-entangled and interconnected porous structures with good adherence to the substrate. Cyclic voltammograms (CV)
of catalysts using the porous thin layer electrode technique were obtained for the catalysts surface evaluation and for Methanol
Oxidation Reaction (MOR) to check the electrocatalytic behavior of these nanocatalyst systems. Polymerization of functionalized
CNT has been improved electrocatalytic activity of nanocatalysts this was attributed to the MWCNT-g-PCA porous structure
and to the better Pt–support interaction through the surface carboxylic groups of the support. Also CV results demonstrate that
the current density and MOR activity of the MWCNT-g-PCA-Pt& Pd is respectively higher than that of the MWCNT-g-PCA-Pt
and MWCNT-g-PCA-Pd nanocatalyst. This improved electrocatalytic performance was mainly due to the fine dispersion of PtPd nanoparticles and bi-functional effect.
Reference
[1]. Madhu Sudan Saha, Arunabha Kundu, , Power Sources 195( 2010) 6255-6261.
[2]. Xin Wang, Wenzhen Li, Zhongwei Chen, Power Sources 158(2006) 154-159.
[3]. Jae Hong Kim a, Kyung-Wan Nam a, Sang Bok Ma, Carbon 44 (2006) 1963–1968.
[4]. Adeli M, Bahari A, Hekmatara H, Brief Rep. Rev,3,(2008) 37.
Adsorption of Gadolinium (III) on Gold Electrode Surface by Using SAMs Thin Films Functionalized with Carboxylic
Acid Groups
Reza Karimi Shervedani*, Zahra Salimian Rizi
Department of Chemistry, University of Isfahan, Isfahan 81746-73441, I.R. IRAN
Gadolinium is used in petroleum industries to produce catalyses, in nuclear researches as neutron absorber, in steel industries and
polishing glassware. Specially, solutions of organic gadolinium(III) compounds are used as intravenous radiocontrast agent in
medical field to enhance image quality of the magnetic resonance imaging (MRI) of all anatomic regions. Alternatively, free
gadolinium(III) toxic and inhibits physiological process (1). This behavior requires developing new methods being compatible
for determination of gadolinium(III) in different environments.Self Assembled Monolayers (SAMs) are the most often employed
templates for the chemical construction of advanced electronic devices and sensors (2). The sensors developed based on SAMs
have been applied to monitor inorganic species (3) and biological molecules (4).In the present study, we report the results
obtained by experimental investigation of gadolinium interaction with SAMs functionalized by carboxylic acid groups such as
mercaptopropionic acid and mercaptosuccinic acid, to construct a new sensor for determination of gadolinium in MRI
pharmaceuticals. For this purpose, we have used electrochemical methods like cyclic and differential pulse voltammetry in
conjunction with electrochemical impedance spectroscopy. The results will be presented and discussed.
Reference
[1] Singh, A. k.; Jain, A. k.; Singh, J. Electrochim. Acta 2009, 54, 5640.
[2] Chah, S.; Yi, J.; Pettit, C. M.; Roy, D.; Fendler, J. H. Langmuir, 2002, 13, 314 .
[3] Shervedani, R. K.; Akrami, Z.; Sabzyan H. J. Phys. Chem. C., 2011, 115, 8042–8055.
[4] Shervedani, R. K.; Pourbeyram, S. Bioelectrochemistry 2010, 77, 100.
Salt-assisted liquid–liquid microextraction with water-miscible Ionic liquid for the determination of Chromium species in
saline samples by flame atomicabsorption spectrometry
Behrooz Majidi, Farzaneh Shemirani
School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
E-mail: shemiran@khayam.ut.ac.ir
Trying to develop more benign extraction techniques than those used nowadays, in this work, a study was conducted using
aqueous two phase systems (ATPS) composed by ionic liquids (ILs) and typical inorganic salts. The new proposed ATPS present
large extraction efficiencies for hydrophilic compounds and represent a new platform for separation techniques. Currently ILs
appear as a potential and alternative replacement for VOC’s due to their negligible vapor pressures and intrinsic character of
“designer solvents”. In this new extraction technique Cr(VI) was complexed with 1,5 diphenyle carbazid (DPC) in an HCl
medium. The IL−ATPS system formed by [bmim][BF4] and Na2HPO4 system was applied to the extraction of Cr(VI) as the
form of Cr(VI)−DPC hydrophilic complex in the ionic 1iquid was also investigated using FAAS. Total chromium is subjected to
a similar extraction procedure after oxidation. Then Cr(III) has been calculated by subtracting Cr(VI) from the total
chromium.Concerning the Chromium extraction, several parameters that could affect the solute extraction were studied in ternary
systems composed by imidazolium-based including the kind and the amount of water-soluble IL, the kind and the amount of
inorganic salts, the pH of the sample solutions and temperature of the systems on the extraction efficiencies were carefully
studied. It is found that over 94% of the Cr(VI) can be extracted into the IL-rich phases with Na2HPO4.The method yielded a
linear range in the concentration from 1.0 to 70.0 μg mL-1 of Cr(VI), and the limit of detection was 0.3 μg mL-1. The relative
standard deviation (R.S.D.) was 3.68% (n=7, C= 10 μg L−1). The proposed extraction technique appears to be suitable as a first
step for the separation and determination of Chromium species from real aqueous environments and food grade salts.
Reference
[1] K.E. Gutowski, G.A. Broker, H.D. Willauer, J.G. Huddleston, R.P. Swatloski, J.D. Holbrey, R.D. Rogers, J. Am. Chem. Soc. 125 (2003) 6632.
[2] Y. Wang, J. Han, X. Xie, C. Li, Cent. Eur. J. Chem. 8(6) (2010) 1185-1191.
[3] M. Ezoddin, F. Shemirani, R. Khani, Desalination 262 (2010) 183–187.
[4] J. Han, Y. Wang, W. Kang, C. Li, Y, Yan, J, Pan, X, Xie, Microchim Acta 169 (2010) 15–22.
Determination of Artificial Sweeteners in Cola Drinks by HPLC
Mona Sargazi1, Massoud Kaykhaii1,*, Jila Darabi Purkalhor2
1Department of Chemistry, Faculty of Sciences, University of Sistan & Baluchestan, Zahedan, Tel: +98 (541) 2446413, Fax: 2446565, E-mail:
kaykhaii@hamoon.usb.ac.ir
2 The Institute of Standards & Industrial Research of Iran, Kermanshah, Iran.
A method for the separation and determination of saccharin, caffeine, benzoic acid and aspartame in beverage samples by high
performance liquid chromatography (HPLC) using a methanol/acetic acid mobile phase is described. Experiments illustrated that
the most important parameter on separation and quantitation is the pH of the eluent. The optimum pH was found to be between
3.3 to 4.2. The beverages to be analyzed were degassed in a sonic bath for 10 min and then filtered through a 0.8-µm filter. A 15
µL of the sample was injected directly onto a reversed-phase HPLC column and the peak heights were used to determine the
level of the additives in the beverage. The chromatogram from the sugar-free cola indicated a number of unidentified components
that were eluted at the beginning of the chromatogram; however they do not interfere with the analytes of interest. Table 1
provides the observed level of the additives in a number of soft drinks from cans and from regular packages. The results that were
obtained for the common additives were similar in the various samples that were analyzed; however, in a few cases, the level of
the sweeteners was varied from the information received from manufacturer of the soft drink.
Table1. Additive amounts in selected beverages (in g.L-1)
Beverage
saccharin
caffeine
benzoic acid
aspartame
Cola 1
Not Found
1.116
Not Found
Not Found
Diet Cola 1
Not Found
1.509
2.000
6.365
Lemon
Not Found
Not Found
2.379
5.678
Orange
Not Found
Not Found
2.332
Not Found
Reference
[1]. Smyly, D.S.; Woodward, B. B.; Conrad, E. C.; J Assoc Anal Chem 1976, 59, 14-19.
[2]. Grayeski, M. L.; Woolf, E. J.; Sfrsub, T. S.; LC 1385, 3, 538-540.
[3]. Delsnoy, M.F.; Pasko, K.M.; Mauro, D.M., D.M.:Korologas, P.C, Krolikowaki, L. J.; Warren, F.V., J Chem Educ 1985, 62, 618-620.
Combination of two immiscible organic solvent hollow fiber liquid–liquid–liquid microextraction and corona discharge
ion mobility spectrometry with novel reagent gas as a detection and separation system for analysis of clomipramine in
biological samples
Ali Akbar Hajialiakbari Bidgoli*, Mohammad Saraji, Ali Moradmand, Taghi Khayamian
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
Clomipramine [3-Chloro- 10,11-dihydro-N,N-dimethyl-5H-dibenz[b,f]azepine-5-propanamine] is a typical tricyclic
antidepressant with a wide clinical spectrum being used in major depressive, panic and obsessive-compulsive disorders [1]. The
general methods for analyzing clomipramine in different biological samples are based on combining a very efficient separation
method with a sensitive detection technique like online-SPE-HPLC-MS-MS [2] and SPME-GC-NPD [3].In this research work, at
first the ion mobility signal intensity of clomipramine with some carboxylic acids such as formic, acetic and propionic acid as the
reagent gases (dopants) has been measured using corona discharge ion mobility spectrometry. The highest abundance of the
clomipramine peak was observed in its IMS spectrum after the addition of the formic acid among all the above-mentioned
dopants. The relationship curves for the concentration of formic, acetic and propionic acid to the response of clomipramine were
studied. Formic acid at 3.7 µmol min-1 levels, acetic acid at 1.1 µmol min-1 levels and propionic acid at 1.0 µmol min-1 levels
exhibited the strongest response of clomipramine. In the next step, a novel and sensitive method based on two immiscible organic
solvents hollow fiber-based liquid–liquid–liquid microextraction coupled to corona discharge ion mobility spectrometry (HFLLLME-CD-IMS) was presented for the analysis of clomipramine in human urine and plasma samples. For the first time, HFLLLME-CD-IMS is described for the detection, separation, and quantitation of multiple analytes in complex matrixes.
Experimental parameters which influence the extraction efficiency of HF-LLLME, such as NaOH concentration as donor
solution, ionic strength of the sample, stirring rate, and extraction time were investigated and optimized. Under the optimum
conditions, analytical parameters such as linearity, precision and limit of detection were also evaluated. The linear dynamic range
was from 1 to 100 µg L-1 (R2 = 0.9980) and the limit of detection was 0.35 µg L-1. Intra–day and inter–day precision of method
were satisfactory with a relative standard deviation (RSD) of 5.9 and 6.7%, respectively. The proposed method is simple, fast
detection, inexpensive, low solvent consumption, and is especially suitable for the analysis of the real sample with complicated
matrix.
Reference
[1] J. Zohar, T.R. Insel, J. Affect. Disord. 13 (1987) 193.
[2] A. Castro, M.M.R. Fernandez, M. Laloup, N. Samyn,G.D. Boeck , M. Wood, V. Maes, M. López-Rivadulla, J. Chromatogr. A 1160 (2007) 3.
[3] S. Ulrich, J. Martens, J. Chromatogr. B 696 (1997) 217.
Modeling of organic reactions using chemometrics methods: toward the quantification of chemo and regioselectivity
Bahram Hemmateenejad*, parisa shadabipour
Chemistry Department, Shiraz University, Shiraz, Iran
Email: Hemmatb@sums.ac.ir
Analysis of the behavior of reactants, products, and determination of mechanism of reactions is an important stage in the study
of reactions, especially in reduction reactions, which is an interested subject in the world of chemistry.Vast variety of reducing
agents have been introduced for reduction process [, , , ]. Highest yield and purity with the least amount of by product is a kind of
dream for synthetic chemists, especially who try for chemoselective reduction reactions in which one of the functional groups in
the reactant molecule is selectively attached by a reagent [].When a reduction process is analyzed by UV spectroscopy, a series of
spectra are recorded as a function of mol ratio (relation between reductant and sample). All the collected UV data contain the
information about all species involved in the chemical process. The characterization of the various components represents a
serious analytical problem and its resolution depends on the number of the reduction products.In this work, we have employed
chemometrics methods on the UV spectra of reduction of Methyl-(4-formyl)benzoate (MFB) with NaBH4 as a component that
have two different carbonyl for selection of the chemo-selective mol ratio.Multivariate curve resolution-alternating least squares
(MCR-ALS) has become a popular chemometric method used for the resolution of multiple component responses in unknown
and unresolved mixtures. MCR-ALS is a soft modeling approach to describe and model processes without explicitly using the
underlying chemical model linked to them []. MCR-ALS decomposes the raw measurements (in our case, a series of spectra as a
function of mol ratio) into a bilinear model that contains the concentration profiles and pure spectra of each absorbing species
contributing to the collected measurements.The different components with two different carbonyl groups must be used, for this
reason the MFB was chosen. Reduction of this molecule is investigated in reaction with NaBH4. The changes in the absorbance
spectra of the ethanolic solution of MFB upon adding NaBH4 are represented in Fig. 1 (a). To resolve the concentration profile
and pure spectra of components involved in the reaction, MCR-ALS was employed. Before starting the MCR analysis, the
number of component in the reaction must be determined. For this purpose, SVD was performed. The resulted obtain from SVD
show that three components were involved in this reaction. In addition, this suggestion was also confirmed by using EFA. After
the chosen of number of components and obtained the initial estimation of concentration profiles by EFA, a MCR analysis was
used. The resulted concentration profiles of the components are shown in Fig1(b), that are more likely to exponential decay for
both reaction steps. Regarding to the concentration profiles which obtained through the MCR analysis, the specific mol ratio in
that
the
reaction
is
chemo-selective
has
been
selected.
(a)
(b)
Fig1.(a) Absorbance spectra of the ethanolic solution of MFB with adding NaBH4 . (b) Concentration profiles of the MFB (A)
and its reduction products (B, C) as a function of Mol ratio calculated by MCR-ALS
Reference
[1] S. D. Burke and R. L. Danheiser; Handbook of Reagents for Organic Synthesis, Oxidizing and Reducing Agents; Wiley- VCH: New York, (1999).
[2] B. T. Cho, S. K. Kang, M. S. Kim, S. R. Ryub, D. K. Anb, Tetrahedron (2006).
[3] G. C. S. da Costa, K. C. Pais, E. L. Fernandes, P. S. M. de Oliveira, J. S. Mendonça, M. V. N. de Souza, M. A. Peralta, T. R. A. Vasconcelos , ARKIVOC (2006).
[4] B. Zeynizadeh, S. Yahyaei. Bull. Korean chem.Soc. (2003).
[5] B. Uysal, B. S. Buyuktas, ARKIVOC (2007).
[6] J. M Amigo, A. de Juanb, J. Coelloa, S. Maspocha, Anal Chim Acta (2006) .
Simultaneous spectrophotometric determination of trace amount of palladium and mercury by chemometrics methods in
aqueous media after preconcentration with alumina nano particles
E. Rokrok, F. Shemirani*, S.M. Sajjadi
School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
E-mail:shemiran@khayam.ut.ac.ir
A simple and inexpensive spectrophotometric method was developed for the simultaneous determination of Hg and Pd at 24-48
ng ml-1 and 6-16 ng ml-1 level respectively after preconcentration using alumina nanoparticles (NP.s) as solid phase extractor.
This sorbent was selected because of its large specific surface area, high adsorption capacity, mechanical strength and low
temperature modification. The method is based on the complex formation of mercury and palladium with Thio-Michler’s Ketone
(TMK) at pH 3.2. Net analyte signal-response surface methodology regression (NAS-RSM) was proposed for optimization of
process parameters of extraction. A Central Composite Face Design (CCFD) with three independent variables: parameters
namely amount of SDS (0.4-1.6 ml), nanoparticles (1.4-2.6 ml) and 1-propanl as eluent (0.6-1.4 ml) were used to study the
response variables. First, the contribution of each analyte in the mixture was calculated by NAS method and was then fitted into a
quadratic polynomial model using multiple regression analysis. The optimum process conditions were determined by analyzing
response surface three-dimensional plot. The predicted optimize condition were 0.7 ml SDS, 1.6 ml NP.s and 0.6 ml eluent.
These optimum conditions were used to evaluate the trail experiment. The proposed method has been applied to the
determination of these metal ions at trace levels in certified reference materials and real samples with satisfactory results.
Reference
[1] A. Mirmohseni, H. Abdollahi, K. Rostamizadeh, Analytica Chimica Acta 585 (2007) 179–184.
[2] B. Hemmateenejad, R. Ghavami, R. Miri, M. Shamsipur, Talanta 68 (2006) 1222–1229.
[3] V.V. Guaracho, N.M.S. Kaminari, M.J.J.S. Ponte, H.A. Ponte, Journal of Hazardous Materials 172 (2009) 1087–1092.
[4] Y. S. Al-Degs, Amjad H. E.Sheikh , M. A. Al-Ghouti, B. Hemmateenejad , G. M. Walker, Talanta 75 (2008) 904–915.
Identification and quantification of aflatoxins in peanut through excitation-emission fluorescence and three-way parafac
and BLLs/RBL calibration methods
Hamid Abdollahi*, Reza Rahmaneian, S.M Sajjadi
Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan, Iran.
E-mail: abd@iasbs.ac.ir
The aflatoxins are a group of mycotoxins produced by certain strain of the fungi Aspergillus flavus and A.parasiticus.Among 18
different types of aflatoxins identified, major members are aflatoxins B1, B2, G1 and G2. Aflatoxins are potentially
toxic,carcinogenic and mutagenic and immunosuppressive agent then the qualitative and quantitative analysis of aflatoxins major
group are very important [1] .HPLC methods use to determine the amount of aflatoxins (B1,B2,G1,G2) in peanut [2]. we use a
rapid, green, and highly sensitive excitation-emission matrix (EEM) fluorescence fluorescence in combination with parallel factor
analysis(parafac) and bilinear least square residual- bilinearization (BLLs/RBL) for analysis of peanut aflatoxins. The shape of
excitation and emission profiles of B1 and B2 were the same and so there is not spectral difference between two forms of B-type
and for G1 and G2, too. Therefore, the three-way was rank overlapped in the excitation and emission modes. To overcome this
problem, each sample EEM was measured at two different pH=2 and pH=9 and then augmented. The three-way data was
constructed by stacking of augmented matrices in the sample direction.The ranges studied in the excitation and emission modes
were λex = 300–380 nm, λem = 450–570. The range of the calibration concentration was 1-8 ppb , 0.5-5 ppb, 1.5-8 ppb ,1.6-16
for B1, B2, G1, G2 respectively. The second-order advantage [3] of this calibration algorithms was exploited, which make it
possible that calibration can be performed even in the presence of unknown interferences like vitamins.
Reference
[1] Cervino C, Knopp D, Weller MG, Niessner R (2007) Molecules 12 641–653.
[2] Baifen Huanga, Zheng Han, Zengxuan Cai, Yongjiang Wu, Yiping Ren (2010) 62-68.
[3] Bro R. PARAFAC. tutorial and applications. Chemometrics and Intelligent Laboratory Systems (1997)149-179.
Spectrophotometric determination of oxymetholone drug after preconcentration using modified maghemite nanoparticles
TayyebehMadrakian*, Mohammad Rahimi, Mohammad Soleimani
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, IRAN
E. mail: madrakian@basu.ac.ir, madrakian@gmail.com
Oxymetholone (17β-hydroxy-2-[hydroxymethylene]-17-methyl-5α androstan-3-one) is a 17α alkylated anabolic-androgenic
steroid and a synthetic derivative of testosterone hormone [1]. The method involves preconcentration of oxymetholone drug on
maghemite nanoparticles modified with sodium dodecyl sulfate (SDS) and spectrophotometric determination of oxymetholone by
complexation with Fe(III) at λ=530 nm. Optimal experimental conditions including pH, adsorbent dosage and contact time have
been established. Desorption experiments by elution of the adsorbent with acetonitril. The calibration graph was linear in the
range 0.015–3.3 µg mL−1 (5.0 ´10-8 -1.0´ 10-5mol L-1) of oxymetholone drug with a correlation coefficient of 0.995. The
detection limit of the method for determination of oxymetholone was 0.004 µg mL−1.The relative standard deviation (R.S.D.) for
1.00 and 2.50µg mL−1 of oxymetholone was 1.65% and 0.77% (n = 5), respectively.This method is simple and rapid procedure
for determination of oxymetholone in human plasma using modified maghemite nanoparticles [2].
Reference
[1] M. Pavlutos, Oliver Fultz, Matthew J. Monberg, “Review of Oxymetholone: A 17a-Alkylated Anabolic-Androgenic Steroid” Clinical therapeutics Vol. 23,
NO. 6,200l
[2] A. Afkhami, R. Moosavi, “Adsorptive removal of Congored, a carcinogenic textile dye, from aqueous solutions by maghemite nanoparticles” Journal of
Hazardous Materials, 174 (2010) 398–403
Liquid chromatography-photodiode array analysis method for simultaneous quantitative determination of the
organophosphorus pesticides diazinon,malathion,fenitrothion,phosalon and fenvalerat in wastewater
Fatemeh Samadi1,*,Zarrin Es,haghi2,Mahmood Ebrahimi2
Islamic Azad University, Young Researchers Club, Mashhad Branch, Mashhad, Iran,
2
Departments of Chemistry, Faculty of Sciences, Payame Noor University, Mashhad, Iran.
1
The use of OCPs is over recent decades to the extent that it has now tightly regulated in the developed world, but OCPs, become
a significant food safety issue. New pre-concentration technique, (SD-LPME) and HPLC-DAD was applied to determine five
pesticides in real samples. Because of higher extraction efficiency and significant sample cleanup, LLLME combined with HPLC
has been successfully used for pre-concentration and cleanup of complicated samples. In this research pesticides in real samples
was digested and after treatment extracted. The effective parameters were investigated and method was evaluated. Under the
optimal conditions, pesticides were enriched by high factor. Good linearity and low detection limit were obtained.For the first
step, the sample solution was placed within a vial. Surfactant was added too. Then organic solvent was added and a stirring bar
was placed in the solution.In the later step a 100µL flat-cut HPLC micro syringe was used to introduce the acceptor phase to the
top center position of the immiscible organic solvent. The mixture was stirred to cause back-extraction. After this period the
microdroplet was picked up by the same HPLC microsyringe and was injected into the HPLC system..The optimised LPME
technique in conjunction with HPLC-DAD is a simple, solvent minimizing and cost effective procedure for analysis of OCPs in
wastewater. The method is precise, reproducible and has a high level of linearity over a wide range of analyte concentrations. The
results obtained with the method described above indicate that this methodology is a good alternative extraction technique for
hydrophilic analytes in real samples and offers highly interesting advantages from an analytical point of view, such as possibility
of extracting and pre-concentrating the analytes of different polarities. In our method; we introduced a reliable qualitative and
quantitative technique for pesticides at low level of concentration in real samples. And this new technique has the very low
detection limit. The method has a proven viability for quantitative analysis of OCPs in real wastewater samples.
Reference
[1] M. Patlak, Envrion. Sci. Technol. 30 (1996) 210.
[2] A.V. Tkalin, Environ. Pollut. 91 (1996) 183.
A Highly-Sensitive SPME Sorbent Combined with Nano Preyssler Acid and Ion Liquide for Pre-Concentration and
Determination of Atnelol and Celecoxib
1
Fatemeh Samadi1,*, Zarrin Es’hagh2, Mahmood Ebrahimi1
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Mashhad Branch, Mashhad , Iran.
2
Departments of Chemistry, Payame Noor University, 19395-4697 Tehran, Iran.
A novel, simple, sensitive and specific pre-concentration technique was developed through confinement of PTMS task-specific
ionic liquid with Nano Preyssler Acid in a silica-gel matrix by sol-gel technique was applied to determine atnelol and celecoxib
in real samples[1,2]. The obtained PTMS-IL/ Nano Preyssler Acid /silica-gel microextraction device was effective for the preconcentration and extraction of these drugs as the complicated compounds in several real samples[2].In this new technique Nano
Preyssler Acid sol was prepared by the sol-gel method via the reaction of tetraphenyl orto silicat(PTMS) with a basic catalyst
(Tris Hydroxy- methyl Amino-methan). The influences of microextraction conditions such as pH, ageing time, Nano Preyssler
Acid contents, performance and desorption conditions,desorption solvent and agigation speed were investigated ..Also,optimum
instrumental condition included of using of a C18 reversed phase column for separation,water-acetonitril-methanol(50:15:35) as
the mobile phase and maximum absorption wavelength for detection was 251 nm.A new affordable, rapid and compatible method
of hollow fiber solid phase microextraction compared to most conventional procedures, was introduced in this work. This
extraction technique requires very little expensive and toxic organic solvents. It is a promising pre-treatment method for the fast,
trace analysis in many complicated matrixes such as biological samples. The method has a high pre-concentration factor and
excellent selective clean-up of these drugs samples as the very complicated analytes. Good linearity and reasonable relative
recovery were also obtained. We used the method to isolate these drugs from real samples and found it to have many advantages
over conventional methods. The experimental operations involved in HF-SPME are very simple. Moreover, this procedure offers
several advantages over traditional extraction techniques such as; a reduction in extraction time, also this method is economical
and easy to use In our method, we introduced a reliable qualitative and quantitative technique for determination atnelol and
celecoxib at low level of concentration in real samples.
Reference
[1]Z.Es’haghi, M. Ebrahimi, M.S. Hossein, J.Chromatogr.A, 1218 (2011) 3400–3406.
[2]Z. Es’haghi, M. Khalili, A. Khazaeifar, G.H.Rounaghi, Electrochim.Acta 56(2011)3139-3146.
[3] Z. Es’haghi, Z. Rezaeifar, G.H.Rounaghi, Z. Alian-Nezhadi, M.Ahmadi-Golsefidi, Anal.Chim.Acta, 689(2011) 122-128.
Voltammetric determination of DNA via its interaction with sulfadiazine on a multi-walled carbon nanotube modified
glassy carbon electrode
Ayemeh Bagheri Hashkavayi, Lida Fotouhi*, Majid M. Heravi
Department of Chemistry, School of Science, Alzahra University. P.O.Box 1993891176, Tehran, Iran
We describe the interaction of sulfadiazine (SD), with double-stranded calf thymuse DNA both in solution and DNA
immobilized on the multi-walled carbon nanotube modified glassy carbon electrode (MWCNT-GCE) by cyclic voltammetry. The
study on the DNA applications is one of interest becomes it is important in drug discovery epidemiology and genetic [1,2]. effect
of accumulation time and accumulation potential were examined. Under the selected conditions, two linear calibration curves for
DNA detection were obtained. Electrochemical measurements were carried out with a Metrohm model 746VA trace analyzer
connected to a 747 VA stand. The MWCNT-GCE was prepared by casting 5 µL of the suspension of MWCNT on the surface of
a GC electrode, which was dried in air for 40 min at room temperature. The DNA immobilized MWCNT-GC modified electrode
(DNA-MWCNT-GCE) was obtained by casting 6µL of DNA- MWCNT hybrid composite on the surface MWCNT-GC modified
electrode accordingly and dried in the air. Accumulation of SD in the presence of DNA at MWCNT-GCE suggesting that the SD
was included completly by DNA at 4min accumulation period at 0.9V. Interaction of SD with DNA immobilized at MWCNTGCE surface was also assessed under various NaCl concentrations, SD has at least two different modes of binding to DNA, first,
a nonspecific, electrostatic interaction, and second, intercalation. It was assumed that positively charged SD was electostatically
attached to the negatively charged phosphate backbone of DNA. Under the optimized conditions, two linear range were obtained
for DNA over the 0.03-0.13 µgmL-1 and 0.6-3.5 µgmL-1. A detection limit of 0.033 µgmL-1 was calculated according to the
YLOD=XB+ 3SB[3]. A relative standard deviations value of less than 1.12% was obtained for 0.7×10 -3 molL-1 DNA. Under the
optimum conditions, the possible interferences of several metal ions and Amino acids were investigated. To evaluate the
applicability of the present method on real matrices, assays were performed in serum The results showed that satisfactory
recovery for DNA could be obtained.
Reference
[1]Anderson, W.F.,1998. Nature 392 (6671), 25-31.
[2]Kay, M., Liu, D., Hoogerbrugge, P., 1997. Proc. Natl. Acad. Sci. U.S.A. 94 (24), 12744-12746.
[3]Miller, J.C., Miller, J.N., 1992. Statistical for Aanalytical Chemistry, 2nd ed., Eliis Horwood Ltd., Chichester, UK.
A theoretical investigation of antioxidant activity of some Oxicams and solvent effects study
Maryam Darvishpoura, Saeed Jameh-Bozorgi a,*and Mohammad Hossein Fekri b
a
Department of Chemistry, Arak Branch, Islamic Azad University, Arak, Iran.
b
Department of Chemistry, Khorramabad Branch, Islamic Azad University, Khorramabad, Iran.
Non-steridar anti-inflammatory drugs (NSAIDS) are of great interest in medicine as they are widely used for mild to
moderate pain relief as well as in the treatment of osteoarthritis and rheumatoid arthritis. Their anti-inflammatory action can be
associated with their antioxidant properties [1]. It should be mentioned that the solvent used may affect the underlying oxidation
mechanism [2].The antioxidant activity of a compound is related to electrochemical parameters, especially its oxidation potential,
which provides an estimate of the energy required to donate an electron. Indeed, the lower the oxidization potential, the easier the
compound will donate an electron and the higher its expected antioxidant activity will be [3]. Accurate theoretical prediction of
electrode potentials can play an important role in designing bioreductive agents. The investigated NSAIDS involved four
oxicams (piroxicam, meloxicam, tenoxicam and lornoxicam). As solvents, methanol, ethanol and acetonitrile were used in order
to unravel the solvent effect on their electrochemical reactivity. The mentioned solvents have considerable effect on the oxidation
potentials of investigated drugs due to the alteration of their polar intermediates solvation. The calculations were carried out at
the level of density functional theory and 6-31g* basis set and then thermochemical corrections were applied to yield Gibbs
energies of redox reactions. The polarizable continuum model (PCM) was used to calculate solvation energies. The model
furnishes the calculated electrode potentials in relatively good agreement with the experimental values [4]. Results show that by
decreasing the solvent polarity, the oxidation potential increases and therefore, the oxidation becomes more difficult and solvent
effect is stronger in the case of piroxicam and tenoxicam compared with meloxicam and lornoxicam.
Reference
[1]. K. parfitt, W. Martindale, The complete drug reference pharmaceutical, London, 1999.
[2]. M. C. Foti, C. Daquino, C. Geraci J. Org. Chem. 2004, 69, 2309-2314.
[3]. S. Mannino, O. Brenna, S. Buratti, M. S. Cosio Electroanalysis, 1998, 10, 908-912.
[4]. F. Tsopelas, M. O. Petropoulou, N. Zikos J. Solid State Electrochem. 2010, 1165.
Multiresidue determination of amitraz and ethion in pistachio nuts using ion mobility spectrometry method
Ali Sheibani*, Hassan Enayati, Javad Karimipour
Department of Chemistry, Islamic Azad University, Yazd Branch, Yazd, Iran.
E-mail address: alisheibani@ymail.com
A new method has been developed for simultaneous determination of amitraz and ethion in pistachio nuts using ion mobility
spectrometry (IMS) with corona discharge as ionization source. Positive ion mobility spectra of pesticides were obtained in air
ambient pressure using IMS. Under optimum conditions, the calibration curves were linear over the concentration ranges of 2-50
and 4-100 ng for amitraz and ethion, respectively. Relative standard deviations (n=10) were 13.1% and 9.6% for amitraz and
ethion, respectively. Pistachio samples were spiked with pesticides, then a extraction step and a cleaning-up step by C18 silica
cartridge were performed for IMS analysis. The results demonstrate the capability of the proposed method in simultaneous
determination amitraz and ethion in real sample.
Reference
[1] H. Yu, T. Le, D. Chen, Journal of Chromatography B 878 (2010) 1746.
[2] M. T. Jafari, Talanta 69 (2006) 1054.
[3] J. J. Jimenez, J. L. Bernal, Analytica Chimica Acta 524 (2004) 271.
Spectroscopic study of some transition metal complexes with a novel triazole ligand
Yaser Nikzad a , Reza E. Sabzi a,b, * , Mortaza Bahram a , Karim Akbari a , Naser Samadi a , Abbas Nikoo a ,
a
Department of Chemistry, Faculty of science, Urmia University, I.R. Iran
b
Institute of Biotechnology, Urmia University, Urmia, I.R. Iran
The interactions between the transition metals and triazole ligand have been widely studied [1–5]. The interactions between a
new triazole ligand, 1,3-bis [5-(pyridine-2-yl)-4-phenyl-3-mercapto-1,2,4-triazole-3-yl] propane, (BPTP) with some metallic
cations were investigated in acetonitrile as a solvent. The metallic cations studied were the cobalt(II), copper(II) and the
nickel(II), which are involved in many biological processes. The UV–visible spectroscopy was used to determine the formation
constants of the complexes. In this project, the BPTP as a new ligand was used on the development of chelators for bivalent metal
ions (Cu(II), Co(II), Ni(II)), in this work the complexation behavior of a newly synthesized ligand with some metallic cations was
studied by model-based analysis. For determination of stability constant, hard-modelling strategy was applied to UV-Visible
spectroscopy data obtained from monitoring the reaction between BPTP and metal ions M(II) (M= Cu,/Co, Ni). In this way, the
concentration profiles of each species and the corresponding stability constants of the reaction were obtained.
Reference
[1] X. He, J.J. Liu, H.M. Guo, M. Shao, M.X. Li, Polyhedron 29 (2010) 1062.
[2] K. Liu, X. Zhu, J. Wang, B. Li, Y. Zhang, Inorg. Chem. Commun. 13 (2010) 976.
[3] Q.G. Zhai, M.C. Hu, Y. Wang, W.J. Ji, S.N. Li, Y.C. Jiang, Inorg. Chem. Commu. 12 (2009) 286.
[4] J.C. Chen, A.J. Zhou, S. Hu, M.L. Tong, Y.X. Tong, J. Mol. Struct. 794 (2006) 225.
[5] M.H. Klingele, S. Brooker, Inorg. Chem. Commun.357 ( 2004) 1598.
Determination of stability constants of a new bis1,2,4-triazole ligand for complexation with cobalt(II) and copper(II)
Abbas Nikoo a , Yaser Nikzad a , Reza E. Sabzi a,b, * , Mortaza Bahram a Karim Akbari a
a
Department of Chemistry, Faculty of science, Urmia University, I.R. Iran
b
Institute of Biotechnology, Urmia University, Urmia, I.R. Iran
Currently, triazole ligands and their derivatives, known for their versatile coordination ability and wide applications as
multidentate bridging ligands, are of considerable interest in constructing coordination polymers [1–5]. In this work, the
complexation properties of a new 1,2,4-triazole ligand, 1,3-Bis [5-(2-hydroxyphenyl)-4-phenyl-4H-1,2,4-triazole-3-yl-thio]
propane, (BHTP) towards some transition metal ions M(II) (M= Co, Cu and Ni) in acetonitrile as a solvent is reported. For this
purpose, hard-modelling strategy was applied to UV-Visible spectroscopy data obtained from monitoring the reaction between
BHTP and metal ions M(II) (M= Co, Cu and Ni). In this way, the concentration profiles of each species and the corresponding
stability constants of the reaction were obtained. The stability constants of complexes are always defined with their free metal,
free ligand and other forms of complexes. These constants are influenced by different parameters such as the type of metal,
ligand, counter ion or solvent. In this paper, these parameters were studied.
According to model-based analysis, the equilibrium constant for M (M= Co and Cu and Ni) as ML and ML2 was determined.
The equilibrium constant of the ML and ML2 complex for M= Co and Cu and Ni was calculated and were 6.45, 1.39 ×109 for
M=Co and 1.36 ×104, 1.94 ×108 for M=Cu and Ni respectively.
Reference
[1] W. Ouellette, A.V. Prosvirin, K.R. Dunbar, B. Hudson, J. Zubieta, Inorg. Chem. 45 (2006) 9346.
[٢] J.P. Zhang, Y.Y. Lin, X.C. Huang, X.M. Chen, Dalton Trans. (2005) 3681.
[٣] H.J. Chen, Z.W. Mao, S. Gao, X.M. Chen, Chem. Commun. (2001) 2320.
[٤] Y. Gong, T.F. Liu, W. Tang, F.J. Wu, W.L. Gao, C.W. Hu, J. Solid State Chem. 180 (2007) 1476.
[٥] H. Park, G. Krigsfeld, S.J. Teat, J.B. Parise, Cryst. Growth 7 (2007) 1343.
The effect of preparation condition on morphology of anodic alumina oxide (AAO) membrane as a template for
construction of nanosensors
Maryam Brari a, Reza E. Sabzi a,b, *, Ali Shahravi a, Roghieh Bargshadi a , asgar razmizadeh a
a
Department of Chemistry, Faculty of science, Urmia University, I.R. Iran
b
Institute of Biotechnology, Urmia University, Urmia, I.R. Iran
Electrochemical anodization technology has long been used as a surface finishing method for various industrial metals, e.g.,
corrosion protection by the formation of oxide film layers on metal surfaces or coloration of a metal by impinging dye into the
porous oxide structure. Recently, anodized porous structures have been widely used as a template for the fabrication of
nanostructures such as quantum dots, nanowires, nanotubes, nanorods, etc. [1-4]. In this study we prepared AAO in different
condition, for this purpose different electrolyte and different voltage was applied. The geometry of the pore structure, such as
interpore distance, pore density, and pore shape, as well as the ordering characteristic, is strongly governed by the electric field at
the metal/metal oxide interface, the electrolyte type, the electrolyte concentration at the metal oxide/electrolyte interface, and the
temperature at the metal/metal oxide interface. Four kinds of acid solutions are used for the anodization of the alumina
membranes: sulfuric, oxalic, phosphoric and acetic acid solutions. The sulfuric acid solution is suitable for the preparation of
alumina membranes with small pores. The oxalic acid solution is suitable for the preparation of alumina membranes with
medium-sized pores while the phosphoric acid solution is used for the preparation of large-pore membranes.
Reference
[1] R.E. Sabzi, K. Kant, D. Losic , Electrochim. Acta 55 (2010) 1829.
[2] K. Kant, R.E. Sabzi, D. Losic, Int. J. Nanosci. 2011 Accepted.
[3] Y. Lei, W. Cai, G. Wilde, Prog. Mater. Sci. 52 (2007) 465.
[4] T. Yanagishita, R. Fujimura, K. Nishio, H. Masuda, Langmuir 26 (2010) 1516.
Preconcentration and Spectrophotometric determination of Amoxicillin with using modified magnetic-multi wall carbon
nanotube
Tayyebeh Madrakian*, Abbas Afkhami, Mazaher Ahmadi, Massoumeh Mohammadnejad
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, IRAN
At this work, we propose a novel method for spectrophotometric determination of amoxicillin on the formation of colored azo
derivative of amoxicillin with p-nitroaniline [1], after preconcentration with modified magnetic multi-wall carbon nanotubes.
Magnetic multi-wall carbon nanotubes modified with dibenzo-18-crown-6 [2] for selective preconcentration of amoxicillin in
presence of other species, and then amoxicillin treated with p-nitroaniline to formation of colored azo derivative of amoxicillin.
The Azo-amoxicillin derivate can be used to the spectrophotometric determination of amoxicillin by spectrophotometric method
after preconcentration with modified magnetic multi wall carbon nanotube. The proposed method is found to be simpler and
more sensitive than any reported methods on amoxicillin. The statistical parameters and the recovery study data clearly indicate
the reproducibility and accuracy of the method. The method can be applied to the accurate determination of amoxicillin in
pharmaceutical preparations.
Reference
[1] Ahmed O. Alnajjar , Mohamed E. El-Zaria, Synthesis and characterization of novel azo-morphine derivatives for possible use in abused drugs analysis,
European J. Med. Chem, 43 (2008) 357-363.
[2] L. Minati , G. Speranza , S. Torrengo , L. Toniutti , C. Migliaresi , D. Maniglio , M. Ferrari ,
A. Chiasera , Characterization of thiol-functionalized carbon
nanotubes on gold surfaces, Surface Science 604 (2010) 1414–1419.
Design of an optical sensor for aluminum determination based on immobilization of Eriochrome Cyanine R on a
triacetylcellulose membrane in real samples
H.Khajehsharifi*, A. Solhjoo, H. Montaseri
Khajeh_h@yahoo.com
Department of Chemistry, Faculty of Sciences Yasouj University, Yasouj, 74731, Iran
The optodes have gained notable practical reliability and can be considerd as an inexpensive and alternative to certain
conventional analytical methods [1]. Our approach is design an optode for determination of Al (ш) by immobilised Eriochorome
Cyanine R (ECR) on triacetylcellulose membrane as a reagent phase. The effective immobilization of ECR is performed using
the formation of an ion pair between ECR and methyltrioctylammonium chloride by a simple approach. All chemicals were
supplied from Merck. The buffer solution pH = 6.0 of ammonia – acetic acid was used. Measuring electronic absorption was
done by a spectrophotometer V – Jasco530, and for adjusting pH, pH meter Metrohm was used. The transparent triacetylcellulose
membranes were produced from waste photographic membrane taps were treated with commercial sodium hypochlorite. Then,
for preparation the membrane, dry membrane was placed in the solution containing ECR, methyltrioctylammonium chloride and
ethylenediamine. Immobilized ECR - methyltrioctylammonium chloride ion pair on a triacetylcellulose membrane provides a
good reagent phase for the development of a sensitive, regenerable and reproducible optical Al (III) sensor. The membrane
responded to Al (III) ions by reversibly changing the color from pink to blue. The linear range of the optode was 3.22 × 10-8 to
3.19 × 10-5M for Al (III) with a limit of detection of 1.2× 10 -8 M at a wavelength of 535 nm.The response time of the optode was
about 16 min, depending on the concentration of Al (III). The optode was successfully applied for the determination of Al (III) in
drinking water and Al–Mg syrup.
Reference
[1] S. Ahuja, N. Jespersen, Comprehensive Analytical Chemistry: Modern Instrumental Analysis, 47, Elsevier Science, 2006 (Chapter 20a).
Multivariate Analysis Applied to the Simultaneous Spectrophotometric Determination of Caffeic acid, Ferulic acid and
Chlorogenic acid in real samples
H. Khajesharifi1*, F. Kariman2, M. Sadeghi1
Department of Chemistry, Yasouj University, Yasouj
2
Department of Chemistry, Islamic Azad University, Firuzabad
Email:khajeh_h@yahoo.com
1
Due to biological activities of Caffeic acid (CA), Ferulic acid (FA) and Chlorogenic acid (CG) could be a good lead compound
for new drug development. So, the simultaneous determination of three analytes with similar structure is needed. Also, reports on
the simultaneous analysis of CA, FA, and CG in biological samples are scarce by spectrometry [1-5].The use of multivariate
calibration for the simultaneous determination of CA, FA and CG is described. Thus, a simple, rapid and inexpensive method for
the simultaneous determination of these anti-oxidants was researched and developed with the aid of chemometrics methods
comparing the principal component regression (PCR) and partial least squares (PLS) models. Although the components show an
important degree of spectral overlap, they have been simultaneously determined with high accuracy and precision, rapidly and
with no need of nonaqueous solvents for dissolving the samples. It is possible to obtain a model adjusted to the concentration
values of the mixtures used in the calibration range. UV-spectra were collected in the 200–350 nm range.The standard curves
were found to be linear over the concentration ranges of 0.1-5.00 μg/mL for CA, FA and CG. The PRESS for CA, FA and CG
with PLS were 0.735,0.525 and,0.9162 that, those NPC were 4 , 5,and 3 but in PCR model the PRESS were 2.7902 , 2.4827
,4.057 and NPC were 6 , 8 , 5,respectively. This procedure allows the simultaneous determination of anti-oxidant in synthetic and
real samples.
Reference
[1] S. Shahrzad, I. Bitsch, J. Chromatogr.A, 1996, 741, 223.
[2] É. Müller Risso, R.. G. Péres, J. Amaya-Farfan, Food Chem., 2007, 105, 1578.
[3] V.L. Lanchote, W.C. Ping, S.R.C.J. Santos, Ther. Drug Monit. 19 (1997) 705–710.
[4] W. Martindale, The Extra Pharmacopeia, 30th edn., The Pharmaceutical Press, London, 1993.
[5] C.S.P. Sastry, T.E. Divakar, U.V. Prasad, Indian J. Pharm. Sci. 1985, 47, 45.
Synthesis and characterization of self-ordered TiO2 nanotubes on the titanium implant surfaces
F. Kheiri a, b*, R.E. Sabzi a, b, E. Jannatdoust c, M.B. Hoseinzadeh d
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
b
Institute of Biotechnology, Urmia University, Urmia, Iran
c
Faculty of Chemical Engraining, Urmia University of Technology, Urmia, Iran
d
Atra Orthoped Urmia Medical Instruments Co, Urmia, Iran
a
Metal anodization is one of the most commonly developed surface treatment techniques, used in a variety of applications [1, 2].
With metal anodization the potential difference across the anodic film may be varied at all, whereas in other methods the ion
concentration gradient and the potential across the film are controlled by the system thermodynamics [3]. As an effective
fabrication technology, the electrochemical anodization process is useful because of its low cost, large area fabrication, good
mechanical adhesion, and electrical conductivity due to the nanotubes being directly connected to the substrate, while the limited
thickness of these anodic TiO2 nanotubes must be adjusted by controlling the anodic conditions, such as the applied voltage,
electrolyte composition, the pH of the electrolyte, duration, and magnetic agitation [4]. The composition of the electrolyte is an
important factor during anodization. In the present work, the structural and morphological features of self-aligned titanium oxide
nanotube arrays grown by electrochemical anodization in variation of the anodization voltage with different electrolyte such as
H2SO4/HF-based, NaHSO4/KF-based, NaF/Na2SO4-based, and organic-based electrolytes. In this study, self-ordered TiO2
nanotubes with a high aspect ratio and a length of 2 m were formed in a neutral aqueous solution of NH4F and (NH4)2SO4 on
the titanium implant surfaces. The authors suggested that controlling the pH at both the tip and bottom layer of the tubes is
important to grow longer TiO2 nanotubes.
Reference
[1] K. Nageh, A. Allam, A. Craig. Solar Energy Materials & Solar Cells. 92 (2008) 1468.
[2] K.C. Popat, M. Eltgroth, T.J. LaTempa, C.A. Grimes, T.A. Desai, Small. 3 (2007) 1878.
[3] O. Kubaschewski, B.E. Hopkins, Oxidation of Metals and Alloys, Butterworth, London, 1953.
[4] S. H. Kang, J.Y. Kim, H. S. Kim. J. Indus and Eng Chem. 14 (2008) 52.
Prediction of dermal penetration rate of industrial chemicals: criteria for skin notation
Hanieh Malekzadeh*, Mohammad H. Fatemi
Department of Chemistry, Faculty of Chemistry, Mazandaran University, Babolsar, IRAN
hanieh.malekzadeh@gmail.com
A dermal penetration rate (flux), of 132 chemicals, is suggested as an index of the dermal absorption potential of industrial
chemicals. In this study, a quantitative structure – property relationship technique has been used for the prediction of dermal
penetration rate by an artificial neural network (ANN) [1, 2]. The best selected descriptors that appears in the model were
calculated by using DRAGON [3] and CODESSA [4] software which are: Number of N atoms, Surface weighted charged partial
negative charged surface area (WNSA3), Difference between partial positively and negatively charged surface areas (DPSA1),
Radial distribution function 4.0 / weighted by atomic Sanderson electronegativities (RDF040e), Molecular electrotopological
variation (DELS), 2th component symmetry directional WHIM index / weighted by atomic Sanderson electronegativities (G2e).
These descriptors were used as inputs for a generated artificial neural network. This network were trained using back-propagation
algorithm and evaluated by the cross-validation method to test the prediction ability of generated model. The results obtained by
ANN was compared with the experimental values as well as with these obtained using the multiple linear regression technique.
The obtained coefficient of multiple determination (R) were 0.932, 0.927 and 0.920 and standard error (SE) were 0.319 and 0.244
and 0.246 for the training and internal and external test sets in MLR model, respectively.
The ANN obtained model had the statistical parameters of R=0.965, SE=0.224 and R=0.938, SE=0.214 and R=0.944, SE=0.238
for training, internal and external test sets respectively. Comparison of these results shows the superiority of the artificial neural
network models for prediction of dermal penetration rate over MLR model. The reliability of ANN model was evaluated by using
leave-many-out cross-validation method (Q2=0.862 and SPRESS=0.305) as well as by y-scrambling which reveals the reliability
of this model.
Reference
[1] Beal, M. T.; Hagan, H. B.; Demuth, M. Neural Network Design, PWS, Boston MA, 1996; pp 75-92.
[2] Bose, N. K.; Liang, P. Neural Network Fundamentals, McGraw-Hill, New York, 1996; pp 241-250.
[3] Todeschini, R.; Consonni, V. Handbook of Molecular Descriptors; Wiley-VCH: Weinheim, Germany, 2000.
[4] Katritzky, A. R.; Lobanov, V. S.; Karelson, M. Comprehensive Descriptors For Structural
QSRR modeling of gas chromatographic retention index of some amino acids and carboxilic acids
Maryam Elyasi*, Mohammad Hossein Fatemi
Laboratory of chemometrics, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
E-mail: maryamelyasi85@yahoo.com
In this work quantitative structure-retention relationship (QSRR) approaches [1,3] were applied for modeling and prediction of
the retention index of some amino acids (AAs) and carboxylic acids (CAs) in clinical monitoring and biochemical diagnosis of
inherited metabolic disorders (IMDs) such as phenylketonuria, maple syrup urine disease, methylmalonic aciduria or isovaleric
aciduria descriptors that were used to encode structural featurs of moleculs in data set were calculated by using a Dragon
software. The genetic algorithm (GA) and stepwise multiple linear regression methods were used to select descriptors [4,5]. Then
support vector machine (SVM), artificial neural network (ANN), and multiple linear regression (MLR) utilized to construct the
nonlinear and linear QSRR models. The obtained results using this techniques revealed that the GA-ANN model was much better
than other models.
The average relative absolute error of GA-ANN models for training, internal and external are; 0.039, 0.039 and 0.080 and the
correlation coefficients are 0.980, 0.980 and 0.934 respectively. Also the obtained statistical parameters of cross-validation test
on GA-ANN model obtained the Q2 =0.943 and SPRESS = 152.16, which revealed the reliability of this model.
Reference
[1] M. Jalali-Heravi, M.H. Fatemi, J. Chromatogr. A 915 (2001) 177.
[2] M.H. Fatemi, J. chromatogr. A 955 (2002) 273.
[3] M.H. Fatemi, H. Shamseddin, J. Sep. Sci 32 (2009) 3395.
[4] E. Pourbasheer, S. Riahi, M.R. Ganjali, P. norouzi, European journal of Medicinal Chemistry 44 (2009) 5023.
[5] Q. Jun, S. Chang-Hong, W. Jia Procedia Environmental Sciences 2 (2010) 1429.
Biosorption of Heavy Metals from Aqueous Solutions by Fruiting Body of Agaricus Bisporus
a
a
Ayasan Rafipour, aMehrdad Forough, bKhalil Farhadi
Department of Chemistry, Faculty of Science, Payame Noor University, Khoy, Iran
b
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
Today, heavy metal pollution is one of the most important environmental problems. Heavy metals as a kind of resource are
becoming shortage and also bring about serious environmental pollutions treating human health and ecosystem. Metals are nonbiodegradable and their presence in streams and lakes lead to bioaccumulation [1]. The use of fungi for bioremediation of
wastewater contaminated by heavy metals may be more advantageous than other biosorbents fruiting bodies of macrofung:
(mushrooms) are considered to be ideal material as biosorbents. It has been demonstrated that many Agaric fungal species exhibit
high biosorptive potentials [2]. In this study, dried and humid fruiting bodies of A.Bisporus were examined as cost-effective
biosorbent in treatment of heavy metals (Cd+2, Cu+2, Pb+2, Zn+2, Fe+3, Ni+2 and Co+2) in aqueous solution. The used adsorbent
showed the highest capacity to adsorb the seven metals in the multi-metal solution. The influence of pH, contact time, adsorbent
dosage, agitation speed on the selectivity and sensitivity of the removal process was investigated. The adsorption of studied
heavy metals increased with increased adsorbent dosage and agitation speed and reached maximum uptake at 5g/L and 100rpm at
pH=5. The equilibrium time was found to follow after 30 min. Langmuir and Freundlich and Temkin adsorption isotherms were
studied. Langmuir isotherm model exhibited better fit to the sorption data of Pb(II), Cd(II), Co(II) and Cu(II) cations than the
Freundlich and Temkin isotherm models, and in about Fe(III), Ni(II) and Zn(II) Freundlich isotherm model has best regression in
compared with other studied isotherm models. Temkin model wasn’t fitted with studied cations well. The pseudo-second-order
adsorption model fitted the experimental data very well. Thermodynamic studies confirmed that process was spontaneous and
endothermic [3].
Reference
[1]. A.K.Bhattacharya, S.K.Das. Chemical engineering journal 123 (2006) 43-51.
[2]. Collin-Hansen C, Pedersen SA, Andersen RA, Steinnes E, J.Mycologia 99 (2007)161-174.
[3]. R. Vimala, Nilanjana Das. Journal of Hazardous Materials 168 (2009) 376–382.
Biosorption of Heavy Metals from Aqueous Solutions by Core Layer of Sea Buckthorn
a
a
Aysan Rafipour, aMehrdad Forough, bKhalil Farhadi
Department of Chemistry, Faculty of Science, Payame Noor University, Khoy, Iran
b
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
Heavy metals as a kind of resource are becoming shortage and also bring about serious environmental pollutions treating human
health and ecosystem. Metals are non-biodegradable and their presence in streams and lakes lead to bioaccumulation [1]. In
recent years, applying biotechnology in controlling and removing metal pollution has been paid much attention, and gradually
becomes hot topic in the field of metal pollution control because of its potential application. Alternative process is biosorption,
which utilizes various certain natural materials of biological [2]. In this study, dried and humid core layer of sea buckthorn was
examined as cost-effective biosorbent in treatment of heavy metals (Cd+2, Cu+2, Pb+2, Zn+2, Fe+3, Ni+2 and Co+2) in aqueous
solution. The used adsorbent showed the highest capacity to adsorb the seven metals in the multi-metal solution. The influence of
pH, contact time and adsorbent dosage on the selectivity and sensitivity of the removal process was investigated. The adsorption
of studied heavy metals increased with increased adsorbent dosage and agitation speed and reached maximum uptake at 5g/L and
100rpm at pH=5. The equilibrium time was found to follow after 30 min. Langmuir and Freundlich and Temkin adsorption
isotherms were studied [3]. Langmuir isotherm model exhibited better fit to the sorption data of Pb(II), Cd(II), Ni(II) and Cu(II)
cations than the Freundlich and Temkin isotherm models, and in about Fe(III), Co(II) and Zn(II) Freundlich isotherm model has
best regression in compared with other studied isotherm models. Temkin model wasn’t fitted with studied cations well. The
pseudo first-order and pseudo second-second order were investigated as kinetic models [4]. Compared with pseudo first-order
model, the pseudo second-order model described the adsorption kinetics much better, indicating a two-step biosorption process.
The present study confirmed that Core Layer of Sea Buckthorn should be useful for the treatment of wastewater containing Cd+2,
Cu+2, Pb+2, Zn+2, Fe+3, Ni+2 and Co+2.
Reference
[1]. A.K.Bhattacharya, S.K.Daschemical engineering journal; 123 (2006) 43-51.
[2]. Jianlong Wang, Can Chem. A review biothechnology advances; 27 (2009) 195-226.
[3]. R. Vimala, Nilanjana Das. A comparative study. Journal of Hazardous Materials 168 (2009) 376–382.
[4]. Liu Y,Hui Xu. Biochem Eng 35 (2007) 174-182.
Trace analysis of bisphenol A in water samples by homogeneous liquid phase microextraction coupled with high
performance liquid chromatography-diode array detection
Parvin Haji Koohkamara, Ramin Maleki *b and Khalil Farhadia
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran.
b
Research Department of Chromatography, Iranian Academic Center for Education, Culture & Research (ACECR), Urmia Branch, Urmia,
Iran*Corresponding author, Fax: 441-2584351
E-mail: malekichem@gmail.com
a
Bisphenol A {2,2-di(p-hydroxyphenyl)propane, BPA} is used as an intermediate in the production of polycarbonates, epoxy
resins, polysulphones, unsaturated polyesters, and polyacrylate resins [1,2]. BPA discharged in to the environment during
manufacturing process and degradation of plastics. Also it migrate from polycarbonate bottles into baby foods. In recent years it
has been shown to produce damage to testes, kidneys, liver, spleen, pancreas, and lungs [3]. Due to the vital importance of BPA
analysis several chromatographic methods have been developed for its quantitative determination [4-6]. In this study a simple
and sensitive method based on homogenous liquid phase microextraction in conjunction with high performance liquid
chromatography-diode array detection has been developed for the quantitative analysis of BPA in water samples. The effect of
extraction solvent (nature and volume), pH of sample solution, ionic strength, extraction time and extraction temperature were
investigated. Under the optimal conditions the linear dynamic range of BPA was from 0.1 to 25.0 µg L-1 with a correlation
coefficient of 0.9999 and a detection limit of 0.06 µg L-1. The relative standard deviation was less than %5.4 (n=3).
Reference
[1]. F. S. Vom Saal,.; Cooke, P. S.; Buchanan, D. L.; Palanza, P.; Thayer, K. A.; Nagel, S. C.; Parmigiani, S.; Welshons, W. V. Tox. Ind. Health 1 (1998) 239.
[2]. T. Yoshida, M. Horie, Y. Hoshino, and H. Nakazawa, Food Addit. Contam., 18, (2001) 69.
[3]. R. L. Gibson, Environment California Research & Policy Center. (2007).
[4]. J. H. Kang, F. Kondo, Y. Katayama, Anal. Chim. Acta 555 (2006) 114.
[5]. Y. Hu, Y. Zheng, F. Zhu, G. Li, J. Chromatogr. A 1148 (2007) 16.
[6]. A. Ballesteros-Gomez et al. / J. Chromatogr. A 1216 (2009) 449.
Layered Double Hydroxide Coating Film as Solid Phase Microextraction Fiber
Hatam Amanzadeha, Amir Abbas Matin*b, Pourya Biparvab , Khalil Farhadia
a
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
b
Research Department of Chromatography, Iranian Academic Center for Education, Culture & Research (ACECR),
Urmia, Iran
Layered double hydroxides (LDHs) are inorganic materials consisting of the hydroxide layers formed with at least two metallic
elements and anions between the layers. Catalytic [1], adsorption [2] and ion exchange [3] properties of LDHs were studied
widely. Recently analytical applications of LDHs as adsorbents for solid phase extraction were studied too [4]. In this study,
layered double hydroxide thin film coating prepared via sol-gel method [5] was introduced as new SPME fiber. As a model
analyte, solid phase microextration of valproic acid (antiepileptic drug) from headspace of sample solution using proposed fiber
was investigated. After optimization of all effective parameters (extraction time: 15 min, extraction temperature: 50 °C,
desorption temperature: 250 °C, desorption time: 2 min, concentration of salt (NaCl): 5 M, agititation rate: 700 rpm, pH: 1.5)
Microextraction of target analyte from pharmaceutical formulations (tablet and syrup) and human serum was carried out.
Quantitative characteristics of the proposed method including linear dynamic range (0.2-200 mg.L-1), LOD (0.07 mg.L-1),
correlation coefficient (0.999) made it suitable for assay of valproic acid in formulations and biological fluids.
Reference
[1] J.L. Shumaker, C. Crofcheck, S.A. Tackett, E. Santillan-Jimenez, T. Morgan, Y. Ji, M. Crocker, T.J. Toops, Appl. Catal. B: Environ. 82 (2008) 120
[2] S. Mandal, S. Mayadevi, Appl. Clay Sci. 40 (2008) 54–62
[3] A.V. Radha, P. Vishnu Kamath, C. Shivakumara, Solid State Sci. 7 (2005) 1180–1187
[4] H. Abdolmohammad-Zadeh, Z. Rezvani, G.H. Sadeghi, E. Zorufi, Anal. Chim. Acta. 685 (2011) 212
[5] K. Katagiri, Y. Goto, M.Nozawa, K. Koumoto, J. Ceramic Soc. Japan 117 (2009) 356–358
Nanocomposite film based on multiwalled carbon nanotube as solid phase microextraction fiber
a
Mohammad Gheshlaghi-Ghadima,b, Amir Abbas Matina,* , Pourya Biparvaa, , Khalil Farhadib
Research Department of Chromatography, Iranian Academic Center for Education, Culture & Research, Urmia, Iran
b
Department of Chemistry, Urmia University, Urmia, Iran
Solid phase microextraction (SPME) as a solvent free sample preparation technique was introduced by Pawliszyn and coworkers
[1]. Design and preparation of novel coatings for use as SPME fiber is one of the important research fields of analytical chemists.
Carbon based fibers have good ability for extraction of organic compounds [2]. In recent years application of carbon nanotubes
(CNTs) as coating material of SPME fibers have been increased [3, 4]. In this study a nanocomposite thin film based on
multiwalled carbon nanaotubes (MWCNTs) and polyvinyl chloride (PVC) coated on stainless steel wire was prepared and its
application as solid phase microextraction fiber was investigated. For this purpose, microextraction conditions of complex
mixture of aromatic (BTEX) and aliphatic hydrocarbons (C5-C34) from oil contaminated environmental water samples using
proposed fiber were optimized. Analytical merits of the method under optimized conditions show that ultra trace concentrations
(ng L-1) of studied compounds are available for determination by capillary gas chromatography.
Reference
[1] C. L. Arthur, J. Pawliszyn, Anal. Chem. 62 (1990) 2145.
[2] M. A. Farajzadeh, A. A. Matin, Anal. Sci. 18 (2002) 77.
[3] H. Liu, J. Li, X. Liu, S. Jiang, Talanta, 78 (2009) 929.
[4] M. Valcarcel, S. Cardenas, B. M. Simonet, Y. Moliner-Martinez, R. Lucena, Trends Anal. Chem, 27 (2008) 34.
Synthesis of nanostructure SBA-15 using rice husk Ash as silica sources
Naser Azizi, Elham Chiani*
Department of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
E-mail: azizi@umz.ac.ir
Rice husk ash (RHA) which is known to be an environment waste was used as a source of silica to synthesize SBA-15 zeolite,
which Si02 can be extracted from rice husk Ash by a suitable alkali solution [1]. SBA-15 is a mesoporous SiO2 with a hexagonal
arrangement of channels with diameters in the range of 2–30 nm. It is expected to be useful in the synthesis of ultrafine, nanorod
arrays, protein separations, and highly efficient catalyst even just in its powder form [2-4]. Pure SBA-15 has been prepared by
direct synthesis non hydrothermal method, in which the rice husk ash (RHA) is used as silicon source and triblock copolymer
(P123) as a structure directing agent and phosphoric acid were used in the synthesis. X-ray fluorescence (XRF) measurements
showed that rice husk ash contained more than 90% of amorphous silica and this raw material is suitable for the synthesis of the
zeolites. Characterization carried out by powder X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron
microscopy (SEM), was to evaluate the efficiency of this non hydrothermal method. The diameter of crystal particles was
calculated from Deby-Scherrer equation which was approximately 21 nm. The micrographs and XRD of the raw material and
products revealed the successful conversion of the amorphous form and XRD of silica to the crystalline form of the zeolites.
Thus, rice husk commonly regarded as agro-waste can be used as a source of silica in the form of RHA to produce the highly
pure SBA of zeolites.
Reference
[1] Kalapathy, U., Proctor, A., Shultz J Bioresource Technol. 73, 257-262, 2000.
[2] Han, Y. J., Kim, J. M., Stucky, G. D., Chem. Mater. 12, 2068-2069,2 000.
[3] Ohtsuka, Y., Arai, T., Takasaki, S., Tsubouchi, N., Energy Fuels. 17, 804-809,2003.
[4] Gao, F., Lu, Q. Y., Liu, X. Y., Yan, Y. S., Zhao, D. Y., Nano Lett. 1, 743-748, 2001.
Simultaneous Determination of Ascorbic Acid, Dopamine, and Uric Acid by Differential Pulse Voltammetry using Tiron
Modified Glassy Carbon Electrode
M. Taei, M. Jamshidi
Chemistry, Department, Payame Noor University,19395-4697 Tehran,I.R. of IRAN.
E-mail: m_taei57@yahoo.com
A highly selective voltammetric method was developed for the simultaneous determination of ascorbic acid (AA), dopamine
(DA), and uric acid (UA) using Tiron polymer film modified on glassy carbon electrode. The modified electrode separated the
anodic oxidation peaks potential of AA, DA and UA with a well-defined peak separation in the present of each other to measure
AA, DA and UA individually or simultaneously without any intermolecular effect. The calibration curves were obtained over the
range of 4.0-792.0 μmol/L AA, 0.2-45.8 μmol/L DA, and 0.06-166.0 μmol/L UA. Detection limits of 1.79 μmol/L AA, 0.07
μmol/L DA, and 0.021 μmol/L UA were obtained at pH 3.0. The interference of potential interfering substances on the
determination of AA, DA and UA were studied, and the results confirm the selectivity of the method. The modified electrode was
used for the determination of AA, DA, and UA simultaneously in real samples such as drugs, urine, and synthesis samples, with
satisfactory results.
Colorimetric detection of S2O42-using CTAB functionalized gold nanoparticles
Maryam Saadat*1 , Khalil Farhadi2 Alireza Salehi Sadaghiani1
1) Payamnour University, Urmia Branch, Urmia, Iran
2) Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
Sodium dithionite is widely used as a reductant in industry. It finds use as a bleaching agent in the textile and paper industries, in
the dyeing of cellulose fibres [1], in the manufacturing of various chemicals, and as a biochemical reductant [2]. Dyeing of cotton
fabric with anthraquinone vat dyes like indanthrenes or indigo occurs in an alkaline sodium dithionite solution through a
reduction reaction [2]. In the methods reported in the literature, dithionite has been determined by iodimetric [3,4],
potentiometric [5], and spectrophotometric [5] titrations, Raman spectroscopy [6], spectrophotometry [2] and ionchromatography [7]. In the present work, a facile, cost-effective colorimetric detection method for S2O42-has been developed by
using cetyltribuytylammonium bromide (CTAB) functionalized gold nanoparticles (CTAB-GNPs) in the presence of 1 M NaCl.
The sensitivity and selectivity of detection was investigated in detail. The S2O42- could be detected by colorimetric response of
GNPs that could be monitored by a UV-vis spectrophotometer or even naked eyes, with detection limit of 0.02mM. The CTAB-
GNPs bound by S2O42- showed excellent selectivity compared to other anions(S2O32-,SO42-,SO32-,NO3-,NO2- ,C2O2H32-,CI-,Br),which lead to prominent color change. This provided a simple and effective colorimetric sensor for detection of S 2O42- without
using enzyme or DNA. The proposed method has been successfully applied for the assay of dithionite in water samples.
Reference
[1] C.W.J. Scaife, R.G. Wilkins, Inorg. Chem. 19 (1980) 3244.
[2] U. Nahr, W. von Bistram, Textil Praxis Int. 46 (1991) 978.
[3] J.P. Danehy, C.W. Zubritzsky, Anal. Chem. 46 (1974) 391.
[4] R. Wollak, Fresenius’ Z. Anal. Chem. 80 (1930) 1.
[5] A. Kurtenacker, Analytische Chemie der Sauerstoffsäuren des
Schwefels, Enke-Verlag, Stuttgart, 1938, p. 166.
[6] B. Meyer, M. Ospina, L.P. Peter, Anal. Chim. Acta 117 (1980).
[7] R. Steudel, V. Münchow, J. Chromatogr. A 623 (1992) 174.
Design a novel method for identification and quantitative determination of alkanolamines degradation in amine
sweetening units
R. Zare-Dorabei*
Department of Chemistry, Iran University of Science and Technology, Tehran, Iran
Most sour gas processing facilities use chemical absorption using alkanolamines to separate H2S and CO2 from the raw gas
through chemical absorption using alkanolamines. The prime alkanolamines are monoethanolamine (MEA), diethanolamine
(DEA), methyldiethanolamine (MDEA), diisopropanolamine (DIPA), and diglycolamine (DGA). Normally the amine processes
are cycles of absorption and desorption in order to permit the use of the absorbent. Due to the closed loop nature of these
processes, non-regenerable contaminants tend to accumulate and can cause major reduction in efficiencies and operational
problems. Two major problems represent a significant threat to an amine gas treating plant: corrosion and instability of
operation, resulting in unscheduled upsets and outages. In this process, contaminant byproducts called Heat Stable Salts (HSS)
are formed and gradually build up to beyond tolerable limits in the amine circulation loop. Amine plant operational problems,
such as excessive foaming, corrosion and capacity reduction, are often attributed to the accumulation of amine heat stable salts.
These heat stable salts lead to costly maintenance problems such as corrosions, frequent filter replacement, foaming in the
absorber column, absorber tower plugging, heat exchanger fouling and a reduction in the amount of amine available for gas
treatment, thereby reducing the unit’s productivity. In order to prevent the HSS from building up beyond critical limits, amine
plant operators have been making conscious attempts to control impurities, especially HSS. Several analytical methods have been
used for low-level monitoring of HSS in various amine matrices. These methods inductively coupled plasma atomic emission
spectroscopy (ICP-AES), UV-Vis spectrometry determination, fluorimetry, ionic chromatoghraphy (IC) and gas
chromatography- mass spectroscopy(GC-MS). This method was applied to the determination of HSS in amine sweetening units.
Reference
[1] N.C. Saha, S.K. Jain, R.K. Dua, Chromatographia, 10 (1977) 368.
[2] Dupart, M.S., Bacon, T.R., and D.J. Edwards, “Understanding corrosion in alkanolamone gas treating plants”, Hydrocarbon Processing, May (1993) 89-94.
[3] Meisen A., Abedinzadegan M., Abry R.G., and Millard M.G., “Degraded Amine
Solutions; Nature, Problems and Distillative Reclamation”, Proc. 45th Annual Laurance Reid
Gas Conditioning Conference, Norman, Oklahoma, (1996)168-189
[4] M.J. Awry, G.A. Junk, Anal. Chem. 57(1985) 790.
Application of N’-[(2-hydroxyphenyl)methylene]benzohydrazide for preparation of a new optical pH sensor
R. Zare-Dorabei*
Department of Chemistry, Iran University of Science and Technology, Tehran, Iran
Optodes have been actively investigated for their potential in practical uses, such as environmental analysis, clinical analysis, biotechnology and process control. Among all sensors, optical pH sensors have received the most attention because of the
importance of pH measurement in various scientific research and practical applications [1]. Optodes are usually based on acid–
base indicators, which can be adsorbed on the surface of support materials [2], chemically immobilized in an appropriate support
[3] or physically entrapped in polymeric matrices [4]. Optical pH sensors are based on pH dependent change of the absorbance or
luminescence of certain indicator molecules. In this study, we report an optical pH sensor based on immobilization of N’-[(2hydroxyphenyl)methylene]benzohydrazide as a new pH reagent on an optically transparent triacetylcellulose membrane. The
films were treated with a clear solution of a 10 ml N’-[(2-hydroxyphenyl)methylene]benzohydrazide (0.03 % m/m) in ethylene
diamine for 2 min at room temperature. The optode was showed a decreasing absorbance at 385 nm with increasing pH. The
membrane is useful for repetitive and reversible pH measurements in the pH range of 4–8.5. The response of the sensor is
reversible with a response time 10 s and relative standard deviation < 1.52 % for seven measurements.
Reference
[1] Wolfbeis, Anal. Chem. 74 (2002) 2663.
[2] A. Safavi, M. Bagheri, Sens.& Actuators B 90 (2003) 143.
[3] S.J. Glenn, B.M. Gullum, R.B. Nair, D.A. Nivens, C.J. Murphy, Anal. Chim. Acta 448 (2001) 1.
[4] P.T. Sotomayor, I.M. Raimundo Jr, A.J.G. Zarbin, J.J.R. Rohwedder, Sens. Actuators B 74 (2001) 157.
Prediction of Anticonvulsant Activity of Some Benzylacetamide Analogues based on Autocorrelation Descriptors
Amir Najafi*a, Soheil Sobhan Ardakani b
Young Researchers Club, Hamedan Branch, Islamic Azad University, Hamedan, Iran
b
Department of Environment, Islamic Azad University, Hamedan Branch, Hamedan, Iran
E-mail: najafi@iauh.ac.ir, am.najafi@yahoo.com
a
Epilepsy is a common neurological condition, affecting 0.5 to 1% of the population worldwide (45-100 million people) [1]. The
search for antiepileptic compounds with a more selective activity and lower toxicity continues to be an area of investigation in
medicinal chemistry. Quantitative structure–activity relationship research field has been widely developed because of its
powerful ability to predict drug activity [2]. These are mathematical equations relating chemical structure to wide biological
properties. A linear quantitative structure activity relationship model is obtained using Multiple Linear Regression (MLR)
analysis as applied to a series of 49 α-substituted acetamido-N- enzylacetamides derivatives with anticonvulsant activity. For the
selection of the best descriptors, the genetic algorithm (GA) method is utilized [3, 4]. AM1 Semiempirical quantum chemical
calculation method was used to find the optimum 3D geometry of the studied molecules. Two types of molecular descriptors
including the 2DAUTO and GETAWAY descriptors were used to derive a quantitative relation between the anticonvulsant
activity and structural properties. From the results was derived that MATS6e is Moran autocorrelation of lag 6 / weighted by
atomic Sanderson electronegativities, MATS5p is Moran autocorrelation of lag 5 / weighted by atomic polarizabilities and
ATS6e is Broto-Moreau autocorrelation of lag 6 / weighted by atomic Sanderson electronegativities belongs to GETAWAY
descriptors. H7v is H autocorrelation of lag 7 / weighted by atomic van der Waals volumes, HATS2u is leverage-weighted
autocorrelation of lag 2 / unweighted and H5m is H autocorrelation of lag 5 / weighted by atomic masses belongs to GETAWAY
descriptors. The high square of the correlation coefficient R2 (0.900) showed the model was satisfactory. Moreover in order to
confirm a predictive ability of the model, a validation test was performed. The results show close agreement between Predicted
and experimental values, which demonstrates the reliability of the model.
Reference
[1] G.S Bell, J.W. Sander, Seizure 11 (2002) 306-314.
[2] M. Karelson, V. Lobanov, A. Katritzky, Chem. Rev. 96 (1996) 1027-1043.
[3] R. Ghavami, A. Najafi, M. Sajadi, F. Djanati, J. Mol. Graphics Modell. 27 (2008) 105-115.
[4] A. Najafi, S. Sobhan Ardakani, Mol. Simulat. 37 (2011) 72-83.
Chemically modified silica gel with 2-((3silylpropylimino) methyl) phenol (SPIMP) for solid phase extraction and
preconcentration of Fe(III), Pb(II), Cu(II), Ni(II), Co(II) and Zn (II) Ions
K. Mortazavi*
Chemistry Department,Islamic Azad university, Gachsaran Branch, Gachsaran, Iran.
2-((3-silylpropylimino) methyl) phenol chemically bonded silicagel successfully were applied for the enrichment of trace amount
of Fe(III), Pb(II), Cu(II), Ni(II), Co(II) and Zn(II) ion subsequent their determination by FAAS. The influences of the analytical
parameters including pH, amount of ligand and solid phase and type and condition of eluting solution and sample volume on the
metal ions recoveries were investigated. The method has high sorption – preconcentration efficiency even in the presence of
various interfering ions that indicate method selectivity, while the relative standard deviation of the method for recovery for all
ions was found to be less than 3.0%, especially for their determination in real samples. Graphical correlation of various
adsorption isotherm models like, Langmuir,Freundlich,Tempkin and Dubinin–Radushkevich have been carried out. The
adsorption of these metal ions has been found endothermic and feasible in nature and various thermodynamic parameters.The
kinetic studies suggest the process following pseudo second order kinetics.
Multiwalled carbonnanotubes(MMWCNTs)modifed with4-(4-isopropylbenzylideneamino)thiophenol as efficient
adsorbent for extraction and preconcentration of some metal ions in environmental and food samples.
K. Mortazavi*
Chemistry Department, Gachsaran Azad University, Gachsaran Branch, Iran
The present article reports on the application of modified multiwalled carbon nanotubes (MMWCNTs) as a new, sensitive, easily
prepared and stable solid sorbent for simultaneous separation and peconcentration of some metal ions including Cd 2+, Ni2+, Pb2+
and Zn2+ ions from various real samples prior to their measurements by flame atomic absorption spectrometry (FAAS). The
proposed
method
is
based
on
utilization
of
multiwalled
carbon
nanotube
modifed
with4-(4isopropylbenzylideneamino)thiophenol (4,4-IPBATP) as chelating agent reagent. The separation parameters for effective
adsorption of this ions, including effects of pH, amount of ligand and carbon, condition of eluent, concentration of metal ions
were examined. The optimum pH value for the separation of metal ions was 6.0. The detection limit (3SDb/m, n=15) of Cd2+,
Ni2+, Pb2+ and Zn2+ ions was 1.6, 2.4, 5.6 and 1.3 ng mL-1 while respective preconcentration factor for Ni2+, Cd2+ ions was 80
and for Pb2+, Zn2+ ion was 20 and 60 respectively with RSD between 1.8-2.6. The proposed procedure was applied to the analysis
of various real samples.
Development of an efficient procedure for determination of some ion after solid phase extraction using a new Schiff base
loaded on Silver nanoparticle loaded on activated carbon
K. Mortazavi*
Chemistry Department, Gachsaran Azad University, Gachsaran, Iran.
The adsorption properties of nanoparticles loaded on activated carbon reflects their huge surface area and graphene-sheet
structure. That is the reason why they have been used recently for solid-phase extraction applications [1-3]. The Silver
nanoparticle loaded on activated carbon modified with a new Schiff base was used for the sorption of some metal ions from
aqueous solutions. The effect of solution pH, initial metal ions solution concentration, condition and temperature and sorption
time on metal ions removal was studied. The equilibrium sorption isotherms have been analyzed by the linear, Freundlich,
Langmuir, Temkin and Dubinin - Radushekevich models. The Langmuir isotherms have the highest correlation coefficients. The
apparent thermodynamic parameters were calculated and the obtained values support the conclusion that the metal ions molecules
sorbs by entropy-driven, endothermic process. The kinetic of the sorption was analyzed using the pseudo-first order, pseudosecond and intraparticle diffusion order kinetic models. The data showed that the second-order equation was the more
appropriate, which indicate that the intraparticle diffusion is the rate limiting factor. The use of low-cost, easy obtained, high
efficiency and eco-friendly adsorbents has been investigated as an ideal alternative to the current expensive methods of removing
metal ions from wastewater.
Reference
[1] J. Wang, S. B. Hocevar, B. Ogorevc, Electrochem. Commun. 2004, 6, 176.
[2] Y. Cai, G. Jiang, J. Liu, Q. Zhou, Anal. Chem. 2003, 75, 2517.
[3] W. Huang, W. Hu, J. Song, Talanta 2003, 61, 411.
Multiwalled Carbon Nanotubes as efficient adsorbent for removal of Bromothymol Blue
Mehrorang. Ghaedia*, Amin. Hemmati yadkuria, Habibollah. Khajesharifia, Mostafa. Roostaa
a
Chemistry Department, Yasouj University, Yasouj 75914-35, Iran
*E-mail: m_ghaedi@mail.yu.ac.ir; shimi1360@yahoo.com
There are several procedures for removal of dyes from waste materials [1,2]. Adsorption process based on application of an
efficient adsorbent suitable for uptake of a dye molecule from solid/liquid interface has been extensively employed because of
advantages such as high efficiency and low cost [3]. In this technique application of nano scale material with high surface area
significantly enhance the removal percentage with high adsorption capacity [4]. In the present study, a new Multiwalled Carbon
Nanotubes (MWCNTs) was synthesized then this new sorbent were used for removal of Bromothymol blue (BTB) and the
kinetic and equilibrium of adsorption process was investigated and experimental data were analyzed to get a sufficient knowledge
on the mechanism, rate and isotherm of adsorption process [5]. The influence of effective variables such as solution pH, contact
time, initial dye concentration, adsorbent amount and temperature on the adsorption efficiency in batch system was examined.
During all experiment BTB contents were determined by UV-Vis spectrophotometer. A comparison of four kinetic models
including the pseudo-first-order, pseudo-second-order, intra-particle diffusion and Elovich on the adsorption system showed that
the removal process followed the pseudo-second-order kinetic model. Adsorption parameters for the Langmuir, Freundlich and
Tempkin isotherms were determined and the equilibrium data were best described by the Langmuir model with maximum
adsorption capacity of 55.25 mg g-1 of adsorbent. Thermodynamic parameters (Gibb’s free energy, entropy and enthalpy) of
adsorption were calculated according to general procedure to take some information about the on-going adsorption process. It
was seen that the adsorption system is feasible and endothermic nature.
Reference
[1] B.K. Nandi, A. Goswami, M.K. Purkait, J. Hazard. Mater, 161 (2009) 387–395.
[2] T.H. Kim, C. Park, J. Yang, S. Kim, J. Hazard. Mater. 112 (2004) 95–103.
[3] Z. Shen, W. Wang, J. Jia, J. Ye, X. Feng, A. Peng, J. Hazard. Mater. 84 (2001) 107-116.
[4] F.Zheng, D.L. Baldwin, L.S. Fifield, N.C. Anheier, C.L. Aardahl, J.W. Grate, Anal. Chem, 78 (2006) 2442.
[5] W. Hong, W. Hongyu, B. Han, B. Du, J. Lu, Microchim Acta, 166 (2009) 41.
A comparison of PCR and PLS to the Simultaneous Spectrophotometric Determination of Ascorbic Acid, Epinephrine
and Tyrosine in pharmaceutical Formulation and Biological Fluids
H. Khajehsharifi*, A. Solhjoo, H. Montaseri
Department of Chemistry, Faculty of Sciences, Yasouj University, Yasouj, Iran
E-mail: khajeh_h@yahoo.com
The UV-spectrometric analysis of a multicomponent mixture containing Ascorbic acid (AA), Epinephrine (EP) and Tyrosine
(TY) by multivariate calibration methods, such as principal component regression (PCR) and partial least-squares regression
(PLS) was described. Ultraviolet spectra of AA, EP and TY[1-5] are overlapping with each other, so these compounds cannot be
measured in the presence of each other with ordinary method, except before using, initial separation of these compounds
performed [6, 7]. So, it is necessary to develop methods for the simultaneous determination of AA, EP and TY. In this research,
the simultaneous spectrophotometric determination of AA, EP and TY has been proposed. Stock solution of AA, EP and TY is
prepared daily by dissolving them in phosphate buffer solution (pH = 7.0). Measuring electronic absorption was done by a
spectrophotometer V – Jasco570. For adjusting pH, pH meter Metrohm was used. PCR and PLS were modeled using PLSToolbox 2.0 under MATLAB version 7.0. The concentration model is based on absorption spectra in the range of 250-350 nm for
36 different mixtures of AA, EP and TY. The calibration graphs were linear in the ranges of 0.3-35, 0.8 – 72 and 0.7-145
µgmL−1for AA, EP and TY with the detection limit of 0.1, 0.4 and 0.3 µgmL−1, respectively. The root mean square errors of
prediction (RMSEP) was 0.3247, 0.1085, 0.7414 for AA, EP and TY, by PLS and 0.5837, 0.1139, 1.4739 by PCR. PCR and PLS
methods were compared on the basis of statistical parameters. These methods were successfully applied to a commercial
pharmaceutical tablet, injection, human serum, and plasma and urine samples
Reference
[1] A. A. Ensafi, B. Rezaeia, S. Z. Mirahmadi Zarea, M. Taei, Sens. Actuators B, 150 ,321.
[2] H. Nohta, T.Yukizawa, Y. Ohkura, M. Yoshimura, J.Ishida, M. Yamaguchi, Anal. Chim. Acta 1997, 344, 233.
[3] M. P. Llavero, S. Rubio, A.Gomez-Hens, D. Perez Bendito, Anal. Chim. Acta 1990, 229, 27.
[4] P. Canizares, M. D. Luque De Castro, Anal. Chim. Acta 1995, 317, 335.
[5] Y.Guo, J.Yang, J.Wu, A. Du, J. Fluores. 2005, 15, 131.
[6] H. Martens, T. Naes, Multivariate Calibration, John Wiley & Sons Ltd: Chichester, 1989.
[7] H. Martens, M. Martens, Multivariate Analysis of Quality: An Introduction; John Wiley: New York, 2001.
Simultaneous determination of catechol and hydroquinone at ultrathin carbon nanoparticles- chitosan composite
film modified electrode
Mandana Amiria , Shahnaz Ghaffaria,*, Abolfazl Bezaatpourb
Department of Chemistry, Payame Noor University, Ardabil, Iran
b
Department of Chemistry, Mohaghegh Ardabili University, Ardabil, Iran
a,*
Hydroquinone (HQ) and catechol (CA) are two important isomers of phenolic compounds [1]. The simultaneous detection of HQ
and CA is highly desirable due to their coexistence as isomers and highly toxic environmental pollutants in environmental
samples [1]. This study represented a modified electrode for simultaneous sensing of CA and HQ with carbon nanoparticlechitosan (CNP-CH) composite. Voltammetric experiments were performed using a Metrohm Computrace Voltammetric Analyzer
model 797 VA. A stock solution of chitosan (CH) was prepared by dispersing of it in acetic acid. The modified suspension was
prepared by dispersing of some CNP in 1ml of CH solution under sonication, the modified glassy carbon electrode (GCE) was
prepared by casting 10µl of the suspension on GCE surface and letting water evaporate. The electrode characterization was
performed by cyclic voltammetry (CV), electrochemical impedance spectroscopy and atomic force microscopy (AFM). A
voltammetric study of hydroquinone and catechol has been carried out at the surface of glassy carbon electrode modified with
ultrathin carbon nanoparticles-chitosan composite film. The modified electrode shows an excellent electrocatalytic effects on the
oxidation of HQ and CA The effect of pH of the buffered solutions and potential sweep rate on the response of the electrode and
peak separation of HQ and CA was studied. The prepared electrode showed high stability and uniformity in the composite film,
short response time, good reproducibility and an excellent catalytic activity toward the electro-oxidation of these compounds
leading to a significant improvement in sensitivity. Differential pulse voltammetry (DPV) was used for quantitative determination
of HQ and CA in presence of each other. A dynamic linear range for hydroquinone and catechol was obtained in the range of
1.0×10-6-1.0×10-3, 8.0×10-7-1.0×10-3 mol L-1, and the detection limits were estimated to be 3.0 ×10-7, 2.5×10-7 and 1×10-5 mol L-1,
respectively. This electrode was applied for simultaneous determination of HQ and CA in real water samples successfully.
Reference
[1] L. Wang, P. Huang, H. Wang, J. Bai, L. Zhang, Y. Zhao, International Journal of Electrochemical Science 2 (2007) 216-225.
Fabrication and characterization of carbon paste electrode modified with a composite of nanofiber polyaniline decorated
by cobalt nanoparticles: Application in voltammetric study
a,*
Mandana Amiria, Khadijeh Nekoiean*,a
Department of Chemistry, Payame Noor University, Ardabil, Iran
Carbon paste electrode have attracted significant interest during last decade because of low background current, low cost, renew
ability of surface and ease of modification. In this paper, polyaniline is used as modifier due to high conductivity, ease of
synthesis, inexpensive monomer and environmental stability. Magnetic cobalt nanoparticles like other metal nanoparticles have
unique properties such as increasing effective surface and charge transfer kinetics. So, combination of nanostructure polyaniline
and cobalt nanoparticles can improve electrochemical behavior of carbon paste electrode. The modified electrode was applied for
viltammetric determination of cysteine. The Co nanoparticles were produced using a direct reduction method. Cobalt
nanoparticles in the form of powder were studied using different characterization techniques such as X-ray diffraction (XRD).
Polyaniline nanofiber was synthesized chemically. For syntheses of cobalt dopedpolyaniline, Co nanoparticles were weighed (1–
10%, by weight) and dispersed in toluene. This suspension was then mixed with polymer solution get cobalt nanoparticlesimpregnated-polyaniline in the form of powder were studied by using different characterization techniques such as transmittance
electrone microscopy (TEM). The electrode properties are studied by cyclic voltammetry, XRD & TEM methods. The modified
electrode has an excellent performance in electrocatalytic activity, selectivity, sensitivity toward medicines and decrease over
voltage. However, it prepares easy and inexpensive can use for a long time. The modified electrode was applied for voltammetric
study of cystein. The effect of some parameters such as pH and scan rate was studied in voltammetric response. Differential pulse
voltammetry (DPV) was used for quantitative determination of cystein. A dynamic linear range for was obtained in the range of
1.0×10-7-1.0×10-9mol L-1, and the detection limits were estimated to be 1.0 ×10-9.
Reference
[1] Sh. Hatamie, S. D. Dhole, J. Ding, S. N. Kale, Journal of Magnetism and Magnetic Materials, 321 (2009) 2135-2138.
[2] W. Li, Ch. L. Johnson, H. Lin. Wang, Polymer, 45 (2004) 4769-4775
[3] H. Zang, G. Cao, Z. Wang, Y. Yang, Z. Shi, Z. Gu, Electrochemistry Communications, 10 (2008) 1056-1059.
Development of a dispersive liquid–liquid microextraction method for spectrophotometric determination of Penicillin G
Potassium in water samples
P. Gharavi Khiavi, S.A.M. Fathi, M.R. Yaftian*
Phase Equilibria Research Laboratory, Department of Chemistry, Faculty of Science, Zanjan University, P.O. Box 45195-313 Zanjan, Iran.
In recent years a new microextraction technique termed dispersive liquid–liquid microextraction (DLLME) was developed. This
technique is a very simple and rapid method for extraction and pre-concentration of organic compounds from water samples [1].
Penicillins are used well known human medicines for treatment of various bacterial infections of skin, ear, respiratory tract, and
urinary trac and as feed additives to promote growth in animal feed in operations [2]. Penicillin G Potassium (the potassium salt
of penicillin G) is a white crystalline powder, odorless, moderately hygroscopic, soluble in water [3]. In this paper, a novel and
simple method for the determination of Penicillin G Potassium in water samples was developed by using dispersive liquid–liquid
microextraction (DLLME) technique combined with spectrophotometric analysis. The procedure is based on the development of
a color reaction of Penicillin G Potassium with bromothymol blue (BTB) and extraction of the color product. the parameters
influencing the process such as type and volume of extractant and disperser solvent, concentration of BTB, pH and salt effect
were optimized (Table 1). In this method, an appropriate mixture of the extraction solvent and the dispenser solvent is injected
into 3330 of IU/mL Penicillin G Potassium aqueous sample (5 mL) by a syringe, providing a cloudy solution. This cloudy
solution can centrifuged (3000 rpm) and the fine droplets sediment at the bottom of the conical test tube. Determination of the
analyte in the remained phase can be performed by UV-Vis spectrophotometer. The calibration curves were obtained under
optimized conditions. The method was applied successfully in the range 1750-6500 IU/mL. The correlation coefficient (r2) was
0.990. The relative standard deviations (n=7) was 8.1%. The limit of detection (LOD) was obtained 0.1146 IU/mL.
Table 1. Summary of optimized conditions of the process.
Extractant solvent
CCl4
Extractant solvent volume
250 µL
Disperser solvent
Acetone
Disperser solvent Volume
1.25 mL
Concentration of BTB
0.9 µmol
pH
3.0
Salt effect
Reference
[1] M. Rezaee, Y. Assadi, M. R. Milani Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, J. Chromatography. A, 1116 (2006) 1–9
[2] M.F. El-Shahat, N. Burham, S.M. Abdel Azeem, J. Hazardous Materials. 177 (2010) 1054–1060
[3] www.chemicalland21.com
Extraction and determination of common herbicides in aqueous samples using dispersive liquid-liquid microextraction
followed by high-performance liquid chromatography
a
Meghdad Pirsaheba,, Tarokh Khodadadia, Kyomars Sharafia, Nazir Fattahi b,*
Department of Environmental Health Engineering-Kermanshah Health Research Center (KHRC), Kermanshah University of Medical
Sciences, Iran
b
Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah, Iran
Recently, the environmental pollution by herbicides has become a serious problem especially marine ecosystem. Alachlor, 2, 4dichlorophenoxyacetic acid and atrazine are three herbicides from different categories of organic compounds which have much
application in agriculture. This herbicides has high range of use in Iran, especially Kermanshah. So, they pollute surface and
ground water in this region. Many analytical approaches have been used for the trace-level analysis of pesticides, herbicides and
metabolites in waters, but HPLC [1] and GC [2] are of more practical interest. Various techniques for extraction of herbicides in
water samples are LLE, SPE, SPME and LPME. In the present work, we have developed dispersive liquid-liquid microextraction
(DLLME) [3-5] followed by high-performance liquid chromatography (HPLC) for determination of herbicides in water samples.
Some important parameters, such as, kind of extraction and disperser solvent and volume of them, extraction time and salt effect
were investigated. Under the optimum condition (1000 mL acetone as a disperser solvent contain 28.0 mL chlorobenzene as a
extraction solvent) the enrichment factor ranged from 103 to 120 and the recovery ranged from 41 to 48%. The linear range was
0.3-200 mgL-1 and limit of detections were 0.05-0.1 µg L-1. The relative standard deviations (RSDs) were in the range of 4.56.2% (n=7). DLLME is a very simple and rapid (less than 3 min) method which requires low volume of sample (5 mL).
Reference
[1] L.Y. Zang, J. De Haven, A. Yocum, G. Qiao, J. Chromatogr. B 767 (2002) 93.
[2] W.H. Deng, C.H. Liu, S.P. Yeh, J. Chromatogr. A 896 (2000) 111.
[3] M. Rezaee, Y. Assadi, M. R. Milani Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, J. Chromatogr. A 1116 (2006) 1.
[4] S. Berijani, Y. Assadi, M. Anbia, M. R. Milani Hosseini, E. Aghaee, J. Chromatogr. A 1123 (2006) 1.
[5] N. Fattahi, Y. Assadi, M.R. Milani Hosseini, E.Z. Jahromi, J. Chromatogr. A 1157 (2007) 23.
A chemometrics approach for simultaneous determination of cyanazine and propazine based on a carbon paste electrode
modified by a novel molecularly imprinted polymer
Mohammad Bagher Gholivand, Masoud Shariati-Rad*, Nashmil Karimian and Maryam Torkashvand
Department of Analytical Chemistry, Faculty of Chemistry, Razi University, Kermanshah, Iran
Triazines are a group of herbicides with increased application in agriculture. They can be present as pollutants, e.g., in water and
fruits [1]. Taking into account the proximity of their analytical signals, the simultaneous analysis of the respective mixtures by
direct measurements, is not possible. On the other hand, the most works on the development of the sensors have been done on
single analye determinations. In a completely rational and designed approach, simultaneous determination of cyanazine and
propazine in environmental and food samples was performed using a molecularly imprinted polymer (MIP) modified carbon
paste electrode [2] and partial least squares (PLS) [3]. Following a theoretical study for finding the best constituents for MIP
preparation, it was synthesized as selective adsorbents after incorporating in a carbon paste electrode for the simultaneous
determination of cyanazine and propazine. The MIP modified carbon paste electrode showed improved qualities such as,
simplicity of electrode preparation, a wider linear range, lower detection limits (DL), higher selectivity, and more stability of the
used modifier. In an experimental design approach, important parameters were identified and their optimum conditions were
selected. The procedure is based on the reduction of cyanazine and propazine after their selective extraction into the carbon paste
electrode. In order to reduce the analysis time, the stripping voltammetric (SV) method was used in which electrode washing step
was omitted while two other steps (analyte extraction and electrochemical measurements) take place in one step. The cathodic
differential pulse voltamograms of the mixtures were analyzed by PLS as a multivariate calibration technique. The developed
sensor was successfully applied for the simultaneous determination of cyanazine and propazine in environmental and food
samples.
Reference
[1] E. M. Thurman, M. Meyer, M. Pomes, C. A. Perry, A. P. Schwab, Anal. Chem. 62 (1990) 2043.
[2] W.M. Yeh, K.C. Ho, Anal. Chim. Acta 542 (2005) 76.
[3] S. Wold, M Sjostrom, L. Eriksson, Chemom. Intel. Lab. Sys. 58 (2001) 109.
Perconcentration Cd(II) by Nanometer SiO2 modified with 5-sulfosalicylic acid as selective solid-phase extractant and
determination by FAAS from water samples
1
Ali MOGHIMI1* -Shahimeh ESFANJANI2
Department of Chemistry, Islamic Azad University Shahre Ray of Branch, Shahre Ray,, Iran
E-mail: alimoghimi@iauvaramin.ac.ir
A new modified nanometer SiO2 using 5-sulfosalicylic acid (SSA) as a solid-phase extractant was used for separation,
preconcentration and determination of Cd(II) in aqueous solutions by inductively coupled plasma atomic emission spectrometry
(FAAS). Its adsorption and preconcentration behaviour for Cd(II) in aqueous solutions was investigated using static procedures
in detail. The optimum pH value for the separation of Cd(II) on the newly designed sorbent was 3.5. Complete elution of the
adsorbed Cd(II) from the nanometer SiO2-SSA was carried out using 2.0 mL of 0.01 mol L−1 of HCl. The time of 90% sorption
was less than 2 min for Cd(II) at pH 2.8. Common coexisting ions did not interfere with the separation and determination of
Cd(II) at pH 2.8. The maximum static adsorption capacity of the sorbent at optimum conditions was found to be 44.01 mg of
Cd(II) per gram of sorbent. The relative standard deviation (RSD) of the method under optimum conditions was 2.9% (n=5). the
results obtained were in good agreement with standard values. The nanometer SiO2-SSA was successfully employed in the
separation and preconcentration of the investigated Cd(II) from the natural water samples yielding 100-folds concentration factor.
Spectrophopometric determination of Eosin B dye after cloud point extraction using triton x-114 as nonionic surfactant
Ardeshir Shokrollahi*, Zahra Malekhosseini
Department of Chemistry, Yasouj University, Yasouj, Iran, 75918-74831
Email: ashokrollahi@mail.yu.ac , Zahra_Mh2007@yahoo.com
Eosin B is a novel antimalaria agent for drug-resistant plasmodium falciparum, therefore, its determination is very important [1].
Cloud point extraction (CPE) is carried out to extract Eosin B dye from aqueous solution using non-ionic surfactant TX-114. The
effects of different operating parameters, e.g., concentrations of surfactant, salt, temperature, pH the equilibration temperature
and time, time of santrifuje have been studied. The calibration curve was linear in the range of 6.67-733.33 ngml -1 with r2
=0.991(n=8). A typical cloud point experiment has been carried out according to following procedure. A aliquot of 15 ml of an
aqueous solution containing 67 ng ml-1 of Eosin B, 0.13 % (w/v) of Triton X-114 in pH 3.5 was prepared. The mixture was left to
stand for 5 min in a thermostat bath at 28 °C. Separation of the phases was achieved by centrifugation for 10 min. The whole
system was cooled in an ice and salt bath so that the surfactant rich phase would regain its viscosity and the bulk aqueous phase
was easily decanted. The remaining micellar phase was dissolved in ethanol to 1 ml and then the absorbance of the solution was
measured at 533 nm. A blank solution was also run using water instead of Eosin B. In this work, we introduced a novel and
sensitive cloud point extraction procedure as a rapid, safe and inexpensive method for the extraction, preconcentration, and
determination of Eosin B spectrophotometrically. The method validation yielded good results and included linearity,
repeatability/reproducibility, sensitivity, recovery and accuracy. The proposed method can be applied to the determination of
Eosin B in the tap water, beshar water and mineral water.
Reference
[1] M. K. Massimine, M. T Mcintosh, L.T Doan, C. E. Atreya, S. Gromer,W. Sirawaraporn, A Elliott, A. K.Joiner, S.K. Anderson, Antimicro. Agents. Chemother.,50
(2006) 3132-3141.
Potentiometric study proton-transfer system of pyridine dicarboxylic acid with 2-aminopyridine and its complexess with
Co2+, Zn2+ and Hg2+ ions
Ardeshir Shokrollahi*, Zahra malekhossieni
Department of Chemistry, Yasouj University, Yasouj, Iran,75918-74831
Email: ashokrollahi@mail.yu.ac.ir
The formation of complexes, in aqueous solutions is a matter of great importance not only in inorganic but also in analytical,
biochemistry and other fields of chemistry and industrial. Dicarboxylate ligands are widely used to assemble supramolecular
network organized by coordination bonds, hydrogen bonds and π-π stacking interactions. On the other hand, the functional
groups, flexibility, symmetry and configuration of the organic ligands also have significant effect on the structures of the
complexes. In this work the protonation constants of 2-aminopyridine (2-apy) and 2,3-pyridine dicarboxylic acid (2-3pydc), the
equilibrium constants for the pydc-2-apy proton transfer system and the stoichiometry and stability of the this system with Co2+,
Zn2+ and Hg2+ ions in aqueous solution at 25±0.1 ◦C and ionic strength of 0.1M and NaNO3 were investigated by potentiometric
pH titration. The overall stability constant, logarithm of b-values, of all species present were evaluated by computer refinement
of pH-Volume data using the BEST computer program[1]. Distribiution diagrams depicted by using Hyss2009 program[2]. The
stoichiometry of one of the most abundant complexes species in solution was found to be simillar to the crystaline cited metal
ion complexes.
Reference
[1]. A. E. Martell, R. J. Motekaitis, Determination and Use of Stability Constants, 2nd ed.,VCH, NewYork, 1992.
[2]. L. Alderighi, P. Gans, A. Ienco, D. Peters, A. Sabantini, A. Vacca, Coord Chem. Rev., 184, (1999), 311
Preconcentration of zinc using Amberlite XAD-4 modified by Dithizone and its determination by flame atomic absorption
spectrometry
Samira Mohajer* ,Mahmoud Chamsaz, Mohammad Hossien Arbab-Zavar, Motahareh khavari
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran
Solid phase extraction has been extensively used to preconcentrate and determine varieties of metal ions [1,2] using different
solid materials [3]. Among these materials, Amberlite XAD-4 has been successfully employed for this purpose [4]. The aim of
this study is to preconcentrate trace amounts of zinc using a column packed with Amberlite XAD-4 treated with dithizone at pH 6
and determine it by flame atomic absorption spectrometry. After running the sample solution, the column was washed with HNO3
and the eluted zinc complex was determined by flame atomic absorption spectrometry. The effects of different parameters
affecting the performance of method such as pH, volume of sample solution, weights of resin, volume and type of acid for elution
were studied. The results show that 0.5 gr of resin would be sufficient for preconcentration of 100 µg of zinc at the optimized pH
of 6. 5 ml of 2 M HNO3 at a flow rate of 1 ml.min-1 would completely remove zinc from the column. The effects of different
interfering ions were also studied and only Co+2 and Cd+2 interfered in zinc determination. Under the optimized conditions, the
detection limit was 0.45 ppb with a relative standard deviation of 3.02 percent (n=10). The calibration curve was linear in the
range of 1-80 ppb of zinc. This method was applied to determine zinc in tap water.
Reference
[1] J.Kubova, V. Neveral, V. Stresko, J. Anal. Atom. Spect. 9 (1994) 241.
[2] M. Soylak, L. Elci, M. Dogan, Anal. Lett. 26 (1993) 1997.
[3] M. Soylak, L. Elci, M. Dogan, Fresen. Environ. Bull. 5 (1996)148.
[4] M.Kumar, D.P.S. Rathore, A.K. Singh, Talanta 51(2009) 1187.
Hollow fiber-based liquid phase micro extraction (HF-LPME) of trace amounts of thorium(IV) ions from water samples
M . Sadeghi, S. A. M. Fathi, A. A. Zamani, M. R. Yaftian*
Phase Equilibria Research Laboratory, Department of Chemistry, Faculty of Science, Zanjan University, P.O. Box 45195-313, Zanjan, Iran
Pedersen-Bjergaard and Rasmussen recently introduced an alternative concept for LPME based on the use of single, low-cost,
disposable, porous, hollow fibers made from polypropylene [1]. In this hollow fiber-based LPME technique, the micro-extract is
contained within the lumen of a porous hollow fiber, so the micro-extract is not in direct contact with the sample solution. As
result, samples may be stirred or vibrated vigorously without any loss of the micro-extracted analyt. Membrane technology and
its inherent accompanying science had been demonstrated in a wide range of applications including: metal ion extraction,
wastewater treatment, fermentation, pharmaceuticals [2]. Both industrial and environmentally important of actinides, their
removal concentration and determination are vastly considered by many research groups. To this aim there are a great number of
studies on the separation of thorium as a symbol of the actinides [3]. Organophosphorus compounds are among the most
extractant used for such target. In the present work, hollow fiber-based liquid phase extraction technique using Bis(2ethylhexyl)phosphoric acid (DEHPA) is used to separate and concentrate trace amounts of thorium(IV) ions from a large volume
of 50ml water sample to a final tiny volume of 25μl. DEHPA dissolved in ethyl acetate and sulfuric acids were used as extractant
and stripping solution, respectively. The equilibrium concentration of the metal in the aqueous phase was measured
spectrophotometrically using arsenazo III. Under optimized conditions i.e. 0.5 M DEHPA in ethyl acetate, initial concentration of
thorium ions 10-4 M, stripping solution 4.1 M H2SO4, a preconcentration factor of 2000 was obtained. Both of the extraction and
stripping were attained after 60 min.. The RSD of the method was 0.41% based on five replicate measurements of thorium ions
(10-4 M). The presented method shows a good selectivity towards a large number of other associated metal ions. This method was
used for removal, concentration and determination of thorium ions in various water samples.
Reference
[1] K. E. Rasmussen, S. Pedersen-Bjergaard Trends in Anal. Chem , 23 (2004) 1.
[2] R. Gonzalez, A. Cerpa, F.J. Alguacil Chemosphere 81 (2010) 1164.
[3] A. A. Zamani, M. R. Yaftian Sep. Purif. Techol. 40 (2004) 115.
Simultaneous voltammetric determination of tyramine and paracetamol using carbon nanoparticles modified glassy
carbon electrode
Jahan Bakhsh Raoof*, Mohaddeseh Amiri-Aref, Mehdi Baghayeri
Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, Mazandaran University, Babolsar,
Iran
Tyramine or p-hydroxyphenylethylamine (TyrA), produced by the decarboxylation of tyrosine. It is one of the biogenic amines,
which were produced as degradation products resulting from microbial activity [1, 2]. Paracetamol (PAR) is an analgesic and
antipyretic drug. It is a safe and effective pain killer employed for the far-flung relief of moderate pain associated with backache,
headache, arthritis and postoperative pain [3]. For these reasons, the development of a fast and sensitive method to measure TyrA
and PAR concentrations would be valuable. In presence study, a sensitive and selective electrochemical sensor was fabricated via
the drop-casting of carbon nanoparticles (CNPs) suspension onto a glassy carbon electrode (GCE). The application of this sensor
was investigated in simultaneous determination of paracetamol (PAR) and tyramine (TyrA) drugs in pharmaceutical preparation
and human urine. The electrochemical response characteristics of the modified electrode toward PAR and TyrA were
investigated by cyclic voltammetry and differential pulse voltammetry. The dependence of peak currents and potentials on pH,
concentration and the potential scan rate were investigated for these compounds at the surface of modified electrode. The results
showed that CNPs enhanced the electroactive surface area and caused a remarkable peak resolution (~220 mV) for these two
compounds. CNPs showed a catalytic effect and accelerated the rate of the electron transfer process. Application of the modified
electrode resulted in a sensitivity enhancement and a considerable decrease in the anodic overpotential, leading to negative shifts
in peak potentials. An optimum electrochemical response was obtained for the sensor in the buffered solution of pH 7.0. Using
differential pulse voltammetry, the prepared sensor showed good sensitivity and selectivity for the determination of PAR and
TyrA in wide linear ranges. Very low detection limits for PAR and TyrA were obtained. The CNPs modified GCE was
successfully applied for PAR and TyrA determinations in pharmaceutical dosage forms and human urine.
Reference
[1] B. J. McCabe-Sellers, C. G. Staggs, M. L. Bogle, J. Food Comp. Anal. 19 (2006) 58−65.
[2] N. F. Atta, A. M. Abdel-Mageed, Talanta 80 (2009) 511−518.
[3] S.F. Wang, F. Xie, R.F. Hu, Sens. Actuator B: Chem. 123 (2007) 495–500.
Utilization of a novel dispersive liquid-liquid microextraction followed by HPLC-UV as an efficient method for the
extraction and determination of quercetin in biological samples
Elias Ranjbari a, Mohammad Reza Hadjmohammadi a,*, Pourya Biparvab
Department of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
b
Research Department of Chromatography, Iranian Academic Center for Education, Culture & Research (ACECR), Urmia Branch, Urmia, Iran
a
Due to its antioxidant activities, quercetin has drawn attention for decades for its efficacy against various pathological conditions
such as cancer, cardiovascular disease, and other oxidative stresses [1, 2]. A simple and efficient method for the extraction of
quercetin as well as its determination in water samples developed using a novel dispersive liquid-liquid microextraction
(DLLME) and high performance liquid chromatography with ultra violet detection (HPLC-UV). The extraction method is based
on the phase separation phenomenon by the fast injection of a mixture of the extracting solvent and dispersive solvent to the
aqueous solution. Inspite of the conventional DLLME, extraction product after centrifugation was withdrawn with a microsyring
from the top of the aqueous solution (instead of the bottom). The extraction parameters such as type and volume of the extracting
and dispersive solvent, pH of sample, stirring rate and extraction time were optimized. Under the optimal conditions (sample
volume: 20 mL; extracting solvent: 150 μL 1-octanol; dispersive solvent: 300 μL acetonitrile; pH of sample: 4.5; stirring rate:
750 rpm; extraction time: 0.5min) extraction recovery and enrichment factor were 92% and 123, respectively. This novel
DLLME procedure provided a wide range of linearity and very low detection limit for quercetin. The method was successfully
applied for the preconcentration and determination of quercetin in a biological sample.
Reference
[1] J.V. Formica, W. Regelson, Food Chem. Toxicol 33 (1995) 1061–1080.
[2] E. Rijke, P. Out, W.M.A Niessen, F. Ariese, J. Chromatogr. A 1112 (2006) 31– 63.
Simultaneous determination of mono and dichloro acetic acid in betaine samples by esterification with palladium nano
particles using static head space gas chromatographic method
Behrouz Akbari-adergani*1, Minoo Sefidsiahbandi2
1- Food and Drug Laboratories Research Center, Ministry of Health and Medical Education, Tehran, Iran
2- Department of Analytical Chemistry, Islamic Azad University, Shahre-Rey Branch, Shahre-Rey, Iran
A new, sensitive and robust method was developed for determination of ultra trace amount of mono and dichloroacetic acid in
betaine media. An ethanol esterification reaction catalyzed by Pd nanoparticles in a head space (HS) vial followed by gas
chromatography with flame ionization detection (GC-FID) was applied for the determination of monochloroacetic acid (MCA)
and dichloroacetic acid (DCA) in betaine samples. The effects of various parameters on the sensitivity of the method were
investigated [1]. The best performance was obtained with an analytical headspace auto sampler coupled with a gas
chromatograph with flame ionization detector [2-4]. The ethanol esterification reaction was based on palladium nano particles as
an efficient heterogeneous catalyst with very high surface to volume ratio. The best conditions including, a 60 m ´ 0.32 mm I.D.
´ 0.25 µm CP-sil 5CB capillary column, nitrogen as carrier gas, 20 min stirring in 120º C as optimized incubation time and
temperature and finally 0.4% w/w for concentration of Pd nanoparticles in betaine sample. The detection limits (LOD) of MCA
and DCA are 0.1 and 0.18 µg.ml-1, respectively. This method has the requisite accuracy, sensitivity, precision and selectivity to
assay MCA and DCA in betaine samples.
Reference
[1]. International Conference on Harmonization (ICH) Quality Guideline ICH – Q7A, Geneva, 2000.
[2]. Y.H.Wang, P.K.Wong, Water Research. 39( 2005 ) 1844-1848.
[3]. M. Humbert, A. Hernandez; 4th world surfactants congress, Barcelona, 3-7 VI 379 (1996).
[4]. M. J. Cardador, A. Serrando, M. Gallego, Journal of Chromatography A, 1209 (2008 )61.
Photoelectrocatalytic Degradation of 3-nitrophenol at Surface of Titanium Foil Electrode Modified by Titaniumdioxide
Using Anodic Oxidation Method
Reza ojani*, Jahan-Bakhsh Raoof, Akbar Khanmohammadi, Ebrahim Zarei
Department of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
*Corresponding author. Tel.: + 98-112-5342301; Fax: +98-112-5342302.
E-mail: fer-o@umz.ac.ir
TiO2-based photocatalytic (PC) and photoelectrocatalytic (PEC) oxidation technique have been proven to be promising and
highly efficient processes that can be used to degrade various recalcitrant organic pollutants, such as dyes, pesticides, herbicides,
aromatics, etc., under UV light irradiation [1]. On the other hand, phenols and their derivatives such as 3-nitrophenol (3-NP) are
well known for their biorecalcitrant and acute toxicity. 3-nitrophenol is an important organic chemical for environmental studies
because of its widespread application in agriculture, industry and commercial product formation preservation. It is highly toxic
and persistent in water and soil [2]. In response it has become a challenge to achieve the effective removal of persistent organic
pollutants from waste water effluent to minimize the risk of pollution problems from such toxic chemicals and to enable its reuse
[3]. In this work, TiO2 photoanode was prepared with anodic oxidation of Ti sheet surface at a constant 20 V biased potential in
aqueous solution. Then, it was calcinated at 500 ˚C for 2 h. Direct photolysis (DP), electrochemical oxidation (EC),
photocatalytic (PC) and photoelectrocatalytic (PEC) degradation of 3-nitroenol were compared at the surface of this electrode.
Results show that the removal rate of 3-nitrophenol in the PEC oxidation was more than that the PC, DP and EC oxidations.
Also, the effects of applied potential, pH and 3-nitrophenol initial concentration on the photoelectrocatalytic (PEC) degradation
of 3-nitrophenol using ultraviolet (UV) illuminated TiO2/Ti electrode were examined and discussed.
Reference
[1] Y. Liu, X. Gan, B. Zhou, B. Xiong, J. Li, C. Dong, J. Bai,W. Cai, J. Hazard. Mater.171 (2009) 678.
[2] S. Ahmed, M.G. Rasul, W.N. Martens, R. Brown, M.A. Hashib, Desalin. 261 (2010) 3.
[3] G. Li, J. Qu, X. Zhang, H. Liu, H. Liu, J. Molecul. Catal. A: Chem. 259 (2006) 238.
Cercis siliquastrum leaves
Sh. Faraji, J. Zolgharnein*
Department of Chemistry, Faculty of Science, Arak University, Arak
Dyes and pigment are emitted into wastewaters from various industrial branches, such as from the dye manufacturing or textile
finishing, and may significantly affect photosynthetic activity in aquatic systems. In this study, adsorption of bromophenol blue
(BPB) onto Cercis siliquastrum leaves has been investigated. The uptake of dye from aqueous solutions has been determined by
UV-Vis spectrophotometry. The effects of initial BPB concentration, pH, temperature and sorbent amount on the adsorption
process have been considered. The Box-behnken design used as a multivariate optimization tool for obtaining maximum removal
of dye from aqueous solution. The kinetics and thermodynamics of BPB adsorption by leaves in aqueous solution are
investigated comprehensively. Kinetic studies show that data are described well by the second-order kinetic model. Equilibrium
modeling results also indicate that Langmuir isotherm can better describe the sorbate (BPB)-sorbent (Cercis siliquastrum leaves)
than Freundlich isotherm. Thermodynamic parameters such as: ∆G, ∆H and ∆S were calculated. The obtained results suggested
that the biosorption of BPB was spontaneous and endothermic process.
Reference
[1] . L.You , Z.Wu ,T.Kim, K.Lee, J. Colloid Interface Sci. 300 (2006) 526–535
[2] . M. A Malana, S. Ijaz, M. N Ashiq, Desalination 263 (2010) 249–257
[3] . M. J. Iqbal, M. N. Ashiq J. Hazard. Mater. B139 (2007) 57–66
Modeling of Maximum Absorption Wavelength of Second-order NLO Chromophores by Artificial Neural Network
Zahra Jamali*, Zahra Zamiraei, Shayan Mokhtar
Environmental research institute of jahad deneshgahi, Rasht, P.B. 41635-3114
E-mail: z.jamali.87@gmail.com
Much attention has been devoted to organic second-order nonlinear optical (NLO) materials due to their larger susceptibilities,
faster response time, ease of processing, and versatility of molecular structural modifications. In particular, poled polymeric
materials are going to play an important role in selected applications, i.e. high-performance electro-optic (EO) modulation,
optical information processing, computing and data storage [1]. These materials are typically made from organic small
molecules, namely chromophores, incorporated into polymer matrixes and poled with an electric or optical field to realize a noncentrosymmetric dipole alignment. A quantitative structure–property relationship (QSPR) study is suggested for the prediction of
maximum absorption wavelength of Second-order NLO Chromophores. Various kinds of molecular descriptors were calculated.
The variable selection method of stepwise was employed to select optimal subset of descriptors that have significant contribution
to the overall maximum absorption wavelength property. Artificial Neural Network (ANN) was employed to model the
quantitative relationship existed between these five selected descriptors and Maximum Absorption Wavelength property. The
resulted model showed high prediction ability with the absolute average relative deviation (AARD) being 1.87, R2 =0.9860 and
the root mean square error (RMSE) being 12.32 for the validation set. All descriptors involved in the model were derived solely
from the chemical structures of the NLO chromophores.
Refrence
[1] Xu J, Zheng Z, Chen B, Zheng Q, (2005). “A Linear Model for Prediction of Maximum Absorption Wavelength of Second-order NLO Chromophores” J. QSAR
Comb. Sci., Vol. 25, No. 4, pp. 372-379.
A QSPR Model for Prediction of Maximum Absorption Wavelength of Second-order NLO Chromophores by Support
vector machine
Zahra Jamali*, Shayan Mokhtar, Zahra Zamiraei
Environmental research institute of jahad deneshgahi, Rasht, P.B. 41635-3114
E-mail: z.jamali.87@gmail.com
Great attention has been devoted to organic second-order nonlinear optical (NLO) materials due to their larger susceptibilities,
faster response time, ease of processing, and versatility of molecular structural modifications. In particular, poled polymeric
materials are going to play an important role in selected applications, i.e. high-performance electro-optic (EO) modulation,
optical information processing, computing and data storage [1]. These materials are typically made from organic small
molecules, namely chromophores, incorporated into polymer matrixes and poled with an electric or optical field to realize a noncentrosymmetric dipole alignment. A quantitative structure–property relationship (QSPR) study is suggested for the prediction of
maximum absorption wavelength of second-order NLO chromophores. Various kinds of molecular descriptors were calculated.
The variable selection method of stepwise was employed to select optimal subset of descriptors that have significant contribution
to the overall maximum absorption wavelength property. support vector machine (SVM) was employed to model the quantitative
relationship existed between these selected descriptors and maximum absorption wavelength property. The resulted model
showed high prediction ability with the absolute average relative deviation (AARD) being 4.40, and the root mean square error
(RMSE) being 29.51 for the prediction set. All descriptors involved in the model were derived solely from the chemical
structures of the NLO chromophores.
Refrence
[1] Xu J, Zheng Z, Chen B, Zheng Q, (2005). “A Linear Model for Prediction of Maximum Absorption Wavelength of Second-order NLO Chromophores” J. QSAR
Comb. Sci., Vol. 25, No. 4, pp. 372-379.
Modelling of high-pressure phase behavior of the binary system carbon dioxide + 1-hexyl-3-methylimidazolium
hexafluorophosphate as an ionic liquid
1
Ebrahim Ghorbani-kalhor*1, Abdolhossein Naseri2, Mohammad Reza soleimanian1
Department of Chemistry, Faculty of Science, Tabriz branch, Islamic Azad University, Tabriz, Iran
2
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
*E-mail: ekalhor@iaut.ac.ir
Recently, ionic liquids (ILs) have been known as a new green chemical revolution. They have unique properties such as low
vapour pressure, non-flammability and chemical stability at high temperatures. It is important to determine the behavior of
binaries of ILs with other solvent. The presence of other solvent in ionic liquid has a significant effect on its behavior. In the
present work, Multiple Linear Regression (MLR), Multiple Quadratic Regression (MQR) and MultiLayer Perceptron (MLP)
Neural Network (NN) models were explored for the prediction of the CO2 solubility in 1-hexyl-3-methylimidazolium
hexafluorophosphate [hmim] [PF6] ionic liquid (IL) as function of mole fraction and temperature. Bubble point pressure at
different temperatures for several isopleths, were used for binary system of CO2 and IL. Solubility of CO2 in [hmim][PF6] were
modelled within concentration, temperature and pressure ranges of 9.8–72.7 mol%, 298.31–363.58 K, and 0.64–94.60MPa,
respectively. To develop and validate of these models, experimental data those are available in the literature were employed. The
models fitting performance was analyzed calculating statistical parameters. The results showed that NN model as a nonlinear
regression model had a very good correlation coefficient (R2) and low relative standard error (RSE) values. Financial support
from Research deputy of Islamic Azad University, Tabriz branch is gratefully acknowledged.
Reference
[1] B. Mokhtarani, A. Sharifi, H. R. Mortaheb, M. Mirzaei, M. Mafi and F. Sadeghian, J. Chem. Thermodynamics 41 (2009) 323–329.
[2] J. S. Torrecilla, J. Palomar, J. García, E. Rojo, and F. Rodríguez, Chemomtr, Intel. Lab. Syst., 93 (2008) 149–159.
[3] A. Shariati, and C. J. Peters, J. of Supercritical Fluids 30 (2004) 139–144.
[4] L. A. Blanchard, Z. Gu, and J.F. Brennecke, J. Phys. Chem. B 105 (2001) 2437–2444.
[5] F. Nami, F. Deyhimi, J. Chem. Thermodynamics 43 (2011) 22–27.
[6] A. Shariati and C. J. Peters, J. of Supercritical Fluids 25 (2003) 109-117.
Optimization of Removal of Bromophenol Blue by Cercis siliquastrum Tree leaves
Sh. Faraji, J. Zolgharnein*
Department of Chemistry, Faculty of Science, Arak University, Arak
Dyes and pigment are emitted into wastewaters from various industrial branches, such as from the dye manufacturing or textile
finishing, and may significantly affect photosynthetic activity in aquatic systems. In this study, adsorption of bromophenol blue
(BPB) onto Cercis siliquastrum tree leaves has been investigated. The uptake of dye from aqueous solutions has been determined
by UV-Vis spectrophotometry. The effects of initial BPB concentration, pH, temperature and sorbent amount on the adsorption
process have been considered. The Box-behnken design as a multivariate optimization tool used for obtaining maximum
removal(R%) of dye from aqueous solution. The kinetics and thermodynamics of BPB adsorption by leaves in aqueous solution
are investigated comprehensively. Kinetic studies show that data are described well by the second-order kinetic model.
Equilibrium modeling results also indicate that Langmuir isotherm can better describe the sorbate (BPB)-sorbent (Cercis
siliquastrum leaves) than Freundlich isotherm. Thermodynamic parameters such as: ∆G, ∆H and ∆S were calculated. The
obtained results suggested that the biosorption of BPB was spontaneous and endothermic process.
Reference
[1] . L.You , Z.Wu ,T.Kim, K.Lee, J. Colloid Interface Sci. 300 (2006) 526–535
[2] . M. A Malana, S. Ijaz, M. N Ashiq, Desalination 263 (2010) 249–257
[3] . M. J. Iqbal, M. N. Ashiq , J. Hazard. Mater. B139 (2007) 57–66
[4] J. Zolgharnein, Z. Adhami, A. Shahmoradi, S. N. Mousavi, Anal. Sci. 25 ( 2010) 111–116.
Adsorption characterization of Pb(II) and Zn(II) onto some Tree Leaves Julangs regia, Nigra, Ficus carica:
Multivariate Optimization, Thermodynamic and Kinetic Studies
J. Zolgharnein, R. Moeanosadat
Department of Chemistry, Faculty of Science, Arak University, Arak
E-mail: J-zolgharnein@araku.ac.ir
Some natural sorbent such as Julangs regia, Nigra and Ficus carica tree leaves were introduced as a new biosorbent for
removing Pb(II) and Zn(II) from aqueous solutions in a batch system. The effective variables such as initial concentration of
metal ion, biosorbent dosage, pH, temperature, and contact time were investigated. Response surface methodology (RSM)
involving Box-Behnken design for three effective factors (initial concentration٫٫ biosorbent dosage and pH) were employed to
optimize the removal efficiency(R %) of Pb(II) and Zn(II). An empirical model was developed and validated applying analysis of
variance and other relevant tests. The optimum conditions of biosorption such as m(amount of sorbent)٫٫ C(initial concentration)
and pH for both Pb(II) and Zn(II) were obtained. The Langmuir and Freundlich isotherms were applied to the experimental data
and the Langmuir model was found to be a better fitting with it. The monolayer adsorption maximum capacity (qmax) for removal
of Pb(II) and Zn(II) by Platanus Julangs regia٫ Nigra and Ficus carica were found to be 115٫٫ 122.4, 100, 83.8٫٫ 50.8 and 59.6
mgg-1 respectively. The pseudo second order rate equation was fitted very well to experimental data. The thermodynamic
parameters: ΔG٫٫ ΔH and ΔS were calculated which indicating that biosorption was endothermic process. Effect of common ions
like potassium٫٫ calcium and magnesium on the removal efficiency of Pb(II) and Zn(II) were also examined. FT-IR spectroscopy
was performed to determine the mechanism of biosorption and characterize the main functional groups that might be involved in
metal uptake and to confirm the presence of Pb(II) and Zn(II) on the sorbent.
Reference
[1] M. R Sangi,. A Shahmoradi,,J. Zolgharnein, G Azimi, M. Ghorbandoost, J. Hazard. Mater, 2008, 155, 513-522.
[2] J. Zolgharnein, A.Shamoradi M.R. Sangi, Talanta 2008, 76, 528 -532.
[3] J. Zolgharnein, Zh. Adhami, A. Shahmoradi, S.N. Mousavi, . Anal. Sci. 2010, 26, 111-116.
[4] J. Zolgharnein, A. Shahmoradi.. J. Chem. Eng. Data. 2010, 55, 3428- 3437.
Characterization Adsorption of binary mixture of Pb (II) and Zn (II) onto Julangs regia Tree Leaves
M. Rastgordani, J. Zolgharnein*
Department of Chemistry, Faculty of Science, Arak University, Arak
Simultaneous removing of binary mixture of Pb(II) and Zn(II) by Julangs regia tree leaves from aqueous solutions in a batch
system was studied. The effective variables such as initial concentration of metal ion, biosorbent dosage, pH, temperature, and
contact time were investigated. Response surface methodology (RSM) involving central composite design (CCD) for effective
factors were employed to optimize the removal efficiency percent (R %) and capacity uptake (q) of binary mixture of Pb(II) and
Zn(II). For both response the empirical models were developed and validated applying analysis of variance and other relevant
tests. The optimum conditions of biosorption such as m(amount of sorbent)٫٫ C(initial concentration) and pH for both Pb(II) and
Zn(II) were obtained. Simultaneous optimization of both responses (R and q) was carried out due to maximum goal of
desirability function was achieved. Simultaneous optimization of R and q and simple optimization of q was more favorable than
that of R from an environmental and economical view. The modified Langmuir and Freundlich isotherms were applied to the
experimental data to describe the equilibrium behavior of sorbates – sorbent interaction. FT-IR spectra were recorded to identify
functional groups involved in the biosorption. Kinetic and thermodynamic studies were also performed to find more detail of
biosorption process.
Reference
[1] M. R Sangi,. A Shahmoradi,,J. Zolgharnein, G Azimi, M. Ghorbandoost, J. Hazard. Mater, 2008, 155, 513-522.
[2 J. Zolgharnein, A.Shamoradi M.R. Sangi, Talanta 2008, 76, 528 -532.
[3] J. Zolgharnein, Zh. Adhami, A. Shahmoradi, S.N. Mousavi, . Anal. Sci. 2010, 26, 111-116.
[4] J. Zolgharnein, A. Shahmoradi.. J. Chem. Eng. Data. 2010, 55, 3428- 3437
Dispersive liquid–liquid microextraction based on solidification of floating organic drop combined with flame
atomic absorption spectrometry for preconcentration and determination of thallium(III) in water samples
Mohadese Hossein-Poor-Zaryabi, Mahmoud Chamsaz∗, Abolfazl Darroudi
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran
A dispersive liquid–liquid microextraction technique based on solidification of a floating organic drop (DLLME-SFO) combined
with flame atomic absorption spectrometry was developed for determination of thallium in water sample. An appropriate mixture
of acetone and 1-undecanol was injected rapidly into the aqueous sample containing an ion pair complex of TlCl4- with brilliant
green and as a result a cloudy mixture was formed. After centrifugation, the test tube was cooled for 5 min. The solidified 1undecanol drop formed on the top of the solution was transferred into a suitable vial and its contents was dissolved in 300µL of
acetone and finally determined by flame atomic absorption spectrometry. Several factors which be affect the extraction process,
such as the type and volume of the extractant and disperser solvents, centrifugation time, concentration of brilliant green,
concentration of HCl, the volume of diluents solvent and interferences were studied. Under the optimum operating conditions, the
calibration graph was linear in the range of 0.24–24µgmL−1 of Tl(III) with a limit of detection of 0.09µgmL−1. The relative
standard deviation (RSD) for five replicate measurements of thallium was 3.6%. The results for determination of thallium in a
certified reference material (unalloyed zinc) and spiked tap water. Demonstrated the high accuracy, recovery and good
applicability of the presented method.
Reference
[1] Mohammad Hossien Arbab-Zavar, Mahmoud Chamsaz, Golam hossien Zohuri, Abolfazl Darroud, J. Hazard. Mater.185 (2011) 38–43.
[2] M.A. Taher , Bull. Korean Chem. Soc. 24 (2003) 1177–1182.
[3] M.H. Arbab-Zavar ,M. Chamsaz, A. Yousefi, N. Ashraf, Talanta 79 (2009) 302–307.
[4]Mohammad Hossien Arbab-Zavar, Mahmoud Chamsaz, Golamhossien Zohuri, Abolfazl Darroudi, ,J. Hazard. Mater.185 (2011) 38–43.
Impedance behavior of poly(vinyl chloride) matrix membrane salicylate-selective electrode
Mohammad Mazloum-Ardakania,*, Hossein Sabaghianb, Hadi Kargarb, Abdolhosein Dehghan-Manshadi b
a
Department of Chemistry, Faculty of Science, Yazd University, Yazd, I.R. Iran
b
Chemistry Department, Payame Noor University, Tehran 19395-4697, Islamic Republic of Iran
Salicylate derivatives are commonly used as effective antimicrobial, antipyretic, and analgesic agents. Aspirin, in particular,
probably remains one of the most widely used drugs of any kind. Salicylate (Sal-) is the main hydrolyzed product of tablet aspirin
or an aspirin like substance, which are commonly used as effective analgesics [1]. Electrochemical impedance spectroscopy (EIS)
is a powerful technique for studying the structure of the electrical double layer formed at the semiconductor electrode/electrolyte
interface, the charge transfer processes in the semiconductor and electrolyte, as well as the parameters defining the limiting steps
of the electrode processes [2,3]. Note that this method measures of the frequency dependences of the real and imaginary
components of the complex impedance of the electrochemical cell [4]. In this work, impedance measurements on salicylate
selective
electrode
based
on
the
complex
{6,6'-diethoxy-2,2'-[2,2-dimethyl-propane-1,3diylbis(nitrilomethylidyne)]diphenolato}-oxo Vanadium(IV) were carried out. EIS was applied to determine charge transfer
resistance (Rct) and double layer capacitance (Cdl). Also, effects of pH and inner solution concentration on impedance spectra
were investigated. Finally, calibration curve was plotted and results were showed Rct increased with decreasing the
concentration’s salicylate. Also, the linear concentration range increased to 1.0×10-1-1.0×10-8 M sodium salicylate, while
obtained concentration range by potentiometric technique was only 1.0×10-1-1.0×10-6 M.
Reference
[1]Mazloum Ardakani, M., Ebrahimi, P., Mansournia, M. R.; Russ. J. Electrochem.; Vol. 44, 1065, 2008.
[2]Macdonald, D. D.; Electrochim. Acta; Vol. 51, 1376, 2006.
[3]Park, S. M., Yoo, J. S.; Anal. Chem.; Vol. 75, 455 A; 2003.
[4]Aroutiounian, V.M., Arakelyan, V.M., Shahnazaryan, G.E., Stepanyan, G.M., turner, J.A., Kocha, S.S., Electrochim. Acta; Vol. 45, 1999, 2000.
Design novel optical sensor for determination of Copper based on immobilization of 4-(2-pyridylazo) resorcinol on a
triacetylcellulose membrane
Ahmad Akrami a,c,*, Mohammad Yousefi-Ghasabeh b, Fatemeh Bagheban-Shahri a,c, Ali Niazi a,c
a
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Arak Branch, Arak, Iran
b
Department of Chemistry, Isfahan University of Technology, Isfahan, I. R Iran
c
Yong Researchers Club, Islamic Azad University, Arak Branch, Arak, Iran
E-mail: ahmad.akrami.62@gmail.com
A novel optical sensor has been proposed for sensitive determination of copper ion based on immobilization of 4-(2-pyridylazo)
resorcinol (PAR) on a triacetylcellulose membrane [1]. Chemical binding of copper ions in solution with a PAR immobilized on
the triacetylcelluse surface could be monitored spectrophotometrically [2-4]. The absorption spectra of the immobilized
triacetylcellulose membrane obtained after being equilibrated in universal buffer solution (pH 5.0) containing different
concentrations of copper ion shown in Fig. 1. These figure show that the formation of the complex on the surface of optode
causes to appear as a new peak at 543 nm. The optode shows excellent response over wide concentration range 0.1-2.7 µg mL-1
copper with a limit of detection of 0.05 µg mL-1 copper. The influence of factors responsible for the improved sensitivity of the
sensor were studied and identified. The response time of the optode was 40 sec for a stirrer solution. The proposed optode was
applied to the determination of copper in water samples.
Absorbance
2.4
1.8
1.2
0.6
0
330
400
470
540
610
Wavelength / nm
Fig. 1. Absorption spectra of optode film in the presence of 0.03 - 3.6 µg mL-1 of copper at pH 5.0
The present optical membrane is prepared using simple and fast approach, which is very safe and economical because of
consuming inexpensive, nontoxic and available reagents. The results of this study show the optode can be successfully applied to
the determination of copper in real samples.
Reference
[1] M. Shmsipur, K. Zargoosh, F. Mizani, H. Eshghi, F. Rostami, Spectrochimica Acta Part A 77 (2010) 319.
[2] R. Zare-Dorabei, P. Norouzi, M. R. Ganjali, Anal. Lett 42 (2009) 190.
[3] N. Alizadeh, A. Moemeni, M. Shamsipur, Anal. Chim. Acta 464 (2002) 187.
[4] H.Y. Luo, X.B. Zhang, J.H. Jiang, C.Y. Li, J. Peng, G.L. Shen, R.Q. Yu, Anal. Sci. 23 (2007) 551.
Simultaneous Spectrophotometric Determination of Titanium and Platinum with Rhodanine by Chemometrics Methods
Ahmad Akrami a,c,* , Gholam-Hassan Vaezi b, Fatemeh Bagheban-Shahri a,c, Ali Niazi a,c
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Arak Branch, Arak, Iran
b
Department of Biology, Faculty of Sciences, Islamic Azad University, Semnan Branch, Semnan, Iran
c
Yong Researchers Club, Islamic Azad University, Arak Branch, Arak, Iran
E-mail: ahmad.akrami.62@gmail.com
a
A simple, novel and sensitive spectrophotometric method was described for simultaneous determination of titanium and
platinum. The method is based on the complex formation of titanium and platinum with Rhodanine at pH 6.5. All factors
affecting on the sensitivity were optimized and the linear dynamic range for determination of titanium and platinum found. The
simultaneous determination of titanium and platinum mixtures by using spectrophotometric method is a difficult problem, due to
spectral interferences. By multivariate calibration methods such as partial least squares (PLS) [1], it is possible to obtain a model
adjusted to the concentration values of the mixtures used in the calibration range. Orthogonal signal correction (OSC) is a
preprocessing technique used for removing the information unrelated to the target variables based on constrained principal
component analysis [2,3]. OSC is a suitable preprocessing method for PLS calibration of mixtures without loss of prediction
capacity using spectrophotometric method. The multivariate calibration is a powerful tool for determinations, because it
extractsmore information fromthe data and allows building more robust models. OSC and PLS calculus were carried out in the
PLS Toolbox, version 2.0 (Eigenvector Technologies). A Hewlett-Packard 8453 diode array spectrophotometer controlled by a
Hewlett-Packard computer and equipped with a 1-cm path length quartz cell was used for UV–vis spectra acquisition. In this
study, the calibration model is based on absorption spectra in the 360–660 nm range for 15 different mixtures of titanium and
platinum. Calibration matrices were containing 0.025–1.60 and 0.05–0.50 µg mL−1 of titanium and platinum, respectively. The
RMSEP for titanium and platinum with OSC and without OSC were 0.026, 0.012 and 0.077, 0.049, respectively [4]. Therefore,
the OSC–PLS model is able to predict the concentrations of each titanium and platinum in the real matrix sample.This procedure
allows the simultaneous determination of titanium and platinum in synthetic and real matrix samples good reliability of the
determination. The good agreement clearly demonstrates the utility of this procedure for the simultaneous determination of
titanium and platinum mixtures without tedious pretreatment in complex samples in synthetic and water samples. A new method
for the simultaneous determination of titanium and platinum using spectrophotometric and OSC–PLS method is proposed.
Reference
[1] A. Niazi, A. Azizi, M. Ramezani, Spectrochim. Acta Part A, 71 (2008) 1172.
[2] B. Rezaei, E. Rezaei, J. Anal. Chem. 61 (2006) 262.
[3] C. Zhang, J. Miura, Y. Nagaosa, Anal. Sci. 21 (2005) 1105.
[4] A. Niazi, B. Jafarian, J. Ghasemi, Spectrochim. Acta Part A, 71 (2008) 841.
Simultaneous voltammetric determination of palladium and platinum by least-squares support vector machines and
partial least squares
Fatemeh Bagheban-Shahri a,c,*, Ahmad Akrami a,c, Ali Niazi a,c, Gholam-Hassan Vaezi b
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Arak Branch, Arak, Iran
b
Department of Biology, Faculty of Sciences, Islamic Azad University, Semnan Branch, Semnan, Iran
c
Yong Researchers Club, Islamic Azad University, Arak Branch, Arak, Iran
E-mail: bagheban60@gmail.com
a
In recent years attention has been directed toward methods of analysis involving multicomponent systems based on chemometrics
methods. Support vector machine (SVM) introduced by Vapnik is a valuable tool for solving pattern recognition and
classification problem. Least-squares support vector machines (LS-SVM) and partial least squares (PLS) have received
considerable attention in the chemometrics for multicomponent analysis [1]. A comparison was made between LS-SVM and PLS
methods by applying them to simultaneous voltammetric determination of palladium and platinum [2-4]. The multivariate
calibration is a powerful tool for determinations, because it extracts more information fromthe data and allows building more
robust models. An adsorptive differential pulse stripping method for the simultaneous determination of palladium and platinum is
proposed [2]. The procedure involves an adsorptive accumulation of palladium and platinum on a hanging mercury drop
electrode (HMDE), followed by reduction of adsorbed palladium and platinum by voltammetric scan using differential pulse
modulation. The optimum experimental conditions are: Thio-Michler's Ketone ( TMK ) concentration of 0.40 mg mL-1 , pH=6.0,
accumulation potential of -600 mV versus Ag/AgCl, accumulation time of 110 s, scan rate of 20mV s-1and pulse height of
100mV. The simultaneous determination of palladium and platinum by using voltammetry is a difficult problem in analytical
chemistry, due to voltammogram interferences. The resolution of mixture of palladium and platinum by the application of leastsquares support vector machines was performed. The linear dynamic ranges were 0.02–2.80 mg mL-1 and 0.015–2.45 mg mL-1 and
detection limits were 3 and 6 ng mL-1 for palladium and platinum, respectively.
Reference
[1] H. Breivik, Acta Anaesthesiol. Scand. 45 (2001) 1059.
[2] A. Niazi, A. Yazdanipour, Pharm. Chem. J. 41 (2007) 170.
[3] J.A. Gunn, C. Shelley, S.W., J. Anal. Toxicol.30 (2006) 519.
[4] A. Niazi, J. Ghasemi, A. Yazdanipour, Spectrochim. Acta Part A, 68 (2007) 523.
Design novel optical sensor for determination of gold based on immobilization of Rhodanine on a triacetylcellulose
membrane
a
Fatemeh Bagheban-Shahri a,c,*, Ahmad Akrami a,c, Ali Niazi a,c, Rooholla Akhtarianb
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Arak Branch, Arak, Iran
b
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Shahreza Branch, Iran
c
Yong Researchers Club, Islamic Azad University, Arak Branch, Arak, Iran
E-mail: bagheban60@gmail.com
A novel optical sensor has been proposed for sensitive determination of gold ion based on immobilization of Rhodanine on a
triacetylcellulose membrane [1]. Chemical binding of gold ions in solution with a Rhodanine immobilized on the triacetylcelluse
surface could be monitored spectrophotometrically [2-4]. The absorption spectra of the immobilized triacetylcellulose membrane
obtained after being equilibrated in universal buffer solution (pH 7.0) containing different concentrations of gold ion shown in
Fig. 1. These figure show that the formation of the complex on the surface of optode causes to appear as a new peak at 458 nm.
The optode shows excellent response over wide concentration range 420-1110 ng mL-1 gold with a limit of detection of 270 ng
mL-1 gold. The influence of factors responsible for the improved sensitivity of the sensor were studied and identified. The
response time of the optode was 25 sec for a stirrer solution. The proposed optode was applied to the determination of gold in
water samples.
Fig. 1. Absorption spectra of optode film in the presence of 380-1200 ng mL-1 of gold at pH 7.0
The present optical membrane is prepared using simple and fast approach, which is very safe and economical because of
consuming inexpensive, nontoxic and available reagents. The results of this study show the optode can be successfully applied to
the determination of gold in real samples.
Reference
[1] M. Shmsipur, K. Zargoosh, F. Mizani, H. Eshghi, F. Rostami, Spectrochimica Acta Part A 77 (2010) 319.
[2] R. Zare-Dorabei, P. Norouzi, M. R. Ganjali, Anal. Lett 42 (2009) 190.
[3] N. Alizadeh, A. Moemeni, M. Shamsipur, Anal. Chim. Acta 464 (2002) 187.
[4] H.Y. Luo, X.B. Zhang, J.H. Jiang, C.Y. Li, J. Peng, G.L. Shen, R.Q. Yu, Anal. Sci. 23 (2007) 551.
Determination of Trace Amounts of Silver by Adsorptive Stripping Voltammetry in the Presence of Thio-Michler's
Ketone using Chemometrics Methods
Fatemeh Bagheban-Shahri a,b,*, Ahmad Akrami a,b, Mohamad-Reza Yousefshahi a, Ali Niazi a,b
a
Department of Chemistry, Faculty of Sciences, Islamic Azad University, Arak Branch, Arak, Iran
b
Yong Researchers Club, Islamic Azad University, Arak Branch, Arak, Iran
E-mail: bagheban60@gmail.com
Silver forms the complexes with Thio-Michler's Ketone (Scheme I) in the acidic solution [1]. An adsorptive differential pulse
stripping method for the determination of silver is proposed. The procedure involves an adsorptive accumulation of silver on a
hanging mercury drop electrode (HMDE) in the presence of Thio-Michler's Ketone, followed by reduction of adsorbed silver by
voltammetric scan using differential pulse modulation [2].
H3 C
N
CH 3
H3 C
N
H3 C
S
Scheme I. Chemical structure of Thio-Michler's Ketone
The optimum experimental conditions are: Thio-Michler's Ketone ( TMK ) concentration of 0.40 mg mL-1, pH=6, accumulation
potential of -700 mV versus Ag/AgCl, accumulation time of 120 s, scan rate of 30 mV s-1 and pulse height of 100 mV. The peak
current is proportional to the concentration of silver over range of 2.2-98.0 ng mL-1, and the detection limit is 0.8 ng mL-1. The
relative standard deviation (n=3) for 0.08 mg mL-1 silver is 0.77%. The calibration matrix for partial least squares (PLS)
regression was designed with 15 samples. Orthogonal signal correction (OSC) is a preprocessing technique used for removing the
information unrelated to the target variables based on constrained principal component analysis [3-4]. OSC is a suitable
preprocessing method for PLS calibration without loss of prediction capacity using electrochemical method. This procedure
allows the determination of silver in synthetic and real samples with good reliability of the determination.
Reference
[1] A. Niazi, B. Jafarian, J. Ghasemi, Spectrochim. Acta Part A, 71 (2008) 841.
[2] J. Gabrielsson, J. Trygg, Crit. Rev. Anal. Chem. 36 (2006) 243.
[3] A. Niazi, S. Sharifi, E. Amjadi, J. Electroanal. Chem., 623 (2008) 86.
[4] A. Niazi, A. Azizi, M. Ramezani, Spectrochim. Acta Part A, 71 (2008) 1172.
Optimization of polymeric citrate membrane electrode based on derivative copper (II) through chemometrics
Mohammad Mazloum-Ardakania,*, Roya Rahimianb, Rasoul Vafazadeha
Department of Chemistry, Faculty of Science, Yazd University, Yazd, I.R. Iran
b
Department of Chemistry, Payame Noor University, Ardakan Center, I.R. Iran
a
Citric acid is often used to inhibit the growth of microorganisms in food [1]. This acid is used as a preservative additive in nonalcoholic beverages at concentrations ranging from 10-3 to 10-1 M [2]. In this paper, a new Poly (vinyl chloride) (PVC) membrane
ion-selective electrode based on derivative copper (II) as carrier for citrate ion was prepared and the central composite design
(CCD) was developed as an experimental strategies for modeling and optimization of some variables on the performance of this
new ion-selective electrode. The parameters that affect the performance of a polymeric membrane electrode are usually the PVC,
plasticizers, ion-pair amounts and pH value [3]. The influence of foreign ions on the electrode performance was also investigated.
The optimized membranes showed a good Nernstian response for citrate ion in linear concentration range 5.0×10-6-2.0×10-1 M
and the detection limit of 2.0×10-6 M at 25 oC. The electrode could be used over a wide pH 5.0-10.0, and have the advantages of
easy to prepare, good selectivity and fast response time. The proposed electrode was successfully use as indicator electrode in
potentiometric titration of citrate ion.
Reference
[1] E. Luque-Peréz, A. Ríos, M. Valcárcel, Anal. Chim. Acta, Vol. 366, 231 (1998).
[2] A. Moreno-Cid, M. C. Yebra, X. Santos, Talanta, Vol. 63, 509 (2004).
[3] K. Farhadi, R. Maleki, M. Shamsipur, Electroanalysis, Vol. 14 760 (2002).
Nickel electroless coating on magnalium powders and investigation of mechanical properties and combustion potential of
same
Mohammad molaei , Mohammad Reza Sovizi *
Department of chemistry, Malek Ashtar University of Technology Tehran, Iran
E-mail: mrsovizi@yahoo.com
This project is divided in two sections. In the first one Magnalium powder has been coated with Nickel by electroless plating
method and SEM-EDX has been used for analyzing of surface morphology and composition of coating. The results showed
Nickel layaers in the magnalium surface had the dense structure and distributed in a homogenous manner. In addition,
pretreatment with HF prevented the corrosion of magnalium during plating process. In the second one, metalized propellant
including coated metal powders (as metal fuel) had been prepared and their mechanical properties and combustion potential was
investigated and was compared with reference sample, (Sample including Magnalium without coating). Mecahnical properties of
propellant sample including coated magnalium with nickel improved rather than reference sample. These properties is including:
young◌s
ُ◌ modulus= 69.12 (Mpa), rupture Elongation= 2.5976 (mm), fracture force= 1039.6555 (N), rupture strain= 3.765% and
rupture stress= 12.03 (MPa). In addition, coated magnalium particles had lower heat combustion in comparison with uncoated
samples but because of their more efficient mechanical properties, it is negligible.
Reference
[1]. Turhan M. C., Lynch R., Killian M. S., Virtanen S.; Effect of acidic etching and fluoride treatment on corrosion performance in Mg alloy AZ91D (MgAlZn),
Electrochimica Acta 2009; 55(1): 250-257.
[3]. Huanga C.A., Wanga T.H., Weirichb T., Neubert V. ;A pretreatment with galvanostatic etching for copper electrodeposition on pure magnesium and magnesium
alloys in an alkaline copper-sulfate bath, Electrochimica Acta 2008; 15: 7235-7241.
Determination of thermal decomposition kinetic parameters of ammonium perchlorate in AP/TiC Nanocomposit
Mohammad Reza Sovizi*, Khosro Babaei,
Department of chemistry, Malek Ashtar University of Technology Tehran, Iran
E-mail: mrsovizi@yahoo.com
In this paper ammonium perchlorat coated on titanium carbide by solvent non solvent method. The SEM and SEMEDX results
show that AP covers the surface of TiC nanoparticles and these methods were used to characterize of their morphology, structure
and composition of nanocomposite. The TGA and DTA methods was used for determination of thermal decomposition kinetic
parameters of ammonium perchlorate in AP/TiC Nanocomposit. The results showed that in present of TiC the thermal
decomposition point of ammonium perchlorate shifted to lower temperatures. By using of Kissinger, Ozawa, Friedman and
Flynn-Wall-Ozawa methods kinetic parameters such as activation energy, constant rate and Arniuos constant were evaluated and
reported for thermal decomposition reaction of AP/TiC nanocomposite at differential heating rates of 5, 10, 15 and 20°C/min .
Reference
[1]. Z. Jun, Z. Weiliang, X. Fuming, Preparation of carbon-coated nano-Fe, Co Particles and their effects on the thermal decomposition of ammonium perchlorate,
Advanced Materials Research, 2010, 152-153, 309-314.
[2]. P. R. Ponminiessary, A. Vasudevan, M. Sebastian, U. A. Chennampilly, K. M. Y. Karukapadath, Oxidation kinetics of nickel nano crystallites obtained by
controlled thermolysis of diaquabis(ethylenediamine) nickel(II) nitrate, Therm. Anal. Calorim. Journal, 2009, DOI 10.1007/s10973-009-0209-y.
[3]. Q. Wang, H. Liu, B. Sun, S. Li, Study on pyrolysis characteris SiCs of Huadian oil shale with isoconversional method, Oil Shale journal, 2009, 26(2), 148-162 .
Ultrasound assisted-temperature controlled ionic liquid micro-extraction procedure combined with flame atomic
absorption spectrometry for determination of trace silver ions in water samples
M. Amjadi*, J.L. Manzoori, S. Hashemzadeh
Faculty of Chemistry, Tabriz University, Tabriz, Iran
Email: Amjadi@tabrizu.ac.ir
Hydrophobic ionic liquid could be dispersed as small droplets in aqueous phase with sonication at high temperature (50 ◦C), and
then they can aggregate as big droplets at low temperature. Based on this phenomenon a new liquid-phase micro-extraction for
the pre-concentration of silver ions was developed. In this experiment, silver ions were extracted from aqueous phase into the
ionic liquid micro-droplets after complexation with dithizone, sonication at high temperature and cooling. Important parameters
affected the extraction efficiency including the pH, amount of chelating agent, volume of ionic liquid, extraction time,
centrifugation time and temperature were investigated. The interference study showed that common coexisting ions in real
samples had no obvious negative effect on the recovery of analyte. The experimental results indicated that the proposed method
had a good linearity ( R2 = 0.9958 ) in the range of 10 - 100 ngmL−1. The precision at 50 ngmL−1 was 2.94% (RSD, n = 5) and the
detection limit was 1.2 ngmL−1. This novel method was validated by determination of silver ions in water samples and the
recoveries in the range of 103-105% were obtained.
Reference
[1]. H. Bai, O. Zhou, G. Xie, J. Xia, Talanta 80, 1638 (2010)
Fabrication of bimetallic Cu/Pt nanoparticles modified carbon paste electrode and its catalytic activity toward hydrogen
evolution reaction
Mohsen sadeghi ,Ali ghaffarinejad , Naghmeh sadeghi*
Department of chemistry, Islamic Azad University, Firoozabad branch, Firoozabad, Fars, Iran
Water electrolysis has been considered as one of the most attractive routes among the existed processes for hydrogen
generation, since the cost of electricity is decreasing, mainly as a result of wind-generated power, hydroelectricity and
nuclear power [1]. Platinum is regarded as ideal catalyst for electrochemical production of hydrogen from aqueous
solution. According to some analysis(2-3), the present resources of Pt are enough to cover only 20% of the automotive
industry needs. So the search for new method to reduce loaded platinum in hydrogen evolution reaction (HER) catalysis
has been a topic of current interest(4-5),deposition of the metallic and bimetallic Cu/Pt species supported on carbon
surfaces by means of substituted phenyl groups(6),and dispersion of the platinum micro particles in polymer matrix(78),are one of the workhorses of electrochemical technology that reduced the cost of anode materials. The film of poly(8hydroxyquinoline) was formed by cyclic voltammetery method on the surface of carbon paste electrode ,p(8-HQ)MCPE,
was prepared. Cu+2ion was adsorbed on the polymer matrix due to complexation with 8-hydroxyquinoline units Copper
nanoparticles galvanic replaced with platinum to fabricate poly(8-hydroxyquinoline)-Pt/Cu composite on the surface of
CPE. Stripping voltammetery of Cu in aqueous 0.1M KSCN+Britton-Robinson buffer, PH=2.0,solution was used to
quantify the copper present on the electrode surface. The amount of platinum was estimated from the electrooxidation
peak of Pt in aqueous 0.1M H2SO4 solution. The nature of Cu/Pt-p(8-HQ) on the surface of CPE was characterized by
scanning electron microscopy.Cu/Pt-(8-HQ) modified CPE can be used as a convenient conducting substrate for electro
catalytic hydrogen evolution reaction (HER). The effects of different parameters such as number of cycles, replacement
time, scan rate of potential and etc were investigated to obtaining optimum condition for HER.in this study, we
demonstrate that poly(8-hydroxyquinoline) prepared on the surface of carbon paste electrode could be used as a suitable
matrix for Cu+2 preconcentration and preparation of Cu nanoparticles loaded p(8-HQ)MCPE. The Cu/Pt-p(8-HQ)/MCPE
could be spontaneously obtained by replacement of copper by platinum.Cu/Pt-p(8-HQ)/MCPE can be used as a
convenient conducting substrate for electrocatalytic hydrogen evolution reaction (HER). The reduction of H+ is
influenced by some factors such as thickness of polymer film, replacement time, acid concentration and scan rate of
potential. This method can be suitable for preparation of other bimetallic nanoparticles based on Cu as the catalyst.
Reference
[1] A. Ursúa, L. Marroyo, E. Gubίa, L. M. Gandίa, Int. J. Hydrogen Energy, 34 (2009) 3221.
[2] Lee K,Zhang J,Wang H,Wilinson DP.Progress in the synthesis of carbon nanotube- and nanofiber-supported Pt electrocatalysts for PEM fuel cell catalysis. Appl
electrochem 2006;3:507-22
[3] Rita M.Technical issues of fuel cell systems for automotive application. Fuel Cells 2002;2:10-4
[4] Gennero MR. Hydrogen evolution reaction on smooth Ni(1-x)+Mo(x) alloys. J Electroanal Chem 1998;448:87_93.
[5] Jukic A, Metikos-Hukovic M. The hydrogen evolution reaction on pure and polypyrrol-coated GdNi4Al electrodes Electrochim Acta 2003;48:3929-37.
[6] Vila N, Van Brussel M, Amours MD,Marwan J,Buess-Herman C, Belanger D. Metallic and bimetallic Cu/Pt species supported on carbon surfaces by means of
substituted phenyl groups. J Electrochem Chem 2007;609:85-93.
[7] Sun L, Ca DV, Cox JA. Electrocatalysis of the hydrogen evolution reaction by nanoparticles and phosphotungstic acid. J Solid State Electrochem 2005;9:816-22
[8] Bouzek K, Magold KM, Juttner K. Electrocatalytic activity of platinum modified polypyrrole films for the methanol oxidation reaction. J Appl Electrochem
2001;31:501-7.
Selective separation of essential phenolic compounds from olive oil mill wastewater (OMWW) across a bulk liquid
membrane followed by HPLC-UV determination
Ali Reza Ghiasvand1,2,*, Shahriar Shadabi1, Payman Hashemi1,2
1
Department of Chemistry, Lorestan University, Khoramabad, Iran
2
Razi Herbal Medicines Research Center, Lorestan University of Medical Sciences, Khoramabad, Iran
Large volumes of Olive oil mill wastewaters (OMWW) especially in Less Developed Countries are discarded every year.
OMWW is very rich in phenolic compounds, have high antioxidant activity, and could be object of significant attention by
pharmaceutical, cosmetic and food industries. Moreover, their biological degradation is the main responsible for their
phytotoxicity and biological difficulties. Recovery of OMWW phenolic compounds would facilitate the waste disposal and, at the
same time, produce valuable natural extracts. The purpose of the present study was efficient transport and selective separation of
caffeic acid (CA), hydroxytyrosol (HTY) and tyrosol (TY) from OMWW using a bulk liquid membrane (LBM). A hand-made 50
mL transport vial consists of two co-axes Pyrex cylinders (20 and 30 mm I.D.) was used. 20 ml of CH2Cl2 was poured at bottom
of the transport vial as liquid membrane. A 5 mL portion of OMWW as donor phase (pH=2.0) and 2.5 ml of double distilled
water, as receiving phase (pH=9.0) were placed on top of BLM. The donor and receiving aqueous phases were separated by
internal Pyrex cylinder (20 mm I.D., two open ends) holed by other one (30 mm I.D., one open end).Various factors influencing
the transport process such as pH of the source phase and receiving phase, nature and volume of BLM, stirring rate and transport
time were investigated. RP-HPLC-UV, gradient elution, using acetonitrile and ammonium acetate buffer (pH=5, 0.01M) was
applied to analyze CA, HTY and TY, in receiving phase. The recoveries for HTY, CA and TY were 28.4±2.0%, 90.1±3.5% and
34.93±2.2%, respectively. Limit of detections (LODs) were obtained to be 5.7×10 -3 mg for HTY, 1.9×10 -4 mg for CA and
1.7×10 -3 mg for TY. Relative standard deviations (RSDs%) were found to 3.8, 4.1 and 3.0% for HTY, CA, and TY, respectively.
The results showed that CA can be separated by high recovery value in the presence of two other phenolic compounds (HTY and
TY). After removing the concentrated CA, further separation of remained (HTY and TY) can be done by using higher transport
times. The proposed method was successfully used to separation of CA, HTY and TY in OMWW samples obtained from olive
oil factories.
Reference
[1] L. Fki, N. Allouche, S. Sayadi, Food Chem. 93 (2005) 197-204.
[2] M.L. Sotoa, A. Mourea, H. Domíngueza, J.C. Parajoa, J. Food Eng. 105 (2011) 1-27.
Extraction and preconcentration of colchicine in plants and pharmaceuticals using DLLME followed by HPLC-UV
determination
Leila Asadkerchi1,*, Ali Reza Ghiasvand1.2, Payman Hashemi1,2, Esfandiar Hasani Moghadam2,3
1
Department of Chemistry, Lorestan University, Khoramabad, Iran
2
Razi Herbal Medicines Research Center, Lorestan University of Medical Sciences, Khoramabad, Iran
3
Agricultural and Natural Resources Research Center of Lorestan, Khoramabad, Iran
Colchicum autumnale (meadow saffron) that has been used in medicine for a long time contains colchicine as the main alkaloid.
Various methods have been reported for direct determination of colchicine, but in this research a new dispersive liquid-liquid
microextraction-high performance liquid chromatography (DLLME-HPLC-UV) was developed for the extraction and
determination of it, for first time. In the proposed DLLME-HPLC-UV method, 500 µL of ethanol (as disperser) containing 100
µL chloroform (as extractant) was rapidly injected, into a 4.5 mL water sample containing the analyte, by a micro-syringe,
resulting is a cloudy solution. After the extraction, phase separation was performed by centrifugation and the enriched analyte in
the sedimented phase were determined by HPLC-UV. Some important parameters, such as the nature and volume of extractant
and disperser, pH of sample solution and salt-addition effect were investigated and optimized with one-at-time and central
composite design (CCD) method.Under the optimum extraction condition, a linear calibration curve (r=0.999) over the range of
0.01-15 µg.mL-1, was obtained for target analyte. Good enrichment factor (55–106) and accepted recoveries (67-92%) were
found for the proposed method. The limit of detection (LOD) was 9.7 ng.mL-1. The relative standard deviation (RSD) for analysis
of 1 ng.mL-1 colchicine, was found to be 1.54%, for seven repeated experiment (n=7). The main advantages of DLLME–HPLC
method are simplicity of operation, rapidity, low cost, high enrichment factor, high recovery, good repeatability and consumption
of hazardous organic solvent of the microliter level. The proposed method was used for the determination of colchicine in and
endemic variety of Colchicum autumnale and pharmaceutical preparation. The results showed good satisfactory agreement with
those obtained by the B. P. pharmacopoeia method and standard methods.
Reference
[1] G. Cocco, D. C. C. Chu, S. Pandolfi, Eu. J. Inter. Med., 21 (2010) 503–508.
[3] M. Rezaee, Y. Yamini, M. Faraji, J. Chromatogr. A, 1217 (2010) 2342-2357.
Application of SFO-LPME combined with HPLC-UV for extraction and determination of Safranal in Saffron samples
Mohammad Biranvand*,1, Mojgan Jamshidi1, Ali Reza Ghiasvand1.2, Payman Hashemi1,2
1
Department of Chemistry, Lorestan University, Khoramabad, Iran
2
Razi Herbal Medicines Research Center, Lorestan University of Medical Sciences, Khoramabad, Iran
Saffron is a dark-red and dried stigma drived from flower of the saffron plant scientifically known as crocus sativus L. saffron is
mostly used as a textile dye or perfume [1] . Recently, solidification of floating drop microextraction (SFODME, SFO - LPME)
as a powerful, rapid and inexpensive new mode of liquid-phase microextraction (LPME) has been developed [2]. In SFODME
small volume of an organic solvent is floated on the surface of aqueous solution. After the completion of the extraction by proper
stirring, the organic solvent is solidified by placing the vial in an ice bath. Finally, the melted droplet is used for analyte
determination. In this research , SFO-LPME method coupled to HPLC-UV has been developed for the extraction and analysis of
safranal in water samples and high quality Iranian Saffron samples. The Different experimental parameters including type and
volume of organic solvent , pH, salt addition effect, temperature ,stirring rate and extraction time were optimized. Under the
optimal experimental condition a linear calibration curve, over the range of 0.1-15 µg.mL-1 (R=0.9978), limit of detection (LOD)
of 0.06 µg.mL-1 , relative standard deviation (RSD%) of 5.8 and Enrichment factor of 252 were obtained. The applicability of
the proposed USAEME method was evaluated by the extraction and determination of safranal in water samples and different
Iranian Saffron samples.
Reference
[1]J.A.Fernandez, Recent Res. Dev. Pl. Sci. 2 (2004) 127.
[2]Durukan, C.A. Sahin, S. BektaS, Microchem. J. 98 (2011) 215-219
Dispersive liquid- liquid microextraction and HPLC determination of Guaifenesin enantiomers; application in study of
stereoselective excretion in human urine
1
Mehdi Hatami1*, Khalil Farhadi1, Assem Abdollahpour2
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
2
Jaber Ebne Hayyan Pharmaceutical Company, Tehran, Iran
A simple, rapid, and efficient method, dispersive liquid–liquid microextraction (DLLME) coupled with HPLC-fluorescence
detector, has been developed for the determination of guaifenesin (GUA) (an expectorant drug) enantiomers in human urine
samples after a dose oral administration of its syrup formulation. Urine samples were collected during the time intervals 0-2, 2-4
and 4-6 h and concentration and ratio of two enantiomers was determined. The ratio of R-(-) to S-(+) enantiomer concentrations
in urine showed an increase with time. GUA has been separated enantiomerically by HPLC on a chiralcel OD [1], chiralpak IA
[2], simulated moving bed chromatography [3] and crystallization [4]. But, these methods were qualitative separations and until
now, there was no quantitave method for study of GUA enantiomers behavior in urine. For microextraction process, a mixture of
extraction solvent (100 µL dichloromethan) and dispersive solvent (1 mL THF) were rapidly injected into 5.0 mL diluted urine
sample for the formation of cloudy solution. Both of enantiomers in the sample were extracted into CH 2Cl2. After extraction,
phase separation was performed by centrifugation and sedimented phase was dried by nitrogen steam. Enriched analytes were
dissolved in mobile phase and finally injected to HPLC. After optimization of HPLC enantioselective conditions and obtaining
some thermodynamic parameters for retention of GUA enantiomers on selected chiral column [5], some important parameters,
such as the kind and volume of extraction solvent and dispersive solvent, extraction time, temperature, pH and salt effect were
investigated and optimized for DLLME process. Under the optimum extraction condition, the method yields a linear calibration
curve in the concentration range from 10 to 2000 ng mL−1 for target analytes. Limit of detections were 3.00 ng mL−1 for both of
enantiomers.
Reference
[1] I. Demian, Chirality 5 (1993) 238–240.
[2] Z. Miriam, Z. Michal, R. Alirio, Sep Sci Technol 44 (2009) 275-303.
[3] C. Langel, C. Grossmann, M. Morbidelli, M. Morari, M.Mazzotti, Journal of chromatography A, 1216 (2009) 8806–8815.
[4] A. A. Bredikhin, Z.A. Bredikhina, S.N. Lazarev, D.V. Savel’ev, Mendeleev Commun. 13 (2003) 104- 105.
[5] I. Slama, E. Jourdan, A. Villet, C. Grosset, A. Ravel, E. Peyrin, Chromatographia 58 (2003) 399.
Study of complex formation of kryptofix 222 with La3+ cation in binary mixed non-aqueous solvents using conductometric
method
S. Dolatshahi . *G . H. Rounaghi
Department of chemistry, Faculty of sciences, Islamic Azad university of Mashhad, Mashhad, Iran
Crown ethers have drawn much attention because of their ability to selectively bind various cations present in solutions. With this
unique property, the potential applications of crow ethers have been found in many diverse and practical areas. The
complexation reaction of macrocyclic ligand, kryptofix 222 (k222) with La3+ cation was studied in cetonitrile (AN), ethylacetate
(EtO Ac), methylacetate (MeOAc) 1,2 dichloroethane (1,2 DCE), with methanol (MeOH) at different temperatures using the
conductometric method. The conductance data show that in all solvent systems, k222 forms 1:1 [ML] complex, but in the case of
1,2 DCE – MeOH binary systems a 1:2 [Ml2] complex is formed in solution. The obtained results show that the stability of
(kryptofix.La)3+ complex is sensitive the composition of the mixed solvents. A non- linear behavior was observed for changes of
log Kf of (kryptofix. La)3+ complex versus the composition of the mixed solvent solutions.The values of the standard
thermodynamic parameters ( DH o c and DS o c ) for formation of (kryptofix. La)3+ complex were obtained from temperature
dependence of the stability constant using the van't Hoff plots. The results show that in all cases, the (kryptofix.La)3+ complex is
entropy stabilized, but depending on the solvent system, it is enthalpy stabilized or destabilized.
Reference
[1] Rounghi, G.H. Ghaemi, A.: complexation of 4' – nitrobenzo – 15– crown -5 with Mg2+ , ca2+, sr2+ , and Ba2+ metal cations in acetonitrile – methanol binary
solution. Russ. J. Inorg. Chem.. 54 , 2003-2008 (2009).
[2] Rounghi, G.H. Razavipanah, E.: complexation of 4' – nitrobenzo – 15– crown -5 with Li+ , Na+, K+ , and NHy2+ cations in acetonitrile – methanol binary solution.
J. Incl. phenom. Macrocycl. Chem. 61 , 313-318 (2009)
Prediction of GC retention indices for nitrogen-containing polycyclic aromatic compounds using classification and
regression tree analysis and adaptive neuro-fuzzy inference systems
K. Zarei*, M. Atabati, M. Alinejad
School of Chemistry, Damghan University, Damghan, Iran
Retention time is a very important parameter for qualitative analysis in chromatography. In this study a successful combination of
feature selection and feature mapping tools, CART and ANFIS, is represented for prediction of retention of nitrogen-containing
polycyclic aromatic compounds. Classification and regression tree (CART) analysis is a statistical method that explains the
variation of a response variable using a set of explanatory variables, so called predictors. The method is based on a recursive
binary splitting of the data into mutually exclusive subgroups containing objects with similar properties [1,2]. The results are
promising and indicate the power of the CART-ANFIS techniques in developing methods with good prediction ability. The
synergism of fuzzy logic (FL) systems and neural networks (NN) has produced a functional system capable of learning, high
level thinking, and reasoning [3]. The network structure that implements FL is referred to as an adaptive neuro-fuzzy inference
system (ANFIS). The goal of ANFIS is to find a model or mapping that will correctly associate the inputs (descriptors) with the
target (property) [4]. In this work, a quantitative structure–property relationship (QSPR) was developed to predict the GC
retention indices for nitrogen-containing polycyclic aromatic compounds. A set 1497 zero to three-dimentional descriptors were
generated by Dragon software and used for each molecule in the data set. Classification and regression tree (CART) were
successfully used as a descriptor selection method using SPSS software. Three descriptors Moreau-Broto autocorrelation
(ATS2V) from 2D- Autocorrelations class, Detour index (w) and connectivity index (χ3) from topological class were selected and
used as inputs for adaptive neuro-fuzzy inference system (ANFIS). The root mean square errors for the calibration, prediction and
validation sets were 9.28, 11.31 and 11.48, respectively. The results were compared with those obtained from artificial neural
network (ANN). The results showed CART-ANFIS can be used as a powerful model for prediction of the GC retention indices
for nitrogen-containing polycyclic aromatic compounds.
Reference
[1] R. Put, C. Perrin, F. Questier, D. Coomans, D.L. Massart, Y. Vander Heyden, J. Chrom. A 988 (2003) 261-276.
[2] M. Atabati, K. Zarei, E. Abdinasab, Bull. Korean Chem. Soc. 30 (2009) 2717-2722.
[3] L.A. Zadeh, Infom. Control 8 (1965) 338-353.
[4] M. Jalali-Heravi, P. Shahbazikhah, Electrophoresis 29 (2008) 363-374.
Spectroscopic Studies on the binding of Idarubicin Hydrochloride with fish sperm DNA
a
Farkhondeh panahi* ,b Reza Hajian
Department of Chemistry, Islamic Azad University branch of Gachsaran, Gachsaran, 75818-63876, Iran
E-mail: fpanahi2009@yahoo.com
b
Department of Chemistry, Islamic Azad University branch of Gachsaran, Gachsaran, 75818-63876, Iran.
E-mail: Hajian@iaug.ac.ir
a
In this paper, lnteraction between Idarubicin Hydrochloride and fish sperm DNA was investigated by spectroscopy [1]. Idarubicin
is a relatively hydrophobic member of the anthracycline family. By use of fluorescence spectroscopy, it is shown that Idarubicin
Hydrochloride binds to DNA with binding constant (K) of 6.7×104 mol-1L [2].The number of binding points of the Idarubicin to
DNA (n), has been determined through spectrofluorometric study as 1.2. Thermodynamic parameters including
DH 0 , DS 0 and DG 0 for the interaction between Idarubicin Hydrochloride and fish sperm DNA have also determined by
spectrophotometry. DNA melting experiments were carried out by monitoring the absorbances of the sample at different
temperatures in the absence and presence of the DNA. The results indicated that Idarubicin Hydrochloride can bind to DNA and
the major binding mode is intercalative binding.
Reference
[1] Zhang, G., Guo, J., Zhao, N., Wang, J., Sensors and Actuators B: Chemical (2009) 144,239-246.
[2] Zhouhua, Z., Yi, L., Xianming, H., Zhenqiang, X., Kun, Z., Chinese Journal of Chemistry, 2009, 27, 681-686
A Study of Peroxyoxalate Chemiluminescence System of 1,4-Dihydroxy-3-methyl-thioxanthone and
Quenching Effect of β-Cyclodextrin
Abdollah Yari*,Maryam Karami
Department of Chemistry, Faculty of Science, Lorestan University, Khorramabad, Iran
E-mail:a.yari@ymail.com
Chemiluminescence (CL), which is the production of light through a chemical reaction, is a sensitive and selective analytical
technique for determination of chemical compounds. [1,3] Recently, the application of CL in food and pharmaceutical industries
and biomedical analyses, owing to its simplicity and a need of simple instrumentation without a light source, has been developed.
[2,4] In this paper, CL behavior of the reaction between bis(2,4,6-trichlorophenyl)oxalate (TCPO) and hydrogen peroxide in the
presence of 1,4-dihydroxy-3-methyl-thioxanthone(DHMTH) as a fluorophore, has been investigated. Effect of solvent and
concentration of TCPO, sodium salicylate (SS), hydrogen peroxide and DHMTH were optimized. The CL signal showed a linear
decay while β-Cyclodextrin was added to the peroxyoxalate (PO-CL) system. The results showed a Stern–Volmer function, from
which Kq value of 2.35 was obtained by computer fitting of the experimental CL intensity to a proper model. The evaluated lower
and upper detection limits of β-Cyclodextrin determination were 4.0×10-6 and 1.0×10-4 M in solution, respectively.
Reference
[1] X. Yan, J.Chromatogr.A 842 (1999) 267.
[2] L.G. Gracia, A.M. Campa, J.F.H. Pérez, F.J. Lara, Anal.Chim.Acta 640 (2009) 7.
[3] A. Yari, M.Saidikhah, J.Lumin.130 (2010) 709.
[4] M. Tsunoda, K. Imai, Anal. Chim.Acta 541 (2005) 13.
Quenching Effect of Alanine on Peroxyoxalate Chemiluminescence of Bis[N-(4-pyridyl)-p-toluen
Sulfonamide] Palladium dichloride
Abdollah Yari*, Ebrahim Mehdipour,Maryam Karami
Department of Chemistry, Faculty of Science, Lorestan University, Khorramabad, Iran
E-mail:a.yari@ymail.com
Peroxyoxalate chemiluminescence (PO-CL) system is a well-known and powerful means of detecting hydrogen peroxide and
variety of fluorophores.[1] PO-CL method has been widely utilized in environmental, pharmaceutical and biomedical analyses
owing to its high sensitivity and a need of simple instrumentation without a light source.[2-4] Here, we are investigating the fast
chemiluminescence (CL) arising from the reaction of bis(2,4,6-trichlorophenyl)oxalate (TCPO) system with bis[N-(4-pyridyl)-ptoluene sulfonamide] palladium dichloride (PTSP) as a novel fluorophore. The optimum concentration of Sodium salicylate (SS)
as catalyst has been studied. The relationships between the chemiluminescence intensity and concentrations of TCPO, (SS),
hydrogen peroxide and PTSP are reported. The plot of the reaction, functioning in a Stern–Volmer fashion, resulted in estimating
Kq of 6.02 × 103. Then the quenching effect of Alanine amino acid were studied, from which the CL system was able to
determine the Alanine concentration in some real samples.
Reference
[1] E.A. Chandross, Tetrahedron Lett. (1963) 761.
[2] A. Yari, M.Saidikhah, J.Lumin.130 (2010) 709.
[3] M.Shamsipur K.Zargoosh, S.M.Hosseini,C.Caltagirone, V.Lippolis, Spectrochim.Acta A 74 (2009) 205.
[4] M. Tsunoda, K. Imai, Anal. Chim.Acta 541 (2005) 13.
Use of prosopis glandulosa torreyana as a natural, low cost and new absorbent for removal of dye (acridine
orange) from aqueous solution via adsorption: kinetic and thermodynamic study of removal process
A. Shokrollahi*, S. Sharifi
Department of Chemistry, Yasouj University, Yasouj, Iran, 75918-74831
Email: ashokrollahi@mail.yu.ac
Many of the industrial dyes are toxic, carcinogenic, mutagenic and teratogenic [1]. Then their removal from wastewater is of
great interest. Acridine Orange (AO) is a nucleic acid selective metachromatic stain useful for cell cycle determination. AO
interacts with DNA and RNA by intercalation or electrostatic attraction respectively. The biological effects of AO, which
includes photodynamic and mutagenic actions of the dye, constitute another large area of research [2]. In the past few years low
cost adsorbents agricultural wastes such as soy meal hull, rice husk and sugar beet pulp have been employed to overcome the
economic disadvantages [3]. In the present investigation, seeds of prosopis glandulosa torreyana are used as adsorbent and it has
been successfully used for the removal of acridine orange, from water samples. The adsorbent is prepared by an acid. The effect
of various parameters such as: pH, amounts of adsorbents, size adsorbent particles and contact time on removal processing was
investigated. The experimental data correlated reasonably well by the Freundlich adsorption isotherm and isotherm parameters
were calculated. The surface morphology studies using SEM proves that, it contains move pore that leads to develop more
adsorption sites. Adsorption process is dependent on pH and temperature and follows pseudo second – order kinetics rate model.
The values of ΔH, ΔS and ΔG results shows that the adsorbent employed has a considerable potential as an adsorbent for the
removal of dye.
Reference
[1] H.A. Mekkawy, M.O. Ali, A.M. El-Zawahry, Toxicol. Lett. 95 (1998) 155.
[2] A.A. Ogunjobi, O.E. Fagade, O.O. David, Afr. Biomed. Res. 10 (2007) 275.
[3] A. mittal, D. kaur, J Mittal, J. Colloid interface sci. 8 (2008) 326.
Rice Bran as an Adsorbent for Removal of Blue G from Wastewater
M. R. Fat’hi, Iman Nikpay*
Department of Chemistry, College of Basic Science, Islamic Azad University,
Gachsaran Branch, Gachsaran, IRAN.
E_mail : fathiemadabadi@yahoo.com , iman_nikpay@yahoo.com
In textile industries large amounts of water and chemicals are used for dyeing process. The wastewaters of these industries
usually consist of a number of contaminates including acids, bases, dissolved solids, toxic compounds and organic dyes.
Activated carbon is the most popular and widely used adsorbent, but it is highly expensive. Therefore, there is a growing interest
in finding low-cost, easily available material for the dye removal for industrial waste. The Capability of rice bran for removal of
Blue G from aqueous solution was studied. An aliquot of the Blue G solution, at pH=5 and 25±1oC was passed through a mini
column containing 0.4g rice bran (100 mesh). The absorbance of Blue G was measured spectrophotometrically at λmax = 668 nm
before and after passing of Blue G through the column. Finally, the percent of removal of Blue G was calculated by using a
calibration curve of Blue G. The effects of various experimental parameters such as particle size rice bran (40, 60, 100 mesh),
temperature (25, 35, 45oC), dye concentration (40, 60, 80 mg/L), the pH of solution (5-9) and electrolyte concentration were
studied; and optimal conditions were selected. It was found that the extent of removal of the dye was related directly to the
surface area of the adsorbent.
Reference
[1].Safa Ozcn, A.; Erdem, B.; Ozcan, A; J. Coll. Inter. Sci. 280(2004) 44-45.
[2].Ei-Daly, H.; Habib, A. F. M., Dye & Pigment. 54(3) (2002) 197-210.
[3].Pandy,H.V.; Prasad,G.; Singh,V.N.; Water Res. 19(1985) 291-296.
Determination of silver by flame atomic absorption spectroscopy (FAAS) after preconcentration using sulfur nanoparticles as a new sorbent
Mozhgan tirnia*, Behzad Aibaghi Esfahani
School of Chemistry, Damghan University
E-mail: mozhgan.tirnia@gmail.com
The increasing use of silver compounds and silver containing preparations in industry and medicine, has resulted an increased
silver content of environmental samples. Silver also enters the environment in industrial waters because it often occurs as an
impurity in copper, zinc, arsenic and antimony ores. Low level exposure to silver compounds is widespread due to the use of
soluble silver compounds to disinfect water used for drinking [1]. Thus, measuring of silver is importance and among
determination of techniques, Solid Phase Extraction (SPE) is one of the most important preconcentration methodologies because
of its simplicity, flexibility to choose the solid phase, high preconcentration factor, low consumption of the organic solvents, low
cost and extraction time for sample preparation [2]. In this paper describes the use of sulfur nano particles as a new sorbent for
separation and preconcentration of trace silver prior to its determination by flame atomic absorption spectrometry (FAAS). In this
method, aqueous solutions that contain of silver ions were adsorbed quantitatively during passage of column through sulfur nanoparticles sorbent. After the preconcentration and separation stage, the analyte was eluted with hydrochloride acid 5.0 M and
determined by FAAS. Different factors such as pH of sample, type and volume of buffer, volume and concentration of eluent,
sample volume, amount of sorbent, flow rate of eluent and sample solution and effect of diverse ions were examined. The limit of
detection based on three times the standard deviation of the blank was 0.458 ng.mL-1. The calibration graph was linear in the
range of 2-40 ng.mL-1. The proposed procedure was applied for silver determination in babol river water, radiology film and
silver sulfadiazine (scald pomade) samples.
Reference
[1]. J. Manzoori, G. Karim-Nezhad, Anal. Chim. Acta. 484 (2003) 155-161.
[2]. H. Parham, N. Pourreza, N. Rahbar, J. Hazard. Mater., 163 (2009) 588-592.
Determination of Nitrite and TCAA Using Electrocatalytic Redox of CdO Nanoparticles Modified Carbon Paste Electrode
M. Najafi*, B. Ahmadian
Imam Hussein University, Faculty of science, Department of Chemistry
Unique properties of carbon paste electrodes which are ease of preparation, low cost and refreshable surface have made modified
carbon paste electrodes as an excellent candidate for chemical sensors [1-5]. In this research cadmium oxide nanoparticles
synthesized by mechanochemical method have been used for modification of electrode [6]. By investigating electrochemical
properties of the electrode using cyclic voltammetry in different conditions pertaining to solution type and pH, optimized
condition has been obtained. Presence of nitrite and trichloroacetic acid (TCAA) in solution showed a great enhancement in peak
currents, due to their electrocatalytic properties for the redox of cadmium oxide. Results show this increment is suitable for the
quantitative determination of Nitrite and TCAA in aqueous solutions.
Reference
[1]. Reddy S. ,et al. ,"Synthesis of CdO Nanoparticles and their Modified Carbon Paste Electrode for Determination of Dopamine and Ascorbic acid by using Cyclic
Voltammetry Technique", Int. J. Electrochem. Sci. ,5 (2010) 10 – 17.
[2]. Miscoria S.A. ,et al. ,"Enzymatic Biosensor Based on Carbon Paste Electrodes Modified with Gold Nanoparticles and Polyphenol Oxidase", Electroanalysis, 17
(2005) 1578–1582.
[3]. Helia H. ,et al. ,"Copper nanoparticles-modified carbon paste transducer as a biosensor for determination of acetylcholine", Biosensors and Bioelectronics, 24
(2009) 2328–2333.
[4]. Siswana M. ,et al. ," Electrocatalytic behaviour of carbon paste electrode modified with iron(II) phthalocyanine (FePc) nanoparticles towards the detection of
amitrole ", Talanta, 69 (2006) 1136-1142.
[5]. Mazloum Ardakani M. ,et al. ,"Electrocatalytic oxidation and nanomolar determination of guanine at the surface of a molybdenum (VI) complex–TiO2
nanoparticle modified carbon paste electrode", Journal of Electroanalytical Chemistry, 624 (2008) 73–78.
[6]. Tadjarodi A., M. Imani, “Synthesis and characterization of CdO nanocrystalline structure by mechanochemical method”, Materials Letters, 65 (2011) 1025-1027
Grafting of Acrylic acid /Acrylamide on poly(ethylene terephthalate Fiber for Removal of Brilliant Green in
Environmental Samples
Nika Shakerin*,Dr Homayoun Ahmad Panahi,Farahnaz Zolriasatain,Zahra Khamse safa,Ataolah Panahyab.
Department of Chemistry, Islamic Azad University, Central Tehran Branch, Iran
A new fibrous adsorbent was prepared by grafting Acrylic acid /Acryl amide (AA/AAm) co-monomers onto poly (ethylene
terephthalate) (PET) fibers. The resulting sorbent has been characterized by FT-IR, elemental analysis, thermogravimetric
analysis (TGA), and studied for removal of trace brilliant green from environmental water samples. The optimum pH value
for sorption of the brilliant green was 6. The sorption capacity of functionalized fiber is 65.5 mg. g−1. The sorbent can be
reused for 5 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of upper 90% was
obtained for the brilliant green with 0.5 M nitric acid as eluting agent. Effect of grafting yield, shaking time and pH of the
medium on adsorption of the brilliant green were investigated. The equilibrium adsorption data of brilliant green on
modified fiber were analyzed by Langmuir, Freundlich, Temkin and Redlich–Peterson models. The method was applied for
brilliant green determination from river water sample.
Reference
[1]. M.Balabanova,L.Popova,R.Tchipeva,Disease-a-Month,50(6),2004,270-279
[2]. http://www.britannica.com/EBchecked/topic/79627/brilliant-green
Application of dispersive liquid-liquid microextraction coupled with flame atomic absorption spectrometry (DLLMEFAAS) for determination of trace amounts of cobalt in water samples
N. Goudarzi, G. Bagherian, Arezoo Afrougheh
E mail: Afroughe@gmail.com
Determination of trace amounts of cobalt is important in industrial, environment, and geochemical samples. A new simple and
reliable method based on dispersive liquid-liquid microextraction preconcentration and flame atomic absorption spectrometry
detection for determination of cobalt was developed. In this work, hydroxynaphthol blue (HNB) was used a complexing agent to
form a complex with cobalt. The effective parameters on the extraction recovery such as pH, type and volume of buffer, ligand
concentration and type of extraction and disperser solvents and also those volumes were investigated. The average relative
standard deviation for five repeated measurements was %0.7. Also, this procedure was used to determine of cobalt in water
samples and its detection limit is 0.15 ppb.
Reference
[1] S. Berijani,Y. Assadi, M. Anbia, M. R. M. Hosseini, E. Aghaee, J. Chromatogr. A 1123 (2006) 1.
[2] F. Ahmadi, Y. Assadi, M. R. M. Hosseini, M. Rezaee, J. Chromatogr. A 1101 (2006) 307.
The feasibility of replacing usual polarimetric method for measuring the sugar beet assay in the Iranian sugar factories
with semi automatic pressure filtration- near infrared polarimetric technique
F. Hozeire1, 3, M. Abdollahian- noghabi* 2 and Z. Es’haghi 3
Khorasan’s Sugar Beet Research & Farming Services Company
2
Sugar Beet Seed Institute, P.O. Box 31585-4114, Karaj, Iran
3
Department of Chemistry, Payame Noor University, 19395-4697 Tehran, Iran
1
Polarimetry is an exact and quick manner to measure the sugar (sucrose) which is in the sugar beets roots. In the sugar factories
of Iran usually is considered sugar beets assay with the sodium light source which wave length is 589 nm with the usual
polarimetric method. In order to purify the root plough in this manner is used of lead acetate. Recently a new method is used
based on a near infrared (NIR) polarimetric. Use of a NIR polarimeter negates the need for lead acetate clarification. The method
is suitable for both juice and raw sugar samples. Sugar of lead (lead acetate) has long been a favorite agent for the mentioned
process. Lead (IV) acetate may be fatal if ingested, inhaled, or absorbed through skin. It causes irritation to skin eyes, and
respiratory tract. It is a neurotoxin too. It affects the gum tissue, central nervous sys here we tem, kidneys, blood, and
reproductive system. Thus because of these serious problems we have tried to study the possibility of replacing the new method
with the usual polarimetric method. In order to do this we have selected the fresh plough specimens from different parts of
Khorasan-e Razavi state randomly and not only extracted but also measured their assays in the two ways. The temperature and
humidity conditions were the same for the two manners. We mixed each of the plough batches to reach a complete homogenous
compound. Then it was divided to two equal parts and measured their assays with the both mentioned methods. Extractions were
occurred under the ambient pressure with the mixing of 26 g. ploughs with 177 ml distilled water and 15 g fossil soil in the semi
automatic pressure filtration- near infrared polarimetric technique (Auto Filt-NIR) manner while in the usual manner we have
extracted 26g plough with 177ml lead acetat solution. We have examined the optimal conditions such as: type and number of the
filter papers, the time and stirring speed the mixture before extraction, time and pressure needed to reach extraction in the Auto
Filt manner-NIR in the three levels. We have resulted that in the Auto Filt manner we can use the usual 4 layer filter paper which
is much cheaper instead of the 2 layers which was introduced in the routine catalogues. The speed and time of the mixing had not
effect in the final assay. According to the experiments sugar percentage that was yielded by Auto filt-NIR was not significant
difference with the old method.
Reference
[1] Van der poel P W, Schiweck H, Schwartz T. Raw Sugar. .I.C.U.M.S.A.(1998)1125.
[2] Singleton V, Horn J, Bucke C, Adlard M, J American Soci. Sugar. Technol. 22(2002) 112.
Extraction of curcumin from turmeric using magnetic iron oxide nanoparticles as solid phase extractor and it's
determination by HPLC
Mohammadreza Hadjmohammadi*, Ghamar Salamat, Vahid Sharifi
Department of chemistry, University of Mazandaran, Babolsar, Iran
Curcumin, a derivative of Curcuma longa, is used extensively in the food industry and researches have shown the health benefits
of this compound [1]. In this work, a novel, simple and rapid method for extraction and determination of curcumin in turmeric
was performed using magnetic iron oxide nanoparticles (MIONs) as solid phase extractor and HPLC. The unique properties of
nanoscale materials offer excellent prospects for designing new methods and instrumentation for chemical analysis [2]. The
MIONs were synthesized according to the method proposed by Laurent et al [3] and the average size of nanoparticles was in the
range of 90 nm determined by atomic force microscopy (AFM). Extraction of curcumin is based on adsorption of Fe 3+–
curcumin complex on MIONs. Desorption of analyte was performed by NaOH solution containing methanol in order to dissolve
analyte. Various parameters affecting the extraction recovery such as: pH, volume and concentration of NaOH as desorbing
reagent, complexation time, extraction time, MIONs weight, concentration and volume of sample, concentration and volume of
Fe +3 and percentage of methanol were investigated and optimized. The optimized parameters were: pH= 2.0, 1.5 mL of 0.2 M
NaOH in 30% methanol, 8 min complexation time, 6 min extraction time, 0.5 g of MIONs weight, 150 ml of 5 ppm curcumin,
and 1.25 ml of 0.1 M of Fe 3+. The intra-day (R.S.D.), inter-day (R.S.D.) precision and enrichment factor were 4.0%, less than
7.0% and 100 respectively. The proposed procedure was successfully applied to the determination of curcumin in turmeric.
Reference
[1] R. M. Srivastava, S. Singh, S. K. Dubey, K. Misra, A. Khar, Inter. Immunopharmacol. 2011, 11, 331–341
[2] M. Trojanwicz, Trends Anal. Chem. 2006, 25, 480–489.
[3] S. Laurent, D. Forge, M. Port, A. Roch, C. Robic, L. V. Elst, R. N. Muller, Chem. Rev. 2008, 108, 2064- 2110
Microwave digestion of marine sediments for heavy metals analysis
Mortazavi, M.S.; Aghajery, N
Persian Gulf and Oman Sea Ecological Research Institute, Post Code 79167-93165 P.O.Box 79145-1597,Bandar Abass,Hormozgan
Email: mseddiq1@yahoo.com
The assessment of trace metals in marine sediments is commonly related to digestion method. This study focused on digestion
condition of marine sediments for determination of Cr,Ni,V,Cu,Fe,and Mn using atomic absorption spectroscopy. The digestion
was achieved by using three mixture including HNo3+HF,HCl+HNo3,and H2So4.The experimental study was conducted using
Certified Reference Material(CRM).Two different programs was examined to determine which was optimal for the digestion of
samples.The accuracy and precision of the two digestion programs for the analysis of CRM were compared. Result of this study
revealed mixture of HNo3+HCl and microwave program providing maximum of power and time resulted in the best analytical
performance.
Optimization of alcoholic assistant dispersive liquid-liquid microextraction for determination of phthalate esters
Mohammad Reza Hadjmohammadi, Mohammad Hosein fathemi, Panteha Shakeri*, Pouria Biparva,
Department of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, I.R. Iran
The sample preparation step in an analytical process typically consists of an extraction procedure that results in the isolation and
enrichment of components of interest from a sample matrix. Extraction can vary in degree of selectivity, speed and convenience
and depends on the approach and conditions used [1]. Recent research has been oriented towards the development of efficient,
economical and miniaturized sample preparation methods. Phthalate esters are used primarily as plasticizers in polymeric
materials to increase their flexibility only through the weak secondary molecular interactions with polymer chains, phthalate
esters may release to the environmental during the production, using and incineration of polymeric materials containing these
compounds [2, 3]. In the present study, a new microextraction technique alcoholic-assisted dispersive liquid-liquid
microextraction (AA-DLLME) method was developed for determination of phthalate esters in environmental samples by HPLC.
A feature of this procedure lies in that alcoholic solvents can be used as extraction solvents and disperser solvents. Factors
affecting the extraction efficiencies of Phthalate esters (volume of extraction solvent, volume of dispersive solvent, salt amount
and stirring time) were investigated by a full factorial design to identify important parameters and their interactions. Based on
pareto chart volume of extraction solvent and salt amount was selected as important factors. Then, a central composite design
was applied to obtain optimum conditions that were as follows: volume of extraction solvent (2-erthyl-1-hexanol): 175 μl and 1.4
g of salt (NaCl) in sample solution. The results demonstrated that the enrichment factors of Phthalate esters were separated in the
range of 190 to 200. The limits of detection were in the range of 1-0.8 ng/mL. The relative standard deviations (R.S.D) for
extraction of phthalate esters were in the range of 5.1-7.2. Finally, this extraction method was successfully used for the fast
determination of phthalate esters in environmental water samples.
Reference
[1] J. Pawliszyn, Anal. Chem. 75 (2003) 2543.
[2] C.A. Staples, D.R. Peterson, T.F. Pakerton, W.J. Adams, Chemosphere 35 (1997) 667.
[3] D. Balafas, K.J. Shaw, F.B. Whitfield, Food Chem. 65 (1999) 279.
Taguchi L16 orthogonal array design for optimization of the removal of Cadmium (II) using Carpinus betulus tree leaves
N-Asanjarani , T.Shariatmanesh, J. Zolgharnein*, A. Zolanvari
Department of Chemistry, Faculty of Science, Arak University, Arak, Iran
E-mail: J-zolgharnein@araku.ac.ir
Taguchi orthogonal design was used as an experimental multivariate optimization approach for the adsorption of the Cadmium
(II) onto Carpinus betulus tree leaves in a batch system. The effective factors on adsorption process such as: temperature (25–55
◦C), amount of sorbent (2–17 g L-1), initial concentration of Cd(II) (20–140 mgL−1), pH (2–6.2), and the mesh size (40-200)
were considered via using an L16 orthogonal array design. Taguchi analysis is based on choosing the best run by analyzing signalto-noise ratio(S/N), whose form depends on the objective of the experiment. So, the removal percentage(R %) of Cd(II) was
transformed into an accurate S/N ratio for a “high is better” response. The pH was found to be the most effective factor for
promoting Cd(II) removal. The best conditions for biosorption of Cd(II) were determined by the Taguchi optimization approach
as: sorbent amount of 12 g L-1, an initial concentration of 20 mg L−1 and pH 3.4. The mesh size and the temperature have not
significant effect on removal process. A non linear approach was used for the fitting the experimental data with Langmuir
isotherm as the best equilibrium model with the maximum capacity uptake of 45.6 mg g-1. The biosorption process was
kinetically fast and followed by a pseudo-second order kinetic model. Thermodynamics investigations showed that biosorption
process was spontaneous and exothermic. FT-IR analysis confirmed that the main functional groups of sorbents have been
involved through the biosorption process. In addition, X-ray diffraction (XRD) analysis was utilized as complementary
confirmation on the biosorption mechanism.
Reference
[1] Ozcan Tan, A. Sahin Zaimoglu, Sinan Hinislioglu, Selim Altun, Taguchi approach for optimization of the bleeding on cement-based grouts, Tunnelling and
Underground Space Technology 20 (2005) 167–173
[2] María P. Elizalde-González, Virginia Hernández-Montoya, Removal of acid orange 7 by guava seed carbon:A four parameter optimization study, Journal of
Hazardous Materials 168 (2009) 515–522
[3] Javad Zolgharnein, Neda Asanjarani, S. Norollah Mousavi, Optimization and Characterization of Tl(I) Adsorption onto Modified Ulmus carpinifolia Tree Leaves,
Clean – Soil, Air, Water 2011, 39 (3), 250–258
Simultaneous Spectrophotometric Determination of Gallium (III) and Thallium (III) Using Multivariate Calibration
Aapproach
N. Asanjarania, T. Shariatmanesha, J. Ghasemib, J. Zolgharneina*
Department of Chemistry, Faculty of Science, Arak University, Arak
b
Department of Chemistry, Khajeh Nasir Toosi University of Technology, Tehran
E-mail: J-zolgharnein@araku.ac.ir
a
The simultaneous determination of Gallium (III) and Thallium (III) mixture is a complicated complex system due to the high
spectral overlapping. There is no any report for simultaneous determination of them. In this study, a new method for the
simultaneous spectrophotometric determination of the Gallium and Thallium based on their complexes formation with 4-(2Pyridylazo)-resorcinol (PAR) is proposed. A comparative study of the results that were obtained for simultaneous determinations
in mixture by using principal component regression (PCR) and partial least-squares regression (PLS) have been presented. The
relative error prediction (RPE) P for Gallium and Thallium and with PCR and PLS were obtained to be PLS: 4.31, 4.70 and PCR:
4.84, 5.05 respectively. The pH effect on the sensitivity and selectivity was studied according to net analyte signal (NAS)
approach. The pH 5.5 was selected as the optimum value to compromise the sensitivity and selectivity of these metal ions. As a
conclusion of this study, it is found that the two multivariate calibration methods are suitable choices to resolve overlapped
absorption spectra of mixture of these ions with PAR.
Reference
[1] R. Ergon, Constrained numerical optimization of PCR/PLSR predictors,Chemom. Intell. Lab. Syst. 65 (2003) 293.
[2] J. Ghasemi, N. Shahabadi,H. R.Seraji, Spectrophotometric simultaneous determination of cobalt ,copper and nickel using nitroso-R-salt in alloys by partial least
squares, Analytica Chimica Acta 510 (2004)121-126.
[3] J. Zolgharnein, A. Shahrjerdi, Gh. Azimi, J. Ghasemi, Spectrophotometric Determination of Trace Amounts of Fluoride sing Al -Xylenol Orange Complex as a
Colored Reagent, Anal. Scien.,25(2009)1249.
Syntheses of new asymmetric triazene ligand and solution studies of two types of Uranium and Thorium complexes with1(2-Ethoxyphenyl)-3-(4-Nitrophenyl)triazene (ENT)
Mohammad Kazem Rofouei*, Salameh Azimi, Samira Mohammad Sharifkhani
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
Email: sally_azimi@yahoo.com
The synthesis of 1-(2-ethoxyphenyl)-3-(4-nitrophenyl) triazene (ENT), [HL], and the reaction of ENT with U4+and Th4+ in
acetonitrile as solvent, resulted in the formation of [UL2] and [ThL], are reported in this article. The resulting absorbance against
[M4+]/[Hl] mole ratio plot, reveals distinct inflection points at a metal-to-ligand molar ratio of about 0.5 and 1 emphasizing the
formation of a 1:2 and 1:1 complexs, respectively. The 1-(2-ethoxyphenyl)-3-(4-nitrophenyl) triazene (ENT) used as ligand and
its structure is shown in Fig. 1. It was synthesized as follows: A 100 ml flask was charged with ice and water and then cooled to 0
°C in an ice-bath. After that, 0.69 g of para nitroaniline and 3.61 g of hydrochloric acid (d=1.18 g mL−1) were added to the
mixture, and then a solution of NaNO2 containing 0.35 g in 10 ml of water was added. Afterwards, 0.68 ml of 2-Ethoxyaniline
was added drop wise with vigorous stirring for a period of 30 min to this mixture. Finally, a solution containing 14.76 g of
sodium acetate in 45 ml of water was added and stirred. The orange-colored product was filtered and dissolved in diethyl ether.
After the evaporation of diethyl ether, a purified sharp pale orange powder, which has a melting point of 101–102 °C, was
produced (yield, 72%). In a typical procedure, the absorbance of 2.0 ml of ligand was measured by UV spectrophotometer. Then
a known amount of the concentrated solution of Uranil (IV) nitrate or Thorium (IV) nitrate solution was added in a stepwise
manner using a 5µl Hamilton syringe. The mole ratio data obtained by the physicochemical method employed were fitted by
using a non-linear least-squares curve fitting program KINFIT. The resulting absorbance against [U4+]/[HL] and [Th4+]/[HL]
mole ratio plot, reveals distinct inflection points at a metal-to-ligand molar ratio of about 0.5 and 1 emphasizing the formation of
a 1:2 and 1:1 complexes. The conditional formation constants were evaluated as log K = 4.83 ± 0.001 and log K =4.28 ± 0.001
for compounds 1 and 2, respectively.
Fig1. 1-(2-Ethoxyphenyl)-3-(4-Nitrophenyl) triazene (ENT)
Reference
[1] M.R. Melardi, M.K. Rofouei and J. Massomi, Anal. Sci. 23 (2007) 67.
Electrocatalytic oxidation and determination of ascorbic acid onto polypyrrole nanostructure
A.R. Feizbakhsh*, SH. Bagheri, A. Ehsani, A. Naeemy
Department of Chemistry, Islamic Azad University, Central Tehran Branch, P.O.Box 14676-86831,Tehran, Iran
E-mail:a.feizbakhsh@yahoo.com
Improving the sensivity, lowering the determination limit and promoting the response rate are important for analytical
determination of biological, pharmaceutical, and environmental research. The sensitivity may be improved by incorporation of a
substrate-recycling scheme [1,2] and several strategies including catalysts, enzymes, mediators, and mesoporous materials [3,4].
Electrochemical analysis has attracted considerable attention because it can analyze not only the electro-active materials.
Convenient operation and lower cost are also favorite factors. Among different conducting polymers, polypyrrole (PPy) is wellknown as a conductive biocompatible polymer with the potential to bring the benefits of conductivity into tissue engineered
constructs. In addition, PPy presented some important characteristics like dopant-mediated tunable physical properties and good
stability in air and aqueous media. Polypyrrole nanostructure film on graphite working electrode was prepared by template-free
method based deposited on a graphite electrode in a solution of 0. 1M PPy in 0.1M different electrolyte with pH=5-7 by means of
normal pulse voltammetry (NPV). The surface morphology of films was studied by using the scanning electron microscopy
(SEM). The electrochemical properties of polypyrrole film investigated by cyclic voltammetry and impedance spectroscopy in
frequency range of 100 kHz to 10 mHz in different dc offset potential and 5mv alternating potential.
The modified electrodes toward ascorbic acid were characterized by potentiostatic method. The experiment’s results show that
the PPy modified electrodes have obvious electrocatalytic effect toward ascorbic acid oxidation. The oxidation current density
has a good linearity in the concentration range of 6.0×10−4 and 1.0×10−2 mol L−1of ascorbic acid. The determination sensitivity
may be significantly affected by the thickness and morphology of PPy film, dopant anions, ton and toff in pulse technique and pH
of the test solution. The method has promising application in determination of ascorbic acid in the real samples
Reference
[1] A. Chaubey, K.K. Pande, M.K. Pandey, V.S. Singh, Appl. Biochem. Biotech. 96 (2001)239.
[2] F.W. Scheller, C.G. Bauer, A. Makower, U. Wollenberger, A.Warsinke, F.F. Bier, Anal. Lett. 34 (2001) 1233.
[3] M. Matsumiya, W. shine , N. Murayama, Sens, Actuator B-Chem. 93 (2003) 309.
[4] T. Ahujaa, I.A. Mira, D.K. Rajesh, Biomaterials 28(2007)791.
Aplication of Double Divisor –Ratio Spectra Derivative Method for Simultaneous Determination of Acetaminophen,
Aspirin and Caffeine in Exedrin Tablet
a
Soltaninezhad, Ahmad* and Hajian, Rezab
Department of Chemistry, Islamic Azad University branch of Gachsaran, Gachsaran, 75818-63876, Iran
b
Department of Chemistry, Islamic Azad University branch of Gachsaran, Gachsaran, 75818-63876, Iran.
E-mail: Hajian@iaug.ac.ir , A_Soltani00@yahoo.com
a
Excedrin is an over-the-counter headache pain reliever, typically in the form of tablets or caplets. It contains acetaminophen
(paracetamol), aspirin, and caffeine [1]. Since UV-visible spectrophotometry is a rapid, sensitive and inexpensive analytical tool,
it is appropriate for dosage control of pharmaceutical preparations. Despite the mentioned advantages, spectroscopy techniques
suffer from multiplicative (matrix effect) and additive (direct interference) errors. Double divisor-ratio spectra derivative method
was presented for the first time [2] as a powerful and simple method for resolving of overlapping spectra. In this work, Double
divisor-ratio spectra derivative method was applied for the simultaneous determination of aspirin, caffeine and acetaminophen in
Excedrin tablet as a new combined pharmaceutical formulation without using a chemical separation procedure. According to our
acknowledge it is the first report for analysis of Excedrin tablet using Chemometrics aspect. This method is based on the use of
derivative of the ratio spectrum obtained by dividing the absorption spectrum of the ternary mixture to a standard spectrum of a
binary mixture as double divisors. The concentrations of three compounds in ternary mixture are determined by using their
respective calibration graphs at a wavelength located in maximum or minimum amplitude of the ratio derivative spectra. The best
wavelengths with high accuracy were chosen as 241.5, 256 and 258.5 for determination of aspirin, caffeine and acetaminophen
respectively. The concentration of double divisors was 2
mol L-1. Britton Robinson buffer (pH=11) was chosen as optimum
pH with high selectivity throughout experiments. The applicability of the proposed method was applied satisfactory to the assay
of Excedrin tablet consist of 325 mg aspirin, 65 mg caffeine and 325 mg acetaminophen.
Reference
[1] http://en.wikipedia.org/wiki/Excedrin, accessed May 2011.
[2] E. Dinc, The spectrophotometric multicomponent analysis of a ternary mixture of ascorbic acid, acetylsalicylic acid and paracetamol by the double divisor-rati
spectra derivative and ratio spectra-zero crossing methods, Talanta, 48 (1999) 1145-1157.
Separation and determination of cochicine in Colchicum autumnale and phamacetutical preparation using SFO - LPME HPLC method
Mojgan Jamshidi*,1, Mohammad Bayranvand1, Ali Reza Ghiasvand1.2, Payman Hashemi1,2, Esfandiar Hasani Moghadam2,3
1
Department of Chemistry, Lorestan University, Khoramabad, Iran
2
Razi Herbal Medicines Research Center, Lorestan University of Medical Sciences, Khoramabad, Iran
3
Agricultural and Natural Resources Research Center of Lorestan, Khoramabad, Iran
Recently, solidification of floating drop microextraction (SFODME, SFO - LPME) as a powerful, rapid and inexpensive new
mode of liquid-phase microextraction (LPME) has been developed [1]. In SFODME small volume of an organic solvent is
floated on the surface of aqueous solution. After the completion of the extraction by prpoper stiringg, the organic solvent is
solidified by placing the vial in an ice bath. Finally, the melted droplet is used for analyte determination. Colchicine as potent
alkaloid, found in the autumn crocus (Colchicum autumnale) possesses significant medicinal properties for centuries in the
treatment of diseasesss and more recently, the familiar Mediterranean fever [2,3]. In this research, SFODME was used for
determination of colchicine in an endemic Colchicum autumnale of Lorestan for the first time. Important extraction parameters
such as type and volume of organic solvent, temperature, salt addition and exposure time on the extraction recovery were
investigated and optimized. Under the optimized extraction conditions a linear range of 0.5-40 ng.mL-1, RSD% of 5.2 and an
enhancement factor of 278 for colchicine were achieved. The proposed method was applied successfully for the extraction and
determination of colchicine in Colgot® tablets and an endemic Colchicum autumnale plant in Lorestan province.
Reference
[1] Durukan, C.A. Sahin, S. BektaS, Microchem. J. 98 (2011) 215-219
[2] G. Cocco, D.C.C. Chu, S. Pandolfi, Eur. J. Int. Med. 21 (2010) 503–508.
[3] H. Wollersen, F. Erdmann, M. Risse, R. Dettmeyer, Legal Madicine 11 (2009) s498-s499.
Determination of stability constants and thermodynamic parameters of complexes of tryptophan with Co2+, Ni+2, Cu+2,
Zn +2, Pb+2 metal ions in water-dioxane solution mixtures at different temperatures by potentiometry
Ebrahim Ghiamati* Maryam Lashkari and Monavar Hasheminia
Chemistry Department, Birjand University, Birjand, 97175-615, Iran
E-mail: eghiamati@yahoo.com
In recent years considerable attention has been paid to the study of complex-forming properties of amino acids with metal ions
due to their outstanding biological significance, as an example to better understand the metabolism of enzyme–catalyzed
reactions in the body. Tryptophan is a one of essential amino acids .It belongs to a group of amino acids that contains side chain
which is aromatic in character. Loss of this amino acid causes some metabolite activities to become dysfunctional in the
body[1,2]. The purpose of this research is to investigate the degree of stability of these complexes at temperatures of 25˚C, 30˚C,
35˚C, 40˚C, to evaluate thermodynamic parameters of ∆H˚, ∆S˚, ∆G ˚ and to examine the various factors that affect the
stability of these complexes. To estimate the stability constants, dilute solution of the metal ions (nitrate salt), the ligand
(tryptophan), and perchloric acid was prepared. Then this solution was potentiometrically titrated with standardized NaOH
solution. After addition of each increment of NaOH, the pH was read. Bjerrum method was used along with a new software
routine called GRCBeta which is a modified version of BEST program. The output of our program gives the pH values versus
concentration of NaOH. The pH readings at intersection of the potentiometric curve at - =0.5 and - =1.5 produced first and
n
n
second stability constant, i.e. Kf1 and Kf2. Our results show that tryptophan makes strong complexes with these metal ions.
Furthermore, using Kf1 and Kf2 we were able to compute thermodynamic parameters. As an example, Table below show the ∆H˚
values for the respective complexes. We will discuss the order of stability of the complexes, the effect of organic solvent, and
pertinent parameters affecting their stabilities in detail.
Complex type
Cu(II)-Trp
Co(II)-Trp
Ni(II)-Trp
Zn(II)-Trp
Pb(II)-Trp
∆H˚
(KJ/mol)
5.70
8.34
9.65
7.93
7.99
Reference
[1] Podsiadly, H.; Karwecka, Z. polyhedron, 2009 ,28,1568- 1572.
[2] Demirelli, H.; Koseoglu, F.; J. Solu. Chem. 2005, 34, 561-577.
Cloud point extraction and spectrophotometric determination of mercury
A. Hosseini, B. Aibaghi Esfahani*
School of chemistry, Damghan University, Damghan, Iran
E-mail: Akramhosseini64@gmail.com
Mercury and its compounds are human, plant and animal hazard due to their protoplasmic poisons. The tolerance limit of
inorganic mercury in aqueous solution is 1 μg L-1. Mining, recovery, use in a variety of products, industrial waste and
accumulation in human body via food are the major sources of mercury pollution. It has a tendency to amalgamate on various
surfaces and capable to form complexes with many reagents [1]. The cloud point extraction technique is based on the fact most
nonionic surfactants form micelles in aqueous solutions and become turbid [2]. Any analyte solubilized in the hydrophobic core
of the micelles will separate and become concentrated in the small volume of the surfactant-rich phase. Accordingly, any species
that interacts with the micellar system, either directly (generally hydrophobic organic compounds) or after a prerequisite
derivatization reaction (e.g. metal ions after reaction with a suitable hydrophobic ligand) may be extracted from the initial
solution and thus also be preconcentrated [3]. A simple, novel and sensitive spectrophotometric method was described for
determination of mercury. The response mechanism is discussed and the effect of different experimental variables is reported.
The procedure uses a salt of chloride (sodium chloride) as a reagent for complex formation with mercury (HgCl4-2), then a
cationic colour (methylene blue) is added to formation of ion pair with mercury complex. This method is based on cloud point
extraction (CPE) for preconcentration of low concentration of mercury in aqueous solutions. The optimized conditions,
interferences (anions and cations) and analytical application of method were investigated. Linear dynamic range and detection
limit for mercury determination were found 1-70 ng ml-1 and 0.7 ng ml-1, respectively. This procedure allowed determination of
mercury in real matrix sample with good reliability and was applied for determination of mercury in the canned Tuna and sea
water.
Reference
[1] Menshawy A. M., Salma A., Asmy A. A.(2008) “New modified cellulose for separation and determination of mercury in environmental water samples” Canadian
J. Anal. Sciences Spec, vol. 53, pp. 206-213.
[2] Fernanda M., Martinez L. D.(2006) “Coupling Cloud Point Extraction to Instrumental Detection System for Metal Analysis” Microchim. Acta, vol. 155, pp. 349364.
[3] Bosch O. C., Sanchez R. F.(2009) “Separation and preconcentration by a cloud point extraction procedure for determination of metals” Anal. Bioanal. Chem, vol.
394, pp. 759-782.
Cloud point extraction and spectrophotometric determination of Zinc
M. shafiee, B. Aibaghi Esfahani*
School of chemistry, Damghan University, Damghan, Iran
E-mail: majids1400@gmail.com
Zinc is the twenty-fifth most common element found in the earth's crust. It is found in association with other metals such as lead,
cadmium and copper. Zinc is present in the atmosphere and is found in water, and all living organisms. It is virtually always
found accompanied by cadmium, for which reason its emission into the atmosphere during metal smelting may cause
considerable environmental damage [1]. Zinc plays a central role in the immune system, affecting a number of aspects of cellular
and humoral immunity [2]. Separation and preconcentration based cloud point extraction (CPE) is an analytical tool that has great
potential to be explored in improving detection limits and other analytical characteristics over those of diverse methods. CPE as a
preconcentration method has many advantages, such as low cost, safety, and speed, and is a simple procedure with a high
capacity to concentrate a wide variety of analytes of widely varying nature with high recoveries and high concentration factors
[3]. A new method for preconcentration and Spectrophotometric determination of Zinc as an ion association with cationic dye
after cloud point extraction from aqueous solution was investigated. This method is based on the spectrophotometric
determination of Zinc in the form of ion pair of Zn(SCN)42- with malachite green after cloud point extraction. The optimal
conditions such as pH, KSCN concentration and temperature were studied. The calibration curve was linear in the range of 10300 ng.mL-1 of zinc and the detection limit was 5.84 ng.mL-1 .The relative standard deviation (RSD) was 4.18% and 2.17% for 50
and 200 ng.mL-1 of zinc, respectively. The interference effect of some anions and cations was also tested. This method was
successfully applied for determination of zinc in multivitamin tablet and sea water.
Reference
[1] Garcia E. A., Blanco Gomis D.(1996) “Sequential Extraction Spectrofluorimetric Determination of Ultratraces of Zinc Using Cryptand 2.2.1 and Eosin”
Mikrochim. Acta, vol. 124, pp. 179-185.
[2]Sabel C. E., Simanen S.,(2010) “A spectrophotometric method for the determination of zinc, copper, and cobalt ions in metalloproteins using Zincon” Anal.
Biochem. Vol. 397, pp. 218-226.
[3] Bosch O. C., Sanchez R. F.(2009) “Separation and preconcentration by a cloud point extraction procedure for determination of metals” Anal. Bioanal. Chem, vol.
394, pp. 759-782.
Flame atomic absorption spectrometric determination of cadmium and lead in water samples after solid phase extraction
on TiO2 nano-particles modified with Alizarin Red S
Neda Baghban, Ali Mohammad Haji Shabani*, Shayessteh Dadfarnia
Department of Chemistry, Faculty of Science, Yazd University, Yazd, 89195-741, Iran
E-mail: hshabani@yazduni.ac.ir; neda_baghban@stu.yazduni.ac.ir
Cadmium and lead are considered two of the most hazardous elements to human health [1]. For the determination of cadmium
and lead in numerous real samples, there is a crucial need for a separation and preconcentration step before analysis by FAAS
due to their low concentration and high levels of concomitant components. Many enrichmentprocedures such as coprecipitation
[2], liquid liquid extraction [3], cloud point extraction [4], and solid phase extraction [5, 6] have been reported for cadmium and
lead in the literature. In this study, a simple and sensitive method for the determination of cadmium and lead in water samples by
flame atomic absorption spectrometry (FAAS) after their preconcentration onto a micro column containing TiO2 nano-particles
modified with Alizarin Red S (ARS) has been developed. The influences of effective parameters such as pH, amount of sorbent,
sample volume, flow rate, eluent type and concentration on the recovery of cadmium and lead were optimized. The effect of
several foreign ions on the recovery of analytes was also investigated. Under the optimum experimental conditions, a
preconcentration factor of 200 was obtained for cadmium and lead and calibration graph for a sample volume of 400 mL gave
good linearity over the range of 0.8–112 of lead and 0.3–12 ng mL−1 of cadmium. The relative standard deviation (n = 10) at 1.0
ng mL-1 level for lead and cadmium were 1.7 and 2.9% and the corresponding limits of detection were 0.24 and 0.09 ng mL−1,
respectively. The method was successfully applied to the determination of lead and cadmium in water samples.
Reference
[1] M.G.A. Korn, G.L. dos Santos, S.M. Rosa, L.S.G. Teixeira, P.V. de Oliveira, Microchem. J. 96 (2010) 12-16.
[2] T. Oymak, S. Tokalioglu, V. Yilmaz, S. Kartal, D. Aydin, Food Chem. 113 (2009) 1314-1317.
[3] E. Carasek, J.W. Tonjes, M. Scharf, Talanta 56 (2002) 185-191.
[4] E.L. Silva, P.d.S. Roldan, J. Hazard. Mater. 161 (2009) 142-147.
[5] E.M. Gama, A. da Silva Lima, V.A. Lemos, J. Hazard. Mater. 136 (2006) 757-762.
[6] N. Burham, Disalination 249 (2009) 1199-1205.
Calculation binding constant(K) and binding site size (S) Interaction of Methotrexate with Fish Sperm DNA by
Spectroscopy and Electrochemistry
1
TAVAKOL Maryam*1
Department of Chemistry, Islamic Azad University branch of Gachsaran, Gachsaran, 75818-63876
Iran. E-mail: maryam_tavakol22@yahoo.com
The specific interaction between a drug and DNA results in some changes in physical and chemical properties and has a potential
importance for a better understanding of its therapeutic efficiency,which may also be used for conformational recognition to find
new structures of DNA[1-2].Various techniques have been extensively employed to study the interaction of these molecules with
DNA,such as spectroscopic methods[3],isothermal calorimetric titration, nuclear magnetic resonance, quartz crystal
microgravimetry.Since many small molecules exhibit redox activity,electrochemical method should provide a useful complement
to the previously used methods for investigation.Moreover, the electrochemical behaviours are valuable in elucidating some
mechanisms of the drug action in vivo.Although the binding modes of several molecules with large conjugated structures have
been delineated and much less attention was paid to the binding of simple hetrocyclic compounds. Methotrexate is an important
and widely used chemotherapeutic agent whose action is mediated by its anti-folk acid activity. The interaction of
Methotrexate(MTX) with fish sperm DNA has been investigated with the use of methylene blue(MB) dye as a spectral probe by
the application of UV-Vis spectrophotometry,spectrofluorometry and voltammetry.The Voltammetric behaviour of Methotrexate
has been investigated at a glassy carbon electrode using Cyclic voltammetry. Binding constants and site size were determind from
the Voltammetric data[4].The apparent binding constant of Methotrexate with DNA has been found to be 1×103 L.mol-1 and
S=0.1bp.The fluorescence signal of MB-DNA with Methotrexate show not changed significantely by addition of MTX. Both UVvis spectrophotometry and Cyclic voltammetry studies confirmed the groove binding and electrostatic interaction between MTX
and ds- DNA.
Reference
[1]. J.H.Griffin and P.B.Dervan, J. Am. Chem.. Soc., 109, 6840(1987).
[2]. A.M. Pyle, N. Turro , J.Am. chem.. soc.,111,3051(1989).
[3]. C.V.Kumar and E.H.Asucion, J.Am.chem. soc.,115,8547(1993).
[4]. M.T.Carter, and A.J.Bard,chem.soc.,111,8901(1989).
Studies on kinetics photodecolorization of mixture of two commercial dyes in aqueous phase using CuO/nanozeoliteX
a
A. Nezamzadeh-Ejhieha*and M. Karimi-Shamsabadib
Department of chemistry, Islamic Azad University, Shahreza Branch
b
Yoang researchers club
E-mail: arnezamzadeh@iaush.ac.ir ,maryamkarimi54@yahoo.com
The photocatalytic decolorization of mixture of two dyes: methylen blue and rhodamine B with different structure have been
investigated using CuO/nanozeolite X photocatalyst in aqueous solution under solar irradiation. The nanometer size faujasite
zeolite X was synthesized by hydrothermal crystalyzation. For ion-exchange experiments 4 g nanozeolite NaX powder was added
to 100 ml of 0.2 M Cu2+solution and shaken for 24h. For preparation of CuO/nanozeolite X the obtained product was calcinated
in air at 450°C. All samples were characterized by X-ray diffraction and scanning electron microscopy. By use of Sherrer̕ s
equation the average particle size of nanozeolite NaX was found to be 5-10 nm. Photocatalytic decolorization of two dyes
depends on the amount of catalyst, concentration of dye. The Reaction kinetics was investigated in detail at initial dyes
concentrations, amount of catalyst. The decolorization kinetics was fitted well to the Langmuire-Hinselwood first order rate law.
To determine the optimal amount of catalyst, experiments were carried out with varying amount of CuO/X nanozeolite (from
0.1g/l -1g/l ). The obtained results showed that, increasing in catalyst mass up to 1g/l, causes a decrease in decolorization rate.
Decolorization of MB and RhB have been investigated from 3 to 15 for MB and RhB. The initial rate of photodecolorization
increased with decreased in dyes concentrations. . Effect of other experimental parameters such as pH and H2O2 and KBrO3 were
studied and satisfactory results were obtained.
Reference
[1] B. Zeng Zhan, M. White, M. Lumsden, Chem. Mater.14(2002) 3636-3642.
[2] A. Nezamzadeh-Ejhieh, Sh. Hushmandrad, Appl. Catal. A. Gen. 388(2010) 149-159
[3] A. Nezamzadeh-Ejhieh, Z. Salimi, Appl. Catal. A: Gen. 390 (2010) 110–118
Extraction and determination of volatile compounds and flavonoids in Matricaria chamomile, cultivated under
hydroponic conditions, using SPME-GC-MS and HPLC-UV
Mehrdad Dalvand*,1, Parinaz Karimian2, Anna Tadevosyan1, Ali Reza Ghiasvand2,3
Institute of Hydroponics Problems, National Academy of Sciences (NAS), Republic of Armenia
2
Department of Chemistry, Lorestan University, Khoramabad, Iran
3
Razi Herbal Medicines Research Center, Lorestan University of Medical Sciences, Khoramabad, Iran
1
Matricaria chamomile is one of the valuable plants of Asteracea family, has been used as a medicinal plants for centuries. Over
millions cups of chamomile tea are consumed daily in the West, for its relaxation benefits. It is well-known medicinal plant in
folk medicine cultivated all over the world. Chamomile essential oil is widely used in medical, cosmetic, and food industries. Its
medicinal effect is mainly spasmolytic, antimicrobial, and disinfective properties. Flavonoids which their presence in Asteracea
family, has long been established, have attracted a great deal of research on their broad distribution in plants, antioxidant
activities, and health effects [1-2]. In this research Matricaria chamomile was cultivated hydroponically, a soilless method of
growing plants using mineral nutrient solutions. In this study three nutritious formulas: Hogland, Coper and Eshnider were used
and similarly a suggested nutritious formula was used to cultivating under hydroponic conditions, and for each one four spices of
chamomile was used. Chemical screening of volatiles of the hydroponically cultivated Chamomile was examined using
ultrasonic-assisted head-space solid-phase microextraction coupled to gas chromatography-mass spectrometry (UA-HS-SPMEGC/MS) method, for the first time. Optimal UA-HS-SPME-GC/MS conditions reported by Ghiasvand's research group was used
for analysis [3]. (z)-β-Farnesene, germacrene-D, chamazulene and β-bisabolenol were the most important determined volatile
components in hydroponically cultivated spices. Some differences were seen among the spices with different nutritious formulas,
as well as between hydroponically and soil cultivated species. A micro-Clevenger system was used for obtaining the essential oil.
Flavonoids were extracted using maceration method. Apigenin, Apigenin-7-glycoside, Quercetin, Luteolin, and Patuletin were
identified and determinate as major flavonoids in hydroponically cultivated Matricaria chamomile.
Reference
[1] Orav, T. Kailas, K. Ivask, Proc. Estonian Acad. Sci. Chem. 50 (2001) 39.
[2] Fraisse, C. Felgines, O. Texier, Food and Nutrition 2 (2011) 1-12.
[3] A.R. Ghiasvand, M. Nasseri, S. Farsizaeh, R. Sadeghi, S. Shadabi, M. Borzoei, Chromatographia 73 (2011) 1031.
Simultaneous Photocatalytic degradation of a mixture of Methyl orange (MO ) and Methylene blue (MB) in water using
Ag-ZnO with multiple rods (multipods) morphology
Mansour Arab Chamjangali، Ghadam Ali Bagherian, Samira Boromand*،Nahid Farzaneh
College of chemistry, Shahrood University of Technology, Shahrood, Iran
E –mail: samira.boromand@yahoo.com
Dyes are one of the most notorious contaminants in aquatic environments because of their huge volume of production from
industries, slow biodegradation and decoloration, and toxicity. This article describes the simultaneous photodegradation of MO
and MB dye by Ag-ZnO with multiple rods morphology in aqueous solution. Zinc oxide (ZnO) particles with multiple rods
(multipods) morphology were successfully prepared via a simple solution route at low temperature. In order to increase the
photocatalytic efficiency of ZnO, nono-silver particles were embed on the surface of multipod structure of zinc oxide by using
photoreduction procedure. Photocatalytic activity of the prepared Ag-ZnO powders was evaluated by simultaneous
photodegradation of MO and MB in an aqueous solution under the ultraviolet irradiation. Results suggested that mixture of dyes
could simultaneously be mineralized in the Ag-ZnO multipod suspension after 80 min.
Reference
[1] -H. KYUNG; J. LEE; W. CHOI ، Environ.Sci.Technol.( 2005), 39, 2376 2382
[2] -T. T. Y. Tan; C.K. Yip; D. Beydoun, R. A Mal, Chem. Eng. J. 95 (2003 ) 179-186
[3] - P. Chen; Li .Gu; X. Xue; Y.Song;, L.Zhu; X.Cao, Materials Chemistry and Physics 122 ( 2010 ) 41 – 48
Effect Of Non-aqueous Solvent On Stoichiometry and Selectivity of Complexes Formed Between 15 -crown-5 With Fe3+
,Y3+,Ni2+ ,and Co2+ Metal Cations
G.H.Rounaghi*, M.Satari
The author to whom correspondence should be addressed .E-mail:ghrounaghi@yahoo.com
Department Of Chemistry,Factuly Of Sciences, Islamic Azad University, Mashhad Branch, Mashhad-Iran
*
Conductance measurements of an electrolyte soloution in the presence of a crown compound provide two valuable prices of
information. The first , is detection of complexation between the crown compound and the cation. Furthermore , the
stoichiometry and the stability constant of the crown compound-cation complexes can be determind from the conductance
data.Macrocycle design parameters, such as cavity size, the type and the number of donor atoms, the type and number of protonionizable groups within and without the macrocycle cavity, chirality's, the substituent groups and steric hindrance and also the
solvent parameters can all be used to abtain the desired selectivities. Due to the ability of crown ethers to bind strongly and
selectively to metal cations and substrate molecules, macrocyclic polyethers and their derivatives can find use in many diverse
processes such as construction of ion-selective electrodes[1,2], phase transfer catalysts[3], extraction of metal ions , chiral
separation, and membrane separation process. The complex formation reactions between Fe3+,Y3+,Ni2+ and Co2+ metal cations
with macrocyclic ligand , 15-crown-5,were studied in acetonitrile (AN) – methanol (MeOH) binary mixtures at different
temperature using conductometric method. The conductance data show that the stoichiometry of the complexes formed between
this macrocyclic ligand and Fe3+,Y3+,Ni2+ and Co2+ cations is 1:1[ML]. The results show , that the selectivity of 15C5 for the
studied metal cations in pure acetonitrile at 15,25,35 and 45 ₒC is : Co2+> Y3+> Ni2+≈ Fe3+. The values of standard
thermodynamic parameter (∆H°c and ∆S°c ) for formation of the complexes which were obtained from temperature dependence of
the stability constants ,using the van't Hoff plots show that the complexes are enthalpy stabilized or destabilized but from entropy
view point they are stabilized.
Reference
[1].Sendil, O.,Pecenek,E.,Ekmekci, G., Somer, G.:preparation and application of potassium ion – selective membrane electrode based on benzo-15-crown-5ether.Curr.
Anal. Chem. 5,53-58 (2009) .
[2]. Shim, J.,Jang, E.J., Chung, K.C.: Lead ion-selective polypyrrole solid-contact electrode based on crown ether. Anal. Lett. 40, 3038-3049 (2007).
[3].Pozzi, G., Quici, S., Fish, R.H.: Perfluorocarbon soluble crown ethers as phase transfer catalysts. Adv. Synth. Catal.350, 2425-2436 (2008)
Competitive Adsorption of dyes (sunset yellow, malachite green) onto cadmium hydroxide nano particle loaded on
activated carbon
M. Ghaedi, N.Mosallanejad*
Chemistry Department, Yasuj University, Yasuj
Chemistry Department, Firuzabad Islamic Azad University. Firuzabad
Email: m_ghaedi@yahoo.com , nargesmosallanejad@yahoo.com
The objective of this work is the study of adsorption of dye solution which is a mixture of two dyes (sunset yellow (SY) &
malachite green (MG)) using cadmium hydroxide nano particle loaded on activated carbon (CHN-AC). (MG), a
triphenylmethane dye, is used asanantifungal, anti-bacterial, and anti-parasitical therapeutic agent in aquacultures and animal
husbandry. It has detrimental effects on intestine and gonads of aquatic organisms. When it was inhaled by human, it may cause
even cancer. Contact of it with skin causes irritation with redness and pain. Therefore, the use of it was banned in many countries.
(SY) is a yellow colouring that is added to a wide range of products such as squash, jelly, jams, soup and sauces. It should be
avoided by anyone suffering from existing allergic conditions, such as asthma or urticaria and a child who has signs of
hyperactivity of ADHD. So we used (CHN-AC) for removal of these dyes. Scanning electron microscopy (SEM) and X-ray
diffraction (XRD) analysis were used to characterize the adsorbent material (CHN-AC). Batch adsorption studies are carried out
by observing the effect of experimental parameters, namely, pH, amount of adsorbents, contact time and temperature. Adsorption
capacity of (CHN-AC) is determined for competitive adsorption of mixture of dyes. For malachite green maximum adsorption
found to be at PH=5 and there is no significant change in amount adsorbed after PH=5. For sunset yellow there is no significant
change in amount adsorbed after PH=5. Optimum adsorbent dose for the dye is 0.04 g/50 ml. The adsorption capacity of CHNAC for the two dyes (malachite green and sunset yellow) increased with temperature. The results generated by this work can be
used for determination of optimum conditions for adsorption of mixture of dyes in aqueous solutions. Dyes are present in mixture
form in various Industrial effluents. This work can be used in design of adsorption columns for dyes removal.
Reference
[1] I.A. Rahman, B. Saad, S. Shaidan, E.S. Sya Resale, Bioresource Technology 96 (2005) 1578–1583.
[2] M. A. Yıldırım, A. Ates, Sens. Actuators A: Physical 155, (2009) 272–277.
[3] M. Arami, N. Y. Limaee, N. M. Mahmoodi,N.S. Tabrizi, J. Colloid Interface Sci. 288 (2005) 371– 376.
Adsorption equilibrium, kinetics and thermodynamics of Malachite Green onto Silver nano particle loaded on activated
carbon
M. Ghaedi, N.Mosallanejad*
Chemistry Department, Yasuj University, Yasuj
Chemistry Department, Firuzabad Islamic Azad University. Firuzabad
Email: m_ghaedi@yahoo.com , nargesmosallanejad@yahoo.com
This study investigates the adsorption potential of Silver nano particle loaded on activated carbon (SN-AC) to remove Malachite
Green (MG) from its aqueous solution. (MG), a triphenylmethane dye, is used as an antifungal, anti-bacterial, and anti-parasitical
therapeutic agent in aquacultures and animal husbandry. It has detrimental effects on intestine and gonads of aquatic organisms.
When it was inhaled by human, it may cause even cancer. Contact of malachite green with skin causes irritation with redness and
pain. Therefore, the use of it was banned in many countries. To this end, the effect of operational parameters including initial pH,
adsorbent dose, contact time, initial dye concentration and temperature were studied in batch adsorption experiments. Silver
nanoparticle preparation is also being experimented upon and studied to find the most cost-efficient and effective way to
synthesize them. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis were used to characterize the
adsorbent material. The experimental equilibrium data were tested by three widely used isotherm models namely, Langmuir,
Freundlich and Dubinin–Radushkevich (D–R). It was found that adsorption of (MG) on (SN-AC) well with the Langmuir
isotherm model, implying monolayer coverage of dye molecules onto the surface of the adsorbent. More than 90% removal
efficiency was obtained within 30 min at adsorbent dose of 0.04 g/50ml for initial dye concentration of 10-15ppm in pH=5.
Kinetics of the adsorption process was tested by pseudo-first-order and pseudo-second-order kinetics, and intraparticle diffusion
mechanism. Pseudo-second-order kinetic model provided a better correlation for the experimental data studied in comparison to
the pseudo-first-order model. Intraparticle diffusion was not the sole rate-controlling factor. A thermodynamic study showed
spontaneous nature and feasibility of the adsorption process. The results indicate that Silver nano particle loaded on activated
carbon can be used as an effective and low-cost adsorbent to remove Malachite Green from aqueous solution rather than various
conventional methods of removing dyes including coagulation and flocculation, oxidation or ozonation and membrane separation
Reference
[1]Z.Bekçi, Y.Seki, L.Cavas. Journal of Hazardous Materials, 161(2009) 1454-1460
[2] M. Arami, N. Y. Limaee, N. M. Mahmoodi, N.S. Tabrizi, J. Colloid Interface Sci. 288 (2005) 371–376.
Kinetics, thermodynamic and equilibrium isotherms of Reactive Sunset yellow adsorption on Silver nano particle loaded
on activated carbon
M. Ghaedi, N.Mosallanejad*
Chemistry Department, Yasuj University, Yasuj
Chemistry Department, Firuzabad Islamic Azad University. Firuzabad
Email: m_ghaedi@yahoo.com , nargesmosallanejad@yahoo.com
The objective of this study was to assess the adsorption potential of Silver nanoparticle loaded on activated carbon (SN-AC) for
the removal of Sunset Yellow (SY) molecules from aqueous solutions. (SY) is a yellow colouring that is added to a wide range of
products such as squash, jelly, jams, soup and sauces. It should be avoided by anyone suffering from existing allergic conditions,
such as asthma or urticaria and a child who has signs of hyperactivity of ADHD. Silver nanoparticle preparation is also being
experimented upon and studied to find the most cost-efficient and effective way to synthesize them. Scanning electron
microscopy (SEM) and X-ray diffraction (XRD) analysis were used to characterize the adsorbent material. Adsorption studies
were conducted in a batch system as a function of solution pH, contact time, initial dye concentration, amount of adsorbent,
temperature, etc. In order to investigate the adsorption processes, pseudo-first-order, pseudo-second-order, Elovich and intraparticle diffusion kinetic models were studied and it followed the pseudo-second-order kinetic model with good correlation.
Equilibrium data fitted well with the Langmuir models. More than 90% removal efficiency was obtained within 30 min at
adsorbent dose of 0.04 g/50ml for initial dye concentration of 20 ppm in pH=1. The adsorption of dye was found to follow a
pseudo-second-order rate equation. Intra particle diffusion model was studied in order to determine the rate limiting step of the
adsorption process. Thermodynamic parameters such as enthalpy (ΔH◦), entropy (ΔS◦), activation energy (Ea), sticking
probability (S*) and Gibb’s free energy changes (ΔG◦) were also calculated. It was found from different evaluated
thermodynamic parameters, ΔH◦, ΔS◦ and ΔG◦ that the sorption of dye by (SN-AC) was feasible, spontaneous and endothermic
process. The (SN-AC) is identified to be an effective adsorbent for the removal of SY from aqueous solutions rather than various
conventional methods of removing dyes including coagulation and flocculation, oxidation or ozonation and membrane separation
Reference
[1] M. Arami, N. Y. Limaee, N. M. Mahmoodi, N.S. Tabrizi, J. Colloid Interface Sci. 288 (2005) 371–376.
[2] H. Huang, X.Yang, Carbohyd. Res. 339, (2004) 2627-31.
[3] X. Wang, Y. Chen, Mater. Lett. 62, (2008) 4366–8.
[4] NTP National Toxicology Program. 6(1981) 80-33.
Spectrophotometric determination of acidity constants of Tropaeolin O in binary Acetonitrile, Dioxane and DMSO-water
mixtures by chemometrics methods
Fatemeh Aghaziyarati Farahani*, Ali Niazi
Department of Chemistry, Islamic Azad University-Arak Branch, Arak, Iran
E-mail: aghaziyarati_farahani_fatemeh@yahoo.com ,ali.niazi@gmail.com
The acidity constants of Tropaeolin O (Figure 1) in binary mixtures of acetonitrile, dioxane and DMSO-water at 25 °C and an
ionic strength of 0.1 M (KNO3) in pure water and aqueous media containing percentages (10-50% w/v), have been determined
spectrophotometrically.
HO
SO 3
N N
OH
Figure 1. Chemical structure of Tropaeolin O
DATa ANalysis (DATAN) program is applied for determination of acidity constants. The used organic solvents were methanol,
ethanol and DMF. The absorption spectra of Tropaeolin O in binary solvent mixtures at various pH values in 290-550 nm
intervals were recorded. Sample spectra of Tropaeolin O in water with pH values ranging from 1.0 to 12.0 at 0.1 M KNO3 is
shown in Figure 2.
Absorbance
2
1.5
1
0.5
0
290
340
390
440
490
540
Wavelength (nm)
Figure 2. Spectra of Tropaeolin O in pure water at 0.1 M KNO3 at different pH values.
The obtained results indicated that acidity constants decrease as the content of an organic solvent in the medium increases. The
acidity constants of all related equilibria are estimated using the whole spectral fitting of the collected data. The DATAN
program [1-3] was applied for determination of acidity constants. The effect of solvent properties on acid-base behavior is
discussed. This indicates that the acid ionization constants of Tropaeolin obtained in various percentages of different solventwater mixtures are governed by electrostatic effects. The amounts of pKa1 and pKa2 are obtained 5.46 and 6.14.
Reference
[1] A. Niazi, M. Ghalie, A. Yazdanipour, J. Ghasemi, Spectrochim. Acta Part A 64 (2006) 660-664.
[2] A. Niazi, A. Yazdanipour, J. Ghasemi, M. Kubista, Coolect. Czech. Chem. Commun. 71 (2006) 1-14.
[3] A. Niazi, A. Yazdanipour, J. Ghasemi, M. Kubista, Spectrochim. Acta Part A 65 (2006) 73-78.
Fabrication of a Terbium(III) PVC-membrane sensor based on 1,4-bis[o-(furan-2-carboxamidophenyl)]-1,4-dithiobutane
as an ionophore
1
Sara Ghanei-Nasab* 1,Hassan Ali Zamani1
Department of Applied Chemistry, Quchan branch, IslamicAzad University, Quchan,Iran,
E-mail: Sara_ghanei1988@yahoo.com
In this study, a new terbium(III) membrane sensor was constructed. The proposed membrane sensor was fabricated based on a
membrane containing 2% sodium tetraphenyl borate (NaTPB) as an anionic additive, 66% dibutyl phthalate (DBP) as solvent
mediator, 2% 1,4-bis[o-(furan-2-carboxamidophenyl)]-1,4-dithiobutane (FCT) as an ionophore and 30% poly vinyl chloride
(PVC).The proposed Tb3+ electrode exhibits a Nernstian slope of 20.7 ± 0.2decade of activity was demonstrated with a response
time of 5 s, and has a lower detection limit [1] of 7.5×10-8 mol L−1.The linear range of the sensors was 1.0×10-7-1.0×10-2 mol
L−1. It works well in the pH range of 2.5–7.8. Moreover, the recommended selective sensor revealed a comparatively satisfactory
selectivity [2] regarding most of the alkali, alkaline earth, some transition and heavy metal ions. The membrane sensor was
employed as an indicator electrode in the potentiometric titration of Tb(III) ions with EDTA.
Reference
[1] E. Bakker, P. Bühlamnn, E. Pretsch, Chem. Rev. 97 (1997) 3083.
[2] Y. Umezawa, K. Umezawa, H. Sato, Pure Appl. Chem. 67 (1995) 507.
Laser Induce Termal Lens Spectrometry of mercury using formation of ionic liquid-capped mercury dithizonate
nanoparticles in water media
Nader Shokoufi*, Leila Bahari nikoo
Faculty of Instrumentation & Material Analysis, Chemistry & Chemical Engineering Research Center of Iran
E-mail: Shokoufi@ccerci.ac.ir
Laser Iinduced-Thermal Lens Spectrometry (LI-TLS) using formation of ionic liquid-capped mercury dithizonate nanoparticles
was used for determination of mercury in water samples. Thermal lens technique has been demonstrated to be a sensitive method
for low-absorbance measurements. In addition beside the ultrasensitivity of technique, it is suited for small volume samples. In
fact, the sensitivity of thermal lens measurements in ILs is comparable to those in organic solvents such as benzene, carbon
tetrachloride, and hexane. Because of the relationship between dn/dT and dρ/dT, it is expected that ILs can serve as an attractive
and superior media not only for thermal lens measurements but also for other photothermal and photoacoustic techniques as well.
The method is based on the nanocomplex formation of mercury dithizonate using water soluble ionic liquid as a stabilizer agent.
The formation of mercury dithizonate complex in aqueous solution will result to precipitation and decrease the termal lens signal
of the complex remarkably. In order to overcome the problem, the reaction of mercury ion with dithizone in the present of ionic
liquids was studied. The detection is based on the increase in termal lens signal resulting to the formation of nanoparticles of
mercury dithizonate. Some effective parameters on determination of mercury were selected and optimized. The parameters
include the type and concentration of ionic liquid, the dithizone concentration, pH and the salt effect were investigated. A notable
advantage of the method is the rapid determination of Hg(II) ions in micro volumes of water samples at ppb levels. Also,
sensitivity of the method is enough for the determination of Hg (II) in variety of water samples.
Reference
[1] C. D. Tran, S. Challa, M. Franko, Anal. Chem.,77 ( 2005)7442-7447
[2] Kitamori, T.; Takeshi, M.; Hibara, A.; Sato, K. Anal. Chem.,76( 2004) 52A-60A.
[3] N. shokoufi, F.Shemirani, Talanta, 73 (2007) 662-667.
[4] N. Shokoufi, A. Hamdamali, Analytica Chimica Acta, 681(2010)56-62.
A new and simple liquid-liquid microextraction procedure based on room temperature ionic liquid for simultaneous
separation of ultra trace amounts of gold and silver in various media and their determination by AAS
Hamid Ashkenani*, Mohammad Ali Taher, Hadi Hassani Nadiki
Department of Chemistry, Shahid Bahonar University of Kerman, Kerman, Iran
Noble metals such as Au and Ag have many applications in industry, jewellery and medicine [1]. Recently considerable interest
has been manifested on using a combination of a chelating agent and room temperature ionic liquids (RTILs) as the “Green
Solvent” to replace the traditional volatile organic solvents in a wide range of application [2]. Moreover, Multi-elements
analytical procedures are attractive in analytical chemistry. A new liquid-liquid microextraction procedure is proposed for
simultaneous separation and preconcentration of ultra trace amounts of Au(III) and Ag(I) in various media by using N-(4-{4[(anilinocarbothioyl)amino]benzyl}phenyl)-N-phenylthiourea as chelating agent and 1-hexyl-3-methylimidazolium
hexafluorophosphate as extraction solvent. In proposed method, the pH of standard or sample solution containing Au and Ag was
adjusted to ~3 and was transferred into a 50 mL conical-bottom polypropylene tube containing a stirrer bar. Afterward, 200 µL of
the chelating agent solution (0.06% (w/v)) and then RTIL were added and the solution was stirred. After the extraction time was
out, the sample vial was transferred into an ice bath to return the solvated RTIL and was centrifuged. Afterwards, the extract in
the tube was diluted with ethanol and introduced into the flame by conventional aspiration. Under optimum conditions, the
enhancement factor of 40.1 and 39.9 for gold and silver were obtained, respectively. The calibration graphs (sample volume: 25
mL) showed the linearity over the range of 9.6-380 µg L−1 (R2=0.9996) for Au and 4.8–290 µg L−1 (R2=0.9995) for Ag. The
method was successfully applied for determination of gold and silver in natural water, wastewater, pharmaceutical, tea and
photographic film samples. The results show that liquid–liquid pretreatment using ionic liquid is a sensitive, rapid, simple, safe
and environmental-friendly method for the simultaneous preconcentration of Au and Ag in various samples. Thus this procedure
it can be used with regular FAAS equipment for trace determination of Au and Ag in routine analytical laboratories.
Reference
[1] I.D.L. Calle, N. Cabaleiro, M. Costas, F. Pena, S. Gil, I. Lavilla, C. Bendicho, Microchem. J. 97 (2011) 93-100.
[2] Dadfarnia, S., Haji Shabani, A.M., Shirani Bidabadi, M., Jafari, A.A., J. Hazard. Mater. 173 (2010) 534-538.
Synthesis of a New Ion Imprinted Polymer for Solid Phase Extraction and Preconcentration of Copper
Hamid Ashkenani*, Mohammad Ali Taher, Fateme Mirrahimi
Department of Chemistry, Shahid Bahonar University of Kerman, Kerman, Iran
Copper is an environmental pollutant, which has been tested and assessed over the past few years from both the toxicological
and human health viewpoints [1]. Molecular imprinting technology has become a powerful method for high selectivity adsorption
of target molecules. Ionic imprinted polymers find broad applications as preconcentration and separation matrixes for metal ions,
such as Cu(II) [2]. In this study, A new Cu(II)-ion imprinted polymer (IIP) was prepared by formation of 1-(2-pyridylazo)-2naphthol (PAN) complex in DMSO following polymerization with ethyleneglycoldimethacrylate (EGDMA), as crosslinking
monomer; in the presence of benzoylperoxide (BPO), as initiator, via bulk polymerization method. The synthesis of IIP was
carried out in two steps: 1. complex formation 2. polymerization. The complex of Cu(II) ion with PAN was prepared by stirring
0.25 mmol of copper(II) nitrate and 0.5 mmol of PAN (dissolved in 10 mL of DMSO). The formation and stoichiometry of
complex was confirmed by UV–VIS absorption spectral studies. In order to prepare Cu (II) imprinted polymer, cross-linker
(EGDMA) and initiator (benzoylperoxide) was mixed with previous solution and followed by purging with N2 gas for 10 min.
The polymerization reaction was carried out in a water bath at 60 °C for 24 h. The synthesized polymer was ground in a mortar
and dried. To remove templates, the remaining particles were treated with 5 mol L-1 of HCl for 1 h (several times). For
preconcentration of Cu(II) ions, aqueous solution containing appropriate amount of Cu(II) was stirred with 100 mg imprinted
polymer for 1 h at pH 5-8. Then, Cu(II)-ion imprinted polymer was separated from the adsorption media by centrifuge and then
HCl solution was added to IIP as eluent and stirred. Imprinted polymer was separated and the concentration of Cu(II) ions in the
desorption media was determined using AAS system. The effect of different parameters, such as pH, sample volume, adsorption
and desorption time, type and least amount of the eluent were evaluated. Furthermore, the distribution ratio and selectivity
coefficients of manganese and other selected ions were investigated.
Reference
[1] E. Shams, A. Babaei, M. Soltaninezhad, M. Soltaninezhad , Anal. Chim. Acta 501 (2004) 119–124
[2] S. Wang and R. Zhang, Microchim. Acta 154 (2006) 73–80
Removal of Direct Red 12B from Wastewater by Hazelnut Shell
Mohammad Reza Fat’hi* 1, arash Asfaram2
Department of Chemistry, College of Basic Science, Islamic Azad University,Gachsaran Branch, Gachsaran, IRAN.
E-mail : 1fathiemadabadi@yahoo.com, 2ar_asfaram@yahoo.com
Removal of Direct Red 12B (acidic dye) from wastewater by hazelnut shell as an adsorbent was studied. The maximum removal
of Direct Red 12B (DR12B) was obtained by passing an aliquot of the DR12B solution at pH 2.5 through a column containing
0.35 g hazelnut shell at room temperature. The effects of different parameters such as pH, dye concentration, solution volume,
amount of adsorbent, adsorbent particle size, temperature were studied and a set of optimum conditions were obtained. The effect
of foreign cations , anions and other dyes on removal efficiency was investigated. The efficiency of adsorbent was also tested
for the removal of dye from Karoon River with 99.7% recovery. The results was showed that hazelnut shell as an adsorbent is a
low cost, potentially efficient and eco-friendly adsorbent for removal of DR 12B from industrial wastewater. Based on batch
experiments, the adsorption data could be fitted by the Langmuir equation with a maximum adsorption amount of 71.44 mg/g.
Reference
[1] Ferrero,F, Dye removal by low cost adsorbents: Hazelnut shells in comparison with wood sawdust, Journal of Hazardous Materials 142 (2007) 144–152.
[2] Sureshkumar. M.V,Namasivayam. C,Adsorption behavior of Direct Red 12B and Rhodamine B from water onto surfactant-modified coconut coir pith, Colloids
and Surfaces A: Physicochem. Eng. Aspects 317 (2008) 277–283.
[3] Dogan.M, Abak .H, Alkan.M, Adsorption of methylene blue onto hazelnut shell: Kinetics, mechanism and activation parameters, Journal of Hazardous Materials
164 (2009) 172–181.
Removal of Direct Blue 86 from Textile Effluents by Pomegranate Peel
Mohammad Reza Fat’hi ٭, Mahsa Nadimpour
Department of Chemistry, College of Science, Shahid Chamran University, Ahvaz, Iran
E-mail : mr_fathi@scu.ac.ir
Effluents discharged from many industries such as dye manufacturing and textile finishing, cosmetic, paper, leather and carpet
are toxic to aquatic life. At the present, there is a growing interest in using low cost, commercially available materials for the
adsorption of dyes. In this study, the potential for the use of pomegranate peel as an adsorbent for removal of Direct Blue 86 (DB
86) from aqueous solution was investigated. Pomegranate peel was washed to remove impurities, boiled with dilute HCl for 40
min and dried in an oven for 2h at 105oC. Then, it was ground in a ball mill and sieved. The dye solution was prepared by
dissolving accurately weighted dye in known volume of distilled water. An aliquot of aqueous solution of DB86 (pH=2, BrittonRobbinson buffer), at 25±1oC was passed through a mini column containing 0.6g powder pomegranate peel (60 mesh). The
absorbance of DB86 was measured spectrophotometrically at λmax =622 nm before and after passing of DB86 through the
column. The effect of parameters such as pH, temperature, electrolyte concentration, desorbing solvent, interfering ions on the
removal efficiency were investigated. The results showed maximum removal of DB86 (99.9%) by pomegranate peel at optimum
conditions from textile effluent and spiked samples of Karoon River .
Reference
[1] K. Kadirvelu, M. Kavipriya, C. karthika, M. Radhika, N. Vennilamani, S. Pattabhi, Utilization of various agricultural wastes for activated carbon preparation and
application for the removal of dyes and metal ions from aqueous solutions, Bioresour. Technol. 87 (2003) 129-132.
Synthesis of chitosan/alumina nano-composite for simultaneous determination of Cu2+, Cd2+ and Ni2+ ions in aqueous
solution
M. R. Fat’hi*, N. Pourreza, A. Hatami
Dep. Of Chemistry, Faculty of Science, Shahid Chamran University, Ahvaz, Iran.
E-mail: mr_fathi@scu.ac.ir
Chitosan, a functional polysaccharide and a renewable biomaterial is prepared by N-deacetylation of chitin. Currently,
chitosan(CS) has found wide application in a variety of areas because of its special set of properties, which include low or no
toxicity, biocompatibility, biodegradability, low immunogenicity, and antibacterial properties CS can be modified easily to create
nano- and microparticles or porous hydrogels.Various methods have been developed for the cross-linking of chitosan, which
commonly result in gel formation. Cross-linkers are molecules with at least two reactive functional groups that allow the
formation of bridges between polymeric chains. The raw materials were obtained in solid form from shrimp shells. The shells
were first immersed in NaOH to remove proteins and in HCl to remove all mineral materials.The resulting insoluble solid is socalled chitin.The chitin was deacetylated in concentrated NaOH. The final product (chitosan) was filtered and washed with
deionized water. The dried CS flakes (0.8 g) were fully dissolved in acetic acid solution. A solution of the CS was added to the
alumina suspension in deionized water. Adsorption of CS on alumina was performed by stirring the mixture for at least 24 h at
room temperature. The excess CS was removed by three centrifugation /dispersion/washing cycles. Then, the CS-coated alumina
was dispersed in distilled water and aqueous solutions of polysulfide and triton X-100 was introduced. The mixture was allowed
to equilibrate by stirring at room temperature for 24 h. The prepared nano-composite was collected by centrifugation and dried in
60˚C for 5 h. Scanning electron microscopy (SEM) images confirmed the presence of chitosan/alumina nano-composite. A
simultaneous preconcentration procedure for the determination of Cu 2+, Cd2+ and Ni2+ by AAS is described. The method is based
on SPE of the metal ions on chitosan/alumina nano-composite in a mini column, elution with HNO3 and determination by flame
AAS.
Reference
[1] M. Bodnar, J. F. Hartmann, J. Borbely.Biomacromolecules 2005, 6, 2521-2527
[2] N. V. Toan, Production of chitin and chitosan from partially autolyzed shrimp shell materials, The Open Biomaterials Journal 2009, 1, 21-24
[3]W.S.Wan Ngah.,L.C.Teong.,M.A.K.M.Hanafiah, Adsorption of dyes and heavy metal ions by chitosan composites:A review. Carbohydrate Polymers 2011, 83,
1446-1456
Removal of blue 56 from wastewater by pistachio shells
Mohammad Reza Fat’hi* 1, Abutaleb Ravanpaykar2,
Department of Chemistry, College of Basic Science, Islamic Azad University,Gachsaran Branch, Gachsaran, IRAN.
E-mail: 1fathiemadabadi@yahoo.com , 2rtaleb63@yahoo.com
Raw agricultural waste is an affordable adsorbent for the removal of industrial contaminants. In the present work, pistachio hull
powder (PHP) was investigated for the removal of dye blue 56(B 56) from wastewater using column method. The effects of pH
(2-10), amount of PHP (0.1–0.4 g), blue 56 concentration (60–80 mg/L), temperature (15–45◦C), mesh adsorbent (40, 60, 80,
100) and electrolyte effect and volume of solution (25-1000 mL) on removal efficiency were investigated. Results show that
removal efficiency of B56 by PHP is as quantitative as its activated carbon (>99%). Based on batch experiments, the adsorption
data could be fitted by the Langmuir equation with a maximum adsorption amount of 80 mg/g.
Reference
[1] Kazemipour, M; Ansari, M; Tajrobehkar,SH; Majdzadeh, M; Reihani ermani, H; Removal of lead, cadmium, zinc, and copper from industrial wastewater by
carbon developed from walnut, hazelnut, almond, pistachio shell, and apricot stone, Journal of Hazardous Materials 150 (2008) 322–327.
[2] Moussavi. GH; Barikbin, B; Biosorption of chromium (VI) from industrial wastewater onto pistachio hull waste biomass, Chemical Engineering Journal 162
(2010) 893–900.
Removal of Blue 56 dye by adsorption on orange peel
M. R. Fat’hi*, A. Zolfi,
Department of Chemistry , College of Basic Science, Islamic Azad University,Gachsaran Branch, Gachsaran, Iran
E-mail :fathiemadabadi@yahoo.com , ali.zolfii@gmail.com
Dyes are used in many industries, such as food, paper, carpet, rubber, plastics, cosmetics and textile in order to color their
products . So the removal of color from waste effluents has become environmentally important. Low-cost and eco-friendly
adsorbents have been investigated as an ideal alternative to the current expensive methods of removing dyes from wastewater.
This paper deals with the removal of Blue 56 dye (B56) from aqueous solutions by orange peel. Orange peel was collected from a
fruit stall and cut into small pieces. The peels were first washed to remove the adhering dirt. They were dried at room temperature
(25oC) for 36h. After drying sieved and powdered. The powdered orange peel was sieved for particles of 40, 60 and 100 mesh
sizes and used as an adsorbent. The effects of pH (2-10), amount of PHP (0.5–2.0 g), blue 56 concentration (60–80 mg/L),
temperature (25, 35, 45◦C), mesh adsorbent (40, 60, 80, 100) and electrolyte effect and volume of solution (25-1000 mL) on
removal efficiency were investigated. Results show that removal efficiency of B56 by PHP is as quantitative as its activated
carbon (>99%). Based on batch experiments, the adsorption data could be fitted by the Langmuir equation with a maximum
adsorption amount of 41.46 mg/g.
Reference
[1] T. Robinson, B. Chandran, P. Nigam, Water Res. 36 (2002) 2824–2830.
[2] K.R. Ramakrishna, T. Viraraghavan, Water Sci. Technol. 36 (1997)189–196.
[3] P. Nigam, G. Armour, I.M. Banat, D. Singh, R. Marchant, Bioresour.Technol. 72 (2000) 219–226.
Selective and sensitive colorimetric sensing of cysteine in aqueous solutions using Silver nanoparticles in the presence of
Ca2+
a
Salahaddin Hajizadeh, bMehrdad Forough, cMostafa Honardoost, aKhalil Farhadi, aReza Emamali- Sabzi
a
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
b
Department of Chemistry, Faculty of Science, Payame Noor University, Khoy, Iran
c
Department of Chemistry, Faculty of Science, Payame Noor University, Urmia, Iran
Cysteine is an amino acid that can be found in many proteins throughout the body, which have more biological importance.
Cysteine plays a critical role in a variety of important cellular functions, such as protein folding, metabolism, detoxification,
redox and disease [1].Thus we develop a new method for cysteine recognition based on aggregation of SDS-Silver nanoparticles
in the presence of Ca2+ ion.SDS-capped Ag NPs prepared by means of the chemical reduction of metal salt precursor (Silver
nitrate, AgNO3) in water with sodium borohydride (NaBH4) in the presence of sodium dodecyl sulfate (SDS) as a stabilizer
[2].Cysteine is capable of absorbing onto Ag NPs surface via the strong interaction between its thiol group and silver [3]. Thus
after addition Cysteine to Ag NPs solution, cysteine bound to the Ag NPs surface, and moved SDS away from the silver surface.
Then cysteine binds with Ca2+ via -COOH and – NH2 group, and induces the aggregation of Ag NPs. As a result the color of
solution changes from yellow to red. The color change was monitored using UV-Vis spectrometry. The ratio of absorption at 524
to 396nm (A524/A396) is linear dependent on the cysteine concentration in the range from 0.25-10µM. Furthermore, amino acid
other than cysteine cannot mediate the color change under the identical condition due to the absence of the thiol groups,
suggesting the selectivity of the proposed method toward cysteine.In conclusion, we have developed a new selective and
sensitive method for detecting cysteine, based on aggregation of SDS-silver nanoparticles in the presence of Ca 2+ ions. The
proposed method is simple, rapid and cost effective. More importantly, it does not require a fluorescent dye, temperature control
unit, and DNA engineering.
Reference
[1] V. Gazit, R. Ben-Abraham, R. Coleman, A. Weizman, Y. Katz, Amino Acids, 26 (2004) 163–168.
[2] K. Song, S. M. Lee, T. S. Park and B. S. Lee, Korean J. Chem. Eng., 26(1) (2009) 153-155.
[3] M. A. Neouze and U. Schubert, Monatsh. Chem., 139(2008)183–195
A new strategy for simultaneous determination of vitamin C, acetaminophen and tryptophan in biological and fruit juice
samples using N-(3,4-dihydroxyphenethyl)-3,5- dinitrobenzamide as an novel mediator and multiwall carbon nanotubes
as a sensor
Hassan Karimi-Maleh, Ail A. Ensafi*, S. Mallakpour
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
Ascorbic acid (vitamin C) has an important role in body health as it is necessary for the formation of collagen, assists in the
absorption of iron by promoting its reduction to the ferrous state and lack of it provokes increased susceptibility to many kinds of
infections and slows down the rate at which wounds and fractures heal [1]. Acetaminophen is a widely used anti-pyretic and
analgesic drug with actions similar to aspirin. It is an effective and safe agent for the relief of mild to moderate pain associated
with headache, arthritis and postoperative pain. Its ready access has resulted in its increased use in attempted suicide [2].In
therapeutic use, acetaminophen is often found associated with ascorbic acid and/or other pharmacologically and biologically
active compounds. The adjunct presence of ascorbic acid to acetaminophen leads to diminished toxicity and intensified positive
effects of acetaminophen [3].On other hand, tryptophan is one of the 20 amino acids and one of the essential ones in human diet.
In the standard genetic code, it is encoded as codon UGG. Tryptophan is commonly synthesized in plants and microorganisms
from shikimic acid or anthranilate [4].Therefore, preparations of new sensors for simultaneous determination of these compounds
are very important. To the best of the authors’ knowledge, no study has yet been reported on the voltammetric method using
carbon nanotubes paste electrodes to simultaneously determination ascorbic acid, acetaminophen and tryptophan. In this study,
N-(3,4-dihydroxyphenethyl)-3,5-dinitrobenzamide modified–multi-wall carbon nanotubes paste electrode was fabricated. The
modified electrode showed excellent electrocatalytic activity toward oxidation of ascorbic acid (vitamin C) (AA), acetaminophen
(AC) and tryptophan (TP) in 0.1 mol L−1 phosphate buffer solution at pH 7.0. In a mixture containing of AA, AC and TP, the
potentials separation are large enough to determine AA, AC and TP individually and/or simultaneously. The obtained catalytic
peaks current were linearly dependent on the AA, AC and TP concentrations with detection limits for AA, AC and TP were 0.01,
0.3 and 0.4 μmol L–1, respectively. The modified electrode was used for the determination of AC, AC and TP in different real
samples with satisfactory results.
Reference
[1] B.A. Fox, A.G. Cameron, Food Science, Nutrition and Health, 5th Edition, Edward Arnold, London, 1989, p. 261.
[2] Boopathi M, Won M-S, Shim Y-B, Anal. Chim. Acta 2004, 512, 191.
[3] Grundmann, U.; Wörnle, C.; Biedler, A.; Kreuer, S.; Wrobel, M.; Wilhelm, W. Anesth. Analg. 2006, 103, 217.
[4] Radwanski, E.R.; Last, R.L.; Plant Cell 1995, 7, 921.
Simultaneous determination of penicillamine, uric acid and tryptophan using a novel modified multiwall carbon
nanotubes paste electrode
Ail A. Ensafi*, H. Bahrami
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
D–penicillamine is a pharmaceutically important thiol compound frequently used as a medicinal agent against a number of
diseases i.e. rheumatoid arthritis [1], cystinuria [2], liver disease or certain skin conditions, heavy metal poisoning and Wilson’s
disease [3].Uric acid the end metabolic product of purine through the liver is present in blood and urine. Abnormal UA level in a
human body could be caused by several diseases such as gout, hyperuricemia, Lesch–Nyan syndrome, as well as cardiovascular
and chronic renal diseases.Tryptophan is one of the twenty amino acids and one of the essential ones in human diet. Tryptophan
is commonly synthesized in plants and microorganisms from shikimic acid or anthranilate. Penicillamine is an active molecule
related to natural amino acids that in contrast to the protein-forming amino acids (such as tryptophan) which are present in the L
form, the natural form is D-penicillamine, the L and DL forms being both toxic and non-active. Therefore, determination of this
amino acid same structure and tryptophan as an amino acid is important. Another hand, uric acid is biological compound that
presence in blood and urine samples and can presence simultaneously with penicillamine. To our knowledge, there is no report
on the electrocatalytic determination of PA, UA and TP using modified CNT–paste electrodes (CNPE).Therefore, in this study
we describe synthesis an application N-(3,4-dihydroxyphenethyl)-3,5-dinitrobenzamide as a new mediator for electrocatalytic
determination of penicillamine (PA), uric acid (UA) and tryptophan (TP) in 0.1 mol L−1 phosphate buffer solution at pH 7.0. In a
mixture containing of PA, UA and TP, the voltammograms of those three compounds can well separated from each other with
potential differences of 300, 610 and 310 mV between PA–UA, UA–TP and PA–TP, respectively. Those potentials separation
are large enough to determine PA, UA and TP individually and/or simultaneously. The obtained catalytic peaks current, were
linearly dependent on the PA, UA and TP concentrations in the range of 0.05–300 μmol L–1, 5–420 μmol L–1 and 1.0 – 400 μmol
L–1, with detection limits for PA, UA and TP were 0.021, 2.0 and 0.82 μmol L–1, respectively. The modified electrode was used
for the determination of PA, UA and TP in different real samples with satisfactory results.
Reference
[1]. Kim HA, Song YW (1997) Rheumatol Int 17(1):5–9
[2]. Joly D, Rieu P, Mejean A, Gagnadoux MF, Daudon M, Jungers P (1999) Pediatr Nephrol 13(9):945–950
[3]. Smolarek C, Stremmel W (1999) Zeitch Gastroen 37(4):293–300
Synthesized And Spectrophotometric study of complexation reaction of (E)-1-(2-hyroxy benzylidene)-4phenylthiosemicarbazie with some transition metal ions acetonitrile solution.
N. Samadi*, M. Ahari , A. Niko
Department of chemistry, Uremia University
E-mail: Samadi76@yahoo.com
A new ligand L were synthesized and the complex formation reaction of a newly synthesized ligand L with some transition metal
ions were studied in acetonitrile Solution using the spectrophotometric and H-NMR and IR methods. The stoichiometry of the
complex were found to be 1:1 from the investigation of electronic absorption spectra
The stoichiometry of the resulting complexes have been determined with mole ratio and continuous variation methods.
Formation constant of complexes evaluated from computer Fitting studies of the whole spectra – mole ratio data. The complex
formation was established by H- NMR and IR.
Reference
[1] M.A. Zevakin, K.V. Grazhdan, V.A. Sharnin, S.V. Dushina, Russ. J. Inorg. Chem. 51 (2004) 495.
[2] V.P. Vasilyev, Analiticheskaya Khimiya , second ed., Drofa, oscow, 2002
[3] Z. Guo, P.J. Sadler, Adv. Inorg. Chem. 49 (2000) 183.
[4] H.D. Selby, B.K. Roland, J.R. Cole, Z.P. Zheng, Macromol. Symp. 209 (2004) 23.
[5] H.D. Selby, Z.P. Zheng, Comments Inorg. Chem. 26 (2005) 75.
Amperometric Biosensor for salicylic acid Determination Based on Polypyrrole-Banana Tissue Composite
Somayeh Heydari* , Mohammad Hossein Arbab Zavar
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, IRAN
In recent years plant tissue biosensors based on materials such as banana, potato, spinach, mushroom, coconut, palm tree, and
asparagus[1-4] have been reported. By investigating enzyme modified electrodes, it has been found in many systems that
enzymes in living tissue are giving better results concerning stability, durability and even sensitivity of the electrodes, than the
electrode with immobilized enzyme alone. In this paper, an amperometric biosensor based on polypyrrole (PPy) coated on a disk
graphite was developed by entrapment of banana tissue on surface the electrode. The PPy-modified bioelectrode showed a high
catalytic activity toward the oxidation of salicylic acid (SA). Procedure PPy-modified bioelectrodes were prepared as follows: A
thick section of the banana pulp was obtained by cutting with a spatula. The electrodes were fabricated by depositing a little
portion of the pulp onto the surface of the disk graphite. The electrosynthesis was performed in a solution containing LiClO4 (0.1
M) and pyrrole (25 mM) by cycling the potential seven times between -0.7 and 1.3V V/SCE at a scan rate of 50 mVs-1. The PPymodified biosensor exhibits good electrocatalytic properties towards oxidation of SA. The determination of SA can be performed
in the range of 1×10-7 to 1×10-4 M with a detection limit of 8.9×10-8M. The low cost, simple, and fast fabrication of the sensor
makes it superior to other techniques. The bioelectrode was applied for the determination of SA in real samples.
Reference
[1] Lima, A. W. O., V. B. Nascimento, J. J. Pedrotti, and L. Angnes. Anal. Chim. Acta. 354(1997) 325–331.
[2] Felix, F. S., M. Yamashita, and L. Angnes. Biosens. Bioelectron. 21(2006) 2283–2289.
[3] Liawruangrath, S., W. Oungpipat, S. Watanesk, B. Liawruangrath, C. Dongduen, and P. Purachat. Anal. Chim. Acta. 448(2001) 37–46.
Electrochemical Behavior of para-Nitroaniline at a new synthetic crown ether-silver nanoparticle modified carbon
paste electrode
Somayeh Heydari* , Mohammad Hossein Arbab Zavar
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, IRAN
Aromatic nitrocompounds are among the most toxic substances which are commonly used in the manufacture of explosives,
pesticides, dyes, plasticizers and pharmaceuticals [1–4]. In this paper, a new synthetic ligand (i.e., 6,7,9,10,17,18,19,20,21,22decahydrodibenzo[h,r] [1,4,7,11,15] trioxadiazacyclonanodecine-16,23dione, DTD)-Ag nanoparticles(AgNP) modified carbon
paste electrode (DTD/Ag-CPE) is fabricated. At it the voltammetric behavior and determination of p-nitroaniline (PNA) is
explored. The influence of various experimental parameters on the electrode response was investigated (i.e. pH, carbon paste
composition, accumulation time). Procedure for DTD/Ag, the graphite particles (64mg), DTD (3 mg) and AgNP (3mg) were
mixed well together .Then the above mixture and the paraffin oil (30 mg) were mulled together by hand mixing (for 20 min) in a
carnelian mortar to obtain a uniformly wetted paste. Both unmodified and modified pastes were pressed into the end of a
polyethylene tube (2 mm i.d.) with copper wire as conductor and the freshly electrode interface was obtain by smoothing on a
glass plate. This modified electrode exhibited high electrocatalytic activities towards the determination of PNA by significantly
decreasing their oxidation overpotentials and enhancing the peak currents. the peak potential shift positively from -0.77V in
unmodified CPE to -0.68 in DTD modified CPE and -0.10 V at the DTD/Ag modified electrode and the peak current increased
significantly, indicating that the this modified electrode can facilitate the reduction of PNA which is attributed to the high
complexing efficieny of the new synthetic ligand and the huge surface area, strong adsorptive abilitiy and catalytic effect of silver
nanoparticles.
Reference
[1] L.E. Hallas, M. Alexander, Appl. Environ. Microbiol. (1983) 45, 1234
[2] L.F. Hanne, L.L. Kirk, S.M. Appel,A.D.Narayan, K.K. Bains, , Appl. Environ.Microbiol. (1993)59, 3505
[3] D.M. Munnecke, Appl. Environ. Microbiol. (1976) 32, 7
[4] J.C. Spain, D.T. Gibson, Appl. Environ. Microbiol. (1991) 32, 812
Voltammetric determination of 4-nitrophenol using a modified carbon paste electrode based on a new synthetic
crown ether/silver nanoparticle
Roya Mohamadzadeh kakhki*, Gholamhossein Rouaghi
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad- Iran
The analysis of phenols and substituted phenols in natural waters and effluents is of prime importance for environmental
control due to their appearance from a wide range of activities.Electrode modification is of great importance in
electrochemistry as they enhance the sensitivity of specific analyte. In general, carbon paste electrodes (CPEs) are popular
in electrochemical techniques, because carbon pastes are easily obtainable at minimal costs and are especially suitable for
preparing an electrode material modified with admixtures of other compounds thus giving the electrode certain predetermined properties[1]. The use of macrocyclic compounds like crown ethers[2] and nanoparticles as modifiers have
gained considerable attention in recent years [3-4]. In this work we developed a novel modified carbon-paste
electrode(CPE) with a new synthetic ligand: 6,7,9,10,17,18,19, 20,21, 22-decahydrodibenzo [h,r][1,4,7,11,15] trioxadiaza
cyclonanodecine -16,23dione(DTD)/Ag nanoparticles (AgNP) was employed for 4-nitrophenol measurment in natural
water. Unmodified carbon paste which used for comparison, was prepared by hand mixing of 70% of graphite powder and
30% of Nujol oil with a mortar and pestle. A modified paste was prepared in a similar fashion, except that the graphite
powder was mixed with a desired weight of modifier. Finally Nujol oil was added to the mixture and this paste was used for
construction of modified carbon paste electrode. Various parameters such as pH, modifier, accumulation time and scan rate
were optimized. The proposed electrode showed a good response towards 4-nitrophenol determination. Under the optimized
conditions the peak current showed a good linear relationship with the nitrophenol concentration in the range comprised
between 1×10−6 mol L−1 and 1×10−4 mol L−1. The developed electrode was successfully applied for the determination of 4nitrophenol in water samples.
Reference
[1] I. Svancara, K. Vytras, J. Barek, J. Zima, Carbon paste electrodes in modern electroanalysis, Crit. Rev. Anal. Chem. 31 (2001) 311.
[2] G.W. Gokel,W.M. Leevy, M.E.Weber, Chem. Rev. 104 (2004) 2723.
[3] J.J. Xu, X.L. Luo, Y. Du and H.Y. Chen, Electrochem. Commun. 6 (2004) 1169.
[4] L. Zhang and X. Jiang, J. Electroanal. Chem. 583 (2005) 292.
Highly selective and efficient transport of lead (ІІ) cations in natural water using a liquid membrane system with
dicyclohexano-18-crown-6 as carrier
Roya Mohammad Zadeh Kakhki*, Gholamhosin Rounghi
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad-IRAN
Industrial effluents containing highly toxic and non-biodegradable heavy metal cations are generated in hydrometallurgy,
electroplating, and electrochemical industry. Lead is one of the most extensively encountered heavy metals in the
environment, Selective removal of Pb2+ cation for environmental remediation and in the treatment of acute and chromic lead
poisoning remains an important objective[1-2]. Selective transport of cationic substrates by membrane carriers is of great
importance in chemistry, biology, and separation sciences. Compared with conventional separation processes, such as liquid–
liquid extraction, membrane techniques are characterized by the technical simplicity and high efficiency in separating or
enriching material from gaseous or liquid mixtures[3-4].The transport experiments employed standardized concentric cells in
which the aqueous source phase (10 cm3) and receiving phase (30 cm3) separated by an organic phase (50 cm3). All transport
experiments were carried out at ambient temperature. The organic layer was stirred by a Teflon-coated magnetic bar. Under
these conditions, not only the mixing process is perfect, but also the interfaces between the organic membrane and the two
aqueous phases remained flat and were well defined. In this work selective transport of lead(ІІ) cation across a bulk liquid
membrane(BLM) containing dicyclohexano-18-crown-6 (DC18C6) as carriers has been studied. Various factors that affect the
transport efficiency of this heavy metal cation have been optimised in order to obtain maximum transport. It has been
observed that in the presence of EDTA as stripping agent and triton X-100 as sufficient surfactant in the receiving phase and
at the optimum pH of 5, lead can transport with recovery 101±2%.The carrier can selectively and efficiently transport Pb(II)
cation from aqueous solutions containing other interfering cations. A possible application of this carrier system and transport
process to the preconcentration and recovery of Pb(II) cation from real samples has also been examined.
Reference
[1]. R. M, Izatt.; , R. S Bradshaw.; S. A ,Nielsen,.; J. D, Lamb, Christensen, J. J.; Sen, D. Chem. Rev. 83 (1985), 271-339.
[2]. R. D , Hancock,. Pure. Appl. Chem.,58 (1986) 1445-1452.
[3] C.S. Kedari, S.S. Pandit, A. Ramanujam, ,Separ. Sci. Technol. 34 (1999) 1907-1923.
[4] D. Mishra, S. Deepa, U. Sharma, Separ. Sci. Technol. 34 (1999) 3113-3124.
Preparation and electrochemical application of a new biosensor based on plant tissue/polypyrrole for the determination
of acetaminophen
Roya Mohamadzadeh kakhki*, Gholamhossein Rounaghi,
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad- Iran
Acetaminophen is a long-established and one of the most extensively employed drugs in the world. The compound is effective
in reducing fever associated with bacterial and viral infections [1]. The ready availability of acetaminophen has resulted in
increased use of the compound in suicide attempts [2]. Conducting polymers have attracted much attention, largely because of
their many applications in solar cells, light-weight batteries, electroanalytical applications, and chemical sensors and biosensors
[3–6]. A graphite electrode was used as working electrode while the platinum wire and Ag/AgCl were used as counter and
reference electrodes, respectively. The acetaminophen ppy /biosensor was fabricated by electropolymerization of pyrrole in a 50
mL 0.2 M pyrrole, 0.1 M LiNO3. polypyrrole formed electrochemically on the bioelectrode by the cyclic voltammetry method.
In this procedure, the potential was scanned from -0.7 to 1.3V at the scan rate 50mVs-1 for seven times.In order to construct ppy
/banana tissue biosensor, a thin layer of the fresh banana pulp was obtained by cutting with a spatula and formed on the base
electrode. After that in the same procedure as we maintained above, the electropolymerization of pyrrole was carried out. In this
way, the banana tissue strongly attached to the electrode surface. The electrode was washed and rinsed in double-distilled water
to remove the unfixed tissues and then was used for the determination of acetaminophen. The advantages of this biosensor for
the determination of acetaminophen are excellent catalytic activity, good detection limit and high exchange current density. The
electrochemical and structural properties of the electrode were assessed using cyclic voltammetry and differential voltammetry
and chornoamprometric techniques. Also this new biosensor was successfully applied for determination of acetaminophen in
biologic samples.
Reference
[1] Fanjul-Bolado P, Lamas-Ardisana PJ, Hernandez-Santos D, Costa-Garcia A ,Anal Chim Acta 638(2009) 133.
[2] Xiong H, Xu H, Wang L, Wang S ,Microchim Acta 167(2009) 129.
[3] Ivaska, A. Analytical applications of conducting polymers. Electroanalysis, 3(1991) 247–254.
[4] Genies, E. M., G. Bidan, and A. F. Diaz. J. Electroanal. Chem. 149(1983) 101.
[5] Li, Y. F. Electrochim. Acta. 42(1997) 203.
[6] Gerard, M., A. Chaubey, and B. D. Malhotra Biosens. Bioelectron. 17 (2002) 345.
A new dispersive liquid–liquid microextraction device for cold column solidification and trapping of organic phase
Payman Hashemi,* Mehdi Safdarian, Malihe Naderlo, Ali Reza Ghiasvand
Department of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran
E-mail:payman_hashemi@yahoo.com
Depending on the nature of the analyte there are many methods for preconcentration, separation and determination such as
liquid-phase microextraction , single-drop microextraction and dispersive liquid–liquid microextraction (DLLME) . A critical
step in all these methods is to separate organic compounds from aqueous phase . We have designed a homemade new portable
device with the ability of temperature programming to solidify and separate micro volumes of organic solvents from aqueous
phase and eliminate the centrifugation step in DLLME method. A column with 3 mm diameter and 40 mm length was drilled in a
block of Plexiglass and filled with glass particles with average diameters of 500 mm. The column block was sandwiched between
a pair of thermal electric coolers (TEC), equipped with two heat sinks and two fans. A temperature sensor was embedded in a
hole in the Plexiglass piece. A controller unit consisted of an interface device with LCD character was assembled and
programmed for column temperature controlling. A 3 ml glass syringe was fixed on top of the column. The column temperature
could be set with an accuracy of 0.1 °C within a working temperature range of -10 to 80 °C. In the developed system, after
formation of a cloudy solution in an ordinary DLLME method, the mixture is passed through the cold column. Therefore, the
organic phase is solidified and trapped in the column and is eluted later using an appropriate solvent. The system was
successfully used for the extraction of curcumin from serum samples. Recoveries higher than 90% and relative a standard
deviation of 2.87% was obtained for 5 replicated analysis of curcumin. The detection limit of curcumin determination was
calculated to be 28 ng mL-1. This device is inexpensive, portable and easily operated and may be adapted to a wide range of
organic solvents. Being a portable device, allows the use of the DLLME system for in-situ applications.
A new dispersive liquid–liquid microextraction device for cold column solidification and trapping of organic phase
Payman Hashemi,* Mehdi Safdarian, Malihe Naderlo, Ali Reza Ghiasvand
Department of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran
E-mail:payman_hashemi@yahoo.com
Depending on the nature of the analyte there are many methods for preconcentration, separation and determination such as
liquid-phase microextraction , single-drop microextraction and dispersive liquid–liquid microextraction (DLLME) . A critical
step in all these methods is to separate organic compounds from aqueous phase . We have designed a homemade new portable
device with the ability of temperature programming to solidify and separate micro volumes of organic solvents from aqueous
phase and eliminate the centrifugation step in DLLME method. A column with 3 mm diameter and 40 mm length was drilled in a
block of Plexiglass and filled with glass particles with average diameters of 500 mm. The column block was sandwiched between
a pair of thermal electric coolers (TEC), equipped with two heat sinks and two fans. A temperature sensor was embedded in a
hole in the Plexiglass piece. A controller unit consisted of an interface device with LCD character was assembled and
programmed for column temperature controlling. A 3 ml glass syringe was fixed on top of the column. The column temperature
could be set with an accuracy of 0.1 °C within a working temperature range of -10 to 80 °C. In the developed system, after
formation of a cloudy solution in an ordinary DLLME method, the mixture is passed through the cold column. Therefore, the
organic phase is solidified and trapped in the column and is eluted later using an appropriate solvent. The system was
successfully used for the extraction of curcumin from serum samples. Recoveries higher than 90% and relative a standard
deviation of 2.87% was obtained for 5 replicated analysis of curcumin. The detection limit of curcumin determination was
calculated to be 28 ng mL-1. This device is inexpensive, portable and easily operated and may be adapted to a wide range of
organic solvents. Being a portable device, allows the use of the DLLME system for in-situ applications.
Reference
[1]M. Rezaee, Y. Yamini, Journal of Chromatography A, 1217 (2010) 2342.
[2]Y. WANG, G. ZHAO, Chinese Journal of Analytical Chemistry, 38 (2010) 1517.
[3]Y. He, H. Lee, Anal. Chem, 69 (1997) 4634.
[5]M. Rezaee, Y. Assadi, Journal of Chromatography A, 1116 (2006) 1.
Application of a new semi-automatic system for the rapid spectrophotometric determination of β-Carotene by cloud point
extraction coupled to cold column solid-phase extraction
Payman Hashemi,* Mehdi Safdarian, Ali Reza Ghiasvand
Department of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran
E-mail:payman_hashemi@yahoo.com
β-carotene, which is the most common carotenoid in foods, exhibits the highest vitamin A activity and is referred to as
provitamin A . For the extraction of carotenoids from samples different systems can be used, like liquid–liquid extraction, solidphase extraction and supercritical fluid extraction. Cloud-point extraction is based on the property that a solute present in aqueous
solution of nonionic surfactant is distributed between two phases. Recently, great attention has been attracted for its great
potential in separation of solutes from several matrices. In this work, for rapid preconcentration and spectrophotometric
determination of β-carotene, a new device was used for semi-automated CPE coupled to cold column solid-phase extraction
(CPE-SPE). Several conditions were optimized for the system using a central composit design method. Under the optimized
conditions, 4 mL aqueous solution of β-carotene and 1 mL Triton x-100 (2% v/v) were mixed and heated (to 70 °C) for 3 min in
CPE-column (10 mm i.d. ´ 70 mm). Then, the turbid solution was passed through the SPE column packed with C18 (3 mm i.d. ´
40 mm). The column was sandwiched between a pair of thermal electric coolers (TEC), equipped with two heat sinks and fans
(set at 0 °C). In this way, the surfactant rich phase is solidified and trapped in the SPE-column and is eluted later using ethanol
(400 µL) in the elution temperature (35 ºC). Finally, the eluate is transferred to a quartz micro-cell for absorption readings. The
system was successfully used for the extraction of β-Carotene from serum samples. Quantitative recoveries and a relative
standard deviation of 1.5% was obtained for 6 replicated analysis of β-carotene. The detection limit of β-Carotene determination
was calculated to be 73 ng mL-1. The new semi-automated CPE-SPE method is much faster than ordinary CPE and requires
lower amounts of surfactant. Due to the short time of sample heating (3 min), no evidence of b-carotene decomposition was
observed.
Reference
[1]M. Jia, H.J. Kim, D.B. Min, Food Chemistry, 103 (2007) 695.
[2]O. Barba, Food Chemistry, 95 (2006) 328.
[3]V.A. Lemos, M.S. Santos, G.T. David, Journal of Hazardous Materials, 159 (2008) 245.
Spectrophotometric determination of trace levels of thiocyanate in biological and seawater samples employing safranineO as ion-pair reagent
a
Shahryar Abbasia*, Rohollah Valinezhadb, Hossein Khania
Department of Chemistry, Islamic Azad University, Ilam Branch, Ilam, Iran
b
Department of Chemistry, Ilam University, Ilam, Iran
The thiocyanate is present in humans as a result of the digestion of some vegetables and as a metabolic product of compounds in
tobacco and smokes containing cyanide [1]. The toxicity of thiocyanate is significantly less than that of cyanide; however,
chronically elevated levels of thiocyanate can inhibit the uptake of iodine by the thyroid gland reducing the formation of thyroxin
[2]. Additionally, in biological samples, where is a metabolic degradation product from tobacco smokes, thiocyanate has been
considered a good indicator for distinguishing between smokers and non-smokers, since elevated levels of thiocyanate are related
to excessive cigarette smoking [3]. The concentration level of thiocyanate is also considered to be important to assure the quality
of vegetables: in fact nutritional effects of glucosinolates, processing effect on oilseed rape and on cruciferous vegetables rich in
indol-3-ylmethyl glucosinolates could be revealed by its presence [4]. Several methods for the determination of thiocyanate such
as spectrophotometry, fluorimetry, capillary zone electrophoresis, ion selective electrode, chromatography, polarography, etc;
have been reported previously. Unfortunately, most of them are rather sophisticated and have used high-cost equipments. In
current paper a simple, low cost and sensitive solvent extractive spectrophotometric procedure for the determination of
thiocyanate ions from the aqueous media has been reported. The method was based on the formation a red colored complex ion
associate (SF+.SCN-) of the thiocyanate ions with the ion-pair reagent safranine-O (SF+.Cl-) in aqueous media. The colored
thiocyanate species were quantitavely extracted into methyl isobuthyl ketone (MIBK). The effect of analytical variables, e.g.
type and volume of organic solvent, ionic strength, etc. on the preconcentration of the thiocyanate from aqueous media by the
reagent SF+.Cl- was investigated. According to the recommended procedure, thiocyanate can be determined in the range 20.0 to
900.0 ng mL-1 with a detection limit of 11.0 ng mL-1. The proposed method was also applied successfully for the determination of
thiocyanate ions in biological and seawater samples.
Reference
[1] A. A. Ensafi., T. Khayamian., R. Tabaraki., Talanta 71 (2007) 2021-2028.
[2] M. Arab Chamjangali., G. Bagherian., N. Salek-Gilani., Spectrochim. Acta part A 67 (2007) 1252-1256.
[3] M. Jesus Seggui., J. Lizondo-Sabater., R. Martinez-Manez., F. Sancenon., J. Soto,Talanta 68 (2006) 1182-1189.
[4] R.D. Montgomery, in: I.E. Liener (Ed.), Toxic Constituents of Plant Foodstuffs, Academic, New York, 1969.
A Novel and Sensitive Method to DeterminationVitaminB2 (riboflavin)in Water and Pharmaceutical Samples Using an
Aqueous Two-Phase System
Sabah shiri*1,2. shahram lotfi
Department of Chemistry, Faculty of Science, The Holy Prophet Higher Education Complex University, Ilam, Iran
٢
Department of Chemistry, Faculty of Science, Pyam Noor University(PNU), GilanGharb,Iran
Email: Sabahshiri5@yahoo.com
١
A novel, simple and more sensitive spectrophotometric procedure has been developed for the determination of VitaminB 2
(riboflavin) that exploits an aqueous two-phase system (ATPS) using a liquid–liquid extraction technique. An ATPS is formed
mostly by water and does not require organic solvent. Other ATPS components used in this study were the polymer, Polyethylene
glycol (EPG 10000),and some salts(i.e.,Na2SO4,Na2CO3 or K2HPO4 + (NH4)2SO4).The method is based on the reaction between
VitaminB2 (riboflavin) and sodium sulfate (Na2SO4) in an acidic medium (pH 6.5), producing the complex anion that
spontaneously extracted in the top phase of the system. The target analyte in the sample was extracted into the polyethylene
glycol phase. After extraction, the analyte in the polyethylene glycol phase was determined by spectrphotometric method using
the analytical wavelength of 526 nm. The influences of effective parameters such as salt (type and amount), polyethylene glycol
(type and concentration), temperature, and pH of sample solution were studied and optimized. The linear range was 1.3–
320 ng ml−1 (R ≥ 0.9991; n = 10) with The relative standard deviation (RSD) for 60 ngml−1 was 3.68%. The method yielded
limits of detection (LODs) of 0.2 ng ml −1 and Recoveries between 96.8% and 106.3% were obtained for the determination of
VitaminB2 (riboflavin) in natural water and pharmaceutical samples.
Reference
[1] S.L. Bhattar,G.B. Kolekar,and S.R. Patil.J.of Luminescence. 2008,128, 3, 306-310
[2] B. J. Petteys, and E. L. Frank, Clinica Chimica Acta 2011, 412,1,38-43
[3] S.Saravanan, J. Raghava Rao, B.Unni Nair,Process Biochemistry ,2008,43,9, 905-911
Aqueous Two-Phase Systems (ATPS): A new Approach for the Determination of Brilliant Blue CFC in Water and Food
Samples
Sabah shiri*1,2, shahram lotfi2
Department of Chemistry, Faculty of Science, The Holy Prophet Higher Education Complex University, Ilam, Iran
٢
Department of Chemistry, Faculty of Science, Pyam Noor University(PNU), GilanGharb,Iran
Email: Sabahshiri5@yahoo.com
١
A new, simple, rapid and sensitive Aqueous Two Phase System(ATPS) method for the determination of brilliant blue FCF( BB)
by spectrophotometry has been developed and applied for determination of brilliant blue FCF in water and food
samples.Polyethylene glycol (PEG-4000), (4.0 g) was added to aqueous solution (15mL) for formation of a homogeneous
solution. To the mixture solution, suitable amount of Na 2CO3 was added, the mixture solution was shaken until the salt was
dissolved, and then it was separated into two clear phases easily and rapidly. The target analyte in the sample was extracted into
the polyethylene glycol phase. After extraction, measuring the absorbance at 634 nm.The effects of different parameters such as,
polyethylene glycol (type and concentration), pH , salt(type and amount) , centrifuge time and temperature on the ATPS of dye
was investigated and optimum conditions was established. Linear calibration curves were obtained in the range of 0.25–
750 ng mL−1 for brilliant blue FCF under optimum conditions. Detection limit based on three times the standard deviation of the
blank (3Sb) was 0.1 ngmL−1. The relative standard deviation (RSD) for 400 ngmL−1 was 3.14%. The method was successfully
applied to the determination of brilliant blue FCF in spiked samples with satisfactory results. The relative recovery between was
96.30 and 102.25%.
Reference
[1] S. Hong LI, Chi Yang HE, Hu Wei LIU, Chinese Chemical Letters. 2005.16, No. 8, 1074-1076,
[2] A.Giessauf, M.Flaim,M.P.Dierich, Re.Würzner . Analytical Biochemistry, 2002,308,2, 232-238
[3] N. Pourreza, M. Ghomi, Talanta, 2011. 84, 1, 240-24.
Voltammetric determination of thiosulfate using modified multiwall carbon nanotubes paste electrode
Fathali Gholami-Orimi*, Vahid nasiri
Department of Chemistry, Islamic Azad University, Qaemshahr Branch, Iran
The detection of thiol-derivative substances is an important field of research as they can be present as contaminants in fuels [1],
act as physiological indicators in biological fluids. Also they were used as markers of food deterioration [2]. Thiosulfate occurs
naturally in hot springs and geysers, and is produced by certain biochemical processes. In the body, thiosulfate converts small
amounts of cyanide ion into harmless products and plays a role in the biosynthesis of cysteine, a sulfur-containing amino acid
that locks proteins into their correct three-dimensional shapes. Thiosulfate is not found in large quantities in nature. It is routinely
used as a titrant to determine concentrations of oxidants such as hypochlorite in bleach and dissolved oxygen in water. It instantly
dechlorinates water, and is used to stop bleaching action in the paper-making industry. Thiosulfate forms water-soluble
complexes with many metals, making it useful in photo processing (where it dissolves excess silver bromide on the surface of
exposed film [8], preventing excessive darkening). Thiosulfate is also useful in the extraction of silver from silver ore, in leather
manufacture. Therefore, measurement of this kind of materials seems to be very important from industrial view point. So, in this
study, we describe application of ferrocene as a mediator and multiwall carbon nanotubes as a sensor for determination of
thiosulfate in aqueous solution pH 8.0. The diffusion coefficient (D), and the kinetic parameters such as electron transfer
coefficient (a), and heterogeneous rate constant (kh), for thiosulfate were also determined using electrochemical approaches.
Under the optimized conditions, the electrocatalytic oxidation peak current of thiosulfate showed two linear dynamic ranges with
a detection limit of 0.3×10-6 mol L-1 thiosulfate. The linear calibration range was 0.8×10-6 to 4.0×10-4 mol L-1 using differential
pulse voltammetry. Finally, this modified electrode was used as new sensor for determination of thiosulfate in real samples such
as water and waste water.
Reference
[1] B. Basu, S. Sathapathy, A.K. Bhatnagar, Catal. Rev. Sci. Eng. 35 (1993) 571.
[2] P.M. Schweizer-Bewrberich, S. Vaihinger, W. Gopel, Sens. Actuat. B 18 (1994) 282.
Selective solid-phase extraction of Cu2+ from aqueous solutions by using surface imprinting technique
a
K. Asgharia and H. Faghihian*b
Department of Chemistry, Islamic Azad University, Shahreza Branch, young researchers club
b
Department of Chemistry, Islamic Azad University, Shahreza Branch
E-mail: faghihian@iaush.ac.ir , ch.asghari_kh87@yahoo.com
A new sorbent for selective solid-phase extraction of Cu2+was prepared by surface imprinting technique. Maximum adsorption of
Cu2+ was obtained at pH 5 after 5 min of contacting time. Maximum static adsorption capacity of Cu(II)-imprinted and nonimprinted functionalized silica gel wasrespectively 67.27 and 56.45 mg.g-1. Using column procedure,the breakthrough curve was
also plotted andthe breakthrough capacity was calculated. The selectivity factor of the sorbent was investigated by batch
procedure. Zn 2+ and Ni2+ were chosen as competitive ions. Tolerance limits of Zn2+ and Ni2+ were respectively 8000 and 10100
mg.L-1. The Cu(II)-imprinted silica gel sorbent show higher adsorption capacity and selectivity factor than non-imprinted one.
The synthesized sorbent has good reusability and stability in room temperature. It was found that by using Langmuir isotherm the
experimental resultscould be well described, indicating the adsorption is monolayer and the surface of the sorbent is
homogenous.
Reference
[1] Wang, Z.; Wu, G. and He, C.; "Ion-imprinted thiol-functionalized silica gel sorbent for selective separation of mercury ions" MicrochimActa, 2009, 165, 151-157.
[2] Liu, Y.; Chang, X.; Wang, S.; Guo, Y.; Din, B. and Meng, S.; "Solid-phase extraction and preconcentration of cadmium (II) in aqueous solution with Cd(II)imprinted resin", Anal. Chim. Acta, 2004, 519, 173-179.
[3] Fan, J.; Wu, C.; Xu, H.; Wang, J. and Peng, C.; "Chemically functionalized silica gel with alizarin violet and its application for selective environmental samples"
Talanta, 2008, 74, 1020-1025.
[4] Zhang, N.; Suleiman, J.S.; He, M. and Hu, B.; "Chromium(II)-imprinted silica gel for speciation analysis of chromium in environmental water samples with ICPMS detection" Talanta, 2008, 75, 536-543.
[5] Jiang, N.; Chang, X.; Zheng, H.; He, Q. and Hu, Z.; "Selective solid phase extraction of nickel(II) using a surface-imprinted silica gel sorbent" Anal. Chim. Acta,
2006, 577, 225-231.
Rapid removal of cobalt ions from aqueous solution using magnetic nanocomposite based on activated carbon
Mahnaz Jafaria, Mohammad Reza Sovizia, Ali Reza Fakharib, Fateme Tajabadia
Department of chemistry, Malek Ashtar University of Technology, P.O. Box 16765-3345, Tehran, Iran
b
Department of Chemistry, Faculty of Sciences, SHahid beheshti University, P.O. Box 19396-4716Tehran, Iran
a
The chemical contamination of water from a wide range of pollutants is a serious environmental problem owing to their potential
human toxicity. Cobalt is one such essential metal that is discharged in the wastewaters of several chemical industries like,
electroplating, textile, paint and petroleum. Cobalt may cause multiple ailments at high concentrations including respiratory
irritation, diminished pulmonary function, vomiting, pneumonia, fibrosis, skin allergy, dermatitis, nervous disorders, memory
loss, deafness and visual impairment [1]. Therefore, it is important to remove this metal from polluted waters. The presented
study investigates application magnetic nanocomposite based on activated carbon (MNC-AC) as an excellent adsorbent for solid
phase extraction and removal of Co2+ ions. The influence of parameters such as pH of the aqueous solution, amount of adsorbent,
chelating agent, contact time, and competitive cations on the extraction efficiency was investigated and optimized using pH 8.5,
contact time 20 min and 80 mg of adsorbent for the maximum removal. After extraction and collection of MNC-AC, the
concentrations of cobalt in the solution were monitored using UV spectroscopy and ICP. The results showed that adsorption
process was very fast (20 min). The kinetic rate model followed a pseudo-second-order. Equilibrium isotherm data were analyzed
according to Langmuir and Freundlich equations. The characteristic parameters for each model have been determined. The
adsorption of Co2+ onto the immobilized material due to good correlation coefficient (~1) obeyed the Langmuir adsorption
models. On the basis of the Langmuir analysis, the maximum adsorption capacities were determined to be 81.3 mg/g. The
obtained results in the present study indicated that the MNC-AC is an efficient adsorbent material for adsorption of cobalt ions
from aqueous solutions. Moreover MNC-AC, carrying target metals, were easily separated from the aqueous solution by applying
an external magnetic field; so, no filtration or centrifugation was necessary.
Reference
[1] Sh.Mona, A.Kaushik, C.P. Kaushik Desalination xxx (2011) xxx–xxx.
Design and fabrication microinterdegitated electrode
Hamid Hadari, Mohammad Reza Sovizi *
Department of chemistry, Malek Ashtar University of Technology Tehran, Iran
E-mail: mrsovizi@yahoo.com
In this project a Interdigitated electrodes was designed and fabricated.A 2cm*2cm silicon bed was chosen and coated by a 50, 20
and 150 nanometer silicondioxide, chromonium and gold layers, respectively. The layers were characterized by quartz crystal
microbalance method. A photoresist layer was deposited and lithographic by UV ray and wet etching. The micro electrode
fabricated contain 15 µm of width, 150 nm of thickness, 5 mm of length, 15 µm of gap . The absorbent contain Polyanilineand
carbon nanotube coated on electrode surface byspin coating(4000 rpm) method. The described electrode is utilized in identifying
and measuring of vapor amount of organic compounds in air as well as fabrication of chemical sensors.
Reference
[1] subodhsrivastava, s.s. Sharma, shwetaagrawal, sumitkumar, m.singh, y.kvijay.study of chemiresistor type CNT doped polyaniline gas sensor, synthetic metals
160(2010)529-534
[2] Chang-Yong Yang, Chi-Lin Li, Chia-Jung Lu. A vapor selectivity study of microsensor arrays employing various functionalized ligand protected gold
nanoclusters, AnalyticaChimicaActa 565 (2006) 17–26
[3] Miso Park, Lakshmi N. Cella , Wilfred Chen, Nosang V. Myung, Ashok Mulchandani , Carbon nanotubes-based chemiresistiveimmunosensor for small molecules:
Detection of nitroaromatic explosives, Biosensors and Bioelectronics 26 (2010) 1297–1301
[4] BurkhardRaguse, Edith Chow, Christopher S. Barton, and Lech Wieczorek, Gold Nanoparticle Chemiresistor Sensors: Direct Sensing of Organics in Aqueous
Electrolyte Solution,Anal. Chem. 2007, 79, 7333-7339
Nitrate removal from industrial waste waters by magnetic nanocomposite based on activated carbon
Fateme Tajabadia, Mohammad Reza Sovizia, Yadollah Yamini b
Department of chemistry, Malek Ashtar University of Technology, P.O. Box 16765-3345, Tehran, Iran
b
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box14115-175, Tehran, Iran
a
Nowadays, removal of nitrate from industrial waste waters such as food and explosive manufactures containing high levels of
nitrate is important. These types of waste waters contaminate environment and the water resource to nitrate. Increasing nitrate
concentrations in drinking water causes two adverse health effects: “blue-baby syndrome” (methemoglobinemia), especially in
infants, and the potential to formation of carcinogenic nitrosamines [1, 2]. In this study magnetic nanocomposite based on
activated carbon (MNC-AC) was synthesized and then applied for removal of nitrate from waste water samples. Effect of various
parameters such as pH, contact time, dosage of adsorbent, stirring speed and competitive onions on the extraction efficiency was
investigated and optimized using pH 3, contact time 15 min and 80 mg of adsorbent for the maximum removal. The
concentrations of nitrate in the solution were monitored using UV spectroscopy and ion-chromatography. The equilibrium and
kinetic of nitrate adsorption was studied. The Langmuir isotherm fit the equilibrium data better than the Freundlich model. Thus
the mono-layer adsorption was confirmed. On the basis of the Langmuir isotherm, the maximum adsorption capacity was
obtained to be 53 mg/g. This adsorption process follows a pseudo-second-order kinetics rate model. The results showed that
equilibrium time of adsorption of nitrate onto MNC-AC is about 15 min therefore the kinetic of nitrate removal is fast. The high
adsorption capacity values for all nitrate solutions in acidic condition (pH 3) were due to the strong electrostatic interactions
between positive sites of adsorbent and the nitrate anion. The adsorption of nitrate on MNC-AC is reversible. Thus MNC-AC
could be repeatedly used for nitrate removal studies in six consecutive adsorption/desorption cycles without detectable losses in
its initial adsorption capacity. Although activated carbon was magnetized and some of its capacity occupied by nanoparticles of
iron oxide, its capacity for adsorption of nitrate is relatively good. Also Results of this study suggest that MNC-AC can be used
for the removal of excess nitrates from waste waters.
Reference
[1] D.Majumdar,N.Gupta, Indian J. Environ. Health 42 (2000) 28–39.
[2] A.Bhatnagar, E.Kumar, M.Sillanpää, Chemical Engineering Journal 163 (2010) 317–323.
Rapid preconcentration and selective determination of nitrate in aqueous samples using solid-phase extraction coupled
with UV spectroscopy
Fateme Tajabadia, Mohammad Reza Sovizia, Yadollah Yamini b, Mahnaz Jafaria
Department of chemistry, Malek Ashtar University of Technology, P.O. Box 16765-3345, Tehran, Iran
b
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box14115-175, Tehran, Iran
a
Nitrate ions are highly soluble in water so Conventional methods for purification of water aren’t able to elimination this anion
completely. Therefore nitrate often exists in drinking waters and considering that it is harmful for health, especially to infants,
Determination of it in drinking water is essential. Spectrophotometric methods based on creation color are sensitive, but aren’t
always suitable to determination the low concentrations of nitrate in drinking waters. The sensitivity of the method has been
greatly increased by preconcentrating. Preconcentrating method based on solid phase extraction are more practical. In this study
magnetic nanocomposite based on activated carbon (MNC-AC) was synthesized and applied for preconcentration of nitrate in
various aqueous samples. Nitrate concentrations in eluent phase were determinate by UV spectroscopy via creation amber color
by reduction of nitrate by cadmium (Cadmium Reduction Method, method 8039). Effect of various parameters such as pH,
contact time, various eluents, temperature and competitive onions on the extraction efficiency was investigated and optimized
using pH 3, contact time 15 min and 1 ml of sodium hydroxide 0.2 M as an eluent for the maximum extraction. At this condition
near 95% recovery of nitrate was obtained. The volume of primal solution of nitrate was 100 mL and the enhancement factor of
the proposed method for the nitrate ion was 112. The method had a linear dynamic range within the range of 30–1000 μgL−1 and
its detection limit (DL) was 9 μgL−1. The results showed that our proposed SPE method can be used successfully for rapid
extraction and determination of nitrate ion from water samples such as rain, tap and mineral waters. Compared to traditional
methods for determination of nitrate, these types of SPE methods have advantages such as (a) low time-consuming due to
magnetically-assisted separation of the adsorbent, which can meet the needs of rapid analysis, (b) MNC-AC adsorbent have
higher surface areas; therefore, satisfactory results can be achieved by using less amounts of the adsorbents and (c) this adsorbent
can be easily synthesized in laboratory.
Cloud point extraction of mercury with Triton-X-100 to its determination in water samples by ETAAS
Mahmoud Chamsaz∗, Mohammad Hossein Arbab-Zavar , Seyyed Ali Taheri and Malihe Dehghani Mohammad Abadi
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Iran
The sensitive determination of mercury at ultra-trace level in environmental samples is always a great interest because of its high
toxicity and bioaccumulation properties [1–2]. A preconcentration step of analyte has to be used before detection when the level
of mercury is very low [3–4]. Cloud point extraction (CPE) method is regarded as a new and green potential alternative method
of preconcentration to conventional liquid–liquid extraction [5] The purpose of this study is to combine CPE with ETAAS in
order to perform a sensitive mercury determination in water samples with minimal requirements of reagents, sample consumption
and time of analysis. Cloud point extraction (CPE) has been used for the pre-concentration of mercury, after the formation of a
complex with diethyldithiocarbamate(DDTC),followed analysis by electrothermal atomic absorption spectrometry (ETAAS)
using triton-X-100 as surfactant. The chemical variables affecting the separation step were optimized and determined as, pH 6.6,
cloud point temperature 90 ◦C, DDTC concentration of 10−4 mol L−1, sample volume of 10 mL. The limit of detection (LOD)
obtained under the optimal conditions was1.2µgL−1. RSD for 10 replicate determinations at 10 µgL−1 Hg was 4.7%. The method
was successfully applied to determine mercury in water samples .
Reference
[1] Chen HT, Chen JG, Jin XZ, Wei DY (2009) Determination of trace mercury species by high performance liquid chromatography–
inductively coupled plasma mass spectrometry after cloud point extraction. J Hazard Mater 172:1282
[2] Li P, Feng XB, Qiu GL, Shang LH, Li ZG (2009) Mercury pollution in Asia: a review of the contaminated sites. J Hazard Mater 168:591
[3] Bagheri H, NaderiM(2009) Immersed single-drop microextraction– electrothermal vaporization atomic absorption spectroscopy for the trace determination of
mercury in water samples. J Hazard Mater 165:353
[4] Leopold K, Foulkes M, Worsfold PJ (2009) Gold-coated silica as a preconcentration phase for the determination of total dissolved
mercury in natural waters using atomic fluorescence spectrometry. Anal Chem 81:3421
[5] Bezerra MD, Arruda MAZ, Ferreira SLC (2005) Cloud point extraction as a procedure of separation and pre-concentration for
metal determination using spectroanalytical techniques: a review. Appl Spectrosc Rev 40:269
Application of Modified ZSM-5 Nanozeolite by Ni and Cu in the Adsorption of Acridine Orange Dye
Abdolraouf Samadi–Maybodia*, Seyed Karim Hassani Nejad–Darzib and Mehdi Ghobakhluoa
(a) Analytical Division, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran, P.O.Box: 47416-95447. Tel/Fax: +98(112)5342350.
(b) Faculty of Basic Science, Babol Noshirvani University of Technology, Babol, Iran, P.O.Box: 71167-47148
Dye containing wastewaters are usually treated by physical or chemical processes [1]. Wastewater from chemical laboratories
and dye manufacturing industries contains various dyestuffs, which are toxic to microorganisms, aquatic life and human beings
[2]. The photocatalysed degradation of Acridine Orange cationic dye has been investigated in aqueous suspensions of titanium
dioxide (TiO2) in the presence of light and oxygen [2]. Qadri et al. [3] reported a method for separation of Acridine Orange using
a magnetic nanoparticles (γ-Fe2O3). In this study, we developed an effective method for the synthesis of ZSM-5 nanozeolite that
modified by nickel and copper. The ZSM-5 nanozeolite was modified by transition metals such as Ni and Cu and was
characterized using X-ray diffraction (XRD), scanning electronic microscopy (SEM) and Fourier transforming infrared (FT-IR)
techniques. Removal of Acridine Orange from wastewaters was performed by modified ZSM-5 nanozeolite using Uv-vis
technique in an aqueous medium. Different parameters such as initial dye concentration (i.e., 25, 30, and 35 mg/L), contact times
(i.e., 20, 40, 60, 80 and 100 min), temperatures (i.e., 298, 323 and 348 K), mixing rate (i.e., 150, 175 and 200 rpm) and pH (i.e.,
3, 5, 7, 9 and 11) were investigated using a PG instrument Ltd−Model T90+ UV spectrophotometer at a maximum wavelength
(λmax) of 477 nm. Results indicated that the Ni-ZSM-5 and Cu-ZSM-5 nanozeolite as an adsorbent was found to increase
efficiency of Acridine Orange adsorption as compared to the unmodified ZSM-5 nanozeolite. It was found that the adsorption
capacity increased with increasing pH values in the studied range. Lower adsorption capacity at lower pH values was probably
due to the presence of excess H+ ions competing with the dye cations for adsorption sites [4].
Reference
[1] T. Robinson, G. McMullan, R. Marchant, , P. Nigam, Bioresource Technol. 77 (2001) 247–255.
[2] M. Faisal, M. Abu Tariq, M. Muneer, Dyes Pigments, 72 (2007) 233–239.
[3] S. Qadri, A. Ganoe, Y. Haik, J. Hazard. Mater. 169 (2009) 318–323.
[4] M.A.M. Lawrence, R.K. Kukkadapu, S.A. Boyd, Appl. Clay Sci. 13 (1998) 13–20.
Functionalized CdS quantum dots as luminescent probes for detection of mercury (II)
M. Shaban, M. R. Ganjali*, P. Norouzi, F. Faridbod
Center of Excellence in Electrochemistry, Faculty of chemistry, University of
Tehran, Tehran, 1417614411, Iran
Masoom_shaban@ut.ac.ir, Ganjali@khayam.ut.ac.ir
In this work, a new CdS QDs was synthesized. A Schiff’s Bases, N,N-bis(salicylidene)-naphthylene-1,8-diamine, was used for
modification of QDs. The proposed CdS QDs shows a selective behavior toward Hg (II) ion in comparison to other common
metal ions. Thus, the Schiff's base-capped CdS QDs was applied as a navel fluorescent nano chemosensor for determination of
Hg (II) ion. This probe is based on the characteristic of fluorescence quenching of functionalized CdS QDs. Under the optimum
conditions, the fluorescence intensity of CdS QDs is linearly proportional to the mercury ions concentration in the range of
1.45×10--8 to 2.16×10-6 M with detection limit of 7.5×10−9 M.
Reference
[1]Leatherdale, C. A.; Woo, W. K.; Mikulec, F. V.; Bawendi, M. G., On the absorption cross section of CdSe nanocrystal quantum dots. J Phys Chem B 2002, 106
(31), 7619-7622.
[2]Michalet, X.; Pinaud, F. F.; Bentolila, L. A.; Tsay, J. M.; Doose, S.; Li, J. J.; Sundaresan, G.; Wu, A. M.; Gambhir, S. S.; Weiss, S., Quantum dots for live cells, in
vivo imaging, and diagnostics. Science 2005, 307 (5709), 538-544.
[3]Walling, M. A.; Novak, J. A.; Shepard, J. R., Quantum dots for live cell and in vivo imaging. Int J Mol Sci 2009, 10 (2), 441-91.
[4]Hosseini1, M.; Vaezi, Z.; Ganjali, M.R.; Faridbod, F.; Dehghan Abkenar,S.; Salavati-Niasari,M., Selective Recognition of Mercury in Waste Water Based on
Fluorescence Enhancement Chemosensor. Sensor Letter 2010, 8, 807-12
[5]Sanchez, C.; Julian, B.; Belleville, P.; Popall, M., Applications of hybrid organic-inorganic nanocomposites. J Mater Chem 2005, 15 (35-36), 3559-3592.
[6]Gerion, D.; Pinaud, F.; Williams, S. C.; Parak, W. J.; Zanchet, D.; Weiss, S.; Alivisatos, A. P., Synthesis and properties of biocompatible water-soluble silicacoated CdSe/ZnS semiconductor quantum dots. J Phys Chem B 2001, 105 (37), 8861-8871.
[7]Huang, C. P.; Liu, H. W.; Tsao, C. Y.; Yin, L. T.; Chiu, S. F.; Chen, T. M., Plate-based biochemical assay using quantum dots as a fluorescent labeling agent.
Sensor Actuat B-Chem 2005, 108 (1-2), 713-720.
[8]Moffitt, M.; Eisenberg, A., Size Control of Nanoparticles in Semiconductor-Polymer Composites .1. Control Via Multiplet Aggregation Numbers in Styrene-Based
Random Ionomers. Chem Mater 1995, 7 (6), 1178-1184.
Potentiometric Study of aminoacridine and 2,6-pyridinedicarboxylic Acid Proton-Transfer System and complexation with
Zn2+ and Cd2+ metal ions in dioxane/H2O (1:1 v/v) solvent
Ardeshir Shokrollahi*, Roghayyeh Aghaei and Zahra Mohamadpour
Chemistry Department, University of Yasouj, Yasouj 75918-79831, Iran
Email: ashokrollahi@mail.yu.ac.ir
Mixed solvents specially alcohol-water or dioxane-water was widely used for potentiometric study of complexation of the
insoluble and low soluble ligands with metal ions in aqueous solutions [1]. In this work the protonation constants of AAcr and
pydc and the pydc-AAcr proton transfer equilibrium constants, the stoichiometry and stability of complexation of this system
with Zn2+ and Cd2+ metal ions in a dioxane/H2O (1:1 v/v) solvent were investigated by potentiometric pH titration method. The
stoichiometry of the most complexes species in solution were compared with corresponding crystalline metal ion complexes.
Ligand protonation constants and stability constants of proton-transfer systems and their complexes with Zn2+ and Cd2+ metal
ions were evaluated using the program BEST described by Martell and Motekaitis [2] The value of the autoprotolysis constant
for dioxane/H2O (1:1 v/v) solution (Ks = [H+][OH-]) was calculated according to the literature[2]. In the case of pydc(L), as
ligand, the most likely species for Zn2+ are: ZnL, ZnL2 and ZnL2H and for Cd2+ are: CdLH, CdL2, CdL2H and Cd2L2H., for AAcr
–M system, the most likely species: for Zn2+ are: ZnQ, ZnQH and ZnQ2 and for Cd2+ is: CdQ, CdQH and CdQ2H, for M-pydcAAcr systems the species are: for Zn2+ are: ZnLQH , ZnL2Q2H3 and ZnLQ2H2; for Cd2+are: CdL2Q2H2 , CdL2Q2H3 and
CdLQ2H2. Structural effects of the ligands on the stability of binary and ternary complexes were discussed.
Reference
[1] V. Uitert, L. G. Fernelius, W. C. J. Am.Chem. Soc. 1953, 75, 451
[2] A. E. Martell, R. J. Motekaitis, “Determination and Use of Stability Constants”, 2nd ed., VCH, New York. 1992.
Concentration Determination of Some Elements in Quercus (Brantii) from Kohgiloye va Boyer Ahmad
a)
Ali Mohammadzadeha,*, Abdolraouf Samadi-Maybodia, Mohammad Hossein Fatemia
Division of Analytical Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
E-mail mohammadzade.ali@gmail.com
Quercus acorns (brantii) grown naturally in different regions of Iran (Kohgiloye va Boyer Ahmad) were studied to detect some
elemental concentrations in order to observe different accumulation levels. Quercus (brantii) is rich in some useful mineral
elements such as K, Fe and Zn [1-3]. The content of these mineral elements are dependent on their region and environmental
conditions. In this study we determined total concentrations of K, Fe and Zn elements and difference among concentrations of
these metals in Q.brantii fruits, leaves and soils in which they are grown (south of Iran, Kohgiloye va Boyer Ahmad) using acid
digests by atomic absorption spectrophotometry. The twigs bearing mature acorns, leaves and soils were collected from their
natural distribution areas in Ysouj, Sisakht and Kakan during September 2010. Chemical analysis: Mature acorns, leaves and
soils from each region were dried at 90°C in aluminium foil for 3 days and ground with mortar and pestle. 1 g dried weight (DW)
of each sample were then wet-digested on a hot-plate using HCl 20% . Mineral analysis were carried out by Atomic Absorption
Spectrometer. Total concentrations were measured at 766.5 nm for K (emission mode), 213.9 nm for Zn and 248.3 nm for Fe
(absorption mode) [4]. Quercus acorn has been a staple food in countries from Iran to Japan. It was also documented that Quercus
have the best range of mineral concentrations having prooxidant activity and health benefits for man and animal feeding during
the autumn. In this study Fe, Zn and K concentrations in some Quercus were observed remarkably high. The results indicates that
the measured concentrations of the elements in all three regions is as follows: Zn> K> Fe.
Reference
[1] Özcan, T., and Gulriz Baycn., Pak. J. Bot., 37, 361, 2005.
[2] Sardans J., Montes F., and Peñuelas J., Spectrochimica Acta Part B 65, 97, 2010.
[3] Aucélio, R.Q., Martins, de Souza R., Calixto de Campos, R. Miekeley N., and Porto da Silveira, C.L.,Spectrochimica Acta Part B 62, 952, 2007.
[4] Jhonston, W.R., and Proctor J., Plant Soil, 46, 275, 1977.
Determination of Cu2+, Ni2+, Zn2+ and Co2+ by flame atomic absorption spectrometry after solid phase extraction on
Helicteres isora as a new adsorbent modified by bis (2, 4- dichlorbenzylidene)- 1, 6- hexanediamine
A. Shokrollahi1 *, H. goodarzi2, M. Montazerozohori1A. Alizade1
1. Department of Chemistry, University of Yasouj, Yasouj, Iran 75918-74821
2. 2. Department of Chemistry, Islamic Azad University of Gachsaran, Gachsaran, Iran
E-mail: ashokrollahi@mail.yu.ac.ir
Solid phase extraction is one of the most used techniques for preconcentration trace metal ions from liquid samples before
analytical determinations mainly by atomic spectrometric methods. Batch and column procedures are two important parts of the
solid-phase extraction. Various solid materials such as activated carbon, cellulose, alumina, silica gel, ion exchange resins, XAD
modified resins and synthetic zeolites have been used for solid phase extraction [1]. Some of these adsorbents are suitable for
preconcentration of metal ions, but their methods of preparation are time-consuming and involve rigid control of conditions.
Also some of them are expensive and costs of regeneration are high. Nowadays, a number of low-cost, commercially available
adsorbents have been tried for extraction. Natural adsorbents such as: fly ash, coconut husk, rice husk, natural zeolites, and plant
bushes have been used for solid phase extraction. In this study, Helicteres isora is introduced as adsorbent for the extraction of
Cu2+, Ni2+, Zn2+ and Co2+ ions [2, 3]. The method is based on the collection of analytes metal ions on Helicteres isora modified by
bis (2, 4- dichlorbenzylidene)- 1, 6- hexanediamine with mediated sds and determination of analytes by flame atomic absorption
spectrometry (FAAS). The effect of various parameters such as: pH, concentration of H 2so4 as a proper eluent, amount of ligand
and size of adsorbent particles on extraction processing was investigated. The method in pH = 4, amount of 40mg of ligand and
size of adsorbent <100 vis and 2mol L-1 of eluent was optimized. Calculated amounts of recoveries varied between 87 and 100%.
The proposed method was applied for determination of cited ions in several real samples.
Reference
[1] A. Shokrolahi, M. Ghaedi, R. Shabani, M. Montazerozohori, F. Chehreh, M. Soylak, S. Alipour, Food and Chemical Toxicology, 48 (2010) 482-489.
[2] S. Vellaichamy, K. Palanivelu, J. Hazard. Mater. 185 (2011) 1131–1139.
[3] N. Pourreza∗, K. Ghanemi J. Hazard. Mater. 161 (2009) 982–987.
Removal of Pb (II) from wastewater by biosorption on corn-husk
S.H.Ahmadi, M.Tajik*, M.H.Amini, K.Tabarheydar
Chemistry & chemical engineering research centre of Iran, 14335-186, Tehran, Iran
The removal of Pb (II) from aqueous solution by adsorption on corn-husk was studied. Different chemical modifications on
biosorbent properties with some acids and bases increase the adsorption capacity compared to raw corn-husk about 100 times.
Batch wise experiments were carried out to study the effect of pH, initial metal ion concentrations, biosorbent mass, ionic
strength, sizes of biosorbent particles, temperature and stirring time. The final concentration of Pb2+ in sample solutions was
determined using atomic absorption spectrophotometer technique. The Langmuir and Fruendlich adsorption isotherms were
considered. The Langmuir model fitted the experimental data best with correlation coefficient R2 = 0.976.
Reference
[1] G.Naja, V.Murphy, B.Volesky, Wiley encyclopaedia of industrial biotechnology, (2010).
[2] X.Li, Y.Tang, F.Luo, colloids and surface 137 (2007) 512-521.
[3] S.Schiewer, S.B.Patil, Journal of hazardus materials 157 (2008) 8-17.
[4] B.Nasernejad, T.Esslamzadeh, Process biochemistry 40 (2005) 1319-1322.
Comparison of conventional hollow fiber based liquid phase microextraction (HF-LPME) and electro membrane
extraction (EME) efficiencies for extraction of ephedrine from biological fluids
S. Molaeia, Y. Yaminib*, L. Fotouhia, S. Seidib
Department of Chemistry, Faculty of Sciences, Alzahra University, P.O. Box 1993891176, Tehran, Iran
b
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran.
E-mail: yyamini@modares.ac.ir
a
Ephedrine is a sympathomimetic amine commonly used as a stimulant, appetite suppressant, concentration aid,
decongestant, and to treat hypotension associated with anaesthesia. Ephedrine may be quantitated in blood, plasma or urine to
monitor possible abuse by athletes, confirm a diagnosis of poisoning or assist in a medicolegal death investigation. In the present
study, two methods were performed and compared for extraction and preconcentration of ephedrine from biological fluids: (1)
electro membrane extraction (EME) and (2) carrier-mediated hollow fiber liquid phase micro extraction (HF-LPME) prior to high
performance liquid chromatography (HPLC). Under electrokinetic migration conditions, ephedrine was extracted from 7 mL
acidic aqueous sample solution across supported liquid membrane (SLM) consist of 2-nitrophenyl octylether (NPOE) and 10%
(v/v) di-(2-ethylhexyl) phosphate (DEHP) immobilized in the walls of hollow fiber, and into a 20 µL of acidified aqueous
acceptor solution located inside the lumen of the hollow fiber with potential difference of 100 V applied over the SLM. At
carrier-mediated hollow fiber conditions, ephedrine was extracted from alkaline samples into toluene and 10% (v/v) tris-(2ethylhexyl) phosphate (TEHP) immobilized in the pores of a porous hollow fiber, and then transported into 20µL of 1mM HCl as
the acceptor solution. Several factors including pH of acceptor and donor phase, the organic solvent used as the SLM, stirring
speed, salt effect and the applied voltage and its duration, were investigated to find the most suitable extraction conditions. Under
the optimized conditions enrichment factors of 130 and 35 for urine and 51 and 8 for human plasma were obtained via EME and
HF-LPME, respectively. The calibration curves showed good linearity with coefficient of estimations higher than 0.986. In the
proposed EME technique limits of detection ranged between 0.005, 0.010 µg mL-1, while in HF-LPME were obtained 0.06, 0.20
µg mL-1 for urine and plasma, respectively. The relative standard deviations of the analysis were found in the range of 5.2-8.6%
(n=3). The results showed that compared with HF-LPME, EME is a much more effective transport mechanism, providing high
extraction efficiencies in very short time.
Reference
[1] S. Pedersen-Bjergaard, K.E. Rasmussen, J. Chromatogr. A 1109 (2006) 183-190.
[2] A.Gjelstad, T. Andersen, K.E Rasmussen, S. Pedersen-Bjergaard, J. Chromatogr. A 1157 (2007) 38-45
Determination of biogenic amines by ionic liquid based ultrasound assisted dispersive liquid-liquid microextraction
simultaneous with derivatization(IL-based USA-DLLME- SD)
Malihe Naderlou *, Payman Hashemi
Department of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran
E-mail:malihe_naderlo@yahoo.com
Biogenic amines are known to occur in a wide variety of fermented and non-fermented foods. The determination of biogenic
amines in food products is critical to assess potential health risks, before consumption. In this work, a combined derivatization
IL-based USA-DLLME method with HPLC-UV analysis was developed for the determination of biogenic amines in human
serum. The analytes were derivatized and preconcentrated, simultaneously, into a micro-drop of anionic liquid. A central
composite design method was used for optimization of the factors in this method. In the optimized conditions, 90 mL acetone and
95 mL ionic liquid ([bmim] PF6) and 10 mL benzoyl chloride (the derivatization reagent) were rapidly injected into 4 mL of the
sample. The sample was a serum sample diluted by 0.1 M HCl and 1.7 mol L-1 sodium hydroxide. The sample solution was
shaken for 2 min and the resulted solution was incubated at 20 °C for 20 min and then sonicated for 10 min. Therefore, ionic
liquid was dispersed into the aqueous solution and a cloudy solution was achieved. In the next step, 2 mL of a 0.4 mol L-1 sodium
chloride solution was added to the mixture and it was centrifuged at 2000 rpm for 6 min. The organic phase was then aspirated
into a microsyringe and injected into the HPLC system for direct analysis. Recoveries between 90 to 105% were obtained for the
serum samples. The detection limits of the method were 0.003, 0.0035 and 0.015 µg mL-1with RSD of 11.4%, 5.9% and 7%
(seven replicates) for agmatine, tryptamine and histamine, respectively.
Reference
[1] A.R. Shalaby, Food Chem., 59 (1994) 305.
[2] S. Yammamoto, H. Itano, H. Kataoka, M. Makita, , J. Agric. Food Chem., 30 (1982) 435.
[3] J. Kirschbaum, K. Rebscher, H. Bruckner, J. Chromatogr. A, 881 (2000) 517.
[4] A.T. Wood, M.R. Hall, J. Chromatogr. B, 744 (2000) 221.
Development and validation of the impurity-indicating chromatographic assay method for methadone
Nadiya Ekbatani1, Zahra Talebpour1,*, S. Kiumars Hosseini2, Alireza Ghassempour3
1
Department of Chemistry, Faculty of Science, Alzahra University, Tehran, Iran
2
R&D Director, Temad Co., km 28 Karaj Makhsoos Road, Tehran, Iran
3
Medicinal Plants and Drugs Research Institute, Shahid Beheshti University, Evin, Tehran, Iran
E-mail: nadiya_ekbatan@yahoo.com
The presence of impurities in drug products should be identified and quantified to evaluate the safety and efficiency of the drug
[1]. Methadone hydrochloride has become one of the most widely used drugs for opiate dependency treatment. Because of its
habit-forming characteristics, it is classified as narcotic, analgesics, opiate agonists, antitussive agents and a substitute for
morphine. The impurity of drug may result from synthesis path, impurities in reactants or degradation pathway [2]. The aim of
this study was to develop and validate gas chromatography method for the determination of methadone in presence of related
impurities and its degradation products for assessment of purity of bulk drug and stability of its bulk dosage forms. Methadone
and its standards were analyzed using a modified gas chromatography. For optimized the temperature programming GC oven
hold at 50 °C for 1 min and then increase to 150 at 5 °C min-1 (held for 1 min), and after that programmed at 15 ºC min-1 to 260
ºC and held to 15 min. The split mode with split ratio of 1:50 was selected. The identification was performed by GC-MS and
confirmed by GC-MS/MS results. The proposed method was validated based on the criteria of linearity, recovery, repeatability,
limits of detection (LOD) and quantification (LOQ). The calibration curves for methadone as dependence of peak area in
concentration range of 200-1500 µg mL-1 were established. The regression coefficient and detection limit were obtained as 0.995,
47 µg mL-1, respectively. The total study showed some impurities and residual solvent in compare to the standards. Also, thermal
stability of bulk drug and dosage forms of methadone was investigated using thermal gravimetric (TG) and differential scanning
calorimetric (DSC) methods.
Reference
[1] Sporkert, F., Pragst, F., J. Chromatogr. B, 746 (2000) 255.
[2] Abd-Elrahman M. I., Ahmed M. O., Ahmed S. M., aboul-Fadl T., El Shorbagi A. Biophys. Chem. 97(2002) 113-120.
Liquid Phase Microextraction of n-alkanes from water samples using Olive Oil Droplets
b
Ramin Malekia, Rahele Tahmasebia,b* , Khalil Farhadi b
Research Department of Chromatography, Iranian Academic Center for Education Culture and Research (ACECR), Urmia, Iran.
a
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran.
E-mail: r.t.tahmasebi@gmail.com
Although n-alkanes constitue only a small portion of organic matter in water but these compounds are important markers of
environmental pollution.The existence of n-alkanes in water are typically in range of ngL-1 to µgL-1.Due to this importance of nalkanes analysis several sample preparation methods such as SPME[1], stir bar sorptive extraction [2] have been developed. In
this work, a novel , simple and efficient method was developed for microextraction of n-alkanes from water samples before gas
chromatographic analysis. Separation and preconcentration is based on the dispertion of olive oil micro-drop (1.0g) as extraction
solvent in vigorously stirred sample solution (500ml) followed by back extraction of analyte fram 0.5ml ethanol as appropriate
back-extraction solvent. The influence of microextraction conditions such as type and volume of oil and back extraction solvent,
volume of aqueous solution, ionic strength, extraction temperature and extraction time were investigated. High enrichment
factors (478-493), low detection limits (0.4-1.9 µgL-1) and good precision (5.6-8.9%) are the main advantage of the proposed
method.
Reference
[1]M.A.Farajzaded,A.A.Matin,Anal.Sci.18(2002)78.
[2]G. Roy, R. Vuillemin, J. Guyomarch,J. Talanta 66 (2005) 540–546
[3]I. Antonio, L.Granadillo, J.Ignacio, A.Sanz-Medel; J. Environ. Monit., 2 ( 2000) 218.
[4]S.L. Chong, D.Wang, J.D.Hayes, B.W.Wilhite, A.Malik; Anal.Chem., 69 (1997) 3889.
Gene selection and classification of microarray data from lung Adenocarcinoma using Weighted Voting Algorithm and
PLS-DA
1
Saeed Masoum*1, Sayed Hamed Saberi1
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, Iran
Tobacco smoking is responsible for over 90% of lung cancer cases, and yet the precise molecular alternation induced by smoking
in lung that develop into cancer and impact survival have remained obscure [1, 2]. Microarray data usually contains a high level
of noisy gene data that include incorrect, noise and irrelevant genes. Before microarray data classification take place, it is
desirable to eliminate as much noisy data as possible. An approach to improving the accuracy and efficiency of microarray data
classification is to make a small selection from the large volume of high dimensional gene expression dataset. An effective gene
selection helps to clean up the existing microarray data and therefore the quality of microarray data has been improved. Selection
of relevant genes for sample classification is a common task in most gene expression study, where researchers try to identify the
smallest possible set of genes that can still achieve good predictive performance [3]. In this research we used Weighted Voting
Algorithm for gene selection and identified some gene (such as: GGH, TTK, AURKA, CCDC59, …) that expression of these
genes strongly differentiated both smokers from non-smokers in lung tumor and non-tumor tissue and used PLS-DA for
classification of Current from Never smoker and Former from Never smoker both in lung tumor and non-tumor tissue.
Reference
[1]Maria Teresa Landi, Tatiana Dracheva ,et al (2008), PLoS ONE 3(2): e1651. doi:10.1371/journal.pone.0001651
[2]Bryant A, Cerfolio RJ (2007) Differences in epidemiology, histology, and survival between cigarette smokers and never-smokers who develop non-small cell lung
cancer. Chest 132: 185–192
[3]Ramón Díaz-Uriarte,Sara Alvarez de Andrés(2006), BMC Bioinformatics 2006, 7:3doi:10.1186/1471-2105-7-3
Improvement of HER on the MnO modified carbon paste electrode by electrodeposited metal hexacyanoferrates on the
electrode surface
Ali Ghaffarinejada,b*, Naghmeh Sadeghi b, Abdolreza Khajehzadehc
Faculty of Chemistry, Iran University of Science and Technology, Tehran 1684613114, Iran
b
Department of chemistry, Islamic Azad University, Firoozabad branch, P.O. Box 74715-117, Firoozabad, Fars, Iran
c
Department of chemistry, College of sciences, Shiraz University, Shiraz 7145685464, Iran
a
The extensive consumption of fossil fuels has not only accelerated their depletion but it has also led to serious environmental
pollution issues. Hydrogen is a clean energy carrier, which can be replaced with these fossil fuels, and can be generated from
clean and green sources. Although Pt is an excellent candidate for hydrogen evolution reaction (HER), but its present resource is
very limit, many attempts have been made to reduce the amount of loaded Pt [1] or replacing it with other catalysts [2]. Relative
to bare carbon paste electrode (CPE), the electrochemical hydrogen production of MnO modified CPE is better. In this study the
effect of electrodeposited hexacyanoferrate (HCF) films (CoHCF, NiHCF and Co-NiHCF) on the MnO modified CPE for HER
was investigated in 2 M H2SO4. The results shown that these modifiers, in the order of Co-NiHCF > CoHCF > NiHCF improve
the performance of the HER by large increasing in the current density and decreasing the overvoltage of hydrogen evolution.
According to ease of preparation and cheapness of HCF films, it can be concluded that these mediators are helpful for improving
the performance of modified electrodes for electrolcatalytic hydrogen generation.
Reference
[1] Raoof JB, Ojani R. Int J Hydrogen Energy 2010; 35: 3937–44.
[2] Yang J, Cheng F, Liang J, Chen J. Int J Hydrogen Energy 2011; 36: 1411–7.
Electrochemical hydrogen production with Shimalite Ni catalyst
Ali Ghaffarinejada,b*, Einollah Maghsoudi b, Arash Siroueinejad c , Naghmeh Sadeghi b
a
Faculty of Chemistry, Iran University of Science and Technology, Tehran 1684613114, Iran
b
Department of chemistry, Islamic Azad University, Firoozabad branch, P.O. Box 74715-117, Firoozabad, Fars, Iran
c
Department of chemistry, College of sciences, Islamic Azad University, Shiraz branch,Shiraz, Iran
Platinum is a good electrode for electrochemical production of hydrogen, but it is expensive and its present resource is very limit.
Therefore huge attempts have been done to reduce the amount of Pt in electrode body [1] or replacing it with other catalysts [2].
In this study carbon paste electrode modified with Shimalite Ni catalyst was used for hydrogen production. This catalyzer
contains Ni, SiO2, iron oxide and alumina; four species that have been used for hydrogen generation [3-6]. Application of this
catalyst causes increasing current density of hydrogen generation at low potentials. In this work some parameters such as pH,
electrolyte type, percentage of catalyst, carbon and paraffin oil were optimized. The best conditions and composition was 13.1%
catalyst, 20% paraffin oil and 2 M H2SO4. According to low cost and high performance of this catalyst, it can be considered as a
good candidate for production of hydrogen without using Pt.
Reference
[1] J.B. Raoof , R. Ojani, Int. J. Hydrogen Energy, 35 (2010) 3937–44.
[2] J. Yang, F. Cheng, J. Liang, J. Chen, Int. J. Hydrogen Energy, 36 (2011) 1411–7.
[3] X. Li, B. Yue, J. Ye, Appl. Catal., A, 390 (2010) 195–200.
[4] A. Boudjemaa, S. Boumaza, M. Trari, R. Bouarb, A. Bouguelia, Int. J. Hydrogen Energy, 34 (2009) 4268-74.
[5] J. Liu, H. Watanabe, M. Fuji, M. Takahashi, Electrochem. Commun., 11 (2009) 107–110.
[6] B. Pierozynski, Int. J. Electrochem. Sci., 6 (2011) 63 – 77.
Electrochemical determination of D-penicillamine drug in presence of mercury
Ali Ghaffarinejada,b*, Fatemeh Hashemi b, Abdolreza Khajehzadeh c
Faculty of Chemistry, Iran University of Science and Technology, Tehran 1684613114, Iran
b
Department of chemistry, Islamic Azad University, Firoozabad branch, P.O. Box 74715-117, Firoozabad, Fars, Iran
c
Department of chemistry, College of sciences, Shiraz University, Shiraz 7145685464, Iran
a
D-Penicillamine (DA) with a trade mark of Cuprimine® is an antirheumatic drug used to treat patients with active rheumatoid
arthritis. It also is classified as a metal binding agent used for treating Wilson's disease, a genetic disease that causes excessive
copper to accumulate in the body [1]. It is also used for mercury poisoning treatment [2]. DA makes complex with mercury. In
this study Hg2+ ions were adsorbed on the carbon paste electrode surface, after adsorption this electrode was exposed to DA
solution. Due to interaction of DA with Hg ions the peak current of Hg is reduced obviously, which is proportional to DA
concentration. For obtaining optimum conditions various parameters such as pH effect, buffer type, Hg2+ concentration, mercury
adsorption time, applied potential range and scan rate were optimized. The linear range by cyclic voltammetry for 20 s adsorption
time of 1mM Hg concentration in acetate buffer (pH 4) was from 0.1 to 10 μM DA. The proposed method was used for
determination of DA in commercial DA capsule as a real sample. This electrode do not required any modifier and the oxidation
potential of DA is reduced about 350mV relative to unadsorbed mercury carbon paste electrode.
Reference
[1] http://www.medicinenet.com/penicillamine/article.htm (visited on June 11, 2011).
[2] Ashbel, S.I., Stroikova, G.D., Khil, R.G. Meditsina Truda I Promyshlennaya Ekologiya 20 (1976) 25.
Development of a specific double beam laser induced thermal lens spectrometer as a powerful and non-destructive
analytical tool
N. Shokoufi, S. Madarshahian
Faculty of Instrumentation and Material Analysis ,Chemistry and Chemical Engineering Research Center of Iran
E-mail: shokoufi@ccerci.ac.ir
Thermal lens spectroscopy (TLS) is a non-destructive, fast and high sensitive photothermal technique for the measurement of
optical absorption and thermo-optical properties of materials. In this study, we developed a specific double beam TLS for low
volume detection of samples. A schematic illustration of our setup is presented in figure 1. The excitation laser beam (532 nm, 50
mW) was modulated with a mechanical chopper and introduced into the convergence lens. Another laser beam (632 nm, 5 mW)
was used as probe beam. These two beams were aligned coaxially by a dichroic mirror and irradiated on the sample cell
containing 1-(2-pyridilazo)-2-naphtol (PAN) that placed at confocal plane of the lens, where the thermal lens effect was induced.
Then the probe beam diverged by the effect. An interference filter (632 nm) blocked the excitation beam and just the probe beam
introduced into the photodiode detector. The signals were illustrated by a digital oscilloscope. As result, we succeeded in
sensitive and micro volume analysis by a home-made double beam thermal lens spectrometry.
Figure 1: Schematic of our experimental setup of TLS.
Reference
[1] S. Bialkowski, etal., Journal of Applied Physics, 107, 2010, 053104.
[2] N. Shokoufi, A. Hamdamali, Analytica Chemica Acta, 681, 2010, 56-62.
[3] S. Chong, W. Min and X. Sunney Xie, The Journal of Physical Chemistry Letters, 1, 2010, 3316-3322.
[4] S. Hiki, K. Mawatari, A. Hibara, M. Tokeshi and T. Kimori, Analytical Chemistry, 78, 2006, 2859-2863
Diode pumped solid state laser induced thermal lens microscopy for micro volume and trace detection
N. Shokoufi*, S. Madarshahian
Faculty of Instrumentation and Material Analysis
Chemistry and Chemical Engineering Research Center of Iran
E-mail shokoufi@ccerci.ac.ir
One of the most promising methods of non-label detection is thermal lens spectrometry (TLS) that can be used as a method for
trace analysis and sensitive detection in micro-space by combining TLS with an optical microscope as thermal lens microscopy
(TLM). Designing a home-made TLM as a routine tool for low volume and trace analysis in liquid samples was the aim of this
work. In this experiment, a continues-wave laser as excitation beam, modulated by a mechanical chopper and introduced into the
optical microscope vent. An invert optical microscope was used for precise focusing of excitation beam onto the micro sample
cell and multiplying the divergence of the probe beam followed by increasing in sensitivity. He-Ne laser was used as probe
beam. These two beams were made coaxial with dichroic mirror on top of the objective lens of optical microscope and then
focused onto a microcell containing 1-(2-pyridilazo)-2-naphtol (PAN) as sample. After passing these two beams through an
interference filter (632 nm), only the probe beam feed into the photodiode detector. The raise and fall of the thermal lens signals
illustrated in figure 1 and correspond to on and off the excitation beam and to thermal lensing phenomenon. Signals were
recorded as the thermal lens signals by a digital oscilloscope. In conclusion, a home-made TLM method was developed for high
sensitive detection of micro samples.
Figure 1: Recorded signals of thermal lens microscopy.
Reference
[1] H. Shimizu, K. Mawatari and T. Kitamori, Analytical Chemistry, 82, 2010, 7479-7484.
[2] N. Shokoufi, A. Hamdamali, Analytica Chemica Acta, 681, 2010, 56-62.
[3] N. Seta, K. Mawatari and T. Kitamori, Analytical Science, 25, 2009, 275-278.
[4] N. Shokoufi, F. Shemirani, Talanta, 73, 2007, 662-667.
Dispersive Cloud Point Extraction for trace analysis
N. Shokoufi*, A. Atabayki
Faculty of Instrumentation & Material Analysis, ,Chemistry & Chemical Engineering Research Center of Iran ,Tehran, Iran
E-mail: Shokoufi@ccerci.ac.ir
A new, very simple, rapid, high enrichment factor and environment-friendly method named Dispersive Cloud Point Extraction
(DCPE) was developed for analyte preconcentration. DCPE is a preconcentration and sample preparation method that have
performances of cloud point extraction (CPE) and Dispersive Liquid Liquid Microextraction (DLLME) methods. In this method,
a specific surfactant (non-ionic, ponpe 7.5) solution which has cloud point temperature near the laboratory temperature was
dispersed in aqueous solution. Thus, micelles formed and aggregated in aqueous solution. Then, surfactant aggregations separates
from aqueous solution and then cloudy solution is formed. After centrifuging, surfactant rich phase are separated and sedimented
in the bottom of the conical test tube. During the formation of cloudy solution, micelles extract and preconcentrate the
hydrophobic analytes. Nickel was used as an analyte and 1-(2-thiazolylazo)-2-naphtol (PAN) as a chromogenic complexing
reagent. Ni (II)-PAN complex formed a red-colored (maximum wavelengths of 559 nm) in PONPE7.5 media. Micro photometry
(MP) was used for determination of analyte in micro volume of remained phase after preconcentration. Different parameters such
as pH, surfactant, ligand, dispersion,
and were optimized. Under the optimum conditions, calibration graph were linear in
the range of 5-200 µgL−1 with limit of detection (LOD) of 1.569 µgL−1. The relative standard deviations (RSD) were lower than
1 %, and the enhancement factor of 96 for 10 mL of sample. Interference effects of some anions and cations were studied. This
method was applied to determination of Ni in natural and waste water samples, food samples, various synthetic and stainless steel
alloys, tea leaves, riceflour and black tea., and human hair, with satisfactory results.
Reference
[1] N. Shokoufi, F. Shemirani, F. Memarzadeh, Anal. Chim. Acta 6 0 1 (2007) 204.
[2] N. Shokoufi, F. Shemirani, M. Shokoufi, Spectrochimica Acta Part A 74 (2009) 761.
[3] Nader Shokoufi∗, Amir Hamdamali, Anal. Chim. Acta, 681 (2010) 56.
[4] D.L. Giokas, E.K. Paleologos, M.I. Karayannis, Anal. Bioanal. Chem.373 (2002) 237.
Spectroscopic and Voltammetric Behaviour of Vitamin B12 in the Present of DNA with the use of Methylene Blue Dye as
a Probe
Zafari, Mitra* a and Hajian, Reza b
Department of Chemistry, Islamic Azad University branch of Gachsaran.
b
Department of Chemistry, Islamic Azad University branch of Gachsaran.
E-mail: Hajian@iaug.ac.ir, E-mail: zafari_m1422@yahoo.com
a
DNA plays a central role in life process since it contains all of the genetic information required for cellular function. However,
DNA molecules are prone to be damaged under various conditions, especially by interaction with some molecules, and this
damage may lead to various pathological changes in living organisms. There is growing interest in exploring the binding of small
molecules with DNA for the rational designing to DNA as well as in understanding how proteins recognize and bind to specific
DNA sequences [1-2]. In this work, Spectrophotometric and Voltammetric methods were used to probe the interaction of
Vitamin B12 with Fish sperm double stranded DNA (ds-DNA). The Voltammetric behaviour of Vitamin B12 has investigated at a
glassy carbon electrode using cyclic voltammetry. The apparent transfer coefficients ( ) and the number of electron transferred
(n) for Vitamin B12 (VB12) in the absent and present of ds-DNA have determined using cathodic Tafel plots on the surface of
glassy carbon electrode. The binding site size (s) with DNA were obtained by voltammetry method. Also apparent binding
constant of Methylene Blue as the important fluorophore probe with DNA was found to be 2.80×105 mol-1 L. The maximum
emission wavelength of VB12 is ca. 364 nm when excited at 350 nm. The fluorescence intensity for VB12 increased significantly
in the titration with DNA [3]. In this paper, spectroscopy, (spectrophotometry and fluorometry) and cyclic voltammetry methods
show that the binding mode between VB12 and DNA is electrostatic and intercalative. This study is very important for elucidating
the molecular interaction mechanism and very useful for screening out or designing more effective drugs with low side effects.
Reference
[1]B.Lambert, J.B.Lepecq,in:W Guschlbauer,W.Saenger (Eds), DNA-Ligand Interactions, From Drug to Plenum, New York, 1986, p.141.
[2]M.P.Singh,T.Joseph,S.Kumar,Y.Bathini,J.W.Lown,Synthesis and sequence-specific DNA binding of a topoisomerase inhibitory analog of Hoechst 33258designed
for altered base and sequence recognition, Chem.Res.Toxicol.5(1992)597-607.
[3] Ensafi, A. A.; Hajian, R.; Ebrahimi, S.; Study on the Interaction between Morin-Bi(III) Complex and DNA with the use of Methylene Blue Dye as a Fluorophore
Probe J. Braz. Chem., Soc. 2009, 20, 266-276.
Application of stir bar sorptive extraction in combination with gas chromatography for the determination of n-alkanes in
water samples
Vahideh Abdollahi1, Ramin Maleki*2 , Khalil Farhadi1
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
2
Research Department of Chromatography, Iranian Academic Center for Education, Culture & Research (ACECR), Urmia Branch, Urmia, Iran
1
The new technique of stir bar sorptive extraction (SBSE) using stirrers 10 mm long coatod with 0.5 mm polyvinyl chloride
(PVC) was used to determine n-alkanes from water samples. The desorption of the extracted analytes was performed with
ultrasonic treatment using 200 µL of ethanol as solvent. The alkanes were determined with gas chromatography (GC) and flame
ionization detection. The detection limits of this method under the given conditions (extraction from a 50 ml sample, 15 min
extraction time and 15 min desorption time) were very low (between 1 to 3 µg L-1). The high correlation coefficients (>0.9961)
and wide LDRs are other advantages of the proposed method.
Reference
[1] M.B. Fernandes, M.A. Sigre, A. Boireau, J. Tronczynski, Estuaries 13 (1997) 281.
[2] R. Eisert, K. Levsen, J. Chromatogr. A 733 (1996) 143.
[3] M. Knutsson, G. Nilv ´ e, L. Mathiasson, J.A. J ¨ onsson, J. Chromatogr. A 754 (1996) 197. [4] A. Ekdahl, K. Abrahamsson, Anal. Chim. Acta 357 (1997) 197.
[5] S. Bowadt, L. Mazeas, D.J. Miller, S.B. Hawthorne, J. Chromatogr. A 785 (1997) 205.
[6] H. Hartmann, J. Burhenne, K. M ¨ uller, H.G. Frede, M. Spiteller, J. AOAC Int. 83 (2000) 762.
[7] A.R. Chaves, S.M. Silva, R.H.C. Queiroz, F.M. Lancas, M.E.C. Queiroz, J. Chromatogr. B: Anal. Technol. Biomed. Life Sci. 850 (2007) 295.
[8] P. Sandra, B. Tienpont, J. Vercammen, A. Tredoux, T. Sandra, F. David, J. Chromatogr. A 928 (2001) 117.
[9] R.H.C. Queiroz, C. Bertucci, W.R. Malfara, S.A.C. Dreossi, A.R. Chaves, D.A.R. Valerio, M.E.C. Queiroz, J. Pharm. Biomed. Anal. 48 (2008) 428.
[10] L.P. Melo, A.M. Nogueira, F.M. Lancas, M.E.C. Queiroz, Anal. Chim. Acta 633 (2009) 57.
Single-walled carbon nanotube as a novel stir bar sorptive extraction (SBSE) for analysis of N-nitrosodiphenylamin
pollutant in water samples with HPLC-UV technique
Samereh Ranjbar Bandforuzi, Zahra Talebpour*
Department of Chemistry, Faculty of Science, University of Alzahra, I.R. Iran
E-mail: ranjbar_65_30@yahoo.com
Stir bar sorptive extraction (SBSE) was introduced in 1999 as a solventless sample preparation method for the extraction and
enrichment of organic compounds from aqueous matrices. The method is based on sorptive extraction. Polydimethylsiloxane is
along conventional coating for SBSE that is available. In comparison to solid phase micro-extraction, a larger amount of sorptive
extraction phase is used and consequently extremely high sensitivities can be obtained [1]. In sorptive extraction (SE), the coating
technology of extraction phase is vitally important to the performance of the device. To date, static coating technology and sol–
gel coating technology are commonly used in SE. The sol–gel process starts with the hydrolysis of alkoxysilane as the sol–gel
precursor by water in proportion molar ratios, followed by polycondensation of hydrolyzed products into a sol–gel network. We
have reported single-walled carbon nanotube (SWNT) coating as extraction phase in stir bar sorptive extraction by sol-gel
technique for the first time and have analyzed N-nitrosodiphenylamin pollutant in water by it. Parameters affecting extraction
such as solvent polarity, extraction and desorption time, solvent desorption and, agitation speed on extraction efficiency were
optimized. Concentration range from 100 to 900 ng mL-1 was investigated and a good linear trend was observed. Finally,
precision, accuracy, limit of detection and concentrate factor of the SBSE-HPLC-UV method have obtained. The thermal
stability of SWNTs coating of the bars was examined by thermal desorption in the TDS unit at 250 °C for 2 h, followed by a GC
run. No peak was observed and no change was observed in the surface of the bars. Chemical stability of SWNTs coating of the
bars was examined by dipping the bars in acetonitrile, methanol and deionized water for 3 h. No change was observed in the
surface of the bars. Surface characteristics of the created sol-gel carbon nanotube coating were studied by scanning electron
microscopy (SEM) and FT-IR spectroscopy.
Reference
[1]F. David, P. Sandra, J. Chromatogra. A 1152 (2007) 54.
[2]R. Jiang, F. zhu, T. Luan, Y. Tong, H. Liu, J. Chromatogr. A 1216 (2009) 4641.
[3]L. Berguiga, J. Bellessa, F. Vocanson, E. Bernstein, J.C. Plenet, Optical materials 28 (2006) 167.
Evaluation of headspace liquid-phase microextraction-gas chromatography for the analysis of benzene in drinks and
beverages containing vitamin C
Zahra Hossainbor and Massoud Kaykhaii*
Department of Chemistry, Faculty of Sciences, University of Sistan & Baluchestan, Zahedan 98135-674; Tel (541) 8052250, Fax 2446888,
Email: kaykhaii@hamoon.usb.ac.ir.
A facile headspace liquid-phase microextraction (HS-LPME) procedure using a mixture of n-hexadecane and n-dodecane (50:50)
as extracting solvent is presented for the trace determination of benzene in drinks and beverages which contain vitamin C. This
work is believed to be necessity because of the recent reports regarding the presence of benzene in vitamin C drinks [1]. This is is
due to the reaction between sodium benzoate and ascorbic acid (vitamin C), which causes benzene formation. In this extraction
method, a mixture of 2 mL adjusting buffer and 0.6 g NaCl was added into a 5.00-mL sample of drink or juice that was put in a
10 mL septum-closed vial in order to extract its benzene from its headspace. Several important parameters influencing the HSLPME extraction efficiency were investigated including extraction solvent and its volume, sample volume, extraction time, salt
addition, extraction temperature, agitation speed and pH of the donor phase. Under the optimized conditions, up to 132-fold
enrichment factor of benzene was obtained with extraction recovery of ≥ 97% and a detection limit of 0.1 µg.L-1.
Reference
[1] Gardner L, Lawrence G (1993) J Agric Food Chem 41:693–695.
Removal of lead(II) from aqueous solutions by nanocomposite silica aerogel activated carbon
Fariba Tadayon1, Mohammad Saber Tehrani 2, Shiva Motahar1*, Mina hoseini2
1
2
Department of chemistry, North Tehran Branch , Islamic Azad University, Tehran , Iran
Department of chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran
E-mail: Shiva.motahar@yahoo.com
In the present investigation, nanocomposite silica aerogel activated carbon of 38 nm prepared by the sol–gel method were used to
adsorb lead ions from aqueous solution. Silica aerogel modified, selectively adsorbed Pb(II) from binary ion systems in the
presence of Cu(II), Ni(II), Al(III), Zn(II), Co(II) , Cr(II), Mn(II), Fe(II), and Ag(I). The adsorption properties of the modified
silica gel, silica aerogel and activated carbon were compared using batch method. Characterization of the as-synthesized material
was carried out using fourier transform infrared spectra (FTIR), differential scanning calorimetry (DSC), nitrogen physisorption
and scanning electron microscope (SEM). Adsorption was dependent on Pb(II) concentration, temperature, pH, adsorbent
dosage, contact time of the system. The optimum pH was found to be in the range of 6. The nanoparticles can rapidly and
quantitatively adsorb Pb from 50 mL of aqueous solution in 10 min. The removal of Pb(II) the equilibrium data followed
Langmuir isotherm equation and the maximum adsorption capacity of the modified silica gel, silica aerogel and activated carbon
was 26.310 mg g-1, 12.980 mg g-1 and 18.510 mg g−1, respectively. The adsorbed Pb(II) on the nanocomposite could be
completely eluted by 1M HNO3 solution. The results showed that modified silica aerogel with activated carbon could be used as
an adsorbent for the effective removal of Pb(II) ions from aqueous solutions. This method is simple, rapid and sensitive and very
suitable for rapid adsorption of Pb(II) ions from large volume of sample solution.
Reference
[1] Zhang, X.,2010, Removal of Pb(II) from water using synthesized kaolin supported nanoscale zero-valent iron, Chem. Eng. J., Vol. 163 , pp. 243–248.
[2]M. Uçurum, A study of removal of Pb heavy metal ions from aqueous solution using lignite and a new cheap adsorbent (lignite washing plant tailings), J. Fuel 88
(2009) 1460–1465.
[3]O¨ zer, 2007, Removal of Pb(II) ions from aqueous solutions by sulphuric acid-treated wheat bran, J. Hazard. Mater., Vol. 14, pp. 753–761.
Design and characteristics of an optical sensor based on immobilization of MWCNTs-g-PCA-Au on a triacetylcellulose
membrane
Nahid Sarlak*a, Zeynab Sameria,c and Keyvan Shaabani b
Department of Analytical Chemistry, Faculty of Chemistry, University of Lorestann, khorram Abad, I.R.Iran.
b
Engineering Research Institute (Iranian Space Agency), Department of Nano Technology & Nanoscience, Tehran, I.R.Iran
c
Member of Young researchers club
*E-mail: sarlak.n@gmail.com
a
In this work a new nanocomposite of MWCNT-graft-poly (citric acid) hybrid materials which was prepared recently [1] with
gold nanoparticles was synthesized and the effect of important factors was examined by changing experimental variables such as
the time of dispersion, pH and temperature. Encapsulation of gold nanoparticles were obtained through UV-visible spectra and
TEM analysis. Gold nanoparticles since a long time are motive of intense research because of their special optical properties and
electrochemical activity. Combination of CNTs and metal nanoparticles has been exploited for applications in biomedical
devices, biosensors, optical devices [2]. MWCNT-g-PCA hybrid materials were used to support and transport gold nanoparticles
by addition a water solution of hydrogen tetrachloroaurate (HAuCl4) to a water solution of MWCNT-g-PCA at ambient
temprature. Then nanoparticles were reduced by NaBH4 (0.01M). TEM experiments were used to evaluate the structure of
MWCNT-g-PCA-Au hybrid materials. The synthetic new nanocomposite was applied for designing an optical sensor. The new
optical sensor was prepared according to the following procedure. The triacetylcellulose membranes were treated with
commercial sodium hypochlorite. Then films were treated with ethylene diamine for 3min at ambient temperature and they were
placed in the MWCNTs-g-PCA-Au solution for 48 hours. Prepared membranes were kept under water when not in use.
MWCNTs-g-PCA-Au is covalently bonded to a transparent triacetylcellulose film. The life time of membrane was very good.
These sensors can be used to measure various chemical species such as cyanide and thiourea.
Reference
[1] M. Adeli, A. Bahari and H. Hekmatara, NANO: Brief Rep. Rev. 3 (2008) 37-44.
[2] L. Minati, S. Torrengo, G. Speranza, Surface Science 604 (2010) 507–511.
Synthesies a new bimetallic MWCNTs-g-PCA-Au/Ag nanocomposite and complexation study of synthetic nanocomposite
by spectrophotometric method
a
NahidSarlak*a, Zeynab Sameria,c Reza Pourrahimb
Department of Analytical Chemistry, Faculty of Chemistry, University of Lorestann, khorram Abad, I.R.Iran
b
Department of Plant Virus Research, Plant Pets and Diseases Research Institute
(PPDRI), Ewin-Tabnak 19395-1454, Tehran, I.R. Iran
c
Member of Young researchers club
*E-mail: sarlak.n@gmail.com
In this paper, we produced a new nanocompoite of Au-Ag bimetallic nanoparticles with CNT-g-PCA. Combination of CNTs and
metal nanoparticles has been exploited for applications in biomedical devices, biosensors, optical devices [1]. Ag–Au
nanoparticles is introduced to the research of the glucose electrode, because silver is the best conductor among metals and gold
has good biocompatibility [2]. In this work we proposed a simple and rapid method for prepration of CNT-g-PCA-Au/Ag with
low cast. We applied a new water soluble nanocomposite (MWCNT-g-PCA) which was prepared recently [3]. Polycondensation
of monohydrate citric acid in the presence of functionalized MWCNT in the melting state was lead to nanotube-graft-poly (citric
acid) (CNT-g-PCA) nanocomposites. A water solution of this hybride material was mixed with a water solution of hydrogen
tetrachloroaurate (HAuCl4) under stirring at ambient temperature and then placed in an ultrasonic bath to well disperse metal ions
in the polymeric shell of hybrid material and then it was reduced by NaBH4 (0.01M). The effect of reaction parameters (such as
pH, temperature, ultrasonic time) on the synthesies of metal nanoparticles with MWCNT-g-PCA was studied by UV-vis
experiments. For preparation of Au/Ag nanoparticles, this solution and water solution of AgNO 3 were mixed as above procedure
and then the final solution was reduced by NaBH4 (0.01M) again. Finally we studied encapsulation of bimetal nanoparticles
through UV-visible spectra and other spectroscopic methods. TEM images and UV-vis spectra were confirmed the formation of
bimetal nanoparticles on the surface of MWCNTs.
Reference
[1] L. Minati, S. Torrengo, G. Speranza, Surface Science 604 (2010) 507–511.
[2] XianglingRen, et al. Sensors and Actuators B 110 (2005) 358–363.
[3] M. Adeli, A. Bahari and H. Hekmatara, NANO: Brief Rep. Rev. 3 (2008) 37-44.
Synthesis, characterization and analytical applications of Ni(II)-ion imprinted polymer
Ali Reza Feyzbakhsh, Homayoun Ahmad Panahi, (Fateme Dadjoo)*, Sahar Afzali, Rozita Abdolahi Fard, Samira Kamali Rosta
Department of Chemistry, Central Tehran Branch, Islamic Azad University, Tehran, Iran
Elham Moniri
Department of Chemistry, Varamin (Pishva) Branch, Islamic Azad University, Varamin, Iran
E-mail: f_dadjoo58@yahoo.com
Ion recognition-based separation techniques have received much attention because of their high selectivity for target ions.[1-6] In
this study, we have prepared a novel ion imprinted polymer (IIP) to remove nickel ions in solution samples. The imprinted
polymer was prepared by copolymerization of Allyl glaycidyl ether / Imminodiaceticacid (AGE/ IDA) with N,N
Dimethylacrylamid as functional monomers in the presence of N,N bismethylenacrylamid as cross linker. At first, AGE/IDA
was prepared and then the ion imprinted polymer was synthesiezed. The polymerization was carried out in bulk with free radical
initiation using 2,2 Azobis isobutyronitryl. The above synthesized polymers were characterized by Fourier transform inferared
Spectroscopy (FT-IR), Elemental analysis, Scanning electron microscope analysis (SEM) and Thermogravimetric analysis
(TGA). The total capacity of IIP was found to be 58.3 mg/g in 20°C, respectively. The optimum pH value for sorption of the
metal ion was 4.5. Less than 5 min and 150 rpm shaking was required for 90% sorption. A recovery of 93.6% was obtained for
the metal ion with 0.1 M, H2SO4 as the eluting agent .The effect of K+ , Mg2+, Ca2+ , Zn2+, Cu2+ and Cd2+ ions was investigated to
evaluate the selectivity. This polymer was applied successfully for Nickel ion determination in environmental samples.
Reference
[1] Y. Guo, B. Din, Y. Liu, X. Chang, S. Meng, J. Liu, Preconcentration and determination of trace elements with 2-aminoacetylthiophenol functionalized amberlite
XAD-2 by inductively coupled plasma-atomic emission spectrometry, Talanta 62 (2004) 207–213.
[2] S.D. Cekic, H. Filik, R. at Apak, Use of an o-aminobenzoic acid-functionalized XAD-4 copolymer resin for the separation and preconcentration of heavy
[3] G. Wulff, Trends in Biotechnology 11 (1993) 85.
[4] K. Mosbach, Trends in Biochemical Sciences 19 (1994) 9.
[5] P.K. Dhal, F.H. Arnold, Macromolecules 25 (1992) 7051.
[6] J.Matsui, I.Nicholls, T. Takeuchi, K.Mosbach, I. Karube, Anal. Chim.Acta 335 (1996) 71.
Preconcentration and Determination Of Cd(II) By New Synthesis Polymer in environmental Sample by FAAS
Ali Reza Feyz Bakhsh, (Rozita Abdolahi Fard)*, Homayoun Ahmad Panahi, Samira Kamali Roosta, Sahar Afzali, Fateme Dadjoo
Department of Chemistry, Central Tehran Branch, Islamic Azad University, Tehran, Iran
Elham Moniri
Department of Chemistry, Varamin (Pishva) Branch, Islamic Azad University, Varamin, Iran
E-mail: rozita138744@yahoo.com
A new polymer was prepared by copolymerization of Allyl glaycidyl ether/Immino di acetic acid with N,Ndimethyl acrylamid
through. The resulting polymer has been characterized Fourier transform inferared Spectroscopy (FT-IR), Elemental analysis,
Scanning electron microscope analysis (SEM) and Thermogravimetric analysis (TGA) and studied for the preconcentration and
determination of trace Cd (II) ions from solution samples. Optimum pH value for sorption of the metal ion was 4.2 the sorption
capacity of the functionalized polymer is 64 mg/g in 20⁰C . Less than 5 min and 150 rpm shaking was required for 99% sorption.
The synthesized polymer can be reused for several cycles of sorption desorption without any significant change in sorption
capacity. A recovery of 94.2% was obtained for the metal ion with 0.1 M HNO3 as the eluting agent .The effect of K+ , Mg2+ ,
Ca2+ , Zn2+, Cu2+, Pb2+ ions was investigated to evaluate the selectivity. This polymer was applied successfully for Cadmium ion
determination in environmental samples.
Reference
[1] Ramstrom,O.Nicholls,I.A. and Mosbach,K.Tetrahedron Asymmetry,5(1994) 649-656
[2] Yano, K.Nakagiri,T.,Takeuchi,T.,Matsui,J.,Ikebukuro,K,and Karube,I., and.chem.Acta,357(1997)91-98.
[3] M. J. Whitcombe, M. E. Rodriguez, P. Villar, E. N. Vulfson, J. Am. Cehm., Soc., 1995. 117, 7105.
[4] G. Vlatakis, L. I. Andersson, R. Muller, K. Mosbach, Nature, 1993. 361, 645.
[5] H. A. Acevedo, F. A. Vazquez, R.G, Wuilloud, R. A. Olsina,L. D. Martinez ., Chemia Analityczna., 2001, 46, 59.
Synthesis and Optimation a New Ion Selective Polymer and Identity of Pb(II) Ion in Environmental Samples by Flame
Atomic Absorption Spectrometry
Homayoun Ahmad Panahi, Ali Reza Feyz Bakhsh ,(Samira Kamali Roosta)*, Rozita Abdolahi Fard,Fateme Dadjoo, Sahar Afzali
Department of Chemistry, Central Tehran Branch, Islamic Azad University, Tehran, Iran
Elham Moniri
Department of Chemistry, Varamin (Pishva) Branch, Islamic Azad University, Varamin, Iran
E-mail: skr_515@yahoo.com
A new polymer was prepared by copolymerization of Allyl glaycidyl ether/Immino di acetic acid with N,Ndimethyl acrylamid.
The resulting polymer has been characterized by Fourier transform inferared Spectroscopy (FT-IR), Elemental analysis, Scanning
electron microscope analysis (SEM) and Thermogravimetric analysis (TGA) and studied for the preconcentration and
determination of trace Pb (II) ions from solution samples. Optimum pH value for sorption of the metal ion was 5.2 the sorption
capacity of the functionalized polymer in 60.15 mg/g in 20⁰C . Less than 5 min and 150 rpm shaking was required for 99%
sorption. The synthesized polymer can be reused for several cycles of sorption desorption without any significant change in
sorption capacity. A recovery of 104% was obtained for the metal ion with 0.1 M HNO 3 as the eluting agent .The effect of K+ ,
Mg2+ , Ca2+ , Zn2+ , Cu2+,Cd2+ ions was investigated to evaluate the selectivity. This polymer was applied succesfully for lead ion
determination in environmental samples.
Reference
[1] M. J. Whitcombe, M. E. Rodriguez, P. Villar, E. N. Vulfson, J. Am. Cehm., Soc., 1995. 117, 7105.
[2] Ramstrom,O.Nicholls,I.A. and Mosbach,K.Tetrahedron Asymmetry,5(1994) 649-656
[3] Yano, K.Nakagiri,T.,Takeuchi,T.,Matsui,J.,Ikebukuro,K,and Karube,I., and.chem.Acta,357(1997)91-98.
[4] Spectrochemical analysis by atomic absorbtion and emission, by: L.H.J.Lajunen
[5] G. Vlatakis, L. I. Andersson, R. Muller, K. Mosbach, Nature, 1993. 361, 645.
[6] H. A. Acevedo, F. A. Vazquez, R.G, Wuilloud, R. A. Olsina,L. D. Martinez ., Chemia Analityczna., 2001, 46, 59.
An optical copper- selective sensor based on a newly synthesized
Lignd, bis (2-hydroxy-1-naphthaldehydene)-4-nitro- 1, 2-Phenylendiamin
M. Ghaedia*, B. Sadeghiana, A. Amiri Pebdania, M. Nejati Biyareha, J. Tashkhourianb, M. Montazerozohorizohorya
a
Chemistry Department, Yasouj University Yasouj 75914-35, Iran
b
Chemistry Department, Shiraz University, Shiraz, Iran
Email :m_ghaedi@mail.yu.ac.ir, b_sadeghian84@yahoo.com
The characterization of an optical sensor membrane is described for the determination of Copper (II) based on the immobilization
of bis (2-hydroxy-1-naphthaldehydene)-4-nitro- 1, 2-Phenylendiamin on a PVC membrane. Recent decades have seen an increase
in the development of optical chemical sensors (optode) as viable alternatives to other types of sensors. The great activity seen in
the field of ion-sensitive optical fiber devices and their application to trace analysis of heavy metal ions has given rise to several
sensing schemes, new indicator dyes and highly diversified methods of immobilization. Both the method of immobilization and
the class of matrix exert a significant effect on the performance of ion-sensitive layers[1,2].In this work the absorption spectra of
free and immobilized ligand were obtained after being equilibrated in buffer solution (pH 4) containing different concentrations
of Copper(II). The spectral change is a result of the addition of Copper (II) ions and the complex formation. The absorbance
maxima of the immobilized bis (2-hydroxy-1-naphthaldehydene)-4-nitro- 1, 2-Phenylendiamin are located at 389 nm. This
optode has a linear range of 1.96 ×10-6–4.76×10-5 mol L−1 for Copper (II) ions of 389 nm. The response time of optode is within
20 min depending on the concentration of Cu2+ ions. The selectivity of the optode to Cu2+ ion in the presence of other metal ions
including Mg2+, Ca2+, Ba2+, Zn2+, Ni2+, Co3+, Mn2+, Cd2+, Bi3+ and Al3+ is high, with the exception of Th+4 ions as the main
interference.
Reference
[1] G.J. Moody, B.B. Saad, J.D.R. Thomas, The development of polymer matrix membranes for ion selective electrodes, Sel. Electrode Rev. 10 (1988) 71–78.
[2] A. Safavi, M. Bagheri, Design of a copper (II) optode based on immobilization of dithizone on a triacetylcellulose membrane,Sensors and Actuators B 107 (2005)
53–58.
Design of a copper (II) optode based on immobilization of bis (2-hydroxy-1-naphthaldehydene)-1, 2-Phenylendiamin
M. Ghaedia*, M. Nejati Biyareha, S. Nasiri Kokhdana, J. Tashkhourianb, M. Montazerozohorizohorya
a
Chemistry Department, Yasouj University Yasouj 75914-35, Iran
b
Chemistry Department, Shiraz University, Shiraz, Iran
Email m_ghaedi@mail.yu.ac.ir, M_nejati1982@yahoo.com
Two types of polymeric support have been used for determination of ions. One of them is based on the nontransparence polymers
such as cellulose papers, and silica [1] and the other is based on the transparence support such as glass, PVC, and/or
triacetylcellulose [2,3]. A new optical sensor for Copper(II) ions is developed based on immobilization of bis (2-hydroxy-1naphthaldehydene)-1, 2-Phenylendiamin on a PVC membrane. Chemical binding of Cu2+ ions in solution with a bis (2-hydroxy1-naphthaldehydene)-1, 2-Phenylendiamin immobilized on the PVC surface could be monitored spectrophotometrically at 383
nm. UV–vis spectra were measured with a Jasco, Model V-570, double beam spectrophotometer. In preliminary experiments, it
was found that the addition of proper amounts of Cu2+ to an acetate solution of bis (2-hydroxy-1-naphthaldehydene)-1, 2Phenylendiamin resulted in a fast change in the color of the solution from yellow to red, while the presence of alkaline earth and
transition-metal ions, such as Ni2+, Pb2+, Co2+, Mn2+, Cr3+ and Cd2+ Ag+ , Hg2+ and Zn2+, showed no observable color change in
the ligand solution. This is most possibly indicative of selective complex formation of the ligand with Cu2+ ions in the acetate
solution. The sensing membrane is capable of determining copper (II) with an outstanding high selectivity over a dynamic range
between 1.8×10−7 and 1.9×10−2M with a limit of detection of 4.0×10−7M. The sensor shows a fast response time (<3 min) and the
membrane can be used for more than 3 months without observing any major deviation. The optode revealed very good selectivity
with respect to many cations including alkali, alkaline earth, transition and heavy metal ions. The proposed sensor could be used
at a neutral pH of 4. It was applied to determination of copper in tea and water.
Reference
[1] A.A. Ensafi, A. Aboutalebi, A versatile stable cobalt optical sensor based on pyrogallol red immobilization on cellulose acetate film. Sensors and Actuators B 105
(2005) 479–483.
[2] S.Sadeghi, S. Doosti, Novel, PVC membrane bulk optical sensor for determination of uranyl ion. Sensors and Actuators B.135, (2008) 139–144.
[3] A. Yari, F. Papi, Highly selective sensing of mercury (II) by development and characterization of a PVC-based optical sensor,Sensors and Actuators B.138 ,(2009)
467–473
Removal of congo red (CR) from aqueous solution by adsorption onto Palladium nanoparticle loaded on Activated
carbon
M. Ghaedi*a, M. Nejati Biyareha, K.Mortazavib , Z.Andikaeya, M.Behfara
a
Chemistry Department, Yasouj University, Yasouj 75914-35, Iran
b
Chemistry Department, Gachsaran Azad University, Gachsaran, Iran.
*E-mail: m_ghaedi@mail.yu.ac.ir; m_nejati1982@yahoo.com
In recent years, some papers had reported several kinds of low cost adsorbents such as leaf, fly ash, activated carbon, red mud,
waste Fe(III)/Cr(III) hydroxide, fungus, montmorillonite, for the removal of congo red (CR) from aqueous solutions. CR
containing effluents are generated from textiles, printing and dyeing, paper, rubber, plastics industries, etc. Due to its structural
stability, CR is difficult to biodegrade. The dye is known to metabolize to benzidine, a known human carcinogen. Exposure to the
dye has been known to cause an allergic reaction. The substance is considered as toxic. The aim of the present work is to explore
the possibility of utilizing rice husk for the adsorptive removal of CR from wastewater. The effect of such factors such as the
initial pH value, salt concentration, flow rate, influent concentration and bed depth on CR adsorption by husk bed column was
investigated [1,2].The adsorption of Congo Red onto Palladium nanoparticle loaded on activated carbon in a batch adsorber has
been studied. Four kinetic models, the pseudo first- and second-order equations, the Elovich equation and the intraparticle
diffusion equation, were selected to follow the adsorption process. Kinetic parameters; rate constants, equilibrium adsorption
capacities and correlation coefficients, for each kinetic equation were calculated and discussed. The apparent thermodynamic
parameters were calculated, and the obtained values support the conclusion that CR molecules sorb by an entropy-driven,
endothermic process.
Reference
[1] G. Crini, Non-conventional low-cost adsorbents for dye removal: A review Technol. 97(2006) 1061–1085.
[2] Z. Aksu, Application of biosorption for the removal of organic pollutants: A review. Process Biochem. 40(2005) 997–1026.
Modification of gold nanoparticle loaded on activated carbon with bis(4-methoxy salicylaldehyde)-1,2-phenylene diamine
as new sorbent for trace metal enrichment of some metal ions
M. Ghaedi*a, M.Nejati Biyareha , S. Nasiri Kokhdana, K. Mortazavib, R.Behfarc
a
Chemistry Department, Yasouj University Yasouj 75914-35, Iran.
b
Chemistry Department, Gachsaran Azad University, Gachsaran, Iran.
c
Department of Chemistry Engineer of Arak univercity, Iran.
*E-mail: m_ghaedi@mail.yu.ac.ir; m_nejati1982@yahoo.com
Important positive and negative roles of heavy metal ions in human health and their [1-3], so that roles in the body is very rich
and varied.In this research, a new simple and efficient procedure for synthesis and characterization of gold nanoparticle loaded on
activated carbon has been reported. Then Au-NP-AC was modified with bis(4-methoxy salicylaldehyde)-1,2-phenylene diamine
(BMSAPD) and efficiently has been described. The efficiency and suitability of this new sorbent (Au-NP-AC-BMSAPD) been
evaluated for enrichment of trace amount of Co2+, Cu2+, Ni2+, Fe2+, Pb2+ and Zn2+ ions from real samples. In this techniques all
understudy metal ions was efficiently retained on this new sorbent following their complexation with (BMSAPD) and then
retained metal ions was efficiently eluted using 6 mL 4 mol L-1 HNO3 and finally the metal content are detected by FAAS. The
analytical parameters including pH, amounts of ligand and solid phase and condition of eluent etc. were optimized. Following
optimization of variable for BMSAPD-Au-NP-AC, preconcentration factor is 200 for all understudy metal ion with detection
limit between 1.4-2.6 ng mL-1. The method has been successfully applied for the extraction and determination of these ions
content in some real samples with recoveries in the range of 95%-99.6% with low relative standard deviation (RSD < 4.0 %).
Reference
[1]M.Ghaedi, F.Ahmadi, M.Soylak, , Simultaneous Preconcentration and Determination of Copper, Nickel, Cobalt and Lead Ions Content by Flame Atomic
Absorption Spectrometry. Ann. Chim. 97, 2007, 277-285.
[2] F. Kabadayi, H. Cesur.. Determination of Cu, Pb, Zn, Ni, Co, Cd, and Mn in road dusts of Samsun City, Environ. Monit. Assess. 168, 2010 , 241-253.
[3]Khajeh, M., Sanchooli, E.. Optimization of Microwave-Assisted Extraction Procedure for Zinc and Iron Determination in Celery by Box–Behnken Design, Food
Anal. Methods 3, 2010, 133-137.
Selective Extraction of Ethambutol in aqueous solution with MIP prior to its Spectrophotometric determination
Mohammad-Hossein Sorouraddin1*, Homa Abbasteh1 , Homa Gheybi2, Ali Akbar Entezami2
1-Department of Analytical chemistry, Faculty of Chemistry, University of Tabriz, Iran
2-Lab of polymer, Faculty of Chemistry, University of Tabriz, Iran
E-mail: soruraddin@tabrizu.ac.ir
Molecular imprinting is a rapidly growing field relevant to science research as well as industrial applications related to
separation, artificial receptors, catalysts, and sensors, since molecularly imprinted polymers (MIPs) have high selectivity,
mechanical strength, and resistance to acids, bases, organic solvents, high pressures, and temperatures. Molecular imprinting
forms selective recognition sites that are complementary both in shape and chemical structure to the template molecule, and after
removal of the template, these sites can bind to the template molecule or closely related structural analogues with similar affinity
and selectivity as natural antibodies. Additionally, MIPs are stable, easy to prepare, inexpensive, and can be reused many times
without decrease in performance [1,2,3]. In this study, a novel method is described for the determination of ethambutol (EMB) in
aqueous solution using molecularly imprinted solid-phase extraction as the sample clean-up technique combined with UV
detection at 262 nm, using acetic acid/sodium acetate buffer solution (pH:5) containing copper(II) sulphate to form the
ethambutol–copper(II) complex. Under the optimum conditions, the calibration graph was linear at the concentration range 5-200
mgL−1 of ethambutol. The molecularly imprinted polymer (MIP) was prepared using methacrylic acid as functional monomer,
ethylene glycol dimethacrylate as cross-linker, tetrahydrofuran as porogen and ethambutol as template molecule. In result, high
recovery (>80%) of EMB was achieved.Various parameters affecting the extraction efficiency of the polymer and optimal
conditions for the MIP cartridges and MIP selectivity are evaluated by checking several substances with similar molecular
structures to ethambutol. As a control, the nonimprinted polymer (NIP) in the absence of the template was prepared and treated
by using the same method.
Reference
[1] Ch. m. Dai, S. U. Geissen, Y. l. Zhang, Y. j. Zhang, X. f. Zhou, Journal of Hazardous Materials , 2010, 184,
156–163
[2]I. A. Nicholls , H. S. Andersson, Ch. Charlton, H. Henschel, B. C.G. Karlsson, J. G. Karlsson, J. O. Mahony, A. M. Rosengren, K. Rosengren, S.Wikman,
Biosensors and Bioelectronics 2009, 25, 543–552
[3] A. F. Faria, M. V. N. De Souza, R. E. Bruns, M. A. L. de Oliveira, Talanta, 2010, 82, 333–339
Very fast synthesis of molecularly imprinted polymer for Napoxen separation
Mohammad-Hossein Sorouraddin1*, Homa Abbasteh1 , Homa Gheybi2, Ali Akbar Entezami2
1- Department of Analytical chemistry, Faculty of Chemistry, University of Tabriz, Iran
2- Lab of polymer, Faculty of Chemistry, University of Tabriz, Iran
E-mail: soruraddin@tabrizu.ac.ir
Molecular imprinting technique is an ingenious way based on ‘‘copy and memory,’’. This technique provides a promising
alternative way to design artificial recognition sites within a synthetic polymer network through the template polymerization
process. In this process, polymerizable functional monomers are prearranged around a template molecule in porogenic solvent.
After the removal of the template by extracting, binding sites complementary to the template molecule both in shape and
chemical functionality, are left within the polymer matrices that allow rebinding of the template with high specificity. MIP is a
kind of porous material of highly crosslinked polymer based on three-dimensionally molecular recognition. It has been exploited
extensively in many different applications including their use as separation materials, chemical sensors, reaction catalysts,
enzyme mimics and so on [1,2]. The standard imprinting polymer was prepared in this work according to the following : 0.35 g
of naproxen (Npx) and 0.28 g of methacrylic acid (MAA) in a 50 mL glass ampoule were dissolved in tetrahydrofuran followed
by adding an appropriate amount of ethylene glycol dimethacrylate ( EGDMA) and an initiator (AIBN). Then the obtained
solution was degassed with a stream of Argon gas for 20 min. Then the polymerization process was allowed to carry out at a
constant temperature ( 55Ċ ) in a water bath. The optimum syntheses conditions for the preparation of the MIP used in this work
was investigated. The results obtained revealed that the longer time of deoxygenation process under vaccume, purity, and
dryness of solvent affects the polymerization process considerably. The 1.5 : 4 : 30 ( Npx : MAA: EGDMA ) portion, the 60 Ċ
polymerization temperature , and 10 mL solvent solution volume were found to be the optimum process conditions leading to the
desired MIP in about 60 min, which is a very good record in comparison whit those reported by some other research workors .
Reference
[1] Z. Zhang, B. Wang, Journal ofAppliedPolymer Science, 2009, 113, 1050–1062
[2] Ch. m. Dai, S. U. Geissen, Y. l. Zhang, Y. j. Zhang, X. f. Zhou, Journal of Hazardous Materials , 2010, 184,
Determination of thebaine in water samples, biological fluids, poppy capsule, and narcotic compounds, using
electromembrane extraction followed by high performance liquid chromatography
Shahram Seidi, Yadollah Yamini, Morteza Moradi, Ali Esrafili, Maryam Rezazadeh
Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran, Iran
Opium poppy species (Papaver somniferum) is among the most important alkaloid and is often used in medicine for pain relief
[1]. On the other hand, as the illegal drugs usage increases, there is also an increased demand to identify their consumption.
Therefore, forensic science laboratories should have specific and sensitive techniques to differentiate between the legal and
illegal intake of opiates. One of the best ways to distinguish between legal and illegal consumption of opiate products is the
detection of marker compounds in urine. Thebaine, an opium alkaloid, has been suggested as a good urinary marker of poppy
capsule use to distinguish from that of illicit heroin [2]. In the present work, electromembrane extraction (EME) coupled with
HPLC-UV was developed for determination of thebaine as a natural alkaloid, in different matrices containing water, urine, poppy
capsule, street heroine, and codeine tablet. Thebaine migrated from 3 mL of sample solutions, through a thin layer of 2nitrophenyl octyl ether (NPOE) immobilized in the pores of a porous hollow fiber, and into a 15µL acidic aqueous acceptor
solution present inside the lumen of the fiber. The variables of interest, such as chemical composition of the organic liquid
membrane, stirring speed, extraction time and voltage, pH of donor and acceptor phases and salt effect in the EME process were
optimized. Under the optimal conditions, thebaine was effectively extracted from different matrices with extraction recoveries in
the range of 45-55%. The good linearity was achieved for calibration curves with a coefficient of estimation higher than 0.997.
Detection limits and intra-day precision (n = 3) were less than 15 µg L-1 and 8.9%, respectively. By selecting an appropriate
organic solvent for SLM, EME can obtain a high selectivity as well as high clean-up. Concerning high preconcentration factors,
short extraction time, as well as satisfactory LODs and RSDs, EME may have a strong potential as a future sample preparation
technique.
Reference
[1] N.W. Turner, M. Cauchia, E.V. Piletska, C. Preston, S.A. Piletsky, Biosens. Bioelectron. 24 (2009) 3322-3328.
[2] S. Lee, Y. Park, E. Han, H. Choi, H. Chung, S.M. Oh, K.H. Chung, Forensic Sci. Int. 204 (2010) 115-118.
Determination of Epinephrine by thiourea modified Glassy Carbon Electrode
M. Ahmadian Yazdely *, M.A. Taher
Department of Analytical Chemistry, Faculty of Chemistry, University of Kerman, I. R. Iran
E-mail: m.ahmadian89@yahoo.com
A Thiourea modified glassy carbon electrode (GCE) was prepared by electropolymerization method for the sensitive
voltametric determination of Epinephrine (EP). The electrochemical response characteristics of the modified electrode for EP
-1
was investigated by cyclic voltammetry (CV) at -0.5 to 0.6 V s and showed good results [1]. The effects of pH on the
catalytic response of EP at the modified electrode were studied over the pH range from 2.0 to 9.0 and then pH=6.0 was selected.
-1
The influence of the scan rate on the electrochemical response of EP at the modified electrode at range 5 to 140 mV s
was investigated. The correlation coefficient R is 0.998, which illustrates that the process of the electrode reaction is
−5
−1
controlled by the diffusion of EP[2]. The influence of various foreign species on the determination of 1.0×10 mol L EP was
investigated. Dopamine had the most interference. The practical analytical utility of the modified electrode was illustrated by
determination of EP in injection samples. The obtained results were shown that the proposed method has a good precision and
can be applied to the determination of EP in real samples[1]. The modified electrode had been prepared and had good stability,
-8
sensitivity and selectivity.The detection limit for EP (2.3×10 M) is much lower, or compares well with other values reported in
literature. The application of the modified GCE has been also tested in injection samples, with good results[3].
Reference
[1] Yan Wang, Zhen-zhen Chen, Colloids and Surfaces B: Biointerfaces 74 (2009) 322–327.
[2]A.J. Bard,L.R. Faulkner,Elecrtochemical Methods,Wiley, New York,1980, P.218.
[3] H. El Bouhouti, I. Naranjo-Rodrguez, J.L. Hidalgo-Hidalgo de Cisneros, M. ElKaoutit, K.R. Temsamani, D. Bouchta, L.M. Cubillana Aguilera,
Talanta 79 (2009) 22–26.
Linear and non linear quantitative structure-property relationship models for retention time index of polycyclic aromatic
hydrocarbons for reversed-phase liquid chromatography analysis
a,b:
Shayan Mokhtar*a, Zohreh Mehrabadib
Department of Chemistry, Firoozabad Branch, Islamic Azad University, Firoozabad, Iran
E-mail: shayanmokhtar@yahoo.com
A Quantitative Structure–Property Relationship (QSPR) analysis and study of polycyclic aromatic hydrocarbons (PAHs) is
Presented. The dataset for this investigation was extracted from a group of 44 molecules of non-substituted PAHs [1]. The
Multiple linear regression (MLR) and the support vector machine (SVM) were used to develop the linear and non-linear models
between the retention time (RT) for reversed-phase liquid chromatography analysis and molecular descriptors of PAHs.
Retention time is a parameter used in chromatographic analysis to separate hydrocarbon mixtures and the time taken for a
compound to travel through the column to the detector in chromatography [2]. the experimental determination of Retention Time
(RT) is time consuming, expensive and the QSPR studies allow a reduction of this cost [3]. The chemical structure of the 44
studied molecules was drawn with the Hyperchem 8.0 software. To optimize the geometry of these molecules, the AM1
geometrical optimization was applied. The Dragon software was used to calculate the descriptors in this research and a total of
1497 molecular descriptors were calculated for each molecule. The two molecular descriptors selected by stepwise regression
method in SPSS 17.0 software were used as inputs for SVM. The results obtained by SVM were compared with those obtained
by the MLR. The SVM model gives better results with the absolute average relative deviation (AARD) 4.24% And mean square
Errors (MSE) 0.062 for the test set, as well as that 5.11% and 0.104 in the MLR model. The prediction results of RT are in very
good agreement with the experimental values. This paper provided a new and effective method for predicting the
chromatography retention time.
Reference
[1] F. A. L. Ribeiro, M. M. C. Ferreira, J. Mol. Struct. (Theochem) 663 (2003) 109.
[2] L. C. Sander, S.A. Wise, Adv. Chromatogr. 25 (1986) 139.
[3] F. Luana, R. Zhanga, et al., Anal. Chim. Acta, 537 (2005) 101.
Spectrophotometric and thermodynamic study on the dimerization equilibrium of Acridine Orange dye in water and
micelles medium chemometrics method
Samane Mollahossieni*,Ali Niazi and Majid Ramezani
Department of Chemistry, Faculty of Science, Islamic Azad University-Arak Branch, Arak, Iran
(E-mail: samane_mollahoseini85@yahoo.com , ali.niazi@gmail.com)
The monomer-dimer equilibrium and thermodynamic in Acridine Orange (Figure 1) dye as ionic dye has been investigated by
means of spectrophotometric and chemometrics methods. Fig.1
Structure of acridine orange
The dimerization constants of these ionic dye have been determined by studying the dependence of their absorption spectra on
the temperature in the range 20-65°C at concentrations of Acridine Orange (2.74´10-5 M) in different pH (Figure 2, in pH=6) and
in different micellar meidum. The monomer-dimer equilibrium of this dye has been determined by chemometrics refinement of
the absorption spectra obtained by thermometric titrations performed. The processing of the data carried out for quantitative
analysis of undefined mixtures, based on simultaneous resolution of the overlapping bands in the whole set of absorption spectra.
The enthalpy and entropy of the dimerization reactions were determined from the dependence of the equilibrium constants to the
temperature (van't Hoff equation).
Absorbance
1
0.8
0.6
0.4
0.2
0
350
400
450
500
Wavelenght
550
600
Figure 2. Spectra of Acridine Orange in pH = 6 in temperatures (20-65 °C)
Reference
[1] J. Ghasemi, A. Niazi, G. Westman, M. Kubista, Talanta, 62 (2004) 835.
[2] J. Ghasemi, A. Niazi, M. Kubista, A. Elbergali, Anal. Chim. Acta, 455 (2002) 335.
[3] A. Niazi, A. Yazdanipour, J. Ghasemi. M. Kubista, Spectrochim. Acta Part A, 65 (2006) 73.
Thermodynamic behavior of complexation process between 4'-Nitrobenzo-18-crown-6 with Y3+ Cation in some pure and
binary mixed non-aqueous solvents
Gholamhossein Rounaghi , Mahboobeh Vafi*
Department of Chemistry, Faculty of Science, Ferdowsi University of Mashhad,Mashhad, Iran.
Crown ethers are known for their ability to strongly solvate cations. In other words the equilibrium is strongly towards the
formation of complex. The oxygen atoms in polar ring, are ideally situated to coordinate with a cation in the interior of the ring,
whereas the exterior of the ring is hydrophobic. The result is that the complexed cations are soluble in nonpolar solvents. Due to
their ability to bind strongly and selectivity to metal cations and substrate molecules, macrocyclic polyethers and their derivatives
can find use in many diverse processes such as construction of ion-selective electrodes [1], phase transfer catalysts [2], extraction
of metal ions [3], chiral separation [4] and membrane separation process [5]. The goal of this investigation is to study the effect
of the nature and composition of the mixed solvents on selectivity and thermodynamic of complexation reactions of 4'Nitrobenzo-18-crown-6 with Y3+ metal cation in pure acetonitrile(AN), ethylacetate(EtOAc), dichloroethane(DCE) and their
binary mixtures at different temperature using the conductometric technique. The conductance data show that in AN-DCE and
AN-EtOAc (mol%EtOAc=75,100) solvent systems, at different temperatures, the stoichiometry of the complex(4´-nitrobenzo18C6.Y)+3 which is formed between 4´-nitrobenzo-18C6 and Y+3 cation is 1:1(ML). But in the case of AN-EtOAc solutions
(mol%EtOAc=25,50), the stoichiometry of the complex is 1:2(ML). Therefor, stoichiometry and reaction mechanism will change
by using of different solvent systems. The stability constants (Kf) of the complex was obtained from fitting of molar conductivity
curves using a computer program, GENPLOT. A non-linear behavior was observed for changes of log K f of this complex versus
the composition of the binary mixed solvents. The stability order of (4´-nitrobenzo-18C6.Y)+3 complex in binary mixed nonaqueous solvents (mol%AN=25) at 25°C is: AN-DCE > AN-EtOAc. The values of enthalpy changes (∆Hoc) for complexation
reactions were obtained from the slope of the van,t Hoff plots and the changes in standard entropy(∆Sºc) were calculated from the
relationship: ∆Gºc,298.15=∆Hºc–298.15∆Sºc. The thermodynamics of complexation reactions between 4´-nitrobenzo-18C6 with Y+3
cation is affected strongly by the nature and composition of the mixed solvents.
Reference
[1] Sendil, O., Pecenek, E., Ekmekci, G., Somer, G. Curr. Anal. Chem. 5, 53–58 (2009)
[2] Pozzi, G., Quici, S., Fish, R.H. Adv. Synth. Catal. 350, 2425– 2436 (2008)
[3 Alivertis, D., Paraskevopoulos, G., Theodorou, V., Skobridis, K. Tetrahedron Lett. 50, 6019–6021 (2009)
[4] Yongzhu, J.,Hirose, K.,Nakamura,T., Nishioka, R., Ueshige,T.,Tobe,Y. J. Chromatogr. A 1129, 201–207 (2006)
[5] Rawat, N.,Mohapatra,P.K.,Lakshmi, D.S.,Bhattacharyya, A.,Manchanda,V.K. J. Membr. Sci. 275, 82–88 (2006)
Determination of Essential Elements in the Hair of Patient with Type 2 Diabetes
Fariba Tadayon1 , Mohammad Saber Tehrani 2, Sahar rajabi nia1
Department of chemistry,North Tehran Branch , Islamic Azad University, Tehran , Iran
E-mail: S.rajabinia@gmail.com (
2
Department of chemistry,Science and Research Branch, Islamic Azad University, Tehran , Iran
1
Diabetes is one of the most common chronic diseases in the word. Many factors such trace elements contributing to the
pathophysiology of type II Diabetes mellitus (DM). The body’s balance of trace elements and minerals can be disrupted by DM.
Certain elements have been identified as essential trace elements that play an important role in the genesis and progression of
diabetes. Their increase or decrease may affect control of diabetes. Several studies have indicated that the deficiency and
efficiency of some essential trace metals may play a role in development of diabetes mellitus. Some toxic metals to be elevated in
biological samples of diabetes mellitus patients. The status of trace elements in diabetes patients is also influenced by their diet,
drugs administered and, to a large extent, by environmental factors. In recent years, interest in human hair as a clinical sample for
analysis of trace element has increased. Several factors contribute to the choice of hair: simplicity of the matrix, higher
concentrations of the trace elements, easier sample collection, transportation and preservation. Hair is sometimes the only
material for the determination of inorganic and organic substances. However, the validity of this biomarker in evaluating the level
of trace elements in the human body is debatable. The aim of this work was to compare the level of trace elements, iron, copper,
nickel, zinc and chromium in hair samples of patients having diabetes mellitus type-2 from Tehran with those of age matched
non-diabetics (ND) as control subjects of the same city. The hairs were washed, and then digest with HNO3, H2O2. The
concentrations of trace elements were determined by flame and atomic absorption spectrophotometer. The result showed that the
elemental content were changed in hair samples of diabetic patients. The ranges of iron, copper, nickel, zinc and chromium in the
samples were between 2.306-27.850 µg g-1, 0.300-5.035 µg g-1, 0.108-4.12 µg g-1, 20.010-71.415 µg g-1 and 0.085-1.076 µg g-1,
respectively.
Reference
[1] Skalnaya, G.M., 2007, Hair trace element contents in women with obesity and type 2 diabetes, J. Trace. Elem. Med. Bio. Vol. 21 S1, pp. 59–61.
[2] Tasneem, K.G., 2008, Evaluation of status of toxic metals in biological samples of diabetes mellitus patients, Diabetes. Res. Clin. Pr., Vol. 80, pp. 280 – 288.
[3] Tormen, l., 2010, Determination of trace elements in biological samples treated with formic acid by inductively coupled plasma mass spectrometry using a
microconcentric nebulizer, Spectrochim. Acta. Part B., Vol. 65, pp. 995-966.
Ltd.
1
Chemical composition of the Nepeta glomerulosa from Iran
Meissam Noroozifar1 , Jafar Valizadeh2, Amene davarimanesh1*, Mohammad Nik Bin1
Department of Chemistry, University of Sistan & Baluchestan, Zahedan P.O. Box 98155-147, Iran.
2
Department of Biology, University of Sistan & Baluchestan, Zahedan, Iran.
E-mail: a.davari88@gmail.com
Nepeta genus (Lamiaceae) is comprised of about 250 species, widely distributed in temperate Europe, Asia, North America,
North Africa and in the Mediterranean region [1]. It is one of the largest genera of Lamiaceae in Iran where 75 species are found,
of which 54% are endemic [2]. Besides being used as antispasmodic, diuretic, febrifuge, diaphoretic, antimicrobial and antiseptic
agents, Nepeta species are used as laxatives in the treatment of dysentery, for tooth troubles and for kidney and liver diseases [1].
In this study, essential oils of aerial parts of Nepeta glomerulosa were estimated. The aerial material of Nepeta glomerulosa
collected from Taftan area of Sistan and Baluchistan province in Iran. The extraction of chemical constituents of essential oil of
aerial parts is accomplished by hydrodistillation using a Clevenger-type apparatus and then was analyzed by GC/MS technique
[3]. Forty-one, components, representing 86.4% of the oil, were characterized. The majorcomponents were 1,4-hexadiene-2,3,4,5
tetramethyl and 4αβ, 7α, 7aα-nepetalactone.
Reference
[1] BISHT, D.S., Constituents and antimicrobial activity of the essential oils of six Himalayan Nepeta species, J. Serb. Chem., Vol.75, pp. 739–747, 2010.ile O
[2] Jamzad, z., Biochemical Systematics and Ecology, Vol. 31, pp. 587–600, 2003.
[3] Dabiri, M., Sefidkon, F., Chemical composition of Nepeta crassifolia Boiss. &Buhse oil from Iran, Flavour Fragr. J., Vol.18, pp. 225–227, 2003.
Application of a new potentiometric method for determination of dichoromate based on a surfactant-modified zeolite
PVC membrane
`Alireza Nezamzadeh-Ejhieh*, Somayeh Hashemi.
Department of Chemistry, Islamic Azad University, Shahreza Branch
Zeolites are strange cation exchangers due to posses a permanent negative charge. When they ion exchanged with a large
molecule such as hexadecyltrimethyl ammuniom (HDTMA) cation, first a monolayer of surfactant forms onto surface of the
zeolite. At concentrations of surfactant higher than its CMC, second layer of surfactant forms on the zeolite surface due to
hydrophobic force of surfactant chains. In this condition ammonium group of surfactant directed to the solution and a charge
reversal takes place from negative to positive on the zeolite surface, In this conditions the obtained surfactant modified zeolite
(SMZ) acts as anion exchanger. In this work, an Iranian natural clinoptilolite modified with HDTMA and the obtained SMZ was
used for modification of PVC membrane towards anion determination. A novel polyvinyl chloride (PVC) membrane electrode
for use in a potentiometric sensor for dichoromate is described. The sensor comprises a surfactant modified clinoptilolite zeolite
(SMZ) as a modifier, dioctyl phthalate (DOP) as a plasticizer and PVC matrix in the ratio of 4:64:33 (modifier:DOP:PVC) (w/w).
The SMZ was prepared by adsorbing the cationic surfactant thexadecyltrimethylammonium (HDTMA) bromide on the external
surface of the zeolite, where R4N+ is the anion-exchange sites of HDTMA surfactant on SMZ. The electrode exhibited a good
selectivity to dichoromate anion as: Cr2O72-> Benzoate>SO42->SO32->I->ClO4->CO32->Br->CN-. Electrode had an excellent linear
responseto Cr2O72- from1.0×10-2 to 1.0×10-6 M with a slope of 29.5 mV per decade, a detection limit of 5.0×10-7 M, and a fast
response time within15 s over the entire concentration solutions of pH 4.0 a 25°C.
Reference
[1] Ramos R. L ;Azuara A. J; “Adsorption of chromium(VI) from an aqueous solution on a surfactant-modified zeolite” Colloids and Surfaces A: Physicochem. Eng.
Aspects 330 (2008) 35–41.
[2] A Nezamzadeh-Ejhieh, E. Mirzaeyan "Oxalate membrane-selective electrod based on surfactant-modified zeolite", Electrochim. Acta (2010) 10.1016/ Accepted
Simultaneous determination of norepinephrine and uric acid using a self-assembled monolayer modified gold electrode
a
Hadi Beitollahi, *a Mohammad Mazloum-Ardakani, b Bibi-Fatemeh Mirjalilib, Ali Akbaric
Environmetal Department, Research Institute of Environmental Sciences, International Center for Sciences, High Technology and
Environmental Sciences, Kerman, Iran
b
Department of Chemistry, Faculty of Science, Yazd University, Yazd, 89195-741, I.R. Iran
c
Department of Chemistry, Payame Noor University , 19395-4697, Tehran , I.R. of Iran
E-Mail: h.beitollahi@yahoo.com
Spontaneous adsorption of organic molecules such as thiols and lipids from solution onto the solid surface of coinage metals such
as copper, silver, and gold can give rise to self-assembled monolayers (SAMs). Gold is the most frequently used substrate
because it does not have a stable oxide under ambient conditions. The most frequent application of SAMs in electroanalytical
chemistry is in the development of sensors and biosensors where the SAM is used to impart selectivity onto an electrode for a
particular analytes [1]. Norepinephrine (NE) is a very important catecholamine neurotransmitter in the mammalian central
nervous system and is often monitored electrochemically in vivo with microfiber electrodes. The oxidation of this compound is
interesting, and this process occurs in the human body. Numerous observations on electrochemical behavior of NE have been
made in many research groups [2]. Uric acid (UA), the end metabolic product of purine through the liver, is present in blood and
urine. Monitoring UA in the blood or urine is important because it can be used as a powerful indicator for an early warning sign
of kidney diseases. Various electrochemical methods have been employed to monitor the level of UA. In the present paper, the
use of a 2-(3,4-dihydroxyphenyl)-1,3-dithialone self-assembled monolayer for the determination of NE and UA was described.
The apparent charge transfer rate constant, (ks=17.37 s-1), and transfer coefficient, (α=0.5), were calculated using cyclic
voltammetry. Also, it has been found that under optimum condition (pH 8.0) in cyclic voltammetry, the oxidation of NE occurs at
a potential about 160 mV less positive than that of an unmodified gold electrode. The values of electron transfer coefficients (α),
catalytic rate constant (k) and diffusion coefficient (D) were calculated for NE, using electrochemical approaches. Finally,
simultaneous determination of NE and UA at the modified electrode was described.
Reference
[1] Asav E.; Akyilmaz, E. Biosens. Bioelectron. 2010, 25, 1014.
[2] Mazloum-Ardakani, M.; Beitollahi, H.; Amini, M. K.; Mirkhalaf, F.; Mirjalili, B.B.F. Biosens. Bioelectron. 2011, 26, 2102.
Combination of solid phase extraction-hollow fiber for ultra preconcentration of some triazole pesticides followed by GCFID determination
Mir Ali Farajzadeh*, Leila Khoshmaram, Mohammad Reza Afshar Mogaddam
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
Sample preparation is an important analytical step especially for the determination of trace analytes in complex sample matrices
[1]. Triazole fungicides are one of the major classes of the pesticides that are widely used in a variety of fruits, vegetables and
grain crops. Their characteristics, such as high chemical and photochemical stability, low biodegradability and easy transport in
the environment, make them persist in soil and water [2]. Thus, there is an increasing need to monitor these fungicides in food
commodities. Several procedures have been developed for the separation and preconcentration of this pesticides from aqueous
samples [2,3]. In this study an extraction and preconcentration technique using solid phase extraction (SPE) along with hollow
fiber (HF) has been developed as an ultra preconcentration technique for some triazole pesticides in aqueous samples. Triazole
pesticides were employed as model compounds to assess the method and they were monitored by GC-FID. Initially aqueous
solution of target analytes was passed through an RP-8 SPE cartridge and then the absorbed analytes were eluted with toluene at
µL-level. In the continuation the collected elution solvent was introduced slowly into an end-closed HF in which evaporation of
solvent was occurred and analytes were precipitated into lumen and pores of the walls of HF. Finally the obtained HF was
mounted on a home-made solid phase microextraction syringe and entered into gas chromatograph injection port. The effect of
various experimental parameters including injection port temperature, desorption time, state of hollow fiber, washing solvent
type, volume and type of the elution solvent, etc. was investigated for finding the optimum conditions. The calibration graphs
were linear in the ranges of 2-1000 ng mL-1 (penconazole and hexaconazole), 5-1000 ng mL-1 (tebuconazole), 15-1000 ng mL-1
(triticonazole) and the detection limits ranged from 0.6 to 4.5 ng mL-1. The relative standard deviations (RSD %) for five
repeated experiments (C = 250 ng mL-1 of each pesticide) varied from 4.5 to 8.7 %. The relative recoveries obtained for analytes
in grape juice samples, spiked with different levels of each pesticide, were in the range of 87-119%.
Reference
[1] Y. Saito, I. Ueta, M. Ogawa, M. Hayashida, K. Jinno, J. Pharm. Biomed. Anal. 2007, 44, 1-7.
[2] C. Wang, Q. Wu, C. Wu, Z. Wang, J. Hazard. Mater. 2011, 185, 71–76
[3] C.G. Zambonin, A. Cilenti, F. Palmisano, J. Chromatogr. A, 2002, 967, 255–260
Development of a new microextraction method based on a dynamic single drop in a narrow-bore tube: Application in
extraction and preconcentration of some organic pollutants in well water and grape juice samples
Mir Ali Farajzadeh*, Djavanshir Djozan, Parisa Khorram
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
In recent years, the development of fast, precise, accurate, and sensitive methodologies has become an important issue. Despite
notable technological advances in the analytical field, most instruments cannot handle sample matrices directly. Therefore, a
sample preparation step is required. For organic trace analysis, this step mainly comprises extractions, which serve to isolate and
enrich compounds of interest from a sample matrix. Liquid–liquid extraction (LLE) [1] and solid-phase extraction (SPE) [2] are
the most common methods. But these methods are time-consuming, tedious, and use large amounts of toxic solvents. Emulsion
formation and low enrichment factor are other disadvantages of LLE. Solid-phase microextraction (SPME) is a solvent-free
microextraction technique [3]. Despite the method advantages, most commercial extractive fibers used in SPME are expensive
and fragile, furthermore, sample carry-over is also a problem. In the present work a new sample preparation technique, the
microextraction method based on a dynamic single drop in a narrow-bore tube, coupled with gas chromatography-flame
ionization detection (GC-FID) was proposed. The extraction device involved a narrow-bore closed end tube in which aqueous
sample containing analytes was filled. A single drop of an organic solvent assisted by an air bubble was used to extract analytes.
To accelerate mass transfer, extractive phase was passed repeatedly through the tube. Parameters affecting the method’s
performance such as selection of extraction solvent type and volume, number of extractions, etc were optimized. The present
analytical approach offers the opportunity of a new practical and reliable methodology for the extraction and preconcentration of
organic pollutants from aqueous samples. The optimized technique in conjunction with GC-FID was considered to be a facile,
economical procedure, and nearly fast for analysis of some pesticides in water and fruit juice samples. This method does not
require any preliminary sample preparation step and also, reduces the volume of solvents used. The method is precise, repeatable,
and has high enrichment factor and large linear range.
Reference
[1] A. Balinova, J. Chromatogr. A 754 (1996) 125-135.
[2] J. Fillion, F. Sauve, J. Selwyn, J. AOAC Int. 83 (2000) 698-713.
[3] C. L. Arthur, J. Pawliszyn, Anal. Chem. 62 (1990) 2145-2148.
Dye removal from aqueous solution using sawdust coated by poly3-methyl thiophene: Thermodynamic and Equilibrium
studies
R. Ansari*, M. Saghanejhad Tehrani, M. Banimahd Keivani
Chemistry Department, Faculty of Science, University of Guilan, Rasht, Iran
E mail: ransari@guilan.ac.ir
Dyes and pigments are important class of pollutants which can affect the nature and quality of water. In this study an efficient
dye adsorbent was developed by poly 3-methyl thiophene coated onto sawdust (termed as P3MTh/SD) and methylene blue (MB),
a typical cationic textile dye was employed as a test probe for adsorption experiments. P3MTh was synthesized chemically via
direct addition of chemical oxidant (FeCl3 in CHCl3) on the surface of sawdust that has already been soaked in monomer solution
[1]. The effects of process variables such as pH, initial dye concentration, contact time, adsorbent dosage and temperature were
investigated using batch adsorption mode. The sorption data were correlated with the Langmuir and the Freundlich adsorption
isotherm models [2]. The Freundlich isotherm exhibited a better fit for the adsorption data than the Langmuir. The monolayer
maximum adsorption capacity of MB calculated from Langmuir isotherm model was 42.92 at 298 K. Thermodynamic parameters
obtained for P3MTh/SD adsorbent suggest that the sorption process is spontaneous and exothermic in nature. The introduced
adsorbent in the current study seems to be a worthwhile adsorbent for removal of basic dyes from aqueous solutions such as
textile wastewaters.
Reference
[1]. Ansari, R.; Fallah Delavar, A. J. of Appl. Polym. Sci 2009, 113 (4), 2293.
[2]. Guoqiang Liu.; Ru Yang.; Min Li. Journal of Non-Crystalline Solids 2010, 356 (4-5), 250.
Basic Dye Removal from Aqueous Solution Using Chemically Modified Sawdust
R. Ansari* M. Saghanejhad Tehrani
Chemistry Department, Faculty of Science, University of Guilan, Rasht, Iran
E mail: ransari@guilan.ac.ir
Methylene Blue (MB) is known as a cationic dye and its large consumption made industries to consider it as a risk factor for
human and occupational health [1, 2]. Sawdust is an agricultural waste that can be used in the treatment of drinking water [3]. In
this study the chemically modification of sawdust by Permanganate potassium (KMnO4/SD) as a high surface area adsorbent has
been proposed to enhance the adsorption capacity of sawdust for removal of MB from wastewaters through solid phase extraction
(SPE). For this purpose the sawdust (35- 50 mesh) was treated with KMnO4 solution in acidic pH. The effects of different pHs,
initial dye concentration, flow rate, salt and bed depth have been studied for SD and KMnO4/SD by passing MB solution at
different conditions through the adsorbent in column system. The concentration of MB in dilute phase was determined by
measuring the absorbance at 635 nm and the breakthrough curve of each factor was obtained. In order to retrieve the KMnO4/SD
adsorbent, desorption study was performed using HCl (0.01M) and NaCl (0.1M) as eluent solutions. The adsorption–desorption
cycles of dye were repeated three times and no clear decrease was resulted in sorption capacity of adsorbent. The adsorption
behavior of KMnO4/SD is strongly pH-dependent and the maximum extraction efficiency was obtained at pH 10. The highest bed
capacity of 226.99 mg g-1 for KMnO4/SD was obtained using 50 mg L-1 of inlet dye concentration, 2.9 cm of bed height and 3.0
mL min-1 of flow rate. In presence of NaCl salt and high concentrations of the dye, the smaller dye volume can be removed.
Thomas model was also used to predict the breakthrough curves under varying experimental conditions and gave good agreement
between experimental and calculated parameters. The results demonstrate the sorption capacity of KMnO4/SD is more than 7.5
times higher than the untreated SD and is effective in removal of basic dyes from wastewaters.
Reference
[1] A. Aleboyeh, M.E. Olya, H. Aleboyeh, J. Hazard. Mater. 162 (2009) 1530.
[2] C. Galindo, P. Jacques, A. Kalt, Chemosphere. 45 (2001) 997.
[3] A. Ahmad, M. Rafatullah, O. Sulaiman, M.H. Ibrahim, R. Hashim, J. Hazard. Mater. 170 (2009) 357.
Production new chelating fibers of polyacrilonitrile for removing Nd 3+ ion from environmental samples
B.Esmaeilpour*,H.Bagheri Sadeghi, H.Ahmad Panahi
Department of Chemistry, Central Tehran Branch, Islamic Azad University, Tehran, Iran
E-mail: Behnaz.esmailpor@yahoo.com
In this work, polyacrylonitrile fibers (PAN) have been modified with Imino Diacetic Acid to produce Polyacrylonitrile-Imino
Diacetic Acid (PAN-IDA)[1,2]. The cyanide groups in PAN fiber was then converted into carboxylic acid groups using thionyl
chloride and finally PAN fibers functionalized with Iminodiaceticacid (IDA) was obtained[3]. Structure of the new fiber was
characterized by different experimental techniques such as Fourier transform infrared spectroscopy (FT-IR),thermo gravimetric
analysis (TGA), scanning electron microscopy (SEM), and elemental analysis (CHN)[4,5] .The PAN-IDA was examined as
chelating material in a series of batch adsorption experiments for removal of Nd (III) ion[1]. In the First stage, optimum pH for
removal of Nd 3+ ions by modified PAN was found and then the other parameters such as effect of temperature, time, interfering
ions and different concentration of metal ion on adsorption were investigated and optimum conditions were attained. The
concentration of Nd ion was determined with ICP method. The modified PAN-IDA fiber showed better adsorption behavior
towards metal ions compared with unmodified fiber and was successfully applied to preconcentration and determination of Nd
ion in environmental water samples.
Reference
[1] P.Tahaei,M.Abdouss, M.Edrissi, A.M.Shoushtari, M.Zargaran, Mat.-wiss. u. Werkstofftech. 2008, 39, 839.
[2] Chen, J. P.; Wang, L. Chemosphere 2004, 54, 397.
[3] Deng, S.; Bai, R.; Chen, J. P. Colloid Interface Sci. 2003, 260, 265.
[4] Liu, R. X.; Zhang, B.W.; Tang, H. X.; React. Funct. polym. 1999, 39, 71.
[5] Marie, J. R., E.; Ronald, D.N.; Per, M. C. Langmuir 2002, 18, 1604.
Application of promazine hydrochloride-multiwalled carbon nanotubes as an electrocatalyst to prepare sensitive sensor
for determination of hydrazine as an environmental pollutant
E. Jamshidimofrad, B. Rezaei*, Ali A. Ensafi
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, Iran
Email: B.rezaei@cc.iut.ac.ir, E.jamshidimofrad@ch.iut.ac.ir
Hydrazine (N2H4) is known as a neurotoxin and a carcinogenic and mutagenic compound, creating blood abnormalities and
irreversible damage within the nervous system. It is famous as a high-energy fuel in rocket–propulsion systems due to its
flammable and detonable characteristics. Strong reducing power to scavenge oxygen assists it to be a metal corrosion inhibitor. It
is also used as plant growth regulators in extractive fields and antimicrobial drugs in pharmaceutical applications. Numerous
methods have been developed for the determination of hydrazine [1–5]. However, these methods had low selectivity and
precision. In this work, we propose promazine hydrochloride as a new mediator for a rapid, sensitive, and highly selective
voltammetric determination of hydrazine using multiwall carbon nanotubes paste electrode (MWCNTPE). The experimental
results showed that the carbon nanotubes paste electrode has a highly electrocatalytic activity for the oxidation of hydrazine in
the presence of promazine hydrochloride as a mediator. Cyclic voltammetry, double potential step chronoamperometry, and
linear sweep voltammetry (LSV) are used to investigate the suitability of promazine hydrochloride at the surface of MWCNTPE
as a mediator for the electrocatalytic oxidation of hydrazine in aqueous media. Kinetic parameters such as electron transfer
coefficient, diffusion constant, catalytic reaction rate constant, k/h, are also determined. Under optimum condition linear dynamic
rang was from 30 µM to 3.5 mM. Detection limit was 9 µM. The proposed method used for the voltammetric determination of
hydrazine in such real samples as pharmaceutical, industrial and environmental.
Reference
[1] J. Wang, M.P. Chatrathi, Capillary electrophoresis chips with thick-film amperometric detectors: separation and detection of hydrazine compounds,
Electroanalysis 12 (2000) 691-694.
[2] H. Xia, H.L. Li, Voltammetric determination of hydrazine based on catalytic reaction in the presence of 4-hydroxy-2,2,6,6-tetramethylpiperdinyloxy (TEMPOL)
radical, Electroanalysis 9 (1997) 1429–1431.
[3] A.M. ElBrashy, L.A. ElHussein, Colorimetric determination of some important hydrazine derivatives, Anal. Lett. 30 (1997) 609–622.
[4] E.A. Malaki, M.A. Koupparis, Kinetic study of the determination of hydrazine, isoniazid and sodium azide by monitoring their reactions with 1-fluoro-2,4dinitrobenzene, by means of a fluoride-selective electrode, Talanta 36 (1989) 431–436.
[5] A.M. Prokai, R.K. Ravichandran, Simultaneous Analysis of Hydroxylamine, N-methylhydroxylamine and N,N-dimethylhydroxylamine by ion chromatography, J.
Chromatogr. A 667 (1994) 298–303.
Application of modified multiwall carbon nanotubes electrode and new organic mediator for determination of
cysteamine
B.Rezaei *, H.Khosropour, A.A.Ensafi
Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111, IR Iran
Email:rezaei@cc.iut.ac.ir
Cysteamine (CA) is the simplest stable aminothiol and a degradation product of the amino acid cysteine. Under the trade name of
Cystagon, cysteamine is used in the treatment of cysteine excretion disorders. Cysteamine cleaves the disulfide bond with
cysteine to produce molecules that can escape the metabolic defect in cystinosis and cystinuria [1]. It is also used for the
treatment of radiation sickness [2]. Cysteamine crosses the plasma and lysosomes and reacts with crystallized cystine within the
lysosomes to form cysteine and cysteine– cysteamine mixed disulfides, leaving through the lysine porter [3]. On other hand, to
the best of our knowledge, a few papers have been reported on voltammetric determination of cysteamine, because the
electrooxidation of cysteamine proceeds very slowly and almost no current response was observed at the usual electrode.
Therefore, in this study, we propose promazine hydrochloride as a new mediator for the rapid, sensitive, and highly selective
voltammetric determination of (CA) using multiwall carbon nanotubes paste electrode (MWCNTPE) as a sensor. The
experimental results showed that the carbon nanotubes paste electrode has a highly electrocatalytic activity for the oxidation of
cysteamine in the presence of promazine hydrochloride as a mediator. Cyclic voltammetry, chronoaamperometry and linear
sweep voltammetry (LSV) are used to investigate the suitability of promazine hydrochloride at the surface of MWCNTPE as a
mediator for the electrocatalytic oxidation of (CA) in aqueous solutions. Under optimum condition (pH=5.0), the peak current
was linear to (CA) concentrations over the concentration range of 2–2850 μmol L−1, using (LSV). The detection limit was 0.8
μmol L−1. Finally, this modified electrode was used for determination of (CA) in some real samples such as drug and urine.
Reference
[1] http://en.wikipedia.org/wiki/Cysteamine, February 06, 2010.
[2] B. P. Lukashin, A. N. Grebeniuk, Radiatsionnaia biologiia,
radioecologiia/Rossiı˘skaia akademiia nauk 2001, 41, 310.
[3] L. Wood, M. Amin Khan, R. Moskal, Brain Res. 2007, 158, 158.
The effect of perlite, humic acid, carbon nano tube and their mix on the removal of heavy metals in cigarette mainstream
smoke.
Shahnaz Hosseinià (1), Farhad Naghizadeh (1), Gholam Reza Moradi Rebati (1), Mohammad Javad Chiechi (2).
1. Tirtash Tobacco Research and Education Center, Behshahr, Iran
2. Chemistry Faculty, Mazandaran University, Babolsar, Iran
Cigarette smoke contains metalic compounds of Cr, Pb, Ni, Co, As, Se and V. This compounds change or derange of body organs
such as brain, nerve, blood vessels, heart vessels, exocrine glands, enzymes, digestive and security systems, reproduction and
urinary channels. Consumption of cigarette causes to exchange of Ca, Zn, and Fe in body by these metals or association of them
and or derange of body systems. There fore must be reducing theses compounds in cigarette smoke. In this study, the effect of
humic acid (HA), mineral perlite (Per), carbon nanotube (CNT) and their mix (HA-Per, HA-CNT, Per-CNT and HA-Per-CNT),
were studied for the reduction of heavy metals and nicotine and tar in cigarette mainstream smoke. All absorbance (10mg Ha,
10mg per, 2mg CNT) were added separately to the filter potion of cigarettes. These were smoked using smoking machine in the
standard ISO method (35 ml puff of 2 s duration taken every minute to a butt length of filter tipping over wrap +3 mm). For
Measurement heavy metals extracted them on filters and blank filter by nitric acid after burring on Electric furnace in 550oc and
analyzed via ICP method. Result showed higher adsorption of heavy metals (total of Cd, As, Pb, Co, Ni, Se and Cr) on HA-Per
mix.
Reference
[1]Th. Matsi, N. Tsotslis, N. Barbayiannis, S. Miele, E. Bargiacchi, O.Kosmidou, O. Olivieri, Heavy Metal Levels in Soil, Irrigation Waters and Five Tob.Types,
Congress. New Orleans. U.S.A. 2002.
[2]A. Nitsch, K. Kalcher, H. Greschonig, Heavy Metals in Tobacco and Tobacco smoke II. Trace Metals Cadmium, Lead, Copper, Cobalt and Nickel in Austrian
Cigarette, and in Particle Phase and Smoke Gas, Beitr. Zur Tabakforsch. Int. , 1991, 15-1, p. 19-32., ISSN. 0173-783X 1991.
[3]J.Ch. Michael, W. Kathleen, L.Mc. Reta, T.C. chris, J. Impaction Collection and Slurry Sampling for the Determination of Arsenic, Cadmium and Lead in Side
stream Cigarette Smoke by Inductively Coupled Plasma- Mass Spectrometry, Environ. Monti. Vol.7, 2005, 1349-1354.
[4] How to Remove Heavy Metal Toxins - Mercury, Lead … from Your Body? Adrian Goad, Engineering and Alternative Health Research, Des.27, 2006.
[5] D. Geier, J. Kern, C. Garver, J. Adams, T. Audhya, R. Nataf, M. Geler, Heavy metal toxicity and detoxification capacity in autism, ,Journal of the Neurological
Sciences ,Monday, September 29, 2008.
The Preparation of Phthalocyanine modified Polypyrrole Electrode for Potentiometric Detection of Ascorbic Acid in Real
Samples
Fatemeh Ghasemi, Ali Mohammad-khah*, Hamid Dezhampanah, Majid Arvand
Department of Chemistry, University of Guilan, Rasht, Iran.
The aim of this study is designing a selective and efficient potentiometric sensor for detection of ascorbic acid.
A solid-contact potentiometric sensor for ascorbic acid based on phthalocyanine immobilized in a polypyrrole film was
fabricated. The response time of the sensor is about 6 s and to have an acceptable life time of about two months without any
considerable divergence in potential (2.5%). A linear response in concentration range from 1.0×10-6-1.0×10-2 M was obtained
with a detection limit of 7.9×10-7 M. Selectivity coefficients were determined by matched potential method (MPM) showed its
good selectivity against some common substances like sugars and organic acids. The relative standard deviation for vitamin C
determination in some of real samples by the proposed method was about 4% compared to the spectrophotometric method. The
proposed electrode has been successfully applied as a sensitive potentiometric sensor for fast and accurate determination of
ascorbic acid in some commercial vitamin products. The use of this electrocatalytic system for the determination of ascorbic acid
a lot of advantages, namely low cost of fabrication, wider dynamic range, and better response time.
Reference
[1]. M. Şahin, L. Özcan, B. Usta, Y. Şahin, Biosensors and Bioelectronics 24 (2009) 3492–3497.
[2]. M. K. Amini, S. Shahrokhian, S. Tangestaninejad, V. Mirkhani, Analytical Biochemistry 290 (2001) 277–282.
[3]. K. Wang, J. J. Xu, K. S. Tang, H. Y. Chen, Talanta 67 (2005) 798–805.
determination of residual monomer, N-vinylpyrrolidone, in polyvinylpyrrolidone by dispersion extraction with HPLC
Mohsen ghorbanhosseinia*, dr.hamid ahmadib ,masumeh salimic
a,c
Azad university, saveh branches
b
chemistry &chemical engineering research center of iran
E-mail: Mohseng.hosseini@yahoo.com
Polyvinylpyrrolidone (Povidone) is an inactive pharmaceutical ingredient (excipient) ,that produces from the polymerization of
the N-vinylpyrrolidone (NVP). At this work, residual monomer (NVP) in Povidone was determined by dispersion extraction,
with HPLC. According to the common pharmacopeias Povidone monograph, one of the main measurements is determination of
residual NVP in polymer matrix which have two main failures, first contaminating of HPLC column by polymer and second
losing of monomers. In this way, monomers extracted by proper solvent that dissolved NVP except Povidone. Ultrasound was
used for dispersing the polymer. For separating of polymers from the solution, 0.5 µm filter has been used. By means of SEM
images, it is found that the smallest dispersed particle is at least 3 µm. All parameters are optimized for extraction. After that, the
filterate solution, which had no polymer, was injected to the HPLC with controlled conditions.
Reference
[1].Polyvinylpyrrolidone_ excipients for pharmaceuticals, V.Buhler, Springer 2005
[2].Polyvinylpyrrolidone. Modern plastics, Fikentscher h, herrle k. 1945; 23(3):157-161212, 214,216,218.
[3].BASF Corporation. Technical literature: soluble kollidon grades, soluble polyvinylpyrrolidone for the pharmaceutical industry, 1997.
[4].Microencapsulation of solid dispersions of nifedipine –novel approach for controlling drug release, Chowdary kp, ramesh kv. Indian drugs 1995; 32(oct):477-483.
[5].Food chemical codex, 6th edn. Bethesda, MD: United States pharmacopeia, 2008; 795.
[6].Determination of NVP and NMP in drugs using polypyrrole-based headspace solid-phase microextraction and gas chromatography–NPD, Analytica Chimica Acta,
Volume 587, Issue 1, 21 March 2007, Pages 82-88, Ali Mehdinia, Alireza Ghassempour, Hasan Rafati, Rouhollah Heydari
Microextraction based on solidification of a floating organic drop followed by flame atomic absorption spectrometry for
the determination of ultratrace of zinc in natural waters
Mahrooz Alaei*, Esmaeil Babenezhad
Department of Chemistry, Islamic Azad University, Qaemshahr Branch, Qaemshahr, Iran
A procedure for the determination of ultratrace of zinc by liquid-phase microextraction based on solidification of a floating
organic droplet separation and flame atomic absorption spectrometry has been developed [1-3]. In this method, 25 µl of 1undecanol as extracting solvent, 100 µl of dithizone 0.006 M as the complexing agent and 1 ml of ammonia buffer (pH=10)
were transferred to the surface of an aqueous sample (5 mL, %5 w/v NaCl) including zinc ions, while being agitated by a stirring
bar. Under the proper stirring conditions, the suspended microdrop can remain at the top-center position of the aqueous sample.
After the completion of the extraction, the sample vial is immersed in a refrigerator for 10min, which results in the solidification
of the 1-undecanol drop that is easily separated. The solidified microdrop was then transferred into a conical vial, where it melted
immediately and diluted to 200 µL with ethanol. Finally, zinc ions in 200µL of diluted solution were determined by micro
sampling-FAAS. Several factors affecting the performance of SFODME, such as nature of the extracting solvent, pH,
complexing agent concentration, extraction time, extraction temperature ionic strength and stirring rate were investigated and
optimized. Under the optimum experimental conditions, the detection limit (3s) was 0.5 µg L−1 with enrichment factor of 200.
The relative standard deviation was 5.2% (n = 5, 15 µg L−1 Zn(II)). The proposed method was successfully applied to the
determination of Zn in spring, tap and sea water samples.
Reference
[1] M. S. Bidabadi, S. Dadfarnia, Al. M. Haji Shabani, Journal of Hazardous Materials, 166( 1) (2009) 291-296.
[2] R. E. Rivas, I.o López-García, M. Hernández-Córdoba, Anal. Methods, 2 (2010) 225-230.
[3] C. A. Sahin, I.Tokgöz, Anal. Chim. Acta. 667(1-2) (2010) 83-87.
Spectrophotometric and thermodynamic study on the dimerization equilibrium of Nile Blue A dye in water and micellar
medium chemometrics method
Somayeh bahiraii*,Ali Niazi and Majid Ramezani
Department of Chemistry, Faculty of Science, Islamic Azad University-Arak Branch, Arak, Iran
E-mail:somayehbahiraii@yahoo.com and ali.niazi@gmail.com
The monomer-dimer equilibrium and thermodynamic in Nile Blue A (Figure 1) dye as ionic dye has been investigated by means
of spectrophotometric and chemometrics methods.
Figure 1. Structure of Nile Blue A
The dimerization constants of these ionic dye have been determined by studying the dependence of their absorption spectra on
the temperature in the range 20-65°C at concentrations of Neutral Red (1.22´10-4 M) in different pH (Figure 2, in pH=6) and in
different micellar meidum. The monomer-dimer equilibrium of this dye has been determined by chemometrics refinement of the
absorption spectra obtained by thermometric titrations performed. The processing of the data carried out for quantitative analysis
of undefined mixtures, based on simultaneous resolution of the overlapping bands in the whole set of absorption spectra. The
enthalpy and entropy of the dimerization reactions were determined from the dependence of the equilibrium constants to the
temperature (van't Hoff equation).
1
Absorbance
0.8
↑
0.6
0.4
0.2
0
450
550
650
Wavelenght
750
Figure 2. Spectra of Nile Blue A in pH = 6 in temperatures (20-65 °C)
Reference
[1] J. Ghasemi, A. Niazi, G. Westman, M. Kubista, Talanta, 62 (2004) 835.
[2] J. Ghasemi, A. Niazi, M. Kubista, A. Elbergali, Anal. Chim. Acta, 455 (2002) 335.
[3] A. Niazi, A. Yazdanipour, J. Ghasemi. M. Kubista, Spectrochim. Acta Part A, 65 (2006) 73.
Application of a simplified matrix solid phase dispersion extractionfor HPLC determination of hesperidin, diosmin and
eriocitrin in Iranian lime juice
Mohammad Reza Hadjmohammadi1, Moazameh Peyrovi1, Iman Saeidi2, Abolghasem Mohammaddust3, Behruz Barfi*,1
1
Department of Chemistry, University of Mazandran, Babolsar, Iran
2
Institute of Standard and Industrial Research of Iran
3
School of medical science, Mashhad, Iran
A simplified sample preparation technique based on matrix solid phase dispersion (MSPD) and HPLC were applied to the
simultaneous determination of hesperidin, diosmin and eriocitrin in Iranian lime juice samples. Different parameters of the
MSPD technique such as the type of dispersant solid-phase, the type and volume of eluting solvent, sample ionic strength and pH
were studied. The best recoveries were obtained with a small volume of lime juice (1 ml), silica-based C18 (1.0 g) as dispersant
solid-phase and 3 ml of methanol as eluting solvent. These compounds were separated using water/acetonitrile/acetic acid
(78:19:3, v/v/v) as a mobile phase at a flow rate of 0.8 ml/min and UV detection at 280 nm. Limits of detection, limits of
quantification, repeatability, and reproducibility of the method for hesperidin, diosmin and eriocitrin were 0.0192-0.0423 µg/mL,
0.0582-0.128 µg/mL, 2.8–4.5% and 3.9–5.2%, respectively. All analytes provided average recoveries from spiked (at 0.15, 5.0,
30, and 50 µg/mL) citrus juice samples ranging from 93.2 to 98.1 %.The method was applied to analysis of lime juice samples
obtained from different locations of Iran.
Reference
[1]. Dillard CJ, German JB(2000) J Sci Food & Agric 80:1744-1756
[2]. King A, Young G,(1999) J Am Dietetic Association 99:213-218
[3]. Lurie S,(2003) In: Hodges DM, (ed) Postharvest oxidative stress in horticultural crops. Food Products Press, New York
Simultaneous determination of Zinc and Copper after preconcentration and separation by DLLME-SFO method coupled
with FI-spectrophotometry and using of chemometrics methods
Tahereh Asadollahi1*, Ali Mohammad Haji Shabani1, Shayessteh Dadfarnia1, Jahanbakhsh Ghasemi2, Masoud Rohani Moghadam1
1
Department of Chemistry, Faculty of Sciences, Yazd University, Yazd, 89195-741, Iran
2
Department of Chemistry, Faculty of Science, K. N. Toosi University of Technology, Tehran, Iran
In this study, the possibility of simultaneous extraction of Cu and Zn with DLLME-SFO followed by its determination by FIA
spectrophotometry and PLS regression analysis was considered and a novel method for simultaneous extraction and
determination of copper and zinc with 1-(2-pyridylazo) 2-naphtol (PAN) as complex agent was developed. The factors
influencing the complex formation and extraction by DLLME-SFO such as volume of extraction and disperser solvents, pH,
concentration of salt and concentration of the chelating agent were optimized. PLS was applied for multivariate calibration and
noise reduction by eliminating the less important latent variables. The data obtained from the experiments were processed by
chemometrics method of partial least squares (PLS). The linear dynamic range for Cu2+ and Zn2+ were 3–30 μg L−1 and 1–
23 μg L−1, respectively. Detection limits were 0.9 μg L−1 and 0.25 μg L−1 for Cu and Zn, respectively. The relative standard
deviations were found to be less than 4.5% for both of metal ions.
Reference
[1]T. Asadollahi, S. Dadfarnia, A.M.H. Shabani, Talanta, 82 (2010) 208.
Preconcentration of Quercetin by DLLME-SFO and determination with FI-spectrophotometry in fruit and vegetable
Tahereh Asadollahi*, Ali Mohammad Haji Shabani, Shayessteh Dadfarnia, Mood Amirkave
Department of Chemistry, Faculty of Sciences, Yazd University, Yazd, 89195-741, Iran
*
Email: tahere996@yahoo.com
Polyphenolic compounds (e.g. quercetin and myricetin) play an important role as natural potent antioxidants, exhibiting various
physiological and biological activities, such as anti-inflammatory, anti-allergic and anti-carcinogenic activities, in the human
metabolic system . A new dispersive liquid–liquid microextraction based on solidification of floating organic drop (DLLMESFO)/flow injection-spectrophotometry (FI) method for separation and preconcentration of trace amounts of quercetin was
developed. 1-undecanol and methanol were used as extraction solvent and disperser solvent, respectively. The factors influencing
the extraction by DLLME-SFO such as volume of extraction and disperser solvents, pH and concentration of salt were
optimized. The optimal conditions were: volume of extraction solvent, 80μL; and pH, 3. The linear dynamic range was 5×10-810-5 molL-1. Detection limits was 10-8 mol L−1. The relative standard deviations (R.S.D., n = 10) were found to be less than 2.2%.
The method was successfully applied to the determination of quercetin in the fruit and vegtable and satisfactory relative
recoveries (95–105%) were achieved.
References
Synthesis of Molecularly Imprinted Polymers for sorption of Mefenamic acid based on the surface of modified silica gel
Mahsa Mahabadi* ,Hayedeh Bagheri Sadeghi, Homayon Ahmad Panahi, Mahsa Oskouei
Department of Chemistry, Central Tehran Branch, Islamic Azad University, Tehran, Iran
E-mail: m_mah2004@yahoo.com
Mefenamic acid is a non-steroidal anti-inflammatory drug used to treat pain, including menstrual pain. It is typically prescribed
for oral administration. Molecular imprinting is a technique of preparing molecularly imprinted polymers (MIPs) which can
specifically recognize the imprinted template molecules. In this work silica gel was used as supporting matrix, mefenamic
acid as template. 2, 2′-azo-bis-isobutyronitrile (AIBN) as the initiator, N,N-Dimetylacrylamide (DMAA), Allyl glycidil
eather/iminodiacetic acid (AGE-IDA) were polymerized and grafted onto modified silica gel surface and was characterized by
FT-IR, and thermogravimetric (TGA) analysis. The effect of different parameters, such as PH, amount of adsorbent , recovery,
adsorption capacity of adsorbent at optimum conditions and interfering species were investigated. This modified support was
used for pre-concentration and subsequent determination of mefenamic acid by high-performance liquid chromatography (HPLC)
in drug capsules.
Reference
[1] Peter A.G Cormack, Amaia Zurutuza Elorza, Journal of Chromatography B, 804 (2004) 173-182.
[2] Mohammad-Reza Rouini, Ali Asadipour et al, Journal of Chromatography B, 800 (2004) 189-192.
Prediction of water-phosphatidylcholine membrane partition coefficient of some drugs by QSAR modeling
Masoomeh Raei Moghaddam, Mohammad Hossein Fatemi*
Faculty of Chemistry, University of Mazandaran, Babolsar, Iran.
Phosphatidylcholine is a phospholipid that is a major constituent of cell membranes [1]. The tendency of drug to remain in blood
or move to other compartments is governed by its ability to passes through cell membranes.Water-phosphatidylcholin membrane
partition coefficient (log MA) can be explaining this property of drugs quantitatively. Since the experimental determination of
this parameter is expensive and time consuming, therefore theoretical estimation of this parameter is necessary. In this work we
estimate this parameter for some drugs from their structural features by using QSAR (Quantitative Structure–Activity
Relationships) approaches [2-3]. The QSAR models were developed by applying multiple linear regressions (MLR), artificial
natural network (ANN), and support vector machine (SVM) for dataset of 46 drugs. During this analysis, the best QSAR models
were identified when using nonlinear models ANN (artificial neural networks).This model has seven descriptors which are:
number of aromatic bonds, negative Burden eigenvalue n.3/weighted by atomic masses(BENm3), Gray autocorrelationlag8/weighted by atomic masses (GATS8e),R maximal autocorrelation of lag6/unweighted(R6u), 3D-Morse-signal 23/weighted
by atomic masses (Mor23m), Leverage-weighted autocorrelation of lag2/unweighted(HATS2u), Moran autocorrelationlag4/weighted by atomic Van der Waals Volumes(MATS4v).The ANN QSAR models produced a reasonable level of correlation
between experimental and calculated log MA (Rtrain = 0.995, Rtest=0.948). The built model was fully assessed by various
validation methods, including internal and external validation, Y-randomization test and cross validation (Q2=0.91). Finally, it
must be pointed out that the developed model was used as a predictive tool with highly satisfying results.
Reference
[1] Han X., Gross R.W., J. Biochemistry 29 (1990) 4922-4996.
[2] Hammet L.P., J. Chem. Rev. 17(1935)125-135.
[3] Hansch C., Stewar AR., J. Med. Chem. 7(1964)691-694.
Adsorption of bromophenol red dye by silver nano particles loaded on activated carbon
M.Ghayedi , M.Ghaedi*
Department of Chemistry, Gachsaran University, Gachsaran Branch, Gachsaran, Iran
*E-mail: m_ghaedi@mail.yu.ac.ir,maryam.ghayedi@gmail.com
The adsorption of bromophenol red onto silver nanoparticle loaded on active carbon and its desorption was investigated. Seeking
solution to pollution problems is a prime concern of many researchers today. In the first The silver nanoparticle loaded on active
carbon were prepared by chemical plating method. This new adsorbent was characterized scanning electron microscopy (SEM),
while it surface functional groups was recognized by FTIR analysis. The silver nanoparticle loaded on active carbon is identified
to be an effective adsorbent for the removal of bromophenol red from aqueous solutions.The various parameters like : effect of
pH, contact time, adsorbent dosage, temperature and initial concentration of dye have been standardized. About 98% dye
removal has been achieved by silver nanoparticle loaded on active carbon. The aim of the present study was to discover the effect
of various experimental parameters such as contact time, adsorbent dosage , dye concentration, pH and temperature on removing
bromophenol red dye from aqueous solution using silver nanoparticle loaded on active carbon adsorbent and the optimal
experimental conditions were ascertained. The optimum values of the parameters were: dye concentration 1.25mg (25ppm), pH 1
and adsorbent dosage 0.01g for maximum removal of dye. Based on the results of the present study indicated that silver
nanoparticle loaded on active carbon adsorbent was an attractive candidate for removing bromophenol red dye from the
wastewater.
Reference
[1]M. Arami, N. Y. Limaee, N. M. Mahmoodi, N.S. Tabrizi, J. Colloid Interface Sci. 288 (2005)371–376.
[2] F. D. Ardejani, K. H. Badii, N.Y. Limaee, N.M. Mahmoodi, M. Arami, S.Z. Shafaei, A.R. Mirhabibi, Dye Pigm. 73 (2007) 178–185.
Kinetics, thermodynamic and equilibrium isotherms of methylene green adsorption on zinc oxide nano particle loaded on
activated carbon
M.Ghayedi , M.Ghaedi*
Department of Chemistry, Gachsaran University, Gachsaran Branch, Gachsaran, Iran
*E-mail: m_ghaedi@mail.yu.ac.ir,maryam.ghayedi@gmail.com
The silver nanoparticle loaded on active carbon is identified to be an effective adsorbent for the removal of bromophenol red
from aqueous solutions.The ability of zinc oxide nanoparticles loaded on activated carbon to remove methylene green from
aqueous solutions was studied. Nano particle have very interesting physicochemical properties, such as ordered structure with
high aspect ratio, ultra-light weight, high mechanical strength, high electrical conductivity, high thermal conductivity, metallic or
semi-metallic behavior and high surface area. In this research, efficiency and performance of zinc oxide nano particle loaded on
activated carbon adsorbents for the removal and recovery of methylene green from wastewater has been compared. Methylene
green was used as the model compound due to its wide range of applications and high stability in the environment. The maximum
removal was 98% in ph7 for 0.75mg of methylene green concentration on 0.01g carbon concentration and 12 min contact time.
The influence of variables including pH, concentration of the dye, amount of adsorbents, contact time and temperature on the dye
removal has been investigated in batch method by one at a time optimization method. The graphical correlation of various
adsorption isotherm models like, Langmuir, Freundlich and Tempkin have been carried out for these adsorbents. Calculation of
various thermodynamic parameters such as, Gibb’s free energy, entropy and enthalpy of the on-going adsorption process indicate
feasibility and endothermic nature of methylene green adsorption on all adsorbents. Rate of adsorption increased with increasing
initial dye concentration but the removal percent of dye decrease with increasing initial dye concentration .
Reference
[1] M. Arami, N. Y. Limaee, N. M. Mahmoodi, N.S. Tabrizi, J. Colloid Interface Sci. 288 (2005)371–376.
[2] F. D. Ardejani, K. H. Badii, N.Y. Limaee, N.M. Mahmoodi, M. Arami, S.Z. Shafaei, A.R. Mirhabibi, Dye Pigm. 73 (2007) 178–185.
Iodide–Selective Electrode Based on bis(trans-cinnamaldehyde)1,3-propanediimine mercury (II) chloride [HgLCl2]
Carrier: Influence of multiwalled carbon nanotubes on the response performance
K. Mortazavia, M. Ghaedi, M. Montazerozohori, Z. Andikaey S. Nasiri Kokhdan
Chemistry Department, Islamic Azad University, Gachsaran Branch, Gachsaran, Iran
Chemistry Department, Yasouj University, Yasouj, 75918-74831, Iran.
* Author to whom correspondence should be addressed. Tel. Fax.(+98)-741-2223048,
E-mail: m_ghaedi@mail.yu.ac.ir or m_ghaedi@yahoo.com
In this research, new iodide-selective electrode based on incorporating of Hg complexe of carbon paste matrices has been
reported. To obtaine good charestristic performance vis. linear range and detection limite, the influence of multiwalled carbon
nanotube (MWCNT-CPE), (lipophilic cationic and anionic additives, and amount of ionophores and nujol) was investigated and
their values was set as carbon powder, MWCNT: Nujol, Carrier: MTOACl, (0.15g, 5mg, 36mg, 26.0mg, 15.6mg) for BCPHgCl 2
respectively. The potentiometric response of the proposed electrode is independent of pH of the test solution over the range of
3.0–11.0 for BCPHgCl2. The selectivity sequence of proposed iodide selective electrode evaluated by different methods such as
separate solution method (SSM) and fixed interference method (FIM) indicate selective response for iodide ions over various
interfering ions[1,2].The electrode exhibited near-Nernstian slope of -58.51 ± 1.00 mV/decade of iodide concentration over the
range 1 × 10-6 – 1 × 10-1 M, with detection limit of ~0.6× 10-6 M for the electrode based on BCPHgCl 2 respectively. They have
relatively fast response time »10s BCPHgCl2, satisfactory reproducibility, and life times of at least two months.
Reference
[1]. Beerand, P.D.; Gale, P.A.; Angew. Chem. Int. Ed. 2001, 40, 486.
[2]. Dietrich, B.; Pure Appl. Chem. 1993, 65, 1457.
Removal of Erionyl Bokdeouy 5BLF from aqueous solution by adsorption onto Gold nanoparticle loaded on Activated
carbon
Mehrorang Ghaedia*, Zahra Andikaeya, Syamak Nasiri Kokhdana, Mina befara, Rezvan behfar b.
a
Chemistry Department, Yasouj University, Yasouj 75914-35, Iran
b
Chemical Engineering Department of Arak University, Arah, Iran
E-mail: M_ghaedi@yahoo.com, Zahra.Andikaey@yahoo.com, Syamak.nasiri@yahoo.com
The adsorption of Erionyl Bokdeouy 5BLF onto Gold nanoparticle loaded on activated carbon in a batch adsorber has
been studied. Four kinetic models, the pseudo first- and second-order equations, the Elovich equation and the intraparticle
diffusion equation were selected to follow the adsorption process. Kinetic parameters; rate constants, equilibrium adsorption
capacities and correlation coefficients, for each kinetic equation were calculated and discussed. The apparent thermodynamic
parameters were calculated, and the obtained values support the conclusion that dye molecules sorb by an entropy-driven,
endothermic process. The aim of the present work is to explore the possibility of utilizing rice husk for the adsorptive removal of
EB from wastewater. The effect of such factors such as the initial pH value, salt concentration, flow rate, influent concentration
and bed depth on dye adsorption by husk bed column was investigated [1-3]. Stock solution was prepared by dissolving require
amount of dye in double distilled water and test solutions were prepared by diluting stock solution to the desired concentrations.
The pH measurements were done using pH/Ion meter model-686 and absorption studies were carried out on Jusco UV-Visible
spectrophotometer model V-570. All chemicals include NaOH, HNO3, KCl, Erionyl Bokdeouy from Merck Germany.
Reference
[1] G. Crini, Technol. 97(2006) 1061–1085.
[2] A.R. Gregory, S. Elliot, P. Kluge, Toxicol. 1 (1991) 308–313.
[3] Z. Aksu, Process Biochem. 40(2005) 997–1026.
Fixed bed studies for adsorption of Congo red anionic dye using sawdust modified by cationic surfactant cetyltrimethylammonium
bromide as a very efficient adsorbent
Reza Ansari *, Babak Seyghali, Ali Mohammad-khah
Chemistry Department, Faculty of Science, University of Guilan, Rasht, Iran
POB 41635-1914, Tel and Fax: 0098-0131-323326
In the present study, the adsorption behavior of Congo Red (CR) a typical anionic dye stuff from aqueous systems onto sawdust
modified by cetyltrimethylammonium bromide, CH3(CH2)15N(CH3)3Br (CTAB) has been attempted via column mode (fixed bed)
studies under various operating conditions. The effects of important factors, such as the value of initial pH, the influent dye
concentration, the flow rate, and bed depth, were studied. Thomas model was applied to experimental data to predict the
breakthrough curves and to determine the characteristic parameters of the column useful for process design. Desorption studies
carried out by the column system using ethanol as eluent for regenerate of the spent adsorbent. In this system the highest bed
capacity of 66.73 mg g -1 was obtained using 50.0 mg L-1 inlet dye concentration, 2.50 cm bed height (0.50g adsorbent) and 3.0
mL min-1 flow rate. The q0 values calculated from the Thomas model is very close to the qc (exp) value obtained experimentally. It
was found that modification of sawdust by cationic surfactant resulted to a great increase in sorption capacity of sawdust.
Electrostatic forces between the positively charged of the active sites in sawdust modified by CTAB and the negatively charged
of anionic dye molecules (CR) seems to be the main reason for this improvement. Desorption studies by the column system for
CTAB/SD suggested that the most of the dye uptaken by CTAB/SD is occurred via strong electrostatic forces, chemisorption as
well as ion exchange processes.
Reference
[1] A.A. Ahmad, B.H. Hameed, Fixed-bed adsorption of reactive azo dye onto granular activated carbon prepared from waste, J. Hazard. Mater. 175 (2010) 298–303.
[2] R. Han, D. Ding, Y. Xu, W. Zou, Y.Wang, Y. Li, L. Zou, Use of rice husk for the adsorption of Congo Red from aqueous solution in column mode, Bioresour.
Technol. 99 (2008) 2938–2946.
Applications of modified biosorbents with dodecyl benzene sulfonic acid for removal of basic dyes from aqueous solutions
using flow systems
Reza Ansari*, Babak Seyghali, Mohammad Ali Zanjanchi
Chemistry Department, Faculty of Science, University of Guilan, Rasht, Iran
POB 41635-1914, Tel and Fax: 0098-0131-3233262,
* E-mail: ransari@guilan.ac.ir
The aim of this study is to develop a cheap technology for removal of basic dyes from textile wastewaters using a continuous
flow system. Sawdust as a suitable natural biomaterial waste was selected as raw material, 4-dodecyl benzene sulfonic acid
surfactant (DBS) was selected as chemical modifier and methylene blue (a typical basic dye) was selected as a test probe in this
research. In order to have a good comparison, the same experiments were performed using unmodified sawdust (SD). The effects
of important parameters, such as the initial value of pH, influent concentration of dye, flow rate and bed depth, were studied. To
find out the regeneratability of the exhausted column, desorption study was also performed. Based on the breakthrough analysis,
the highest column capacity of 130 mg g-1 was obtained for the DBS modified sawdust. The dye uploaded column was easily
desorbed using dilute HCl as regenerant solution with high performance. According to the bed depth service time analysis
(BDST), a column with characteristics: 1.0 cm diameter, bed depth of 5 cm, inlet dye concentration of 50 mg L-1, flow rate of 3
mL min-1 could treat about 300 mL for SD at pH 6 and 900 mL for DBS/SD at pH 10 (optimum pH value). Decreasing the bed
height made the breakthrough curves become steeper showing faster saturation. Regeneration of the biosorbents (SD and
DBS/SD) in column was performed using cost effective chemicals and reused for three adsorption/desorption cycles without
losing any considerable sorption capacity at least after three runs. It was found that modification of biosorbents with anionic
surfactants such as DBS is an economic, environmentally friendly and efficient rout for removal of cationic dyes from
wastewaters.
Reference
[1] A. Adak, M. Bandyopadhyay, A. Pal, Fixed bed column study for the removal of crystal violet (C. I. Basic Violet 3) dye from aquatic environment by surfactantmodified alumina, Dyes and Pigments, 69 (2006) 245-251.
[2] R.P. Han, Y.F. Wang, W. Yu, W. Zou, J. Shi., H. M. Liu, Biosorption of methylene blue from aqueous solution by rice husk in a fixed-bed column, J. Haz. Mater,
141 (2006) 713-718.
Three-phase hollow fiber microextraction based on two immiscible organic solvents for tricyclic antidepressant drugs
determination: Comparison with conventional three-phase hollow fiber microextraction
Mahnaz Ghambarian, Yadollah Yamini*, Ali Esrafili
Department of Chemistry, Faculty of Sciences, Tarbiat Modares University, P.O. Box: 14155-175, Tehran, Iran
The aim of this research was to compare the extraction efficiencies of two modes of three-phase hollow fiber microextraction
(HF-LLLME) based on aqueous and organic acceptor phases for analysis of tricyclic antidepressant (TCAs) drugs. Subsequent
HPLC-DAD was used for determination of these compounds. TCAs are widely used for the treatment of a variety of depressive
states and other psychiatric disorders [1]. The therapeutic concentration range for most tricyclic antidepressants is approximately
100 – 300 µg L-1, while toxic effects can occur when plasma concentrations exceed 500 µg L-1 [2]. Therefore, methods for
determining the concentrations of tricyclic antidepressants in human samples are required for diagnosis and effective treatment of
intoxication and for forensic purposes. In order to investigate the ability of new concept of HF-LLLME based on organic
acceptor solvent in comparison with aqueous acceptor phase, four TCAs were subjected to different extraction conditions and
central composite design was applied as a powerful tool to optimize the obtained data. Both methods were characterized by good
linearity and high repeatability but HF-LLLME with organic acceptor was provided higher extraction efficiency and then lowers
LODs. Calibration curves were linear (r2 > 0.996) from range of 0.2 to 200 µg L-1. LODs for all individual TCAs ranged from
0.08 to 0.2 µg L-1 using HPLC-DAD and an improvement in sensitivity of several orders of magnitude was achieved using single
ion monitoring GC-MS analyses (0.04 µg L-1) due to compatibility of this technique with GC instrument. The application
feasibility of HF-LLLME/GC-MS and HPLC-DAD in TCA drugs monitoring was demonstrated by analyzing urine and plasma
samples, and the recoveries of target drugs for the spiked sample ranging from 87.9 % to 109.2 % indicated an excellent antiinterference capability of the developed method.
Reference
[1] Furlanut, M., Benetello, P., Spina, E., Clin. Pharmacokinet. 1993, 24, 301 – 318.
[2] G.M. Greenway, S.J.L. Dolman, Analyst 124 (1999) 759.
Removal of Endosulfan by Nano-alumina: Characterization and Sorption Studies
Mahboubeh Saeidi*and Monireh Farrokhzadeh
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, Iran
Indiscriminate use of pesticides in the modern agricultural practices leads to several environmental problems. One of such
problems is the contamination of surface and ground water by pesticide [1]. Nanomaterials have a number of key
physicochemical properties (e.g. larger surface area than bulk particles, enhanced reactivity and self-assembly) that make them
particularly attractive as separation media for water purification [2].
Endosulfan (C, Ć-(1, 4, 5, 6, 7, 7-hexachloro-8, 9, 10-trinorborn- 5-en-2, 3-ylene) (dimethyl sulfite)) is a chlorinated insecticide
used in many countries and is liposoluble and persistent in the environment [3].
The present study was conducted to evaluate the feasibility of nano-alumina for endosulfan removal from solution. Nanoparticles
of Al2O3 were prepared using ultrasonic waves and calcined at 500◦C. The nature and morphology of sorbent was characterized
by XRD and SEM analysis. Endosulfan was removed by Al2O3 nanoparticles and also operational parameters such as pH, amount
of adsorbent, buffer volume, concentration of endosulfan and contact time was investigated. All absorbances was measured at
λmax= 269 nm. Removal of endosulfan was happened in 10 hours by using nanoparticles of Al2O3. The endosulfan sorption has
been well explained using Freundlich isotherm model. Results from this study demonstrated the potential utility of nano-alumina
for endosulfan removal from environment.
Reference
[1] P. C. Mishra, R.K. Patel, J. Hazard.Mater. (2008)152, 730-736.
[2] P. Jovančić, M. Radetić, Handbook of Environmental Chemistry/water pollution, vol.5, Springer-Verlag.Berlin Heidelberg, 2008, pp.239-264
[3] C.R. Worthing .A Worked Compendium, 7th ed. British Crop Protection Council, London, p 233(1983) 925
Dispersive liquid liquid microextraction combined derivatization for analysis histamine by HPLC-UV
1
Somayeh Beyranvand1,*, Payman Hashemi1
Department of Chemistry, Lorestan University, Khoramabad, Iran
Histamine is one of the biogenic amines with worldwide poisonous problems. Therefore, its quantitation is of great importance.
In this work, a combined derivatization-DLLME method with HPLC-UV analysis was developed for the histamine
determination. A 6% trichloroacetic acid solution was used for the precipitation of proteins from canned tuna fish samples and
dissolution of the analyte. The analyte was then derivatized and preconcentrated, simultaneously, by a DLLME method into a
micro-drop of chloroform. A central composite design method was used for optimization of the factors in the DLLME method. In
the optimized conditions, a mixture of 650 mL acetone and 100 mL chloroform containing 10 mL benzoyl chloride (the
devatization reagent) was rapidly injected into 4 mL of the sample. The sample contained 6% trichloroacetic acid and 1.4 mol L-1
sodium hydroxide. After 30 min, 2 mL of a 0.35 mol L-1 sodium chloride was added to the solution and the mixture was
centrifuged. The sedimented micro-drop was transferred into a microvial in which chloroform was evaporated and displaced by
100 mL ethanol before injection of the sample to the HPLC column. Recoveries between 96.7 to 101.2% were obtained for the
tuna fish samples. The detection limit of the method was 0.06 mg kg-1 of histamine with an RSD of 5.3% for six replicates.
Reference
[1] Y.H. Tsai, H.F. Kung, T.M. Lee, H.Ch. Chen, Sh.Sh. Chou, Ch.I. Wei, D.F Hwang, J. Food Control. 16.(2005) 579-585.
[2] N Fattahi, Y. Assadi, M.R. Milani Hosseini, E. Zeini Jahromi, J Chromatography A, 1157, (2007) 23-29.
Essential oil components of Satureja macrosiphoon, an endemic species from Iran
1
Javad Hadian1, Mohammad Reza Kanani1, Somayeh Beyranvand2,*, Alinazar Salehnia 2
) Department of Agriculture, Medicinal Plants and Drug Research Institute, Shahid Beheshti University, G. C., Evin, Tehran, 1483963113, Iran
(phone/fax: 98-21-29903023; e-mail: j_hadian@sbu.ac.ir)
2
) Department of Research and Development (R&D), Khorraman Pharmaceutical Co, Khoramabad Industrial city, 68135-579, Khoramabad ,
Iran
Satureja macrosiphoon is an endemic species growing wild in southwestern parts of Iran. Aerial parts of this species were
collected at full flowering stage from Ilam province of Iran in order to study its chemical compositions. The essential oils were
obtained by hydro-distillation. Quality and quantity of chemical composition of essential oil were determined by GC and GCMS. A total of fourty two compounds were identified as p-cymene (4.2%), γ terpinen (3%), trans- sabinene hydrate (15%),
linalool (9.9%), borneol (8.1%), cis-sabinene hydrate (8.1%), 4- terpineol (14.8), carvacrol (5.7%) and and were the major
identified compounds. In comparison with other Satureja species, Satureja macrosiphoon represented a new chemotype which
has not previously reported.
Reference
[1] J. Hadian, M. Hosseini mirjalili, M.R. Kanani, A. Salehnia, p. Ganjipoor, Chemistry and Biodiversity 8 (2011) 902-914
[2] M. Pezhmanmehr, D. Dastan, S. Nejad Ebrahimi, J. Hadian, Jeobp 13 (2010) 123-129
Biophysical Study of Interaction between Sm3+ ion with Human Serum Albumin by Fluorescence Spectroscopy and
Potentiometric Electrode
a
Farnoush Faridboda,*, Ali Akbar Sabouryb
Endocrinology & Metabolism Research Center, Tehran University of Medical Sciences, Tehran, Iran
b
Institute of Biochemistry and Biophysics, University of Tehran, Tehran, Iran
E-mail: faridbodf@tums.ac.ir; faridbodf@gmail.com
Interaction of lanthanides with biochemical macromolecules is interesting because they have similar ionic radii to calcium but
with higher charge density. They have a higher affinity for Ca2+ sites on biological macromolecules. Thus, they can be useful
probes to study the interactions between Ca2+ ion and biologically important macromolecules. Calcium dependent enzymes can
either be inhibited by lanthanides, or in some cases be activated to a similar or greater extent than by calcium [1,2]. Since the
biophysical effects of these ions are not well known, in this study, for the first time the interaction of Sm3+ ion, one of the
lanthanide member, and human serum albumin (HSA), the most important protein of human plasma, was investigated by
fluorescence spectroscopy and designed potentiometric Sm3+ ion selective electrode at 27 and 37 ºC in biological pH 7.4 [3].
According to the obtained results, interaction of HSA with Sm3+ ion showed a set of two binding sites with negative cooperativity. Also, thermodynamic parameters (ΔH˚, ΔG˚ and ΔS˚) of the interaction were calculated and indicated that the
concentration of this ion causes conformational changes on the structure of HSA which increasing the number of hydrophobic
contacts of HSA.
Reference
[1] S.P. Fricker, Chem. Soc. Rev. 35 (2006) 524-533.
[2] J.C. Zhang, S.J. Xu, K. Wang, S.F. Yu, Chinese Sci. Bull. 48 (2003) 2170–2175.
[3] M.R. Ganjali, F. Faridbod, A. Divsalar, A.A. Saboury, P. Norouzi, G.R. Behbehani and S. Abdolahzadeh, Int. J. Electrochem. Sci. 5 (2010) 852-866.
Introducing a new optode based on immobilization of complex "Bordeaux C" on triacetylcellulose membrane for
measuring pH in the acidic solutions
M.R. Ba Ezzat*,1, F. Rasti Jahromi1, Z. Bagheri1, R. Zomorrodi1, A.A. Amiri2
(1) Department of chemistry, Firoozabad Branch, Islamic Azad University, Firoozabad, Iran
(2) Department of chemistry, Shiraz Branch, Islamic Azad University, Shiraz, Iran
In this paper, design and construction of an optical pH sensor for low pH values based on immobilization of complex
"Manganese, 4-[(4-chloro-5-methyl-2-sulfophenyl)azo]-3-hydroxy-2-naphthalenecarboxylic acid" with Commercial name
"Bordeaux C" on triacetylcellulose membrane is described. At wavelength of 474 nm, maximum value of membrane absorption
was obtained. This reversible and repeatability sensor is suitable for measuring pH values in the range of 1-5. All produce
membranes will color change from orange to red, with at least two weeks life time. The sensor response time is about 6
minutes. Wide linear range, high repeatability (RSD=2/22%) and easy production Method are good specification of this
sensor. Use of this optical sensor is suggested for measurement of acidic pH values and without use of electrochemical systems,
and for real samples include large metallic ions. This method was used for measuring pH of white vinegar solution and 0.1 M
HCl solution , and good results was obtained.
Reference
[1] A.safavi,M.sadeghi,Spectro. Chim Acta, A 66 (2007)575.
[2] A. Safavi , M.Pakniat ,Anal. Chim.Acta,335 (1996) 227.
[3] W.Wroblewski, E. Roniecka,A.Dybko,Z.Brzozka,sens. Actuators B.,48 (1998)471.
[4]Erika Pringsheim, Ewald Terpetschnig, Otto.S.Wolfbeis,Anal. Chim. Acta,357 (1997)247.
[5] D.wencel, B.D.MacCraith, C.Mc Donagh, Sens. Actuators B, 139 (2009)208.
[6] A.Safavi, A.R.Banazadeh,Anal. Chim. Acta 583 (2008)326.
[7] A.Safavi,Mozhgan Bagheri, Sens. Actuators B 90 (2003)143.
[8] Jie Lin,trends in Anal. Chim., 19 (2000)9.
[9] A.A. Ensafi, A. Kazemzadeh, Microchem. J., 63 (1997)381.
[10] Y. kostov, S. Tzonkov, L.Yotova,M. Krysteva,Anal. Chim. Acta, 280 (1993)15.
Synthesis, characterization and analytical applications of CU(II)-ion imprinted polymer
L. Baramakeh1,*, Z. Bagheri2, F. Rasti Jahromi2, H. Bagheri3
(1) Department of chemistry, Marvdasht Branch, Islamic Azad University, marvdasht, Iran
(2) Department of chemistry, Firoozabad Branch, Islamic Azad University, Firoozabad, Iran
(3) Department of chemistry, Islamic Azad University, Fars Science Research Branch, Iran
Ionic imprinted polymers have been applied as selective sorbents in several analytical techniques, including liquid
chromatography, capillary electrophoresis and solid-phase extraction. In this paper, the printed polymer synthesis method ionic
imprinted polymer, (IIP), of the synthesized polymers in comparison with similar non-printed polymer selective separation of
small amounts of copper in natural tissuesare consided placed. Parameters are involved in the separation of this study, the printed
polymer ion-ion selectivity than copper (II) binary complexes with copper (II) was prepared Pyrogallol. Polymerization to do
around this complex and produced bypyrogallol monomer and cross linker formaldehyde in time 24 hours at temperature of 50
Celsius was done them and ion coppe-printed (as targets) usinga solution of 0.1 M nitric acid, the figure came out of the polymer .
The FT-IR apparatus was identified and interpreted .After the printed polymer synthesis, the parameters such as effective pH,
amount of polymer on absorption, polymer absorption time ,temperature, concentration and volume of nitric acid to separate the
optimalcation polymer surface were studied . The optimal pH value for the quantitative preconcentration is 5, and full desorption
is achieved by 1M HNO3. The results suggested that these IIPs can be used several times without considerable loss of adsorption
capacity.
Reference
[1] S.E. Manahan, Environmental Chemistry, 6th ed., Lewis Publishers, Boca Raton, 1994.
[2] Z. Zhang, S. Dai, et al., Ion-imprinted zeolite: a surface functionalization methodologi
[3] International Agency for Research on Cancer (IARC), in: Proceedings of the Meeting of the IARC Working Group on Beryllium, Cadmium, Mercury and
Exposures in the Glass Manufacturing Industry, Scand. J.Work. Environ. Health. 19 (1993) 360.
[4] H.G. Seiler, A. Sigel, H. Sigel, Handbook on Toxicity of Inorganic Compounds, Marcel Dekker, New York, 1998.
Cd2+ Carbon Paste Electrode Based on New Nano-composite
H. Ghaedi *, A. Shirzadmehr, S. A. Hashemi, H. Bagheri
Faculty of Engineering, Islamic Azad University, Bushehr Branch, Bushehr, Iran
A novel carbon paste ion selective electrode for Cd2+ ions based on 2,2´-thio-bis[4-methyl(2-amino phenoxy) phenyl
ether](TBMAPPE) as an ionophore was prepared. To have a high performance sensor with enhanced mechanical resistant for
determination of Cd2+ ions in water and in waste water samples. TBMAPPE was used as a sensing material in new composite
carbon paste electrode. The carbon paste were made based on a new nano-composite including multi-walled carbon nanotube
(MWCNT), nanosilica, and a typically room temperature ionic liquid. The constructed nano-composite electrode showed better
sensitivity, selectivity, response time, response stability and lifetime in comparison with typical Cd2+ carbon paste sensor. The
new electrode exhibited a Nernstian response (29.5±0.01mV decade-1) toward Cd2+ ions in the range of 5.0×10-8-1.0×10-1 mol L-1
with a detection limit of 7.9×10-9 mol L-1. The proposed modified Cd2+ sensor can be used over the pH range of 4.5 to 6.5.
Reference
[1] G. Shul, J. Sirieix-Plenet, L. Gaillon and M. Opallo, Electrochem. Commun. 8, 1111 (2006).
[2] D. Wei and A. Ivaska, Anal. Chim. Acta 607, 126 (2008).
[3]- Ali A. Ensafi, S. Meghdadi, S. Sedighi, Desalination 242, 336 (2009).
Nonenzymatic fructose detection at carbon paste modified electrode with nickel-poly (isonicotinic acid) coating through
new strategy
Banafsheh Norouzi* and Mitra Enayati
Department of Chemistry, Faculty of Industry and Engineering, Islamic Azad University Ghaemshahr Branch, Ghaemshahr, Iran
E-mail: norouz2020@yahoo.com
Determination and measurement of carbohydrates have considerable importance in food industry, biotechnology, environmental
and clinical diagnostics [1]. The most serious problem of the enzymatic carbohydrate sensor is their lack of stability due to the
intrinsic nature of enzyme. To resolve this problem, previous studies had shown attempts where the carbohydrate concentration
can be determined without using enzymes [2-4]. Recently, modified electrodes with metallic microparticles electrodeposited into
the polymeric matrix have been used for the oxidation of carbohydrates [5] and amino acids [6]. These studies showed that metalpolymer electrodes are easy to prepare, stable for long time periods with good detection limits and wide linear responses. All
these results encouraged us to continue the studies with new polymer materials. In this work, electrolytically deposited Ni on
isonicotinic acid film covered carbon paste electrode was used as anode for the electrooxidation of fructose in alkaline medium.
The electrochemical behavior and electrocatalytic activity of the electrode were studied using cyclic voltammetry and
chronomethod studies. The capability of this modified electrode for catalytic oxidation of fructose was demonstrated. The
amounts of electron transfer coefficient, diffusion coefficient and rate constant of the electrocatalytic oxidation reaction are
obtained. Also, the electrocatalytic oxidation peak currents of fructose exhibit a good linear dependence on concentration and its
quantification can be done easily.
Reference
[1] D.C. Johnson, S.G. Weber, A.M. Bond, R.M. Wightman, R.E. Shoup, I.S. Krull, Anal. Chim. Acta 180 (1986) 187.
[2] Y. Sun, H. Buck, T.E Mallouk, Anal. Chem. 73 (2001) 1599.
[3] E. Shoji, M.S. Freund, J. Am. Chem. Soc. 123 (2001) 3383.
[4] M. Yousef Elahi, M.F. Mousavi, S. Ghasemi, Electrochim Acta 54 (2008) 490
[5] R. Ojani, J.B. Raoof, P.S. Afagh, J. Electroanal. Chem. 571 (2004) 1.
[6] P. Akhtar, C.O. Too, G.G. Wallace, Anal. Chim. Acta 339 (1997) 201.
Investigation on cysteine-capped CdS nanoparticle quantum dots as fluorescence probe of As(V) ion
Mohammad saied hosseini bojd ٭Sahar nazemi
Chemistry Department, Birjand University, Birjand, 97175-615, Iran
E-mail:mshosseini1336@yahoo.com
Water soluble luminescent CdS quantum dots(QDs) capped by cysteine was synthesized in aqueous solution at room temperature
as colloial state, fluorescence spectra and IR confirm that the particles is formed.The prepared L-cysteine-capped nanoparticles
was used as fluorescene probe for As(V) detection via its reduction to As(III) ions. The fluorescence quenching L-cysteinecapped CdS nanoparticles depended on the concentration and pH of As(V) solution. The fluorescene intensity of CdS QDs is
linearly proportical to As(V) concentration in the range 9.5×10-7 to 2.8×10-5 mol/L. The interference effects of ions commonly
found in water which can be present in waste water was found to be negligible.
Solid-phase extraction of Ni(II) on agar modified with triphenyl pyrylium perchlorate and determination by flame
atomic absorption spectrometry
N. Pourreza, A. Mouradzadegun, S. Mohammadi*
Department of Chemistry, College of Science, Shahid Chamran University, Ahvaz Iran.
The importance of the determination of heavy metal ions, such as nickel, in environment samples can hardly be overemphasized
because they have undoubtedly a serious potential hazard to the human organism. Nickel has been classified as one of 13 priority
metal pollutants for its widespread use [1]. Flame atomic absorption spectrometry (FAAS) presents desirable characteristics, such
as low costs, operational facilities, high analytical frequency and good selectivity among these techniques [2, 3]. However, the
direct determination of trace elements by FAAS is generally difficult due to the low concentration of metals in the samples. This
problem can be suppressed by using a separation or preconcentration procedure before the detection [4]. A sensitive and simple
method for the preconcentration and determination of trace amounts of Ni (II) by atomic absorption spectrometry is described.
The method is based on the retention of Ni (II) on Agar modified with triphenylpyrylium perchlorate as an adsorbent. The
adsorbed metal ion are eluted from the column by H2SO4 (0.5 mol L-1) and determined by flame atomic absorption spectrometry.
The effects of various factors such as pH, type and concentration of eluent and its volume, amount of adsorbent, flow rate of
sample and volume of sample were investigated. The calibration graph was linear in the range of 2-200 ng mL-1 of Ni (II).
Detection limit based on 3Sb was 1.6 ng mL-1 and relative standard deviation (RSD) for seven replicate measurements of 20 and
150 ng mL-1 of Ni (II) was 4.9 and 3.2% respectively. The suggested method was applied to determination of Ni in rice and water
samples.
Reference
[1] A. R. Fakhari, A. Rajabi Khorrami, H. Naeimi, Talanta, 66 (2005) 813.
[2] D. Citak, M. Tuzen, M. Soylak, Food and Chemical Toxicology 47 (2009) 2302.
[3] V. A. Lemos, C. G. Novaes, M. A. Bezerra, J. Food Compos. Anal. 22 (2009) 337.
[4] V.A. Lemos, C.G. Novaes, A. Silva Lima, D.R. Vieira, J. Hazard. Mater., 155 (2008)128
A graphite electrode modified by enzymatic reaction of laccase with dopamine for electrocatalysis of N-acetyl-l-cystein in
presence of tryptophan
Jahan Bakhsh Raoof*, Reza Ojani, Mehdi Baghayeri
Electroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry, Mazandaran University, Babolsar,
Iran
Bioelectrochemistry has received increased attention in recent years [1]. Biosensors are one of important usage of
bioelectrochemistry into analytical applications [2, 3]. The polymer-modified electrodes have been widely used as biosensors for
their good stability, attractive catalytic ability, and broad potential window [4]. This study demonstrates a new electrochemical
sensor for the selective determination of N-acetyl-l-cystein (NAC) in presence of tryptophan (Trp) with laccase based biosensors
prepared by trapping ferrocene carboxylic acid (FCCA) into laccase-poly dopamine (PDLA) layer confined onto graphite
electrode. The method described here is essentially based on the chemical reaction properties of DA in presence of laccase
including oxidation, intramolecular cyclization and disproportionation reactions to finally give a polymeric layer. The efficient
entrapment and analytical performance of FCCA in the polymeric layer (PDLA) was confirmed by electrochemical methods. The
electro-catalytic peak currents of differential pulse voltammograms increased linearly with NAC and Trp concentrations in the
ranges of 0.2-15.0 μM, 0.1-10.0 μM with a detection limit of 0.087 and 0.052 μM, respectively. The FCCA-PDLA modified
graphite electrode (FCCA-PDLA-MGE) provides an effective sensor for determination of NAC in presence of Trp in real
matrices.
Reference
[1] G. Gilardi, A. Fantuzzi, Trends Biotechnol. 19 (2001) 468.
[2] A. Lindgren, T. Ruzgas, L. Gorton, L. Stoica, A. Ciucu, Analyst 124 (1999) 527.
[3] F.A. Armstrong, G.S. Wilson, Electrochim. Acta 45 (2000) 2623.
[4] Q.M. Zhou, Q.J. Xie, Y.C. Fu, Z.H. Su, X.E. Jia, S.Z. Yao, J. Phys. Chem. B 111 (2007) 11276.
A novel coating process of anti corrosion, anti fungal and anti algae on galvanized steel sheet
1*
Mahboubeh Masrouirnia1*, Fateme Helmi2 ,Zarrin Es’haghi2
Department of Chemistry , FacµLty of Sciences, Mashhad Branch, Islamic Azad University P.O. Box 91735-413,Mashhad ,Iran.
2
Department of Chemistry, Payame Noor University, 19395-4697 Tehran, I.R. of IRAN,
Important advantage of zinc plating of steel protects it sacrificially from corrosion. The main difference between different zinc
plating processes is the type of the plating bath. Cyanide baths are strongly alkaline solutions and containing cyanide ions [1].
The best way to increase the corrosion resistance of electroplated or galvanized zinc articles, as well as zinc die castings, is
through anodizing [2]. The aim of this paper is anodizing (electrochemical oxidation) in a suitable electrolyte to make a new
coating with characteristic properties and corrosion resistance on the surface of galvanized steel. Alkaline zinc plating bath was
used in solution of zinc cyanide and α-naphthol.the .Effect of Voltage, concentration of reagents, pH, time and thickness coating
which play important roles to this phenomenon, were optimized. Our results showed under anodizing condition at 45 seconds and
pH13.2 is corrosion resistance for 85 hours in salt spray determination. In this study α-naphthol is used as anti fungal and anti
algae compound .This coating was resistance minimum 7 days against of fungal and algae.
Reference
[1] M. Tencer, , Applied surface science 252(2006) 8230.
[2] S. Jakobson, D. Crotty, R. Griffin, D. Phipps, E. Rubin, Metal Finish. 96 (1998)
Fabrication of Electrochemical Theophylline(TP) Sensor Based on MnO2 Nanoparticles , Ionic Liquid and Chitosan
Modified Glassy Carbon Electrode
Samira mansouri majd, Abdollah salimia,b*
a-Department of Chemistry, University of Kurdistsn, P.O.Box 416, Sanandaj-Iran
b-Nanotechnology Research Center of Kurdistan University,P.O.Box,416,Sanandaj-Iran
1,3-Dimethylxanthine or theophylline (TP) is a drug widely used in treatment of asthma , chronic bronchitis and emphysema. The
plasma level generally accepted for effective broncho dilation in adults is 5–20 µg mL-1. Levels below this range are usually nontherapeutic, while higher levels may cause toxicity. The interest in monitoring the levels of TP in plasma has led to the
development of a variety of methods, such as high-performance liquid chromatography, spectrophotometry, capillary
electrophoresis, thin layer chromatography and immunoassay [1]. The mention methods have some limitations such as low
sensitivity, time consuming of preparation, complexation of methods and high cost instruments. Nanostructures are suitable
matrixes due to their high electrical conductivity, wide electrochemical working windows, large surface area, high
biocompatibility, chemical and photochemical stability and electrochemical activity. Manganese dioxide is a kind of metal oxide
nanoparticles that has been thoroughly investigated and applied in a large variety of applications especially in electrocatalysis due
to its superior electrochemical performance, environmentally friendly, easy preparation, low toxicity and lower cost [2, 3, 4].
Different methods have been used for preparation of MnO2 nanostructures. In the present study cyclic voltammetry was used for
electrodeposition of manganese oxide nanoparticles onto glassy carbon electrode modified with ionic liquid (IL) and chitosan
(Cs) biopolymer. Surface morphology of this modified electrode was studied by field emission scanning electron
microscoy(FESEM). The electrochemical behavior and stability of the modified electrode was investigated by cyclic
voltammetry technique. The modified electrode shows catalytic activity toward theophylline oxidation at pH range, 3-7. Finally
this modified electrode was used for micro molar detection of theophylline using differential pulse voltammetry technique.
Reference
[1] Y-H. Zhu, Z-L. Zhang, D-W. Pang, Electroanalytical Chemistry, 581 (2005) 303
[2] Y.H. Bai, Y. Du, J. J. Xu, H.Y. Chen, Electrochemistry Communications, 9 (2007) 2611
[3] Y. Lin, X. Cui, L. Li, Electrochemistry Communication, 7 (2005) 166
[4]Y. Li, H. Xie, J. Wang, L. Chen, Matterial Letters, 65 (2011) 403
A kinetic spectrophotometric method for determination of ultra trace amounts of novobiocin.
Mohsen Keyvanfarda*, Nazila Najjarianb
Department of Science, Majlesi Branch, Islamic Azad University, Isfahan, Iran
Department of Chemistry, Shahreza Branch, Islamic Azad University, Isfahan, Iran
Email: keyvan45638@yahoo.com
Novobiocin is an aminocyclitol antibiotic produced by Streptomyces niveus. Novobiocin is approved for use in dry dairy cattle as
a mastitis tube and as a premix for chickens and ducks. Novobiocin is available in combination with tetracycline and
prednisolone for oral use in dog. Highest concentration of novobiocin is found in the small intestine and liver. The drug is
approximately 90% protein bound and is distributed into milk. Novobiocin is primarily eliminated in the bile and faces.
Approximately 3% is excreted into the urine and urine level is usually less than those found in serum [1]. These, include HPLC
[2], Liquid chromatography tandem mass spectrometry (LC-ESI-MS/MS) [3]. These methods either lack sufficient sensitivity or
are time consuming. In order to overcome these problems, we developed and validated a rapid, sensitive and selective kinetic
spectrophotometric method for the determination of novobiocin. The method is based on the inhibition effect of novobiocin on
the reaction of amido black and periodate in acidic and micellar medium. The method development includes the optimization of
the reagent concentration and temperature. The reaction was monitored spectrophotometrically by measuring the decrease in the
absorbance of amido black at 615 nm with a fixed-time method. Under the optimum experimental conditions (H2SO4: 0.2 M;
CTAB: 1.4×10−3 M; amido black: 4.2×10−5 M; KIO4: 1.2×10−3 M and temperature of 30±0.1 °C) the decrease in the absorbance
of amido black is proportional to the concentration of novobiocin in the range of 4-32 ppb with a fixed time of 0.5-6.0 min from
the initiation of the reaction. The limit of detection is 3.7 ppb novobiocin. The relative standard deviation for the determination of
4, 8 and 12 ppb novobiocin was 0.14%, 0.41% and 0.75% respectively. The effects of certain foreign ions upon the reaction rate
were determined for the assessment of the selectivity of the method. The new developed method was found to have fairly good
selectivity and sensitivity. The method was applied to the determination of novobiocin in milk, human serum, and dog serum and
urine samples.
Refrence
[1]. www.elephantcare.org
[2]. K. Tsuji, P. D. Rahn, M. P. Kane, J. Chromatograp. A, 235 (1), 1982, 205-214.
[3]. K. Inoue, S. Nitta, T. Hino, H. Oka, J. Chromatograp. B, 877 (4), 2009, 461-464.
A new kinetic spectrophotometric method for the determination of sodium cromoglycate by its catalytic effect on the
reaction between amaranth and periodate in acidic and micellar medium
Mohsen Keyvanfarda*, razieh shakerib
Department of Science, Majlesi Branch, Islamic Azad University, Isfahan, Iran
Department of Chemistry, Shahreza Branch, Islamic Azad University, Isfahan, Iran
Email: keyvan45638@yahoo.com
Sodium cromoglycate, an antiasthma drug discovered during the 1960s, was found not to be a bronchodilator or an antagonist of
inflammatory mediators but it did inhibit the immediate response to allergen in a variety of in vitro and vivo experimental
models. It was an effective, inhaled, prophylactic drug in allergic and exerciseinduced asthma, showed promise as a steroidsparing drug, and inhibited immediate and. [1]. These, include LC-MS-MS [2], stripping voltammetric [3]. These methods either
lack sufficient sensitivity or are time consuming. In order to overcome these problems, we developed and validated a rapid,
sensitive and selective kinetic spectrophotometric method for the determination of sodium cromoglycate. The method is based on
the catalytic effect of sodium cromoglycate on the reaction of amaranth and periodate in acidic and micellar medium. The method
development includes the optimization of the reagent concentration and temperature. The reaction was monitored
spectrophotometrically by measuring the decrease in the absorbance of amaranth at 518 nm with a fixed-time method. Under the
optimum experimental conditions (H2SO4: 2.38 M; TBAB: 1.1×10−3 M; amaranth: 1.4×10−4 M; KIO4: 4×10−4 M and temperature
of 25±0.1 °C) the decrease in the absorbance of amaranth is proportional to the concentration of sodium cromoglycate in the
range of 4-36 ppb with a fixed time of 0.5-4.0 min from the initiation of the reaction. The limit of detection is 2.7 ppb sodium
cromoglycate. The relative standard deviation for the determination of 12, 20 and 28 ppb sodium cromoglycate was 0.40%,
0.32% and 0.53% respectively. The effects of certain foreign ions upon the reaction rate were determined for the assessment of
the selectivity of the method. The new developed method was found to have fairly good selectivity and sensitivity. The method
was applied to the determination of sodium cromoglycate in drug, human serum and urine samples.
Refrence
[1]. S. R. O'Donnel, F. R. Coulson, C. S. Bigg, Pulmonary Pharmacology & Therapeutics.13, 2000, 43-52
[2]. M. L. Ozoux, j. Girault, j. M. Malgouyat, O. Pasquier, J. Chromatograp. B 765, 2001, 179-185.
[3]. F. C. Pereira, A.G. Fogg, M. V. B. Zanoni, Talanta 60, 2003, 1023-1032.
Simultaneous determination of Cd, Pb in rice samples by closed-vessel microwave assisted digestion and differential pulse
anodic stripping voltammetry
Mahsa Ostad Gholami,a,b,c* Behrouz Janat d, Shahram Shoeibi b,c,d, Behrouz Akbaib,c,hosein rastegar b,c mohamad rasool hadiani b
a
Department of chemistry, Islamic Azad University of Shahr-e-rey unit, Tehran, I. R. Iran
b
Food and Drug Laboratories Research Center, Ministry of Health and Medical Education, Tehran, I. R. Iran
c
Food and Drug Control Laboratories, Food and Drug Deputy, Ministry of Health and Medical Education, Tehran, I. R. Iran
d
Food and Drug Deputy, Ministry of Health and Medical Education, Tehran, I. R. Iran
This work present, optimalization and apply closed-vessel microwave assisted digestion and differential pulse anodic stripping
voltammetry for simple and quick extraction and determination simultaneouse of the heavy metals lead and cadmium in trace
level concentration .Rice samples prepared by 5 ml concentration nitric acid 65% (HNO3) and 2 ml hydrogen peroxide 30% (
H2O2) with microwave digestion . mix of acetic acid and sodium acetat have been Widel recommended for supporting
electrolyte( PH = 4.8 ). The voltammetric parameters comprise: deposition potential, −1.20V; deposition time, 90 s; stirring
speed, 2000 rpm; scan rate, 0.059Vs−1; pulse amplitude, 0.05V and pulse duration, 0.04 s. The current–potential curves were
registered in the potential intervals of −0.66 to −0.56V and−0.48 to −0.35V, for Cd and Pb, respectively The recovery of Pb, Cd
in 3 concentration levels (n=3) was in range of 91.09 - 97.5% and 100 - 103.1 % respectively. The method was proved to be
repeatable with RSD lower than 15%. The limits of quantification for pb 9 ng/g and Cd 3 ng/g . Differential pulse anodic
stripping voltammetry was shown to be a simple, rapide, sensitive and selective method for Pb and Cd determination in sample
rice. Sample preparation is an important step to be considered and closed-vessel microwave assisted digestion was shown to be
adequate for organic matter destruction to the voltammetric.
Reference
[1] clinio locatelli ,Giancarlo torsi electroanalyical chemistry 509 (2001) 80-89
[2] Ilia rodushkin , Thomas ruth , asa huhtasaari analytica chemical acta 378 (1999)191-200
[3]Joaquim A. No´bregaa,*, Lilian C. Trevizana, Geo´rgia C.L. Arau´joa,b, Ana Spectrochimica Acta Part B 57 (2002) 1855–1876 Rita A. Nogueirab
[4] M´onica Cecilia Vargas Mamania, Luiz Manoel Aleixom Journal of Pharmaceutical and Biomedical Analysis 37 (2005) 709–713
Simultaneous Determination of Acetaminophen, Pseudoephedrine, and Dephenhydramine Maleate in Coldax Tablet by
the Aspect of Net Analyte Signal
HAJIAN, REZA, SALEH KAMAEI, ESMAT*
1- Department of Chemistry, Islamic Azad University, Gachsaran branch, Gachsaran, 75818-63876, Iran.
2- Department of Chemistry, Islamic Azad University, Gachsaran branch, Gachsaran, 75818-63876, Iran.
E-mail:esmatsalehkamaei@yahoo.com,Hajian@iaug.ac.ir
In this work a new modification of the standard addition method called "net analyte signal standard addition method (NASSAM)"
[1,2] has presented for the simultaneous spectrophotometric determination of Acetaminophen, Pseudoephedrine, and
Dephenhydramine in cold stop tablets. Because of the structural similarities, their spectra are highly overlapped and
determination of cold stop composition is not possible by direct spectrophotometry. Therefore, we used NAS aspect to solve this
problem. Because the vector of NAS is orthogonal to the spectra of interferents, its vector length is only depending on the analyte
present in the mixture. The proposed method combines the advantages of standard addition method with those of net analyte
signal concept. Therefore the norm of NAS can be directly correlated to the analyte concentration in standard addition plots.
Some advantages of NASSAM include simplicity, inexpensive, precise and affordable and it also requires no complex pretreatment. The limits of detection (LOD) for Acetaminophen, Pseudoephedrine, and Dephenhydramine were found 0.32 and 0.22
and 0.08 mol L-1 respectively. The pharmaceutical compounds were determined in concentration ranges of 5.0 ´ 10-6 -١.0 ´ 10-4
mol L-1 with the average recoveries of 99.4–100.5%.
Reference
[1] K. A. Zeynali, M. Bastami, Spect. Chim. Acta.75 (2010) 589.
[2] K. A. Zeynali, M. R. Majidi, M. Tahmasebpour, J. Serb. Chem. Soc.74 (2009) 789
Analysis of phenol in occupational air by solid-phase microextraction and post on-fiber derivatization in combination
with gas chromatography–mass spectrometry
Ali Es-haghi a*, Masoud Baghernejad b, Habib Bagheri b
Department of Physico Chemistry, Razi Vaccine & Serum Research Institute, P.O. Box 31975/148, Karaj, Iran
Department of Chemistry, Sharif University of Technology, P. O. Box 11365-9516, Tehran, Iran
Phenol is a widely employed chemical which is used as disinfectant and antiseptic in medicinal preparations such as mouthwash
and sore throat lozenges and in biotechnology derived products such as vaccines and antiserum. It is also a constituent of
phenolic resins and employed in the manufacture of nylon and other synthetic fibers [1, 2]. Phenol is absorbed into the human
body following dermal, oral or inhalatory exposure and is associated with headache, fainting, vertigo, and mental disturbances
[3]. To limit and control the potential exposure and the health risk of workers engaged in the production areas monitoring
programs of this volatile and risky compound are required. Hence, air sampling can be considered as a standard tool for
quantitative respiratory exposure risk assessment. Solid Phase MicroExtraction (SPME) is a well-known and powerful sampling
and sample preparation method which its feasibility for air-sampling has been shown previously [4]. The extraction efficiency of
SPME is predominantly determined by intermolecular and steric interactions between the analyte species and the extracting
phases. Among many different coating technologies sol-gel method has gained more attraction as it is simple, rapid, flexible in
coating composition, and coating operational stability [5]. In this study, a SPME method followed by on-fiber derivatization and
gas chromatography- mass spectrometry detection (GC–MS) was developed for the analysis of phenol in the air. The application
and feasibility of three different sol-gel based SPME fibers with different polarities, polar and nonpolar poly(dimethylsiloxane)
(PDMS) and polyethylene glycol (PEG), have been studied. Influencial parameters such as fiber coating type, type of
derivatization reagent, derivatization time and temperature, extraction time and desorption parameters were investigated and
optimized. The developed method is rapid, simple, easy and inexpensive and offers high detection sensitivity and reproducibility.
Under the optimized conditions, a detection limit of 5 ng L-1 and RSD of 5% at were obtained. Linear ranges were obtained in the
range of 20 ng L-1 to 500 µg L-1 with correlation coefficient of > 0.99. The optimized method was applied to the sampling of
phenol from the production area of tuberculin purified protein derivative of Razi Vaccine & Serum research institute.
Reference
[1] A.S. Whiteley, M.J. Bailey, Appl. Environ. Microbiol. 66 (2000) 2400.
[2] V. Arutchelvan,V. Kanakasabai, S. Nagarajan,V. Muralikrishnan, J. Hazard. Mater. 127 (2003) 238.
[3] Bruce W, Meek ME, Newhook R, J Environ Sci Heal C. 19 (2001) 305.
[4] G. Ouyang, J. Pawliszyn, Anal. Bioanal. Chem. 386 (2006) 1059.
[5] H. Bagheri, A. Es-haghi, M.R. Rouini, J. Chromatogr. B 818 (2005) 147.
Doehlert Design as a Response Surface Approach for Optimization of Removal of Pb(II) from aqueous solution by
Catalpa Speciosa Tree Leaves
T. Shariatmanesh, N. Asanjarani, J. Zolgharnein*
Department of Chemistry, Faculty of Science, University of Arak, Arak
Multivariate experimental design techniques are becoming increasingly widespread in analytical chemistry and other science.
Multivariate optimization, which allows the simultaneous study of several control variables, are faster to implement and costeffective than traditional univariate approaches. So we have stimulated to use this technique for optimization of removal of Pb(II)
from aqueous solutions by Catalpa Speciosa tree leaves as a new and efficient biosorbent. In order to reduce the large number of
experiments and achieving the highest removal efficiency of Pb(II), a set of full 23 factorial design were performed in duplicate
(16 experiments). The main interaction effects of the three factors including sorbent mass, pH and initial concentration of metalion were considered. By using Student’s t-test and analysis of variances (ANOVA), the main factors, which had the highest effect
on the removal process, were identified. Twenty-six experiments were designed according to Doehlert matrix design to obtain a
mathematical model describing functional relationship between response and main independent variables. The most suitable
regression model, that fitted the experimental data extremely well, was found according to the lack-of-fit-test and adjusted R2
value. Finally, after checking for possible outliers, the optimum conditions for maximum removal of Pb(II) from aqueous
solution were obtained. The best conditions were calculated to be: initial concentration of Pb(II) = 40 mg L−1, pH 4.9 and sorbent
amount equal to 27.3 g L−1. The applicability of different kinetic and isotherm models for the biosorption process was evaluated.
The nature of the possible Pb(II) and sorbent interactions was examined by the FT-IR technique. The potentiometric study
confirmed that the carboxylic group is the main active sites present in this tree leave which involved with Pb(II).
Reference
[1] J. Zolgharnein, A. Shahmoradi, M. R. Sangi, Talanta 76 (2008) 528–532
[2] F. Pagnanelli, M. Petrangeli Papini, , M. Trifoni, and F. Vegli, Environ. Sci. Technol. 34 (2000), 2773-2778.
[3] S. Schiewer, B. Volesky, Environ. Sci. Technol., 29 (1995) 3049-3058
[4] D. L. Massart, B. G. M. Vandeginste, L. M. C. Buydens, S. De Jong, P. J.Lewi, J. Smeyers-Verbeke, Handbook of Chemometrics and Qualimetrics, Part A,
Elsevier, Amsterdam 1997.
[5] J. ZolgharneinN. AsanjaraniS. N. Mousavi, Clean – Soil, Air, Water, 39 (2011) 250–258
Characterization and Multivariate Optimization of Adsorption of Ag + Onto Cersis siliquastrum Tree Leaves
T. Shariatmanesh, N. Asanjarani, J. Zolgharnein*
Department of Chemistry, Faculty of Science, Arak University
The Cersis siliquastrum tree leaves were introduced as a biosorbent for silver ion from aqueous solution in a batch system. The
effective variables such as: initial pH, temperature, initial metal ion concentration and sorbent amount were investigated.
Response Surface Methodology (RSM) as a multivariate optimization tool for maximizing the adsorption of Ag + was applied. A
quadratic empirical model was proposed during running of Central Composite Design (CCD) approach. The model adequacy was
checked by such diagnostic tests such as: analysis of variance (ANOVA), lack of fit, residuals distribution, and over-fitting tests.
The Langmuir isotherm was well fitted to experimental equilibrium data which describe the sorbent-sorbate behavior in aqueous
solution. Kinetic studies confirmed that the biosorption process followed the pseudo-second order model. The nature of silver
(I) and biosorbent interactions were examined by the intraparticle diffusion consideration and FT-IR and XRD spectra analysis.
In this study, finding the underlying mechanisms of silver ion binding to the biosorbent has been also interested. The FT-IR
spectrum and potentiometric titration analysis confirmed that carboxylic and amine groups are the main active sites of biosorbent
which involved in metal removal process. Some evidences such as: the Gibbs free energy value (∆G0), D-R isotherm parameters,
BET surface area and competitive role of alkaline and alkaline earth metal ions confirmed that metal uptaking by biosorbent was
mainly due to physical adsorption.
Reference
[1] J. Zolgharnein, Z. Adhami, A. Shahmoradi, S. N. Mousavi, Anal. Sci. 25 ( 2010) 111–116.
[2] M. Iqbal, A. Saeeda, S. Iqbal Zafar J.Hazard. Mater. 164 (2009) 161–171.
[3] F. Pagnanelli_, S. Mainelli, S.D. Angelis, L. Toro, Water Research 39 (2005) 1639–1651
[4] S. Schiewer, B. Volesky, Environ. Sci. Technol., 29 (1995) 3049-3058.
[5] N. Das, Hydrometallurgy 103 (2010) 180–189.
[6] M.A. Marin-Lara, F. Hernainz, M. Calero, G. Blazquez, G. Tenorio, Biochemical Engineering Journal 44 (2009) 151–159.
[7] J. Zolgharnein, N.Asanjarani, S. N. Mousavi, Clean – Soil, Air, Water 2011, 39 (3), 250–25
Determination of tramadol in body liquid using dispersive liquid-liquid microextraction by Gas chromatography- mass
spectrometry
Vahid Nasirian*,Saeed Habibollahi, Nahid Tavakkoli
Department of Analytical Chemistry, payame noor University, Iran
E-mail: vahid.nasirian@yahoo.com
Tramadol is a widely prescribed analgesic used in the treatment of moderate to severe pain. Tramadol was classified as a
"controlled drug" long after its approval for use in Iran. Analysis of drugs of abuse in urine has been used in routine forensic
toxicology as an alternative to blood in studying addiction history of drug abusers[1].In this work, dispersive liquid-liquid
microextraction was applied for preconcentration and determination of tramadol from body liquid. Dispersive liquid-liquid
microextraction (DLLME) has become a very popular environmentally benign,sample-preparation technique, because it is fast,
inexpensive, easy to operate with a high enrichment factor and consumes low volume of organic solvent[2]. In determination of
tramadol by GC-MS was used 2- nitro phenole as internal standard (IS). We operated for the qualitative analysis in scan mode
while for the quantitative analysis in SIM mode, selecting the ion m/z = 58, 263 for tramadol and m/z =139 for IS. For the
extraction, 1 ml dispersive solvent (ethanol) and 30.0 µl extraction solvent (carbon tetra chloride) was injected rapidly into a
glass tube with conical bottom containing aqueous solution of tramadol. This injection led to a cloudy water solution, caused by
the fine droplets dispersion of the immiscible extraction solvent in the aqueous sample. The final step of the microextraction
procedure, to collect dispersed tinny carbon tetra chloride droplets in the bottom of the conical test tube was centrifugation. In
order to obtain optimum condition of the extraction, parameters affecting on the extraction such as: extraction and dispersive
solvent type and their volume, salt effect, pH, ultrasonic waves effect, time of extraction, rate and time of centrifuging.
Consequently, after optimization, enrichment factor and limit of detection (LOD) were 346 and 0.9 ng/mL, respectively. Also
relative standard deviation (R.S.D), correlation coefficient and linear rang was 3.2 %(n=7) , 0.995 and 0.9-700 ng/mL
respectively. The proposed method was applied to the analysis of real samples such as: saliva, urine and plasma, successfully.
Reference
[1] M. Merslavic, L. zupancic-Krlig, J.of Chromatography B, 693 (1997) 222-227
[2] M. Rezaee, Y.Yamini, M. Faraji, J.of Chromatography A, 1217 (2010) 2342-2357
Fabrication of a Sol-gel and Gold nanoparticles modified carbon paste electrode based on N–Acetyl–L–Cystein for
potentiometric determination of copper ion
Mohammad Hossein Mashhadizadeh, Matineh Jalaeyan Mehri*
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
Chemical modification of electrode surfaces is a strategy for improving the analytical performance of conventional electrode
materials for specific applications, especially electroanalysis and sensors [1]. Gold nanoparticles (GNPs) have been demonstrated
to be very appropriate for the development of modified electrodes due to their good conductivity and excellent catalytic activity
and large surface area-to-volume ratios [2]. Sol-gel chemistry involves fabrication of materials through the hydrolysis and
condensation of suitable alkoxysilane precursors. It has a great popularity in the field of electrochemical sensors, because it
provides simple and unique low-temperature methodology to prepare a three-dimensional network suited for the encapsulation of
many different molecules [3]. In this paper we investigate the potentiometric behavior of Cu2+ carbon paste electrode modified
with Sol-gel and Gold nanoparticles based on N–Acetyl–L–Cystein as an ionophore. N–Acetyl–L–Cystein is a water-soluble
ionophore, therefore 3-(mercaptopropyl) trimethoxysilane (MPTS) was used for designing a three-dimensional interfacial
structure of Sol-gel in order to capture the ionophore. The electrode composition of 34 mg paraffin oil, 60 mg graphite powder, 6
mg N–Acetyl–L–Cystein as an ionophore in addition of 100 µl Gold nanoparticles and 100 µl Sol-gel exhibits the stable potential
response to Cu2+ ions over a concentration range of 1.4×10-6 to 4.4×10-2 M with a lower detection limit of 6.3×10−7 M and a
Nernstian slope of 29.1 mV decade−1 of Cu2+ activity. The potentiometric response of the electrode is independent of pH of test
solution in the pH range of 4.0-6.0. It has a fast response time of 5s and can be used for at least 40 days without any considerable
divergence in potentials. This sensor presented good selectivity and sensitivity towards the Cu 2+ ions over a wide variety of
cations including alkali, alkaline earth, transition and heavy metal ions. The proposed electrode was successfully used as a
potentiometric sensor for determination of copper ions in spiked and natural water samples.
Reference
[1] M. H. Mashhadizadeh, H. Khani, Anal. Methods, 2 (2010) 24.
[2] M. C. Daniel, D. Astruc, Chem. Rev., 104 (2004) 293.
[3] B. Wang, B. Li, Z. Wang, G. Xu, Anal. Chem., 71 (1999) 1935.
Simultaneous determination of dopamine, N-Acetylcysteine and folic acid at an acetaminophen ruthenium oxide nanoscale islands modified glassy carbon electrode surface
Fatemeh Chatraei*, Hamid R. Zare
Department of Chemistry, Yazd University, Yazd, 89195-741, Iran
E-mail: chatraee1@yahoo.com, hrzare@yahoo.com
A lot of research has been conducted in recent years on the attractive properties of nanoparticles and their electrochemical and
electrocatalytic behavior [1]. Due to different oxidation states of ruthenium, its compounds have been used as excellent electron
transfer mediators for modification of different electrode surfaces. Acetaminophen (AC) has been used comprehensively all over
the world as a pharmaceutical pain reliever. Also, N-Acetylcysteine (NAC), dopamine (DA) and folic acid (FA) are important
biological compounds. In the present work, we described the preparation of an AC ruthenium oxide nanoparticles (RNP)
modified glassy carbon electrode (AC-RNP-GCE) and its application for electrocatalytic determination of NAC in pH 7.0. The
reversibility of AC at AC-RNP-GCE surface is significantly improved in comparison with GCE alone. The charge transfer
coefficient, α, and the charge transfer rate constant, ks, for electron transfer between AC and AC-RNP-GCE were calculated as
0.52 and 15.57 ± 0.62 s-1, respectively. Differential pulse voltammetry (DPV) exhibits two linear dynamic ranges of 0.8 - 7.3 µM
and 7.3 - 1000.0 µM and detection limit of 6.3 µM for NAC. Also, we evaluated the analytical performance of the modified
electrode in quantification of NAC in the presence of DA and FA.
Reference
[1] H. Heli, M. Hajizadeh, A. Jabbari, A.A. Moosavi-Movahedi, Biosens. Bioelectron. 24 (2009) 2328.
Sensitive Spectrophotometric Determination of Diethyl phosphorodithioic acid Using CuO Nanoparticles
Mahboubeh Saeidi*, Reihaneh Aboutalebi
Department of Chemistry, Faculty of Science, Vali-e-Asr University of Rafsanjan, Iran
There is increasing interest in pesticide transformation products, because they can be present at higher level than the parent
pesticide itself [1].Analytical nanoscience and nanotechnology currently provide one of the most promising avenues for
development in analytical science derived from their two main fields of action, namely the analysis of nanostructure materials
and their use as tangible tools [2]. In this work a simple and effective spectrophotometric method for the determination of
transformation product of Ethion (Diethyl phosphorodithioic acid) using CuO nanoparticles in the presence of polyethylenglycol
(PEG) as a stabilizing agent is described. CuO nanoparticles were prepared according to the method described in literature [3].
The calibration curve derived from absorbance measurements at λmax = 417 nm were linear with concentration of Diethyl
phosphorodithioic acid in the range of 0.5 – 60 ppm. The detection limits (3σ), molar absorptivity, sandell´s sensitivity and
relative standard deviation (%RSD) were 0.0113ppm, 3724 L.mol-1cm-1,4.8 µg.cm-2 and 1.86%, respectively. The method was
successfully applied to the determination of Diethyl phosphorodithioic acid in water and soil samples.
Reference
[1] V. Andreu, Y. Pico′, Trends in Anal. Chem. 23(2004) 772
[2] M. Valcàrcel, B.M. Simonet, Anal. Bioanal. Chem.399 (2011)1-2
[3] R. Ranjbar-Karimi, etal. Physica B 405, (2010)3096-3100
Magnetic solid phase extraction of vitamin B12 from pharmaceutical real samples
*
Elham Tahmasebi, Yadollah Yamini*, Leila Ranjbar
Department of Chemistry, Tarbiat Modares University, P. O. Box 14115-175, Tehran, Iran
Vitamin B12 is an essential nutrient linked to human growth and cell development. Also, vitamin B12 is an important component
of several enzymes and is involved in the metabolism of certain amino acids [1]. Vitamin B12 deficiency results in pernicious
anemia and is also manifested by neurological changes which could culminate in brain damage [2]. In recent years, there have
been more interests in applying magnetic solid phase extraction (SPE) in sample preparation [3]. In this study, modified Fe3O4
nanoparticles by an anionic surfactant (sodium dodecyl sulfate (SDS)) were employed as an SPE adsorbent for extraction and
preconcentration of trace amounts of vitamin B12 followed by ICP-OES determination in different real samples. The main factors
affecting the extraction efficiency such as pH of the sample solution, amount of surfactant and adsorbent, extraction time, salt
effect and desorption conditions were investigated and optimized. Under the optimum conditions, preconcentration factor of 184,
linear dynamic range of 2.5-500 µg L-1 with good correlation of determination (R2>0.999), limit of detection of 1.0 µg L-1 and
relative standard deviation less than 6.2% were obtained. Finally, optimum conditions were applied for extraction of vitamin B12
from some pharmaceutical samples. The experimental results showed that the proposed magnetic solid phase extraction is simple
and efficient approach for analysis of trace amounts of vitamin B12.
Reference
[1] G.F.M. Ball, Bioavailability and Analysis of Vitamins in Foods, Chapmann & Hall, London, 1998, p. 497.
[2] Ball G.F.M., Vitamins in Foods, Analysis, Bioavailability and Stability, CRC Press, Boca Raton, FL, USA, 2006.
[3] X. Zhao, Y. Shi, T. Wang, Y. Cai ., G. Jiang, J. Chromatogr. A, 1188 (2008) 140–147.
A new triazene derivative, immobilized on the triacetyl cellulose membrane as an optical Ni2+ sensor
ElahehKhazaeli*, Kamal Alizadeh, Behrooz Rezaei
Department of Chemistry, Lorestan University, Falakolaflak St., Khorramabad, Iran
An optical sensor for the direct measurement of Nickel ion was developed. The basic element of this optode is the immobilization
of 1-p-tolyl-3-(3-(trifluoromethyl)phenyl)triaz-1-ene 1-oxide on a triacetyl cellulose membrane. Spectrophotometric studies of
complex formation between the triazene derivative, L and Ni2+, Zn2+, Mn2+, Cu2+, Cd2+, Co2+, Ag+, Hg2+, and Pb2+ metal ions in
non-aqueous solvents indicated a substantially larger stability constant for the Nickel ion complex. Consequently, the new
triazene derivative L was used as an appropriate ionophore for the preparation of a selective Ni2+ optical sensor, by its
immobilization on a transparent photographic film tapes. The effects of pH, reagent concentration and reaction time on the
immobilization of L were studied. A linear response curve was observed for the membrane sensor in Ni2+ concentration range of
1.15×10-9 – 4.44×10-5 M with an R2 value of 0.99 at pH=5.7. The detection limit(3σ) of the method for Ni2+ was 1.0×10-9 M. No
significant interference from 100 times concentrations of a number of potentially interfering ions was observed for the Nickel ion
determination. The sensor showed a good durability and short response time with no evidence of reagent leaching. The sensor
was successfully applied for the determination of Ni2+ in environmental water samples.
O
H
N
N
CF3
N
H3C
1-p-tolyl-3-(3-(trifluoromethyl)phenyl)triaz-1-ene 1-oxide, L
Reference
[1].K. Alizadeh, R. Parooi, P. Hashemi, B. Rezaei, M. R. Ganjali, J. Hazardous Materials, 186(2011)1794-1800.
[2].P. Hashemi, M.M. Abolghasemi, K. Alizadeh, R. Afzari Zarjani, Sens. Actuators B 129 (2008) 332.
Electrochemical Determination of Tyrosine at the Surface of Pyrolytic Graphite Electrode Modified with New Coccine
Multi-Walled Carbon Nanotubes
Saeed Shahrokhian* , Shiva Ebrahimi
Department of Chemistry, Sharif University of Technology, Tehran 11155-9516, Iran
A new tyrosine (Tyr) sensor has been fabricated by immobilizing new coccine (NC) at the surface of a pyrolytic graphite
electrode (PGE) modified with multi-wall carbon nanotubes (MWCNTs). Tyrosine (Tyr) is the precursor of dopamine, thyroxin
and neurotransmitters in mammalian central nervous systems [1]. Many methods have been applied for the measurement of
tyrosine [2],[3]. Some of these methods need multi-step sample clean-up procedures and are time-consuming, while some
methods need expensive apparatus. Recently, electrochemical methods have been found in many applications in the
determination of electroactive amino acids [4].The NC/MWCNT modified PGE shows enhanced voltammetric responses toward
Tyr electro-oxidation. Effect of different electrochemical parameters were investigated by linear sweep voltammetry (LSV).
LSVs of Tyr solutions were obtained at PGEs modified with MWCNTs and NC/MWCNT films, and also at a bare electrode.
There is a very small anodic peak for Tyr at the surface of the bare PGE. In these voltammograms, the peak current was enhanced
by a factor of 5 and 18 at the MWCNT/PGE and NC/MWCNT/PGE, respectively, compared to that at the bare PGE. In the
obtained optimum condition at the surface of the modified electrode (NC/MWCNT/PGE), two linear ranges 5.0×10−7–7.0×10-6
mol L−1and 7.0×10-6–7.0×10-5 mol L−1for the oxidation of the Try were obtained with the detection limit of 0.05 µM. The
proposed sensor showed excellent sensitivity, selectivity and stability in voltammetric responses. These excellent properties make
the prepared sensor suitable for analysis in pharmaceutical and clinical preparations.
Reference
[1] Q.Xu, SF.Wang, Microchim Acta 151 (2005) 47-52.
[2] C. J. Lee, J. Yang, Anal Biochem 359 (2006) 124-131.
[3] L. Sabine, P. G. Jean, S. Joelle, B. Bernard, J Chromatogr B 696 (1997) 9-17.
[4] S. M. MacDonald, S. G. Roscoe, Electrochim Acta 42 (1997) 1189-1200.
Development of cluod point extraction technique for preconcentration and spectrophotometric determination of trace
cetyl pyridinium chloride
1
Abedin Samira*1, Haydeh Baghery Sadeghi1, Ali Reza Zarei 2
Department of Chemistry, Central Tehran Brench,Islamic Azad University, 2 Department of Chemistry, Faculty of Materials, Maleke Ashtar
University of Technology, Tehran ,Iran.
Corresponding Author E_mail: abedinsamira@yahoo.com
Cetyl Pyridinium chloride(CPC) is a cationic quaternary ammonium compound in some types of mouth washes, tooth pastes,
lozenges, throat sprays, anti-sore throat sprays, breath sprays and nasal sprays. It is an antiseptic that kills bacteriaand other
micro- organisms. It has been shown to be effective in preventing dental plaque and rediucing gingivitis. It has also been used as
an ingredient in certain pesticides [1, 2]. In this work, a cloud point extraction method for the determination of trace amount of
CPC is described. The method is based on the color coupling reaction of CPC with NaOH in alkaline media and micelle
mediated extraction of yellow dye product using of nonionic surfactant Triton X114.Effects of reaction and extraction parameters
were studied and optimum parameters were stablished. Linearity was obeyed in the range of 0.5-450µg /ml of cetyl pyridinium
chloride.The
interference
effects
of
some
cations
anions
were
also
tested.
Reference
[1] Sergio Rodriguez-Morales, Xiang ZHOU, Hamid Salari,Rafael Castillo, Philip J. Breen, cesar M. Compadre Journal of choromatography 1062(2005)258-289 [2]
Riyad Ahmed Al_Okab, Akheel Ahmed Syed, Journal of molecular liquids 137(2008)110-115
Solid phase preconcentration of Cu (II) traces by modified octadecyl silica membrane disks with 1-(2-hydroxynaphtalene
1-eyl) ethane oxime and determination by flame atomic absorption spectrometry
Mehdi hosseini, Nasser Dalali*, Saeid Mohammadnejad
Phase Separation and FIA-Lab., Department of Chemistry, Faculty of Science, Zanjan University;
*Email: Nasser_zn@yahoo.com
Although trace amounts of copper is essential for mammals and plants, its higher concentration is a wide spread anthropogenic
polutant. Hence its determination is important [1]. Flame atomic absorption spectrometry is the main instrumental technique for
determination of this metal ion, but has low sensitivity. Solid phase extraction is a common technique with low consumption of
organic solvents used for preconcentration of most analytes [3]. In this work, a rapid, highly sensitive and selective method for
preconcentration/extraction of trace amounts of Cu (II) ions using C18-membrane disk modified with 1-(2-hydroxynaphtalene1eyl)ethane oxime and determination by flame atomic absorption spectrometry is presented. Extractions were performed with 47
mm diameter×0.5 mm thickness Empore membrane disks containing octadecyl-bonded silica. The synthesized ligand showed
selective behavior for separation of Cu (II) ion in presence of Cd (II), Ni (II), Co (II), Zn (II), Pb (II), Ag (I), Na (I), Mg (II), Al
(III), Mn (II), Cr (III) and Fe (III) ions. The effects of analytical parameters were investigated for optimization of the presented
procedure. Maximum capacity of the membrane disks modified by 4.0 mg of the ligand was found to be 420 μg of Cu2+ ion. The
breakthrough volume is larger than 2000 ml. The preconcentration factor was 200. The limit of detection is 0.14μg/L. The
method was applied to the recovery of Cu2+ ions from different water samples. Based on the obtained results, the determination
of Cu (II) ions yields quantitative recoveries. The system showed reproducibility and reliability in analytical data, with an RSD
value of lower than 3% on seven experiments. The modified membrane disk can be used for at least 20 experiments without any
loss in its sorption behavior. The system was successful in preconcentration of Cu (II) from large sample volumes (~2000 mL).
The method is simple, accurate and economical.
Reference
[1] Prasad, A.S.; Oberleas, D. Trace Elements in Human Health and Disease, Academic Press, 1976.
[2] Aranda, P.R.; Gil, R.A.; Moyano, S.; De Vito, I.; J. Hazard. Mater. 16 (2009) 1399–1403.
[3] Hosseini, M.; Dalali, N.; Karimi, A.; Dastanra, K.; Turk. J. Chem., 34(2010) 805-81
Di (n-propyl) thiuram disulfide bonded on structure silica gel as a novel sorbent for separation and preconcentration of
copper ion from aqueous samples
Mehdi Hosseini, Nasser Dalali*, Saeideh Fattah pour
Phase Separation and FIA-Lab., Department of Chemistry, Faculty of Science, Zanjan University, Zanjan
, *Email: Nasser_zn@yahoo.com
Copper is an essential element for enzymes, but above a healthy limit it accumulates in the liver, causing diarrhea, vomiting,
transpiration [1]. Frequently, a preconcentration step is required for the determination of ultra-trace amounts of copper by flame
atomic absorption spectrometry FAAS, due to its low sensitivity. Several methods have been proposed and used for
preconcentration and separation of trace elements [2]. Among them, solid-phase extraction (SPE) is one of the most effective
methods because of simplicity, rapidity and ability to attain a high concentration factor [3]. In this work, a newly synthesized
sorbent, di (n-propyl) thiuram disulfide bonded on silica gel, was applied for separation and preconcentration of copper ion from
aqueous samples. Factors influencing the sorption and desorption of copper ion were investigated. An aqueous solution
containing sodium thiosulfate was used as eluent in order to selectively desorb the adsorbed copper ion from the surface of the
sorbent. The effect of coexisting ions in binary mixtures, containing copper ion and the foreign ion, on percent recovery of
copper ion was investigated. The relative standard deviation under optimum conditions was 2% (n = 6). A glass cylinder packed
with 0.22 g of sorbent prepared was used as an operational column. Copper ion solution at pH 6.0 was passed through the
column. The adsorbed copper ion was eluted with 0.5M sodium thiosulfate solution with pH 5. Recommended system describes a
simple, rapid and economical method. Applied sorbent (DNTD/SG) in this system was better than silica gel (SG) itself for
efficient and selective separation and preconcentration of copper ions from aqueous samples. Fast adsorption and desorption
kinetic of the sorbent made a high flow rate possible with quantitative recovery of copper ion in a short period of time. A
preconcentration factor of 150 was obtained for enrichment of lower concentration levels of copper ions (0.01μg/mL) in aqueous
samples.
Reference
[1] Parmeggiani, L. Encyclopedia of occupational health and safety, in: Proceedings of the 3rd International Labor Organization, vol. 1, Geneva, 1983.
[2] Mizuike, A. Enrichment Techniques for Trace Analysis, Springer, Heidelberg, 1983.
[3] Hosseini, M.; Dalali, N.; Karimi, A.; Dastanra, K.; Turk. J. Chem. 34 (2010) 805-814.
Determination of phthalates during their removal in polluted soil in Tehran's Refinery by using phytoremediation and
qualitative analysis of produced metabolites in various times with GC-MS
Ravanbakhsh Shirdam* and Somayeh Hajipour
Assistant Professor, University of Environment, P.O. Box 31746-118, Karaj, Iran.
*E-mail: shirdamr@yahoo.fr
Phthalic acid esters (PAEs) which are widely used in the plastic, coatings, and cosmetics industries [1, 2]. They are distributed in
sediment, natural water, wastewater and soils. Even at very low concentration, they are suspected of teratogenic, mutagenic and
carcinogenic [3,4,5,6]. Phthalates can be removed by various methods. One of them is phytoremediation. In the present
investigation, it was hypothesized that different microorganisms may present different capabilities during phytoremediation of
soils and plants contaminated with PAEs [7]. The samples of petroleum-contaminated soils were collected from the south-east of
Tehran's refinery and transported to the laboratory in sterile bags. Plants were grown in the pots containing mentioned soils. The
plants were harvested and soil and plant samples were collected from each pot after 30, 60 and 120days. Mentioned samples were
extracted (EPA method 3550). For determining and measuring, PAEs were analyzed by using capillary column gas
chromatograph HP-6890N, equipped with a mass selective detector HP-5973 and an enhanced data analysis in SCAN mode. In
each period, peak of phthalates is decline gradually and finally after 120days, phthalate is removed from samples and there's no
indicator peak in their chromatograms. Phthalates with longer side chains than DEP are occasionally converted to those with
shorter chains by β-oxidation. Then, DEP is further converted to PA by two pathways, de-esterification and trans-esterification
pathway. Concentration of 4 significant PAEs (DEP, DBP, DiBP, DEHP) were determined by using external standards in 2
ranges (low and high concentration) and their calibration curves have been obtained for each compound by r2 greater than 0.9.
LOD, LOQ, RSD and recovery of the mentioned samples were calculated too. By using these parameters the method has been
valid. According to this study, phytoremediation is recommended as a good technology to remove these compounds from various
environments.
Reference
[1] Bodzek, M.; Dudziak, M.; Luks-Betlej, K. Desalination. 2004, 162, 121.
[2] Zeng, F.; Cui, K.; Xie, Z.; Wu, L.; Liu, M. Environmental Pollution. 2008, 156, 425.
[3] Dargnat, C.; Teil, M.; Chevreuil, M.; Blanchard, M. Science of the Total Environment, 2009, 407, 1235.
[4] Li, J.; Chen, J.; Zhao, Q.; Li, X.; Shu, W. Chemosphere. 2006, 65, 1627–1633.
[5] Shailaja, S.; Ramakrishna, M.; Venkata Mohan, S.; Sarma, P.N. Bioresource Technology. 2007, 98, 1561.
[6] Al-Mudhaf, H. F.; Alsharifi,F. A.; Abu-Shady A-S. L. Science of the Total Environment. 2008, xx, xxx-xxx.
[7] Meagher, R.B., 2000. Phytoremediation of toxic elemental and organic pollutants. Curr. Opin. Plant Biol. 3, 153–162.
Synthesis, Characterization, and Fluorescence Studies of N'-(2-aminobenzoyl)-3-hydroxy-2-naphthohydrazide and It
Zn(II), Ni(II), Co(II), Cu(II) Complexes
M.K.Papan*1,SH.Mozaffari ,N.Shahghobadi,M.Karimzade Yonjali
Department of Chemistry ,Payame Noor University(PNU),TEHRAN,IRAN
N'-(2-aminobenzoyl)-3-hydroxy-2-naphthohydrazide (H2L), and its Zn(II), Ni(II), Co(II), Cu(II) complex were synthesized. The
structures of the ligand were characterized by H-NMR,IR spectra and MASS spectrometry. The results show that the molecular
composition of these complexes is ML 1/2H2O and they are tetradentate complexes, in which the metal ions are coordinated by
three nitrogen atoms (-C-N) and one oxygen atoms (Ar–OH). The fluorescence of the ligand and its complexes in different
solvents and pH conditions have also been studied in details. An enhancement of the fluorescence intensity of the ligand can be
observed clearly in the presence of Zn(II), but quenching occurs for the other metal ions.
Reference
[1] Holm, R.H.; O’Connor, M.J. The stereochemistry of bis-chelate metal(II) complexes. Prog. Inorg. Chem. 1971, 14, 241–401.
[2] Hamada, Y.; Sano, T.; Fujita, M.; Fujii, T.; Nishio, Y.; Shibata, K. Blue electroluminescence in thin films of azomethin-zinc complexes. Jpn. J. Appl. Phys. 1993,
32 (4A), L511–L513.
[3] Kumar, D.V.G.; Weng, N.S.; Smith, P.J. Group IV organometallic compounds. IX. Preparation and spectroscopic studies of complexes of bis(bcarbomethoxyethyl)tin dichloride. Inorg. Chim. Acta 1981, 49
(2), 149–152.
[4] Wu, D.; Hurtubise, R.J. Fluorescence properties of 1-naphthol, 2-naph-thol and 1,2,3,4-tetrahydronaphthol in aqueous alcohol solvents with and without bcyclodextrin. Talanta 1993, 40 (6), 901–907.
[5] .Zhao, M.G.; Han, J.H.; Qi, J.S. A new method for the synthesis of oligoethyleneglycol ditosylates. J. ShanXi Univ. (in Chinese) 1992, 15 (4), 362–364.
[6] Zhao, M.G.; Han, J.H.; Qi, J.S. A new method for the synthesis of oligoethyleneglycol ditosylates. Chem. Abstr. 1993, 119, 249644.
[7] Atkinson, I.M.; Lindoy, L.F.; Matthews, O.A.; Meehan, G.V.; Sobolev, A.N.; White, A.H. New macrocyclic ligands. V. Synthetic, crystallographic and
computational studies of a new N2O6-heteroatom cage. Aust. J. Chem. 1994, 47 (6), 1155–1162.
Study of microstructre of nano cobalt coating obtained by pulse electrodeposition method
1
, M. Siadat Cheraghi, M. Karimzadeh Yonjali, N.shahghobadi * M.K.Papan
School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
Electrical deposition using pulse current in contrast to direct current is employed as a method for fabrication of more
homogeneous and denser coatings with a lesser amount of porosity. In this study, coating of cobalt by means of electroplating
using an acidic bath containing saccharin and also employing pulse and direct currents was investigated, and the effect of current
density on the coatings morphology were studied as well. Microstructural and compositional investigations of the fabricated
coatings were performed by employing SEM and XRD. The obtained results show that, by using pulse current, the deposited
coating would be more uniform, denser, and also more refined in comparison to the ones fabricated using direct current.
Moreover, by making use of a current density up to 100 mA/cm2, grain size values of the cobalt coating decreases at first, but on
further increasing of this parameter, the grain size values increases.
Reference
[1] M. S. Bhuiyan, B. J. Taylor, M. Paranthaman, J. R. Thompson and J. W. Sinclair, 'Microstructure and Magnetic Properties of Electrodeposited Cobalt Films',
Journal of Materials Science, 43,(2008),1644-1649.
[2] S.H. Kim, K.T. Aust, U. Erb, F. Gonzalez, and G. Palumbo, 'a Comparison of the Corrosion Behavior of Polycrystalline and Nanocrystalline Cobalt', Journal of
Scripta Materialia, 48,(2003),1379–1384.
[3] H. Nakano, K. Nakahara, S. Kawano, S.Oue, T. Akiyama and H. Fukushima, 'Effect of Electrolysis Factors on Crystal Orientation and Morphology of
Electrodeposited Cobalt', Journal of Applied Electrochemistry 32,(2002),43–48.
[4] O. E. Kongstein, G. M. Haarberg, and J. Thonstad, 'Current Efficiency and Kinetics of Cobalt Electrodeposition in Acid Chloride Solutions. Part I: The Influence
of Current Density, pH and Temperature', Journal of Appl Electrochem, 37,(2007),669–674.
[5] A. B. Soto, E. M. Arce, M. Palomar-Pardavé and I. González 'Electrochemical Nucleation of Cobalt onto Glassy Carbon Electrode from Ammonium Chloride
Solutions', Journal of Electrochimica Acta, 41,(1996), 2647-2655.
[6] L. Brossard, 'Cobalt black electrodes for the oxygen evolution reaction from electrolysis of 40 wt% KOH ', Journal of Hydrogen Energy, 17,(1992),671-676.
[7] S.S. abd el Rehim, Magdy A.M. Ibrahim and M.M. Dankeria 'Electrodeposition of cobalt from gluconate electrolyte', Journal of Applied Electrochemistry
32,(2002),1019–1027.
Comparison between the dispersive liquid-liquid micriextraction and cloud point extraction methods for extraction and
determination of Cu in environmental samples
Mostafa Golshekana, Shahab Shariatib,*, Parastou Azizic
Young Researchs Club, Rasht Branch, Islamic Azad University, Rasht, Iran
b
Islamic Azad University, Rasht Branch, Department of Chemistry, Rasht, Iran.
c
Payame Noor University, Abhar Branch, Department of Chemistry, Abhar, Iran.
a
Copper is both vital and toxic for many biological systems[1,2]. It plays an important role in environmental and health studies. In
the present study, tow simple and efficient extraction methods based on dispersive liquid-liquid microextraction (DLLME) and
cloud point extraction (CPE) prior to UV-Vis spectrophotometry were developed for the preconcentration and determination of
copper ions in environmental samples. Briefly, in both methods, cupperic ions (Cu II) were reduced to cupperous (Cu I) with
addition of hydroxyl amine hydrochloride and formed hydrophobic chelates with neocuproine. In DLLME method, a proper
mixture of acetonitrile (as dispersive solvent) and choloroform (as extraction solvent) was rapidly injected into the solution and a
cloudy solution was formed. After centrifugation, choloroform was sedimented in the bottom of conical tube and was diluted
with 100 µL of methanol for further UV-Vis spectrophotometry measurement. For CPE method, the copper was quantitatively
extracted from aqueous samples as neocuproine complex of it in the presence of Triton X-114 as a nonionic surfactant and
preconcentrated into the small volume (about 30 µL) of the surfactant-rich phase after centrifugation. For both extraction
methods, Orthogonal array design (OAD) was employed to study the effects of different parameters on the extraction efficiency.
A comparison between the figures of merit of the DLLME method and CPE method for extraction and determination of Cu are
summarized in Table 1. The results shown that, the DLLME method, applied in the present work, has some advantages in CPE
method including; easy of access, rapidly, simplicity and low cost of the extraction device. Finally, the accuracy of the proposed
method was successfully evaluated by determination of trace amounts of copper in different water samples and satisfactory
results were obtained.
Table 1.Comparison of the characteristic data between DLLME and CPE methods.
a
Method
SV (mL) a
LOD (µg L-1) b
R.S.D % c
PF d
Detection
DLLME
CPE
5
10
0.33
1.8
4.0
3.0
63.6
37.2
UV-Vis
UV-Vis
Sample volume
b
limit of detection
c
relative standard deviation
d
preconcentration factor
Reference
[1] I. H. Scheinberg, A. G. Morell, Ceruloplasmin, in: G.L. Eichhorn (ed.), Elsevier, New York, 1973, 1, 306-343.
[2] N. N. Greenwood, A. Earnshow, Chemistry of Elements, Pergamon, New York., 1984.
Model based multiway investigation of Neutral Red interaction with synthetic DNA using excitation-emission fluorescence
Mohsen Kompany-Zareh*, Nasrin Khajeh
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran.
Studying of binding interaction between drugs and deoxyribonucleic acid (DNA) are important not only in sense of mechanism
of approach of drugs, but also for guiding the design of new drugs.[1,2] DNA-intercalating molecules have played an important
role in the treatment of human cancer. Determination of binding constants is crucial in sense of mechanism approach[3,5].
Neutral Red (NR) is among intercalating drugs with double strand DNA [6, 7]. There is a pH dependent equilibrium between
protonated form (positive charged) and alkanolamine form (neutral) of NR, with pKa = 6.81 [8].In this research, the interaction
of NR with DNA under physiologic pH condition (pH =7.5) was monitored by changes in the intrinsic fluorescence of NR as a
result of complex formation. Two considered sequences of DNA were d (CCCCCCC) 2, d (ACACACA) 2. We abbreviate the two
sequences of DNA as CC-DNA and AC-DNA, for simplicity. Three-way data arrays were recorded by measuring excitationemission fluorescence during the normal and reverse titration of neutral red with DNA in constant pH. It is well known that the
fluorescence intensity of nucleic acid itself is very weak [9, 10]. So, the measured fluorescence intensity is from free NR
(protonated and deprotonated) and bound NR to the DNA.Three-way data arrays of both titration experiments were analyzed
individually and also simultaneously with the aid of soft and hard chemometrics methods. There was a rank deficiency in
concentration mode, because the equilibrium concentrations of protonated and alkanolamine forms of NR were linearly
dependent, when performing the titration in a constant pH. It was also the case for NR-DNA complexes. There was rank
deficiency in both emission and excitation modes, as well, that because of the high overlap in spectral profiles. So the soft and
hard methods resolved the resultant spectra of both forms of NR and formed complexes. At first direct trilinear decomposition
algorithm (DTLD) and then parallel factor analysis (PARAFAC) were used to evaluate concentration and spectral profiles of
components simultaneously present in the system. Soft methods were not able to analyze the system properly. Pseudo rank equal
to 3 in all three modes, especially in concentration mode and the resolved equilibrium concentration profiles suggested that both
1:1 and 2:1 complexes of two forms of NR with synthetics DNA oligomers can be formed, simultaneously. Hard-modelled
trilinear decomposition (HTD) method was used to estimate the equilibrium constants simultaneously. The results show that NR
(protonated and deprotonated) binds to DNA with two step binding mechanism. Resultant equilibrium constants of DNA.NR and
DNA.NR2 were estimated successfully, employing both simulated and experimental three-way data. The values for the resultant
equilibrium constants of both forms of NR with d (CCCCCCC) 2 DNA were in order of 105 and 1011 for complexation of 1:1 and
2:1, and The values for the resultant equilibrium constants both forms of NR with d (ACACACA) 2 DNA were in order of 105 and
1011 for complexation of 1:1 and 2:1, respectively. The different experiments of each sequence also evidence it. So mechanism
and stoichiometry of interaction of NR with DNA is same for different sequence.
Reference
[1] Y.T. Wang, F.L. Zhao, K.A. Li, S.Y. Tong, Anal. Chim. Acta, 396 (1999) 75.
[2] H.P. Xie, X. Chu, J.H. Giang, H. Cui, G.L. Shen, R.Q. Yu, Spectrochim. Acta Part A, 59 (2003) 743.
[3] L.P. Bai, Z.Z. Zhao, Z. Caib, Z.H. Jianga, Bioorg & Medicinal Chem., 14 (2006) 5439.
[4] J.F. Stoddart, Chem. Soc. Rev., 8 (1979) 85.
[5] I.O. Sutherland, Chem. Soc. Rev., 15 (1986) 63.
[6] Wei Sun, Maoxia Yang, Kui Jiao. Int. J. Electrochem. Sci. 2 (2007) 93.
[7] Xiue Jiang, Li Shang, Zhenxin Wang and Shaojun Dong. Biophys chem 118 (2005) 42.
[8] Zhenxin Wang, Zheling Zhang, Dianjun Liu, Shaojun Dong. Spectrochim Acta Part A 59 (2003) 949.
[9] Tarek M. El-Gogary, Eman M. El-Gendy. Spectrochim Acta Part A 59 (2003) 2635.
[10] Jesse J. Salk, J. Aquiles Sanchez, Kenneth E. Pierce, John E. Rice, Kevin . Soares , Lawrence J. Wangh. Anal Biochem 355 (2006) 157.
Decomposition of 2, 4-dichlorophnol by TiO 2 nanoparticles synthesized in presence of ultrasound irradiation
M. Heydari, M.A. Zanjanchi*, M. Arvand, R. Ansari
Department of Chemistry, Faculty of Science, University of Guilan, Rasht, Iran
TiO2 has a variety of functional applications including Photocatalysis. This material has been studied extensively in recent years
as a photocatalyst to deal with environmental pollution, water purification, wastewater treatment, and hazardous waste control
and air purification [1]. Titania has three different crystalline phases; rutile, anatase and brookite, among which rutile is in the
thermodynamically stable state while the latter two phases are in the metastable state [2]. When solutions are exposed to strong
ultrasound treatment, bubbles are implosively collapsed by acoustic fields in the solution. High-temperature and high-pressure
fields are produced at the center of the bubbles. The collapse of bubbles generates localized hot spots. .This effect is known as
acoustic cavitation. More uniform dispersion of the nanoparticles, higher surface area, better thermal stability and phase purity
are some of the advantages of ultrasonication method [3].In this work,
TiO2 nanoparticles were synthesized by the ultrasound treatment. The precursor material was titanium chloride. The effect of
ultrasound treatment on the crystalline and morphology of the products were fully investigated. By varying the ratio of water and
TiCl4 in the synthesis solution dominate phase of Titania changed. The XRD pattern of the sample with rutile phase is shown in
Fig.1. The behavior of Titania in photocatalytic decomposition of 2, 4-dichlorophenol in aqueous solution was studied (Fig.2).
With this photocatalyst, 2, 4-dichlorophenol will be degraded in nearly 2h time.
Reference
[1] W. Guo, Z. Lin, X. Wang, G. Song, Microelectron Eng 66 (2003) 95.
[2] Y.K. Sung, S.C. Tae, H.S. Chae, Catal Lett 118 (2007) 224.
[3] P.S. Awati, S.V. Awate, P.P. Shah, V. Ramaswamy, Catal Commun 4 (2003) 393.
Linear sweep Voltammetric Determination of isosorbide dinitrate (ISDN) using electrochemically surface manipulated
nano gold electrode
Behrooz Zargar*, Hooshang Parham and Kaveh Movlaee
Chemistry department, Faculty of Sciences, Shahid Chamran University, Ahvaz, Iran
A nanostructure thin film was formed on a gold working electrode using continuous pulsed-potential method. This modified
electrode was exploited as a sensitive detection system for the determination of isosorbide dinitrate (ISDN). Reduction peak
current of ISDN was used for determination by linear sweep voltammetric method. It was demonstrated that this proposed
method could be easily used for the analysis of ISDN in pharmaceutical samples. To evaluate the validity of the proposed method
obtained data were compared with those obtained from HPLC method and well agreement between results was seen. Effects of
various parameters on the system have been optimized. Under the optimum conditions, this method showed linear dynamic range
from 0.16 to 800 (µg mL−1) with a calibration equation of Ip=0.010C-0.006 (R2=0.999), where C is the concentration of ISDN in
µg mL−1 and Ip is the peak current in µA. Limit of detection (3Sb/m) and limit of quantification (10Sb/m) were calculated to be
0.037 and 0.12 µg mL−1, respectively. RSD for 8 times analysis of 10 and 600 µg mL−1 of ISDN are 1.4% and 3.2% respectively.
To our knowledge, the proposed method showed lower LOD with respect to other electrochemically reported methods.
Reference
[1] B. Rezaei, S. Damiri, Electochim. Acta, 55 (2010) 1801.
[2] H. Siyu, L. Xinyu, L. Qingyu, M. Mianwu, L. Tengfa, W. Hongqiang, J. Zhiliang, Materials Letters, 64 (2010) 2296.
[3] A.K. Wanekaya, W. Chen, N.V. Myung, A. Mulchandani, Electroanalysis 18
(2006) 533.
[4] W. Yang, J.J. Gooding, D.B. Hibbert, J. Electroanal. Chem. 516 (2001) 10.
The removal of lead ions by nano-porous of silica aerogel synthesized by using sodium silicate precursor
Hamid RezaPouretedal* and MaryamKazemiZahrani
Islamic Azad University, ShahrezaBranch, Shahreza, Iran
The pollution of water resources with heavy metals has been causing worldwide concern in the last few decades. Namely, some
metals can have toxic or harmful effects on many forms of life. Wastewater from many industries contains one or more toxic
heavy metals [1, 2]. Metals that are significantly toxic to human beings and ecological environments are cupper (Cu), mercury
(Hg), chromium (Cr), lead (Pb), manganese (Mn), cadmium (Cd), etc. In adsorption processes, adsorbents with high specific
surface areas are needed. Small pores, such as micropores and mesopores, result in large specific surface area responsible for
adsorption. Pore size, pore distribution and surface area, as well as pore surface chemistry, are the major factors in the adsorption
process [3,4].Furthermore, one of the most important properties of silica aerogels is also the possibility to modify their surface
chemical nature with the incorporation of organic functional groups[5]. Industrial-grade waterglass (sodium silicate solution) was
used as a source of the cost-effective silica sols. Aqueous colloidal silica hydrosol obtained from the ion-exchange of an
industrial waterglass that was used as an inexpensive starting material. After gelation and aging, the poreswater of silica hydrogel
was sequentially exchanged with n-Hexane by multiple solvent exchanges using acetone as an intermediate exchanging solvent.
Surface modification of gel surface was controlled using organosilane. Surface-modified gel was carefully dried at atmospheric
pressure. The ability of modified silica aerogel with organosilane to remove Pb(II) from aqueous solutions was assessed using
batch adsorption technique under equilibrium conditions. Adsorbent exhibits very high adsorption potential for heavy metal ion
and the removal of more than 85%was achievedat optimized conditions.
Reference
[1] L.Hartiger,Handbuch der Abwasser – und Recycling technics Munchen, Carl HanserVerlag, Wien, 1991.
[2] R.T. Yang, Adsorbents: fundamentals and Application, WileyInterscience, 2003.
[3] S.W. Hwang, H.H. Jung, S.H. Hyun, Y.S. Ahn, J. Sol-Gel Sci. Technol. 41 (2007) 139.
[4] A.P. Rao, A.V.Rao, G.M. Pajonk, Appl. Surf. Sci. 253 (2007)6032.
[5] T. Chaisuwan, T. Komalwanich, S. Luangsukrerk, S. Wongkasemjit, Removal of heavy metals from model wastewater by using polybenzoxazine aerogel,
Desalination 256 (2010) 108-114.
Novel method for determination of carbamate pesticides in water samples by TCIL-dispersive liquid–liquid
microextraction combined with high performance liquid chromatography
a
Mohammad Saber Tehrania, M. H. Givian-Rada, Leili Akhoundia*, Mahmood Akhoundi b
Department of Chemistry, Islamic Azad University, Science and Research Branch,Tehran, Iran. bshahid Beheshti Univercity
*Akhoondi239@yahoo.com
A novel method for the determination of carbamates pesticides (metolcarb, carbofuran, carbaryl, methiocarb, tiodicarb,
propoxure and methomyl) in water samples was developed by tempreture controlled ionic liquid dispersive liquid–liquid
microextraction (TCIL-DLLME) using [C6MIM][PF6] as an extraction solvent prior to analysis by high performance liquid
chromatography whit UV detection (HPLC-UV). Some experimental parameters that influence the extraction efficiency were
studied and optimized to obtain the best extraction results. Under the optimum conditions for the method, the calibration curve
was linear in the concentration range from 0.1 to 10 ng mL-1 for all the carbamates pesticides, with the correlation coefficients
(r2) varying from 0.981 to 0.998. Good enrichment factors were achieved ranging from 20 to 48-fold, depending on the
compound. The limits of detection (LODs) (S/N = 3) were ranged from 0.05 to 0.1 ng mL_1 for six carbamates. The proposed
method offers advantages in reduction of the exposure danger to toxic solvents used in the conventional liquid–liquid extraction,
simplicity of the extraction processes, rapidity, and sensitivity enhancement. The method has been successfully applied to the
analysis of the pesticide residues in environmental water samples.
Reference
[1] Chen Y., Guo Z. Wang X. Qiu C., (2008), j. Chromatogr. A,
[2] H. Sheikhloie, M. Saber-Tehrani, P. Abrumand-Azar, S. Waqif- Husain, Acta Chromatographica ,
2009, 21, 577-589.
[3] B. K. Kgamer, D. B. Ryan. Proceeding of the 2000 Confreences On
Hazardouse Waste Research.,
[4] L.Sun, H. K. Lee. J. Chromatoger. A. 2008, 1014, 165
N. V. Plechkova. K. R. Sseddon. Chem. Scie. Vol. 37(2008)123. ]5[
[6] J.Vichapong, R. Burakham Talanta. 2011, xxx-xxx.
Electroactivity and electrochromic properties of polyaniline/sulfonated polyaniline composite at different pH.
Masdarolomoor F.* , Wallace G. G.
* Shahrood university of Technology, Chemistry Department.
Polyaniline (PAn) is an important conducting polymer with electrochemical characteristics. The electrochemical behavior of PAn
is related to the switching between different oxidation states, leucoemeraldine, emeraldine (the conducting form) and
pernigraniline. These three oxidation states have different colors resulting in electrochromic properties of polyaniline. The
electrochemical and electrochromic properties of PAn are limited to acid electrolytic media 1. In this study, sulfonated polyanion,
poly(2-methoxyaniline-5-sulfonic acid) (PMAS) was used as dopant for PAn 2 providing an acidic microenvironment to stabilize
PAn. The pH effect on electroactivity and electrochromics of PAn/PMAS was investigated. PAn/PMAS films were evaporatively
cast onto GC or ITO glass electrodes from an aqueous dispersion of PAn/PMAS and characterized by cyclicvoltammetry. The
PAn/PMAS films were found to be electroactive in the pH range 1 to 7. During the potential scan from -0.2 V to 0.9 V a color
change from pale yellow to green to dark blue was observed at pH 1, 2 and 3, however at pH 4 and 5, switching between green
and blue was observed. The results are promising for applications requiring mild conditions.
Reference
[1] Yin-Hou Chena, Jau-Yann Wua and Yi-Chang Chung, Preparation of polyaniline-modified electrodes containing sulfonated polyelectrolytes using layer-by-layer
techniques. Biosensors and Bioelectronics,Volume 22, Issue 4, Pages 489-494
[2] Masdarolomoor, F., Innis, P.C., Ashraf, S., Kaner, R., and Wallace, G.G., Nanocomposite of polyaniline/poly(2-methoxyaniline-5-sulfonic acid). Macromolecular
Rapid Communications, 2006, 27(23): p. 1995-2000
Preparation and characterization of electrochemically co-deposited silica sol-gel/copper nanocomposite and their
application as a novel SPME stationary phase and its application through extraction of some pollutants
P. Abroomand-azarã , M. Saber-tehrani, S. Mohammadi-azar
Islamic Azad University, Department of Chemistry, Science and Research Branch, Tehran, Iran
Solid-phase microextraction (SPME) developed by Belardi and Pawliszyn [1, 2]. This technique is based on distribution of the
analytes between the sample (or its headspace) and the stationary phase coated on a solid support (fiber). Notwithstanding
various advantages of SPME, conventional fibers of this method encounter with many drawbacks such as [3]: (a) low
recommended operation temperature; (b) instability in organic solvents (particularly in use with LC); (c) stripping of coating; (d)
short lifetime of fibers and (e) finally their high cost. The reasons of these disadvantages are the lack of the proper chemical
bonding of stationary phase coating with the fiber surface, and the relatively high thickness of the conventional fibers [4]. In this
study electrochemically co-deposited of silica sol-gel/copper nanocomposite introduced as a novel and single-step technique for
the preparation of efficient and unbreakable SPME fibers that have strong interaction between the substrate and the coating. The
prepared nanocomposite films are used as SPME fibres and their applicability was evaluated through extraction of some
polycyclic aromatic hydrocarbons (PAHs) from the headspace of aqueous samples. The different parameters that affect the
structure and composition of the deposited films including applied potential, electrodeposition time and precursor concentrations,
also parameters affecting the extraction efficiency such as extraction temperature, extraction time and salt content were
optimized. The results showed that morphology and grain size of the films are strongly affected by the ratio between the sol-gel
monomer and copper ions. Furthermore, the potential of deposition also affects the composition of the films as it controls the
kinetics of sol-gel/copper co-deposition. Characterization of the deposited films was accomplished by scanning electron
microscopy and FT-IR.
Reference
[1] Belardi R. P., Pawliszyn J., Water Pollut. Res. J. Can., 24 (1989)179–191
[2] Arthur C. L., Pawliszyn J., Anal. Chem., 62 (1990)2145–2148
[3] Kumar A., Gaurav, Malik A. K., Tewary D. K., Singha B. Anal Chim Acta, 610 (2008) 1–14
[4] Sarafraz-Yazdi A., Sepehr S., Es’haghi Z., Piri Moghadam H., chromatographia, 72 ( 2010) 923–931
Multiwavelength Specrophotmetric Determination of Stability constants of 2-(o-Arsenophenylazo)1.8dihydroxynaphthalene 3,6disulphonic acid with Th(IV), U(IV) and Zr(IV) Ions in organic-water Mixed Solvent
a
Sh.Lotfi*,a, Sh.Ghahri saremi a, J.Ghasemib
Department of Chemistry, faculty of science, Payame Noor University(PNU), Iran
b
Department of Chemistry,faculty of science, K.N. Toosi University, Tehran, Iran
Email:Sh.lotfei@gmail.com
The important stability constants in analytical chemistry is not doubt. In a complicated mixture, Knowledge of the
thermodynamic stability constants of possible reaction that may occur within that mixture, together with the concentrations of the
reactants, enables the existence and concentration of resulting species to be determined [1,2]. The toxic effect of some metals in
the environment becomes enhanced when any derived complexes can be leached by underground water from a mine, land-fill
site, or wast dump [3]. The complexation reactions between 2-(o-Arsenophenylazo)-1.8dihydroxynaphthalene 3,6disulphonic
acid (Arsenazo) and Th(IV), U(IV) and Zr(IV) ions at 25oC and 0.1M ionic strength and constant pH are performed in mixed
aqueous solvents of ethanol (EtOH), dimethylsulfoxide(DMSo) spectrophotometrically. The spectrophotometry data obtained
were processed through the software SQUAD to calculated the complecxation constants of the metal-indicator and to establish an
adequate base of the models which considered the structure of the indicator, and the actual metal species in the aqueous solution.
Surprisingly as percent of organic solvent increases in solution, the stability constants decreased. This trend can be attributed to
the stabilization of the components involved in the complextion reaction by the constitutes of the solvent mixtures.
Reference
[1] D.J. Leggett, S.L. Kelly, L.R.Shiue, Y.T.Wu, D.Chang, K.M.Kadish Talanta 30 (1983) 579.
[2] M. Meloun, J. Čapek, P. Mikšík, R.G. Brereton, Anal. Chim. Acta 423(2000)51.
[3] A.E. Martell, R.J. Motekaities, Determination and Use of Stability Constants, Verlag Chemie Weinheim, 1988.
Spectrophotometric Determination of Acidity Constant of Alizarin Red S (ARS) in Water and Water-Surfactant Micellar
Media Solutions
a
Sh.Lotfi*,a,Sh.ghahri saremi a,s.shiri b
Department of Chemistry, faculty of science, Payame Noor University(PNU), Iran
b
Department of Chemistry, high school secretary, Ilam, Iran
Email:Sh.lotfei@gmail.com
Aqueous micellar media are widely used in different areas of analytical chemistry and several reviews concerning their analytical
applications have been published [1,2]. One important property of micelles is their ability to solubilize a wide variety of
compounds which are insoluble or slightly soluble in water. Another important effect of micellar systems is that they can modify
reaction rates and, to some extent, the nature of the products [3]. Acid dissociation constants are important parameters to indicate
the extent of ionization of molecules in solution at different pH values. The acidity constants of organic reagents play a
fundamental role in many analytical procedures such as acid-base titrations, solvent extraction, complex formation, and ion
transport [4]. The acidity constants of Alizarine Red S in water, water-Triton X-100, water-Triton X-114 and water-CTAB
micellar media solutions at 25 ◦C and an ionic strength of 0.1M have been determined spectrophotometrically. To evaluate the
pH-absorbance data, a resolution method based on the combination of soft- and hard-modeling is applied. DATAN program
applied for determination of acidity constants. The absorption spectra of Alizarine Red S in pure water at various pH values at
350–700 nm intervals were recorded. The pKa1 is changed slightly in different percentages of X-100 and X-114, but pKa2 values
increase and, beyond that, pKa2 values almost not changed. The pKa1 values are increased with increase of CTAB percentages
and pKa2 values increase and, beyond that, pKa2 values almost not changed. However, results show that, the effect of surfactant is
seen in the spectra of HL− than H2L and L2− species, These changes are due to the hydrophobic and electrostatic interactions of
reactants with micellar aggregates.
Reference
[1] W.L. Hinze, in: W.L. Mittal (Ed.), Solution Chemistry of Surfactants, vol. 1, Plenum Press, New York, 1979.
[2] E. Pellezzeti, E. Pramaura, Anal. Chim. Acta 117 (1980) 403.
[3] E. Pellezzeti, E. Pramaura, Anal. Chim. Acta 128 (1981) 273.
[4] A. Niazi, M. Ghalie, A. Yazdanipour, J. Ghasemi, Spectrochimica Acta Part A 64 (2006) 660.
Mixed micelle-mediated cloud point extraction used for spectrophotometric determination of tramadol in the human
blood and urine samples
a
Sharam.Lotfi*,a, Arash.Babakhanian b,sabah shiric
Department of Chemistry, faculty of science, Payame Noor University(PNU), Iran
b
Department of Chemistry,faculty of science, razi University, Iran
c
Department of Chemistry, high school secretary, Ilam, Iran
Email:Sh.lotfei@gmail.com
Tramadol is an analgesic drug with a similar chemical structure to codeine. Its analgesic effect is mediated through inhibition of
noradrenaline re-uptake, both increased release and decreased re-uptake of serotonin in the spinal cord, and a weak effect on mu
opioid receptors [1]. Several analytical methods for determination of tramado and its metabolites have been used such as gas
chromatography [2], mass spectrometry and fluorescence detection [3]. All these methods used are sophisticated and high cost in
the laboratory studies. In this novel study, coupling the cloud point extraction strategy as a preconcentration method with the
spectrophotometric monitoring device was used to detect the trace amount tramadol . The mixture of a nonionic surfactant
(Triton X-114) and a cationic surfactant (CTAB) was utilized as a suitable micellar medium for preconcentration and extraction
of tramadol. Tramadol was extracted with 0.3 (w/v) Triton X-114 and 0.5 ml of 1*10 -5 mol L−1 CTAB at pH= 9 The enriched
mass was dissolved in the appropriate amount of DMF solvent and determined by the spectrophotometer at the wavelength 389
nm. Enrichment factor of was obtained for the preconcentration of target molecule. Under the optimal conditions, linearity was
obeyed in the ranges of 55–570µgL−1 of tramadol concentration. The interference effect of a few interferes such as vitamins,
amino acids, sugars, and metal ions on the extraction efficiency of tramadol were tested. Finally, the optimized conditions
developed were successfully utilized for the determination of tramadol in the human blood and urine samples with satisfactory
results.
Reference
[1] Stamer UM, Stuber F. Analgesic efficacy of tramadol if coadministered with ondansetron. Anesth Analg 2001;93:1626.
[2] Poulsen L, Arendt-Nielsen L, Brosen K, Sindrup SH. The hypoalgesic effect of tramadol in relation to CYP2D6. Clin Pharmacol Ther 1996;60:636—44.
[3] Ceccato A, Vanderbist F, Pabst J-Y, Streel B. Enantiomeric determination of tramadol and its main metabolite O-desmethyltramadol in human plasma by liquid
chromatography-tandem mass spectrometry. J Chromatogr B 2000;748:65–76.
Simple and Reliable Method for Determination of Melamine Residue in Milk Powder by Reversed Phase HighPerformance Liquid Chromatography with uv Detection
Ali Roozbahani٭
Nuclear Science Research School, Nuclear Science and Technology Research Institute
P.O.BOX: 11365-3486- Tehran- Iran
Melamine (MEL, 1,3,5-triazine-2,4,6-triamine, C3H6N6) is a nitrogen-rich chemical (66.7% by mass). Because of this property,
it has been illegally used as the food additive to increase the apparent protein content in food products. Kjeldahl test is the
traditional method to measure the protein content. However, Kjeldahl test determines the protein content only by analysing total
nitrogen content, without identifying its sources. Melamine has low oral acute toxicity. But the chronic administration of high
concentrations can induce renal pathology and even death, especially in babies and children. In the spring of 2007, MEL
contaminated pet food sickened or killed thousands of cats and dogs in the United States. In September 2008, MEL-contaminated
milk powders even led to health problems for thousands of infants in China. In this study a simple, precise and accurate method
for the determination of melamine residue in milk powder is developed using reversed phase high-performance liquid
chromatography. The separation is performed on a C18 column (250mm×4.6mm I.D., 5µm particle size) at 30ºC. The mobile
phase (10mM Heptane-1-sulfonic acid sodium salt/ACN 80:20) is pumped at a flow rate of 0.5mLmin−1 with detection at 240
nm. The conditions of the extraction, and separation were investigated and optimized. The linearity is satisfactory in the range of
0.1–50 µg/mL with a correlation coefficient of 0.9998. Under the optimal conditions, the method limit of detection (LOD) and
method limit of quantification (LOQ) were 45 µg /kg and 140 µg /kg, respectively. The recovery of melamine for milk powder
samples spiked with 0.20–5 mg/kg was in the range of 83–101% with the RSDs (n = 3) of 3.1–4.9%.
Reference
[1] Melamine-contaminated powdered formula and urolithiasis in young children.
Guan, N. The New England Journal of Medicine, 360(11), (2009), 1067–1074.
[2] A sensitive and validated method for determination of melamine residue in liquid milk by reversed phase high-performance liquid chromatography with solidphase extraction
Hanwen Sun, Lixin Wang, Lianfeng Ai, Shuxuan Liang, Hong Wu. Food Control 21 (2010) 686–691
[3] A rapid, acetonitrile-free, HPLC method for determination of melamine in infant formula Gopalakrishnan Venkatasami, John R. Sowa Jr Analytica Chimica Acta
665 (2010) 227–230
[4] Analytical methods and recent developments in the detection of melamine
Fengxia Sun, Wei Ma, Liguang Xu, Trends in Analytical Chemistry 29, No. 11, (2010)1239-1249
Removal of anionic dye eosin Y from aqueous solution using modified montmorillonite
Shahla Elhami*, Ladan Esmaeilzadeh
Department of Chemistry, Science and Research Branch, Islamic Azad University, Khuzestan, Iran
*E-mail: Sh.elhami@ khouzestan. Srbiau.ac.ir
Adsorption on inorganic or organic matrices, decolorization by photocatalysis[1], chemical precipitation, chemical oxidation [2]
and cloud point extraction [3] are among the techniques employed for the removal of dyes from wastewaters. Adsorption has
been found to be superior to other techniques for wastewater. Consequently, cheaper and more economic adsorbents were
considered or developed, including clays and clay minerals. Eosin is anionic dye (C20H6Br4Na2O5) in nature and highly toxic [4].
EosinY, a heterocyclic dye containing bromine atoms is used in the fields of dyeing, printing, leather, printing ink and fluorescent
pigment, etc [5]. In this study, adsorbent prepared from montmorillonite and modified with diethylenetriamine are both
environmentally friendly. Adsorbent was successfully used to remove the eosin from an aqueous solution in a batch system. The
Na-MMT and modified montmorillonite was characterized by XRD, and FT-IR. The effect of solution pH (pH=4), adsorbent
dosage(8g/L), contact time(30 min), agitation rate (80 rpm) and initial dye concentration(100mg/L), on adsorption of eosin have
been studied. The Langmuir and Freundlich adsorption models were studied to describe the isotherms, and the data fitted well
with Freundlich model.
Reference
[1] Sh. Zhao, J. Li, L. Wang, X. Wang, Degradation of Rhodamine B and Safranin-T by MoO3:CeO2 Nanofibers and Air Using a Continuous Mode Clean: Soil, Air,
Water, 2010, 38,268.
[2] C. E. G. Ilha1, A.J. M. G. dos Santos, J. R. SouzaDe, Degradation of Monoazo Pigments Red 53:1 an Red 48:2 by Fenton, Photo-Fenton and UV/Peroxide
Reactions, Clean: Soil, Air, Water,2009,37,799.
[3] N.Pourreza, Sh.Elhami, Removal of malachite green from water samples by cloud point extraction using Triton X-100 as non-ionic surfactant, Environ. Chem.
Lett. 2010,8,53.
[4] MK Purkait M.K. Purkait, S. DasGupta and S. De J Environ Manage. 2005,76,135-142
[5] Reza Ansari* and Zahra Mosayebzadeh IRAN POLYM J .2010,19,541-551
Preconcentration of Cadmium with Solid Phase Extraction using modified sawdust
and its Determination by Flame Atomic Absorption Spectrometry
Shahla Elhami*, Shahnaz karami
Department of Chemistry, Science and Research Branch, Islamic Azad University, Khouzestan, Iran
*E.mail:Sh.Elhami@Khouzestan.Srbiau.ac.ir
Cadmium is a highly toxic element and usually found in trace amount environmental samples. A new method of solid phase
extraction (SPE) was applied to preconcentration of trace amount of cadmium prior to their determination by flame atomic
absorption spectrometry (FAAS). In recent years, separation and preconcentration methods have been reported, in which the
common adsorbents of cadmium were active carbon modified [1], microcrystalline naphthalene [2]. In this study a new adsorbent
for determination of ultratrace level of cadmium in various matrices was modified. Adsorbent prepared from sawdust and
modified with diethylentriamine are both environmentally friendly. Scanning electron microscope (SEM) and fourier transform
infrared spectroscopy (FTIR) result of sawdust were compared to modified sawdust. This method is based on the fact that Cd (II)
forming in aqueous phase cadmium tetrachloride complex (CdCl42-) and adsorption of the cadmium (II) complexes on a column
containing modified sawdust then elute from column with nitric acid solution and determination by FAAS. The preconcentration
factor was 100 (5mL elution volume) for a 500 mL sample volume, it's comparable to other methods [3, 4]. The effect of pH
(pH=4), type of buffer (format buffer), volume of buffer (2mL), concentration of elute (2M), sample value, weight of adsorbent
(0.3g) and interfering ions have been investigated. The method was applied to determination of cadmium in different samples.
Reference
[1] K. Chalapathi, G. P. Maddaiah. J. Chem. Pharm. Res, 2010, 2 (2), 27-35
[2] H.Cesur, B.Bati. Turk J chem. 26 (2002), 29-35.
[3] G.Xiang, Y.Huang ,Y.Luo, J.Microchim Acta.(2009),165,273-242.
[4] N. Y. Sreedhar, P. R. Prasad, M. S. Nayak, D. Rekha, C. N. Reddy. Bull. Korean Chem. Soc. (2007), 28, 1375
Chemically deposited silica sol-gel on TiO2 nanotube array/Ti wire as a highly porous and efficient SPME fiber
P. Abroomand-azarã , S. Mohammadi-azar, M. Maghsoodi-shorabi, M. Saber-tehrani
Islamic Azad University, Department of Chemistry, Science and Research Branch,Tehran,Iran
Solid phase microextraction (SPME) is a relatively new technology that has attracted considerable attentions due to its high
sensitivity, rapidity, simplicity and free of solvents [1]. It is evident that future advancements in SPME technology greatly
depend on new breakthroughs in the area of new coating material developments and new techniques for their deposition. Maybe
one of the simplest methods to increase SPME fibers efficiency is coating of stationary phase on porous supports. In this project
we used a nanoporous support for preparation of SPME fibers for the first time. Liu et. al. [2] prepared highly oriented TiO2
nanotubes on Ti wire by an electrochemical (potentiostatic anodization) method in a two-electrode electrochemical cell. In this
study a silica based sol-gel was coated on highly oriented TiO2 nanotubes on Ti by dip-coating methodology and used as a highly
porous and efficient SPME fiber. The prepared fibers characterized for their surface morphology, porosity, and film thickness
using Scanning electron microscopy (SEM) and FTIR. SEM analysis revealed the thin and nanoporous film formation on the
wire surfaces. The efficiency of fibers was evaluated through extraction of some polycyclic aromatic hydrocarbon (PAH)
compounds. Several methods were used to support modification for increasing its adherence to stationary phase. Then some
parameters affecting extraction efficiency such as extraction temperature, extraction time and salt content were optimized. The
results confirmed the higher porosity and subsequently their higher efficiency rather than previous fibers that prepared on metal
or silica supports.
Reference
[1] C.L. Arthur and J. Pawliszyn, Anal. Chem., 1990. 62.
[2] H. Liu , D. Wang ,L. Ji , J. Li , S. Liu , X. Liu , S. Jiang, J. Chromatogr. A, 2010, 1217.
Spectrophotometric simultaneous determination of tyramine,tryptamine and dopamine in real samples
by orthogonal signal corection-partial rest squares regression
H. Khajesharifi1*, .A. rahmanian2 , M. Sadeghi1
Department of Chemistry, Yasouj University, Yasouj
2
Department of Chemistry, Islamic Azad University, Firuzabad
1
Email:khajeh_h@yahoo.com
This work describes a quantitative spectroscopic method for the analysis of ternary mixtures of tyramine (TY), tryptamine (TP),
and dopamine (DP) using multivariate data models based upon ultraviolet spectroscopy. By multivariate calibration methods,
such as partial least squares regression(PLS) and its combination with orthogonal signal correction(OSC), it is possible to obtain
a model adjusted to the concentration values of the mixtures used in the calibration range. The calibration model is based on
absorption spectra in the 200-260 nm range for 36 different mixtures of TY, TP and DP. The calibration graphs were linear in the
concentration range of 5.2092-138.912, 1.6022–42.066 and 5.6892-151.712 µgmL−1for TY, TP and DP, respectively. The limit
of detection was found to be 0.9, 0.13and 0.28 µgmL−1L for TY, TP and DP, respectively. The NPC for TY, TP and DP were 4,
3, and 5, and PRESS were 7.1318, 4.3454, and 8.9245, respectively. Evaluation of the prediction errors for the prediction set
reveals the OSC-treated data give substantially lower root mean square error of prediction (RMSEP) values than original data.
Both methods were applied to the quantitative evaluation of TY, TP and DP in laboratory and pharmaceutical samples, and
produced satisfactory results.
Reference
[1] Thienpont L, Van Landuyt K, Stoeckl D, Saeyens W, de Keukeleire D (1995) J Chromatogr B 665:63
[2] Kochancsky C, Strein T (2001) J Chromatogr B 747:217
[3] Murakita H (1988) J Chromatogr 431:471
[4] M. Izquierdo-Pulido, A. Marin´e-Font, M.C. Vidal-Carou, J. Food Sci. 59 (1994) 1104.
[5] M.H. Silla-Santos, Int. J. Food Microbiol. 29 (1996) 213.
[6] M.C. Vidal-Carou, A. Ambatlle-Espunyes, M.C. Ulla-Ulla, A. Marin´e Font, Am. J. Enol. Vitic. 41 (1990)
160.
Electrochemical Monitoring of Photoelectrocatalytic Degradation of Rhodamine B Using TiO 2 Film Modified Graphite
Electrode
Reza Ojani*, Jahan-Bakhsh Raoof, Ebrahim Zarei
Electroanalytical Chemistry Research Laboratory, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran
E-mail: fer-o@umz.ac.ir
Among the various semiconductor photocatalysts, TiO2 has attracted due to its ready availability, non-toxic nature,
photochemical properties and effective catalytic activity. However, there are two inherent problems in using TiO2 particle
suspensions for toxic water purification such as the difficulty of separating and recovering the photocatalyst particles from
aqueous phase [1] and a very low quantum yield (less than 10% in generally) due to high degree of recombination between
photogenerated charge carriers (electrons and holes) [2], in which TiO2 particles behave as short-circuited microelectrodes under
band gap excitation. To solve the problems, researchers after many efforts and attempts carried out photoelectrocatalytic
oxidation as an advanced oxidation method by applying a positive potential bias to TiO2 film. The externally applied anodic bias
can withdraw the excited electrons to a counter- electrode and results in a decrease in the recombination rate of photogenerated
electrons and holes [3]. In this work a commercially available TiO2 powder (Degussa P25) has been used to prepare film on
graphite plates. The photoelectrochemical degradation of rhodamine B as a model was investigated using this photoelectrode.
Direct photolysis (DP), electrochemical oxidation (EC), photocatalytic (PC) and photoelectrocatalytic (PEC) degradation of
rhodamine B were compared at the surface of this electrode. The effects of applied potential, pH and initial rhodamine B
concentration on the photoelectrocatalytic degradation of rhodamine B using ultraviolet (UV) illuminated TiO2/graphite film
electrode were examined and discussed. Results show that the best responses for PEC are obtained at applied potential 1.2 V vs.
Ag/AgCl/KCl (3M), pH 4.0 and initial rhodamine B concentration 4.2 mg L-1.
Reference
[1] A. Choi, W. Termin, M.R. Haffmann, J. Phys. Chem. 98 (1994) 13669.
[2] C. Kormann, D.W. Bahnmann, M.R. Haffmann, Environ. Sci. Technol. 25 (1991) 494.
[3] X.Z. Li, F.B. Li, C.M. Fan, Y.P. Sun, Water Res. 36 (2002) 2215.
Improvement cleaning performance towards protein soils in laundry detergents by immobilization everlase on the silica
nanoparticles
a
Majid Soleimani a, Azam Khania, kolsoom Najafzadehb
Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran
b
Department of Instrumental laboratoary, Mahde taban, Qazvin, Iran
This work aims to understand the effect of immobilization enzyme on nanoparticles and how such immobilization affect
enzyme’s performance as catalysis in detergents for enhancing removal of soils. The silica nano particles were employed as
supports for immobilization of everlase and immobilized everlase was used at the formulation of detergent powder. Then effect
of everlase immobilization on the removal of protein based soil was investigated in cotton fabrics as the soil model. Also free and
immobilized everlase stability compared toward temperature and humidity. UV spectrometer and FTIR analysis for investigation
immobilization process and the laundering performance for quantification enzymatic activity toward the soil substrate are used.
The results show that, the stability and also cleaning efficiency of immobilized enzyme on protein soil in cotton fabric is much
more than free enzyme.
Stripping Voltammetry of Cerium (IIl) with a Chemically Modified Carbon Paste Electrode Containing Functionalized
Nonporous Silica Gel
Hamid Khoshsafara*, Mehran Javanbakht b
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
b
Department Of Chemistry, Amir Kabir University, Tehran, Iran
a
Nanoporous the silica-based organic-inorganic hybrids are attractive electrode modifiers, because they are usually highly porous
solids made of a mechanically stable inorganic backbone displaying large specific surface areas, which are likely contain a high
number of organic functional groups accessible to external reagents or analytes[1-3]. This research introduces the design of an
adsorptive stripping voltammetric method for the cerium(III) determination at a carbon paste electrode, chemically modified with
dipyridyl-functionalized nanoporous silica gel (DPNSG-CPE). The electroanalytical procedure comprised two steps: the Ce(III)
chemical accumulation at −200 mV followed by the electrochemical detection of the Ce(III)/dipyridyl complex, using anodic
stripping voltammetry. The factors, influencing the adsorptive stripping performance, were optimized including the modifier
quantity in the paste, the electrolyte concentrations, the solution pH and the accumulation potential or time. The resulting
electrode demonstrated a linear response over a wide range of Ce(III) concentration (1.0–28 ng mL−1). The precision for seven
determinations of 4 and 10 ng mL−1 Ce(III) was 3.2% and 2.5% (relative standard deviation), respectively. The prepared
electrode was used for the cerium determination in real samples and very good recovery results were obtained.
Reference
[1] Mehran Javanbakht, Hamid Khoshsafar, Mohammad R. Ganjali, Alireza Badiei, Parviz Norouzi and Abed Hasheminasab, Determination of Nanomolar
Mercury(II) Concentration by Anodic-Stripping Voltammetry at a Carbon Paste Electrode Modified with Functionalized Nanoporous Silica Gel, current analytical
chemistry, 2009, 5, 35-41
[2] M.R. Ganjali, H.A. Zamani, P. Norouzi, M. Adib, M. Rezapour,M.Aceedy, Zn2+ PVC-based membrane sensor based on 3-[(2-furylmethylene)amino]- 2-thioxo1,3-thiazolidin-4-one, Bull. Korean Chem. Soc. 26 (2005) 579–584.
[3] M.R. Ganjali, H.A. Zamani, P. Norouzi, M. Adib, M. Accedy, Novel calcium sensor based on [2-(2-hydroxyphenyl)imino]-1,2-diphenylethanone, Acta Chim.
Slov. 52 (2005) 309–316.
[4] H.A. Zamani, G.h. Rajabzadeh, M.R. Ganjali, S.M. Khatami, Highly selective and sensitive copper(II) membrane sensors based on 6-methyl-4-(1phenylmethylidene) amino-3-thioxo-1,2,4-triazin-5-one as a new neutral ionophore, Electroanalysis 24 (2005) 2260–2265.
Solid Phase Extraction And Atomic Absorption Determination Of Trace Amount Of
Ni(ІІ) in Water Samples
Soleimani, Majid * , khani, Azam
Department of chemistry , Imam Khomeini International UniversityQazvin , Iran
E-mail : m-soleimani@hotmail.com;a.khani1359@gmail.com
A simple, highly sensitive, accurate and selective method for the determination of trace amounts of Ni+2 ions in water samples is
proposed. The method is based on the separation and preconcentration of Ni+2 on octadecyle silica column 2,2´ Diamino-4,4´
Bithiazole (DABTZ) as a new ligand. For this, metal complex with DABTZ chelate was retained on the column. The retained
analytes on the column were recoverd with 3.5 ml of Methanol. The metal ion in effluent were determination by atomic
absorption spectrometry. The optimum preconcentration conditions have been investegated . The obtained recovery was nearly
90 to 95 by elution of the column octadcyl silica column with minimal amount of solvent and concentration factor of
121achieved by passing 400 ml of sample through of the column . The relative standard deviation ( 3 replicate analyte ) %2.02
was obtained. The limit of detection, sensitivity and correlation coeffition of the proposed method are 14.87-1 ng· mL-1, 6.48
µg·mL-1 and 0.994, respectively.
Preparation and characterization of Ni/porous carbon composite (Ni-C) structures as a new material for electrochemical
supercapacitor
a
A.R. Madrama, F. Khasheib*
Department of Applied Chemistry, Malek Ashtar University of Technology, Isfahan, Iran.
b
Department of Chemistry, Payame Noor University, Isfahan, Iran.
E-mail:khafm@yahoo.com
Electrochemical double layer capacitors, also called supercapacitors, store energy using either ion adsorption (EDLC) or fast
surface redox reactions (pseudo-capacitors). Recently, supercapacitors have attracted interest as an energy storage device with
high power density, high charge/discharge cycle life and high energy efficiency. Supercapacitors are able to store and deliver
energy at relatively high rates (beyond those accessible with batteries) because the mechanism of energy storage is simple
charge-separation (as in conventional capacitors). The vast increases in capacitance achieved by supercapacitors are due to the
combination of: (A) an extremely small distance that separates the opposite charges, as defined by the electric double-layer; (B)
highly porous electrodes that embody very high surface-area. In this research work, the cathodic electrodeposition method was
used for the deposition of composite Ni/porous carbon (Ni-C) on copper substrate. The electrodeposition of Ni-C electrodes was
performed in a two-step method under optimized conditions: first a layer of Ni was deposited on copper from bath (i) including
1.14M NiSO4.6H2O, 0.19M NiCl2.6H2O, 0.49M H3BO3, at 25 oC, PH 4.6, and a current density of 22 mAcm-2 for 30 min. In the
final step (ii) 8 gL-1 porous graphite carbon powders with 1 µm average size of particles, was added to the bath (i), and
electrodeposition was performed at a current density of 16 mAcm-1, 25 oC for 3 h, to prepare Ni-C composite electrode. However,
this approach is characteristic with binder-free processing: the use of binder is undesirable for the fabrication of composite
electrodes, since binder can be attributed to cause an increased resistance and reduced specific capacitance (SC). The prepared
electrodes were studied using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), cyclic
voltammetry (CV) and electrochemical impedance spectroscopy (EIS). We have introduced a simple and low cost method for
preparation of the Ni-C composite electrodes as a new material for supercapacitors. The prepared Ni-C materials showed
moderately specific capacitance (~30 mF cm-2) that can be used in some commercial low power supercapacitors.
Reference
[1] R. Karimi Shervedani, A.H. Alinoori and A.R. Madram, J. New Mat. Electrochem. Systems, 11, 259-265 (2008).
[2] R. Karimi Shervedani, A.H. Alinoori and A.R. Madram, J. Hydrogen Energy 33, 2468-2476 (2008).
Preconcentration of Copper with Solid Phase Extraction using modified sawdust
and it’s Determination by Flame Atomic Absorption Spectrometry
Shahla Elhami*, Marjan Sharifi
Department of Chemistry, Science and Research Branch, Islamic Azad University, Khouzestan, Iran
*E-mail: Sh.elhami@ khouzestan. Srbiau.ac.ir
Preconcentration step prior to determination of copper ions is usually necessary, because of low levels of copper in
environmental samples. Nevertheless, several techniques for the preconcentration or determination of copper have been proposed
including activated carbon [1], diacetyl monooxime [2], modified microcrystalline naphthalene [3], modified silica gel [4] and 4phenylenediamine propyl silica xerogel [5] as sorbents. In this study, a new adsorbent for determination of ultratrace level of
copper ion in aqueous sample by atomic absorption spectrometry was modified. Adsorbent prepared from sawdust and modified
with diethylenetriamin are both environmentally friendly. Scanning electron microscope (SEM) and Fourier transform infrared
(FTIR) results of sawdust were compared to modified sawdust with diethylenetriamin. The analyte was adsorbed on modified
sawdust as (CuCl42-) complex. The adsorbed metal complexes were then eluted from the column with a nitric acid solution and
determined by flame atomic absorption spectrometry (FAAS). The effect of different variables such as pH(pH=4), concentration
of reagent(0.08M), the concentration of the eluent(1M), amount of sorbent (0.2g), type of buffer(format buffer), buffer
volume(4mL), etc, on the quantitative recoveries of copper ion were investigated. The effects of interfering ions on the retention
of the analyt were also examind.The method is simple, accurate and economical. It was applied for determination of copper ion in
deferent samples with satisfactory results.
Reference
[1] Tehrani M S, Rastegar F, Parchehbaf A,Rezvani Z. Chinese J Chem, 2005, 23, 1437.
[2] Ghaedi M, Shokrollahi A, Ekrampour F, Aghaei R.Bull Chem Soc, 2009, 23, 337.
[3] Cesur H and Bati B. Turk J Chem, 2002, 26, 599.
[4] Matoso E, Kubota L T and Cadore S. Talanta, 2003, 60, 1105.
[5] Vaghetti J C P, Zat M, Bentes, K R S, Ferreira L S, Benvenutti E V and Lima E C.
J Anal At spectrum, 2003, 18, 376.
Simultaneous extraction / separation of zinc and cadmium from nickel
and cobalt with liquid membranes using aliquat 336
Nasser Dalali*, Hadi Habibi, Fereidoon Rahmani
*Corresponding author: Phase separation &FI-Lab, Chemistry Department, Faculty of Sciences, Zanjan University, Zanjan, Iran
Email:Nasser_zn@yahoo.com
Separation of metal ions from a mixture of cations and selective removal of a particular cation from an aqueous stream are of
interest in a variety of fields, such as the recovery of precious metal ions from the waste, hydrometallurgy, etc. The separation
methods used include precipitation, solvent extraction, chromatography and membrane separation. Of all these techniques, the
membrane separation technology is of interest [1].The membrane separation method is of interest as it has several advantages
over other separation methods like cost effectiveness, energy efficient and offers a high pre-concentration factor with a high
degree of selectivity. They have shown great potential, especially in the cases where solute concentrations are relatively low and
other techniques cannot be applied efficiently, since they combine the processes of extraction and stripping in a single step
operation [2]. Quaternary ammonium salts exist as stable cation–anion pairs over a wide range of pH. Aliquat336 has been
studied extensively for extraction of metal chloride complexes [3]. The work presented is aimed at the recovery of cadmium and
zinc from zinc plants waste. Extraction and separation of zinc and cadmium from nickel and cobalt from chloride solutions across
a bulk liquid membrane by using aliquat336 as carrier dissolved in chloroform has been studied. The effect of the fundamental
parameters influencing the transport process, e.g. concentration of chloride and concentration of target ions in the feed phase,
carrier concentration and type of organic solvent in the membrane, type of stripping reagent in the receiving phase, and time
dependency of the process has been investigated and discussed. The transported amount ions (initial concentration 1×10−4 M, 10
ml) from a 0.6 M sodium chloride solution across chloroform solution of aliquat336 (0.025 M, 20 ml) into the receiving phase
(distilled water, 5 ml) was found to be 95.80%, 91.34%, 0.356% and 0.46% for Cd, Zn, Co and Ni, respectively after 4 h.
Reference
[1] J. Ramkumara, S.K. Nayakb, B. Maiti , J. Memb. Sci. 196 (2002) 203–210.
[2] T.R. Reddy, J. Ramkumar, S. Chandramouleeswaran, A.V.R. Reddy, J. Mem .Sci. 351 (2010) 11–15.
[3] B. Wassink, D. Dreisinger, J. Howard, Hydrometallurgy 57 (2000) 235–236.
Determination of PAHs from saffron samples with solid phase microextraction fiber based on sol–gel technique using gas
chromatography-flame ionization detection
Ali Sarafraz-Yazdi*, Feryal Ghaemi, Amirhassan Amiri
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Iran
E-mail: asyazdi@.um.ac.ir
A method for the determination of polycyclic aromatic hydrocarbons (PAHs) in aqueous saffron sample by direct immersion
solid-phase microextraction (DI-SPME) and gas chromatography-flame ionization detector (GC-FID) has done for the first time
using sol-gel technique that was applied for preparation of SPME coating fiber for extraction. In this work SPME fiber based on
sol–gel technique which were made with poly(ethylene glycol) modified with multi walled carbon nanotubes (MWCNT). SPME
is an innovative, solvent free extraction method that is fast, economical and versatile. This technique is based on the partition
equilibrium of target analytes between the sample matrix and a polymeric stationary phase coated on the surface of a fused silica
fiber. The sol–gel coating technique offers important advantages compared to conventional SPME coatings. The porous structure
of the sol–gel coating offers a high surface area; allowing high extraction efficiency and the coating composition can be altered
with a relative ease to give different selectivity characteristics. Strong adhesion of the coating on the support due to chemical
bonding is a very important characteristic which increases the coating stability toward organic solvents and high desorption
temperatures. MWCNTs have high surface area, ability to establish π–π interactions, excellent chemical, mechanical and thermal
stability, etc. make them very attractive as adsorbents in SPE and SPME devices. Some parameters affecting extraction efficiency
were optimized. Parameters affecting extraction efficiency, such as: SPME fiber coating, desorption time, desorption
temperature, extraction time, stirring speed and salting effect were investigated and optimized. Under the optimal conditions, the
detection limits (S/N=3) were 0.001–0.01 ng mL–1. The relative standard deviations (R.S.D.) for one fiber (Repeatability) (n=5)
were obtained from 2.1 up to 7.3% and between fibers or batch to batch (n=3) (Reproducibility) in the range of 6.9–8.9%.
Reference
[1] R. P. Belardi, J.B. Pawliszyn, Water Pollut. Res. J. Can., 24 (1989) 179.
[2] C. L. Arthur, J. Pawliszyn, Anal. Chem., 62 (1990) 2145.
[3] A. Sarafraz-Yazdi, S. Sepehr, Z. Es’haghi, H. Piri Moghadam, Chromatographia, 72 (2010) 923.
[4] A. Sarafraz-Yazdi, H. Piri Moghadam, Z. Es’haghi, S. Sepehr, Anal. methods, 2 (2010) 746.
Development of dispersive liquid–liquid microextraction for concentration of Cu2+, Cd2+ and Co2+ metal ions in real
samples and determination by FAAS
Mehdi Hosseini, Haghigheh Fathi, Nasser Dalali*
Separation and FIA-Lab ., Department of Chemistry, Faculty of Sciences, Zanjan University, Zanjan Email:Nasser_zn@yahoo.com
In spite of substantial technological advances in analytical field, most instruments cannot directly handle complex sample
matrixes yet. As a result, a sample-preparation step is commonly involved before instrumental analysis [1]. The main aim of
sample preparation is to clean up and concentrate the analytes of interest, while rendering them in a form that is compatible with
the analytical system. Dispersive liquid–liquid microextraction (DLLME) was introduced by Assadi and co-workers in 2006 [2].
It is a simple and fast micro extraction technique based on the use of an appropriate extractant, i.e., a few micro liters of an
organic solvent such as chlorobenzene, chloroform or carbon disulfide with high density and a disperser solvent such as
methanol, acetonitrile or acetone with high miscibility in both extractant and aqueous phases [3]. A fast, simple and efficient
method for the separation/preconcentration of Cd(II), Cu(II) and Co(II) metal ions was developed using dispersive liquid–liquid
microextraction (DLLME) technique. The procedure is based on complexation of Co(II) with 1-nitrozo 2-naphtol and dithizone
for Cd(II) and Cu(II), then extraction of the complex using DLLME technique. Some important parameters analytical were
investigated and optimized in detail. Under the optimum conditions, the calibration graphs were linear over the range of 5-500, 51000 and 10-500 µg l−1 for Cd(II), Cu(II) and Co(II), respectively. Limit of detection (LOD) were obtained 2.5, 3.0 and 1.4 µg
l−1, respectively. Relative standard deviations (R.S.D) for 6 replicate determinations of metal ions at 10 µg l−1 concentration level
were calculated to be 1.4, 3.6 and 1.3, respectively. The method was successfully applied to real water samples the amounts of
implicit metal ions found in these samples using the proposed method were similar with those obtained by a standard method.
Reference
[1] M. Hosseini, N. Dalali, A. Karimi, K. Dastanra, Turk .J. Chem., 38 (2010) 805.
[2] M. Rezaee, Y. Assadi, M.R. Milani Hosseini, E. Aghaee, F. Ahmadi, S. Berijani, J. Chromatogr. A, 1116 (2006) 1.
[3] Wen-Hsien Tsaia, Hung-Yi Chuang, Ho-Hsien Chen, Joh-Jong Huang, Hwi-Chang Chend, Shou-Hsun Chengd, Tzou-Chi Huanga, Anal. Chim. Acta, 656 (2009)
56.
On-line cloud point extraction coupled to FAAS for concentration of trace amounts of copper (II) ions in presence of
Indane-1,2,3-trone 1,2-dioxime
Mehdi Hosseini, *Nasser Dalali, Saeid Mohammadnejad, Mina Sadrara
Phase Separation and FIA-Lab., Department of Chemistry, Faculty of Science, Zanjan University, Zanjan
Nasser_zn@yahoo.com
A powerful technique to effectively enhance atomic absorption spectrometry’s sensitivity and selectivity is flow injection on-line
analyte preconcentration and matrix elimination [1,2]. Cloud point extraction (CPE) exhibits much more environmentally benign
properties, and it is safer because small volumes of noxious surfactants are used instead of toxic organic solvents. CPE is an
attractive technique [3] that reduces the consumption and exposures to a solvent and it also reduces disposal costs and extraction
time that has been used for preconcentration of metal ions after the formation of sparingly water-soluble complexes. Here A
cloud point extraction-flow injection procedure is developed for on-line determination of trace amounts of copper (II) by flame
atomic absorption spectrometry. Copper (II) was extracted by using the non-ionic surfactant, Triton X-114 after complex
formationation with indane-1,2,3,-trione 1,2-dioxime at pH 6. After the cloud point having been obtained in the reaction coil at
50˚C, the surfactant-rich phase containing the complex was collected in a mini-column packed with cotton. Then the complex
was eluted into the nebulizer of flame atomic absorption spectrometer by passing methanol containing 2 M nitric acid at a flow
rate of 6.0 mL min−1. The chemical and flow variables including pH, reagent and surfactant concentration, sample and eluent
flow rates etc. affecting the extraction and determination were optimized and the enhancement factor was estimated. With 3 min
preconcentration time, the obtained enrichment factor was 40, which could be further improved by increasing the
preconcentration time. The detection limit (3Sb m-1) LOD =0.42 µg L−1was obtained. The proposed method was applied to the
determination of copper (II) in various real samples.
Reference
[1] Z. Fang, Flow Injection Atomic Absorption Spectrometry, John Wiley & Sons Ltd., West Sussex, England, 1995.
[2] Z. Fang, Spectrochim. Acta Part B 53 (1998) 1371-1380.
[3] M.F. Silva, L. Fernandez, R.A. Olsina, D. Stacchiola, Anal. Chim. Acta 342 (1997) 229–238.
Solid phase extraction of trace amount of Ni (II) ions in real samples using surfactant-coated alumina modified with 1nitrozo-2-naphthol prior to determination by FAAS
Mehdi Hosseini, Masoumeh Kazemi, Nasser Dalali*, Saeid Mohammadnejad
FIA-Lab ., Department of Chemistry, Faculty of Sciences, Zanjan University, Zanjan Email:Nasser_zn@yahoo.com
The importance of the determination of heavy metal ions, such as nickel, in environmental samples can hardly be over
emphasized because nickel is the metal component of the enzyme urease and as such considered to be essential to plants. More
attention has been focussed on the toxicity of nickel in low concentrations [1]. Direct determination of these heavy metals
appears to be a difficult task as the concentration of them is close to or below the detection limits of most of the analytical
instruments. Separation and preconcentration methods can solve these problems. For dissolve of this problem, used solid phase
extraction which has serious advantages [2]. Among solid-phase adsorbents, Sodium dodecyl sulfate (SDS)-coated alumina is
very useful for preconcentration of metal complexes [3] because of its good physical properties such as porosity, high surface
area as chemical homogeneous non-ionic structures. In present work, a simple, fast and sensitive method for
preconcentration/extraction of Ni (II) ions prior to their determination by flame atomic absorption spectrometry is reported. The
method is based on the extraction of target ion via complexation with 1-Nitrozo-2-naphthol immobilized on SDS-coated alumina.
The, sample containing trace amount of Ni(II) ion was passed through the modified adsorbent at a flow rate of 4 mL min−1 with
the aid of a peristaltic pump. The adsorbed analyte was then eluted from the column with 1.5 mL of 0.3 mol L−1 nitric acid at a
flow rate of 4 mL min−1. The target ion content of the effluent was then analyzed by flame atomic absorption spectrometry. The
influences of the analytical parameters were investigated. The recoveries of analytes were generally higher than 99% with a low
relative standard deviation (RSD< 4.8%). The method is simple, accurate, and economical and showed reproducibility and
reliability in analytical data.
Reference
[1] E. Merian, Metals and their Compounds in the Environment, VCH, New York, pp. 1101 (1991).
[2] M. Hosseini, N. Dalali, A. Karimi, K. Dastanra, Turk. J. Chem. 34 (2010) 805-814.
[3] S. Saracoglu, M. Soylak, L. Elci, Anal. Lett. 15 (2002) 19-27.
Spectrophotometric determination of Praseodymium by Alizarin Red S after cloud point extraction
Sara Aghaei Gavari*, Ali Niazi and Mohammad Alimoradi
Department of chemistry, Faculty of Sciences, Islamic Azad university, Arak Branch, Arak, Iran
(E-mail: sara.aghaei64@gmail.com, ali.niazi@gmail.com)
A cloud point extraction process using the nonionic surfactant Triton X-114 for extracting Praseodymium from aqueous
solutions was investigated. The method is based on the complexation reaction of Praseodymium (III) with Alizarin Red
S and micelle-mediated extraction of the complex.The optimal extraction and reaction conditions (e.g., pH, surfactant
concentration, reagent concentration, thermostatic bath) were studied by Leave-One-Out and Box-Behnken methods. The
analytical characteristics of the method (e.g., limit of detection, linear range) were obtained. Linearity was obeyed in the
range of 1-40 ngmL-1 of Praseodymium (III) ion. The detection limit of the method was 0.33 ngmL-1 of Praseodymium
(III) ion. The method was applied to the determination of Praseodymium in water samples.
Reference
[1] A. Niazi,T. Momeni-Isfahani, Z. Ahmari, J.Hazard.Mater. 165 (2009) 1200.
[2]T. Madrakian, A. Afkhami, A. Mousavi, Talanta 71 (2007) 610.
[3]A. Niazi, J. Ghasemi, A. Yazdanipour,Specrochim.Acta Part 68 (2007) 523.
[4] R.Leardi,Anal.Chim.Acta 625 (2009) 161.
Prediction of electrophoretic mobility of carboxylic and sulfonic acids in capillary electrophoresis
based on multiple linear regression and support vector machine
a,b:
Zohreh Mehrabadi*a, Shayan Mokhtarb
Department of Chemistry, Firoozabad Branch, Islamic Azad University, Firoozabad, Iran.
E-mail: z.mehrabadi@iauf.ac.ir
A quantitative structure–mobility relationship (QSMR) was developed for the absolute mobilities of 115 carboxylic and sulfonic
acids in capillary electrophoresis (CE) based on the descriptors calculated from the structure alone [1]. Electrophoretic mobility
(μ) is the most important parameter governing the separation of solutes in capilary electrophoresis [2]. Electrophoretic separation
is based on the difference in migration of ions under a certain applied electric field. Generally, the migration behavior is denoted
by electrophoretic mobility, which is dependent on both the molecular structure and the separation condition. Therefore, the
prediction of the mobilities of ions by theoretical calculation will relieve analysts of a large number of costly and time consuming
experiments to develop a faster optimization process in CE [3]. The Multiple linear regression method (MLR) and Support
Vector Machine (SVM) were utilized to construct the linear and nonlinear prediction models, respectively. The structures of the
compounds were drawn with Hyperchem 8.0 program and the final optimum 3-D geometries were obtained with the semiempirical AM1 method in Hyperchem And different descriptors (1497descriptors) were calculated by the Dragon software. The
molecular descriptors selected by stepwise regression were used as inputs for SVM. The results obtained using SVM were
compared with those obtained using the MLR method. The predictive correlation coefficients (R) for the test set given by MLR
and SVM were 0.8650 and 0.9559, respectively. Also the absolute average relative deviation (AARD) 9.80% and 6.44% were
obtained with MLR and SVM respectively, which shows the performance of SVM model is better than that of the MLR model.
The prediction results are in very good agreement with the experimental values.
Reference:
[1] Y. Cheng, H. Yuan, Anal. Chim. Acta, 565 (2006) 112.
[2] H. X. Liu, R. S. Zhang, Anal. Chim. Acta, 525 (2004) 31.
[3] R. L. Kay, Pure Appl. Chem., 63 (1991) 1393.
A new Citrate ion selective electrode based onsurfactant modifiednanoclinoptilolite zeolite
AlirezaNezamzadeh-Ejhieh*a,b,MahdiehHasheminejada
a
Department of Chemistry, Islamic Azad University, Shahreza
b
Razi Chemistry Research Center (RCRC), Islamic Azad University, Shahreza Branch
E-mail address: arnezamzadeh@iaush.ac.ir
A novel high-selective potentiometric sensor for citrate was prepared with a PVC membrane as a plasticized poly(vinyl
chloride).The resulting membrane electrode incorporating %32 PVC, %65 dioctylphthalate (DOP) as plasticizer, %2 surfactant
modified zeolite (SMZ).Nernstian response slope of 29.8 mV per decade over the concentration range of 5 × 10 - 1× 10 M
citrate .The electrode exhibits a fast response time ≤10 s, a detection limit of 1 × 10 , and can be used over a wide pH rang of
5-11 .The electrode shows improved selectivity in comparison to most of the previously reported citrate-selective electrodes. It
was successfully applied to the determination of citrate ion in natural water sample and drug samples.
Reference
[1] M. Kim, Food Chem. 99 (2006) 851–857.
[2] E. F. Flores, Anal. Chem. 53(1970) 17–20.
[3 ]C. M. F. Ribeiro, C. D. Matos, Anal. Chim.Acta 471 (2002) 41–49.
[4] E. l. Peres, A. Rios, N.Valcarcel, Anal. Chim.Acta 366(1998)231.
[5 ]M. R. Kova, S. C. Uvanova, M. Dzivak, J. Rimar, Z. Gaval, Mater. Sci. 8(2004) 397–404.
Speciation and spectrophotometric determination of ultra trace amounts of
azide ion in environmental water samples by dispersive liquid–liquid
microextraction
Ali Reza Zarei, ReihanehHajiaghabozorgy*
Faculty of Chemistry and Chemical Engeneering, MalekAshtar University of Technology, Tehran, P.O.Box 15875-1774, Iran
E-mail:bozorgy_2009@yahoo.com
Sodium azide (NaN3) is widely used for a variety of technological applications including agriculture in the production of
pesticides and herbicides [1], biomedical sciences as preservative in diagnostic reagents , the automotive industry as a propellant
for air bags, and for the production ofdetonators and other explosives in military purposes. Sodium azide is a highly toxic
compound classified as a first-class poison [2]. It is more harmful to the heart and the brain than the other organs, because the
heart and the brain use a lot of oxygen. The threshold limit value (TLV) for sodium azidewas reported 5.0 mg m-3 [3]. Hence, the
determination of trace amounts of azide ion is very important for evaluating the toxicity of an environmental sample. In this
paper, we developed a novel, simple, rapid and high sensitive method for preconcentration and spectrophotometric determination
ofultra trace amounts of azide ion (N3-) in water samplesusing dispersive liquid-liquid microextraction (DLLME) technique. The
method is based on ion association formation of azide ion with malachite green and extraction of the ion pairing product using
DLLME technique.Some important parameters, such as reaction conditions and the kind and volume of extraction solvent and
disperser solventwere studied and optimized. Under the optimum conditions, the calibration graph was linear for the range of0.25
to 50ng mL−1 with limit of detection of 0.15ng mL−1. Relative standard deviation for five replicate determinations of azide ion at
10 ng mL−1 concentration level was calculated to be 1.54%. Average recoveries for spiked samples were determined to be
between94–105%.The interference effect of some cations, anions, and organic compounds was also tested. The proposed method
was successfully applied for determination of azideionin water samples.
Reference
[1] A. Yanagi, Pflanzen.-Nachr. Bayer 54 (2001) 5.
[2] R. Casiday, R. Frey ,” Gas Laws Save Lives:The Chemistry Behind Airbags Stoichiometry and the Gas Constant Experiment”www .chemistry .wustl .edu/∼e
dudev /Lab Tutorials /Airbag s/ airbags.html (May 30, 2007).
[3]A.Blackman,Chem.Mag.(2003),http://neon.otago.ac.nz/chemistry/magazine/magazine.php?csNum=31 (May 30, 2007).
Simultaneous determination and investigation electrooxidation behavior of ascorbic acid
and dopamine on the zeolite modified carbon pace electrode
Maryam Abrishamcar*, Shahla Elhami, Azam Izadi
Department of Chemistry, Islamic Azad University, Khozestan Science and Research Branch, Ahvaz, Iran. Email:m.abrishamkar@umz.ac.ir
Ascorbic acid is distributed widely in both animal and plant kingdoms. Among animal organs, the liver, leukocytes and anterior
pituitary lobe show the highest concentration levels of ascorbic acid. Vitamin C, a water-soluble vitamin, which is essential to
metabolism and is consumed on a large scale, is electroactive and, therefore, a variety of methods have been developed for its
analysis. Spectrophotometric methods have been applied for the analyses of vitamin C in pharmaceutical preparations and fruit
juices [1, 2]. Zeolite-modified electrode (ZMEs) which have been widely studied recently, form a subcategory of the chemically
modified electrodes [3, 4]. In this study a novel modified carbon paste electrode was proposed for electrooxidation of ascorbic
acid in the low concentration range in the present of dopamine as interference. The effect of solution pH was investigated and the
optimum pH condition was 5-6. The linear dynamic for determination of ascorbic acid was found to be 0.5-5 mM and the
calculated detection limit was 9.03*10-5M. Obtained results showed that proposed electrode was comparable with other modified
electrode for determination and oxidation of ascorbic acid in the presence of dopamine.
Reference
[1] T. Rohani, M. A. Taher, Talanta, 78(2009)743.
[2] S.P. Arya, M. Mahajan, P. Jain, Anal. Sci. 14 (1998) 889.
[3] M. Kuronen, R. Harjula, J. Jernstrom, J. Phys. Chem. 2 (2000) 2655.
[4] A.Walcarius, P. Mariaulle, L. Lamberts, J. Electroanal. Chem. 463 (1999) 100.
Investigation on the reaction between Al (III) and 3-hydroxy-naphtalene-2-carboxylic acid
by spectrofluorimetric method and its application to the measurement of Al (III) in water samples
Mohamad saied Hoseini*, Tahereh Pourmahmood Hesari
Chemistry Department, Birjand University, Birjand, 97175-615, Iran
E-mail: mshosseini1336@yahoo.com
A rapid and sensitive method for the trace level determination of aluminium based on the formation of a complex with 3hydroxy-naphtalene-2-carboxylic acid (HNA) in 5 percentage of methanol is reported.The fluorescence intensity of the system
was greater than that of the system without aluminium. This method is very sensitive and selective for the direct determination of
aluminium ion. The optimum conditions are a 3-hydroxy-naphtalene-2-carboxylic acid concentration of 1×10-5 mol/L and pH
4.50(acetic acid-sodium acetate buffer). The method has been applied successfully to the determination of trace amount of Al
(III) in the range of 5×10-8to 5×10-6mol/L in water samples. Many of the co-existing ion in water sample including
Mg(II),Co(II),Cu(II), Ni(II),Zn(II),Mn(II),Pb(II),Ca(II), Na+ and Cd(II) are not interfered in the determination[1,2].
Reference
[1] Mostafa, G. A. E; Hassanein, M. M; Abou-El-Sherbini, K. S; GÖrlitz, V. Controlled-pore silica glass modified with N-propylsalicylaldimine for the separation and
preconcentration of trace Al(III), Ag(I) and Hg(II) in water samples, Anal. Sci 2003, 19, 1151-1156.
[2] Reyes, J. F. G; Barrales, P. O; Díaz, A. M. Development of a solid surface fluorescence-based sensing system for aluminium monitoring in drinking water, Talanta
2005, 65, 1203-1208.
Combination of magnetic solid phase extraction by octadecyl functionalized magnetic nanoparticles
and dispersive liquid-liquid microextraction followed by gas chromatography
for determination of ultra-trace levels of plasticizes in water samples
Mohammad Farajia,b, Yadollah Yaminia, and Mahnaz Adelic
Department of Chemistry, Tarbiat Modares University, Tehran, Iran.
b
Quality Control Lab, Jaber Ebne Hayyan Pharmaceutical Company, Tehran, Iran.
c
Knowledge Development & University Relatioship Department, Iran Khodro Company, Tehran, Iran
a
In this research, synthesis, characterization and application of octadecyl functionalized magnetic nanoparticles (C18-MNPs) were
developed. For this purpose, first C18-MNPs was synthesized and well characterized with different characterization techniques
including SEM, TEM, PCS, XRD, EDXD, VSM, FT-IR, Zetasizer and TGA techniques. Results showed that MNPs were well
functionalized with octadecyl group. When applying magnetic solid phase extraction (MSPE) methods to large sample volumes
(500-1000 mL), commonly about 1-5 mL of eluent is needed. Therefore, in order to getting maximum achievable enrichment
factors, usually extraction method followed by an evaporation step which it is time and energy consuming step. To overcome this
limitation, for the first time combination of MSPE and dispersive liquid-liquid microextraction (DLLME) methods was
investigated in our research group. By combination of these methods, the tedious step can be removed and also superior
enrichment factor can be achieved. The MSPE-DLLME method by using C18-MNPs was investigated for perconcentration of
some of plasticizes (Di(2-ethylhexyl) phthalate (DOP), Di-(2-ethylhexyl) adipate (DOA) and Di-butyle phthalate (DBP)) from
water samples. Effects of significant parameters on the extraction efficiency of plasticizers by applying MSPE-DLLME methods
were investigated. Under the optimum conditions, the calibration plots were linear in the range of 0.01–100 µg L−1 and superior
enrichment factors in the range of 17749-21287 were obtained. Also, detection limits of the proposed method were between
0.002 and 0.003. The method was successfully applied to extraction of plasticizers from water samples and satisfactory results
were obtained. Obtained results showed that, the method is simple, rapid and very sensitive and it can be applied for rapid
extraction of other organic compound from large volume of sample solution.
Extraction of trace amounts of lead on novel di pyridile amine functionalized mesoporous silica
from natural samples
,H.Ebrahimzadeh ª’ *, A. A. Asgharinezhada, E.Morovati b
ªDepartment of Chemistry, Shahid Beheshti University, G.C., Evin, Tehran, Iran
b
Department of Chemistry, Islamic Azad University, Saveh, Iran
Corresponding Author E-mail address: h-ebrahim@sbu.ac.ir
The toxicity and effect of trace heavy metals on human health and the environment has attracted considerable attention and concern in
recent years. Lead is one of the most toxic heavy metal elements for animals and human. Consequently, the development of reliable
methods for the removal and determination of lead in biological and water samples is of particular significance [1]. Direct
determination of this heavy metal appears to be difficult task as the concentration of them is close to or below the detection limits of
most of the analytical instruments. Therefore separation and preconcentration methods can solve these problems. The most commonly
used method is solid phase extraction, which provides advantages such as preconcentration of trace metals from larger volumes of
sample, reduction or elimination of matrix interference, prevention of contamination [2]. In this work a simple and rapid method was
applied for extraction, preconcentration and determination of trace amount of lead in natural samples by using functionalized
mesoporous silica. The effects of concentration and volume of eluent, pH of the solution, flow rate of extraction, sample volume and
of potentially interfering ions on the efficiency of preconcentration and recovery was investigated. Under optimal conditions, the
extraction efficiency for lead was greater than 95.5% with the adsorption capacity greater than 50 mg g−1and limit of detection (LOD)
lower than 0.06 ng mL−1. The preconcentration factor was greater than 150 for lead and relative standard deviation (RSD) of the
method was <1%. Modified mesoporous silica is remarkable sorbent which can be used in solid phase extraction conveniently, and it
has advantages of simplicity, rapidness, selectivity and reproducibility. High capacity factor, low detection limit and high enrichment
factor are other benefits of these solid phases compared with others. Trace metal ions at ppb level in high economical volume samples
can be determined and separated by this solid phase due to their high preconcentration factor.
Reference
[1] F.Shemirani,M.Ezoddin, J.Hazard.Mater.178(2010)900-905.
[2] H.Ebrahimzadeh, N.Tavassoli, Talanta.81(2010)1183-1188.
Development and validation of a high-performance liquid chromatography–tandem mass
spectrometric method for quantification of thimerosal in biological products
using semi-automated liquid–liquid extraction on 96-well plate
a.
b.
Ali Es-haghi a*, Mahdiar Khakinejad b, Habib Bagheri b
Department of Physico Chemistry, Razi Vaccine & Serum Research Institute, P.O. Box 31975/148, Karaj, Iran
Department of Chemistry, Sharif University of Technology, P. O. Box 11365-9516, Tehran, Iran
Thiomersal is an organomercury compound. This compound is a well established antiseptic and antifungal agent. It has been used
as a preservative in vaccines, immunoglobulin preparations, skin test antigens, antivenins, ophthalmic and nasal products, and
tattoo inks [1]. Thiomersal's main use is as an antiseptic and antifungal agent. In multidose injectable drug delivery systems, it
prevents serious adverse effects such as the Staphylococcus infection that, in one 1928 incident, killed 12 of 21 children
inoculated with a diphtheria vaccine that lacked a preservative [2]. Thiomersal is very toxic by inhalation, ingestion, and in
contact with skin, with a danger of cumulative effects. It is also very toxic to aquatic organisms and may cause long-term adverse
effects in aquatic environments [3]. Regulatory control of these preservatives is important, as it provides assurance that the
biological product has been adequately preserved and that excessive amounts of mercury are not being added to final product. As
the samples in quantification ques is usually high in vaccine industry, so developing a high throughput method is rather essential.
In this study, for the first time, a high-throughput ultrasonic-assisted micro-liquid-liquid extraction on 96 well-plates followed by
fast performance liquid chromatography-tandem mass spectrometry was developed to analyze thiomersal in biological samples.
The previously used methods are rather time consuming and tedious using ditiazon complexing agent and UV-Vis
spectrophotometry. Very fast chromatography runs couple by ion trap MS2 determination, makes this analysis fast, selective and
sensitive. Influential parameters affecting the reliability of the method such as Ion trap parameter, liquid chromatography and
extraction parameters. The optimum extraction parameters obtained at 1% NaCl concentration, PH=2, 1-decanole as extracting
solvent and extraction time of 5 min. Under the optimized conditions, LOD and LOQ of 1 µgL-1 (S/N= 3) and 10 µgL-1 (S/N=
10) were respectively obtained. The method showed linearity in the range of 10-200 µgL-1 with correlation coefficient of > 0.99.
The relative standard deviation was less than 8% at 20 µgL-1.
Reference
[1] Bigham M, Copes R (2005). "Thiomersal in vaccines: balancing the risk of adverse effects with the risk of vaccine-preventable disease". Drug Saf 28 (2): 89–101
[2] "Thimerosal in vaccines". Center for Biologics Evaluation and Research, U.S. Food and Drug.
[3] "Safety data sheet, Thiomersal Ph Eur, BP, USP" (PDF). Merck. 2010.
Modified Carbon Paste Electrode by Multiwall Carbon Nanotubes/Ionic liquid/a New Derivative
of Hydroquinone for Determination of Hydrazine
M. Mazloum-Ardakani* a, A. R. Khoshrooa, M. A. Sheikh-Mohseni a, A. akbaria
a
Department of Chemistry, Faculty of Science, Yazd University, Yazd, I.R. Iran
Hydrazine (HZ) is widely used as a raw material in the manufacture of agricultural chemicals, a powerful reducing agent in fuel
cells, intermediates in industrial preparations of pesticides, plant growth regulators, polymerization catalysts, corrosion inhibitor
and antioxidant. It is also very important in pharmacology, because it is recognized as a carcinogenic, hepatotoxic and mutagenic
substance. It has been reported that HZ and its derivatives have adverse health effects. Therefore, sensitive detection of HZ is
practically important for environmental and biological analysis [1]. In this study, we describe a sensitive and selective
electrochemical method for determination of HZ using modified carbon paste electrode with multiwall carbon nanotubes/ionic
liquid/a new derivative of hydroquinone. In the first part of the work, cyclic voltammetry was used to investigate the redox
properties of this modified electrode at various scan rates. The apparent charge transfer rate constant, ks, and transfer coefficient,
α, were calculated. In the second part of the work, the mediated oxidation of HZ at the modified electrode was described. The
oxidation peak potentials of HZ at modified electrode in cyclic voltammogram was occurred around 230 mV (at pH 7.0) while
this peak potential at unmodified carbon paste electrode was appeared around 750 mV at the same scan rate of 100 mV s–1. The
values of electron transfer coefficients (α), catalytic rate constant (k), diffusion coefficient (D) and detection limit were calculated
for HZ, using electrochemical approaches. Finally, this method was used for the determination of HZ in water samples, using
standard addition method.
Reference
[1] K. Yamada, K. Yasuda, N. Fujiwara, Z. Siroma, H. Tanaka, Y. Miyazaki, T. Kobayashi, Electrochem. Commun. 5 (2003) 892.
[2] Bard A.J., Faulkner L.R., Electrochemical methods. Fundamentals and applications., 2ed, 2001, Wiley, New York
Electrochemical detection of L-dopa on graphene modified electrode using differential pulse voltammetry
a
M. Arvanda,*, N.Ghodsi b, M. Ansarifardb, M. Kaykhaiib
Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box: 1914, Rasht, Iran
b
Department of chemistry, Faculty of Science,University ofSistan&Baluchestan, Zahedan, Iran
Email: arvand@guilan.ac.ir
3,4-dihydroxy-L-phenylalanine (L-dopa) is the intermediate precursor of the neurotransmitter dopamine. Unlike dopamine, Ldopa easily enters the central nervous system [1]. L-dopa, as one of catecholamines, is widely used as a source of dopamine in
the treatment of most patients with Parkinson’s disease and epilepsy [2]. Graphene is ideally suited for implementation in
electrochemical applications due to its reported large electrical conductivity, large surface area, unique heterogeneous electron
transfer rate, and low production costs [3].This work reports the synthesis of graphene using a Brodie method and its application
for the electrochemical determination of L-dopa in real samples. Electrochemical measurements were performed at glassy carbon
electrode modified with graphene via drop casting method. Cyclic voltammograms of L-dopa at graphene modified electrode
showed an increased current intensity compared with glassy carbon electrode. All the measurements were done in phosphate
buffer solution (pH 6.4)and the oxidation peak was observed at 350 mV vs. SCE.Effect of scan rate showed that oxidation of Ldopa on graphene modified GCE was surface controlled. As the electrode progress is controlled by the adsorption of L-dopa,it is
very import to investigate the effects of accumulation time. The oxidation peak current of L-dopagradually increased with
increasing accumulation time from 0 to300 s, and reached the maximum current response at 300 s. Furtherincreasing the
accumulation time, there is no significant increase inthe current response. This phenomenon is probably due to the
saturatedadsorption of L-dopa on the graphene modified surface, and nochange is observed when increasing the accumulation
time.
Reference
[1] M.F.S. Teixeira, M.F. Bergamini, C.M.P. Marques, N.Bocchi,Talanta 63 (2004) 1083–1088.
[2] G.Hu, L. Chen, Y. Guo, X. Wang, S. Shao, Electrochim.Acta 55 (2010) 4711–4716.
[3] M.H.Parvin, Electrochem. Commun. 13 (2011) 366–369.
Determination mineral elemet and Antioxidant activity of semenovia suffruticosa
Mohammad Ansari Moghaddam*1, Jafar Valizadeh2, Nasrin Kazemipour2,
Malek Taher Maghsoodlou1, Mohammad Nik Bin1, Ameneh Davarimanesh1
Department of Chemistry, Faculty of Science, university of Sistan & Baluchestan, I. R. Iran
Department of Biology, Faculty of Science, university of Sistan & Baluchestan, I. R. Iran
E-mail: m.ansarimoghadam65@gmail.com
Semenovia suffruticosa is one of plant of the family apiaceae only in the region of sistan and Baluchistan taftan Iran is growing.
Mineral elements plant s.suffruticosa for the first time is measured. In this study, dry ashing method is used and the absorption of
element was measured by atomic absorption spectroscopy (AAS). Highest percentage of calcium and potassium in plant
s.suffruticosa shows. Abundance of element in this plant is as follows: K> Ca> Fe> Mn> Cr> Mg> Na. The antioxidant activity
of the different extracts of aerial parts of semenovia suffruticosa was investigated1. The antioxidant potentials of the extract
compounds were established by using three radical-scavenging assays, namely, DPPH scavenging, besides β-carotene bleaching
assay and FRAP assay. The antioxidant activity is compared with synthetic antioxidant, namely BHT3. The demonstrated
modified spectrophotometric method makes use of the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical and its specific absorbance
properties2. The absorbance decreases when the radical is reduced by antioxidants2. In contrast to other investigations, the
absorbance was measured at a wavelength of 517 nm. for β-carotene bleaching assay the absorbance was measured at a
wavelength of 490 nm. And FRAP assay wavelength of 593nm. semenovia suffruticosa collected from taftan in sistan and
baluchestan. IC50 ethanolic extract in DPPH and β-carotene assay were 46.26 and 932.01. Ethanolic extract of this plant in the
three methods had the most antioxidant activity. The antioxidant activity of n-hexan extract was less than ethanolic extract. Ethyl
acetate and water extracts the antioxidant activity were very little demonstrated.
References
[1] Samir Jaoua, Antioxidant constituents from Lawsonia inermis leaves: Isolation, structure elucidation and antioxidative capacity, Food Chemistry 125 (2011) 193–
200.
[2] Kai Marxen, Determination of DPPH Radical Oxidation Caused by Methanolic Extracts of Some Microalgal Species by Linear Regression Analysis of
Spectrophotometric Measurements, Sensors 2007, 7, 2080-2095.
[3] Alavi Leila, Chemical composition and Antioxidant Properties of Essential Oils (lippia citriodora, thymus daenensis ).
Fabrication of a Eu3+ PVC Membrane Sensor Based on
1,4-bis[o-(thiophene-2-carboxamidophenyl)]-1,4-dithiobutane (TCD)
1
Neda Rohani,*1 Hassan Ali Zamani,1
Department of Applied Chemistry, Quchan branch, Islamic Azad University, Quchan, Iran
nedarohani2011@yahoo.com
A novel Eu3+ PVC membrane sensor has been constructed, based on a new symmetrical Schiff’s base namely 1,4-bis[o(thiophene-2-carboxamidophenyl)]-1,4-dithiobutane (TCD). The electrode performance includes a Nernstian slope of 19.5
0.6 mV per decade across a wide concentration range between 1.0 × 10-2 and 1.0 × 10-6 M and a detection limit of 6.7 ×10-7 M
[1]. This sensor showed high selectivity [2, 3] with respect to common alkaline, alkaline earth, transition, heavy metals and
specially lanthanide ions, except for Eu3+, and could be used over a pH range of 2.7-8.8. It can be used for at least 2 months
without any considerable divergence in potentials and it has a relatively fast response of ~5 s. The proposed sensor was
effectively used as an indicator electrode in the potentiometric titration of Eu3+ ions with EDTA.
Reference
[1] E. Bakker, P. Buhlmann, and E. Pretsch, Carrier-based ion-selective electrodes and bulk optodes. 1. General characteristics,Chem. Rev, 97, 3083, 1997.
[2] Y. Umezawa, K. Umezawa, and H. Sato, Recommended methods for reporting K (pot,a, b) values (IUPAC Technical Report), Pure & Appl. Chem. 67, 507,
1995.
[3] M. R. Ganjali, A. Tamaddon, P. Norouzi, and M. Adib, Novel Lu(III) membrane sensor based on a new asymmetrically S–N Schiff’s base, Sens. Actuators B,
120, 194, 2006.
Determination of vincristine and vinblastine in catharantous roseous plant by application
of hollow fiber based liquid-liquid-liquid microextraction followed by HPLC-DAD
Mohammad Saraji1*, Azar Shams1, Bahman Farajmand1, Majid Talebi2
Department of Chemistry, Isfahan University of Technology, Isfahan, I. R. Iran
2
Department of Biotechnology, College of Agriculture, Isfahan University of Technology, Isfahan, I. R. Iran
1
Vincristine and vinblastine are natural anticancer medicines which are 2 of 130 alkaloids that can be found in catharantous
roseus. However, only few (~11) of this high number of chemical entities are usually analyzed and even fewer (~8) are available
commercially. For more than 30 years, different analytical techniques have been developed to isolate and determination
catharantous roseus metabolites, and then allowing revealing the therapeutic potential of catharantous roseus compounds
[1,2].In this study, hollow fiber based liquid-liquid-liquid microextraction was applied for extraction of these alkaloids from
stems and leaf plant. Extracted compounds was quantified with HPLC-DAD. The main parameters affected on the extraction
efficiency such as solvent, pH of acceptor phase, pH of donor phase, extraction temperature and time were studied and optimized.
Analytical figures of merit were determined under optimized conditions. Limit of detection of proposed method was calculated 3
µg/L for both medicines. Relative standard deviation (n=5) were between 2 and 2.7 % for vincristine and vinblastine,
respectively. Linear dynamic range was between 10 and 500 µg/L for both compounds. The method was applied for
determination the analytes in real plant samples. The dried plant sample was extracted in acidic solution. After filtering the
solution, the analytes in extracted sample was determined by HF-LLLME-HPLC. Results showed that the method is applicable in
analysis of these medicines in plant.
Reference
[1]. Steve Hisiger, Mario Jolicoeur, Phytochem Rev (2007) 6:207–234
[2] C. Tikhomiroff, M. Jolicoeur, Journal of Chromatography A, 955 (2002) 87–93
Heterogeneous photodegradation catalysis of 2,4-dichlorophenol using FeO/P zeolite catalyst
Alireza Nezamzadeh-Ejhieh∗, Zahra ghanbari mobarake
Department of Chemistry, Islamic Azad University, Shahreza
Email: arnezamzadeh@iaush.ac.ir, Ghanbarizahra15@yahoo.com
Chlorinated phenols are widely used in industry and in daily life. They have severe problems to the environment, because they
are carcinogens and mutagens. These contaminants are generated from a number of industrial manufacturing processes such as
pesticide, paint, solvent, pharmaceutical, wood preserving chemicals, coke-oven and pulp industries [1]. Nowadays,
heterogeneous photocatalysis processes are one of the most efficient methods for destroying organic pollutants and dyes in
aqueous media [2]. In this paper, the photocatalytic degradation of 2,4-dichlorophenol as the deputy of organic pollutant in
aqueous solutions with FeO/P zeolite as a photocatalyst under UV irradiation has been studied. Photo- catalyst was prepared by
ion exchanging process of parent synthetic zeolite NaP with ammonium iron(II) sulfate hexahydrate aqueous solution (0.1 M) for
24 h followed by drying and calcination at 350 °C for 8 h. Photocatalyst was characterized by X-ray diffraction and FT-IR. The
effect of key operating parameters such as catalyst dosage and initial pH of the solutions were studied on the photodegradation of
2,4-dichlorophenol. The optimum values were 0.25 g L−1 of the photocatalyst and natural pH of the solution.
Reference
[1] M. Kilic; Z. Cinar ;"Hydroxyl radical reaction with 4-chlorophenol as a model forheterogeneous photocatalysis", J. Mol. Stract. 851 (2008) 263-270.
[2] A. Nezamzadeh-Ejhieh; S. Hushmandrad; "Solar photodecolorization of methylene blue by CuO/X zeolite as a heterogeneous catalyst", Appl. Catal. A: General
388 (2010) 149–159.
Efficient Desulfurization of Gasoline Using Coupling Technique: Oxidation and Ionic Liquid Extraction
a
Najmeh Farzin Nejada, b*, Esmaiel Shamsa*, Mohammad Kazem Aminia
Department of Chemistry, Faculty of Science, University of Isfahan, Isfahan 81746-73441, Iran
b
Analytical Department, Research Institute of Petroleum Industry, Tehran, Iran
*
e-mail address: e_shams@chem.ui.ac.ir , farzinnejadn@ripi.ir
Thiophene and its aromatic derivatives are the major objectionable sulfur compounds present in petroleum fractions. Sulfur
compounds in fuels lead to SOx emission, resulting in serious environmental pollutions and cause acid rain, ozone and smog
generation. The current practice of desulfurization in the refineries is hydro-desulfurization (HDS), which requires high operating
temperature and pressure. However, it is difficult to remove poly-aromatic sulfur compounds, such as benzothiophene,
dibenzothiophene and their derivatives using HDS method.In this paper an efficient desulfurization process for gasoline has been
investigated based on a combination of two steps; an oxidative desulfurization by using an oxidizing agent in the first step and
extractive desulfurization in an ionic liquid in the second step. In the first step, desulfurization of gasoline has been carried out in
acetonitrile solvent using H2O2 as an oxidizing agent in the presence of formic acid as a catalyst. In the next step, 1-butyl-3methylimidazolium-tetrachloro aluminate [BMIM][AlCl4] as the ionic liquid was used for the removal of the residual sulfur
compounds. The results demonstrated that the combination of the two steps, i.e., coupling of oxidation and ionic liquid extraction
can efficiently remove sulfur compounds from gasoline. This coupling process was found to be capable of removing up to 90%
of the sulfur compounds in gasoline in under the optimal conditions of 1:1 volume of extracting solvent to gasoline, reaction
temperature at 50 oC and reaction time of 60 min. The gasoline before and after the two steps was analyzed for total sulfur
content using X-ray fluorescence technique according to ASTM-D2622 and UOP-357 methods. Gas chromatography with sulfur
chemiluminescence detector (GC-SCD) was used to identify and quantify some sulfur compounds in various commercial
gasolines.
Reference
[1] Nie, Y.; Li, C.X.; Sun, A.J.; Meng, H.; Wang, Z. Energy & Fuels 2006. 20(5), 2083.
[2] Jiang, X.; Nie, Y.; Li, C.; Wang, Z. Fuel 2008, 87, 79.
[3] Schmidt, R. Energy & Fuels 2008. 22(3), 1774.
[4] Molaei-Dehkordi, A.; Sobati, M.A.; Nazem, M.A. Chine. J. Chem. Eng. 2009. 17(5), 869.
[5] Te, M.; Fairbridge, C.; Ring, Z. Appl. Catal. A 2001. 219, 267.
[6] Nehlsen, J.; Benziger, J.; Kevrekidis, I. Ind. Eng. Chem. Res. 2006. 45(2), 518.
Head Space Solid Phase Microextraction for Analysis of Essential Oils
Marzieh Torabbeigi*1, Parviz Abroomand Azar2, Mohammad Saber Tehrani2, Zahra Aghaei Meibodi3
1
Faculty of Health, Safety and Environment. Shahid Beheshti University, M.C., Tehran, Iran
2
Science and Research Branch, Islamic Azad University, Tehran, Iran
3
Department of chemistry, East Branch of Tehran ( Ghiam Dasht), Islamic Azad University, Tehran, Iran
* E-mail: torabbeigi@gmail.com
Applications of SPME methods in biological and environmental samples have been reported and compiled [1], only a few papers
have appeared to be related to headspace applications of volatile compounds, flavour and fragrances and their components
analysis. It is worthwhile to mention that HS-SPME is a non-destructive modern application for trapping/extracting volatiles,
fragrances, etc. It is a fast, easy, convenient and effective technique with good future prospects [2-4].The extraction of essential
oils with new and simple analytical method, Head space solid phase microextraction (HS-SPME), in comparison with traditional
method, hydrodistllation (HD), for Astrodaucus orientalis, A. O., Perovskia Abrotanoides, P. A., Vitex pseudo-negundo, V. P. N.,
Hypericum hiterllium H. H. and Lavandula angustifolia, L. A. was investigated. The HS-SPME method was done in optimum
condition and PDMS fiber was used as extraction phase. The results show (Fig 1) that HS-SPME method with PDMS fiber as
nonpolar extracts more monoterpene and sesquietrpene hydrocarbons but this method doesn't able to isolate oxygenated
compounds than HD.
Fig 1- the percentages of monoterpene and sesquietrpene hydrocarbons and oxygenated compounds isolated by HD and HS-SPME
References
[1] C. L. Arthur, and J. Pawliszyn, J. Anal. Chem., 62, 2145 (1990).
[2] Z. Zhang, and J. Pawliszyn, J. Anal. Chem., 65, 1843 (1993).
[3] A. Steffen, and J. Pawliszyn, J. Agric. Food Chem., 44, 2187 (1996).
[4] A. J. Matich, D. D. Rowan, and N. H. Banks, Anal. Chem., , 68, 4114 (1996).
OPTICAL SENSOR BASED ON SOL-GEL DERIVED THIN FILM FOR HIGH ACIDITY MEASUREMENTS
Abdollah Yari*, Maryam dinarvand
Department of Chemistry, Faculty of Science, Lorestan University, Khorramabad– Iran
E-mail address:a.yari@ymail.com
The sol-gel process is a suitable method for fabricating materials employed in chemical and biochemical sensors. Sol-gel
technology enables the production of porous glasses at ambient temperature. The procedure involves the hydrolysis and
condensation of a silicon alkoxide precursor to give a porous silica network which can be densified further using subsequent heat
treatments [1-3]. Due to widespread usage of concentrated aqueous strong acids such as hydrochloric acid and nitric acid in many
important chemical processes [4], the development of analyzers for monitoring their concentration has been special of
interest.This study shows that Orang(1) indicator entrapped in porous silica glass thin films using sol-gel method in order to
fabrication optical sensors for high acidity measurements ([H+]=1.0-11.0). This sensor is highly sensitive, reasonably reversible
and responds rapidly to the acidity changes with a response time of 1 minute. The sensor have long lifetime greater of 4 months.
Reference
[1] A. Yari and H.A. Abdoli, J.Hazardous Mater. 178 (2010) 713–717.
[2] A. Kazemzadeh, R. Kashanaki and M. R. Hassanzadeh, Sens. Transduc. J. 113 (2010) 56-62.
[3] G. Cabello-Carramolino, M.D. Petit-Dominguez, Anal Chim Acta 614 (2008) 103–111.
th
[4] “Encyclopedia of chemical technology” 4 ed., Wiley, New York, Vol. 13, (1995).
A Novel Sensor Based on Multi-walled Carbon Nano-tube and Nickel Hydroxide Nano-particles
composite Modified Glassy Carbon Electrode for Simultaneous Determination
of Ascorbic Acid, Dopamine and Uric Acid
Majid Amini khah, Ali Babaei*, Ali Reza Taheri
Department of Chemistry, Faculty of Sciences, Arak University, Arak, Iran
Dopamine (DA) is one of the excitatory neurotransmitters. The loss of DA in human body may lead to some serious diseases
such as Parkinson’s diseases Alzheimer’s disease and schizophrenia [1]. Uric acid (UA) is the primary end product of purine
metabolism in the human body. It has been shown that abnormal levels of UA cause many diseases, like gout and hyperuricaemia
[2]. Ascorbic acid (AA) is one of the most important vitamins in biological systems. UA and AA are both present in biological
fluids such as blood and urine [3]. A large challenge for detection of DA is the resolution between DA and coexisting species
such as AA and UA.In this work a novel chemically modified electrode is constructed based on multi-walled carbon nano-tube
(MWNTs) and Nickel hydroxide nano-particles (NHNPs) composite modified glassy carbon electrodes. The proposed electrode
is evaluated as a sensor for simultaneous trace determinations of AA, DA and UA in pharmaceutical and biological samples. The
measurements and electrochemical characterization of AA, DA and UA on the modified electrode was investigated using cyclic
voltammetry (CV) and differential pulse voltammetry (DPV) methods in phosphate buffer solution (pH 6.5). The new modified
electrode displayed excellent catalytic function for the oxidation of AA and DA and resolved the overlap voltammetric response
of DA and UA into two well-defined voltammetric peaks using differential pulse voltammetry (DPV) method. The calibration
curves for AA, DA and UA species were linear for the whole concentrations range investigated as 5.0–2100 μM and 2100-5500
μM for AA, 0.8–280 μM for DA and 0.5–200 μM for UA with good correlation coefficients. Our novel sensor showed good sensitivity, selectivity
and stability.
References
[1].Wightman, R.M., May, L.J., Michael, A.C., 1988. Anal. Chem. 60, 769A–779A.
[2].Dutt, V.S.E., Mottola, H.A., 1974. Anal. Chem. 46, 1777–1781.
[3] Raoof, Ojani.,J.B., Kiani, A., 2001. J.Electroanal.Chem. 45, 515-516
Simple regression model and partial least squares regression for simultaneous
spectrophotometric determination of arsenic (III) and antimony (III)
Mahdi Hashemi, Zahra Nazari ß
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
The Silver diethyldithiocarbamate (SDDC) procedure is a well known method for spectrophotometric determination of arsenic
(As) and antimony (Sb). Simultaneous determination of As (III) and Sb (III) by SDDC procedure is imposible because of highly
overlapping of their absorbance spectra. In this work a simple regression model SRM and a partial least squares (PLS) regression
were performed to resolve highly overlapping spectrophotometric signals obtained from mixture of As (III) and Sb (III). In a
binary mixture of the As and Sb system, a five level factorial design (52) was used to produce a full set of 25 samples. A three
level set was derived from this to produce a calibration set of nine samples, a long with the remaining 16 samples used for an
independent test set. The prediction error of As (III) and Sb (III) for SRM were 3.45 % and 4.50 % and for PLS were 2.98 %
and 3.70 %, respectively. Two methods were successfully applied to the simultaneous determination of As (III) and Sb (III) in
real water samples.
Reference
[1] Arbab-Zavar, M. A., Hashemi, M., 2000, “Evaluation of electrochemical hydride generation for spectrophotometric determination of As (III) by silver
diethylditiocarbamate”, Talanta, Vol. 52, pp. 1007-1014.
[2] Afkhami, A., Bahram, M., 2006, "Cloud point extraction simultaneous spectrophotometric determination of Zn, Co, Ni in water and urine samples by
1-(2-pyridyazo)2-Naphthol using partial least squares regression", Micro. Chim. Acta, Vol. 155, pp. 403.
[3] Bambang, K., Andrew, A. V., Ramaier, N., 2001, “Simple regression model using an optode for the simultaneous determination of zinc and cadmium mixtures in
aqueous sampeles”, Anal Chem., Vol. 17, pp. 181-186.
[4] Billo, E. J., 1997, “Excel for chemists-A comprehensive guide”, Wiley, New York.
Continuous cloud point extraction for sequential spectrophotometric determination
of arsenic (III) and antimony (III) using silver diethyldithiocarbamate procedure
Mahdi Hashemi, Zahra Nazari ß
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
A continuous cloud point extraction method for selective separation of As (III) and Sb (III) and sequential determination of these
spices using silver diethyldithiocarbamate procedure in an on-line hydride generation system has been developed. The cloud
point extraction was carried out using cetyl trimethylammonium bromide (CTAB) as cationic surfactant, sodium
diethyldithiocarbamate (NaDDC) as chelating agent and I3-as induced phase separation agent at room temperature. Under
optimized conditions Sb as SbDDC was quantitatively extracted into the surfactant rich phase and As remind in the aqueous
phase. After phase separation in a separating column, each phase was separately introduced into the continuous hydride
generation system for final determination. The effect of interferences and their possible mechanism were discussed. The
developed method is applicable to the determination of 5-45 μg of As (III) and Sb (III). An absolute detection limit (3Sb) of 0.72
μg and 0.54 μg were obtained for As and Sb, respectively. The precision (R.S.D) for five replicate determination of 15 μg of As
(III) and Sb (III) were 1.88% and 2.16%, respectively. The method was successfully applied for the simultaneous determination
of As (III) and Sb (III) in spiked tap water and artificial sea water.
Reference
[1] Hashemi, M., Modasser, P., 2007, “Sequential spectophotometric determination of inorganic arsenic species by hydride generation from selective medium
reactions and clour bleching of permanganate”, Talanta, Vol. 73, pp. 166-171.
[2] Arbab-Zavar, M. A., Hashemi, M., 2000, “Evaluation of electrochemical hydride generation for spectrophotometric determination of As(III) by silver
diethylditiocarbamate”, Talanta, Vol. 52, pp. 1007-1014.
[3] Frenandes D. E., Campa, M. R., Garcia, E. S., Valdes-Hevia, M. C., Temprano, Y., Fernandes, B. A., Gayon, J. M. M., Sonz-MEdel, A., 1995, “Effects of
organisd media on the generation volatile species for atomic spectrometry” ,Spectro. Chim. Acta, Vol. 50B, pp. 377-391.
Flame atomic absorption spectrometry determination of Manganes ions after extraction
by a new modified nano alumina in food and environmental water samples
1
Karim Samadifar1, Ali Mirabi * 1, Ebrahim Babaei 1
Department of Chemistry, Islamic Azad University, Qaemshahr Branch, Iran
E-mail: mirabi2012@yahoo.com
Undoubtedly, solid phase extraction (SPE) is one of the best alternatives for traditional severe liquid-liquid extraction (LLE)
methods. A new solid-phase extraction sorbent was used for the preconcentration of Mn(II) ions prior to flame atomic absorption
spectrometry. It was prepared by immobilization of PAR on nano-alumina coated with sodium dodecyl sulfate. Sorbent with
modified nanometer-sized alumina was used to preconcentrate and separate Mn in food and environmental water samples. A
microsample introduction system was employed for the nebulization micro-volume of diluted solution into FAAS. The ions on
the sorbent were eluted with hydrochloric acid. Some effective parameters on the extraction and preconcentration of Mn (II) ions,
such as pH, sample volume, amount of sorbent, and concentration of the chelating agent, were studied. Under the optimum
conditions, the enrichment factor 50 was obtained from only 5 ml of water sample. The calibration graph was linear in the range
15- 300 µgL−1 with detection limits of 4.9 µgL−1. The relative standard deviation (RSD) for ten replicate measurements of 50
µgL−1 of manganes was 3.5%. The proposed method has been applied to the determination of Mn ions at trace levels in certified
reference materials and real samples such as rice, tabbaco, orange, green pepper, black tea, honey, potato, spinach, mangostin,
tomato, strawberry, carrot, apple, kiwi, mushroom, cucumber, lettuce and natural water with satisfactory results.
Reference
[1] S. B. Jadhav, S. P. Tandel, S. P. Malve, Talanta, 2001,Volume 55, , Pages 1059-1064
[2] Guangyu Yang, Zhangjie Huang, Qiufen Hu, Jiayuan Yin, Talanta, 2002, Volume 58, Pages 511-515
[3] M. Ezoddin, F. Shemirani, M.R. Jamali, Journal of Hazardous Materials, 2010, Volume 178, Pages
900–905
Use of modified nano sorbent materials for extraction and determination
of trace amounts of copper ions in food and natural water samples
1
Navid Hosseini1, Ali Mirabi *1, Mohammad Reza Jamali 2
Department of Chemistry, Islamic Azad University, Qaemshahr Branch, Iran
2
Department of Chemistry, Payam Noor University, Behshahr, Iran
E-mail: mirabi2012@yahoo.com
A new solid-phase extraction sorbent was used for the preconcentration of Cu(II) ions prior to that determination by flame atomic
absorption spectrometry. It was prepared by immobilization of PAR on nano-alumina coated with sodium dodecyl sulfate.
Sorbent with modified nanometer-sized alumina was used to preconcentrate and separate Cu in food and environmental water
samples. A microsample introduction system was employed for the nebulization micro-volume of diluted solution into FAAS.
The ions on the sorbent were eluted with nitric acid. Various influencing parameters on the separation and preconcentration of
Cu(II) ions, such as pH, sample volume, amount of sorbent, and concentration of the chelating agent, were studied. Linearity is
maintained between 10 and 750 μgL-1 of Cu(II), for an 5 mL sample. With 5.0mL sample an enrichment factor of 50 was
obtained. The detection limits of this method was 3.0 µgL−1 and the R.S.D.s was 2.7% (n = 10). The proposed method has been
applied to the determination of Cu ions at trace levels in certified reference materials and real samples such as rice, tabbaco,
orange, green pepper, black tea, honey, potato, spinach, mangostin, tomato, strawberry, carrot, apple, kiwi, mushroom, cucumber,
lettuce and natural water with satisfactory results.
Reference
[1] S. B. Jadhav, S. P. Tandel, S. P. Malve, Talanta, 2001,Volume 55, , Pages 1059-1064
[2] Guangyu Yang, Zhangjie Huang, Qiufen Hu, Jiayuan Yin, Talanta, 2002, Volume 58, Pages 511-515
[3] M. Ezoddin, F. Shemirani, M.R. Jamali, Journal of Hazardous Materials, 2010, Volume 178, Pages 900–905
Separation and preconcentration of trace amounts of zinc ions with modified nano sorbent materials
in food and natural water samples and determination by flame atomic absorption spectrometry
1
Homa Shahnazi1, Ali Mirabi *1, Mohammad Reza Jamali 2
Department of Chemistry, Islamic Azad University, Qaemshahr Branch, Iran
2
Department of Chemistry, Payam Noor University, Behshahr, Iran
E-mail: mirabi2004@yahoo.com
Undoubtedly, solid phase extraction (SPE) is one of the best alternatives for traditional severe liquid-liquid extraction (LLE)
methods. A new solid-phase extraction sorbent was used for the preconcentration of Zn(II) ions prior to flame atomic absorption
spectrometry. It was prepared by immobilization of PAR on nano-alumina coated with sodium dodecyl sulfate. Sorbent with
modified nanometer-sized alumina was used to preconcentrate and separate Zn in food and environmental water samples. A
microsample introduction system was employed for the nebulization micro-volume of diluted solution into FAAS. The ions on
the sorbent were eluted with hydrochloric acid. Some effective parameters on the extraction and preconcentration of Zn (II) ions,
such as pH, sample volume, amount of sorbent, and concentration of the chelating agent, were studied. Under the optimum
conditions, the enrichment factor 50 was obtained from only 5 ml of water sample. The calibration graph was linear in the range
10- 200 µgL−1 with detection limits of 3.0 µgL−1. The relative standard deviation (RSD) for ten replicate measurements of 50
µgL−1 of zinc was 3.1%. The proposed method has been applied to the determination of Zn ions at trace levels in certified
reference materials and real samples such as rice, tabbaco, orange, green pepper, black tea, honey, potato, spinach, mangostin,
tomato, strawberry, carrot, apple, kiwi, mushroom, cucumber, lettuce and natural water with satisfactory results.
Reference
[1] S. B. Jadhav, S. P. Tandel, S. P. Malve, Talanta, 2001,Volume 55, , Pages 1059-1064
[2] Guangyu Yang, Zhangjie Huang, Qiufen Hu, Jiayuan Yin, Talanta, 2002, Volume 58, Pages 511-515
[3] M. Ezoddin, F. Shemirani, M.R. Jamali, Journal of Hazardous Materials, 2010, Volume 178, Pages 900–905
Competitive bulk liquid membrane (BLM) and polymer inclusion membrane(PIM) transport of Cu(II), Zn(II),
Ni(II),Pb(II), Co (II) and Ag(I) cations using (2,2'-[(E,E)-1,1'-(2,2-dimethylpropane-1,3-diyldinitrilo) diethylidyne]
diphenol as carrier
A.Nezhadali a, M. Akbarpour b*, I. Sheikhshoaie c
Department of Chemistry, Payame Noor University (PNU), Mashhad, Iran.
b
Department of Chemistry, Payame Noor University(PNU) , Bojnourd, Iran.
c
Department of Chemistry, Faculty of Science, Shahid-Bahonar University of Kerman, Kerman, Iran .
E-mail:m_chemist82@yahoo.com
a
The competitive transport of some metal cations, Zn2+, Pb2+, Co2+, Ni2+,Cu2+ and Ag+ with bulk liquid membrane (BLM) and
polymer inclusion membrane(PIM) transport using (2,2'-[(E,E)-1,1'-(2,2-Dimethylpropane-1,3-diyldinitrilo) diethylidyne]
diphenol (L1) [1] as carrier were studied. The bulk liquid membrane (BLM) method was consisted 10 -4M solution of L1 as carrier
in the membrane phase. The feed source phase containing of an equimolar mixture of the metal cations (10-4M) and the receiving
phase containing of buffered at pH=3. The highest transport was related to Zn2+and the lowest percentage was for Ag+. The
polymer inclusion membranes(PIM) method were prepared by mixing a solution of cellulose triacetate (CTA) in
dichloromethane with solution containing of a plasticizer (NPOE) in dichloromethane and L1 (3×10-3M ). The feed source was
containing of a 30 mL an equimolar mixture of the metal cations (10-4M ) and the receiving phase was containing 30 mL of
suitable stripping agent (a buffer solution at pH=3). The cell was enclosed by a water jacket and thermostated at 25 °C for 24 h.
All transport runs were terminated after 24 h and atomic absorption spectroscopy (Shimadzu- 670) was used to determine the
amount of each of the metal cations. The results show that for both methods (BLM and PIM) the selectivity of L1 for zinc(II)
cation is higher than the other cations.
Reference
[1] M.Montazerozohori, M. H.Habibi, A. Hojjati, R. Mokhtari, Y. Yamane,T. Suzuki, Acta Crystallographica Section E. 2009.
Quantification of mercury at trace level in fish meat by application of combined hollow fiber
based liquid 3-phase microextraction and in-situ differential pulse voltammetry
Bahman Farajmand, Mohammad Saraji*, Ali-Asghar Ensafi and Ali-Reza Allafchian
Department of Chemistry, Isfahan University of Technology, Isfahan, Iran
Over the last two decades, the need has increased for the determination of extremely low concentrations of mercury in various
samples because it accumulates in living tissues, thereby causing many harmful effects [1,2]. In this research, combined hollow
fiber based liquid 3-phase microextraction and in-situ differential pulse voltammetry was used for quantification of mercury in
fish meat. Hg(II) was extracted from 8 mL aqueous solution (donor phase) through a thin phase of organic solvent with a
complexig agent inside the pores of a polypropylene hollow fiber and finally into a 10 µL acidic acceptor solution inside the
hollow fiber. Three microelectrodes designed and constructed for the purposes of this study were placed into the two ends of the
hollow fiber inside the acceptor solution, and voltammetric analysis was performed in-situ during the extraction. Main factors
affected on extraction and electrochemical signal were investigated. Under the optimized conditions, an enrichment factor of 260
was achieved and the relative standard deviation (R.S.D.) of the method was 7.8% (n = 5). The calibration curve was obtained in
the range of 0.05–5 µgL−1 with a reasonable linearity (R2 > 0.994) and the limit of detection (LOD) was found to be 0.01 µgL−1.
Proposed method was used for determination of Hg(II) in real samples. Therefore proper amount of meat samples were cut and
heated with sulfuric acid solution for 15 min then the aqueous phase was decanted, filtered, adjusted the pH and applied for
microextraction procedure.
References
[1]. J.W. Moore, E.A. Moore, Pollution Chemistry, Academic Press, New York, 1976, p. 460.
[2]. C. Baird, Environmental Chemistry, W.H. Freeman, New York, 1995, pp. 352–363.
Investigation of Electrode Kinetics Using CV, SCV, EIS and FT-EIS
S. Ahmad Mozaffari *
Department of Chemical Technologies, Iranian Research Organization for Science and Technology (IROST), P.O. Box: 15815-3538, Tehran,
Iran ,
E-mail: mozaffari@irost.org
In this paper a new attempt for obtaining electron transfer kinetic parameters at modified gold electrode/electrolyte interface
using Fourier transform electrochemical impedance spectroscopy (FTEIS) compare to cyclic voltammetry (CV), staircase cyclic
voltammetry (SCV) and electrochemical impedance spectroscopy (EIS) is presented. In FTEIS analysis, a set of
chronoamperometric currents recorded upon applying a series of small potential steps during an SCV experiment provides a
complete description of an electron transfer reaction at the modified electrode/electrolyte interface in forms of equivalent circuit
elements. Conversion of the circuit elements and data approximation allows electrode kinetic parameters including electron
transfer rate constant (ko), transfer coefficient (α), and diffusion coefficient (D) to be determined. The electrode kinetic
parameters were also obtained by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) experiments. The
results showed that FTEIS analysis can be effectively applied for calculation of elektrokinetic parameters compare to the other
electrochemical methods.
Reference
[1] C. C. Moser, C. C. Page, R. Farid, P. L. Dutton, J. Bioenerg. Biomembr., 27 (1995) 263.
[2] T. Ruzgas, L. Wong, A. K. Gaigalas, V. L. Vilker, Langmuir, 14 (1998) 7298.
[3] S.-M. Park, J.-S. Yoo, Anal. Chem., 75 (2003) 455A.
[4] F. Sundfors, J. Bobacka, A. Ivaska, A. Lewenstam, Electrochim. Acta, 47 (2002) 2245.
[5] B.-Y. Chang, S.-M. Park, Anal. Chem., 79 (2007) 4892.
[6] R. S. Nicholson, Anal. Chem., 37 (1965) 1351.
[7] S. A. Mozaffari, T. Chang, S.M. Park, J. Phys. Chem. C, 113 (2009) 12434.
[8] S. A. Mozaffari, T. Chang, S.M. Park, Biosens. Bioelectron., 26 (2010) 74-79.
Voltammetric determination of clozapine at in situ surfactant-carbon ionic liquid electrode:
Application to analysis of some real samples
M. Arvand*, M. Ghasempour Shiraz, A. Mohammad-Khah
Department of Chemistry, Faculty of Science, University of Guilan, P.O. Box: 1914, Rasht, Iran
Clozapine is an effective antipsychotic drug treating schizophrenia. Owing to its importance, researchers used many analytical
methods to study it, including capillary zone electrophoresis, high-performance liquid chromatography, spectrophotometry, etc.
There were some reports about electrochemical study of clozapine due to its electroactivity [1].Carbon paste electrodes (CPEs)
are very popular due to their wide anodic potential range, low residual currents, ease of fabrication, easy surface renewal and low
cost. Chemically modified electrodes (CMEs) are used to lower the detection limits compared to plain carbon paste electrodes
(PCPE). Various modifiers, such as macrocyclic compounds, copper complexes, phthalocyanine and nanomaterials have been
employed successfully as modifiers for carbon paste electrodes [2].Ionic liquids (ILs) have triggered a new genre for their
amazing electrical and physical properties such as no measurable vapor pressure, good thermal and chemical stability, high
conductivity, and low toxicity [3]. In addition, surfactants at trace levels have also been employed successfully as modifiers. In
view of the desirable characteristics of ILs and surfactants, electrochemical processes may occur in a facile manner on surfactantIL modified carbon paste electrodes. In this study the electrochemical properties of clozapine at an in situ surfactant – carbon
ionic liquid electrode was observed by adsorptive stripping voltammetry (AdSV). After optimization of analytical parameters
such as pH, surfactant concentration, accumulation and in situ modification time, employing this electrode at pH 3.5, the peak
currents for clozapine molecule were found to vary linearly with its concentration in the range of 10–9 – 10–7 M with the detection
limit of 1.65 × 10–10 M using AdSDPV. The prepared modified electrode showed several advantages, such as a simple
preparation method, high sensitivity, very low detection limit. Furthermore, the proposed method was employed for the
determination of clozapine in pharmaceutical formulations, urine and blood serum samples and the obtained results were found to
be satisfactory.
Reference
[1] F. Huang, S. Qu, S. Zhang, B. Liu, J. Kong, Talanta 72 (2007) 457.
[2] B.J. Sanghavi, A.K. Sirvastava, Elecrochim. Acta 55 (2010) 8638.
[3] N. Maleki, A. Safavi, F. Tajabadi, Anal. Chem. 78 (2006) 3820.
Spectrophotometric determination of mercury by using dispersive liquid-liquid micro extraction
and study of effective parameters based on Box-Behnken method
Sima Habibi* ,Ali Niazi and Majid Ramezani
Department of Chemistry , Faculty of Science , Islamic Azad University- Arak branch, arak, Iran
E-mail: hb.sima@yahoo.com and ali niazi@gmail.com
A simple, rapid and sensitive method is proposed for determination of ultra trace amounts of mercury from different samples. In
this study, a new method based on dispersive liquid-liquid micro extraction (DLLME) was proposed by using CCl4, acetonitrile
and dithizone as extraction solvent, disperser solvent and chelating reagent, respectively, for the spectrophotometric
determination of mercury. The influence factors relevant to DLLME such as, volume of extractant and disperser solvent,
concentration of chelating reagents, pH were optimized with leave-one-out and Box-Benken methods.
Under the optimal
condition, the limits of detection for mercury was (0.015 ngmL-1) with enhancement factors of (414). The analytical curve
absorbance was linear over the range of (0.05-0.6 ngmL-1) Hg. The proposed method was applied to the determination of mercury
in fish and human hair samples with satisfactory analytical results.
Reference
[1] X. Wen, Q.Yang, Zh.Yan, Q. Deng, Microchim J ,97(2011)249.
[2]M. Shamsipur, M. Ramezani, M. Sadeghi, Microchim Acta (2009)235.
[3] P. Ling ,H. sang, Anal.Bio chem 380(2008)21.
Electrochemical Determination of Morphine at carbon ceramic electrodes
M. R., Majidi*, E. Alipour , S. Baghi
Electroanalytical Chemistry Laboratory, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
E-Mail: sr.majidi@gmail.com
Morphine was the main alkaloid in poppyseeds having pharmacological and toxicological activity. Morphine was usually used
for treating acute and chronic pain. But excessive or habitual use of morphine causes toxic symptom. Additionally, morphine was
reported to be important indicators of poppy drug abuse, which lead to a lot of society problems. Thus, the rapid separation and
determination of morphine in biological fluids was of vital interest in clinical toxicology, control of drug abuse and forensic
cases. Chromatographic separation techniques, such as high performance liquid chromatography (HPLC) with UV detection[1]
and MS detection [2], gas chromatography (GC) with MS detection [3] and electrochemical methods[4] had been reported for the
determinate of morphine. Here electrochemical determination of Morphine at carbon ceramic electrode was described. Several
parameters effecting determination of morphine on the carbon ceramic electrode were investigated and optimum conditions were
suggested. This sensor was successfully used for determination of low concentrations of Morphine in real samples using DPV.
Reference
[1] M. Mabuchi, S. Takatsuka, M. M. Oka, K. Tagwa, J. Pharmaceut. Biomed. 35 (2004)563
[2] A. Sheibani, M. R. Shishehbore, E. Parizi, Spectro. Chim. Acta. A. 77 (2010)535
[3] U. Hofmann, S. Seefried, E. Schweizer, T. Ebner, G. Mikus, M. Baum, J. Chromatogr. B. 727 (1999)81
[4] M. H. Pournaghi-Azar, A. Saadatirad, J. Electro. Anal. Chem. 624 (2008)293 .
Detection of some single base mismatches in the nucleic acid sequences using a DNA hybridization biosensor
Masoud Ayatollahi Mehrgardi*, Malihe Abdollai
Department of chemistry university of Isfahan, Isfahan 81746-734410 Iran
E-mail address: m.mehrgardi@sci.ui.ac.ir , Maliheh.abdollahi.m@gmail.com
Biosensors are small devices employing biomoleculesas recognition elements [1].There are a lot of types of biosensors such as
DNA biosensors, enzyme and glucose biosensors.There is a great interest in the development of DNA biosensors and they have
attracted a considerable attention as recognition devices [2].The various techniques such as surface plasmon resonance (SPR),
optical and electrochemical techniques have been applied for DNA biosensors. AlthoughSPR and optical techniques are very
advantageous but they are expensive and time consuming. Because of simplicity, high selectivity and
sensitivityelectrochemicalbiosensors have attracted increasing attention [3].Different methods have been applied for the
electrochemical detection of DNA hybridization. The electroactive labels are generally used as redoxprobes for electrochemical
detection of DNA hybridization [4].In this research, an electrochemical DNA biosensor has beenconstructed for detection of
single base mismatches. Herein biosensor, Nile blue was used as an electroactive probe. Thensingle base mismatches in the DNA
sequences were monitored using different voltammetric technique. At first the surface of glassy carbon electrode (GCE) is
oxidized and thencalcon carboxylic acid(CCA) is electrochemically polymerized on surface of electrode. The amino –
functionalized DNA is immobilized on this electrode using EDC/NHS chemistry. Finally, the probe DNA is hybridized with
different target DNA and hybridization phenomena is followed by CV and DPV methods.
Reference
[1]. Brajter-Toth, A” Electroanalytical Methods for Biological Materials “,Marcel Dekker, Inc,New York,2002.
[2]wang,J. Electroanalysis 2005, 17, 7-14.
[3]. Uygun,A.Talanta . 2009,79,194–198
[4]. Li,F.Han,X.Biosensors and Bioelectronics.2011,2619-2625
Electrochemical behavior study of quercetin using sol-gel electrode modified with
multi wall carbon nano tubes and its analytical applications
M. R., Majidi*, A. Naseri, A. Zahiri
Electroanalytical Chemistry Laboratory, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
E-Mail: sr.majidi@gmail.com
Quercetin, one kind of flavonoids, is widely distributed in the plant kingdom. The many studies have revealed various beneficial
effects on human health, such as anticancer activity due to their polyphenolic nature with radical-scavenging activity. Owing to
their electrochemical activity, over the past few years, a lot of studies were focused on this fields, for example, the electroanalysis
of quercetin, the interactions of quercetin and DNA, the properties of quercetin and copper-chelating , the determination of
quercetin by capillary electrophoresis and it’s determination by HPLC using electrochemical detection[1]. Most flavonoids are
electrochemically active at modest oxidation potentials, electrochemical methods are preferable with advantages of higher
sensitivity and less interferences from non-electroactive substances[2]. Recently, multi-wall carbon-nanotubes have been found
to be an excellent electrode material for the determination of quercetin[3]. In the present work, sol-gel electrode was modified by
multi-walled carbon nano tubes and was used for electrocatalytic oxidation of quercetin. The electrode was characterized by
scanning electron microscopy (SEM) and the chemical behavior of quercetin was studied at proposed electrode using cyclic
voltammetry. Also, electrochemical response of quercetin on different electrodes were compared. It was shown that quercetin has
better electrochemical response on MWCNT modified sol-gel electrode compared with other electrodes. The effect of various
experimental parameters including pH, scan rate of DPV on voltammetric response of quercetin was investigated. Then, the
linear range of calibration curve of quercetin was obtained, Under optimmized conditions the modified electrode. Also, the effect
of various potentially interferences were investigated. Finaly, the modified electrode was used for determination of quercetin in
real samples such as apple juice[3].
Reference
[1]. G. P. Jin, J. Bohe, Z. B. Rui, F. S. Meng, Electro. Chim. Acta 51 (2006) 4341-4346
[2]. G. J. Volikakis, C. E. Efstathiou. Talanta 51 (2007) 775-785
[3]. X. Qin Lin, J. B. He, Z. G. Zha. Sensors. Actuators B. 119 (2006) 608-611
Comparison of Microwave-Asisted Hydrodistillation and Hydrodistilation in Extraction
of the Essential Oils from Aerial Parts of Levisticum officinale Koch.
Mehran Moradalizadeh*, Mohammad Reza Akhgar
Department of Chemistry, Faculty of Science, Kerman Branch, Islamic Azad University, Kerman, Iran.
*E-mail: mo_mehran@yahoo.com
The genus Levisticum, belongs to the Umbelliferae family, is represented in the flora of Iran by only one species as Levisticum
officinale Koch. (Lovage) [1]. This plant has been cultivated in European countries for a long time [2, 3]. In this work, the
essential oils from aerial parts of levisticum officinale, separately obtained by hydrodistillation (HD) and microwave-assisted
hydrodistillation (MAHD) and analyzed by GC and GC/MS. Air-dried aerial parts of the plant were hydrodistilled for 3 h using a
Clevenger-type apparatus and at 600 W for 20 min using an adapted microwave distillation. GC analysis was carried out using a
Hewlett-Packard 6890 instrument coupled to a flame ionization detector (FID). Compounds were separated on a HP-5 capillary
column. GC/MS analysis was performed using a Hewlett-Packard 5973 mass spectrometer coupled to a HP 6890 gas
chromatograph equipped with a HP-5MS capillary column. All constituents of the oils were identified on the basis of their mass
spectra characteristics and retention indices. α-Terpinyl acetate (62.75%) and carvacrol (19.53%) were the main components
among the 14 constituents characterized in the oil extracted with MAHD, representing 93.27% of the total components detected.
Also 24 compounds were identified in the oil extracted with HD, representing 90.60% of the total oil, with α-terpinyl acetate
(40.18%), β-phellandrene (7.58%) and α-terpineol (6.25%) as the major constituents. α-Terpinyl acetate was the main constituent
in both the extraction methods.
Reference
[1] V. Mozaffarian, A Dictionary of Iranian Plant Names. Farhang Moaser, Tehran (1996).
[2] A. Raal, E. Arak, A. Orav, T. Kailas, and M. Müürisepp, J. Essent. Oil Res., 20, 318 (2008).
[3] Z. Szebeni-Galambosi, B. Galambosi, and Y. Holm, J. Essent. Oil Res., 4, 375 (1992).
Preparation and Application of a Flexible Drug Delivery System for
the Magnetically Controlled Release of Ciprofloxacin
Mohammad Hossein Mashhadizadeh*, Mitra Amoli-Diva, Kamyar Pourghazi
Faculty of Chemistry, Tarbiat Moalem University, 49 Mofateh Avenue, Tehran, Iran
In recent years, the integration of nanotechnology with biology and medicine has utilized functionalized nanopatrticles in
molecular biology, therapeutics and bio-separation [1-2]. Among various nanostructure materials, magnetic nanoparticles such
as magnetite due to remarkable phenomena such as supperpara magnetism and high field saturation have been growing interest in
various filed such as MRI, magnetically assisted drug delivery and biomacromolecular purification [3-4].In this study, we
prepared a silica coated magnetic nanoparticles drug delivery system for controlled release of ciprofloxacin. Magnetic
nanoparticles were prepared by coprecipitation of Fe2+ and Fe3+ with NH4OH then functionalized with 3-aminopropyl tri ethoxy
silane. The nanoparticles characterized by transmission electron microscopy (TEM) and fourier transformation infrared
spectroscopy (FTIR). The drug delivery behaviors of nanoparticles were studied by selecting ciprofloxacin as a model drug. Drug
loaded nanoparticles released the ciprofloxacin completely (within 9 h) at pH=7.2 but only a small part of ciprofloxacin (15%)
was released at pH=5.5.
Reference
[1] J. L. Zhang, R. S. Srivastara, R. D. K. Misra, Langmuir, 23 (2007) 634-635.
[2] L. Zhang, Y. Ni, X. Wang, G. Zhao, Talanta 82 (2010) 196-2010.
[3] Y. Sha, C. Deng, B. Liu, J. Chromatogr. A. 1198 (2008) 27-33.
[4] N. S. Satakar, J. Z. Hilt, J. Controlled rele. 130 (2008) 246-251.
Preparation DNA biosensore in the basis of gold nanoparticles for detection of triplex structure
J. B. Raoof*, R. Ojani, Z. MOusavi, E. Hamidi Asl
Eletroanalytical Chemistry Research Laboratory, Department of Analytical
Chemistry, Faculty of Chemistry, University of Mazandran, Babolsar, Iran
E-mail address: j.raoof@umz.ac.ir
The analysis of DNA is one of the key health issues facing our society today and is applied in monitoring of gen expression, in
forensic, in pharmaceutical applications, consumer products and food control [1].Electrochemical DNA hybridization detection
methods are mainly classified into two direct and indirect protocols. Direct methods are mainly related to the intrinsic
electrochemical activity of the nucleobases such as guanine and adenine in the DNA chain [2]. While indirect DNA hybridization
detection method is based on incorporation of an electroactive label [3,4].Triplex oligonucleotides are promising genedrugs,
which might be used in an anti-gene strategy, that attempt to modulate gene activity in vivo. Triplexes can be universal drugs that
exhibit sequenc-especific recognition of duplex DNA. This is an exciting possibility because in contrast to other DNA-binding
drugs, the recognition principle of triplexes is very simple [5].In this paper, we employed differential pulse voltammetry (DPV)
for development of electrochemical DNA biosensors based on carbon past electrode (CPE) and nano- gold modified carbon past
electrode (NGCPE). The sensor relies on immobilization of a 15-mer single stranded oligonucleotide probe for detection of target
DNA. Alteration in guanine oxidation signal following hybridization of the probe with complementary target DNA provides a
means to detect the selectivity of the biosensor. Some of the parameters such as probe immobilization conditions including
potential (0/5 V) and time (5 min) were optimized. Also, selectivity of the biosensore was carried out using DPV method.
Utilization of nano- gold as incorporated particles into a carbon past electrode improves the electrochemical signal of this
biosensing procedure. Eventually, the limit of detection is calculated for NGCPE and the sensitivity of the biosensor is
investigated.
Reference
[1] S. Siddiquee, N. A. Yusef, A. B. Salleh, S. G. Tan, F. Abu Bakar, L. Y. Heng,. Sens. and Actuat. B 147 (2010) 198.
[2] K. Wu, J. Fei, W. Bai, S. Hu, Anal. Bioanal. Chem. 376 (2003) 205.
[3] J. B. Raoof, M. S. Hejazi, R. Ojani, E. Hamidi Asl Int. J. Electrochem. Sci. 4 (2009) 1436.
[4] J. B. Raoof, M. S. Hejazi, R. Ojani, S. M. Golabi, E. Hamidi Asl, Bioelectrochem. 78 (2010) 141.
[5] M. D. Frank-Kamenetskii, S.M. Mirkin,. Ann. Rev. Biochem. 64 (1995) 65.
A Novel Dichromate-Sensitive Fluorescent Nano-chemosensor using new Functionalized SBA-15
Morteza Hosseini 1, Mohammad Reza Ganjali2, Zahra Rafiei-Sarmazdeh2,
Farnoush Faridbod3, Hassan Goldooz4, and Ali Reza Badiei5
1
Faculty of New Sciences & Technologies, University of Tehran, Tehran, Iran
2
Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran
3
Endocrinology & Metabolism Research Center, Tehran University of Medical Sciences, Tehran, Iran
4
Department of Chemistry, Tarbiat Modares University, Tehran, Iran
5
School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
*Corresponding author e-mail address: smhosseini@khayam.ut.ac.ir
A novel fluorescence nano-chemosensor for Cr2O72- anion has been developed by assembly of fluorescent aluminum complex of
8-hydroxyquinoline (8-HQ) within the channels of modified SBA-15. SBA-SPS-AlQx shows a fluorescence emission at 486 nm.
The observed remarkable fluorescence of SBA-SPS-AlQx quenches in presence of Cr2O72- anion. The results showed that this
fluorescent nano-material can be a useful chemo-sensor for determination of dichromate anions in aqueous solutions. The linear
detecting range of fluorescent nano- chemosensor for Cr2O72- anion was 0.16-2.9 µM. The lowest limit of detection (LDL) was
also found to be 1.4 ng/ml in aqueous solutions. SBA-SPS-AlQx showed selectively and sensitively fluorescence quenching
response toward Cr2O72- ion over than I3-, NO3-, CN−, CO32−, Br−, Cl−, F−, H2PO4 − and SO42− ions, which was due to the higher
stability of its inorganic complex with dichromate ion.
Selective Detection of Dihydrogen Phosphate Anions in Water with a New Holmium Complex as Fluorescent Probe
a
Morteza Hosseinia Mohammad Reza Ganjali b, Farnoush Faridbodc, Hassan Goldoozd, Alireza Badieie ,
Department of Life Science Engineering, Faculty of New Sciences & Technologies, Unversity of Tehran, Tehran,Iran
b
Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran
Endocrinology & Metabolism Research Center, Tehran University of Medical Science, Tehran, Iran
d
Department of Chemistry, Tarbiat Modares University, Tehran, Iran
e
School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
c
Holmium bis 8-Hydroxyquinoline-5-sulfonic acid chloride (HoQS2Cl(H2O)2 ) was synthesized for the first time and developed as
a fluorescent chemosensor for recognition of H2PO4- anions in aqueous solution. The intensity of emission band at 499 nm
increased along with HPO4-2 the appearance of new blue-shifted emission band at 520 nm. In aqueous solution, the red shift of
fluorescent emission upon H2PO4- binding is due to the formation of a 1:1 metal ligand complex. The sensor shows a linear
response toward H2PO4- in the range of 1.6´10-7M to 1.0´10-5 M. The new fluorescent probe exhibits high selectivity toward
H2PO4- ions over a large number of interfering anions.
A selective fluorescent sensor for Lutetium based on hexagonal mesoporous structures
Morteza Hosseini,*a Mohammad R. Ganjali,b Forouzan Aboufazeli,b Farnoush Faridbod,c Hassan Goldooz,d Alireza Badieie and Parviz
Nourozib
a
Faculty of New Sciences & Technologies, University of Tehran, Tehran, Iran. E-mail: smhosseini@khayam.ut.ac.ir; Fax: +98-(21)-66495291;
Tel: +98-(21)-61112788
b
Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran, Iran
c
Endocrinology & Metabolism Research Center, Tehran University of Medical Sciences, Tehran, Iran
d
Department of Chemistry, Tarbiat Modares University, Tehran, Iran
e
School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
A
novel
Lu3+
sensitive
fluorescent
chemosensor
is
constructed
through
the
preparation
of
8-hydroxyquinoline functionalized mesoporous silica with ordered hexagonal array structure (SBA-SPS-Q). The material was
found to demonstrate selective interactions with Lu3+, most probably due to the presence of the fluorophore moiety at its surface.
Fluorescence measurements revealed that the emission intensity of the Lu3+-bound mesoporous material increases significantly
upon addition of various concentrations of Lu3+, while the mono-, di-, trivalent cations result in either unchanged or weakened
intensities. The enhancement of fluorescence is attributed to the strong covalent binding of Lu3+, evident from the large binding
constant value (2´106 M-1).
The fabrication of the cold vapor generator and slotted quartz tube atomizer
for determination of Cd and Hg in ppb and ppt ranges
A.Valadkhani, M.H Amini, K. Kargosha*
Chemistry and Chemical Engineering Research Center of Iran
A slotted quartz tube (SQT) was fabricated with dimensions of 140 mm in length, i.d. 15mm and o.d. 17mm. Two slots with 100
and 80mm length and 1mm width with an angle of 120 degree with respect to each other were cut on the tube. This atomizer was
positioned 5mm above the burner of a conventional AAS. The laminar air/acetylene flame was allowed to enter the slot below the
SQT (longer slot). Sample solution were aspirated into the flame and analyte atoms were trapped inside of the SQT and HCL
radiation which was directed inside of the SQT absorbed by these analyte atoms and a transit signal was obtained. Deposition of
the lithium nitrate solution on inside surface of the SQT was shown to enhance the signal and extends the tube life. After
optimization of the affecting factors such as dimensions of the SQT and its slots, position of the SQT in flame, stoichiometry of
flame gases and duration of sample aspiration, 2-3 times signal enhancement was obtained with respect to conventional flame
AAS for Cd and Hg. D.L of 0.005 ppm for Cd and 0.6 ppm for Hg was achieved with this SQT method. To improve the detection
limit for Hg, a laboratory made cold vapor generator (CVG) was interface to specified dimensions quartz T-tube which was
located in front of radiation source (HCL). The T-Tube acts as an atomizer and the atomic absorption measurement was carried
out inside this tube. The CVG was purged out and directed into the atomizer, the cold vapor prevent the water vapor entering the
atomizer, the cold vapor was passed through a laboratory made gas-liquid separator and also on ice bath prior to entering the
atomizer. Under optimized conditions, a detection limit of 60 ppt with RSD of 5.6% was obtained with this home-made Hg cold
vapor t-tube atomizer.
Reference
[1] Determination of mercury in fish by cold vapour atomic absorption spectrometry using an automatic mercury analyzer, Food Chemistry 100 (2007) 853–858.
[2] Applications of a slotted tube atom trap and flame atomic absorption spectrometry: determination of bismuth in copper-based alloys with and without hydride
generation, Analytica Chimica Acta 311 (1995) 93-97.
Fabrication of Adenosine Aptasensor Based o n Immobilization Of Aptamer Onto Glassy Carbon Electrode Modified
With MWCNTs/ Ionic liquid and chitosan Nanocomposite
Faezeah Shahdostfard, Abdollah Salimi*
Department of Chemistry, University of Kurdistan, P.O.Box 416 Sanandaj- Iran
E-mail: Absalimi@uok.ac.ir & faeze-shahdoostfard@yahoo.com
Since screened through the systematic evolution of ligands by exponential enrichment(SELEX) process from random RNA or
DNA libraries, aptamer has been widely used in the analytical assays of biomolecules [1]. Because of their specific binding
abilities and many advantages over antibodies such as simple synthesis, easy labeling, good stability, and high sensitivity,
aptamers are starting to appear in biosensor applications for drugs and proteins detection[2-5]. Adenosine, an endogenous
nucleoside, has potent biological activities including extension of the blood vessels, increment of the blood flow of the arteries,
anti-arrhythmia and improvement of the oygen supply of cardiac muscle. Some evidences indicate that in has some important
function in the immune system. Furthermore, it is a vital drug intermediate in the systhesis of ATP, adenine, adenylic acid and
vidarabine. In the present study, a simple and label-free method was proposed to study the interaction between aptamer and
adenosine based on immobilization of aptamer and methylene blue (MB+) onto glassy carbon electrode modified with
MWCNTs/ILs/CHIT (multi walled carbon nanotubes-ionic liquid- chitosan) nanocomposite. At the first nanocomposite and
glutaraldehyde immobilization onto glassy carbon electrode.Then, a 3'Amine capture probe containing twelve bases was
immobilized on the glutaraldehyde by amide coupling. Aptamer probe containing thirty two bases, which was designed to
hybridize with capture DNA sequence and specifically recognize adenosine, was then immobilized on the electrode surface by
hybridization reaction. MB+ was abundantly adsorbed on the aptamer probe by the specific interaction between MB+ and guanine
base in aptamer probe. MB+ anchored aptamer probe can be forced to dissociate from the sensing interface after denosine
riggered structure switching of the aptamer. The peak current of MB+ linearly decreased with the concentration of adenosine over
a range of 500 pM - 20 nM with a detection limit of 20 pM. In addition, we examined the selectivity of this electrochemical
biosensor for cytidine, uridine and guanosine that belonged to the nucleosides family and possessed a similar structure with
adenosine. The proposed aptasensor was used to detect adenosine in human serum samples.
Reference
[1]. J.Wang, F.Wang, Sh.Dong, Journal of Electroanalytical Chemistry, 626 (2009) 1-5
[2]. X. Zuo, S. Song, J. Zhang, D. Pan, L.Wang, C. Fan, J. Am. Chem. Soc. 129 (2007) 1042-1043
[3]. R.Y. Lai, K.W. Placo, A.J. Heeger, Anal. Chem. 79 (2007) 229-233
[4]. J. Liu, Y. Lu, Angew. Chem., Int. Ed. 45 (2005) 90-94
[5]. J. Wang, Y. Jiang, C. Zhou, X. Fang. Anal. Chem. 77 (2005) 3542-3546
Characterization of the aromatic profile in apple boosted fragrance by Gas Chromatography-Mass Spectrometry
(GC/MS)
Ali Gholami , Salehe Ghaheri*
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, I. R. Iran.
E-Mail: s_ghaheri@yahoo.com
Today, flavors and fragrances are applied in cosmetic and health care industries. So, qualification and quantification of fragrances
and flavors components have great importance. This study is about the characterization of the aromatic profile in boosted apple
fragrance. On the other hand, gas chromatography has been known as unique and powerful technique in separation of volatile
complex mixtures. Combination of two components, gas chromatography and mass spectrometry, into a single GC/MS system
forms an instrument capable of separation mixture into their individual components and identifying of each component. In this
study, this technique has been suggested for identifying boosted apple fragrance composition. The qualitative analyses of the
apple boosted fragrance were carried out by using a model HP 5973 Agilent GC/MS equipped with a 30 m × 0.25 mm i.d.
Inowax (Poly ethylen glycol) column with 0.25 µm i.d. film thickness. The initial oven temperature was held at 80 °C for 2 min.
It was then increased at 2°C/min to 220°C, the injection port and ionizing source were kept at 280°C. The split ratio was 1:30
with 2 µL of sample injected. Mass spectrum were scanned from m/z= 20 to 360. Compound identifications were made by
comparison of the mass spectrum with those of corresponding reference standards. In the first step, sample without any primary
separation, has injected to GC/MS system. In the other step, sample, with primary separation as fractional distillation and steam
distillation has injected to GC/MS system. Results comparison of these experiments and analysis of same results show that
primary separation made a better identification. Identified compounds are: Benzenethanol, alpha ,alpha dimethyl, 2-Propanol,1,1oxybis, Alpha isomethyle ionone, Dipropylen glycol, 1- propanol, 1-(2-hydroxy propoxy), gamma iso methyl ionone and 2 (3H)Furanone- 5-heptyldihydro
Reference
[1] Komata Akihiko et al, Fragrance Enhancer, Publication number: JP62120313 (A), 1987
[2] Schulte-Elte, Cycloaliphatic compounds as odor and taste-modifying agents, United States Patent 3,937,723, 1976
[3] Poucher, The Raw Materials of Perfumery, Chapman & Hall: London, 1991
[4] Marsili, Sensory Directed Flavor Analysis, Published by Taylor & Francis Group, 2007
Electrooxidation of Ethylene Glycol on Pd, Pt and Au nano-particle supported
on carbon-ceramic electrode (CCE) in alkaline medium
Esmaeil Habibi, Habib Razmi
Electrochemistry Research Laboratory, Azarbaijan University of Tarbiat Moallem
A fuel cell (FC) is an electrochemical conversion device that generates directly electric energy from the combustion of a
chemical product. Methanol is promising fuel that have been investigated in fuel cells, but impediments such as toxicity and
possibility of environmental problem because of high miscibility to water inhibit the applications of direct methanol fuel cells
(DMFCs). A recent trend of investigations, considering drawbacks of methanol, is the use of polyols like ethylene glycol.
Ethylene glycol is less toxic than methanol and can be massively produced by microbial fermentation [1].Platinum based catalyst
is the most studied anodic material in fuel cells. However, very high cost of this electrocatalyst is not economic for fabrication of
fuel cells components. It is well known that the kinetics of alcohol oxidation processes in an alkaline medium instead of an acidic
one significantly increases. Especially, in this medium Pt-free catalysts such as silver, Gold and palladium can be used for
oxidation of alcohols with remarkable electrocatalytic ability [2].In our previous work, CCE was introduced as a high
performance substrate for deposition of platinum nanoparticles and it was revealed that the catalytic activity of Pt particles
strongly depend on the nature of electrode substrate [3].Here considering interesting features of CCE [3] we used it as substrate
for potentiostatically preparation of Pd and Au nanoparticles . After preparation of Pd|CCE and Au|CCE, the physicochemical
characterization of electrodes studied by SEM and XRD, next they were used for the electrooxidation of ethylene glycol in
aqueous alkaline solutions by using of several techniques such as CV, EIS and CA and results were compared with Pt|CCE. In
continuation, the kinetic parameters of ethylene glycol oxidation, i.e. Tafel slope and activation energy were determined on
modified electrodes. The present study presents a promising choice of Pd and Au|CCE as a catalyst for ethylene glycol
electrooxidation in alkaline medium.
Reference
[1] Z.X. Wang, J. Zhuge, H.Y. Fang, B.A. Prior, Biotechnol. Adv. 19 (2001) 201.
[2] P.K. Shen, C. Xu, Electrochem. Commun. 8 (2006) 184.
[3] H. Razmi, E. Habibi, H. Heidari, Electrochim. Acta 53 (2008) 8178.
Direct ethanol fuel cell based on platinum alloy nano-particle anode promoted by α-PbO2
Esmaeil Habibi, Habib Razmi
Electrochemistry Research Laboratory, Azarbaijan University of Tarbiat Moallem
Due to expectation of high energy generating efficiency in FCs; a large amount of research is being conducted in this area.
Among several alcohols such as methanol, ethanol, propanol and butanol, which can be used in a direct alcohol fuel cells
(DAFCs), ethanol is the most promising one due to considerable energy capacity (8 kWh/kg), nontoxicity, biological
renewability, easy handling and storing unlike hydrogen fuel [1]. Pt and Pt based catalysts such as Pt-Ru, Pt-Sn and ... are the
best anodic materials that exhibit catalytic properties for the oxidation process of alcohols to proceed at a sufficient rate in fuel
cells also many works has been reported focusing on the contribution of different oxide species to the electro-catalytic oxidation
of alcohols [2].In this work we studied the electrooxidation of ethanol on a carbon ceramic electrode (CCE) modified with Pt
alloy and α-PbO2 nano-particles. Due to the fact that catalysis is a surface effect, the increase of effective surface area of catalyst
is a necessity [3]. So, considering the high porosity of CC [4], the catalyst particles are dispersed on CCE surface. Firs, CCE
prepared by using of sol-gel technique and the surface of it electrochemically modified by α-PbO2. Next, Pt and Pt alloys
potentiostatically doped in PbO2 film. After preparation of modified electrodes the physicochemical characterization of they
studied by SEM and XRD. In the next section electrochemical properties of electrocatalysts characterized by cyclic voltammetry
(CV) in acidic medium. Finally, electrooxidation of ethanol on modified electrodes was studied by using of several techniques
such as CV, electrochemical impedance spectroscopy (EIS) and chronoamperometry (CA). It was found that the addition of lead
oxide to Pt and Pt alloy increases the electrooxidation current of ethanol in acidic medium. Also high stability of current density
(in chronoamperometry study) on α-PbO2 modified electrodes can be probably attributed to the low poisoning effect of catalystPbO2/CC in comparison with catalyst /CC.
Reference
[1] F. Delime, J.M. Leger, C. Lamy, J. Appl. Electrochem. 28 (1998) 27.
[2] Hugo B. Suffredini, Giancarlo R. Salazar-Banda, Luis A. Avaca, J. Power sources 171 (2007) 355.
[3] H. Razmi, E. Habibi, J. Solid state electrochem. 18 (2009) 1897.
[4] H. Razmi, E. Habibi, H. Heidari, Electrochim. Acta 53 (2008) 8178.
Application of solid-phase microextraction fiber based on sol–gel technique with gas chromatography-flame ionization
detector for determination of furan in baby-food and juice samples
Ali Sarafraz-Yazdi*, Maryam Abbasian, Amirhassan Amiri
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Iran
E-mail: asyazdi@um.ac.ir
The headspace solid-phase microextraction (HS-SPME) method with coating synthesized by sol-gel technology coupled with gas
chromatography-flame ionization detector (GC-FID) was proposed for determination of furan at trace levels in food samples.
Furan is a five-member ring colorless chemical with boiling point of 31°C and high volatility. The presence of furan, which can
be formed during Maillard reaction, in food is a cause of public concern, since this substance was classified by the International
Agency for Research on Cancer (IARC) as possibly carcinogenic to human. Sol–gel coatings possess higher thermal and solvent
stability than conventional coatings, because of the direct chemical bonding to the fused silica surface. On the other hand, CNTs
have a very large surface area, which makes them potentially useful in nanotubes reinforced materials, such as the sorbents for
SPME. In this work, according to our previous study combination of OH-functionalized multi-walled carbon nanotubes
(MWCNTs) and poly(ethylene glycol) as the main sol ingredients to prepare new high-performance SPME fiber were used.
Experimental parameters including extraction time, extraction temperature, stirring speed, ionic strength, desorption temperature
and time were evaluated and optimized. Under optimized conditions, the linear range was 0.0005-10 ng/mL, limit of detection
(S/N=3) was 0.00025 ng/mL and limit of quantification (LOQ) was 0.0005 ng/mL. Relative recoveries for the spiked samples
with 0.1 ng/mL of furan were ranged from 95-103%. The proposed HS-SPME-GC-FID method was successfully applied for the
extraction of furan in two environmental food samples (baby food and fruit juice), and the concentrations of the target were found
in the range of 0.026 to 0.128 ng/mL.
Reference
[1] National Toxicology Program (NTP) Ninth Report on Carcinogenesis, Furan CAS No. 110-00-9 Carcinogenicity), 1993.
[2] International Agency for Research on Cancer, IARC Monographs on the Evaluation of Carcinogenic Risks to Humans, vol. 63, 1995.
[3] A. Sarafraz-Yazdi, H. Piri Moghadam, Z. Es‘haghi, S. Sepehr, Anal. methods, 2 (2010) 746.
[4] A. Sarafraz-Yazdi, S. Sepehr, Z. Es‘haghi, H. Piri Moghadam, Chromatographia, 72 (2010) 923.
Electrochemical behavior of palladium complex loaded on to IL / CNT-Composite,
application to electroreduction of hydrogen peroxide
R. Hallaja*, Abdol R. Hajiporb , F. Abrishamib, A. Salimia
Department of Chemistry, Kurdistan University, P.O.Box 416,Sanandaj,.Iran
b
Pharmaceutical Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan 84156, IR Iran
E-mail; Rhallaj@uok.ac.ir; Rhallaj@yahoo.com
a
Recently, Carbon nanotube- ionic liquid composites were used to construction of sensors and biosensors. One major advantage of
this electrode compared to other modified electrodes is its extremely low capacitance and background currents [1]. High
conductivity and large surface area are another advantage of this composite. Due to the large polarity of ionic liquid and excellent
adsorption capability of carbon nanotubes for the most organic and organometalic compounds, the IL/CNTs-Composite is
suitable material to immobilization of molecules and biomolecules [2]. In this work the IL/CNTs-Composite was used to loading
the palladium complex. The immobilization of Pd-Complex was done by simply immersing of glassy carbon modified IL/CNTs
electrode into Pd-Complex acetonitrile solution. Scanning electron microscopy (SEM) and cyclic voltammetry was used to
characterization of modified electrode. The GC/IL/CNT/Pd-complex showed well defined redox couple that can be used as a
shuttle of electron during the oxidation and reduction of species at the surface of electrode. Electrocatalytic activity of
GC/IL/CNTs-Pd-Complex electrode was evaluated by voltammetric techniques. The results shows that the IL/ CNTs/Pd-complex
electrodes have exhibited strong and stable electrocatalytical response towards important biomolecule related to human health,
such as NADH and also molecular oxygen. The advantages of this sensor are excellent catalytic activity, high sensitivity, good
reproducibility and simplicity of preparation at short time periods. The used Pd-Complex was synthesized by refluxing
homoveratrylamine and 2,6-dichlorobenzaldehyde in a 1:1 molar ratio in ethanol for 2h. The formed Schiffbase was reacted with
Pd(OAc)2 (1:1) in CH2Cl2 followed by treatment in situ with NaBr gave the insoluble dimeric complexe with bromine bridges
[3].
Reference
[1] R. Torabi Kachoosangi, M. M. Musameh, I. Abu-Yousef, J. M. Yousef, S. M. Kanan, L. Xiao, S. G. Davies, A. Russell, R. G. Compton, Anal. Chem., 2009, 81,
435–442.
[2] S. Shiraishi, H. Kurihara, K. Okae, D. hulicova, A.Oya, Electrochem. Comm. 2002, 4, 593-598
[3] S. Tollari, S. Cenini, C. Tuunicc, G. Palmisano, Inorg. Chim. Acta, 1998, 18-23.
Comparison of Temperature-Controlled Dispersive and Hollow Fiber Microextraction Techniques
Using Ionic Liquid for Determination of Tributyl and Triphenyltin in Water
Hossein Sheikhloiea,*, Mohammad Saber Tehranib, Syed Waqif Husainb
Department of Basic Sciences, Maragheh Branch, Islamic Azad University, Maragheh, Iran.
b
Department of Chemistry, Science and Research Branch, Islamic Azad University, Tehran, Iran.
*E-mail: H.Sheikhloie@IAU-Maragheh.ac.ir
a
In this work two liquid phase microextraction techniques termed ionic liquid based hollow fiber liquid phase microextraction (ILHF-LPME) and temperature-controlled ionic liquid dispersive liquid phase microextraction (TCILDLPME) were used for the
extraction of tributyltin (TBT) and triphenyltin (TPhT) in environmental water samples that the European Union has listed them
as priority pollutants [1]. After extraction, the ionic liquid phase was injected directly into the high performance liquid
chromatography (HPLC) system for determination. In TCILDLPME ionic liquid ([C6MIM][PF6]) was dispersed directly into the
aqueous solution under the drive of temperature, and the analytes will more easily migrate into the ionic liquid phase because
much larger contact area exists. This method has been compared with HF-LPME. In HF-LPME the acceptor phase was
([C4MIM][PF6]), providing a two-phase extraction system compatible with high performance liquid chromatography. The effects
of various experimental parameters on the extraction were investigated in each method and operating conditions were also
optimized. To evaluate the applicability of the proposed methods, they were then successfully applied for the analysis of
environmental water samples. The results showed that extraction time of TCILDLPME is very short. The best repeatability and
low detection limits (LOD, S/N=3) were achieved for TCILDLPME as compared with HF-LPME. Furthermore, extraction
efficiency and recovery in the TCILDLPME is higher than HF-LPME. The methods were also compared with extraction of the
same analytes by single drop microextraction using ionic liquid as green solvent [2].
Reference
[1] Dadfarnia Sh, Haji Shabani A M (2010) Anal. Chim. Acta, 658, 107.
[2] Sheikhloie H, Saber Tehrani M, Abroomand Azar P, Waqif Husain S (2009) Acta chromatographica, 21, 577.
Preparation a Monolithic loop by molecularly imprinted polymers for on-line extraction and determination of Tramadol
in human plasma and urine with high performance liquid chromatography
Mohammad Mahdi Moeina, MehranJavanbakhta,٭, BehrouzAkbari-aderganib
a
Department of Chemistry, Amirkabir University of Technology, Tehran, Iran, E-mail: mehranjavanbakht@gmail.com, Tel: +98-21
64542764;Fax: +98-21 64542762
b
Food & Drug Laboratory Research Center, Food & Drug Department, Ministry of Health and Medical Education, Tehran, Iran
In this paper, a novel solid phase extraction (SPE) method for the determination of Tramadol (TRD) in plasma by molecularly
imprinted monolithic loop was developed. Using tremadol as the template, methacrylic acid (MAA) as the functional monomer,
ethylene glycol dimethacrylate (EGDMA) as the cross-linker andchloroform as the solvent, a tremadol imprinted monolithic loop
was prepared by in situ molecular imprinting technique for the first time, and the optimal synthesis conditions and the selectivity
of TRD imprinted monolithic loop were investigated. The high selectivity of the sorbent in an on-line molecularly imprinted
monolithic HPLC loop permitted a simple and rapid analysis of this drug inurine samples showed with limits of detection (LOD)
and quantification (LOQ) of 0.33 ng mL-1 and 0.10 ng mL-1, respectively. These limits for tramadol in plasma samples were 1.1
and 3.3 ng mL-1, respectively.
Reference
[1] M. Javanbakht, H. Namjumanesh, B. Akbari-Adergani, Talanta 80 (2009) 133.
[2] M. Javanbakht, N. Shaabani, B. Akbari-Adergani, J. Chromatogr. B 877 (2009) 2537.
[3] M. Javanbakht, A.M.Attaran, M.H.Namjumanesh, M.Esfandyari-Manesh, B. Akbari-aderganic, J.Chromatogr. B, 878 (2010) 1700
[4] M. M. Moein, M. Javanbakht, B. Akbari-Adergani, J. Chromatogr. B, 879 (2011) 777.
Development of a simple hollow fiber based liquid–liquid–liquid microextraction method to extract and preconcentrate of
amlodipine in plasma and urine samples followed by RP-HPLC
a
Hassan Heidaria, Habib Razmi, , Abolghasem Jouybanb
Analytical Research Lab., Faculty of Sciences, Azarbaijan University of Tarbiat Moallem, P. O. Box: 53714-161, Tabriz, Iran
b
Faculty of Pharmacy and Drug Applied Research Center, Tabriz University of Medical Sciences, Tabriz, Iran
Amlodipine besylate (AMB) is a dihydropyridine type long acting calcium channel blocking agent and it is clinically used in the
treatment of hypertension and chronic stable and vasospastic angina. Therapeutic dosage of amlodipine usually results in
relatively low plasma concentrations ranging from 1 to 25 µg L-1. Therefore, sensitive and specific methods are essential for
monitoring of AMB drug in clinical samples. Audunsson [1] introduced an alternative concept for liquid phase microextraction
that was developed by Thordarson et al. [2] and Pedersen-Bjergaard and Rasmussen [3] based on hollow fibers made of
polypropylene. The technique can be used in different ways. The most commonly reported is the liquid–liquid–liquid system,
which was used to extract ionizable and chargeable compounds from aqueous samples.The aim of this study is to develop and
evaluate a new, simple and precise analytical method for determination of AMB in biological samples by the combination of HFLLLME with HPLC-UV detection. The effect of different parameters such as organic solvent, pH of donor phase and acceptor
phase, temperature, stirring rate and extraction time were controlled and optimized. The optimized method was applied to real
matrices such as urine and plasma. Under optimal conditions, a linear calibration curve over the range of 0.5 - 300 µg L−1 was
obtained (r2 > 0.9989) and enrichment factor of 192 and detection limit (LOD) of 87 ng L−1 were calculated. The extraction
recoveries of AMB in plasma and urine samples were 103.2% and 97.2% with R.S.D.s of 6.4% and 4.8%, respectively.
Therefore, the method provides good enrichment factor (192 fold) along with excellent sample clean-up, good repeatability and
reproducibility and low detection limit for the spiked urine and plasma samples.
Reference
[1] G. Audunsson, Anal. Chem. 58 (1986) 2714.
[2] E. Thordarson, S. Pálmarsdóttir, L. Mathiasson, A. Jönsson, Anal. Chem. 68 (1996) 2559.
[3] S. Pedersen-Bjergaard, K.E. Rasmussen, Anal. Chem. 71 (1999) 2650-2656.
Optimization of ultrasound-assisted emulsification-microextraction with light density organic solvent
followed by RP-HPLC for determination of amlodipine
in biological and environmental samples
Hassan Heidari, Habib Razmi
Analytical Research Lab., Faculty of Sciences, Azarbaijan University of Tarbiat Moallem, P. O. Box: 53714-161, Tabriz, Iran
Modern trends in analytical chemistry are towards the simplification and miniaturization of sample preparation, as well as the
minimization of the used organic solvent. As a result, several procedures have been developed for the extractions, such as singledrop liquid-phase microextraction (SDME), solid-phase microextraction (SPME) and hollow fiber-based liquid-phase
microextraction (HF-LPME). Very recently, a microextraction technique for aqueous samples, known as ultrasound-assisted
emulsification–microextraction (USAEME) has been proposed [1]. USAEME procedure combines microextraction system and
ultrasonic radiation in one step. To the best of our knowledge, in this work USAEME was applied to plasma sample for the first
time and also, there is no report on the use of USAEME for the analysis of amlodipine besylate (AMB). The aim of the current
work was to develop a simple, inexpensive and sensitive method based on ultrasonic radiation to assist the emulsification of low
density extractant solvent used for the preconcentration of AMB in biological and environmental samples before the
quantification by RP-HPLC-UV. The parameters with significant effects on extraction efficiency were identified using a
Plackett–Burman design and their levels were optimized using a Box–Behnken response surface method to improve extraction.
In this work, due to develop a very simple homemade device that is compatible with organic solvents with density lighter than
water and easily can be washed after use, organic solvents with low density comfortably used for the USAEME.The developed
method was successfully applied to biological and environmental sample analysis. Under the optimal USAEME conditions,
extraction recoveries of AMB in plasma and water samples were 28% and 57.4%, respectively, corresponding to the enrichment
factor of 16 in plasma and 164 in water sample. Good linearities (r2= 0.9953 for plasma sample and 0.9980 for water samples) of
analyte were achieved in the range of 10–2500 µg L−1 (plasma sample) and 1-250 µg L−1 (water sample). The detection limits of
0.407 and 0.038 µg L−1 were obtained for plasma and water samples, respectively.
Reference
[1] J. Regueiro, M. Llompart, C. Garcia-Jares, J.C. Garcia-Monteagudo, R. Cela, J. Chromatogr. A 1190 (2008) 27-38.
Investigation of the effect of air temperature an oil percent and Lipoic acids amaunt of Brassica spiecies
in Golestan province
Negar Riazya*,Abolfazl Farajib ,Mohamad Alimoradia,Elham Faghanib,Ali Afzali Nezhada
a. Department of chemistry,Islamic Azad University,Arak Branch, Iran.
b.researcher of Agricultural and Natural Resources Research Center of Gorgan
negar_riazy1985@yahoo.com
After oilseeds, crops are the second major source of food supplies across the world. these products in addition to having a rich
source of fatty acids , may also contain protein. according to this issue that over 85 percent of the country’s oil requirements are
supplied through imports , elimination in producting the oilseed in country is so important. Golestan province is the most
important position in cultivation of oilseeds in the country. Oilseed such as Brassica napus. since the rainfall over the major parts
of the country take place with an approximately delay , and Brassica napus cultivation procedure would have an interrupt , so
knowing qualitative changes oil genotypes is very important.This research were conducted to evaluation environmental
conditions impact from different dates of planting on the composition fatty acid in eight Genotypes from different species of
Brassica.The evaluated Genotypes included two Genotypes of Brassica Juncea J98,Bard 1,two Genotypes of Brassica
compestris,Rinbow and candel and four Genotypes of Brassica napus L.,Hayola 401,shiralee,RGS003 and Select 4.The
experiment was performed in the from of random blocks base in agricultural year 2009-2010 and in three separated dates.In this
research Extraction and measuring percentage of total lipid by soxhlet method and combination of fatty acid in seeds injected to
Gc(Gas chromatography).
Refrence
[1] R. Amarowicz, R. Naczk and F. Shahidi, Antioxidant activity of various fractions of nontanin phenolics of canola hulls, of Agri and food chemistry, 49 (2000)
2755-2759.
[2]
G. Robbelen, R.K.Downey, A. Ashri, Oil Crops of the word their breeding and utilization Mc Graw- HILL pub.co, 1989
A Convergent Paired Electrochemical Synthesis of complex Fe(II)-3-methyl catechol. Reaction of 3-methyl catechols with
Fe(II).
A. Afzali Nezhada *,D. Nematollahib ,Z. Mahmoodia, N. Riazya
a. Department of chemistry,Islamic Azad University,Arak Branch, Iran.
b. Bu Ali Sina University, Department of Chemistry, Iran.
afzali.ali00@gmail.com
In Electrochemical synthesis of Complex Fe (II) -3-methyl catechols , Fe is used as Anode in solvent Acetonitrile in presence of
3-methyl catchol and it's derivatives. In this method, two Hydrogen in 3-methyl Catechol were substituted by Fe (II) and
Complex is easily produced.For doing this, Hydrogen is released in cathode. In order to formation of complex with Fe,
3methyl catechol and other its derivatives were deproteinated. In order to performing this examination, all syntheses were done in
fixed current. Spectrophotometry methods of FT-IR and UV-Vis and Atomic Absorption sepctrophotometry are used for
investigation and confirmation of obtained complexes. Obtained Complexes were confirmed and ratio of combination of Fe with
3-methyl catechol was determinated. High efficient and pure synthesis of Fe (O2Ar) without separation of anode and cathode
cell, were done successfully. This synthesis is important for obtaining coordinated compounds by reactions with pure metals
.This method is a rapid and selective method and is one of the most useful, easy and high efficient methods compared to
conventional methods for obtaining new compounds. Since chemical stages are reduced in this method, Synthesis of products is
quantative.
Refrence
[1] N. Kumar, D.G. Tuck. Inorg. Chem., 22, 1951 (1983).
[2] J.L. Hencher, M. Khan, F.F. Said, R. Sieler, D.G. Tuck. Inorg. Chem., 21, 2787 (1982).
[3] H.E. Mabrouk, D.G. Tuck. J. Chem. Soc., Dalton Trans., 2539 (1988).
[4] J.S. Banait, B. Singh, H. Kaur. J. Indian Chem. Soc., 82, 555 (2005).
[5] Y.J. Yang, L.Y. He, Q.F. Zhang. Electrochem. Commun., 7, 361 (2005).
Determination of ephinephrine in the presence of uric acid based on self-assembled monolayer
of derivative of thiophene on gold electrode
S.M. Goreishi* , Z. Moghadam, M. Motaghedifard
Department of Analytical Chemistry, Faculty of Chemistry, University of Kashan, Kashan, I.R. Iran
E-mail: s.m.ghoreishi@kashanu.ac.ir
Self-assembled monolayers (SAMs) have recently become very important due to their potential applications to biosensors,
nanotechnology and biomolecular electronics [1]. SAMs provide a convenient, flexible, and simple system with which to tailor
the interfacial properties of metals, metaloxides, and semiconductors [2]. Gold is the most frequently used substrate because it
does not have a stable oxide under ambient conditions. The thiol groups chemisorb onto the gold surface via the formation of a
gold–thiol bond [3]. Epinephrine (EP) is one of the important neurotransmitters in mammalian central nervous systems and it
exits in the nervous tissue and body fluid in the form of large organic cations. The changes of its concentration may result in
many diseases [4]. In this work the application of self-assembled monolayer (SAM) on gold electrode for the electrochemical
determination of EP in the presence of uric acid was studied. The electrode modification process was characterized by cyclic
voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The EIS was used to evaluate pKa of the adsorbed
derivative of thiophene on gold surface in the presence of Fe(CN)63−/4− as a redox probe. Prior to modification, the gold electrode
was polished, and ultrasonicated in absolute ethanol and in distilled water. After each polishing step followed by electrochemical
pretreatment of the gold electrode by cycling the potential between 0 and 1.50V at a scan rate of 100 mV s-1 in 0.50 M H2SO4
solution until a constant background of CV curve was obtained. The cleaned electrode quickly immersed in the 10 mM derivative
of thiophene ethanolic solution. The electrochemical behaviors of EP on modified electrode were studied in phosphate buffer
solution (pH.6). the electrochemical behavior of EP was characterized by CV, differential Pulse voltammetry, linear sweep
voltammetry, amperometric titration, double potential step chronoamperometry.
Reference
[1] S.K. Aryaa, P.R. Solanki, M. Datta, B.D. Malhotra, Biosens. Bioelectron. 24 (2009) 2810–2817.
[2] J. Ch. Love, L. A. Estroff, J. K. Kriebel, R.G. Nuzzo, G.M. Whitesides, Chem. Rev. 105 (2005) 1103-1169.
[3] R. Karimi Shervedani, M .Khosravi Babadi, Talanta. 69 (2006) 741–746
[4] Z. Yang, G. Hu, X. Chen, J. Zhao, G. Zhao, Colloids Surfaces B. 54 (2007) 230–23
Heterogeneous photodegradation catalysis of 4-nitrophenol using ZnO/nanoclinoptilolite
Alireza-Nezamzadeh-Ejhieh*, Setareh-Khorsandi
Department of Chemistry, Islamic Azad University, Shahreza Branch
Email:arnezamzadeh@iaush.ac.ir, setareh_khorsandi@yahoo.com
Important organic contaminants in industrial wastewaters are phenols and phenolic compounds. An attractive, sludge free
alternative for the treatment of a wide range of organic pollutants in wastewater, is the use of advanced oxidation processes
(AOPs). Among the various AOPs, semiconductor mediated photocatalysis has been accorded great importance due to its
potential to destroy a wide range of organic and inorganic pollutants at ambient temperatures and pressures, without the
production of harmful products. Recently, supporting of the semiconductors onto the zeolites has been widely used [1-3]. In this
work, the photocatalytic degradation of 4-nitrophenolin aqueous solutions with ZnO/nanoclinoptilolite catalyst under UV
irradiation was carried out. Photocatalyst was prepared by ion exchange of nanoclinoptilolite with Zn(II) aqueous solution (0.1
M) followed by draying and calcination at 450 °C. A 20 mL solution of 10 ppm 4-nitrophenol at pH=8 containing catalyst was
introduced into a reactor and irradiated. The absorbance of samples at λmax=400 was measured using UV-Vis spectrophotometer
before and after irradiation and were used for degradation efficiency.
Reference
[1]S. Lathasree, A. Nageswara Rao, B. SivaSankar, V. Sadasivam, K. Rengaraj,"Heterogeneous photocatalyticmineralisation of phenols in aqueous solutions" J. Mol.
Catal. A: Chem. 223 (2004) 101–105.
[2]M.B. Kasiri, H. Aleboyeh, A. Aleboyeh, "Degradation of acid blue 74 using Fe-ZSM5 zeolite as a heterogeneous photo-Fenton catalyst", Appl. Catal. B: Environ
84 (2008) 9-15.
[3]W. Song, G. Li, V. H. Grassian, S. C. Larsen, "Development of improved materials for environmental applications: nanocrystalline Na-Y zeolites", Environ. Sci.
Technol. 39 (2005) 1214-1220.
Chemically Bonded Carbon Activated as Efficient Material for Solid Phase Extraction of Some Metal Ions
M. Ghaedi a*, M. Montazerozohori a, N.Rahimib, M. Nejati Biyareh a
a)
Chemistry Department, Yasouj University Yasouj Iran 75914-353.
b)
Chemistry Department, Firozabad Azad University, Firozabad, Iran.
*E-mail: m_ghaedi@mail.yu.ac.ir; neda.rahimi1986@yahoo.com
Important positive and negative roles of heavy metal ions in human health and their [1-3], so that roles in the body is very rich
and varied. carbon activated modified with 1-((2-(2-(trimethoxysilyl) ethylamino) ethylimino) methyl) naphthalene-2-ol has
been used for the solid phase extraction of some metal ions. The influences of the analytical parameters including pH, amounts of
reagents and amount of solid phase, eluting solution conditions (type and concentrations), sample volume and influence of
interference of many ions on metal ions recoveries were investigated. The metal ions retained on chemically modified AC
efficiently was eluted using 10 mL of 4 mol l-1 HNO3 solution was determined by flame atomic absorption spectrometry. Relative
standard deviations (n=10) was between 1.7-2.9 %, while the detection limit was between 1.0-2.6 ng ml-1 (3Sb, n = 10) and
preconcentration factor was 100 for all understudy metal ions . The sorption capacity of activated carbon modified by ligand for
all investigated metal ions was higher than 30 mg g−1. The proposed method was successfully applied for the extraction and
determination of analytes in different samples.
Reference
[1] Ghaedi ,M., Ahmadi, F., Soylak,M., 2007 Simultaneous Preconcentration and Determination of Copper, Nickel, Cobalt and Lead Ions Content by Flame Atomic
Absorption Spectrometry. Ann. Chim. 97, 277-285.
[2] Kabadayi, F., Cesur, H. 2010. Determination of Cu, Pb, Zn, Ni, Co, Cd, and Mn in road dusts of Samsun City, Environ. Monit. Assess. 168, 241-253.
[3] Khajeh, M., Sanchooli, E. 2010. Optimization of Microwave-Assisted Extraction Procedure for Zinc and Iron Determination in Celery by Box–Behnken Design,
Food Anal. Methods 3, 133-137.
Highly efficient removal of Acid 37 by Bis (2- hydroxy ethyl) amine functionalized nanoporous SBA-15
1
Leila Hajiaghababaei1, Saeedeh Aboozari*1, Alireza Badiei2
Department of Chemistry, Islamic Azad University, Shahre Rey Branch, Tehran, Iran
2
Department of Chemistry, University of Tehran, Tehran, Iran
The ordered mesoporous materials belong to an important class of molecular sieve materials. Their large surface area, ordered
pore structure and nanometer-sized pores offer a unique environment for chemical separations. On the other hand, in most
industrial wastewaters, the removal of one or two problematic pollutants from the effluent can mean a significant saving in the
treatment cost. Dyes used in the textile industry are one such example. Therefore, in this study, Bis (2- hydroxy ethyl) amine
Functionalized Nanoporous SBA-15 molecular sieve was prepared to evaluate its application as a novel adsorbent for removal of
Acid red 37 dyes [Fig 1] from wastewater sample.
To a solution of 10 ml of the sample containing 500 μg Acid red 37, 8mg of functionalized SBA-15 was added and the mixture
was stirred for at least 5 minutes. The resulting mixture was filtrated. Then, dyes concentration in extracted solution was
measured by UV/visible spectrophotometer and the percentage of removing was calculated. The effect of several variables such
as amount of adsorbent, stirring time and pH has been studied and adsorption isotherms were obtained. Finally, the application of
removing this dye from real samples was examined by laboratory wastewater samples. For all samples, percentage of removal
was found more than 98%.
Reference
[1] Ka Yee Ho, Gordon McKay, and King Lun Yeung, Selective adsorbents from ordered mesoporous silica, Langmuir 2003, 19, 3019-3024.
Spectrofluorimetric Method for Determination of Human Serum Albumin Using Terbium-Danofloxacin Probe
Amir. M. Ramezani 1, Jamshid L. Manzoori1,*, Abolghasem Jouyban2
Department of Analytical Chemistry, Faculty of Chemistry, University of Tabriz, Tabriz, Iran
2
Drug Applied Research Center and Faculty of Pharmacy, Tabriz University of Medical Sciences, Tabriz 51664, Iran
1
Study on proteins, due to their importance in life science, has been a very active area for chemists and biologists for the past
decades. Several procedures have been reported for the detection and quantification of proteins in different samples [1-2].
Lanthanides have found applications in different fields of biomolecular and medical research. Luminescence of lanthanide
chelates has created interest mainly due to their unique properties, such as their long Stokes shift and exceptional decay times,
allowing efficient temporal discrimination of background interferences in assays. A spectrofluorimetric method is developed for
the determination of human serum albumin (HAS) using terbium-danofloxacin (Tb3+-Dano) as a fluorescent probe. HSA can
remarkably enhance the fluorescence intensity of the Tb3+-Dano complex at 545 nm. The enhanced fluorescence intensity of
Tb3+-Dano is proportional to the concentration of HSA. The optimum conditions for the determination of HSA were investigated
and the results indicated that the maximum response is observed at: pH = 7.8, [Tb3+] = 8.5Í10-5 M and [Dano] = 1.5Í10-4 M.
The method was evaluated in terms of the linearity of the calibration graphs for standard solutions, serum and plasma samples;
accuracy; precision and limit of detection. This method is simple, practical and relatively free from interference effects. It was
successfully applied to the determination of a number of real biological samples.
Reference
[1] H. Tkakusa, K. Kicuchi, Y.Urno, H. Kojima, T. Nagano, Chem. Eur. J., 9 (2003) 1479.
[2] K .J. Farnaz, M. Nitz, B. Imperiali, Chem. BioChem., 4 (2003) 265.
Modified BINOL Podands and Their Application in Spectrophotometric Determination of Toxic Metal ions
Hamid khoshsafar*, Hanif fattahi
Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran
The determination of trace amount of heavy metal ions has received considerable attention in the battle against environmental
pollution. In the determination of heavy metal ions, various method including ICP-MS [1], ion chromatography [2], anodic
stripping [3], and electrochemical atomic absorption spectroscopy [4], have been used. The determinations of cations have been
performed using different legends such as podands. In recent years podands, open chain ligands attracted increasing interested as
anion activators in homogeneous and heterogeneous systems [5]. New dinaphthosulfide podand (NAPH-S-Q-U) was synthesized.
The structure of this compound was confirmed by IR, 1H NMR, 13C NMR, and Mass spectra. A simple, efficient, and sensitive
procedure is described for the spectrophotometric determination of a trace amount of Ag+, Hg2+ , Cr3+, Pb2+ , and Ni2+ cations in
the presence of Mn2+ , Co2+ , Cd2+ cations using the podand. Formation constants of 1:1 complexes were determined from the
absorbance-mole ratio data and found to vary in the order Pb2+ > Ni2+ > Hg2+ > Cr3+ > Ag.+
Reference
[1]T. Kato, S. Nakamura, and Mirita, Anal. Sci.6,623 (1990)
[2]S. Okawa, K. Yamazaki, and T.Ishikaw, Bunsekik Gaku, 47, 961(1998)
[3]J. F. Staden and M.C. matoetoe, Anal. Chim. Acta 411,201 (2000)
[4]K.Cundeva and T. stafilvo, Anal. Lett, 30,833(1997)
[5]P. Seigle-Ferrand, S.B. Sdira, C. Feleix, R. Lamartine, C, Bavoux, Material Science and Engineering C 26, 181-185 (2006)
Equilibrium studies of methyl violet sorption from aqueous solution using fiber palm as a low cost adsorbent
Maryam Abrishamkar*, Shahla Elhami, Fatemeh Mohamad ali Kheirabadi
Department of Chemistry, Islamic Azad University, Khozestan Science and Research Branch, Ahvaz, Iran. Email:m.abrishamkar@umz.ac.ir
Removal of synthetic dyestuff such as methyl violet from aqueous solution is an essential point in the waste water treatment
processes due to the frequent appearance of dyestuff in effluents of various industries such as textiles, paper, rubber, plastics and
cosmetics wastewaters. The presences of dyes in water streams are undesirable since even a very small amount of these coloring
agents is highly visible. Nevertheless, much of them are considered as toxic materials in environmental point of view [1-3]. Fiber
palm as an agricultural waste products have been successfully used for the removal of a hazardous methyl violet dye from
aqueous media. Batch adsorption investigations have been made by measuring effect of pH, contact time, adsorbent doze, sieve
size and concentrations of dye solution. Equilibrium isotherms were analyzed by Langmuir and Freundlich models. The
adsorption capacity was found to be 229.9 mg/g by Langmuir isotherm for the particle size of 0.25 mm. The maximum removal
of 99.6% was obtained at nature pH 5 for an adsorbent dose of 0.1g/50mL dye concentration.
Reference
[1] G. Crini, Bioresour. Technol. 97 (2006) 1061-1085.
[2] J. J. M. Orfao, A. I. M. Silva, J. C. V. Pereira, S. A. Barata, I. M. Fonseca, P. C. C. Faria, M. F. R. Pereira, J. Colloidal Interface Sci. 296 (2006) 480-489.
[3] S. B. Hartono, S. Ismji, Y. Sudaryanto, W. Irawaty, J. Ind. Eng. Chem. 11 (2005) 864-869
Simultaneous Determination of Sulfadiazine and Trimethoprim in Bovine
Milk and Pharmaceutical Compounds by Cloud Point Extraction (CPE) and Net Analyte Signal Standard Addition
Method (NASSAM)
HAJIAN REZA 1, MOUSSAVI ESMAT 2
Department of chemistry, Islamic Azad University, Gachsaran branch, Gachsaran, 7581863876, Iran.
E-mail: Hajian@iaug.ac.ir
2
- Department of chemistry, Islamic Azad University, Gachsaran branch, Gachsaran, 75818-63876, Iran.
E-mail: Esmat.mussavi@gmail.com
1
Net Analyte Signal Standard Addition Method [1,2] has presented for the simultaneous determination of sulfadiazine and
trimethoprim by spectrophotometry in some Pharmaceutical compounds and bovine milk. The method combines the advantages
of standard addition method with the net analyte signal concept which enables the extraction of information concerning a certain
analyte from spectra of multi-component mixtures. In this work an attempt was made to calculate NAS vectors and attribute them
to the analyte concentration using standard addition method to solve matrix effect. This method has some advantages such as: the
use of a full spectrum realization, therefore it does not require calibration and prediction step and only a few measurements
require for the determination. Also the method can be applied for the determination of analyte in the presence of known
interferents. Cloud point Extraction (CPE) based on the phenomenon of sulubilization used for extraction of sulfadiazine and
trimethoprim in bovine milk [3]. It is based on the induction of micellar organized media by using Triton X-100 as an extracting
solvent. The limits of detection (LOD) for sulfadiazine and trimethoprim were found 0.86 and 0.92 mol L-1 respectively. The
average recoveries and relative standard deviations were in the range of 99.4–100.5% and 0.87–1.63% respectively in the
analysis of Neuton and Trimetosul as the two important injectable suspensions in veterinary. Also the average recoveries for
fortified milk samples at 10 mol L -1 were in the range of 99.4–100.5%.
Reference
[1] K. A. Zeynali, M. Bastami, Spect. Chim. Acta.75 (2010) 589.
[2] K. A. Zeynali, M. R. Majidi, M. Tahmasebpour, J. Serb. Chem. Soc.74 (2009) 789.
[3] W. Zhang, C. Duan, M. Wang, Food Chemistry 126 (2011). 779.
Chemically Bonded Silica gel as Efficient Material for Solid Phase Extraction of Some Metal Ions in Food Samples
M. Ghaedi a*, M. Montazerozohori a, H.R.Moazen b, M. Nejati Biyareh a
a)
Chemistry Department, Yasouj University Yasouj Iran 75914-353.
b)
Chemistry Department, Firozabad Azad University, Firozabad, Iran.
*E-mail: m_ghaedi@mail.yu.ac.ir; ironasid@yahoo.com
Generally, dues to uptake of heavy elements by human diet, their determination in food and waters is very important [1-3]. in
the content of environmental protection, food and agricultural chemistry as well as high purity materials. However, the direct
determination of metal ions in complex matrices is limited due to their usually low concentrations and matrix interferences.Silica
gel with 4-methoxy-6-((2-( trimethoxysilyl) ethylamino) ethylimino) methyl) phenol has been used for the solid phase extraction
of some metal ions in food samples. The influences of the analytical parameters including pH, amounts of reagents and amount of
solid phase, eluting solution conditions (type and concentrations), sample volume and influence of interference of many ions on
metal ions recoveries were investigated. The metal ions retained on chemically modified Silica gel efficiently was eluted using
١٠ mL of ٦ mol l-1 HNO3 solution was determined by flame atomic absorption spectrometry. Relative standard deviations (n=10)
was between 1.6-3.0 %, while the detection limit was between 1.0-2.6 ng ml-1 (3Sb, n = 10) and preconcentration factor was 100
for all understudy metal ions . The sorption capacity of Silicagel modified by ligand for all investigated metal ions was higher
than ٢٠ mg g−1. The proposed method was successfully applied for the extraction and determination of analytes in different
samples.
Reference
[1]Narin, I., Soylak, M., Elçi, L., Doğan, M. 2001. Separation and Enrichment of Chromium, Copper, Nickel and Lead in Surface Seawater Samples on a Column
Filled with Amberlite XAD-2000, Anal. Lett., 34, 1935-1947.
[2]Soylak, M., Turkoglu, O. 1999. Trace Metal Accumulation Caused by Traffic in Agricultural Soil near a Motorway in Kayseri-Turkey, J. Trace Microprobe
Techn., 17, 209-217.
[3]Dogan, Y., Ugulu, I., Baslar, S. 2010. Turkish Red Pine as a Biomonitor: A Comparative Study of the Accumulation of Trace Elements in the Needles and Bark.
Ekoloji, 19, 88-96.
Electrochemical hydride generation of Sb(III) and Sb(V) in non-aqueous media
M. H. Arbab-Zavar, N. Ashraf, N. Yaghoobi*
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Mashhad, Iran.
E-mail: n.yaghoobi.chem@gmail.com
In this work, the influence of various protic and aprotic organic solvents (methanol (MeOH), ethanol (EtOH), isopropanol
(PrOH), acetonitrile (AN), and dimethylsulfoxide (DMSO) on the electrochemical hydride generation (ECHG) of antimony
species was evaluated. Stibine (SbH3) has been produced from Sb(III) and Sb(V) by an ECHG batch cell [1,2]. The hydrides,
react with silver diethyldithiocarbamate (SDDC) in a basic organic medium and a red colored complex is formed. Detection is
performed using a UV-Vis spectrophotometer in the wavelength of 510 nm. The results of the experiments showed a better
performance for ECHG in the presence of 4 organic solvents i.e. MeOH, EtOH, PrOH, and AN. Among them, the most effective
solvent was AN. DMSO caused a reduction in the efficiency of ECHG systems. For antimony, the analytical performance of the
method was evaluated in the optimized conditions (optimized oprating ECHG condition and also optimized solvent and % V/V
organic solvent /water) which shows an improved performance of the electrochemical hydride generation systems in the terms of
sensitivity and interference tolerance. The proposed method was characterized by a linear calibration range of 10 µg to 60 µg for
Sb(III) with a detection limit of 2.29 µg. The relative standard deviation was 5.2% (n = 5) for Sb(III). Also, a linear calibration
range of 5 µg to 60 µg and a detection limit of 2.21 was obtained for Sb(V). The relative standard deviation Sb(V) was 7.1% (n =
5).
Reference
[1] M. H. Arbab-Zavar, M. Chamsaz, A. Youssefi, M. Aliakbari, Anal. Chim. Acta 546 (2005) 126–132.
[2] E. Denkhaus, A. Golloch, X. M. Guo, B. Huang, J. Anal. At. Spectrom. 16 (2001) 870–878.
Application headspace solvent microextraction and gas chromatography–flame ionization detection
for analysis of petroleum and gasoline in water samples
Somayeh baghipour*1 Ali Reza Fakhari2
Department of Chemistry, Shahid Beheshti University, Tehran, Iran.
2
Environmental research institute of jahad deneshgahi, Rasht, P.B. 41635-3114
s.baghipour@gmail.com
1
Gasoline is a complex mixture of over 500 hydrocarbons that may have between 5 to 12 carbons. Alkans type compounds, either
straight chain or branched compounds are present is greatest amounts. Smaller amounts of alkan cyclic and aromatic compounds
are present. Very small or trace amounts of alkenes are present in gasoline Petroleum range hydrocarbons (C5±C11) comprise
mixture of aliphatic-straight chain and aliphatic-branched and aliphatic-cyclic and aromatic. Environmental contamination by
petroleum hydrocarbons is the most common site contamination issue encountered by environmental professionals.
Environmental contamination by petroleum and gasoline hydrocarbons is the most common site contamination issue encountered
by environmental professionals. Environmental pollution measured using methods purge and trap [2], headspace sampling
techniques or direct aqueous injection (DAI), with gas chromatography–photoionization (GC–PID), flame ionization (GC–FID)
or mass spectrometric (GC–MS) detection [3]. Recently, solid-phase microextraction (SPME), has been used to extraction and
determination of many environmental pollutants in the last few years, efforts have been directed towards miniaturizing the
liquid–liquid extraction procedure by greatly reducing the solvent to aqueous phase volume ratio, leading to the development of
the solvent microextraction (SME) methodologies [4]. In this study, a simple, rapid and efficient method for the extraction and
determination of petroleum and gasoline in water samples by the headspace solvent microextraction (HSME) and gas
chromatography at sub (ppm) level is described and comparison. Some significant variables such as type of solvent extraction,
extraction time, headspace and microdrop volumes, temperatures of sample solution, stirring rate were optimized. Using
optimum extraction conditions for gasoline (n-hexadecane extracting solvent, extraction time 15 min, headspace volume 7 ml,
micro drop volume 3 µl, temperature of sample solution 30ºC, stirring rate 1000 rpm) a detection limit of 0.5 ppm and a good
linearity (R2> 0.9995) in a calibration range of 5–500 ppm were achieved. Using optimum extraction conditions for petroleum (nhexadecane extracting solvent, extraction time 25 min, headspace volume 6 ml, micro drop volume 3 µl, temperature of sample
solution 50ºC, stirring rate 1000 rpm, 10% (w/v) NaCl) a detection limit of 1.2 ppm and a good linearity (R2> 0.9989) in a
calibration range of 10–500 ppm were achieved. The optimized conditions were applied to the tap sample in order to evaluate the
application of this method to real sample.
References
[1] M. Rosell, S. Lacorte, D, Barcel´o, Journal of Chromatogr. A 1132 (2006) 28.
[2]J.L.P. Pavon, S.H. Martin, C.G. Pinto, B.M. Cordero. Anal. Chim. Acta 629(2008) 6.
[3] M.K. Zanjani, Y Yamini, S Shariati Journal of Hazardous Materials B 136 (2006) 714.
An efficient structured ZnO/nanoclinoptilolite for degradation
of Reactive phenylhydrazine organic pollutant
under UV light
Alireza Nezamzadeh- Ejhieh*, F. Khodabakhshi-Chermahini
Department of Chemistry, Shahreza Branch, Islamic Azad University, Shahrza, Isfahan, Iran, P.O. Box311-86145
In the present study, the photocatalytic degradation of phenylhydrazine (PHZ) organic pollutant in aqueous solution by
photocatalyst ZnO/nanoclinoptilolite using advanced oxidation processes (AOPs) has been investigated. Heterogeneous
photocatalysis is a branch of advanced oxidation processes (AOPs) which transforms the toxic organic pollutants into nontoxic
products like CO2 and H2O. The catalyst preparation was characterized by FT-IR and X-ray diffraction techniques. Nano powder
of natural clinoptilolite zeolite was mechanically prepared by using a planetary ball mill (dry milling of clinoptilolite zeolite),
then particles of zinc oxide were supported by calcinations of Zn2+ exchanged nanoclinoptilolite at 450°C. The effects of
parameters, such as the amount of catalyst, initial pH values and initial concentration on the photocatalytic degradation PHZ were
investigated to find desired conditions and the best condition. The results presented here show that the ZnO-nanoclinoptilolite
particles can be used as photocatalyst in the degradation of phenylhydrazine.
Reference
[1] A. Nezamzadeh-Ejhieh, Z. Salimi,Appl.catal.A: Gen.390 (2010) 110–118.
[2] A. Charkhi, H. Kazemian, M.Kazemeini, Powder Technol. 203 (2010) 389-396.
[3] M. A. Gondal, M. N. Sayeed, A. Alarfaj, J. Chem. Phys. Lett. 445 (2007) 325–330.
A new N4O2 Schiff base ligand possessing two naphthalene groups as
a new dual fluorescence chemosensor for Cu2+ and Fe3+ ions
Reza Azadbakht, Maisam Parviz* and Esmail Tammari
Department of Chemistry, Payame Noor University, Iran
Chemosensor can be used to detect metal cations in environment, food and biological systems with the advantages of simplicity,
high selectivity and sensitivity [1]. A new macrocyclic chemosensor (3-((2-((4-(2-((3-hydroxynaphthalen-2-yl) methyleneamino)
benzylamino) butylamino)methyl) phenylimino)methyl)naphthalen-2-ol) (L) containing two naphthalene fluorophores has been
synthesized. The fluorescent properties of this receptor has been studied in the presence of various metal ions such as Na+, Ag+,
Cr3+, Mn2+, Fe2+, Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+. When increasing concentrations of Cu2+ and Fe3+ ions were
introduced, the emission of L was drastically changed. This special change was not observed when other metal ions were used;
such highly selective fluorescent response indicates that this receptor can easily discriminate Cu 2+ and Fe3+ ions from other similar
species.
OH
HO
N
N
NH
HN
(1)
Reference
[1] Hui-Miao Zhang, Wen-FuFu, Shao-MingChi, JunWang, Journal of Luminescence 129 (2009) 589–594.
Tea waste: A green and economical biosorbent for removal of Cd(II), Hg(II) and Pb(II)from wastewater
Mohsen Tahmasbi*, Majid Soleimani, Majid Ghahraman Afshar, Morteza Aghajanzadeh
Department of Chemistry, Imam Khomeini International University, P.O. Box: 288, Qazvin, Iran
G-mail: afshar.analyst@gmail.com
This study describes the use of tea waste for the removal of Cd(II), Hg(II) and Pb(II) from wastewater. The parameters pH,
contact time, initial metal ion concentration, and temperature were investigated. Equilibrium, thermodynamic and kinetic studies
were carried out for the biosorption of Cd(II), Hg(II) and Pb(II) ions from aqueous solution using the tea waste. Langmuir and
Freundlich isotherm models were applied to describe the biosorption of the metal ions onto Tea waste. The adsorption studied in
batch mode using flame atomic absorption spectroscopy for metal estimation. The tea waste was characterized on the basis of FTIR, TGA and DTA.. The initial concentration of Cd(II), Hg(II) and Pb(II) solutions were 1, 100 and 100 ppm respectively. 0.5 g
of biosorbent was contacted with 5 mL of each metal ion solution in a sealed flask agitated vigorously by a magnetic stirrer using
a water bath maintained at a constant temperature. The maximum biosorption recovery of Cd(II), Hg(II) and Pb(II) were 84.3 ,95
and 82.68 %, respectively. Study concluded that tea have good potential as an adsorbent to remove toxic metals like Cd(II),
Hg(II) and Pb(II) from water.
Refrence
[1] M.K. Mondal, Journal of Environmental Management 90 (2009) 3266–3271.
[2] Emine Malkoc , Yasar Nuhoglu, Separation and Purification Technology 54 (2007) 291–298.
[3] Emine Malkoc, Yasar Nuhoglu, Chemical Engineering Science 61 (2006) 4363 – 4372.
[4] Emine Malkoc, Yasar Nuhoglu, Journal of Hazardous Materials B135 (2006) 328–336.
[5] Radojka Razmovski, Marina ˇS ´ciban, Ecological Engineering 34 (2008) 179–186.
[6] B.M.W.P.K. Amarasinghe , R.A. Williams , Chemical Engineering Journal 132 (2007) 299–309.
Optimization of RP-HPLC conditions of gamma-butyrolactone and its precursors in reaction mixture
Behzad Hosseini Pour, Majid Soleimani, Majid Ghahraman Afshar*
Department of Chemistry, Imam Khomeini International University, P.O. Box: 288, Qazvin, Iran
G-mail: afshar.analyst@gmail.com
A rapid and sensitive method was developed for simultaneous analysis of γ-butyrolactone and its precursors in synthesis
environment. The method was comprised a simple dilution of the reaction mixture in mobile phase was followed by liquid
chromatography UV-Visible spectrophotometery analysis. Chromatograms was achieved using C18 column, mobile phase consist
of 42%acetonitrile, 58%buffer which buffer was 20 mM phosphate PH=3 with phosphoric acid, flow rate was 1ml/min and wave
length of detector was 210nm. This procedure, which had a total analysis time less than 25 min was fully validated and applied to
the analysis of organic samples. The limit of quantification was around 2 ppm for all analytes, the relative error (RSD) for aryl
aldehyde was 0.93%. This study proves this simple and rapid method was useful for simultaneous separation of organic
synthesis. This method provides a simple, fast, and sensitive procedure to separate and determinate unsaturated gammabutyrolactones and its precursors in reaction mixture. This component indicates antitumour virtues consequently purification of
this agent perhaps be useful for laboratories that they are active in pharmaceutical industry.
Reference
[1] P.A. Grieco, Synthesis 31 (1975) 67-71.
[2] Gammill, R. B. Wilson, C. A. Bryson, Synth. Commun 245 (1975) 5-9.
[3] Mohammad Bayat, Hossein Imanieh, Tetrahedron Letters 51(2010) 1873–1875.
[4] M. Richoll, Ivelisse Colon, Journal of Chromatography A 1127 (2006)147–153.
[5] Mantai, Z. Mesmer, R. Duane Satzger, J. Forensic, Sci 43(3) (1998) 489–492.
Electrocatalytic detection of isoproterenol using ferrocene–multiwall carbon nanotubes paste electrode
as a sensor with differential pulse voltammetry
A.A. Ensafi*. E. Khoddami. H. Karimi-Maleh, B. Rezaei
Department of Chemistry, Isfahan University of Technology, Isfahan 84156–83111, Iran.
A sensitive and selective electrochemical method for the determination of isoproterenol (ISPT) was developed using a ferrocenemultiwall carbon nanotubes paste electrode (FCMWCNTPE). The fabrication of FCMWCNTPE and its electrocatalytic effect for
the electrochemical oxidation of ISPT were investigated using electrochemical impedance spectroscopy (EIS) and voltammetric
methods. The cyclic voltammetric results indicate that FCMWCNTPE remarkably enhance the oxidation of ISPT in a wide pH
range of 2.0–5.0, which is leading to considerable improvement of anodic peak current for ISPT, and allow the development of a
highly sensitive voltammetric sensor for determination of ISPT in pharmaceutical and urine samples. The differential pulse
voltammetry (DPV) exhibited two wide linear dynamic ranges and a lower detection limit of 0.07 µM for ISPT. It has been found
that under the optimum condition (pH 5.0) in cyclic voltammetry, the oxidation of ISPT occurred at a potential about 140 mV
less positive than that of unmodified carbon paste electrode. The kinetic parameters such as electron transfer coefficient, α, and
catalytic reaction rate constant, kh, were also determined using electrochemical approaches. Finally, the proposed method was
used to determination of ISPT in plasma and pharmaceutical samples.
Preparation of SnPW/MWCNT/RTILs modified electrode and its application
for the simultaneous determination of uric acid, tyrosine and epinephrine.
Meissam Noroozifar*, Mozhgan Khorasani-Motlagh, Zahra Matbouie
Department of Chemistry, University of Sistan and Baluchestan, Zahedan, Iran, P.O.
Box98155-147, Email: mnoroozifar@chem.usb.ac.ir
A nano-composite material consisting of multi-walled carbon nanotubes(MWCNTs)/Sn(II)-Tungstophosphoric Acid and a room
temperature ionic-liquid BMIMPF6(1-butyl-3-methylimidazolium hexafluorophosphate) was prepared and used to construct a
novel biosensor for the simultaneous determination of epinephrine (Ep), uric acid (UA) and tyrosine (Tyr).Linear calibration
plots were obtained over the range of 5.8×10-7-1.5×10-5,7.8×10-6-1.6×10-4 and4.2×10-6-1.1×10-4 mol.L−1 with detection limits of
4.2×10−8,5.6×10−7 and 2.8×10−7 mol.L−1 for Ep, UA and Tyr, respectively. The practical analytical utilities of the modified
electrode were demonstrated by the determination of epinephrine, uric acid and tyrosine in urine and human blood serum
samples.
Reference
[1] N. Giordano, P. Staiti, A.S. Aricb, Electrochim. Acta 42 (1997) 164.
[2] Y. Liu, L.H. Shi, M.J. Wang, Z.Y. Li, H.T. Liu, J.H. Li, Green Chem. 7 (2005) 655.
[3] L. Zheng, J.F. Song, Talanta 73 (2007) 943.
[4] F. Zhao, L. Liu, F. Xiao, J. Li, R. Yan, B. Zeng, Electroanalysis 19 (2007) 1387.
Elctrochemically synthesis of Gold nanoparticles on CNT/GCE: Application as an enhanced material
for sensitive voltammetric determination of Tinidazole
a
S. Shahrokhiana *, S. Rastgar
Department of Chemistry, Sharif University of Technology, Tehran 11155-9516, Iran
The unique properties of nanoparticle materials (enhanced mass transport, high surface area) can often be advantageous in
electroanalytical techniques[1,2]. Uniform dispersion of metallic nanoparticles decorated on CNT surfaces can yield ideal
nanocatalysts for application in chemically modified electrodes[3,4] . In this work, a highly sensitive electrochemical sensor for
the determination of Tinidazole (Tin) was fabricated by electrodeposition of gold nanoparticles (AuNPs) onto carbon nanotube
(CNT) film pre-cast on a glassy carbon electrode (GCE). The surface morphology and nature of the hybrid film (AuNPs-CNT)
deposited on glassy carbon electrode has been characterized by scanning electron microscopy (SEM), cyclic voltammetry (CV)
and electrochemical impedance spectroscopy (EIS) techniques. The peak currents possess a linear relationship with the
concentration of Tin in the range of 0.1 µM to 10 µM, and the detection limit is 10 nM (S/N = 3). In addition, the modified
electrode was used to determine Tin concentration in pharmaceutical and biological samples with satisfactory results. We have
successfully demonstrated that the gold nanoparticles can be electrochemically deposited in the MWCNT matrix at room
temperature and in a short time of the electrodeposition. The prepared Pt-Ru-CNT nanocomposite is used as a modifier film on
the surface of GC electrode that showed an effective electocatalytic role in the reduction of Tinidazole. The proposed sensor
showed excellent sensitivity, selectivity and stability in voltammetric responses.
Reference
[1] F. W. Campbell, R. G. Compton, Anal. Bioanal. Chem. 396 (2010) 241 .
[2] G. G. Wildgoose, C. E. Banks, R. G. Compton, Small, 2(2006) 182.
[3] S. Shahrokhian, M. Ghalkhani, M. K. Amini, Biosens. Bioelectron. 24 (2009) 3235.
[4] M.Ghalkhani, S. Shahrokhian, Talanta 80 (2009) 31.
Synthesis, characterization and photocatalytic activity of MCM-41/ZnO and MCM-48/ZnO
Hamid Reza Pouretedal ٭and Mina Ahmadi
Islamic Azad University, Shahreza branch, Shahreza, Iran
Since the discovery of the M41S family of ordered mesoporous adsorbents by scientist at Mobil Oil, the two most
investigated materials, MCM-41 with a 2-D hexagonal structure and MCM-48 with a 3-D cubic structure, are
synthesized [1]. A larg number of preparation methods have been developed to synthesize mesoporous materials, such
as hydrothermal synthesis under ambient temperature. Among these methods, synthesis under ambient temperature is
paid wildly attention [2]. In this study, the impregnation synthesis of Zn-doped MCM-41 & MCM-48 was done by
using direct and indirect solvothermal method. The mesoporous materials of MCM-41 and MCM-48 were synthesized
hydrothermally at ambient temperature conditions from ethyl orthosilicate as Si source and cetyltrimethylammonium
bromid (CTAB) as template. The reaction mixture was stirred vigorously at room temperature and then the solid
produced was filtered, washed, dried and calcined in air at 550˚C for 6 h. The obtained substrates were characterized by
XRD and FT-IR techniques. A comparative study in structural properties of ZnO/MCM-41 & MCM-48 materials was
evaluated. The performance of these substrates toward the photocatalytic degradation of congo red in aqueous solution
was studied. The photocatalytic activity is in relation with their structural properties and aggregation. The nanocrystals
of ZnO has attracted considerable attention as a photocatalyst for the degradation of organic pollutants in water and
air.The results show that all the samples produced by direct synthesis method, are used as the active components of
catalyst [3,4].
Reference
[1] D. Kumar, K. Schumacher, C. du Fresne von Hohenesche, M. Grün, K.K. Unger, "MCM-41, MCM-48 and related mesoporous adsorbents: their
synthesis and characterization Physicochem. Eng 187-188(2001)109-116.
[2] X. Song, P. Qu, N. Jiang, H. Yang, G. Qiu, "Synthesis and characterization of MCM-41 materials assembled with CeO 2 nanoparticles", Physicochem.
Eng. 313–314 (2008) 193–196.
[3] W. Lu, G. Lu, Y. Luo, A. Chen, "A novel preparation method of ZnO/MCM-41 for hydrogenation of methyl benzoate", J. Mol. Catal. A. Chem. 188
(2002) 225–231.
[4] Z. Wangcheng, L. Guanzhong, G. Yanglong, G. Yun , W. Yanqin, W. Yunsong, Z .Zhigang, L. Xiaohui, "Synthesis of cerium-doped MCM-48
molecular sieves and its catalytic performance for selective oxidation of cyclohexane", J. Rare. Earths. 26-4 (2008) 515.
Synthesis, characterization and phptocatalytic activity of SBA15/ZnO and SBA15/ZnS
Hamid Reza Pouretedal*and Sara Basati
Islamic Azad University, Shahreza branche, Shahreza, Iran
Zinc oxide (ZnO) and zinc sulfide (ZnS), important wide-band-gap semiconductor materials, has been widely investigated for
many applications. The nanocrystalline ZnO and ZnS have also great potential in photocatalysis for the degradation of organic
pollutants. For a heterogeneous catalyst, it is important to have a large surface area and a great number of reactive sites per unit
area. A simple solvothermal impregnation method was used to prepare Zn nanoparticles supported on SBA-15. Owing to
mesoporous silica’s uniform pore size, hexagonal array of one-dimensional cylindrical channels, high chemical stability and large
surface area, they can provide a new environment for host–guest chemistry to model nanocomposites of size-confined quantum
[1]. The ZnO and ZnS nanoparticles confined in SBA-15 were prepared through the two methods. In direct method, the SBA15
was impregnated by ZnS/ZnO nanoparticles [2, 3]. In the other method, the precursor of Zn(NO3)2·4H2O were impregnated by
synthesized SBA15 at 25◦C for 48 h. Then, the thioacetamide solution was added to the mixture at 80◦C under static conditions.
The ZnS/SBA15 resultant was dried at room temprature. The ZnO/SBA15 was obtained with calcination of Zn2+/SBA15 at 500
◦
C in air. The substrates of ZnS/SBA15 and ZnO/SBA15 were characterized by using FT-IR and X-ray diffraction. The
photocatalytic activity of obtained substrates were studied in photodegradation of congo red dye [4]. The conditions were
optimized to achive to the highest of photodegradation yield.
Reference
[1] G.D. Mihai, V. Meynen, M. Mertens, N. Bilba, P. Cool, E.F. Vansant, "ZnO nanoparticles supported on mesoporous MCM-41 and SBA-15: A comparative
physicochemical and photocatalytic study", J. Mater. Sci. 45 (2010) 5786–5794.
[2] Ch. Wu, L.Shen, Q. Huang, Y. C. Zhang, "Synthesis of Na-doped ZnO nanowires and their antibacterial
properties", Powder Technol. 205 (2011) 137–142.
[3] N.Uekawa, T. Matsumoto, T.Kojim, F.Shiba, K. Kakegawa, "Synthesis of stable sol of ZnS nanoparticles by heating the mixture of ZnS precipitate and ethylene
glycol", Colloids Surf. A. 361 (2010) 132–137.
[4] M. Movahedi, A.R. Mahjoub, S. Janitabar. Darzi, "Photodegradation of congo red in aqueous solution on ZnO as an alternative catalyst to TiO2", J. Iran. Chem. 6
(2009) 570-577.
A rapid and precise spectrophotomeric method for the determination of uranium (VI)
in bacterial leach liquors using arsenazo (III)
*Abbas Rashidi, Hassan Golmohammadi, Seyed Jaber Safdari, Mohammad-ali Firoz-Zare
Nuclear Science and Technology Research Institute, Tehran, Iran
Among the practical applications of biotechnology is mineral biotechnology which deals with the bioprocessing of ores of many
kinds. Bioprocessing of low-grade ores of uranium is being carried out commercially [1]. Uranium behaves differently from
many other metals due to its variable oxidation state and tendency to form a wide variety of positive, neutral and negative
charged complexes at acidic pH. In this report, a short, sensitive and reliable spectrophotometric method for the direct
determination of uranium (VI) in bacterial leach liquors, obtained by the action of Thiobacilus ferrooxidans from low-grade
uranium ores, has been developed. Arsenazo (III) formed an intense pink-violet complex at pH 2.0±0.1, which showed maximum
absorbance at 655 nm. Arsenazo (III) (1,8-dihydroxynaphtalene-3,6-disulfonic acid-bis(azophenyl arsenic acid)) which is a
bisazo dye based on chromotrophic acid and o-amino-phenylarsonic acid, is commonly used for the determination of thorium and
uranium(IV), but it also gives a very sensitive color reaction with uranium (VI) [2,3]. The bacterial leach liquor from uranium
bearing ore is joined with other ions such as Al, Ca, Cu, Co, Fe, etc. in addition to uranium. Interferences due to these different
metal ions were successfully masked by diethylenetriamine penta-acetic acid (DTPA) without inhibiting the formation of
uranium (VI)-arsenazo (III) complex. Effects of pH, dye concentration and complexan concentration on color development and
optimum reaction time were investigated. This method could also be used for detection of low levels of uranium (VI) in mine
waters, acid leach liquors and tailing liquid. The present model was found to obey Beer's law up to 10 µg cm-3. The results
obtained were found to be in close agreement with values determined by other spectrophotometric methods such as inductively
coupled plasma (ICP).
Reference
[1] Egnik, J.W., Carmichael, A.J., Hamilton, M.M., Tardiff, W., Health Phys. 2000, 78, 143.
[2]Khan, M.H., Warwick, P., Eran, N., Chemosphere, 2006, 63, 1165.
[3] Pranvera, L., Alqi, C., Safet, D., Filip, L., Asian J. Chem. 2000, 12, 732.
Spectrophotometric determination of ferric, ferrous and total iron in uranium bioleach liquors
*Abbas Rashidi, Hassan Golmohammadi, Seyed Jaber Safdari, Mohammad-Ali Firoz-Zare
Nuclear Science and Technology Research Institute, Tehran, Iran
There are many practical cases where the concentration of iron ions in aqueous solution has to be determined quantitatively [1,2].
The oxidation of iron sulfides and ferrous ions by bacterial cells such as Thiobacillus ferrooxidans is of great importance in
surface and ground water chemistry [3]. Presently used analytical methods for the measurement of the concentrations of both
ferrous and ferric iron in aqueous solutions have certain limitations. o-phenanthroline is generally used for the spectroscopic
determination of iron (II). The determination of trace iron (II) is usually interfered by the presence of iron (III) when ophenanthroline colorimetric method is used. A complexing agent might be found to modify phenanthroline method. This
complexing agent had to be colorless, stable and soluble under the conditions of assay. Among the complexing agents, sodium
fluoride is found to be the most suitable in ferrous-ferric solutions. A comparative result showing the effect of sodium fluoride to
minimize the interference of ferric ions in determination of iron (II) in ferrous-ferric solution is presented in this report. A rapid
and precise method for measurement of ferric and total iron in bacterial leach liquors is also reported. The determination of both
ferric and total iron concentrations are made in the same solution at different light wavelengths, which significantly reduces the
error of the analytical procedure. The method is based on the colorimetric measurement of red colored ferric-sulfosalicylate
complex formed at low pH. After the addition of ammonia which leads to increase in pH, the 5-sulfosalicylic acid (SSA) forms a
yellow complex with all the iron ions in solution. The wavelengths of maximal light absorbance for both these complexes were
determined. They were 500 and 425 nm, respectively. The relationship between both the ferric and total iron concentrations and
light absorbance obeys Beer’s law under the conditions studied. The optimal ratio and volumes of the reagents used were
determined. The cultivation media for the iron-oxidizing bacteria, Thiobacillus ferrooxidans found to have no effect on the iron
determination.
Reference
[1] Pepper, S.E., Borkowski, M., Anal. Chim. Acta, 2010, 663,172.
[2] Petel, K.S., Shukla, A., Goswami, A. J. Anal. Chem. 2001, 369, 30.
[3] Ehrich, H.L., Geomicrobiology, Marcel Dekker, New York, 1990.
Application of natural nanoclinoptilolite zeolite modified by surfactant in cephalexin drug delivery
Alireze Nezamzadeh*, Sanaz Tavakoli Gheinani
Department of Chemistry, Shahreza Branch, Islamic Azad University, P.O. Box 311-86145, Shahreza, Isfahan, Iran
arnezamzadeh@iaush.ac.ir
The use of porous materials as host systems for medical applications has been considered in recent years [1]. The combined
adsorption onto purified natural clinoptilolite (NZ) of the cationic surfactant (HDTMA) and the model drugs cephalexin has been
studied in order to design systems for the storage and release of drugs [2]. We have studied the drug solutions before and after the
contact with the zeolitic materials in a wide range of time, concentration of surfactant and drug, quantity of clinoptilolite and pH
values by UV spectroscopy [3]. Cephalexin, or 7-[(aminophenylacetyl)amino]-3-methyl-8-oxo-5-thia-1-azabicyclo [4.2.0] oct-2ene-2-carboxylic acid, is a semi-synthetic drug in a class of antibiotics called α-aminocephalosporins [4].The drug adsorption
assays showed that only the NZ–HDTMA composite adsorbs a considerable amount of drug, in particular of cephalexin, which
was evaluated by UV spectroscopy. It was proven by means of TG that the composites are more stable thermally when the
admicelles contain cephalexine in their interior. The studies by IR spectroscopy indicated that the zeolite structure remained
unchanged after the modification with the surfactant and the drug [5]. The drug releasing was studied in a wide range of time,
volume of water, pH values and also in presence of some other ions.
Reference
[1] M. Grce; K. Pavelić; "Antiviral properties of clinoptilolite", Micropor. Mesopor. Mater. 79 (2005) 16–165.
[2] T. Farías, L. Charles de Ménorval, J. Zajac, A. Rivera; "Adsolubilization of drugs onto natural clinoptilolite modified by adsorption of cationic surfactants",
Colloids Surf. B 76 (2010) 421–426.
[3] T. Farías, A.R. Ruiz-Salvador, A. Rivera; "Interaction studies between drugs and a purified natural clinoptilolite", Micropor. Mesopor. Mater. 61 (2003) 117–125.
[4] E.P.C. Lai; S.Q. Wu; "Moleculary imprinted solid phase extraction for rapid screening of cephalexin in human plasma and serum", Anal. Chim. Acta. 481 (2003)
165-174.
[5] A. Rivera; T. Farías; "Clinoptilolite–surfactant composites as drug support: A new potential application", Micropor. Mesopor. Mater. 80 (2005) 337–346.
Kinetic spectrophotometric method for the determination of uric acid in human urine
M. Reza Shishehbore*, Ali Sadeghiane, A. Hossein Naseri
Department of Chemistry, Islamic Azad University, Yazd Branch, Yazd, Iran
E-mail address: shishehbore47@yahoo.com
Kinetic spectrometric method is a powerful analytical technique for the determination of different species [1-3]. In this study, a
simple, rapid and sensitive kinetic spectrophotometric method for trace amounts determination of uric acid was developed.
Thionine was oxidized by bromate in acidic media and uric acid has inhibitory effect. The reaction was followd
spectrophotometrically at 601nm (λmax). Under optimum experimental condition (H2SO4, 0.6 mol L-1; Thionine, 33 µmol L-1;
bromate, 1.1 mmol L-1; temperature, 25 ˚C and 300 S) uric acid can be determined over the range 1–17 µg mL-1 with two linear
segments. The limit of detection and relative standard deviation were 0.61 µg mL-1 and 2.5%, respectively. The proposed method
was successfully applied for the determination of uric acid in human urine sample.
Reference
[1] S. Abbasi, R. Valinezhad, H. Khani, Spectrochim. Acta A 77 (2010) 112-116.
[2] M. R. Shishehbore, A. Sheibani, R. Jokar, Anal. Sci. 21 (2010) 497-501.
[3] S. S. Mitic, R. J. Micic, R. M. Simonovic, Food Chem. 117 (2009) 461-465.
Application of Aqueous Two Phase System for Extraction of Sorbic Acid
N. Badkiu*1, A. Daneshfar2, A. Yeganeh-faal1, M, S. Shiri٣
Department of Chemistry, Payam noor University (PNU),Hamadan, Iran
2
Department of Chemistry, Faculty of Sciences, Ilam University, Ilam, Iran
3
Department of Chemistry, Faculty of Sciences ,Payam noor University(PNU), Ilam, Iran
Email: Nadiebadkiu@yahoo.com (Nadie Badkiu)
1
In this research work a simple and very fast aqueous two-phase system (ATPS) followed by UV-Vis spectrphotometric method
was developed and applied for determination of sorbic acid in soft drink samples. Polyethylene glycol (PEG), (3.0 g) was added
to aqueous solution (20 mL) for formation of a homogeneous solution. To the mixture solution, suitable amount of (NH 4)2SO4
was added, the mixture solution was shaken until the salt was dissolved, and then it was separated into two clear phases easily
and rapidly. The target analyte in the sample was extracted into the polyethylene glycol phase. After extraction, the analyte in the
polyethylene glycol phase was determined by spectrphotometric method using the analytical wavelength of 256 nm. The
influences of effective parameters such as salt (type and amount), polyethylene glycol (type and concentration), temperature, and
pH of sample solution were studied and optimized. Under optimized experimental conditions, calibration plot was found to be
linear in the range of 10-3000 ng mL-1, with coefficient of determination of 0.9989. The limit of detection was 3.9 ng mL-1. The
proposed procedure was successfully applied to the determination of sorbic acid in spiked samples with satisfactory results. The
relative recovery was 98.40%, and relative standard deviation was 2.5 %.
Reference
[1] Luiza. H. M. Silvaand. Antonio. J. A. Meirelles. J. Chem. Eng. Data 2001, 46, 251-255
[2] M. T. Zafarani-Moattar, R. Sadeghi . J. Chem. Eng. Data 2004, 49, 297300
[3] Sara.C.Silve´rio,P.P.Madeira, O.Rodr,Jose.´A.Teixeira, J.Chem.Eng.Data .2008, 53,1622–1625.
A new solid-phase extraction method coupled with high performance liquid chromatography
for enrichment and determination of Polycyclic aromatic hydrocarbons
from environmental water samples
Vahid Khalili Fard*, Yadollah Nikpour, Kamal Ghanemi, mahdi fallah
Department of Marine Chemistry, Faculty of Marine Science, Khoramshahr Marine Science and Technology University, Khoramshahr, Iran
Polycyclic aromatic hydrocarbons (PAHs) are a class of organic compounds containing two or more fused aromatic rings of
carbon and hydrogen atoms. They gained great concern from scientists owing to their carcinogenic properties. The extremely low
concentrations in environment and the complexity of their matrices make determination of PAHs challenging tasks. Sometimes it
could not be solved even with modern instruments, such as HPLC or GC. These difficulties could be overcome by the
development of combined methods of analysis including a preconcentration step before final determination of them. In current
study a solid phase extraction method using of sulfur micro-particles as a adsorbent coupled with high-performance liquid
chromatography (HPLC) was developed for preconcentration and determination of polycyclic aromatic hydrocarbons in water
samples, specially in environmental samples such as seawater. Influence of Several condition parameters, such as type and
concentration of organic modifier, amount of adsorbent, eluent solvent and its volume, breakthrough volume, sample loading
flow rate, and sample pH on the method performance were investigated and modified to obtain maximum SPE efficiency. The
calibration curves of 10 PAHs extracted were linear in the range of 0.05–80 µg L−1, with the regression coefficients (r2) between
0.9934 and 0.9995. the relative standard deviation (RSD) values of this method for 10 target PAHs were in the range 2.5% to
6.1%. Method recoveries ranged in 80.8-102%, 81.4-103%, and 80.3-107.2% for real spiked samples from river water, seawater
and petrochemical waste water, respectively. Under optimized conditions, Limits of detection (LODs, S/N= 3) of the 10 PAHs
were obtained in the range of 0.007–0.048 µg L−1. The optimized method was successfully applied to the determination of PAHs
in river water, seawater and petrochemical waste water. This new SPE method provided several advantages, such as simplicity,
low cost adsorbent, low detection limits, and short analysis time.
References
[1] Oliferova, L., Statkus, M., Tsysin, G., Zolotov, Y., 2007. Talanta 72, 1386-1391.
A novel MEPS-HPLC method for the analysis of oleuropein, caffeic acid and tyrosol in human serum
Payman Hashemi,* Zeinab Khoshdel, Mehdi Safdarian, Akram Rahimi, Ali Reza Ghiasvand
Department of Chemistry, Faculty of Science, Lorestan University, Khoramabad, Iran
E-mail:payman_hashemi@yahoo.com
Microextraction by packed sorbent (MEPS) is a new technique for sample preparation. [2] the method is a miniaturized, semiautomated, solid phase extraction (SPE) technique that can be connected on-line with LC or GC. [1,3] MEPS procedure, if
compared to conventional extraction technique (LLE and SPE), is more selective, simple and rapid in execution, limiting the use
and volumes of organic solvents and minimizing the time of one analysis. [4]
In this work, approximately 1–2 mg of the solid sorbent was packed into a micro-syringe or its needle (100–250 μL) and the
syringe was connected to a designed device for semi-automated MEPS which had the possibility of programming for different
steps. In the experimental procedure, the sorbent was first conditioned with 3×100 μL methanol flowed by 3×100 μL water. After
that, sample plasma was drawn onto the syringe up and down once or several times. It is important that plasma samples are drawn
slowly to obtain good percolation between sample and support. The sorbents was then washed once with 100 μL of water to
remove proteins and other interfaces. The analytes were then desorbed by 80 μL acetonitrile and injected to HPLC. The sorbent
was cleaned with 3´100 μL acetonitrile before the next run.
For optimization, some factors affecting the performance of MEPS such as number of adsorption and elution, elution volume and
pH were studied by response surface method. [1] The type of sorbent, carry-over, leakage and washing volume were
investigated by one at the time method. The highest recovery was obtained using CMK-3 sorbent. Good results were obtained in
terms of precision (RSD 2%, 2% and 3% for CA, Ty and OE, respectively), LOD 7.54×10-7 M, and recovery (85% for CA, 30%
for Ty and 100% for OE). The new method was successfully applied to the determination of the biophenols in human serum
samples.
Refrence
[1] Z. Altun, M. Abdel- Rehim, Anal. Act, 630 (2008) 116-123ta
[2] R. Mandrioli, L. Mercolini, D. Lateana, G. Boncompaghi, Journal chromatography B 879 (2011) 167-173
[3] Z. Altun, M. Abdel- Rehim , L. G Blomberg, Journal chromatography B 813 (2004) 129-135
[4] M. Addolorata Saracino, A. de Palma, G. Boncompaghi, M. Augusta Raggi, talanta 81(2010)1545-1553
A highly selective lead-sensitive electrode based on a new Nano-Composite
Abbas Afkhami *, Ali Shirzadmehr
Faculty of Chemistry, Bu-Ali Sina University, Hamedan, Iran
In this work a highly selectivite potentiometric methodology, using a new nano-composite carbon paste electrode, for the
determination of Pb(II) ions in aqueous solution was proposed. For modification of the electrode a typically room temperature
ionic liquid was applied as a super conductive binder, and multi-walled carbon nanotubes (MWCNTs) were used in the
composition of the carbon paste to improve conductivity and transduction of chemical signal to electrical signal, and nanosilica
material was used to improve the response and mechanical resistant of the electrode. Moreover, the new lead-selective ligand
[3-(2-methoxybenzylideneamino)-2-thioxothiazolidin-4one] was synthesized and incorporated as an ionophore to this
composition caused to significantly enhanced selectivity toward Pb(II) ions over a wide concentration range of 8.5×10-9-1.0×10-1
M with a lower detection limit of 3.5×10-9 M and a Nernstian slope of (29.92±0.01mV decade-1) of Pb(II) activity. The electrode
has a short response time (~6 s) and the potentiometric response of prepared sensor is independent on the pH of the test solution
in the pH range 4.5 to 8.0. A fixed interference method indicated that the electrode has an excellent selectivity for Pb(II) ions
over alkali, alkaline earth and other heavy metal ions. The proposed electrode has been also found to be a powerful indicator
electrode for potentiometric titration of Pb(II) ions with EDTA. The electrode can be used to accurately monitoring the Pb(II)
pollution in environmental waters.
Reference
[1] A. Walcarius, Electroanalysis 13, 701 (2001).
[2] A. Safavi, N. Maleki, F. Honarasa, F. Tajabadi and F. Sedaghatpour, Electroanalysis 19, 582 (2007).
[3] D. Wei and A. Ivaska, Anal. Chim. Acta 607, 126 (2008).
[4] Y. Wang, W.Z. Wei, X.Y. Liu and X.D. Zeng, Mat. Sci. Eng. C 77, 737 (2008).
[5] H. Abbastabar-Ahangar, A. Shirzadmehr, K. Marjani, H. Khoshsafar , M. Chaloosi and L. Mohammadi, J. Incl. Phenom. Macrocycl. Chem. 63, 287 (2009).
Determination of triazole fungicides using liquid phase microextraction by gas chromatography in environmental samples
Hakimeh Assadi1,2, Ali Sarafraz-Yazdi* 1 , Wan Aini Wan Ibrahim2
Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia,
81310 UTM Johor Bahru, Johor, Malaysia
2
Department of Chemistry, Faculty of Science, Ferdowsi University of Masshad, Iran
1
A hollow fiber liquid phase microextraction (HF-LPME) and gas chromatography mass spectrometry (GC-MS) method for the
separation and determination of triazole fungicides namely penconazole, hexaconazole, diclobutrazole and diniconazole is
described. In this thechnique, water sample was placed into a 10 mL glass vial equipped with PTFE-coated magnetic stir bar. A
10 μL microsyringe with a cone tip was used. The hollow fiber was cut manually into 1.5 cm lengths prior to use and after that
was cleaned with acetone in ultrasound bathroom and then dried. A 4 μL of organic solvent (include toluene as extractant solvent
and methidathion as internal standard) was withdrawn into the syringe followed by an equal volume of water. The needle tip was
inserted into the hollow fiber, and the assembly was immersed in toluene for about 30 seconds in order for the solvent to
impregnate the pores of the fiber wall. After solvent impregnation, the water in the syringe was injected to flush the hollow fiber
to remove the excess organic solvent from the inside of the fiber. The prepared fiber was removed from the solvent and then
immersed in the aqueous sample. Finally the organic solvent in the syringe was injected completely into the hollow fiber. The
sample solution was stirred at 720pm during the extraction. After 20 min extraction, the organic solvent in the hollow fiber was
withdrawn into the syringe and then injected into the GC-MS for analysis. The injection volume was 1 μL [1-3]. Under the
optimal extraction conditions, the method showed good linearity, acceptable reproducibility (RSD%=6-9%), low limit of
detection (0.3-0.8μg.L-1) and satisfactory relative recoveries. The developed HF-LPME method was applied for the determination
of fungicides in farm, river and tap water and also grape juice samples.
Reference
[1] H.-J. Pan, W.-H. Ho , Analytica Chimica Acta 527 (2004) 61.
[2] Y. He, H.K. Lee, Anal. Chem. 69 (1997) 4634.
[3] G. Shen, H.K. Lee, Anal. Chem. 74 (2002) 648.
The adsorption of Sunset Yellow dye onto the chitosan particles from aqueous solution
M. Abedi1* and S. Jafari2
Department of Chemical Technologies, Iranian Research Organization for Science and Technology, Tehran, Iran, Department of
Chemistry, Islamic Azad University, Share Ray Branch
Email: mabedi50@yahoo.com
Sunset Yellow is a synthetic yellow azo dye, manufactured from aromatic hydrocarbons from petroleum. When added to foods, it
is denoted by E Number E110 [1]. This dye is used in formulation of many pharmaceuticals, foods, cosmetics and specially
beverages in Iran. Therefore the considerable amount of this dye is discharged to environment. The aim of this paper is to explore
the potential of chitosan particles as a biodegradable adsorbent for removal of Sunset yellow from the aqueous solutions.
Chitosan particles were prepared from shrimp skeleton after acid hydrolyzing and then deacetylation in 50% (w/v) sodium
hydroxide solution at refluxing condition for 6 hours. The FTIR spectra of synthesized chitosan showed 62% degree of
deacetylation. The adsorption of Sunset Yellow from aqueous solution onto prepared chitosan particles at fixed dose (100 mg/100
ml) was performed using batch experiments at different dye concentrations (2.64 – 6.19 × 10-4 M) and reaction time of 30 min.
After separation of dye solution, the residual concentration of dye was determined using a calibration curve prepared at 482 nm
using a UV-Vis spectrophotometer (Perkin Elmer lambda 25, USA). The experimental results were employed for plotting of
Langmuir and Freundlich isotherms to determine the adsorption capacity of the adsorbent. As the Langmuir isotherm is based on
homogeneous adsorption, the possible mechanism for the adsorption process of the chitosan and the anionic dye is the
electrostatic interactions between the anionic groups at Sunset Yellow dyes and the positive protonated amine groups on chitosan
molecules, when the amount of protonated amine groups reached the complete neutralisation of the anionic charges, the removal
of the dyes reached a maximum (94.5 mg dye per gram of chitosan). The Freundlich adsorption describes heterogeneous
adsorption; another mechanism for the adsorption is the interaction of one molecule of chitosan with several dye molecules
contributing to the formation of flocculants [2]. From the slops and intercepts of Langmuir and Freundlich isotherms, the
parameters of Sunset Yellow adsorption on chitosan calculated. It is evident from these data that the surface of chitosan particles
is made up hetrogeneous adsorption patches that adsorb anionic dyes more efficiently in comparison with other absorbents.
Refrence
[1] R.M. Wood, Analytical methods for food additives. Boca Raton: CRC Press. ISBN 1-85573-722-1 (2004).
[2] A. Szyguła, E. Guibal, M. Ruiz, A. Maria Sastre, Colloid Surf. A: Physicochem. Eng. Aspects, 330, 219–226 (2008).
Applying Ni-Tio2 Nanocomposite Coating by Electroplating Process and Investigation
of Its Corrosion in NaOH, NaCl and HNO3 Solution
P. Baghery*, M. Frazam, A.B. Mousavi
Petroleum University of Technology, Abadan, Iran
Pouria.baghery@yahoo.com
Ni-TiO2 nanocomposite coatings with various contents of TiO2 nanoparticles were prepared by electrodeposition in a Ni plating
bath containing TiO2 nanoparticles to be codeposited. The influences of the TiO2 nanoparticles concentration in the plating bath,
the current density and the stirring rate on the composition of nanocomposite coatings were investigated. The composition of
coatings was studied by using energy dispersive X-ray system (EDX). The corrosion performance of coatings in 0.5M NaCl, 1M
NaOH and 1M HNO3 as corrosive solutions was investigated by potentiodynamic polarization and electrochemical impedance
spectroscopy methods (EIS). It was found that Best processing conditions for producing Ni-TiO2 nanocomposite coatings are
30g/L, 5 A/dm2 and 180rpm as the TiO2 nanoparticles concentration in the plating bath, current density and the stirring rate,
respectively. With increasing of TiO2 nanoparticles content in the coating, the polarization resistance increases, the corrosion
current decreases and the corrosion potential shifts to more positive values.
Reference
[1] A.Ciubotariu, L. Benea, M. Varsanyi, V. Dragan, Electrochemical impedance spectroscopy and corrosion behaviour of Al2O3–Ni nano composite coatings, J.
Electrochim. Acta 53 (2008) 4557–4563.
[2] Z. Ahmad, Principles of Corrosion Engineering and Corrosion Control, first ed., Elsevier, London, 2006.
[3] S.C. Wang, J.Wei. Wen-Cheng, Kinetics of electroplating process of nano-sized ceramic particle/Ni composite, J. Mater. Chem. Phys. 78 (2003) 574–580.
[4] J. Fransaer, J.P. Celis and J.R. Roos, Mechanisms of composite electroplating, J. Metal Finish. 91 (1993) 97-100.
[5] D. Galvan, Y.T. Pei, J.Th.M. De Hosson, Influence of deposition parameters on the structure and mechanical properties of nanocomposite coatings, J. Surf. Coat.
Technol. 201 (2006) 590–598.
[6] M.A. Baker, Advanced characterisation of nanocomposite coatings, J. Surf. Coat. Technol. 201 (2007) 6105–6111.
[7] A.M.J. Kariapper, J. Foster, Further studies on the mechanism of formation of electrodeposited composite coatings, J. Trans. IMF 52 (1974) 87-91.
Applying Ni-Cr/Tio2 Nanocomposite Coating by Pulse-reverse Electroplating Process and Investigation
of Its Corrosion in NaOH and NaCl Solution
A.B. Mousavi*, M. Peykari and G.R. Rashed
Petroleum University of Technology, Bovarde street, Abadan, Iran
Atefeh_put@yahoo.com
Ni/Cr-TiO2 nanocomposite coatings with various contents of TiO2 nanoparticles were prepared by pulse-reverce
electrodeposition in a Ni/Cr plating bath containing TiO2 nanoparticles to be codeposited. The influence of the TiO2
nanoparticles concentration in the plating bath, the current density and the stirring rate on the composition of nanocomposite
coatings was investigated. The surface morphology and the composition of coatings were studied by scanning electron
microscope (SEM) and energy dispersive X-ray system (EDX). The corrosion performance of coatings in alkaline and salty as
corrosive solutions was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy methods. It
was found that Best processing conditions for producing Ni-Cr/TiO2 nanocomposite coatings are 30g/L, -20A/dm2 and 250rpm
as the TiO2 nanoparticles concentration in the plating bath, the cathodic current density and the stirring rate, respectively. the
morphology of the Ni/Cr-TiO2 nanocomposite coating is smoother than that of pure Ni/Cr coating. The codeposited TiO2
nanoparticles were uniformly distributed in the Ni/Cr matrix. With increasing of TiO2 nanoparticles content in the coating, the
polarization resistance increases, the corrosion current decreases and the corrosion potential shifts to more positive values.
Reference
[1] Shu-hao D.(2003), “The electrochemical behavior of pulse-plated nanocrystalline iron-nickel-chromium alloy”, Anti-Corrosion Methods and Materials, Vol. 50
NO. 4, pp. 267 – 270.
[2] N. Perez, Electrochemistry and Corrosion Science, Kluwer Academic Publishers, boston, 2004.
[3]Ciubotariu A.C (2008), “Electrochemical impedance spectroscopy and corrosion behavior of Al2O3-Ni nano composite coatings”, Electrochemical Acta, Vol. 53
NO. 13, pp. 4557– 4563.
[4] Chandrasekar M.S. (2008); “Pulse and pulse reverse plating-Conceptual, advantages and applications”, Electrochemical Acta, Vol.53 No. 8, pp. 3313 – 3322.
[5] S.C. Wang, Kinetics of electroplating process of nano-sized ceramic particle/Ni composite, J. Mater. Chem. Phys. 78 (2003) 574–580.
[6] J. Li, Y. Sun, X. Sun, J. Qiao, Mechanical and corrosion-resistance performance of electrodeposited titania–nickel nanocomposite coatings, J. Surf. Coat. Technol.
192 (2005) 331-335.
[7] M.A. Baker, Advanced characterization of nanocomposite coatings, J. Surf. Coat. Technol. 201 (2007) 6105–6111.
[8] Yao Y. (2007), “Effect of SiO2 nano-particulates on corrosion behavior of Ni-W/SiO2 nanocomposite coatings”, Anti-Corrosion Methods and Materials, Vol. 54
No. 6, pp. 336 – 340.
[9] Z. Ahmad, Principles of Corrosion Engineering and Corrosion Control, first ed., Elsevier, London, 2006
Synthesis a new nanocomposite by using phenol and MWCNT-graft-poly (citric acid)
hybrid materials and UV-Vis spectroscopic study of synthetic nanocomposites
and it,s application at the genomic DNA extraction
Nahid Sarlak1*, Sayed Mostafa Jafari1, Sayed Mahmoud Zabeti2,3
Department of Chemistry, Faculty of science, University of lorestan, khoramabad, I.R. Iran.
*Email: sarlak.n@gmail.com
2
Department of plant breeding, Faculty of agriculture, University of lorestan, khoramabad, I.R. Iran.
3
Razi Herbal Medicine Research Center, Lorestan University of Medicinal Sciences Khoramabad, I. R. Iran
1
In this work, we prepared a new nanocomposite by using a new water soluble nanocomposite MWCNT-g-PCA
which was prepared recently [1] and phenol in aqueous solution. The effect of important factors for synthesis
this new nanocomposite was examined by changing experimental variables such as the time of dispersion, pH
and temperature. The structure and characteristics of this system was investigated using UV-Vis spectroscopy
and microscopy methods. Encapsulation of phenol by the polymeric shell of this nanocomposite also
investigated. Phenol is necessary for separation of DNA in start-point of many of molecular biology methods
[2]. For applying the new nanocomposite, first we prepared plant samples in three growing steps and then used
of the encapsulated phenol for DNA extraction and purify process. This nanocomposite helps to remove
proteins. By measuring the ratio of the optical density (OD), OD260/OD280 it is possible to measure the
concentration of DNA by biophotometer instrument. Pure DNA have OD ratio of 1.8-2.0, in this study OD ratio
was obtained 1.9. Gel electrophoresis is use for separating large molecules (DNA fragments) from a mixture by
size. In this study, quantification of DNA can be achived by running the DNA sample on 0.8% agarose gel
stained with ethidium bromide [3]. The result bands were shown that DNA extraction of has high quality.
Finally the nanocomposite was isolated from DNA in contaminations successfully.
Reference
[1] M. Adeli, A. Bahari and H. Hekmatara, NANO: Brief Rep. Rev. 3 (2008) 37-44.
[2] T.J. Kang, and M.S. Yang 2004, Rapid and reliable extraction of genomic fromvarious DNA wild-type and transgenic. BMC Biotechnology.doi: 10.1186/14726750-4-20.
[3] Vinod K K (2004) Total genomic DNA extraction, quality check and quantitation. In:Proceedings of the training programme on “Classical and modern plant
breeding techniques – Ahands on training ", Tamil Nadu Agricultural University, Coimbatore, India.
MultiwavelengthUV-Vis spectroscopy study on the acidity constants of a new synthesized Schiff base
in three different environments
1
Hamid Soltani Afarani1,*Kamal Alizadeh1, Mohammad Reza Ganjali2
Department of Chemistry, LorestanUniversity,Falakolaflak St., Khorramabad, Iran
E-mail: hamidsoltani2010@gmail.com
2
Center of Excellence in Electrochemistry, University of Tehran, Tehran, Iran
Different methods to determine the dissociation constants acids and bases were provided, through these
methods,spectrophotometric technique due to simplicity, low cost, easy to use, was usedmore. In this work, a multiwavelength
spectrophotometric study of a new synthesized Schiff base in immobilized and dissolved forms in 0.20 M phosphate salts as
buffer solutions of varying pH were recorded. The recorded absorbance data for the each forms of compound were collected in a
data MDF file and then subjected to principal component analysis to deduce the number of chemical components coexisting in
the reaction system. The data were then introduced into the DATAN 3.1 program to refine the pure spectra, concentration profiles
and acid dissociation constants of the mentioned molecule. Not unexpectedly, different apparent pKa values were obtained. The
acidity constants for the immobilized form of the 2-((2-(2,4-dinitrophenyl)hydrazono)methyl)phenol were different from the
dissolved form. The influence of covalent immobilization of the studied molecular structure on an epoxy activation of agarose
membrane with a thickness of 0.2 mm from 4% agarose solution, and celluloseacetate membrane on the ionization constants was
investigated.
O–
O
N+
N+
O–
O
N
N
H
HO
Chemical structure of the title compound
Reference
[1] G. J. Mohr, O. S. Wolfbeis, Anal. ChimActa 292 (1994) 41-48.
[2] E. Wang, K.F. Chow, V. Kwan, T. China, C. Wonga, A. Bocarsly, AnalyticaChimicaActa 495 (2003) 45–50.
Optimization of Separation of Flavonoids in Micellar Liquid Chromatography using Experimental Design
and Derringer’s Desirability Function
Mohammad Reza Hadjmohammadi, Seyed Saman Seyed Jafar Nazari*
Department of Chemistry, University of Mazandaran, Babolsar, Iran.
E-mail address: s.nazari@umz.ac.ir
Flavonoids are one of the most important groups of phenolic compounds occurring in plants [1]. Separation of Flavonoids is
commonly performed by HPLC with different types of reverse phase columns and hydro-organic mobile phases with gradient
elution [2]. Micellar liquid chromatography (MLC) is a rather uncommon mode of reversed phase HPLC that employs aqueous
solution of surfactants above the critical micellar concentration as mobile phase [3]. The purpose of this work was to separation
optimization of five Flavonids Myricetin, Quercetin, Hesperetin, Naringenin and Apigenin in MLC. Derringer’s desirability
function [3], a multi-criteria decision making method was used to simultaneous optimization of resolution and analysis time. The
factors studied were the concentration of sodium dodecyl sulfate [SDS], alkyl chain length of the alcohol used as the organic
modifier (N), volume percentage of organic modifier (Vm), volume percentage of acetic acid (AcOH) in mobile phase and flow
rate. The experiments were performed according to a face-centered cube half fractional central composite design to map the
chromatographic response surface. The chromatographic response functions (CRFs) formed using two sigmoidal desirability
functions and were considered as the responses of design. The sigmoidal functions were used to transform the optimization
criteria, resolution and analysis time, into the desirability values. The qualities of the obtained chromatograms in each experiment
were calculated using CRF and model was built by the use of multiple linear regression (MLR) to correlate the obtained CRFs to
the experimental factors and their interactions. The developed MLR model showed good descriptive and predictive ability
(R2=0.9531 and F=11.16). A grid search program was written to find the optimum chromatographic conditions. The optimum
mobile phase composition for isocratic separation of these compounds using a C18 column was [SDS] = 0.40 mM; 11.2% v/v
butanol, 1.4 % v/v AcOH and at a flow rate 1.1 mL/min. Using this optimum condition, baseline separation with a minimum
resolution 1.2 and a run time less than 19 min were achieved.
References
[1] N.C. Veitch, R.J. Grayer, Nat. Prod. Rep. 25 (2008) 555.
[2] E. Rijke, P. Out, W.M.A. Niessen, F. Ariese, C. Gooijer, U.A.Th. Brinkman, J. Chromatogr. A 31 (2006) 1112.
[3] P. Ebrahimi, M.R. Hadjmohammadi, J. Chemmometrics 21 (2007) 35.
Multiway study of Fluorescence Resonance Energy Transfer in nanoscale semiconductor labeled DNA
Somayeh Gholami and Mohsen Kompany-Zareh*
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731, Iran.
This study is application of bulk measurement in simple, rapid and sensitive detection of DNA, which is critical in diagnosing
genetic diseases. Most DNA detection systems (microarrays, for example) regardless of their need for target amplification require
separation of unhybridized DNA strands from hybridized strands immobilized on a solid substrate. Here, we demonstrate a
hybridization detection method using oligonucleotide functionalized quantum dots as nanoprobes and second order
spectrofluorometeric Excitation -Emission data (2D-PLE). In this study, two nucleic-acid functionalized CdSe/ZnS quantum dots
(QDs), each with discernible emission wavelengths, at 605 and 705 nm, were designed to hybridize in juxtaposition with the
complementary oligonucleotide target capC which was one of the three anthrax-related genes to form a sandwiched
nanoassembly. In this system there was no need to functionalize the target DNA. The resulting assembly brings the QD acceptor
and the QD donor in to proximity, leading to fluorescence emission from the high energy QD (donor) by means of Fluorescence
Resonance Energy Transfer (FRET) on illumination of the low energy QD (acceptor). So, hybridization was monitored by
following the fluorescence resonance energy transfer. As a result, detection of sandwiched nanoassembly as a third component
indicated the presence of target. Using highly informative 2D-PLE data and applying PARAFAC method to deal with such data
an estimate of concentration and spectral profiles were obtained. In the next step using model based chemometric methods,
complex formation constants of both double and ternary complex forms were calculated. This is the first report on determination
of complex formation constants of this sandwiched nanoassemblies.
References:
Removal of alizarin yellow dye from aqueous solutions by sorption on the modified montmorillonite
with diethylenetriamine
Shahla Elhami*, Hadis Drikvandi
Department of Chemistry, Science and Research Branch, Islamic Azad University, Khouzestan, Iran
*E-mail: Sh.elhami@ khouzestan.Srbiau.ac.ir
The present study is related to the removal of alizarin yellow using modified nanoclay. Alizarin yellow is an azo dye having
carboxylate and nitro groups, alizarin has undesirable effects not only on the environment but also on human beings. Clays are
natural environment-friendly materials [3] with high specific surface area and now widely used for the adsorption [1]. They are
often in cationic form while clay minerals bear negative charges on their surfaces [1-2]. Alizarin yellow dye removed by
montmorillonite after modification with diethylenetriamine. Adsorption of alizarin yellow was studied as a function of pH,
amount of adsorbent, shaking time and agitation rate. The results showed that in the optimum conditions such as pH=4.5,
adsorbent dose of 6 g/L , contact time of 35 min and agitation rate at 110 rpm for a concentration of 100µg mL-1 can remove
more than 91 % of the dye. This method needs less time [4] in comparison with many other methods. . The achieved conditions
were applied for various concentrations of the dye (10 – 200 µg mL-1) and in all the cases an efficiency of more than 90% is
attainable. Adsorption isotherms of Langmuire and Freundlich were studied which was well in line with Freundlich equations.
The method was applied for the removal of dye from real samples of different waters.
References
[1] Xiaoling Zhang, Hanlie Hong, Zhaohui Li Junfang Guand, Laura Schulz, Removal of azobenzene from water by kaolinite, 170 (2009) 1064.
[2] Yunfei Xi, Ray L. Frost, Hongping He, Modification of the surfaces of Wyoming montmorillonite by the cationic surfactants alkyl trimethyl, dialkyl dimethyl and
trialkyl methyl ammonium bromides, J Colloid interf sci,305(2007)150.
[3] Peng Liu, Liuxue Zhang, Adsorption of dyes from aqueous solutions or suspensions with clay nano-adsorbents, Sep purify technol 58(2007)39.
[4] V. K. Gupta, Imran Ali, V. K. Saini, Tom Van Gerven, Bart Van der Bruggen, and Carlo Vandecasteele, Removal of Dyes from Wastewater Using Bottom Ash,
Ind. Eng. Chem. Res.,44( 2005)3655.
Removal of Congo Red, an Anionic Dye, from aqueous solutions using Modified Sawdust
Shahla Elhami*, Seyedeh Zeinab Mousavi
Department of Chemistry, Science and Research Branch, Islamic Azad University, Khouzestan, Iran
*E-mail: Sh.elhami@ khouzestan. Srbiau.ac.ir
Congo-Red (CR) dye is a carcinogenic dye which comes in the effluents of textile industries during dyeing and rinsing processes.
There are many processes to remove CR molecules from colored effluents and the treatment methods can be divided into three
categories: (1) physical methods such as adsorption [1,2]; (2) chemical methods such as ozonation [3], photo degradation [4] and
electrochemical process [5]; and (3) biodegradation [6]. In this work, the technique was found to be very useful for a better
removal of Congo-Red dye from water samples. Adsorbent prepared from sawdust and modified with diethylenetriamine are both
environmentally friendly. Scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) results of sawdust were
compared to modified sawdust with diethylenetriamine. Adsorbent was successfully used to remove the congo red from an
aqueous solution in a batch system. The effects of various experimental parameters (e.g. initial pH, sorbent dose, dye
concentration, contact time, and stirring speed etc.) were investigated. The removal of congo red remained above 99.5% for 100
mg/L of congo red solution when 4 g/L of absorbent was used. The experimental requirements (contact time=90 min and sorbent
dose) are better than some of the previously reported methods for the removal of congo red [1,2]. In order to test the reliability of
the proposed removal methodology, it was applied to the removal of concentrations of congo red from tap water and river water
samples.
References
[1] E. Bulut, M.O. zacar, I. Ayhan¸ J. Hazard. Mater. 154 (2008) 613.
[2] S. Chatterjee, M.W. Lee, S. H. Woo, Bioresource Technol. 101 (2010) 1800.
[3] P. Gharbani, S. M. Tabatabaii, A. Mehrizad, Inter. J. Environ. Scie. Tech. 5 (2008) 8.
[4] R.K. Wahi, et al, J. Mol. Catal. A –Chem. 242 (2005) 48.
[5] M.F. Elahmadi, N.Bensalah, A. Gadri, J. Hazard. Mater. 168 (2009) 1163.
[6] K.P. Gopinath, et al., Bioresource Technol. 100 (2009) 6295.
Determination of volatile organic compounds in environmental water samples
using solid-phase microextraction poly(ethylene glycol)/multi-walled carbon nanotubes fiber
based on sol–gel technique with gas chromatography-flame ionization detector
Ali Sarafraz-Yazdi*, Mehdi Mosadegh, Amirhassan Amiri
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, Iran
E-mail: asyazdi@um.ac.ir
The sol–gel technology was applied for the preparation of solid-phase microextraction (SPME) fiber for extraction of the
volatile organic compounds (VOCs) from environmental water samples using the gas chromatography-flame ionization
detector (GC–FID). The compounds studied were methyl tert-butyl ether (MTBE), tetrahydrofuran (THF), benzene, Nheptane, methyl isobuthyl ketone (MIBK), toluene, tetrachloroethylene, ethylbenzene and O-xylene. Sol–gel coatings
possess higher thermal and solvent stability than conventional coatings, because of the direct chemical bonding to the fused
silica surface. The coating fiber was prepared from polymer poly(ethylene glycol) (PEG) reinforced with multi-walled
carbon nanotubes (MWCNTs). CNTs as a kind of effective sorbent nanomaterials, have been successfully used as the SPME
fiber coating for analysing organic compounds. CNTs with large accessible specific surface area and unique electrical,
mechanical, and chemical properties is applied as an extracting phase in the sol-gel SPME network. Important parameters
affecting the extraction efficiency include desorption temperature, extraction temperature, extraction time, salt effect and
stirring speed were investigated and optimized. Under the optimal conditions, the dynamic linear range of PEG/CNT fiber
was 0.002–2000 ng mL-1 ,and the detection limits (S/N = 3) was 0.001–0.5 ng mL-1, respectively. The relative standard
deviations (RSD) for one fiber (Repeatability) (n=3) were obtained between 3.23–5.80% and between fibers or batch to
batch (n=3) (Reproducibility) in the range of 5.06–8.77%. The sol–gel PEG/CNTs fiber has good performance and therefore
relatively better figures of merits and experimental results such as thermal stability (up to 320 °C), average of life time (over
150 times) and repeatability in comparison to conventional fibers. Five environmental water samples were analyzed with this
method. These samples were spiked with 50 ng mL–1 VOCs to assess the accuracy of the method and relative recovery
percentages obtained 88–112%.
References
[1] R.P. Belardi, J.B. Pawliszyn, Water Pollut. Res. J. Can. 24 (1989) 179.
[2] C.L. Arthur, J. Pawliszyn, Anal. Chem. 62 (1990) 2145.
[3] A. Sarafraz-Yazdi, A. Amiri, Trends Anal. Chem. 29 (2010) 1.
[4] S.L. Chong, D.X. Wang, J.D. Hayes, B.W. Wilhite, A. Malik, Anal. Chem. 69 (1997) 3889.
Selective Recognition For Co (II) Based on Fluorescence quenching
of a New Complex, 4'-(phenyl)-2,2':6',2"-terpyridine
Roshanak Ghobadian*a, Mohamad javad Chaichia, Ali Nemati Kharat Gaziani b
a.Department of Chemistry, University of Mazandaran, Babolsar, Iran
b.School of Chemistry,University College of Science, University of Tehran,Tehran, Iran
A new ligand, 4'-(phenyl)-2,2':6',2"-terpyridine, complexation with some metal ions based on a 1:1 metal complex formation in
methanol has been investigated by fluorescence spectroscopy and UV–Vis absorbance. The experimental results revealed that
some of these cations have the ability to quench the intrinsic fluorescence of the ligand through a quenching procedure. The
experimental results showed that Co2+ ion has the best interaction with the ligand molecule over than Ni2+, Zn2+, Pb2+, Hg2+, Ca2+,
Na1+, Ag1+, Cu1+ and Cd1+ ions. So a novel and simple fluorescence quenching method for selective Co (II) sensing was
investigated.
References
[1] Wolfbeis OS (2000) Fiber-optic chemical sensors and biosensors.Anal Chem 72:81R–89R
[2] esvergne JP, Czarnik AW (eds) (1997) Chemosensors for ion
and molecule recognition. Kluwer, Boston
[3] Gokel AW (ed) (1996) Comperhensive supramolecular chemistry. Pergamon, Oxford, p 1
Preparation and application of a novel solid-phase microextraction fiber by sol–gel technology
on the surface of titanium wire for determination of BTEXs in aquatic samples
a.
b.
Ali Es-haghi a*, S. Maryam Hosseini b, Zahra Monsef khoshhesab b
Department of Physico Chemistry, Razi Vaccine & Serum Research Institute, P.O. Box 31975/148, Karaj, Iran
Department of Chemistry, Payame noor university, P. O. Box 878, Qazvin, Iran
Solid-phase microextraction (SPME) is a well-known and powerful sampling and sample preparation method which has gained
increasing industrial applications in trace analysis in many areas including environmental, food, and drug fields [1]. The
extraction efficiency of SPME is predominantly determined by intermolecular and steric interactions between the analyte species
and the extracting phases. Several fiber coatings with different polarities are commercially available. In addition many different
SPME fiber coatings have been developed using different techniques such as physical deposition, electrodeposition and sol–gel
technology [2]. Among these coating technologies, sol-gel method has gained more attraction as it is simple, rapid, flexible in
coating composition and operationally stable coating can be obtained [3]. Moreover, our previous investigations have shown,
these kinds of coating can extract numerous substances from real matrixes [4-5]. In this study a novel
polydimethylsiloxane(PDMS)-coated SPME fiber was prepared based on sol–gel technique. On one hand, commonly used friable
fused silica rode was replaced by titanium wire which can provide high strength, and prolong the fiber life cycle. On the other
hand titanium isopropoxide was employed as the precursor which provides a sol solution containing Ti-OH groups in the
hydrolysis of precursor during the sol-gel processes. These Ti-OH groups have more tendencies to the molecularly similar group
on the substrate so, a more stable and uniform coating can be obtained. The applicability of this fiber was assessed for the
headspace SPME (HS-SPME) of benzene, toluene, ethylbenzene and xylenes (BTEX) from water sample followed by gas
chromatography–mass spectrometry (GC-MS). The parameters influencing adsorption (extraction time, temperature, stirring rate,
and salt addition) and desorption (desorption time and temperature) of the analyte on the fiber were investigated and optimized.
Under the optimized conditions, LODs and LOQs of 75-250 ngL-1 (S/N= 3) and 0.25-2 µgL-1 (S/N= 10) were respectively
obtained. The method showed linearity in the range of 0.25-1000 µgL-1 with correlation coefficient of > 0.98. The relative
standard deviation was less than 8%.
Reference
[1] J. Pawliszyn, ed., Handbook of SPME, Chemical Industry Press, 2009.
[2] S. Sungkaew, C. Thammakhet, P. Thavarungkul, P. Kanatharana, Anal. Chim. Acta 664 (2010) 49.
[3] A.K. Gaurav, A.K. Malik, D.K. Tewary, B. Singh, Anal. Chim. Acta 610 ( 2008) 1.
[4] H. Bagheri , E. Babanezhad, A. Es-haghi, J. Chromatogra. A 1152 (2007) 168.
[5] H. Bagheri, A. Es-haghi, F. Khalilian, M.R. Rouini: J. Pharm. Biomed. Anal. 43 (2007) 1763.
Development and validation of flame atomic absorption spectroscopy technique (FAAS)
for the determination of Aluminium in biological products
Ali Es-haghi a*, Farshid shabani a, Masoud Ghader b
a. Department of Physico Chemistry, Razi vaccine & serum research institute, P.O. Box 31975/148, Karaj, Iran
b. Department of human bacterial vaccine, Razi vaccine & serum research institute, P.O. Box 31975/148, Karaj, Iran
Adjuvant is a main component of vaccines in their final bulk formulations which enhances the immune response against coinoculated antigens. Aluminium adjuvants have demonstrated safety profile for use in human and veterinary vaccines; however,
these adjuvants have been associated with severe local reactions such as erythema, subcutaneous nodules and contact
hypersensitivity [1]. Therefore, Aluminium content should be well regulated and an accurate determination of Aluminium is
necessary in the production of vaccines for quality control purposes. The analytical methods employed for the determination and
quantitation of Aluminum includes spectrometric methods based on the reaction of Aluminum with Aluminon or 8hydroxyquinoline; titrimetric method involving EDTA, and atomic absorption spectroscopy [2-4]. In quality control laboratories
estimation of Aluminium in biological products is generally performed using spectrophotometric method which in some cases
shows inadequate quality. In the present study a flame atomic absorption spectroscopy (FAAS) technique for quantification of
Aluminum in human bacterial (DTP and dT) and foot mouth disease (FMD) vaccines has been developed and validated. In order
to liberate Aluminium from sample complex matrix, acid digestion was applied. Influential parameters on digestion such as kind
of acids and temperature for different matrixes were optimized. Interference effect of matrix components on the final response
has been studied. The developed method was found to be linear in the range of 10-120 mgL-1 with detection limit of 3.33 mgL-1
based on three standard deviation of the blank. The procedure was found to be accurate for different vaccines with recoveries of
92.0 and 98.0% for two different kinds of vaccines.
References
[1] S. Plotkin, W. Orenstein, P. Offit, Vaccines, Elsevier Inc (2009).
[2] J. Komarek , R. Cervenka, T. Ruzicka, V. Kuban, Pharma. Biochem. analysis 45 (2007) 504-509.
[3] A. Mishra, S. R. Bhalla, S. Rawat, Biologicals 35 (2007) 277-284.
[4] J. Scancar, R. Milacic, I. Falnoga, M. cemazar, P. Bukovec, J. Pharma. and Biomed. Analysis 22 (2000) 993-1002.
Study of Electropolymerization of Tyramine on Copper and its Corrosion Protection Performance
Arezoo Jamali, Khalil Farhadi*, Sepideh Bani Saeid
Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
Electropolymerization is a method of synthesis and deposit of thin layers of polymers on conducting substrates [1]. Electroactive
polymer films can act as physical barrier against aggressive species (such as O2, H+ and Cl−) and can provide anodic protection to
metals [2]. For this purpose, polymers like polyaniline , polypyrrole, polythiophene , polyindole and polyphenol were studied
[3]. Because of its low resistivity and its improved electro-migration performance copper is a widely used reactive metal in
electrical and electronic devices.[4]. This motivates studies aiming to develop better quality coatings for anticorrosive
applications [2]. I this study, for the first time, we have synthesized the polytyramine coating on Cu substrate by
electropolymerization of tyramine and examined the ability of this coating to serve as protective coating against the corrosion of
Cu. The synthesis of polytyramine film was achieved on copper electrodes from monomer containing oxalic acid solution by
using a cyclic voltammetry technique. The corrosion performance of polytyramine coated samples were investigated in 3.5%
NaCl solutions using Tafel plots and open circuit potential–time (Eocp–t) curves. The electrodeposited coatings were
characterized by cyclic voltammetry (CV), FTIR-ATR spectroscopy and scanning electron microscopy (SEM). The obtained
results showed the shift of corrosion potential toward positive values for electropolymerized copper and a significant decrease in
corrosion current in comparison with bare copper, so that the polytyramine coating could be used as an important protection
against corrosion of copper.
Refrence
[1] Y. Samet, D.Kraiem, R.Abdelhédi, Prog. Org. Coat., 2010, In press.
[2 ]A.T. Ozyılmaz, T. Tuken, B. Yazıcı, M. Erbil, Prog. Org. Coat.52 (2005) 92–97.
[3] A. Yagan, N.O. Pekmez, A. Yildiz, J. Electroanal. Chem.578 (2005) 231–238.
[4] P. Herrasti , A.I. del Rio, J. Recio, Electrochim. Acta 52 (2007) 6496–6501.
Preparation of textile including conductive polymer
M.R. Nateghi, M. Heshmati
Chemistry Department, Islamic Azad University, Yazd Branch, Yazd, Iran
The term 'conductive textiles' is used for a broad range of products with widely differing specific (surface) conductivity. A new
approach for making conductive yarn materials is the use of intrinsically conductive organic polymers. Conductive fibers can be
produced by chemical polymerization of a suitable monomer in the presence of an oxidant as reaction initiator. In the present
research, effect of conductive polymer coatings on reduction of electrical resistivity of the two cellulose yarns (vicose and
acetate) has been studied. For this purpose, acetate and viscose yarns were coated with poly pyrrole as conductive polymer via
oxidation of pyrrole by Fe3+ as the oxidizing agent. Electrical resistivity of coated yarns according to the equation
L was
s=
π r 2R
calculated. Also, thermal resistance and mechanical strength of the fibers have been measured. Results showed that mechanical
strength of the two fiber samples remains without considerable changes after 24h polymerization reaction.
Reference
[1] Y. Xia, Y. Lu, Composites Science and Technology 68 (2008) 1471-1479
Solid phase extraction and spectrophotometric determination of trace amounts of malachite green in water samples using
nanoparticles of layered double hydroxides
Shabnam Rafiei*1 ; Mehdi Aghaei2 ; Hatam Amanzadeh2 ; Khalil Farhadi2
1) Department of Chemistry, Urmia Payam nour University, Urmia, Iran
2) Department of Chemistry, Faculty of Science, Urmia University, Urmia, Iran
Malachite green (MG) is a triphenylmethane dye, originally used as a dyeing agent in the textile industry but it was also widely
used in fish farming industry for many decades [1]. However, MG has now become a highly controversial compound due to its
effects on the immune system, and its carcinogenic properties. Due to the vital importance of MG analysis in water samples,
several sample preparation methods such as magnetic-solid phase extraction (SPE) [2], cloud point extraction [3], SPE using
surfactant coated alumina [4], diol-SPE [5] and cyano-SPE [6] have been used before detection steps. In the present work, a
simple and reliable method has been developed for the rapid analysis of trace levels of MG from water samples using
nanoparticles of layered double hydroxides coupled with spectrophotometric detection. The effects of pH, flow rate of sample
solution, and adsorbent dosage have been investigated. Ten micrograms of MG from 100 mL (pH 5-7) of aqueous phase could
be quantitatively extracted using a microcolumn containing 100 mg of sorbet at flow rate 5 mL min-1. The collected MG
molecules were eluted with 0.5 mL of ethanol and determined spectrophotometrically at 622 nm. The calibration curve indicated
a linear range (10–100 µg L-1) with good linearity (r=0.9947). The limit of detection (LOD) of the proposed method for
determination of MG is 3.2 µg L-1. Finally the proposed method was successfully applied for the separation and preconcentration
of malachite green with high enrichment factor (about 200) from water samples and the analysis of MG from fish farming water
samples.
Reference
[1] S.J. Culp, F.A. Beland, Malachite green: a toxicological review, J. Am. Coll. Toxicol. 15 (1996) 219–238.
[2] I. Safarik, M. Safarikova, Detection of low concentrations of malachite green and crystal violet in water, Water Res. 36 (2002) 196-200.
[3] N. Pourreza, S. Elhami, Spectrophtometric Determination of Malachite Green in Fish Farming Water Samples after Cloud Point Extraction Using Nonionic
Surfactant Triton X-100, Anal. Chim. Acta 596 ( 2007) 62– 65.
[4] K. Farhadi, R. Maleki , N. Mohammad-Nezhad, N. Samadi, Determination of malachite green residue in water samples after preconcentration on surfactant-coated
alumina, Spect. Lett. 43 (2010) 101-107.
[5] K. Mitrowska, A. Posyniak, J. Zmudzki, Determination of malachite green and leucomalachite green in carp muscle by liquid chromatography with visible and
fluorescence detection. J. Chromatogr. A 1089 (2005) 187-192.
[6] K. Sagar, M.R. Smyth, J.G. Wilson, K. Mclaughlin, High-performance liquid chromatographic determination of the triphenylmethane dye, malachite green, using
amperometric detection at a carbon fibre microelectrode, J. Chromatogr. A 659 (1994) 329-336.