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The First Regional Symposium on Bioelectrochemistry

Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P32]
Simultaneous determination of tryptophan and dopamine at iron (III)
doped zeolite modified carbon paste electrode
A. Babaei*, B. Bakhoday, S. Mirzakhani
Department of Chemistry, Faculty of Sciences, Arak University, Arak, Iran
E-mail: a_babaei@araku.ac.ir
Tryptophane (Trp) is of great importance in the biochemical, pharmaceutical and
dietetic fields as it is precursor molecule of some hormones, neurotransmitters and other
relevant bimolecules [1]. Dopamine (DA) plays an important physiological role in the
functioning of central nervous system, cardiovascular, renal and hormonal systems as an extra
cellular chemical messenger. Extreme abnormalities of DA concentration levels may lead to
some illness like Parkinsons disease and schizophrenia [2]. Determination of DA and related
catecholamine compounds is significant for neurochemistry and brain-science studies [3].
In this work a new sensitive and selective method for determination of Trp and DA is
introduced. The method is based on differential pulse voltammetry of the accumulated
samples on iron (III) doped zeolite modified carbon paste electrode. The analytical
performance was evaluated with respect to the carbon paste composition, accumulation
potential, pH of solution and accumulation time and optimum condition was obtained. The
linear calibration range for Trp in the presence of 30 M DA and was from 0.9 to 90M, with
a correlation coefficient of 0.9995, and a detection limit of 0.24 M. A linear relationship was
found for DA in the range from 0.4 to 120 M containing 50 M Trp, with a correlation
coefficient of 0.9987 and a detection limit of 0.17 M. The proposed method was used for
determination of Trp, and DA in some biological systems with satisfactory results.

REFERENCES
[1] G. Chen, J.S. Cheng, J.N. Ye, Fresenius J. Anal. Chem. 370 (2001) 930.
[2] T.E. Smith, Textbook of Biochemistry with clinical correlation, Wiley, New York (1992).
[3] R.M. Wightman, L.J. May, A.C. Michael, Anal. Chem., 60: (1988) 769A.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P33]
A sensitive simultaneous determination of adrenaline and tyrosine using
zeolite modified carbon past electrode doped with iron (III)
A. Babaei*, S. Mirzakhani, B. Khalilzadeh
Department of Chemistry, Faculty of Sciences, Arak University, Arak, Iran
E-mail: a-babaei@araku.ac.ir
Adrenaline (Ad) plays a very important role in the functioning of central nervous
system, renal, hormonal, and cardiovascular system [1]. Extreme abnormalities of Ad levels
cause symptoms for several diseas. Tyrosine (Tyr) is a vital constituent of proteins, which are
indispensable in human nutrition for establishing and maintaining a positive nitrogen balance
[2]. Tyrosin play as a precursor for dopa, dopamine, thyroxin, noradrenalin and adrenalin as
hormone or neurotransmitter in mammalian central nervous systems [3].
In this work a new sensitive and selective method for determination of Ad and Tyr is
introduced. The method is based on differential pulse voltammetric determination of the
accumulated samples on iron (III) doped zeolite modified carbon paste electrode. The
analytical performance was evaluated with respect to the carbon paste composition,
accumulation potential, pH of solution and accumulation time and optimum condition was
obtained. A linear dynamic range from 910-7 to 2.1610-4 M for adrenaline in presence of
30 M Tyr in phosphate buffer solution was obtained with a correlation coefficient of 0.9998
and a detection limit of 4.410-7 M. For Tyr in the presence of 25 M Ad a linear calibration
range in the range 1.210-6 to 910-5 M with a correlation coefficient of 0.9988 and a
detection limit of 3.2810-7 M was obtained. The proposed sensor showed a good
reproducibility, and high stability for the detection of both Ad and Tyr. The analytical
performance of this sensor has been evaluated for a relatively wide concentration range of Ad
and Tyr spiked to biological samples with satisfactory results.
REFERENCES
1. J.R. Cooper, F.E. Bloom, R.H. Roth, The Biochemical Basis of Neuropharmacology, , Oxford Univ. Press,
1982.
2. J.P. Jin, X.Q. Lin, Electrochem. Commun. 6 (2004) 454-460.
3. G. Beck, C. Hanusch, P. Brinkkoetter, N. Rafat, J. Schulte, K. van Ackern, B. Yard, Anaesthesist, 54 (2005)
1012-1020.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P34]
Potentiometric determination of trace levels of amantadine using a
modified carbon-paste electrode
F. Jalali* and R. Maghooli
Department of Chemistry, Faculty of Science, Razi University, Kermanshah, Iran
E-mail: fahimehjalali@yahoo.com
Amantadine is a tricyclic aminohydrocarbon with antiviral activity directed uniquely against
influenza a virus. It has also been approved for treatment of Parkinson's disease [1, 2].

Some analytical methods have been reported for the determination of amantadine in pharmaceutical
preparations and in biological fluids. The HPLC method requires derivatization of amantadine to produce a
chromophore detectable by UV or fluorescence spectroscopy. The GC method requires derivatization of
amantadine to improve the volatility and avoid column interactions. The step of formation of the derivative
compound increases the time of sample preparation and cost of the methods.
In this work, a chemically-modified carbon-paste electrode has been described for the sensitive and
selective determination of amantadine. -Cyclodextrin was used as the modifier. The electrode shows a
near-Nernstian response of 51.0 1.0 mVdecade-1 for amantadine in the concentration range of 6.3 10 -10
M 7.1 10-7 M at 25 C. The optimum pH value was maintained at 4.5 using a 0.02 M acetate buffer.
The limit of detection of the electrode was 6.3 10-10 M of amantadine. The electrode responded very fast
(<60 s) to the changes in the concentration of amantadine and its lifetime was more than three months. The
relative standard deviation of the measurements for a 2.0 10 -7 M of amantadine was 0.68% (n=7). The
application of the modified carbon-paste electrode to the determination of amantadine in its pharmaceutical
preparations shows a relative error of 2%. The recovery of amantadine (2.5 10-8 M) from a blood-serum
sample was 94%. The selectivity of complexation between amantadine and -cyclodextrin [3] and the
absence of inner solutions in the construction of the sensor [4] are among the main causes of the very good
detection limit of the electrode.
REFERENCES
1- A.M. Rudolph, R.A. Kamei, K.J. Overby, Rudolphs Fundamentals of Pediatrics, p. 308. McGraw-Hill
Professional (2002).
2- Y. Kawaoka, Influenza Virology, p. 169
3- R.I. Gelb, L.M. Schwartz, D.A., J. Chem. Soc. Perkin Trans. II (1984) 15-21.
4- E. Bakker, E. Pretsch, Potentiometric sensors for trace level analysis, TrAC, 24(2005), 199-207.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P35]
Selective determination of dopamine in the presence of ascorbic acid and
uric acid on a carbon paste electrode modified with silica gel
Z. Nasri* & E. Shams
Department of Chemistry, University of Isfahan, Isfahan, I.R. Iran,
E-mail: Z.Nasri@chem.ui.ac.ir
Dopamine (DA) is an important neurotransmitter. Extreme abnormalities of DA
concentration levels may lead to Parkinsons disease [1]. The electrochemical determination of
dopamine is complicated by the coexistence of ascorbic acid (AA) and uric acid (UA) which
can be oxidized at a potential close to that of dopamine at almost all electrode materials which
results in overlapped voltammetric response [2]. The successful route to overcome the problems
of selectivity is to modify the electrode surface [3].
A carbon paste electrode (CPE) modified by amorphous silica gel was used for detection
of dopamine (DA) in the presence of high concentration of ascorbic acid (AA) and uric acid
(UA). Silica gel is an amorphous inorganic polymer, its surface chemistry is dominated by the
surface hydroxyl groups with a pKa about 7 [4]. Cyclic voltammetry of Fe(CN)63-/4- as a
negatively charged probe revealed that the surface of the silica gel modified CPE had a high
density of negative charge. As a result, the modified carbon paste electrode could inhibit the
voltammetric response of AA (pKa = 4.10) and UA (pKa = 5.75) while the redox reaction of
dopamine (pKa=8.89) was promoted. The effect of various experimental parameters on the
voltammetric response of dopamine was investigated. Under the chosen conditions, the
differential pulse voltammetry peak current was found to be linear with the DA concentration in
the range 210-7 to 1.510-5 mol L-1. The detection limit of the proposed method was found to be
5.0 10-9 mol L-1 for DA determination. In addition, the electrode possesses attractive
properties such as high sensitivity, ease of preparation, surface regeneration by simple
polishing, repeatability and high stability.

The authors gratefully acknowledge the University of Isfahan providing research facilities.
REFERENCES
1. R.N. Adams, Anal. Chem., 48 (1976) 1126A.
2. A. Domenech, H. Garcia, M.T. Domenech-Carbo, Anal. Chem., 74 (2002) 562.
3. M. Kooshki, E. Shams, Anal. Chim Acta, 587 (2007) 110.
4. P. Antonio, K. Iha, M.E.V. Suarez-Iha, Talanta, 64 (2004) 484.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P36]
Electrochemical evaluation of naltrexone HCl in pharmaceutical dosage
form and human plasma using glassy carbon electrode modified with nafion
doped carbon nanoparticles
S. Shahrokhiana, F. Ghorbani Bidkorbehb*, A. Mohammadi c& R. Dinarvand
a ,b

Department of Chemistry, Sharif University of Technology, Tehran, Iran, bDepartment of

Pharmaceutics, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, Iran,


c

Department of Drug & Food Control, Faculty of Pharmacy, Tehran University of Medical
Sciences, Tehran, Iran
E-mail: fghorbani@ruzi.tums.ac.ir
Naltrexone is an opioid antagonist which is commonly used for the treatment of narcotic

addiction and alcohol dependence. A voltammetric study of Naltrexone HCl (NAL) has been
carried out at the surface of Glassy Carbon Electrode Modified with Nafion Doped Carbon
Nanoparticles (CNPs). The electrochemical oxidation of NAL was investigated by cyclic
voltammetry and differential pulse voltammetry. The dependence of intensities of currents
and potentials on pH, concentration and scan rate was investigated. Application of the
modified electrode resulted in a sensitivity enhancement of about 20 orders of magnitude in
detection of NAL and a negative peak shift was achieved. The electrode characterization by
electrochemical methods and atomic force microscopy (AFM) showed that CNPs enhanced
the electroactive surface area and accelerated the rate of electron transfer. A linear dynamic
range of 1-100 M with detection limit of 0.1M was obtained in phosphate buffer, pH=3.
Based on this study, sample, rapid, sensitive and selective differential pulse voltammetric
method was developed for the determination of NAL in dosage form and human plasma. No
electroactive interferences were found in biological fluids from the endogenous substances
and additives present in capsules.
Keywords: Voltammetry, Naltrexone HCl, Nafion, Carbon Nanoparticles, Human Plasma
REFERENCES
1. Goyal, R.N., Tyagi, A., Bachheti, N., Bishnoi, S., Electrochimica Acta 53 (6)(2008), pp. 2802-2808.
, 92 (2007) 1192-1203.
2. Uslu, B., Topal, B.D., Ozkan, S.A., Talanta 74 (5) (2008), pp. 1191-1200.
3. Shahrokhian, S., Amiri, M., Microchimica Acta 157 (3-4) (2007), pp. 149-158.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P37]
Influence of gold nanoparticles modified electrode for the voltammetric
determination of trace amount of resorcinol
M. Behpour, M. Rezaei* & S.M. Ghoreishi
Department of Chemistry, Faculty of Science, University of Kashan, Kashan, Iran
E-mail: m75rezaei@gmail.com
A carbon paste electrode modified with gold nanoparticles (Au-CPE) achieved by
thoroughly mixing pure graphite powder with colloidal gold nanoparticles and paraffin. The
modified electrode has been proposed for voltammetric determination of trace amount of
resorcinol (RES). RES is an antiseptic and disinfectant, and is used 5 to 10% in ointments in
the treatment of chronic skin diseases such as psoriasis and eczema. It can be included as an
anti-dandruff agent in shampoo or in sunscreen cosmetics. In large doses it is a poison and one
kind of environmental pollutant. Resorcinol is also used as a chemical intermediate for the
synthesis of pharmaceuticals and other organic compounds. It is used in the production of
diazo dyes and plasticizers and as a UV absorber in resins. The cyclic voltammogram of RES
at the Au-CPE in 0.1 mol L-1 phosphate buffer solution (pH 7) shows that the oxidation
processes of RES is irreversible and linear relationship between the anodic peak current and
the square root of scan rate indicates a diffusion controlled oxidation process at the Au-CPE.
The Au-CPE exhibits obvious catalytic ability to RES since it not only greatly enhances the
oxidation peak current of RES, but also decreases the oxidation over potential. The
relationship between the oxidation peak current and the concentration of RES was examined
using differential pulse voltammetry. It is found that the oxidation peak current is proportional
to the concentration of RES over the range from 8.0 10-7 to 4.0 10-3 mol L-1, and the
detection limit reached 1.8 10-8.

REFERENCES
1. S.E. Blanco, M.C. Almandoz, F.H. Ferretti, Spectrochimica Acta Part A, 61 (2005) 93-102.
2. L. Ag, C. Pea-Farfal, P. Yez-Sedeo, J.M. Pingarrn, , Talanta, 74 (2007) 412-420.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P38]
Application of carbon paste electrode modified with gold nanoparticles for
determination of trace amount of acetaminophen
by electrochemical method
S.M. Ghoreishi, S. Sadeghzadeh*, M. Behpour
Department of Chemistry, Faculty of Science, University of Kashan, Kashan, I. R. Iran
E-mail: s.m.ghoreishi@kashanu.ac.ir,
The electrochemical study of acetaminophen has been made by using a bare and
modified carbon paste electrode (MCPE) as working electrode and Pt, SCE as counter and
reference electrode respectively (fig 1). Cyclic voltammograms of the MCPE exhibited two
stable redox waves with anodic peak potential at 422.0 mV and cathodic peak potential at
200.0 mV in phosphate buffer solution pH 7.00(fig 2). The potential curves were recorded
using different concentrations of acetaminophen. The oxidation reactions were studied in a
potential range from -0.1 to +0.9 V by using a carbon paste electrode modified with gold
nanoparticles (nAuCPE)(fig 3). The oxidation of acetaminophen occurs at +0.32V;
meanwhile, the current has a linear variation for the following concentration range: 510-9810-3. The best potential variation range for different scan rate, pH solution and buffer
volume were studied. The performance of the electrode was vertified by the determination of
acetaminophen in dosage form tablet. The result obtained in the recovery study was
comparable to its labeled.
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REFERENCES
1. R. Sandulescu*, S. Mirel, R. Oprean, Journal of Pharmaceutical and Biomedical Analysis, 23 (2000) 7787
*

2. K. Tungkananuruk , N.Tungkananuruk, D. Thorburn Burns , KMITL Sci. Tech. J, 5 (2005) 547-551

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P39]
Salicylate poly(vinyl chloride) membrane electrode based on
trioctylmethyl ammonium chloride ion exchanger
M. Mazloum Ardakani, M.A. Sheikh Mohseni*, A. Benvidi
Department of Chemistry, Faculty of Science, Yazd University, Yazd, Iran
E-mail: m.a.sh.mohseni@gmail.com
Plasticized poly(vinyl chloride) (PVC) membrane based sensors have been widely used
in clinical laboratories and in environmental and industrial applications [1]. One of the
interesting aspects of development of potentiometric sensors is the construction of electrodes
that respond to biological compounds. Salicylic acid is one of the common metabolites of
acetylsalicylic acid (Aaspirin), which is widely used as an analgesic and an inflammatory
agent as well as to prevent heart attacks [2]. Therefore, the development of simple procedures
for its determination is of practical interest. Freiser and coworkers developed the first
electrodes for determining salicylic acid [3]. In this work we developed a new salicylateselective electrode based on the trioctylmethyl ammonium chloride as the ion exchanger. The
treatment of membrane investigated in two different paths, in one path membrane put on the
PVC tube with inner solution and in another path membrane glued on a glassy carbon
electrode (solid contact ISE). Both sensors show a Nernstian response (561.0 and 57.71.0
mV/decade, respectively) to salicylate ions over a very wide concentration ranges (310-61
M and 110-61 M, respectively) in the pH of 7.5. The detection limits of these sensors are
110-6 and 810-7, respectively. The electrodes possess satisfactory reproducibility, very short
response time (~ 10 s) in the whole concentration ranges, and discriminating ability for
salicylate ions with respect to the most common organic anions and inorganic ions that exist
in pharmaceutical sample. The selectivity coefficients were better for membrane that glued on
glassy carbon electrode. Two electrodes could be used in pH rang 5.0 to 12.0. The electrodes
were successfully used for determination of salicylate in pharmaceutical samples.
REFERENCES
1. M.S. Frant, Analyst 119 (1994) 22932301.
2. A. Relman, N. Engl. J. Med. 318 (1988) 245246.
3. C.J. Coetzee, H. Freiser, Anal. Chem. 40 (1968) 20712071.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P40]
Carbon paste electrode modified with multi-walled carbon nanotube/cobalt
salophen complex for differential pulse voltammetric determination of
2-mercaptonicotinic acid
S. Shahrokhiana, b, Sh. Yadegari*a
a

Department of Chemistry, Sharif University of Technology, Tehran, Iran, bInstitute for


Nanoscience and Technology, Sharif University of Technology, Tehran, Iran
E-mail: yadegarishahab@yahoo.com
Nicotinic Acid (niacin) plays interesting roles in biology and in the metabolism reactions of

body. 2-Mercaptonicotinic acid is an interesting derivative of niacin that is used as an


intermediate for agrochemicals, feed additives, pharmaceuticals and animal food enrichments.
Niacin and their derivatives are used for the prophylaxis, acts to reduce plasma cholesterol, as a
vasodilator and to treat pellagra. 2-Mercaptonicotinic acid has been described as versatile ligand
which forms metal complexes useful in medicine, due to their physiological properties.
Organometalic compounds of 2-Mercaptonicotinic acid exhibit strong cytotoxic activity.
Antitumor activity among heavy metal complexes of 2-mercaptonicotinic acid has been reported.
Biological and antibacterial applications of 2-mercaptonicotinic acid made it a good lead for
identification and determination with electroanalytical methods analysis. The electrocatalytic
oxidation of 2-mercaptonicotinic acid is investigated on the surface of the multi-walled carbon
nanotube (MWCNT)/cobalt salophen-modified electrode using cyclic voltammetry (CV) and
differential pulse voltammetry (DPV). Using the modified electrode, the kinetics of the electrooxidation of 2-Mercaptonicotinic acid is considerably enhanced, by lowering the anodic
overpotential through a catalytic fashion. The mechanism of the electrochemical behavior of 2Mercaptonicotinic acid at the surface of the modified electrode is analyzed by investigating the
effect of sweep rate and pH on the responses of CV method. The prepared modified electrode
showed voltammetric responses with high sensitivity and selectivity for 2-Mercaptonicotinic acid,
which makes it very suitable for sub-micromolar detection of 2-Mercaptonicotinic acid.
REFERENCES
1. Saeed Shahrokhian, Leila Fotouhi, Sensors and Actuators B, 123 (2007) 942949.
2. Marianna N. Xanthopoulou , Sotiris K. Hadjikakou, etal. Journal of Inorganic Biochemistry, 96 (2003) 425
434
3. Silvia Marchal , Virtudes Moreno, et al. Polyhedron, 18 (1999) 36753682

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P41]
Electrocatalytic oxidation of cysteamine with ferrocyanide as a
homogeneous mediator at the surface of carbon paste electrode
R. Ojani, J. Raoof, F. Tofighi*
Electroanalytical Chemistry Research Laboratory, Faculty of Chemistry, Mazandaran
University, Babolsar, Iran
E-mail: fer-o@umz.ac.ir
Cysteamine (-mercapto-ethylamine) is the chemical compound with the formula
HSCH2CH2NH2. Cysteamine bitartrate is currently the only drug approved for the treatment
of cystinosis, arave autosomal recessive disease caused by the abnormal intralysosomal
accumulation of the amino-acid cystine within various tissues [1]. It is also used for
treatment of radiation sickness [2]. In this work, the electrocatalytic oxidation of cysteamine
has been studied at the surface of carbon paste electrode in the presence of ferrocyanide as a
homogeneous mediator in aqueous media using cyclic voltammetry (CV) and
chronoamperometry techniques. The results show this mediator can catalyze the cysteamine
oxidation in an aqueous buffered solution. It has been found that under the optimum
condition (pH 7.00) the oxidation of cysteamine in the presence of ferrocyanide occurs at a
potential about 460 mV less positive than the absence of this mediator. The electrocatalytic
oxidation peak current of cysteamine exhibits a linear dependency to its concentration in the
ranges of 3 10-5 M 6 10-3 M and 8 10-6 M 5 10-4 M using CV and differential
pulse voltammetry (DPV) methods, respectively. The detection limits (3) were determined
as 1.7 10-5 M and 1.93 10-6 M by CV and DPV methods, respectively. This method was
also used for the determination of cysteamine in human plasma by standard addition
method.
REFERENCES
1. W.A. Gahl, J.G. Thoene, J.A. Schneider, N Engl J Med, 347 (2002) 111121.
2. B.P. Lukashin, A.N. Grebeniu, Radiatsionnaia biologiia, 41 (2001) 310312.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P42]
Electrochemical determination of ascorbic acid at the surface of a graphite
electrode modified with multi-walled carbon nanotube/surfactant
S.M. Ghoreishi, M. Motahary*, M. Behpour, E. Hajisadeghian
Department of Chemistry, Faculty of Science, University of Kashan, Kashan, I. R. Iran
E-mail: s.m.ghoreishi@kashanu.ac.ir
Multi-walled carbon nanotubes (MWCNT) were dispersed into water in the presence of
tetradecyltrimethylammonium bromide (TTAB), and then a MWCNT - TTAB film-coated
graphite electrode (GE) was fabricated. The voltammetric determination method of ascorbic
acid was investigated on this modified electrode by using different kinds of electrochemical
techniques. The electrochemical response of ascorbic acid at bare GE and MWCNT-TTAB
modified GE were compared, suggesting that the MWCNT-TTAB- modified GE significantly
increased the oxidation peak current of ascorbic acid. The suggestive method was successfully
used to determine ascorbic acid in tablets. The electrochemical behavior of 2.010-5 M
ascorbic acid at MWCNT- TTAB modified GE,

in 0.2 M B-R buffer (pH 7.0) was

investigated using cyclic voltammetry (CV), shown in Fig. A. In order to elucidate the unique
properties of MWCNT, the electrochemical response of 3.0 10-5 mol L-1 ascorbic acid at two
different working electrodes (i.e. bare GE, MWNCT- TTAB film-coated GE) were compared
by differential pulse voltammetry (DPV) Fig. B. Effects of pH and scan rate on the peak
current of 2.0105 mol L-1 ascorbic acid at MWCNTsTTAB film-coated GE were studied.
The relationship between the peak current of ascorbic acid and its concentration (c) was
investigated by SWV the range from 7.010-7 to 9.510-5 mol L-1 and obeys the following
equation: ipa = 79.64+ 10+6 C (r = 0.997, ipa in A, C in mol L-1) Fig. C.
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REFERENCES
1. J. Bakhsh Raoof, R. Ojani, S. Rashid-Nadimi, Electrochimica Acta, 50 (2005) 4694-4698.
2. S. Jo, H. Jeong, S. Ra Bae, S. Jeon, Microchemical Journal, 88 (2008) 16
3. B. Fang, Sh. Jiao, M. Li, H. Tao, Anal Bioanal Chem, 386 (2006) 21172122.

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The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P43]
Voltammetric determination of methimazole using a carbon paste electrode
modified with a schiff base complex of cobalt
S. Shahrokhiana, b, M. Ghalkhani*a
a

Department of Chemistry, Sharif University of Technology, Tehran, Iran, bInstitute for


Nanoscience and Technology, Sharif University of Technology, Tehran, Iran
E-mail: shahrokhian@sharif.edu.ir
The electrochemical behavior of methimazole, as an antithyroid agent, is investigated

on the surface of a carbon-paste electrode modified with a newly synthesized Schiff base
complex of cobalt. The prepared modified electrode showed an efficient catalytic role in the
electrochemical oxidation of methimazole, leading to remarkable decrease in oxidation
overpotential and 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 PHs of the buffer solutions. The
differential pulse voltammetry is applied as a very sensitive analytical method for the
determination of sub-micromolar amounts of methimazole. A linear dynamic range of 110-6
to 110-4 M with a detection limit of 510-7 M is resulted for methimazole. The modified
electrode is successfully applied for the accurate determination of methimazole in
pharmaceutical and clinical preparations. The linear range in calibration curves remains
constant in addition to tablet preparations of methimazole and also in spiking to the synthetic
human serum samples. In comparison to calibration curves in background buffer solution, the
slope of the curves showed a variation less than 3% in determinations in background solutions
of tablet and human synthetic serum samples. These results showed high efficiency of the
Voltammetric procedure for accurate determination of methimazole in drug and clinical
preparations. The modified electrode can be prepared very easy and renewed in its surface by
simple polishing. The reproducibility of the electrode response, based on ten measurements
during two month, was 3.2% for the slope of the calibration curve.
Keywords: Methimazole, Modified electrode, Voltammetry, Cobalt Schiff base complex
REFERENCES
1. S. Shahrokhian, M. Amiri, J. Solid State Electrochem, 11 (2007) 1133-1138.
2. J.K. Liu, H.C. Yeo, E. Overvik-Douki, T. Hagen, S.J. Doniger, D.W. Chhu, G. A. Brooks, B.N. Ames, J.
Appl. Physiol, 86 (2000) 21-28.
3. I. Takayo, J. R. Kirchhoff, Anal. Chem, 72 (2000) 5755-5760.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P44]
Silver nanoparticle modified carbon nanotube paste electrodes for
simultaneous determination of dopamine and ascorbic acid
J. Tashkhourian*a, M.R. Hormozi Nezhada,b, J. Khodavesia, S. Javadia
a
b

Department of Chemistry, Faculty of Sciences, Persian Gulf University, Bushehr, Iran,

Institute for Nanoscience and Nanotechnology, Sharif University of Technology, Tehran,


Iran
E-mail:tashkhourian@pgu.ac.ir
In recent years, noble metal nanoparticles have been extensively studied and various

approaches have been employed for the preparation of metal nanoparticles [1]. Nanoparticles
can display some unique advantages over macroelectrodes when used for electroanalysis.
Therefore, much work has been carried out into their formation, characterization and
employment for the detection of many electroactive species. Carbon nanotubes (CNTs) have
attracted significant scientific attention because their interesting phenomenal electrical,
chemical and mechanical properties and these forms of carbon have been studied for their
electrochemical behaviors [2].
Dopamine (3,4-dihydroxyphenyl ethylamine) (DA) is an essential neurotransmitter in
mammalian central nervous system and has been a matter of great interest to neuroscientists
and chemists. Similarly, ascorbic acid (vitamin C)(AA) has been used in preventing and
treating cold, and other diseases. So, detection of DA and AA contained in samples plays an
important part in the study of physiology mechanism and clinical diagnoses [3].
In the present work, Ag-nanoparticles modified multiwalled carbon nanotube paste
electrode was constructed. The results of cyclic and differential pulse voltammetric
investigations show that the modified electrode possesses an effective response for the
electrochemical oxidation of DA and AA and a peak potential separation nearly 71mV is
resulted for two compounds. Linear range 4.010-6 to 6.410-4M for dopamine and 2.010-3
to 6.010-5 M for ascorbic acid was obtained and the electrode was used for determination of
these compounds in real samples.
REFERENCES
1. M.W. Christine, R.G. Compton, Anal. Bioanal. Chem., 384 (2006) 601619.
2. J.J. Gooding, Electrochimica Acta, 50 (2005) 30493060.
3. S. Shahrokhian, H.R. Zare-Mehrjardi, Electrochimica Acta 52 (2007) 63106317.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P45]
Electrochemical determination of methimazole by copper nanowire carbon
paste modified electrode
M.H. mashhadizadeha, K. Eskandari*a, A. Shafieeb
1

Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran, bFaculty of Pharmacy and
Pharmacaceutical Sciences Research Center, Tehran University, Tehran, Iran
E-mail: kha_esk@yahoo.com
Methimazole (2-mercapto-1-methylimidazole) is drugs of the thioimidazole family

widely 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. In human body
methimazole is metabolized to N-methylimidazole and sulfite via sulfenic and sulfinic acid
intermediates that are associated with the cytotoxic effects [1]. The determination of
methimazole is important in many areas including clinical chemistry and pharmaceutical
formulations. Several analytical procedures have been described for the determination of
methimazole this work the determination of methimazole with copper nanowire carbon paste
modified electrode by square wave voltammetry (SWV) method is reported. Carbon pastes
are well known as useful materials for the fabrication of various electrometric sensors for
analytical propose. The operation mechanism of such chemically modified carbon paste
electrodes (CMCPEs) depends on the properties of the modifier used to important selectivity
towards the target species [2]. The determination of methimazole was investigated by square
wave voltammetry (SWV) in 0.1 mol/l phosphate buffer solution (PBS) at pH 7.4 at a copper
nanowire carbon paste electrode. Methimazole can produce a sensitive anodic peak at 460 mV
(versus SCE) in pH 7.4 phosphate buffer solutions. Under the optimized conditions, the peak
current is linear to methimazole concentration in the range of 8 10-7 to 3.06 10-5 M, and
the detection limit is estimated to be 3.9 10-7 M after an accumulation for 60 s on open
circuit. The electrode was used in 50-300 mV and 25 Hz. The resulting electrode shows good
stability (more than one month).
REFERENCES
1- A.C. Edward In: C.M. Smith and A.M. Reynard, Editors, Textbook of Pharmacology, Saunders, Philadelphia
(1992), 652656.
2- Mehmet Aslanoglu, Nesrin Peker, Journal of Pharmaceutical and Biomedical Analysis 33 (2003) 1143-1147.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P46]
Electrocatalytic oxidation of L-cysteine with a stable copper-cobalt
hexacyanoferrate electrochemically modified carbon paste electrode
A. Abbaspour, A. Ghaffarinejad*
Chemistry Department, College of Sciences, Shiraz University, Shiraz, Iran
E-mail: a.ghaffari@yahoo.com
A

stable

composition

of

hybrid

copper-cobalt

hexacyanoferrate

film

was

electrodeposited on a carbon paste electrode. There are a few reports for using this hybrid as
mediator, but all of them require almost 12hr conditioning time before usage [1]. Contrary to
previous reports this electrode does not require any conditioning and can be used immediately
after film formation. The Electrocatalytic activity of this film was investigated and showed a
good electrocatalytic effect for oxidation of L-Cysteine (Cys) in phosphate buffer solution in
pH range of 1-7. A linear range of 6M to 1mM of Cys and an experimental detection limit of
5M of Cys were obtained using cyclic voltammetry method. The diffusion coefficient of Cys
and catalytic rate constant for electrocatalytic reaction were also calculated. The major
problem reported in electro oxidation of Cys is poisoning of electrode surface with reaction
product, but in this study oxidation of Cys had no significant fouling effect on the modified
electrode surface for the concentrations below 0.5mM of Cys.
We gratefully acknowledge the support of this work by the Shiraz University Research
Council.
REFERENCES
1. X. Cui, L. Hong, X. Lin, J. Electroanal. Chem., 526 (2002) 115-124.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P47]
Modification of glassy carbon electrode using nafion doped carbon
nanoparticles: application to voltammetric detection of guanine in the
presence of adenine
S. Shahrokhian, A. Taheri*, M. Amiri
Department of Chemistry, Sharif University of Technolog, Tehran, Iran,
E-mail: shahrokhian@sharif.edu.ir
Detection of purine bases and purine-containing compounds represent a challenging and
important task owing to the importance of these compounds in a variety of biochemical
processes. Guanine and adenine are the building blocks of both DNA and RNA that play a
crucial role in protein biosynthesis, and the storage of genetic information; in addition,
guanine has the lowest oxidation potential and is believed to play a key role in the oxidation
of DNA. Recently there have been considerable efforts in the development of electrochemical
methods for detection of nucleic acids in biological samples based on guanine oxidation. In
this work, a modified glassy carbon electrode using carbon nanoparticles (CNPs) doped with
nafion was applied for voltammetric detection of guanine in the presence of adenine. Guanine
and adenine produced well-defined oxidation peaks at about +0.6 and +0.9 V, respectively in
pH 7 phosphate buffer. Application of the modified electrode resulted in a sensitivity
enhancement of about three orders of magnitude in detection of guanine and a negative peak
shift up to 0.08 V. The electrode was characterized by using electrochemical methods and
atomic force microscopy (AFM). It was found that CNPs enhanced the electroactive surface
area and accelerated the rate of electron transfer. Detection limit of guanine was found 1 10-7
M by using differential pulse voltammetry and the linear range in these determinations was
from 0.1 to 10 M. Aciddenatured DNA showed two oxidation peaks corresponding to
guanine and adenine residues. The proposed method can be used to estimate the guanine
contents in DNA with good selectivity and sensitivity.
REFERENCES
1. N. Mogharrab, H. Ghourchian, M. Amininasab, Biophysical Journal, 92 (2007) 1192-1203.
2. H. Hanaee, H. Ghourchian, A.A. Ziaee, Analytical Biochemistry, 370 (2007) 195200.
3. .J. Wang J., Chen G., Muck A., Shin D., Fujishima A.: J. Chromatogr. A. 1022, 207 (2004)
4. Amiri M., Shahrokhian S., Psillakis E., Marken F.: Anal. Chim. Acta 593, 117 (2007)
5. White B., Smyth R.M., Stuart J.D., Rusling J.F.: J. AM. CHEM. SOC. 125, 6604, (2003)
6. Gao Z.: Sensors and Actuators B 123, 293 (2007)

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P48]
Self-assembled monolayer of calix [4] crown-5-ether:
electrochemical ALT immunosensor.
A. Amiri*a, b, W. Hong Taob, S. Urrahmanb, E.Y. Choib
a

Chemistry Department, Central Tehran Campus, Islamic Azad University, Tehran, Iran,
b

Biomedical Department, Hallym University, Chuncheon, South Korea


E-mail: afsaamiri@gmail.com

The development of the immunosensors with variety of formats has recently exploded
because of its application in clinical diagnostics and biological aspects. The electrochemical
biosensors have many advantages over the conventional methods because it is fast,
inexpensive, more accurate, and more convenient to handle. In present research study it has
been investigated general considerations protocols with the competitive immune- reaction.
The Alanine aminotransferase (ALT-1) monoclonal antibody successfully immobilized on 1,
3-dimethoxy, 2, 4- dithiol- Calix[4]crown-5-ether on the gold surface. Horseradish peroxidase
(HRP) has been used extensively as the label enzyme. Its activity determined by using TMB
as electrochemical substrate based on enzyme immunoassay.
The optimal Immobilizing concentration of the Alt-1 antibody and antigen HRP
conjugated in antibody immobilized system and also antigen, antibody HRP conjugated in
antigen immobilized system has been determined by using cyclic voltammetry. ALT-1 was
detected by the competitive immunoreactions based on antibody immobilized systems and
antigen immobilized system both on the surface of Calixcrown chip. The detection limit was
evidently extended from 1 ng/ml to 0.1ng/ml by the signal enhancements. The result shown
that Antibody immobilized system is two times more effective than antigen immobilized
system.
Acknowledgement, This research was supported by Brain Korea 21(BK21).
REFERENCES
1. A.P.F. Turner, Biochemistry-biosensors sense and sensitivity, Science 290 (5495) (2000) 13151317.
2. S. Laschi, M. Franek, M. Mascini, Electroanalysis 2000, 12, 1293

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P49]
Inhibition of acid corrosion of carbon steel using aqueous extract of Datura
stamonium leaves
M. Behpoura,*, S.M. Ghoreishia, N. Soltania, M. Khayat Kashania,b
a

Department of Chemistry, Faculty of Science, University of Kashan, Kashan, Iran,


b

Barij Essence Pharmaceutical, Kashan, Iran


E-mail: m.behpour@kashanu.ac.ir

Hydrochloric acid solutions are normally used for pickling of steel and for its chemical and
electrochemical etching, processes that normally lead to substantial loss of the metal to corrosion.
Among the several methods of corrosion control and prevention, the use of corrosion inhibitors [1, 2]
is very popular. For this reason, many researches were conducted to study its corrosion properties and
to find out suitable chemical compounds to be used as corrosion inhibitors for it in acidic solutions.
However, most of used compounds are dangerous for human and environment. Extracts of naturally
occurring products contain mixtures of compounds and are biodegradable in nature. These compounds
having nitrogen and sulfur as constituent atoms were studied as corrosion inhibitor in HCl medium [3,
4].
This work is devoted to examining the aqueous extract of Datura stamonium leaves as an
inhibitor for corrosion of C-steel in 2 M HCl solution. The inhibitive action of the aqueous extract of
Datura stamonium leaves toward the corrosion of C-steel in 2 M HCl solution was investigated using
electrochemical impedance spectroscopy (EIS) measurements, Tafel polarization and cyclic
voltammetry. It was found that the extract acts as a good corrosion inhibitor for the tested system. The
inhibition efficiency increases with increasing extract concentration. The inhibitive action of the
extract is discussed with a view to adsorption of its components onto the steel surface, making a
barrier to mass and charge transfer. The adsorption of extract components onto the steel surface was
found to be a spontaneous process and to follow the Langmuir adsorption isotherm. It was found also
that such adsorption increases the activation energy of the corrosion process. The results of cyclic
voltammetry showed that the presence of Datura stamonium extract decreases the charge density in the
transpassive region. The inhibition efficiency is greatly reduced as the temperature is increased.
REFERENCES
[1] M. Crobu, A. Scorciapino, B. Elsener, A. Rossi, Electrochim. Acta, 53 (2008) 3364-3370.
[2] Ph. M. Barkhudarov, P.B. Shah, E. Watkins, D.A. Doshi, C.J. Brinker, J. Majewski, Corros. Sci., 50 (2008)
897-902.
[3] A.Y. El-Etre, Appl. Sur. Sci. 252 (2006) 85218525.
[4] P. B. Raja, M. G. Sethuraman, Mat. Lett. 62 (2008) 113116.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P50]
Corrosion inhibition of mild steel by plant extract in HCl medium
M. Behpoura, S.M. Ghoreishia, M. Khayat Kashani*a,b, N. Soltania
a

Department of Chemistry, Faculty of Science, University of Kashan, Kashan, I. R. Iran,


b

Barij Essence pharmaceutical, Kashan, Iran.


E-mail: m.khayat@kashanu.ac.ir

Corrosion inhibitors are chemical compounds usually used in small concentrations whenever a
metal is in contact with an aggressive medium. A number of heterocyclic compounds [1-2] have been
reported as corrosion inhibitors and the screening of synthetic heterocyclic compounds is still being
continued. Though many synthetic compounds showed good anticorrosive activity, most of them are
highly toxic to both human beings and environment. The safety and environmental issues of corrosion
inhibitors arisen in industries has always been a global concern. These inhibitors may cause reversible
(temporary) or irreversible (permanent) damage to organ system viz., kidneys or liver, or to disturb a
biochemical process or to disturb an enzyme system at some site in the body. The toxicity may
manifest either during the synthesis of the compound or during its applications. These toxic effects
have led to the use of natural products as anticorrosion agents which are eco-friendly and harmless. In
recent days many alternative eco-friendly corrosion inhibitors have been developed, [3-4].
In the present work the inhibition effect of Zataria multiflora extract on the corrosion of mild
steel in 5% and 15% aqueous hydrochloric acid solution has been investigated by Tafel polarization
and electrochemical impedance spectroscopy (EIS). The corrosion inhibition efficiency increases on
increasing plant extract concentration till 3000 ppm. The effect of temperature on the corrosion
behaviour of mild steel in 5% and 15% HCl with addition of plant extract was studied in the
temperature range 50 80C. Plant extract is able to reduce the corrosion of steel more effectively in
15% HCl than in 5% HCl. The adsorption of this plant extract on the mild steel surface obeys the
Langmuir adsorption isotherm. GCMS analysis of plant extract shows that this plant extract contains
plant acids or its esters and derivatives of terpineol, isoxazolidine and imidazolinedione. The
derivatives of isoxazolidine and imidazolinedione are known to contain nitrogen groups and are
responsible for the corrosion inhibition properties of this plant extract.
REFERENCES
1. C. Kst, K. C. Emregu, O. Atakol, Corros. Sci. 49 (2007) 28002814.
2. M. Elayyachya, B. Hammoutia, A. El Idrissi, Appl. Surf. Sci. 249 (2005) 176182.
3. A.Y. El-Etre, J. Colloid Interface Sci. 314 (2007) 578583.
4. A.Y. El-Etre, Mat. Chem. Phys. 108 (2008) 278282.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P51]
The surface photovoltaic properties of
, , , -tetrahydroxylphenylporphyrin (THPP)
and , , , -tetraphenylporphyrin (TPP) affected by nano-TiO2
R. Rahimi*1, M. Rabani
Department of Chemistry, University of Science and Technology, Tehran, Iran
E-mail: Rahmatollah.Rahimi@gmail.com
Nano-crystals photovoltaic cells using a dye photosensitizer in an n-type nano structured
TiO2 semiconductor have attracted great interest as a novel type of solar cell [1, 2]. Plenty of
works have been done on modifying the surface of nano- TiO2 to increase PET and improving its
absorption characteristics. Different bonding modalities affect surface photovoltaic properties [3].
The resultant sol of TiO2 was dried and divided into three shares. these three shares were heated
for 2 h at 400, 640 and 750 C, respectively, which were denoted as A, B and C. An amount of 0.2
ml THPP solution and 0.1 g A, B and C were sufficiently blended, respectively. And for TPP, 0.1
g A, B and C were also blended with 0.2 ml TPP solution, respectively. Thus six samples were
got. These samples were dried under vacuum for 2 h. The SPV of samples were measured on
surface photovoltage spectrometer. In the UVvis absorption spectrum, five absorption peaks
appear at 420 nm (Soret band), 519, 558, 596 and 653 nm (Q band). From the SPS of TPP/TiO2, a
new photovoltage peak is observed in 300380 nm compared with the absorption spectrum of
TPP, which is attributed to bandband transition of TiO2. Peaks of SPV have little change on
Soret band and Q band, which indicates that the interaction between TPP and nano-TiO2 is weak.
The degeneration of energy level of THPP and red shift of the photovoltage peaks of THPP are
observed as the size of nano-TiO2 decreasing using surface photovoltage (SPV) technique, while
that of TPP have little change [4]. The energy levels of THPP are degenerated by nano-TiO2 of
different sizes. The reason for that is the existence of hydroxyls of THPP, which interact with the
surface of nano-TiO2 through hydrogen bond. In addition, the hydroxyls of THPP increase the
density of electron atmosphere of inner ring of THPP. This causes that THPP bonding to d-orbital
of ionic titanium occurs easily.
REFERENCES
1- B. ORegan, M. Gratzel, Nature 335, 737, 1991.
2- M. Gratzel, Nature 414, 338, 2001.
3-Y.H. Lin, D.J. Wang, Q.D. Zhao, M. Yang, Q.L. Zhang, J. Phys. Chem. B 108, 3202, 2004.
4- Ziheng Li, Dejun Wang, Yingyan Shi, Ping Wang, Xingqiao Wang, Materials Chemistry and Physics, 90,
203206, 2005.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P52]
Modification of a carbon paste electrode for voltammetric determination of
phenylhydrazine
S. Shahrokhian, R. Bazl*
Department of Chemistry, Sharif University of Technology, Tehran, Iran
E-mail: shahrokhian@sharif.edu.ir
A carbon-paste electrode (CPE) chemically modified with the cobalt(II)-5-nitrosalophen
(CoNSaL) as a Schiff base complex was used as a highly sensitive and fairly selective
electrochemical sensor for the determination of minor amounts of phenylhydrazine (PHZ).
PHZ is a strong oxidant agent, which is extensively used in industry, laboratory and
therapeutic setting. A variety of toxic effects of PHZ have been reported, including hemolytic
anemia, hypoxia, inflammation, alteration in the liver, kidney, central nervous system,
autoimmune disturbance and cancer. The prepared modified electrode shows very efficient
electrocatalytic activity for anodic oxidation of PHZ via substantially decreasing of anodic
overpotential for PHZ. The mechanism of electrochemical oxidation of PHZ using CoNSalmodified electrode was thoroughly investigated by the cyclic (CV) and differential pulse
voltammetry (DPV). The results of the voltammetric studies using the modified electrode
show two irreversible anodic waves for the oxidation of PHZ in alkaline pH and only one
wave in neutral and acidic media. The obtained linear range for PHZ in DPV measurements
was in the range of 10-4 to 10-6M in buffered solution with pH 6.0. The modified electrode has
good reproducibility (RSD 2.5%), low detection limit (10-7 M) and high sensitivity for the
detection of PHZ with a very high stability in its voltammetric response. The DPV method
using the modified electrode exhibited a reasonable recovery for a relatively wide
concentration range of PHZ spiked to synthetic human serum sample.
REFERENCES
1.

S. Shahrokhian., Leila fotouhi, Sensors and Actuators B. 12B, 942,949 (2007)

2.

E.S. Jamasbi., A. Rouhollahi., S. Shahrokhian., S. Haghgoo., S. Aghajani, Electrochim. Talanta. 71, 1669,
1674 (2007).

3.

Jacqueline Arguello, Herica A. Magosso, Richard Landers, Yoshitaka Gushikem, Journal of


electroanalytical chemistry. (2008)

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P53]
Using mesoporous silica particles to control release, drug delivery and
biosensor systems
A. Fallah-Shojaiea, M. Giahib, F. Mirsafa-Moqadam*a
a
b

Department of Chemistry, Faculty of Science, University of Guilan, Rasht, Iran,

Department of Chemistry, Faculty of Science, Lahidjan Branch, Islamic Azad University,


Lahidjan, Iran
E-mail: a-fallah@guilan.ac.ir
In this study, at first we want to describe the ability of mesoporous material for

adsorption of drug molecules with spectroscopic methods and then with conductometric
method, our main porous is to validation a new electrochemically method for adsorption
studies with use of different zeolites. With respect to these points that the most of drug
compounds have an ionic structure and our specific mesoporous material, MCM-41, have a
good ability to adsorb positive ions or natural molecules, with justifying the pore size of
mesopore with ion size or molecule diameter the adsorption process will be complete. In our
spectroscopical study the measurement bases is up to the change in drug molecule
concentration and therefore decrease in the peak height in the other hand we know that the
drug molecule has an ionic structure, so increasing the amount of ion adsorption will cause a
decrease in total solution conductivity. We suspect to find a good relationship between these
tow methods of measurement.
REFERENCES
1. Brian G. Trewyn, Supratim Giri, Igor I. Slowing and Victor S.-Y. Lin, Chem. Commun., 1039 (2007) 3236
3245.
2. Narasimhan Gokulakrishnan, Arumugam Pandurangan, Pradeep Kumar Sinha J Chem Technol Biotechnol
82(2007) 2532.
3. Y. MARCUS and S. GLIKBERG, Y. MARCUS, Pure & Appl. Chem 57(1985). 855- 864.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P54]
Application of quartz crystal nanobalance for determination of
vanillylmandelic acid
A. Mirmohsenia, M. Shojaeib & M. Farbodi*a
a

Faculty of Chemistry, University of Tabriz, Tabriz, Iran, bFaculty of Animal Sciences,


University of Tabriz, Tabriz, Iran
E-mail: farbodi@tabrizu.ac.ir
In the course of this work, with respect to the importance of determination of

vanillylmandelic acid (VMA) in body fluids of peisients with neuroblastoma, a simple, rapid
and sensitive nano-biosensor based on EQCN was developed for determination of VMA in
solution. An electrochemical deposition method was used for modification of quartz crystal
with a thin layer of polypyrrole (PPy). Determination was based on frequency shifts of
PMMA modified quartz crystal electrode due to the adsorption of VMA at the surface of
modified electrode. Measurements were carried out by exposure of PPy modified electrode
directly to the VMA solutions. The frequency shifts were found to be linear against the
concentration of VMA in the range between 50 and 250 ppm with correlation coefficient of
above 0.993. The sensitivity factor of 0.293 Hz ppm1 was found.
We are most grateful the continuing financial support of this research project by the
University of Tabriz.
REFERENCES
1. J.L. Young, L.G. Ries, E. Silverber, J.W. Horm, R.W. Miller, Cancer, 58 (1986) 598.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P55]
The study of aspirin via electronic structure method
V.S. Farzadfar*, H.S. Farzadfar
Applied Science and Technology Educating Center of Kashan, Worker House, Kashan, Iran
E-mail: hamidehfar2006@yahoo.com
Aspirin known as 'acetylsalicylic acid has a chemical formula of C9H8O4. Aspirin is
analgesic, anti-inflammatory, antipyretic and is an inhibitor of platelet aggregation. It inhibits
fatty acid cyclo-oxygenase by acetylation of the active site of enzyme and the
pharmacological effects of aspirin are due to the inhibition of the formation of cyclooxygenase products including prostglandins, thromboxanes and prostacyclin. Aspirin is
prepared by chemical synthesis from salicylic acid, by acetylation with acetic anhydride. We
can calculate electronic energies and atom bonds in aspirin with Gaussian software and
investigate spatial models for interaction with cells, substrate and other drugs. The adsorption
depends on certain properties of the aspirin molecule such as functional groups, electron
density at donating atoms, aromaticity, and electronic structure of the molecule. Theoretical
studies can predict molecular parameters related to the best interaction and adsorption.

REFERENCES
1. S. Bilgic, N. Caliskan, Applied surface science. 152 (1999) 107-114
2. E. Stupnisek-Lisac, S. Podbrscek, j. Appl. Electrochem. 24 (1994) 779

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P56]
Amperometric detection of glucose at renewable sol-gel derived carbon
ceramic electrode modified with nickel complex
M. Roushani*a, M. Shamsipura, H. Sharghib
a

Department of Chemistry, Razi University, Kermansh, Iran, bDepartment of Chemistry, Shiraz


University, Shiraz, Iran
E-mail: mahmoudroushani@yahoo.com
A new enzymeless glucose sensor has been fabricated by nickel complex dispersed sol-

gel derived ceramic graphite composite. The electrochemical properties and stability of
modified electrode was evaluated by cyclic voltammetry in pH range 7-13. The redox couple
of Ni2+, Ni3+- was shown both as a solute in electrolyte solution and as a component of a
carbon based conducting composite electrode. The catalytic activity of the modified CCE
toward glucose oxidation was investigated at pH rang of 13-7 by cyclic votammetry. The
modified electrode showed excellent electrocatalytic activity toward glucose electroxidation
at

pH=13

value[1].

The

modified

electrode

was

used

for

insulin

detection

chronoamperometrically at pH 13. Under optimized condition in amperomtry method, the


concentration calibration range, detection limit and sensitivity were 50 nM -3000 M, 50 nM
and 3.9nA/M, respectively. The inherent stability at wide pH range, high sensitivity, low
detection limit, low cost and ease of preparation are of advantageous of this glucose sensor. in
addition ,the fabrication of CCE with nafion and nickel complex was employed to eliminate
the interference of ascorbic acid during the catalytic oxidation of glucose. The capability of
the modified electrode for direct glucose quantification in human blood serum matrix is also
discussed.
Keywords: glucose, Carbon ceramic electrode, Sol-gel, Nickel Complex, Amperometric
detector, ascorbic acid.
REFERENCES
[1] A. Salami, M. Rousahni, Electrochemistry Communication 7 (2005) 879-887.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P57]
Investigation of the electrochemical behavior of catechol and 4-methyl
catechol in the presence of methyl mercapto thiadiazole as a nucleophile:
application to electrochemical synthesis
S. Shahrokhian, S. Rastgarkafshgarkolaie*
Department of Chemistry, Sharif University of Technology, Tehran, Iran
E-mail: shahrokhian@sharif.edu.ir
One of the prime principles of green chemistry is to develop an alternative reaction medium,
which is the basis for the development of many cleaner chemical technologies and electrochemical
synthesis in water. 1,3,4-thiadiazoles are a class of heterocycles which have attracted significant
interest in medicinal chemistry and they have long been the subject of pharmaceutical interest as a
result of their potent biological activities by virtue of N=C-S toxophoric moiety. the 1,3,4-thiadiazole
derivatives have been reported to possess a wide range of pharmaceutical and biological activities
including antimicrobial, antibacterial, antiparasitic, anti-fungal, anti-inflammatory, antituberculosis,
leishmanicidal and antihypertensive. They are also useful as HIV integrase inhibitors and the
angiogenesis inhibitors.On the other hand; Catechols are important species in chemistry and biology,
because of their facility to undergo electron transfer. For instance, they are involved in the primary
photoelectron doner-acceptor center in bacterial photosynthesis.catechols and their quinone derivatives
are abundant in nature and play important roles in many biological systems. Several drugs such as
doxorubicin, daunorubicin and mitomycin C, used in cancer chemotherapy, contain quinones, and
other quinones exhibit antitumour and antimalarial activities. So, potential biological activities of
catechols and 1,3,4-thiadiazoles derivatives made them good leads for the synthesis of new
compounds. In our work, Electrooxidation of catechol and 4-methyl catechol in the presence of 2mercapto-5-methyl-1,3,4-thiadiazole as a nucleophile in aqueous buffered solutions was studied by
cyclic voltammetry and controlled-potential coulometry. The electrochemical synthesis of Michael
addition product has been successfully accomplished by controlled-potential coulometry in a divided
H-type cell and the reaction product was characterized by spectrophotometric, 1H and

13

C NMR,

elemental analysis and mass spectrometric methods.


REFERENCES
1. J. Matysiak, A. Opolski, Bioorg. Med. Chem. 14 (13) (2006) 4483-4489.
2. M. Behrouzi-Fardmoghadam, F. Poorrajab, S.K. Ardestani, S. Emami, A. Shafiee, A. Foroumadi, Bioorg.
Med. Chem. 16 (2008) 4509-4515.
3. O. Nekrassova, N.S. Lawrence, R.G. Compton, Electroanalysis, 16 (2004) 1285-1291.
4. S.Shahrokhian, M.Amiri, Electrochem. Commun, 7 (2005) 68-73.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P58]
Studies of stability and reactivity of radical anion and comportement
electrochemistry of 1-carboethoxy-1-nitro spiro (2,5) octane
in medium aprotic
A.R. Sardashti*a, J. Lessard b
a

Department of Chemistry, Faculty of Science, Sistan and Baluchistan University, Zahedan,

Iran, bLaboratory of Organic Electrochemistry, University of Sherbrooke, Qubec, Canada


E-mail: asardashti65@gmail.com
We have undertaken a study of the electrochemical

behavior of the substituted

nitrocylopropanes radical anion generated by electroreduction of at glassy carbon in an


aprotic medium [1] can undergo,an hemolytic C-N bond cleavage leading to the formation of
the cyclopropyl radical and nitrite ion or an hemolytic C-C bond cleavage leading to the
distonic radical anion or an heterolytic C-C bond cleavage leading to the distonic in the
present study x=COOMe),1-nitro-spiro[2,5]-Octane-1-carboxylic acid methyl ester have been
prepared accordingly to a method previously reported[2].
A typical cyclic voltammogram at glassy Carbon in dry acetonitrile is presented in
Figure 1 in the particular case of (X=NO2).The reduction to the corresponding radical anion
occurs at -2.144 V/Ag, AgCl.
The presence of this peak constituents a strong evidence that nitrite is being produced
during the reduction process and that the radical anion undergoes a hemolytic C-N bond
cleavage. The microcoloumetry results showed that one electron transfer reactions occurs
between Nitro functional of sample and radical anion formation.
Keywords: NitroCyclopropane, Stability and reactivity of radical anion, comportment
electrochemistry, Cyclo voltammetry, microcoloumetry
REFERENCE:
1. Z.R. Zheng, D.H. Eans, E. Soazara chan-shing, J. Lessard, J. Am. Chem. Soc., 121, 9429 (1999).
2. A.B. Charrette, R.P. Wurtz, T. Oi, J. Org. Chem., 65, 9252-9254 (2000)

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P59]
Simultaneously determination of epinephrine and uric acid with a modified
carbon paste electrode and investigation of electrochemical behavior
M. Mazloum Ardakania, Z. Taleata, H. Beitollahia, H. R. Zarea and H. Naeimib
a

Department of Chemistry, Faculty of Science, Yazd University, Yazd, b Department of


Chemistry, Faculty of Science, Kashan University, Kashan
E-mail: mazloum@yazduni.ac.ir
Epinephrine (EP) is a very important catecholamine neurotransmitter in the mammalian

central nervous system. The oxidation of this compound is interesting, and this process occurs
in the human body. Catecholamine drugs are also used to treat hypertension, bronchial
asthma, organic heart disease, and are used in cardiac surgery and myocardial infarction [1].
Similarly, Uric acid (UA) is the primary product of purine metabolism [2]. Continuous
monitoring of UA in the body fluid is essential since its abnormal concentration levels lead to
several diseases, such as hyperuricaemia and gout [3].Various chemically modified electrodes
have been suggested for promoting the oxidation and detection of EP [4]. We have employed
a carbon paste electrode (CPE) chemically modified with 2, 2'-[3, 6-dioxa-1, 8-octanediylbis
(nitriloethylidyne)]-bis-hydroquinon (DOH) to study of electrocatalytic oxidation of EP in
presence

of

UA

using

cyclic

voltammetry,

differential

pulse

voltammetry,

chronoamperometry and chronocoulometry as diagnostic techniques. The electron transfer


coefficient, , for EP at the surface of modified CPE was determined using CV technique. The
diffusion coefficient, D= 4.210-5 cm2s-1of EP was also estimated using chronoamperometry
and choulometry. The heterogeneous charge transfer rate constant, ks, and the charge transfer
coefficient, , between DOH and CPE were calculated as 3.71 s-1 and 0.66 respectively. The
differential pulse voltammetry response of the modified electrode was linear against the
concentration of EP in the range 10.01000.0 M. The limit of detection was found 0.8 M
(k=3). The proposed procedure was also successfully applied to determination of EP in
pharmaceutical sample.
REFERENCES
[1] M.E. El-Kommos, F.A. Mohamed, A.S.K. Khedr, J. Assoc. Anal. Chem. 73 (1990) 516.
[2] H .Kaur, B. Halliwell, Chem. Biol. Interact. 73 (1990), 235247.
[3] E. Miland, A.J.M. Ordieres, P.T. Blanco, M.R. Smyth, C.O. Fagain, Talanta 43 (1996) 785796.
[4] S.-M. Chen, K.-C. Lin, J. Electroanal. Chem. 523 (2002) 93.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P60]
Thermodynamic investigation of DNA-dendronized polymer nanocluster
with modification of charge distributions
S. yazdinezhad* , A. Nikakhtar
Department of Chemistry, University of Birjand, Birjand, Iran
Email: simin_yazdinezhad@yahoo.de
The concept of gene therapy is simple-deliver exogenous, therapeutic genes to the body to
treat genetic-based diseases. Many of the cationic polyelectrolyte vectors such as dendrimers
[1,2] developed to date have formed nanoclusteres with DNA via electrostatic interaction. All
of these polymers possess amino groups, at least a portion of which are protonated at neutral
pH, to enable electrostatically driven self-assembly with DNA. The polymer can condense
DNA to sizes compatible with cellular uptake while providing steric protection from nuclease
degradation [3].The dendronized polymers are new class of dendimers which In the solution
DNA could be wrapping around the dendronized polymer.
In the previous [4,5] work we considered the homogenous charge distribution on DNA and
dendrinized polymer. In order to modify model we calculated the locations of negative
charges on DNA as a supercoil. The locations of positive charges were determined by
minimization of the repulsion force in dendronized polymer.

Here we illustrate the

electrostatic free energy of nanocluster systems are dependent on temperature. Therefore the
enthalpies and entropies of systems are calculated by using Gibbs-Helmholtz equation.
Comparison between the results of this work and the previous ones indicate that the
distribution of charges in nanocluster is very important factor on thermodynamic properties of
nanocluster and also on prediction of transfiction properties in gene therapy.

References

[1]. Luo, D., and Saltzman, W. M. Synthetic DNA delivery systems, Nat. Biotechnol.
18(2000) 33-37.
[2]. A. Nikakhtar, A. Nasehzadeh and G.A. Mansoori, J.Iran. Chem.Soc., 3(2006) 185190.
[3]. Sharon Y. Wong, Jeisa M. Pelet, David Putnam, Prog. Poly. Sci., 32(2007) 799-837.
[4]. A. Nikakhtar, A. Nasehzadeh, J.Iran. Chem.Soc., 4(2007) 310-317.
[5]. A. Nikakhtar, A. Nasehzadeh, and G. A. mansoori, J. Iran. Chem. Soc., 4(2006) 151167.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P61]
A sensitive simultaneous determination of paracetamol and mefenamic acid
using copper (II) doped zeolite modified carbon paste electrode
A. Babaei*, B. Khalilzadeh
Department of Chemistry, Faculty of Sciences, Arak University, Arak, Iran
E-mail: a-babaei@araku.ac.ir
The measurements were carried out by application of the differential pulse voltammetry
(DPV) method. Paracetamol (PCT), is important and extensively used in pure form and
pharmaceutical preparations [1]. Mefenamic acid (MFA) is a nonsteroidal anti-inflammatory
drug with analgesic and antipyretic properties. It is used to relieve the symptoms of many
diseases such as rheumatoid arthritis, osteoarthritis, nonarticular rheumatism, and sport
injuries [2].
In this work a chemically modified carbon paste electrode based on Cu(II) doped
zeolite-containing graphite paste was constructed. The linear relationship between oxidation
peak current and concentration of PCT in the presence of 15 M MFA in Briton Robinson
buffer (pH = 11) was 0.25 M to 900 M, with a correlation coefficient of 0.9987, and a
detection limit of 0.1 M (S/N = 3). The linear correlation between oxidation peak current and
concentration of MFA in the range of 0.3 M to 100 M containing 50 M PCT with a
correlation coefficient of 0.9991 and a detection limit of 0.04 M was obtained. The
analytical performance of this sensor has been evaluated for detection of PCT and MFA in
human serum, human urine and medicine.
Acknowlegement, the authors gratefully acknowledge the research grant provided by reseach
council of Arak University.

REFERENCES
1. A.C. Moffat (Ed.), Clarkes Isolation and Identification of Drugs, 2nd ed., The Pharmaceuticals Press, London,
1986.
2. J.R. Vane, Nat. New Biol. 23 (1971) 232235.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P62]
Carbon molecular wire electrode for determination of NADH
A. Safavi, N. Maleki, F. Honarasa*, F. Tajabadi
Faculty of Science, University of Shiraz, Shiraz, Iran
E-mail: fhonarasa@gmail.com
Direct oxidation of nicotinamide adenine dinucleotide (NADH) at bare electrode
surfaces takes place with high overpotentials [1]. The most serious problem with previously
used electrodes is deactivation as a result of the irreversible adsorption of oxidation products
on the surface [2]. Herein a new carbon composite electrode using molecular wire is going to
be employed for studying the electrochemical behavior and determination of NADH. The
electrochemical oxidation of NADH is of great interest because it is required as a cofactor in a
large number of dehydrogenese-based biosensors [3, 4].
Carbon molecular wire electrode (CMWE) shows a well defined oxidation peak for
NADH at ~460mV which is lower than the corresponding response of CPE and GCE.
Moreover, the electrode is not fouled upon repitative analysis of NADH. A detection limit of
1M NADH was obtained experimentally and the linear range was 5M to 10M of NADH.
The electrochemical oxidation response was reproducible and the electrode response was
stable over a long period of time. The relative standard deviations for peak potentials and
current for 12 scans on a single electrode were 1.2% and 3.8%, respectively.
Acknowledgement, the authors wish to acknowledge the support of this work by the Office of
the Governor of Fars Province, Iran and Shiraz University Research Council.

REFERENCES
1. P.J. Elving, C.O. Schmakel, K.S.V. Santhanam, Crit. Rev. Anal. Chem., 6 (1976) 1-67.
2. H. Jaegfeldt, J. Eelectroanal. Chem., 110 (1980) 295-302.
3. F. Pariente, E. Lorenzo, F. Tobalina, H.D. Abruna, Anal. Chem., 67 (1995) 3936-3944.
4. T. Huang, A. Warsinke, T. Kuwana, F.W. Scheller, Anal. Chem., 70 (1998) 991-997.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P63]
Novel nanocomposite electrode as a glucose biosensor
A. Safavi a, b, N. Maleki a, b, E. Farjami*a, b
a

Department of Chemistry, College of Sciences, Shiraz University, Shiraz, Iran,


b

Nanotechnology Research Institute, Shiraz University, Shiraz, Iran


E-mail: elahe_farjami@yahoo.com

Glucose sensing is greatly important in biotechnology, clinical diagnostics and food


industry. The greatest problem with enzymatic glucose sensors is naturally insufficient
stability and loss of enzyme activity during immobilization process [1] which affect
sensitivity and reproducibility of glucose sensors.
Direct electro-oxidation of glucose on conventional carbon and noble metal electrodes
[2] was limited by the slow kinetics and surface fouling due to the adsorption of reaction
intermediates in which repetitive pulsed potentials are required to remove adsorbed products.
Enzymatic free electro-oxidation of glucose is greatly enhanced at Ni and Cu compared to the
other electrodes as a result of their electrocatalytic effect mediated by Ni+2/Ni+3 or Cu+2/Cu+3
redox couples [3].
In this work we report the fabrication of a novel non-enzymatic composite electrode
based the use of a nanocomposite electrode made of nano-scale nickel hydroxide, graphite
powder and an ionic liquid. In this way, an extraordinary stable nanosensor could be
fabricated as glucose biosensor. Long term stability, high sensitivity and selectivity as well as
good reproducibility and high resistivity towards electrode fouling resulted in an ideal
inexpensive amperometric glucose biosensor applicable for complex matrices.
Acknowledgement, the authors wish to acknowledge the support of this work by the Office of
the Governor of Fars Province, Iran and Shiraz University Research Council.
REFERENCES
1. Wilson, R.; Turner, A.P.F. Biosens. Bioelectron 7 (1992) 165-185.
2. Li, Y.; Song, Y.Y.; Yang C.; Xia, X.H. Electrochem. Commun. 9 (2007) 981-988.
3. Luo, P.F.F.; Kuwana, T. Anal. Chem. 66 (1994) 2775

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P64]
A graphite composite electrode based on SE-30 as a binder and its
application to biosensing
A. Safavi, N. Maleki, F. Tajabadi*
Department of Chemistry, University of Shiraz, Shiraz, Iran
Email: safavi@chem.susc.ac.ir
A new graphite composite electrode was constructed by mixing graphite powder with
chromatography stationary phase, SE-30, as the binder. The electrochemical behavior of the
resulting electrode prepared with different percentages of SE-30 has been evaluated with
respect to the electrochemistry of ferricyanide and were compared with that of traditional
carbon paste electrode (CPE). The new electrode has a lower resistance and higher electron
transfer kinetics compared to the carbon paste electrode. An approximately ten fold increase
in the rate constant found for the composite suggests a more pristine surface which supports
reversible electron transfer under typical electroanalytical conditions. The proposed electrode
provides a remarkable increase in the rate of electron transfer of biomolecules such as
nicotinamide adenine dinucleotide (NADH) and cysteine and shows a low surface fouling
effects. The electrode shows highly promising results when used as an amperometic sensor
for biocompounds such as NADH. A detection limit of 0.110-6 M can be estimated on the
basis of the signal-to-noise of 3 for NADH.
Acknowledgement. The authors wish to acknowledge the support of this work by the Third
World Academy of Sciences, Iran Chapter (TWASIC) and Shiraz University Research
Council.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P65]
Electrochemical oxidation of D-penicillamine with catechol as a
homogeneous indicator at carbon paste electrode: application to
voltammetric detection of D-penicillamine
J. Raoof, R. Ojani, M. Amiri-Aref*, F. Chekin
Electroanalytical Chemistry Research Laboratory, Faculty of Chemistry, Mazandaran
University, Babolsar, Iran
E-mail: j.raoof@umz.ac.ir
D-Penicillamine (3-mercaptovaline, D-PA) is an unphysiological sulfur-containing
amino acid that belongs to the aminothiol family with hydrogen atom in the beta-carbon of
cysteine replaced by the methyl group. This compound is derived from hydrolytic
degradation of penicillin but it does not have antibiotic activity [1]. D-PA is a thiol drug
used in the treatment of Wilsons disease [2], as antifibrotic agent to treat scleroderma [3]
and as antirheumatic drug to treat patients with active rheumatoid arthritis [4].
In this study, the utilization of catechol as homogeneous electrochemical indicator in
the presence of D-PA at carbon paste electrode (CPE) has been investigated in aqueous
media using cyclic voltammetry (CV), differential pulse voltammetry (DPV) and double
step potential chronoamperometry methods. The results show that D-PA participates in
Michael type addition reactions with catechol to form the corresponding thioquinone
derivatives. The reoxidation of the adduct leads to an increase in the oxidative current which
is proportional to the concentration of D-PA. Therefore, in the optimum condition (pH =
7.00) in CV, the oxidation of D-PA occurs at a potential about 343 mV less positive than
that in the absence of catechol at the surface of CPE. The anodic peak current of the carbon
paste electrode in the presence of catechol was linear with D-PA concentration from 104 M
to 103 M with a detection limit (3) of 5.8 10-5 M in CV. The proposed electrode is
useful for the quality control and routine analysis of D-PA in pharmaceutical formulations.
REFERENCES
1. J.M. Walshe, Mov. Disord. 18 (2003) 853-859.
2. A. Czonkowska, J. Gajda, M. Rodo, J. Neurol. 243 (1996) 269-273.
3. E.C. LeRoy, M. Trojanowska, E.A. Smith, Clin. Exp. Rheumatol. 9 (1991) 173-177.
4. N. Wangfuengkanagul, O. Chailapakul, Talanta, 58 (2002) 1213-1219.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P66]
Alcohol biosensor based on self-assembled monolayer of nanostructural
cysteine induced amplification of electrocatalytic NADH oxidation
A. Barzegar*a,b and A.A. Moosavi-Movahedib
a

Research Institute of Fundamental Sciences, University of Tabriz, Tabriz, Iran


b

Institute of Biochemistry and Biophysics, University of Tehran, Tehran, Iran

The electrochemical NADH detection is of great interest, because the NAD pyridine
nucleotides are ubiquitous in all living systems and are required for the reactions of more
than 450 oxidoreductase enzymes. The direct electrochemical conversion of both
nicotinamide adenine dinucleotides (NAD+ and NADH) is severely afflicted with the high
overvoltage and the abortive side reactions. Most of the problems in such systems, however,
can be overcomed by the ultra-microelectrodes (UMEs) employment. In this research, it
was illustrated that the bare Au UME was unable to oxidize NADH in subsequent sweeps
(ill-defined oxidation peak at around 0.9 V), as the ordinary Au electrodes. Nonetheless, the
successive potential cycles at Au Cys-UME, unlike the bare one that required a large
overpotential, not being fouled by the oxidation product or the intermediate complexes
during the NADH oxidation process. This Cys-UME could prevent fouling and was found
to be stable and ill-defined under subsequent potential sweeps and different NADH
concentrations. The NADH oxidation presented a linear correlation between the peak
current and the NADH concentrations (1 mM - 5 mM). Also, an excellent electro-catalytic
activity was observed towards the NADH oxidation with activation over potential about 250
mV lower than that of the bare electrode. The facilitated electro-catalytic activity for the
NADH oxidation and reproduction of the enzymatically active NAD+, obtained at the
modified Cys-Au UME, improved the development of the enzymatic ethanol biosensors.
Keywords: Biosensors, Self-assembled monolayers, NADH, Cysteine

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P67]
Voltammetric determination of cycteine at a carbon paste electrode
modified with Cu(II)-salen complex
S. Kakhki* & E. Shams Soolari
Department of Chemistry, University of Isfahan, Isfahan, Iran
The electrochemical behavior of a carbon paste electrode modified (CPEM) with N,N
ethylenbis(salicylideneiminato)copper(II) complex ([Cu(II)-Salen]) was investigated as a
new sensor for cystein. The Britton-Rabinson buffer with pH 5, 10% modifier in electrode,
potential scanning rate of 20 mVs-1 and puls height of 50 mV were used as the optimum
condition for the determination of cysteine using carbon paste electrode modified with
Cu(II)-Salen complex. Under these optimum conditions, the resulting electrode
demonstrated linear response with cysteine concentration in the ranges of 1-10 and 10-80
M. The effects of potential interfering species were studied, and it was found that only
thiocyanate ion interfered in cysteine determination and the proposed procedure was free
from most other interferences.

The authors gratefully acknowledge the University of Isfahan providing facilities for this
work.

REFERENCES
1. S.A. Wring, J.P. Hart, B.J. Birch, , Analyst 117 (1989) 15631570.
2. J. Kulys, A. Drungiliene, Chemically, Anal. Chim. Acta 243 (1991) 287292.
3. L.A. Allison, R.E. Shoup, Anal. Chem. 55 (1983) 812.
4. G. Zhiqiang, S.S. Kok, A. Ng, Z. Yimin, Anal. Chim. Acta 343 (1997) 4957.
5. J.L. Anderson, E.F. Bowden, P.G. Pickup, Anal. Chem. 68 (1996) 379R444R.

The First Regional Symposium on Bioelectrochemistry


Oct. 13-15, 2008

University of Tehran
Institute of Biochemistry & Biophysics

[P68]
Determination of phosphate in blood serum by using EIS

R. Karimi Shervedani* & S. Pourbeyram


Department of Chemistry, University of Isfahan, Isfahan, Iran
Preparation and application of a new sensor for determination of phosphate in blood
serum is described by electrochemical impedance spectroscopy (EIS) in the presence of
appropriate redox reaction probe. The sensor was based on gold-mercaptopropionic acid
self-assembled monolayer (Au-MPA- SAM) modified electrode. Parameters influencing the
method were optimized. Possible interferences from the coexisting ions were also
investigated. The results demonstrated that sensor could be used for determination of
phosphate in the presence of various ions. The validity of the method and applicability of
the sensor were successfully tested by determining of phosphate in blood serum. The long
term storage and stability of the electrode was studied.

The authors gratefully acknowledge the University of Isfahan providing facilities for this
work.

REFERENCES
1. S.O ,Engblom, Biosens. Bioelectron. 13(1998) 981994.
2. O. Reynes, C. Bucher, J. C. Moutet, G. Royal,E.S. Aman, Inorg. Chim Acta, 361(2008)17841788.
3. H. Aoki, K. Hasegawa, K. Tohda, Y. Umezawa, Biosens. Bioelectron. 18(2003)261-267.
4. M. A. Rahman, D. S. Park, S. C. Chang, C. J. McNeil, Y. B. Shim, Biosens. Bioelectron. 21(2006)11161124.
5. R. K. Shervedani, S.A. Mozaffari, Anal. Chem. 78(2006) 4957-4963.

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