Electrochimica Acta 50 (2004) 77–84

Voltammetric studies of a cobalt(II)-4-methylsalophen modified

carbon-paste electrode and its application for the simultaneous
determination of cysteine and ascorbic acid
Saeed Shahrokhian∗,1 , Mohammad Karimi
Department of Chemistry, Sharif University of Technology, Tehran 11365-9516, Iran

Received 29 March 2004; received in revised form 23 June 2004; accepted 17 July 2004
Available online 20 August 2004

Abstract

A carbon-paste electrode (CPE) chemically modified with the cobalt(II)-4-methylsalophen (CoMSal) as a Schiff base complex was used as a
highly sensitive and fairly selective electrochemical sensor for simultaneous determination of minor mounts of ascorbic acid (AA) and cysteine.
This modified electrode shows very efficient electrocatalytic activity for anodic oxidation of both AA and cysteine via substantially decreasing
of anodic overpotentials for both compounds. The mechanism of electrochemical oxidation of both AA and cysteine using CoMSal-modified
electrode was thoroughly investigated by cyclic voltammetry and polarization studies. Results of cyclic voltammetry (CV) and differential
pulse voltammetry (DPV) using this modified electrode show two well-resolved anodic waves for the oxidation of AA and cysteine, which
makes it possible for simultaneous determination of both compounds. A linear range of 1 × 10−4 to 5 × 10−7 M for cysteine in a constant
concentration of 1 × 10−4 M AA in buffered solution (as a background electrolyte) was obtained from DPV measurements using this electrode.
The linear range, which is obtained for AA in the presence of 1 × 10−4 M cysteine, was in the range of 1 × 10−4 to 1 × 10−6 M. The modified
electrode has good reproducibility (RSD ≤ 2.5%), low detection limit (sub-micromolar) and high sensitivity for the detection of both AA
and cysteine with a very high stability in its voltammetric response. Differential pulse voltammetry using the modified electrode exhibited a
reasonable recovery for a relatively wide concentration range of cysteine spiked to a synthetic human serum sample.
© 2004 Elsevier Ltd. All rights reserved

Keywords: Ascorbic acid; Cysteine; Cobalt(II)-4-methylsalophen; Carbon-paste electrode; Modified electrode; Electrocatalysis; Cyclic voltammetry; Differ-
ential pulse voltammetry

1. Introduction the target analyte in a coordination fashion, these electrodes

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 biologically important compounds [1–3]. 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 electrode. With respect to
relatively selective interaction of the electron mediator with
∗ Corresponding author. Tel.: +98 21 6005718; fax: +98 21 6012983.
E-mail address: shahrokhian@sharif.edu (S. Shahrokhian).
1 ISE member.
are capable to considerably enhance the selectivity in the
electroanalytical methods.
Transition metal complexes such as phthalocyanines
[4–11], porphyrins [12–14], Schiff bases [15,16], hexa-
cyanometallates [17] and aquacobalamin [18] are well known
as electron mediators in the electrocatalytic oxidation of
some biologically important compounds. Among these com-
pounds, electrocatalytic oxidation of biological thiols (e.g.
cysteine, glutathione, penicillamine) and vitamins such as
l-ascorbic acid (vitamin C, AA) has been more interested in
medicine, veterinary science, toxicology, diagnosis of certain
metabolic disorders and in the determination of nutritional
value of foods [19–22]. Cysteine is known as an active site in

0013-4686/$ – see front matter © 2004 Elsevier Ltd. All rights reserved
doi:10.1016/j.electacta.2004.07.015
78 S. Shahrokhian, M. Karimi / Electrochimica Acta 50 (2004) 77–84
the catalytic activity of enzymes known as cysteine protease.
It is also found in the structure of vasopressin, an anti-diuretic
hormone [23]. Cystinuria is a hereditary malfunction in which
the transmitter of the brain for cysteine and some other basic
amino acids in epithelial cells are damaged and large amounts
of these amino acids are excreted in urine [24,25]. Cysteine
also has several pharmaceutical applications; namely, it is
used in some antibiotics and for the treatment of skin dam-
ages [26,27] and as a radio-protective agent [28]. Therefore,
measurement of cysteine in body fluids is very important from
the biological and pharmacological stand points. l-Ascorbic
acid (vitamin C) is an essential nutritional factor with many
important biochemical functions [29]. This compound has
been the subject of many electrochemical investigations, and
on the basis of such studies, several methods have been devel-
oped for its determination in various samples [5,14,30–34].
Both these two compounds show high activity for electrocat-
alytic oxidation at the surface of the most reported modified
electrodes. Therefore, to design a selective method for simul-
taneous determination of both compounds is very interesting
in the development of electroanalytical methods based on
chemically modified electrodes.
The present studies related to the electrochemical oxi-
dation of AA and cysteine at the surface of carbon-paste
electrode (CPE) modified with a newly synthesized Schiff
base complex of cobalt (cobalt(II)-4-methyl salophen, (CoM-
Sal)). Due to very good resolution of the voltammetric waves
of these two compounds, a differential pulse voltammetric
(DPV) method has been developed for the detection of trace
amounts of AA and cysteine in the mixture solutions with
acceptable accuracy and sub-micromolar detection limit.
2. Experimental
2.1. Materials
The complex N,N -bis (salicylidene)-4-methyl-1,2-
phenylenediamino-cobalt(II) chloride (cobalt(II)-4-me-
thylsalophen), was synthesized and purified as reported pre-
viously [35–37]. Identification of the structure of synthesized
complex was performed by IR, 1 H and 13 C-NMR, UV–Vis
and elemental analysis. Graphite powder, spectroscopic
mineral oil (Nujol), AA and cysteine were purchased from
Merck. All other chemicals were of analytical reagent grade
from Merck. Tablets of AA as pharmaceutical samples
were prepared from Daro Pakhsh Company. All aqueous
solutions were prepared with doubly distilled deionized
water.
Stock solutions of ascorbic acid (AA) and cysteine were
freshly prepared as required in 0.10 M phosphate and acetate
buffer at the desired pH (2.5–7.0), purged with pure nitro-
gen gas (99.999%) for 5 min and protected from light dur-
ing investigation. d,l-Alanine, l-arginine, l-aspartic acid,
glycine, l-histidine, l-lysine, d,l-methionine, glutathione,
l-phenylalanine, l-serine, d,l-tryptophan, d,l-penicillamine
and citric acid for preparation of synthetic human serum were
purchased from Merck and from the analytical-reagent grade.
Voltammetric experiments were carried out in the buffered so-
lutions of cysteine and ascorbic acid, deoxygenated by purg-
ing the pure nitrogen (99.999% from Roham Gas Company).
During the experiments, nitrogen gas was passed over the
surface of test solutions in order to avoid entrance of oxygen
into the solution.
2.2. Apparatus
Voltammetric experiments were performed with a
Metrohm Computrace Voltammetric Analyser model 757
VA. A conventional three-electrode system was used with
a carbon-paste working electrode (unmodified or modified),
a saturated Ag/AgCl reference electrode and a Pt wire as
the counter electrode. A digital pH/mV/Ion meter (Cyber-
Scan model 2500) was applied for the preparing of the buffer
solutions, which were used as the supporting electrolyte in
voltammetric experiments.
2.3. Preparation of modified electrode
The unmodified carbon-paste electrode was prepared by
mixing graphite powder with appropriate amount of mineral
oil (Nujol) and thorough hand mixing in a mortar and pes-
tle (∼75:25 (w/w)), and a portion of the composite mixture
was packed into the end of a Teflon tube (ca. 2.5 mm i.d.).
Electrical contact was made by forcing a copper pin down
into the Teflon and into the back of the composite. The modi-
fied electrode was prepared by mixing unmodified composite
with CoMSal (2% w/w) and then homogenized by dissolving
it in dichloromethane. The mixture was stirred in a magnetic
stirrer till the solvent evaporated, completely. The modified
composite was then air dried for 24 h and used in the same
way as unmodified electrode.
3. Results and discussions
3.1. Cyclic voltammetric response studies
Results of our previous works were showed that CoS-
alophen (as a Schiff base complex) in comparison to
phthalocyanine complexes of cobalt, which is widely
used in the detection of biological thiols and AA, has a
considerably more catalytic effect in lowering of anodic
overpotentials of the analyte process and enhancement
of anodic peak current. In this work, we applied a Schiff
base complex of cobalt with more lipophilic properties
in order to make more stability in the matrix of modified
CPE for the simultaneous determination of cysteine and
AA. Fig. 1 shows the cyclic voltammograms of AA and
cysteine at the surface of unmodified (dashed lines) and
CoMSal-modified carbon-paste electrode in the acetate
buffer solution with pH 5.0. As can be seen in Fig. 1(A),
 S. Shahrokhian, M. Karimi / Electrochimica Acta 50 (2004) 77–84
Fig. 1. Cyclic voltammograms of 1 mM (A) ascorbic acid, and (B) cysteine at the surface of unmodified CPE (dashed lines) and CoMSal-modified CPE (solid
line), in 0.1 M acetate buffer solution with pH 5.0. Sweep rate was 100 mV s−1 .
the direct oxidation of AA at the surface of the unmodified
electrode shows a relatively broad anodic wave with a peak
potential around 402 mV (versus Ag/AgCl). On the other
hand, at the surface of modified electrode a considerable
decrease in anodic overpotential (more than 100 mV) with
a considerable enhancement in the anodic peak current is
seen. Fig. 1(B) shows that the direct oxidation of cysteine
at the surface of unmodified electrode is very sluggish and
an evident anodic peak cannot be obtained in the range of
the swept potential. However, a very sharp anodic wave at a
considerably lower anodic (positive) potential is resulted, by
using the CoMSal-modified electrode. These observations
clearly reveal that the CoMSal in the matrix of modified CPE
as an electron-mediator is able to catalyze effectively the
electrochemical oxidation of AA and cysteine. The catalytic
current using this modified electrode, is proportional to the
substrate concentration (in a linear range of 1 × 10−4 to 1 ×
10−3 M of both AA and cysteine with correlation coefficients
more than 0.999). For both compounds, at all potential sweep
rates, no cathodic peak is observed on the reverse scan,
which confirms the EC mechanism with coupled irreversible
chemical reactions hindered to the electron transfer step
[38]. For electro-oxidation of cysteine in solutions with pH
≤ 4.0, a linear relationship is observed between anodic peak
current (Ip,a ) and potential sweep rate (υ1/2 ), which reveals
an adsorption-like behavior for analyte in such condition.
Results of the present work and also our previous works
on the application of phthalocyanine and Schiff base com-
plexes of cobalt have been shown that the values of less than
2% (w/w) of modifier causes to a considerable decrease in the
peak current along with the broadening of peaks and also pos-
itive shift in peak potential. On the other hand, values more
than 2% (w/w) of the modifier resulting to increase of back-
ground (capacitive) current in conjunction with a graduate
decrease in peak current. Therefore, a value of ∼2% (w/w)
79
of CoMSal is used as the optimum value of the modifier in
the matrix of CPE.
For the electrocatalytic oxidation of AA, the anodic peak
potential shifts to more negative values upon the increasing
of pH of the buffer solution, which nearly level-off in pHs
greater than 5 (Fig. 2(A)). A similar behavior can be observed
for cysteine with a considerably smaller slope in the graph
of peak potential with respect to pH. Based on these obser-
vations, we may conclude that proton is contributed with a
greater stoichiometry coefficient in the electrochemical oxi-
dation of AA, compare to cysteine. As can be seen in Fig. 2(B)
for AA, by increasing the pH of buffer solution to the value
of 4.0 the anodic peak current is enhanced and afterwards, a
slight decrease can be observed. For the oxidation of cysteine
the decreasing is resulted in solutions with pH greater than
5.0. First effect may be related to the deprotonation step
in the electrochemical oxidation of these compounds at the
surface of modified electrode which is prior to the electron
transfer step. On the other hand, in solutions with higher
pHs (greater than 5.0) air oxidation of these compounds
by dissolved oxygen leads to decreasing the sensitivity of
voltammetric responses. Such a behaviors has been reported
for the electrocatalytic oxidation of AA using the modified
electrodes with iron phthalocyanine [5], cobalt pyridopor-
phyrazin [14] and the electrochemical oxidation of sulfhydryl
compounds at the surface of the modified electrodes with
cobalt phthalocyanins [9,10,13] and Schiff bases [15,16].
The effect of potential sweep rate on the anodic peak
current, by using the modified electrode showed that for
both AA and cysteine, the peak current is linearly pro-
portional to the square root of potential sweep rate (υ1/2 )
for the range of 10–150 mV s−1 with reasonable correla-
tion coefficients (R2 ; 0.9993 for AA and 0.9911 for cys-
teine). These observations exhibit that the electro-oxidation
of both compounds at the surface of modified electrode and
80 S. Shahrokhian, M. Karimi / Electrochimica Acta 50 (2004) 77–84

Fig. 2. Variation of (A) anodic peak potential, and (B) anodic peak current with pH of buffer solution at the modified electrode for 1 mM of cysteine and
ascorbic acid. Sweep rate was 100 mV s−1 (0.1 M acetate is used for pH 4, 5 and 0.1 M phosphate is used for pHs 2, 3, 6, 7).

in the range of scan rate studied is a diffusion-controlled

process. A greater slope, which is obtained for the plot
of AA (1.214 ␮A mV−1/2 s−1/2 ) with respect to cysteine
(0.990 ␮A mV−1/2 s−1/2 ), may be related to more electron
transferred in the mechanism of the electrocatalytic oxidation
of AA. Variation of current function plots (Ip /Cυ1/2 versus
υ1/2 ) for both AA and cysteine at the surface of the modified
electrode show negative slopes, which are typical of catalytic
processes for the electro-oxidation of AA and cysteine.
For the electro-oxidation of cysteine in buffered solutions
with pH ≤ 4.0, another anodic peak may be observed for
potentials considerably lower than the above-mentioned dif-
fusion peak. The peak current for this new wave shows a
linear dependence to potential sweep rate, which indicates
an adsorption-like behavior in the mechanism with a step of
irreversible pre-coordination of thiolate anion of cysteine as
an axial ligand to the metal center of catalyst (CoMSal) before
the electron transfer step. By increasing the pH of buffer solu-
tion, as can be seen in Fig. 3, the intensity of this adsorption-
like pre-peak is decreased, so that for pH greater than 4.0 can-
not be observed. Such a behavior has already been observed
for the electro-catalytic oxidation of 2-mercaptoethanol at
Fig. 3. Cyclic voltammograms of 1 mM cysteine at the modified electrode in
the surface of graphite electrode modified with perchlori-
buffered solutions with various pHs. Potential sweep rate was 100 mV s−1 .
nated iron phthalocyanine [9] and thioglycolic acid at CPE
modified with cobalt phthalocyanine [4]. A reason for ob-
serving the adsorbed pre-peak in more acidic conditions may of sweep rates and in pH 5.0 are shown in Fig. 4. The results
be due to the protonation of thiolate form and formation of of the slope of Tafel plots show values of αna between 0.40 to
more equilibrium concentration of the RSH, which has more 0.46 for AA and 0.36 to 0.45 for cysteine at the surface of the
hydropobic properties for adsorption at the lipophile surface modified electrode, respectively. By considering a value of
of CPE. 0.5 for α in these nearly symmetric waves, the one-electron
The Tafel plot and its corresponding slope were used for transfer process is confirmed for the rate-determining step of
the elucidation of the mechanism of electrode processes. these processes.
The results of polarization studies (log I/E plots) for electro- In the light of the above mentioned results and previous
catalytic oxidation of AA and cysteine at the surface of the works on the electro-catalytic oxidation of AA [5,14] and
modified electrode were obtained in various sweep rates. cysteine [10,11,15] at the surface of electrodes modified with
These plots for 0.001 M of two compounds for two values transition metal complexes as electron mediator, the follow-
 S. Shahrokhian, M. Karimi / Electrochimica Acta 50 (2004) 77–84
Fig. 4. Polarization curves for 1 mM of cysteine and ascorbic acid in buffered
solutions with pH 5.0 (acetate, 0.1 M) and in two various sweep rate.
ing mechanisms may be suggested for the catalytic effect of
CoMSal in the modified carbon-paste electrode:
Mechnism of AA oxidation:
2Co(II)MSal → 2Co(III)MSal + 2e−
2Co(III)MSal + C6 H8 O6 → 2Co(II)MSal
+ C6 H6 O6 + 2H+
(C6 H8 O6 : ascorbic acid, C6 H6 O6 : dehydroascorbic acid)
Mechanism of cysteine oxidation:
RSH + H2 O → RS− + H3 O+
Co(II)MSal → Co(III)MSal + e−
Co(III)MSal + RS− → Co(II)MSal + RS·
RS· → 1
RSSR
2
Results of previous studies on the catalytic effect of ph-
thalocyanine complexes of cobalt in the electrochemical ox-
idation of thiols have been shown that, Co is capable to
catalyze the thiol oxidation in both +2 and +3 oxidation
states [10,11,15,16]. These results are shown that in more
acidic conditions, the most probable oxidation process that
occurred, is referred to catalytic effect of Co(III)/Co(II) sys-
tem. On the other hand, in the neutral and some extent alkaline
conditions, oxidation of thiols and also AA is catalyzed by
Co(II)/Co(I) mediator couple [3–6,13,14]. Based on the re-
sults of the present work and also from the previous studies,
it is confirmed that in the applied conditions (pH ≤ 5), the
Co(III) complex (CoIII MSal) catalyzes the electrochemical
oxidation of AA and cysteine.
81
Fig. 5. Cyclic voltammogram of a mixture of 1 × 10−4 M cysteine and 1
× 10−4 M AA at unmodified CPE (dotted line), and modified CPE (solid
line) in solutions with pH 5.0 (acetate, 0.1 M) and sweep rate 100 mV s−1 .
Differential pulse voltammograms for this mixture is shown with dashed
curve.
(1)
3.2. Voltammetric studies in mixtures of AA and cysteine
In the electrochemical sensing of cysteine using unmod-
ified electrodes in biological fluids (e.g. serum samples)
(2)
minor amounts of reducing agents such as, AA and peni-
cillamine are seriously interfering agents. Our previous
work on the electrocatalytic oxidation of penicillamine
using Co(II)salophen-modified CPE showed that the most
(3) catalytic effect may be observed in solutions with pH 3.0
[16]. By using CoMSal in this work, an anodic peak for
(4) penicillamine is resulted with a peak potential of 0.726 V
(versus Ag/AgCl), which is 162 mV more positive, compared
(5)
to cysteine in the same sweep rate (100 mV s−1 ). Due to the
(6) sharpness of anodic waves, the difference in peak potentials
is sufficient for the resolution of voltammetric signals.
Therefore, penicillamine as a biological interfering thiol
cannot be a serious interference in the voltammetric detection
of cysteine. Results of the cyclic voltammetric studies using
CoMSal-modified CPE show that the anodic oxidation waves
for AA and cysteine, due to large difference in half-wave
potentials, well resolved and makes this electrode suitable as
a sensitive voltammetric sensor for the detection of cysteine
in the presence of AA. Cyclic voltammogram for 5 × 10−4 M
cysteine in the presence of an amount of 1 × 10−4 M AA
in buffered solution with pH 5.0 (0.1 M acetate) is shown in
Fig. 5. At the surface of the unmodified electrode a broad and
weak anodic wave is resulted for AA that cannot separate
from the very broad and also very weak wave of cysteine (the
curve with the dotted line). On the other hand, in the case of
82 S. Shahrokhian, M. Karimi / Electrochimica Acta 50 (2004) 77–84

Fig. 6. Differential pulse voltammograms of solutions containing (I) constant 1 × 10−4 M AA and (A) 5 × 10−7 , (B) 1 × 10−6 , (C) 5 × 10−6 , (D) 1 × 10−5 ,
(E) 5 × 10−5 and (F) 1 × 10−4 M cysteine; (II) constant 1 × 10−4 M cysteine and (A) 1 × 10−6 , (B) 5 × 10−6 , (C) 1 × 10−5 , (D) 5 × 10−5 , (E) 1 × 10−4 of
AA. Supporting electrolyte in all measurements was 0.1 M acetate buffer with pH 5.0.

the modified electrode, two well-defined anodic waves for
AA and cysteine are observed with nearly 360 mV difference
in peak potentials (the wave with solid line). In these
conditions, the peak separation is large enough to determine
AA and cysteine individually and of course, simultaneously.
Differential pulse voltammetry using CoMSal-modified
electrode was used as a method with high sensitivity, low
detection limit and a very good resolution for the detection
of cysteine in the presence of AA and other potentially
interfering biological thiol such as mercapto-d-valine
(d-penicillamine). With respect to complete resolution of
anodic peaks of two compounds, this modified electrode
is applied successfully for the simultaneous detection of
AA and cysteine in a mixture. A typical differential pulse

Fig. 7. Differential pulse voltammograms of solutions; (I) 0.1 M acetate buffer (pH 5.0), and (II) human synthetic serum containing 0.1 M acetate buffer spiked
with various concentrations of cysteine (A) 4.0 × 10−6 , (B) 7.9 × 10−6 , (C) 2.0 × 10−5 , (D) 3.8 × 10−5 , (E) 5.7 × 10−5 , (F) 7.4 × 10−5 and (G) 1.1 × 10−4 M.
 S. Shahrokhian, M. Karimi / Electrochimica Acta 50 (2004) 77–84
voltammograms of the mixture of 1 × 10−4 M cysteine and 1
× 10−4 M AA in a buffered solution with pH 5.0 is shown in
Fig. 5 (the curve with dashed line). Differential pulse voltam-
mograms for various concentrations of cysteine in acetate
buffer solutions with pH 5.0 in the linear range of 5 × 10−7 to
1 × 10−4 M and in the presence of a constant concentration
1 × 10−4 M of AA is shown in Fig. 6(I). These differential
pulse voltammograms for AA in the linear range (1 × 10−6
to 1 × 10−4 M) and in a constant background of 1 × 10−4 M
cysteine containing the same electrolyte (acetate buffer with
pH 5.0) is brought in Fig. 6(II). The voltammetric detection
limit for cysteine using this electrode is obtained as 2 ×
10−7 M (S/N = 3) and slope variation for six replicate is 2.2%.
For AA at the surface of the modified electrode, the detection
limit of 8 × 10−7 M is resulted with a slope variation of 2.5%.
Fig. 7 represents the DPVs for various concentrations of
cysteine from 4.0 × 10−6 to 1.1 × 10−4 M in acetate buffer
with pH 5.0 as background electrolyte (I) and also in the
presence of a constant background of human synthetic serum
(II). The concentration of each component in the human syn-
thetic serum was chosen to be near to its normal level in
the real human serum, except cysteine, which does not ex-
ist in this sample [39]. Voltammetric calibration curves for
the peak current versus cysteine concentration in both back-
ground electrolytes (acetate buffer and synthetic serum) was
linear in the same range of 4.0 × 10−6 to 3.0 × 10−5 M
with the same calibration sensitivity. The slope of calibration
curve for the variation of the peak current versus cysteine con-
centration in pure buffer solution as background electrolyte
(pH = 5.0) was 35.65 ␮A M−1 (R2 = 0.9963). The slope for
the measurements in a background of human synthetic serum
with the same pH was 35.06 ␮A M−1 (R2 = 0.9963). These
results show an excellent recovery for the cysteine spiked to
the synthetic serum and indicate that the complex matrix of
serum sample does not interfere with the voltammetric deter-
mination of cysteine.
4. Conclusions
The carbon-paste electrode modified with cobalt-4-
methylsalophene can be used for electrocatalytic oxidation
of cysteine and ascorbic acid and simultaneous detection of
these compounds in mixture solutions, with high sensitivity
and low detection limit (sub-micromolar). In the presence
CoMSal as an electron mediator, with respect to unmodi-
fied electrode, the anodic overpotential for cysteine and also
AA significantly decreases and the anodic peak current con-
siderably enhanced in the CV and DPV methods. Complete
resolution of anodic peaks for these compounds improved
the selectivity of method and makes it possible for sensi-
tive detection of cysteine in the presence of an excess of AA
in slightly acidic solutions (pH 5.0). The detection method is
successfully applied for the determination of cysteine in com-
plex matrix of human synthetic serum. The working electrode
surfaces can be prepared and renewed easily by the mechan-
83
ical polishing. The prepared modified electrode showed very
good reproducibility, low detection limit (sub-micromolar)
and a high stability for detection of cysteine and AA in clin-
ical and pharmaceutical preparations.
Acknowledgement
The authors gratefully acknowledge financial support of
the Research Council of Sharif University of Technology.
They are grateful to Professor Gholam Abbas Parsafar for his
useful suggestions. The authors thank Islamic development
Bank (IDB) for financial supports in order to purchase NMR-
500 MHz (Bruker) instrument.
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