Electrochimica Acta 52 (2007) 46224629

Electrocatalytic oxidation of some amino acids on a nickelcurcumin

complex modied glassy carbon electrode
S. Majdi
a
, A. Jabbari
a,
, H. Heli
b
, A.A. Moosavi-Movahedi
b
a
Department of Chemistry, Faculty of Science, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran, Iran
b
Institute of Biochemistry and Biophysics, University of Tehran, Tehran, Iran
Received 10 December 2006; received in revised form 10 December 2006; accepted 13 January 2007
Available online 30 January 2007
Abstract
This study investigated the electrocatalytic oxidation of alanine, l-arginine, l-phenylalanine, l-lysine and glycine on poly-Ni(II)curcumin lm
(curcumin: 1,7-bis [4-hydroxy-3-methoxy phenyl]-1,6-heptadiene-3,5-dione) electrodeposited on a glassy carbon electrode in alkaline solution.
The process of oxidation and its kinetics were established by using cyclic voltammetry, chronoamperometry and electrochemical impedance
spectroscopy techniques. Voltammetric studies indicated that in the presence of amino acids the anodic peak current of low valence nickel species
increased, followed by a decrease in the corresponding cathodic current. This indicates that amino acids were oxidized on the redox mediator which
was immobilized on the electrode surface via an electrocatalytic mechanism. Using Lavirons equation, the values of and k
s
for the immobilized
redox species were determined as 0.43 0.03 and 2.47 0.02 10
6
s
1
, respectively. The rate constant, the electron transfer coefcient and the
diffusion coefcients involved in the electrocatalytic oxidation of amino acids were determined.
2007 Elsevier Ltd. All rights reserved.
Keywords: Alanine; l-Arginine; l-Phenylalanine; l-Lysine; Glycine; Nickelcurcumin; Modied electrode; Electrocatalysis; Impedance spectroscopy
1. Introduction
Amino acids are essential building blocks of biological
molecules [1] and play key roles in many neuro-chemical
response mechanisms, such as memory, appetite control and
pain transmission [24]. The disruption of amino acid regu-
lation has been linked to many disorders such as Huntington,
Alzheimer and Parkinson diseases [24]. The development of
a simple and universal detection method for these compounds
would improve our understanding of their biological role and
facilitate the design of new drugs for these diseases. However,
the determination of underiviatized amino acids is not simple
since these compounds lack natural chromophore or uorephore
for photometric and urometric detections.
The oxidation and adsorption behaviors of amino acids on
electrode surfaces are relevant to the interfacial behaviors of
proteins and also to the medical and industrial problems asso-
ciated with the proteins adsorption on the surfaces [57]. The

Corresponding author. Tel.: +98 21 44 219 952; fax: +98 21 22 853 650.
E-mail address: jabbari@kntu.ac.ir (A. Jabbari).
problem with the application of electrochemical methods for
amino acid and protein analysis is the lack of electrochemically
active groups in most of these compounds. Thus, a derivatization
procedure must be used prior to determination of amino acids.
Two approaches are adopted: the rst approach is to derivate the
analyte with an electrochemically active group prior to deter-
mination. The second approach is to generate in situ chemical
reactions on electrode surfaces to produce electrochemically
active products for detection [8].
Extensive research has been directed towards the develop-
ment of electrocatalysts aimed at lowering the normally large
overpotential and raising the faradaic current encountered in
the electro-oxidation of materials. A great deal of interest has
recently focused on the materials immobilized on the electrode
surface and is capable of mediating fast electron transfer under
the effect of external electric elds, namely chemically modied
electrodes [912].
Construction of electrode materials that are based on macro-
cyclic complexes that behave as fast electron transfer mediators
for solution species is of great interest [1316]. Although
electrochemistry and electrocatalytic properties of macrocyclic
complexes of some transition metals have been investigated
0013-4686/$ see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2007.01.022
S. Majdi et al. / Electrochimica Acta 52 (2007) 46224629 4623
[13,1519], few studies about the behavior of electropolymer-
ized lms in aqueous alkaline solution exist. One such study
reported that nickel macrocyclic complexes can be easily elec-
tropolymerized onto an electrode surface in alkaline solution
to form modied electrodes that catalyze oxidation of several
substrates [2022].
The resulting lms from polymeric metal complexes which
contain Ni(II)/Ni(III) redox couple showed high catalytic activ-
ity towards electro-oxidation of organics containing OH and
NH
2
groups [20,21] such as carbohydrates and amino acids.
In these polymeric metal complexes, nickel oxyhydride species
act as redox mediators between a substrate and an electrode in
many electro-oxidation processes. Moreover, the procedure of
their preparation is simple and the properties of the resulting
coating can be controlled carefully [20,21,23].
Following our recent studies on the electrocatalytic oxidation
of some organics and pharmaceuticals [912], we employed a
Ni(II)curcumin complex chemically modied glassy carbon
electrode for the study of electrocatalytic oxidation of some
amino acids in alkaline solutions.
2. Materials and methods
All chemicals used in this work were purchased from Merck
as analytical reagent grade chemicals and used without fur-
ther purication. The Ni(II)-ammonia complex was prepared
via the dissolution of 4 mM NiCl
2
in a 25% ammonia solution.
Electrochemical measurements were carried out in a conven-
tional three electrode cell (from Metrohm) powered by an
electrochemical system comprising of an AUTOLAB system
with PGSTAT30 and FRA2 boards (Eco Chemie, Utrecht, The
Netherlands). In impedance measurements, a frequency range of
100 kHz to 25 mHz was employed, the ac voltage amplitude was
10 mV and the equilibrium time was 5 s. The system was run by
a PC through the FRA and GPES 4.9 softwares. A glassy car-
bon (GC) disk electrode (from Azar Electrode Co., Iran) which
was modied, a dual Ag/AgClsaturated KCl (from Metrohm)
and a platinum disk (from Azar Electrode Co. Iran) were used
as working, reference and counter electrodes, respectively. All
studies were carried out at room temperature.
The GC electrode was further polished on a polishing micro-
cloth with 0.5 M alumina powder and rinsed thoroughly with
redistilled water prior to the modication. The electrode was
placed in 100 mMNaOHcontaining 10 mMcurcumin and 4 mM
Ni(II)-ammonia complex, subsequently applying the poten-
tial between 200 and 800 mV with a potential sweep rate of
100 mVs
1
in a cyclic voltammetry regime. An excess of cur-
cumin was used for completion of Nicurcumin complexation.
The modied electrode has been denoted as NCGC throughout
the text.
3. Results and discussion
The electrochemical oxidation of curcumin and
Ni(II)curcumin complex was carried out at the GC elec-
trode in aqueous 100 mM NaOH solution by using multiple
scan cyclic voltammetries. Consecutive cyclic voltammograms
Fig. 1. Consecutive cyclic voltammograms 8 mM curcumin in 100 mM NaOH
solution using a GC electrode. Potential sweep rate was 100 mVs
1
. The cycle
number is indicated on each voltammogram.
of 8 mM curcumin in 100 mM NaOH solution are depicted in
Fig. 1. Curcumin undergoes an irreversible oxidation process
and produces an anodic peak located at 333 mV in the rst
cycle, however in the following sweeps the peak disappears
from the voltammogram. This is the fouling effect of the
electrode surface (blocking the surface via chemical attachment
of a layer which alters the kinetics of the heterogeneous
electron transfer process of curcumin electro oxidation). The
anticipated chemical structure of curcumin molecule and the
main possible reactions involved in the electro-oxidation of
the curcumin molecule were depicted in Scheme 1A. In strong
alkaline solutions, phenol converts into phenolate ion I which
is readily oxidized and generates free-radical II. The presence
of methoxy group in the monomer makes the reaction possible.
The methanol molecule can be eliminated from radical II
by alkaline hydrolysis giving an anion radical III, which is
Scheme 1.
4624 S. Majdi et al. / Electrochimica Acta 52 (2007) 46224629
Fig. 2. Consecutive cyclic voltammograms of 100 mM NaOH solution contain-
ing 10 mM curcumin and 4 mM Ni(II)ammonia complex using a GC. Potential
sweep rate was 100 mVs
1
. The cycle number increases from inner to outer.
Inset: The rst cycle in main panel.
converted to a highly reactive O-quinone (IV) via another
one-electron reaction. Then O-quinone species are adsorbed on
the electrode surface [20].
Consecutive cyclic voltammograms recorded using the GC
electrode in 100 mM NaOH solution containing 10 mM cur-
cumin and 4 mMNi(II)-ammonia complex are depicted in Fig. 2
and the anticipated chemical structure of the Ni(II)curcumin
complex is also shown in Scheme 1B. In the early stages of
potential cycling, oxidation of curcumin causes the appearance
of an irreversible peak (Fig. 2, inset). However, in the later
sweeps, a pair of peaks appears due to a lmgrowth and immobi-
lization of Ni(II)curcumin on the electrode surface. Although
curcumin undergoes an irreversible oxidation process and the
product of the reaction is adsorbed at the GC surface, either
curcuminor its oxidationproduct canact as a substrate for immo-
bilization of nickel ions on the electrode surface. Moreover, the
charged nickel species, their corresponding redox transition, and
involvement of ionic species penetration into the lm from the
bulk of solution, makes the lm an ionic conductor (vide infra).
Fig. 3Arepresents cyclic voltammogram of NCGCelectrode
in 100 mM NaOH solution recorded at different potential sweep
rates in a wide range of 21000 mVs
1
. A pair of well dened
peaks with the mid peak potential of 395 mV in the voltammo-
gram appears and the peak-to-peak potential separation (with
the potential sweep rate of 10 mVs
1
) is 130 mV. The voltam-
mogram is similar to that previously reported [11,20,23] and
the redox transition involved is attributed to the Ni(II)/Ni(III)
species. The peak-to-peak potential separation is deviated from
the theoretical value of zero and increases at higher potential
sweep rates. This indicates a limitation in the charge-transfer
kinetics arising from chemical interactions between the elec-
trolyte ions and the modier lm, dominated electrostatic
factors, and/or non-equivalent sites present in the lm.
Laviron derived general expressions for the linear potential
sweep voltammetric response for the case of surface-conned
electro-reactive species at small concentrations [24]. The expres-
sions for peak-to-peak separation (E
p
) >200/n mV where n is
the number of exchanged electrons, are as follows:
E
pa
= E
0
+Aln

1
m

(1)
E
pc
= E
0
+Bln

(2)
lnk
s
= ln(1 ) +(1 ) ln ln

RT
nFv

(1 )nF E
p
RT
(3)
where A=RT/(1 )nF, B=RT/nF, m=(RT/F)(k
s
/n), E
pa
and E
pc
are anodic and cathodic peak potential respectively, and
, k
s
and are electron transfer coefcient, apparent charge-
transfer rate constant and potential sweep rate, respectively.
From these expressions, can be determined by measuring
the variation of the peak potential with respect to the poten-
tial sweep rate, and k
s
can be determined for electron transfer
between the electrode and surface deposited layer by measuring
the E
p
values. Fig. 3A, inset shows the plot of E
p
with respect to
the logarithm fromcyclic voltammograms recorded for NCGC
electrode in 100 mMNaOHsolution recorded at potential sweep
rates 21000 mVs
1
for anodic (a) and cathodic (b) peaks. It can
be observed that for potential sweep rates of 2001000 mVs
1
the values of E
p
are proportional to the logarithm of the poten-
tial sweep rate indicated by Laviron. Using the plot and Eq.
(3), the values of and k
s
were determined as 0.43 0.03 and
2.47 0.02 10
6
s
1
, respectively.
Another point in the voltammograms represented in Fig. 3A
is that the anodic and cathodic peak currents are proportional
to the potential sweep rate at low values from 1 to 30 mVs
1
(Fig. 3B and C). This can be attributed to an electrochemical
activity of an immobilized redox couple at the surface. Fromthe
slope of this line and using [25]:
I
p
=

n
2
F
2
4RT

vA

(4)
where I
p
is the peak current, A the electrode surface area and

*
is the surface coverage of the redox species and taking
the average of both cathodic and anodic currents, the total sur-
face coverage of the electrode with the modier lm of about
4.02 0.03 10
8
mol cm
2
was derived. In the higher range
of potential sweep rates (601000 mVs
1
, Fig. 3D and E), the
peak currents depend on square root of the potential sweep
rate, signifying the dominance of a diffusion process as the
rate limiting step in the total redox transition of the modier
lm. This limiting diffusion process which was also reported for
other Ni-modied electrodes [13,14] may occur for the charge
neutralization of the lmduring the oxidation/reduction process.
Fig. 4 shows cyclic voltammograms of NCGC electrode in
100 mM NaOH solution in the absence (a) and presence of var-
ious concentrations of alanine (b: 10, c: 25, d: 30, e: 50 and f:
70 mM) in the potential range of 200800 mV by using a poten-
tial sweep rate of 100 mVs
1
. At NCGC electrode, oxidation
of alanine resulted in a typical electrocatalytic response. The
S. Majdi et al. / Electrochimica Acta 52 (2007) 46224629 4625
Fig. 3. (A) Main panel: cyclic voltammograms of NCGC electrode in 100 mM M NaOH solution. Potential sweep rates from inner to outer are: 2, 5, 10, 20, 30, 40,
50, 75, 100, 200, 300, 400, 500, 600, 700, 800, 900 and 1000 mVs
1
. (A) Inset: Plot of E
p
vs. log for cyclic voltammograms depicted in the main panel for anodic
peaks (a) and cathodic peaks (b). (BE) The dependency of anodic (B) and cathodic (C) peak currents on the potential sweep rate at lower values (130 mVs
1
) and
the proportionality of anodic (D) and cathodic (E) peak currents on the square roots of sweep rate at higher values (601000 mVs
1
).
anodic charge greatly increased with respect to observed for the
modied surface in the absence of alanine and it was followed
by decreasing the cathodic current upon increasing the concen-
tration of alanine in solution. In the presence of 25 mM alanine
with the potential sweep rate of 100 mVs
1
, the anodic charge
associated with the anodic peak was quantitatively 98.9%of that
of the corresponding cathodic peak, while in the absence of ala-
nine, this ratio was 48.0%. The anodic charge in the positive
sweep was proportional to the bulk concentration of alanine and
any increase in the concentration of alanine caused an almost
proportional linear enhancement of the anodic charge. In addi-
tion, an anodic peak in the beginning of the cathodic half cycle
appeared. The appearance of an anodic peak in the forward as
well as in the reverse sweep was the distinct feature of electro-
catalytic oxidation of amino acids on noble metals [1]. Also,
the cathodic current that ensued from the oxidation process in
the reverse cycle indicated that the rate determining step cer-
tainly involves alanine and was incapable of reducing the entire
high valence nickel species formed in the oxidation cycle. More-
over, the regeneration of the anodic peak in the cathodic half
4626 S. Majdi et al. / Electrochimica Acta 52 (2007) 46224629
Fig. 4. Main panel: cyclic voltammograms of the NCGE electrode in 100 mM
NaOH solution in the absence (a) and the presence (b) 10 mM; (c) 25 mM; (d)
30 mM; (e) 50 mM; (f) 70 mM of alanine in the solution. Potential sweep rate
was 100 mVs
1
. Inset: Dependency of the charge under the anodic peak on the
concentration of alanine in solution.
cycle indicated that an intermediate(s) generated in the anodic
sweep did not have enough time to undergo full oxidation and its
consumption continued even after the potential sweep had been
reversed. These results indicated that alanine was oxidized by
active nickel moiety via a cyclic mediation redox process. Nickel
species were immobilized on the electrode surface and the one
with a higher valence oxidized alanine via a chemical reaction
which resulted in the generation of low valence nickel. Along
this line, the high valence oxide was regenerated through the
external electrical circuit. The redox transition of nickel species
present in the lm is: and alanine is oxidized on the modied
surface via the following reaction present in the lm is:
Ni(II) Ni(III) +e (5)
and alanine is oxidized on the modied surface via the following
reaction:
Ni(III)curcumin +Alanine
Intermediate +Ni(II)curcumin (6)
Ni(III)curcumin +Intermediate
Product +Ni(II)curcumin (7)
NCGC electrode exhibited similar electrocatalytic responses
for other amino acids, l-arginine, glycine, l-lysine and l-
phenylalanine, thereby exhibiting its capability for selective
oxidation of amino acids.
Double steps chronoamperograms were recorded by setting
the working electrode potentials to desired values and were used
to measure the catalytic rate constant on the modied surface.
Fig. 5A shows double steps chronoamperograms for the modi-
ed electrode in the absence (a) and presence (b: 10, c: 15, d:
20, e: 25 and f: 30 mM) of alanine over a concentration range of
Fig. 5. (A) Double steps chronoamperograms of NCGC electrode in 100 mM
NaOHsolution with different concentrations of alanine of: (a) 0 mM, (b) 10 mM,
(c) 15 mM, (d) 20 mM, (e) 25 mM and (f) 30 mM. Potential steps were 500 mV
and 290 mV, respectively. (B) Dependency of transient current on t
0.5
. (C)
Dependence of I
catal
/I
d
on t
0.5
derived from the data of chronoamperograms of
(a and d) in panel (A).
1050 mM. The applied potential steps were 500 and 290 mV,
respectively. Plotting of net current with respect to the minus
square roots of time, presented a linear dependency (Fig. 5B).
Therefore, a diffusion-controlled process was dominated. By
using the slope of this line, the diffusion coefcient of alanine
can be obtained according to Cottrells equation [25]:
I = nFAD
1/2
C
1/2
t
1/2
(8)
where D is the diffusion coefcient and C is the bulk concentra-
tion. The mean value of the diffusion coefcient of alanine was
found to be 1.00 0.05 l0
6
cm
2
s
1
.
Chronoamperometry was also be used for the evaluation of
the catalytic rate constant according to [25]:
I
catal
I
d
=
1/2

1/2
erf(
1/2
) +
exp ()

1/2

(9)
where I
catal
and I
d
are the currents in the presence and absence
of alanine, =kCt is the argument of the error function, k is the
catalytic rate constant and t is elapsed time. In the cases where
>1.5, erf(
1/2
) is almost equal to unity and the above equation
can be reduced to:
I
catal
I
d
=
1/2

1/2
=
1/2
(kCt)
1/2
(10)
From the slope of the I
catal
/I
d
versus t
1/2
plot, presented in
Fig. 5C, the mean value of k for alanine was obtained as 3.65
S. Majdi et al. / Electrochimica Acta 52 (2007) 46224629 4627
Table 1
The electrocatalytic reaction rate constants (k), the diffusion coefcients (D) and
the electron transfer coefcient () for the amino acids
k (cm
3
mol
1
s
1
) D (cm
2
s
1
)
Alanine 3.65 0.02 10
5
1.00 0.05 10
6
0.41 0.03
l-Phenylalanine 9.53 0.05 10
3
1.48 0.02 10
6
0.53 0.04
Glycine 2.03 0.02 10
6
1.40 0.02 10
6
0.52 0.03
l-Lysine 1.45 0.02 10
5
1.35 0.04 10
6
0.54 0.04
l-Arginine 9.73 0.03 10
5
1.86 0.03 10
6
0.43 0.03
0.02 l0
5
cm
3
mol
1
s
1
. Similar chronoamperograms were
collected for l-arginine, glycine, l-lysine and l-phenylalanine.
The values of D and k obtained according to the method
described in the above for these amino acids were reported in
Table 1.
Fig. 6A illustrates cyclic voltammograms of 30 mM alanine
using NCGC electrode recorded at different potential sweep
rates. The oxidation current of alanine on the modied surface
increased linearly with the square root of the potential sweep rate
(Fig. 6B), which indicated the mass transfer controlled process.
Also, the value of electron transfer coefcient for the reaction
can be obtained from the following equation [26]:
E
p
=

RT
2F

lnv +constant (11)

which is valid for a totally irreversible-diffusion controlled pro-
cess. Using the dependency of anodic peak potential on the
Fig. 6. (A) Cyclic voltammograms of the NCGE electrode in 100 mM NaOH
solution in the presence of 30 mM alanine at various potential sweep rates of 2,
5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 150, 200, 300, 400, 500, 600, 700, 800,
900, 1000, 1100, 1200, 1300, 1400 mVs
1
, 1500 mVs
1
. (A) Dependence of
anodic peak current during the forward sweep on the square roots of potential
sweep rate. (C) Dependence of the peak potential on log for the oxidation of
alanine at NCGC electrode obtained from the data of panel (A).
Fig. 7. Main panel: Nyquist diagrams of NCGCelectrodes recorded at oxidation
peak potential as dc-offset for 20 mM, 20 mM, 20 mM, 50 mM, 50 mM of ala-
nine, l-arginine, glycine, l-lysine and l-phenylalanine, respectively, in NaOH
100 mMsolution. Inset: Typical cyclic voltammogramof the NCGEelectrode in
100 mM NaOH solution in the presence of 40 mM of l-arginine in the solution.
Potential sweep rate was 100 mVs
1
.
natural logarithmof the potential sweep rate (Fig. 6C), the value
of electron transfer coefcient was obtained as 0.41 0.03.
Similar cyclic voltammograms were recorded for l-arginine,
glycine, l-lysine andl-phenylalanine. Values of were obtained
according to this method for these amino acids and were reported
in Table 1.
The electrochemical impedance spectroscopy was also
employed to shed light on the oxidation mechanism. The results
indicated that although in the regime of cyclic voltammetry,
different amino acids represented similar patterns for electro-
catalytic oxidation, Nyquist diagrams represented very different
patterns. Fig. 7 shows the Nyquist diagrams of NCGC elec-
trode recorded at oxidation peak potential as dc-offset for some
selected concentrations of the amino acids. The Nyquist dia-
gram of NCGC electrode in l-arginine solution represented one
slightly depressed capacitive semicircle which can be related
to the combination of charge transfer resistance of transition
of Ni(II)/Ni(III) redox couple in the presence of l-arginine and
the double layer capacitance. The equivalent circuit compati-
ble with this Nyquist diagram was depicted in Scheme 2. In this
electrical equivalent circuit, R
s
, CPE
dl
and R
ct
represent solution
resistance, a constant phase element corresponding to the dou-
ble layer capacitance and the charge transfer resistance. In this
circuit the charge transfer resistance of the electrode reaction
is the only circuit element that has a simple physical meaning
describing how fast the rate of charge transfer during l-arginine
electro-oxidation changes with the electrode potential while the
surface covered by reaction intermediate(s) is kept constant.
Scheme 2.
4628 S. Majdi et al. / Electrochimica Acta 52 (2007) 46224629
Scheme 3.
In order to obtain a satisfactory tting of Nyquist diagrams,
it was necessary to replace the double layer capacitance with a
constant phase element, CPE
dl
, in the corresponding equivalent
circuit. The most widely accepted explanation for the presence
of this distributed element and the appearance of depressed
semicircles in Nyquist plots, is microscopic roughness, caus-
ing an inhomogeneous distribution in the solution resistance as
well as in the double layer capacitance [27]. The result indi-
cated that l-arginine was oxidized on NCGC electrodes without
any signicant adsorption of reaction intermediate(s). This was
also supported by cyclic voltammetry studies which imply that
electrocatalytic oxidation of l-arginine on NCGC electrodes
represented no signicant anodic peak in the reverse sweep (see
Fig. 7, inset). The Nyquist diagram recorded for NCGC elec-
trode in the presence of alanine also showed a slightly depressed
capacitive semicircle due to the combination of charge transfer
resistance of transition of Ni(II)/Ni(III) redox transition. How-
ever, the Nyquist diagram rolled over at low frequencies and
presented an inductive behavior. The equivalent circuit related
to the Nyquist diagram recorded in the presence of alanine was
depicted in Scheme 3. In this electrical equivalent circuit, L and
R
ads
are the electrical elements compatible with the adsorption
of reaction intermediate(s). It was reported that adsorption of
reaction intermediates during the electrocatalytic oxidation of
organics can cause the inductive behavior in Nyquist diagrams
[9,28]. The inductive feature that appeared in Nyquist diagrams
is often found in electrochemical measurements of electrocat-
alytic reactions controlled by intermediate absorbed species
[29]. In general, the inductive behavior appears in Nyquist plots,
when the variation of the electrode potential causes a variation of
faradaic current density via affection of both the strength of the
electric eld in the double layer and another variable, usually
surface coverage of adsorbed intermediate(s) [30]. In electro-
catalytic reactions, the inductive behavior takes place when the
faradaic current is governed by the occupation of an intermedi-
ate state, which decreases when the applied potential increases
[29].
The Nyquist diagram of NCGC electrodes in l-lysine solu-
tion represented two depressed capacitive semicircles. The high
frequency semicircle was related to the combination of charge
transfer resistance of transition of Ni(II)/Ni(III) redox couple in
the presence of l-lysine and the double layer capacitance. The
low frequency semicircle was related to the adsorption of reac-
tion intermediate on the electrode surface. The equivalent circuit
compatible with the Nyquist diagram recorded in the presence
of l-lysine was depicted in Scheme 4. CPE
ads
and R
ads
are the
electrical elements related to the adsorption of reaction inter-
mediate(s). Because the electrocatalytic oxidation of l-lysine
depicted capacitive semicircle in the Nyquist diagram, it can be
Scheme 4.
Scheme 5.
deduced that reaction intermediate(s) of electrocatalytic oxida-
tion of l-lysine on NCGC electrode must be quite different in
their adsorption nature (mode of adsorption, charge of adsorbed
species, type of adsorbed atom, etc.) fromthat for alanine and/or
the electrocatalytic oxidation of the amino acids that take place
via different rate-limiting steps.
Nyquist diagrams of NCGC electrode in glycine and l-
phenylalanine solutions represented quite different patterns with
respect to the other amino acids. The equivalent circuit compati-
ble withthe Nyquist diagramrecordedinthe presence of l-lysine
was depicted in Scheme 5. Nyquist diagrams at high frequencies
represented a capacitive semicircle related to the combination
of charge transfer resistance of transition of nickel species in the
presence of glycine and l-phenylalanine and the double layer
capacitance. However, the diagrams represented negative differ-
ential resistance and rolled over the real axis at low frequencies
and went to the second quadrant. In this electrical equivalent cir-
cuit CPE
1
and R
1
<0 are the electrical elements describing the
low frequency response. The diagram crossed the negative real
axis at some nite frequencies (hiddennegative differential resis-
tance) indicating a dynamic instability of the stationary state.
This negative impedance is characteristic of systems capable of
exhibiting galvanostatic potential oscillation [31].
4. Conclusion
This work presented the preparation and usefulness of a
modied electrode consisting of nickel ions loaded into a
poly-Nicurcuminmatrixandelectrodepositedina solutioncon-
taining Nicurcumin complex on GC electrode. The electrode
was electro-catalytically active around 400 mV/Ag, AgCl where
the GC electrode possessed no activity. Chronoamperometric
works showed a large anodic current at the oxidation potential
of low valence nickel in further support of the mediated electro-
oxidation. The values for the catalytic rate constant and electron
transfer coefcient for oxidation and diffusion coefcient were
obtained for some amino acids. The different impedance behav-
iors for different amino acids revealed that the amino acids
oxidized on the modied surface via different mechanisms and
rate-limiting steps.
S. Majdi et al. / Electrochimica Acta 52 (2007) 46224629 4629
Acknowledgements
The authors gratefully acknowledge the support of this work
by Research Council of K.N. Toosi University of Technology
and University of Tehran. The authors are also grateful to Miss
G. Ghafourifar, Miss Z. Jabbari and Dr. F. Ricks for their fruitful
collaboration.
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