Bioelectrochemistry 85 (2012) 44–49

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Bioelectrochemistry
journal homepage: www.elsevier.com/locate/bioelechem

A novel voltammetric sensor for amoxicillin based on nickel–curcumin complex

modified carbon paste electrode
Reza Ojani ⁎, Jahan-Bakhsh Raoof, Saeed Zamani
Electroanalytical Chemistry Research Laboratory, Faculty of Chemistry, University of Mazandaran, Babolsar, Iran

a r t i c l e i n f o a b s t r a c t

Article history: The electrocatalytic oxidation of amoxicillin was investigated on a nickel-based (Ni(II)–curcumin) chemically
Received 1 January 2011 modified electrode. This modified electrode was prepared by electropolymerization of complex (curcumin =
Received in revised form 16 November 2011 1,7-bis[4-hydroxyl-3-methoxyphenyl]-1,6-heptadiene-3,5-dione) in alkaline solution. For the first time, the
Accepted 28 November 2011
catalytic oxidation of amoxicillin was demonstrated by cyclic voltammetry, chronoamperometry, chronocou-
Available online 7 December 2011
lometry and amperometry methods at the surface of this modified carbon paste electrode. The obtained re-
Keywords:
sults showed that NiOOH acts as an electrocatalyst for oxidation of amoxicillin. This electrocatalytic
Carbon paste electrode oxidation exhibited a good linear response for amoxicillin concentration over the range of 8 × 10 −6–
Curcumin 1 × 10−4 M with a detection limit of 5 × 10−6 M. Therefore, this electrocatalytic method was used as a simple,
Amoxicillin selective and rapid method able to determine amoxicillin in pharmaceutical preparations and biological
Electrocatalytic oxidation media.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction fluids [15,16]. The advancements in electrochemical techniques in

Antibiotics of the β-lactam group are important antimicrobial
agents that are widely used to treat human and animal infectious dis-
eases, on the one hand, and to increase agricultural products, on the
other. Amoxicillin (Scheme 1) is the only phenolic penicillin and a
spectrum β-lactam antibiotic. β-Lactam antibiotics present a struc-
ture based on a β-lactam ring which is responsible for the antibacter-
ial activity and variable side chains that explain the major differences
in their chemical and pharmacological properties. It is usually chosen
because it is better absorbed, following oral administration, than
other β-lactam antibiotics [1–3].
Various analytical methods have been reported for the separation
and determination of amoxicillin based on spectroscopy [4–7], capillary
electrophoresis [8,9], high-performance liquid chromatography [10–12]
and electrochemical methods [13,14]. In spite of the fact that HPLC has
been the widely-used technique to determine this group of drugs, it suf-
fers from some disadvantages, such as necessity to a large amount of
high purity organic solvents, long equilibration and derivation treat-
ment. Moreover, the low solubility of amoxicillin in the organic solvents
makes it challenging to develop procedures based on the extraction and
pre-concentration steps.
Electrochemical techniques have shown to be excellent proce-
dures for the sensitive determination of organic molecules, including
drugs and related molecules in pharmaceutical sample and biological
⁎ Corresponding author.
E-mail address: fer-o@umz.ac.ir (R. Ojani).
drug analysis are attributed to their simplicity, low cost, and relatively
short time of analysis, compared with the other techniques. As a
result, sample preparation usually consists of dissolving the pharma-
ceutical sample in a suitable solvent and performing a direct analysis
on an aliquot of this solution.
Modified electrodes can be prepared by deposition of various mate-
rials, such as organic compounds, conducting polymers, metal oxides,
etc. on various electrode surfaces. In recent years, electrodes coated
with metallated electroreactive polymers have attracted increasing at-
tention [17]. Indeed, recent studies on developing new electrode mate-
rials concentrated on the use of macrocyclic complexes in the form of
immobilized complexes that behave as fast electron-transfer mediators
for solution species. Although electrochemistry and electrocatalytic
properties of macrocyclic complexes of some transition metals have
been well studied [18], few data about their behavior as electropoly-
merized films in aqueous alkaline solution exist. Recently, it has been
shown that nickel macrocyclic complexes can be easily electropolymer-
ized onto an electrode surface to form modified electrodes that cata-
lyzed oxidation of several substrates [19–21]. Chemically modified
electrodes with nickel compounds were also developed by deposition
of nickel metal, nickel oxide, or nickel complexes on a traditional elec-
trode surface via chemical, electrochemical, or physical routes [22–26].
Previously, we used the metal–polymer modified carbon paste elec-
trode for electrocatalytic oxidation of some biological compounds
[27,28] and methanol [29,30]. The results of these studies were promis-
ing, showing that metal–polymer modified carbon paste electrodes
have some advantageous properties. They are easy to prepare, they re-
main stable for a long time with high reproducibility. Further, they have

1567-5394/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.bioelechem.2011.11.010
 R. Ojani et al. / Bioelectrochemistry 85 (2012) 44–49
Scheme 1. Oxidation reaction of amoxicillin.
detection limits as well as wide linear range responses. All these results
encouraged us to pursue the inquiries with new polymer materials.
According to our knowledge, electrocatalytic oxidations of amoxicillin
have not been reported in the literature by any catalyst. In this work,
we decided to combine the above mentioned advantageous features
again for the aim of electrocatalytic oxidation of amoxicillin by prepar-
ing the nickel–curcumin complex modified carbon paste electrode (Ni/
CR/CPE). Also, the study aimed at examining the applicability of this
modified electrode to determine amoxicillin in some real samples.
2. Experimental
2.1. Reagents and materials
The curcumin, sodium hydroxide, nickel chloride, and ammonia so-
lution, used in this work were of analytical grade from Merck and used
without further purification. To prepare the [Ni(NH3)4] 2+ complex,
NiCl2 (4 mM) was dissolved in 25% ammonia solution with NH3 as a
complex agent of the Ni(II) ion. All solutions were prepared with doubly
distilled water. High viscosity paraffin (density: 0.88 g cm−3) from
Fluka was utilized as the pasting liquid for the carbon paste electrode.
Graphite powder (particle diameter: 0.10 mm) from Merck was utilized
as the working electrode (WE) substrate. All other reagents were of an-
alytical grade. Amoxicillin capsules were prepared from Zakaria Tabriz
Pharmaceutical Co., Tehran, Iran.
2.2. Sample preparation
In order to analyze the capsules, the average mass of three capsules
was calculated. The capsules were finely powdered and homogenized in
a mortar. An appropriate, accurately-weighed amount of the homoge-
nized powder was transferred into a 100 ml calibrated flask containing
50 ml of 0.1 M sodium hydroxide solution. The contents of flask were
sonicated for 10 min; the undissolved excipients were removed by fil-
tering and then diluted to volume with the same supporting electrolyte.
Appropriate solutions were prepared by taking suitable aliquots of the
clear filtrate and diluting them with 0.1 M sodium hydroxide.
2.3. Instrumentation
Electrochemical experiments were carried out on 746VA Trace
Analyzer Metrohm potentiostat with a Metrohm voltammetry cell
in a three-electrode configuration. An Ag/AgCl saturated KCl elec-
trode, carbon paste electrode and a platinum wire were exploited as
reference, working and auxiliary electrodes, respectively.
45
2.4. Preparation of modified working electrode
A mixture of graphite powder and paraffin was blended by hand
mixing with a mortar and pestle for preparation of carbon paste.
The resulting paste was then inserted in the bottom of a glass tube
(internal radius: 1.7 mm). The electrical connection was implemen-
ted by a copper wire lead fitted into the glass tube. A fresh electrode
surface was generated rapidly by extruding a small plug of the paste
with a stainless steel rod and smoothing the resulting surface on
white paper until a smooth shiny surface was observed. In order to
prepare nickel–curcumin complex modified carbon paste electrode
as working electrode, it was placed in 0.1 M NaOH containing
10 mM curcumin and 4 mM Ni(II)–ammonia complex and the elec-
trode potential was cycled between 0 and 700 mV at a scan rate of
100 mV s −1 for 60 cycles in a cyclic voltammetry regime. After the
modification procedure, the electrode was thoroughly rinsed with
0.1 M NaOH and cycled between 200 and 800 mV until a reproducible
cyclic voltammogram was obtained. This experiment was conducted
in a solution containing an excess amount of curcumin to complete
the Ni–CR complex formation.
3. Result and discussion
3.1. Preparation and properties of the Ni–curcumin electrode
The formation and growth of an electropolymerized film of Ni–
curcumin on the carbon paste electrode (Ni/CR/CPE) using multiple
scan cyclic voltammetry in a 0.1 M NaOH solution are depicted in
Fig. 1. In the preliminary stages of potential cycling (Fig. 1, inset), an
irreversible peak appears which is due to curcumin oxidation. After
around 10 potential cycling, a pair of peaks appears which indicates
the formation of an electroreactive film formed on the surface and
the corresponding currents rise during further cycling. The voltam-
mograms exhibited a continuous increase of the peak current intensi-
ties, indicating a progressive deposition of the electroactive material,
which forms a film as a result of the anodic electropolymerization of
the curcumin complex. A number of well-defined peaks observed in
both the anodic and cathodic half cycles were attributed to the
Ni(II)–CR/Ni(III)–CR transition. The cyclic voltammograms of the Ni/
CR film are consistent with previous studies of the electrochemical
behavior assigned to the Ni(II)/Ni(III) process in GC electrode [22].
Fig. 1. Consecutive cyclic voltammograms of 0.1 M NaOH solution containing 10 mM
curcumin and 4 mM [Ni(NH3)4]2+ complex using a carbon paste electrode. Potential
sweep rate was 100 mV s−1. The cycle number increases from inner to outer (1, 15,
20, 25, 30, 35, 40, 45, 50, 55 and 60). Inset: first cycle in the main panel.
46 R. Ojani et al. / Bioelectrochemistry 85 (2012) 44–49
Fig. 2. Electrochemical responses of electrodes: a) CR/CPE and b) Ni/CR/CPE, in 0.1 M
NaOH solution, scan rate 10 mV s−1.
The oxidation (Epa = 0.47) and reduction (Epc = 0.27) peaks did not
change in further potential cycling. The modified electrode was stable
in alkaline media. The inert and stable complex of Ni(II)/CR in alkaline
solution was reported previously [31]. In these polymeric nickel-
based complexes, nickel oxyhydroxide species act as redox mediator
center in many electrooxidation processes [32,33].
The surface coverage of the immobilized active substance Ni/CR in
the films can be evaluated from the charge under the current–poten-
tial wave (Fig. 2b) with correction for the baseline (Γ⁎ = Q/nFA). The
value of Γ⁎ for Ni/CR/CPE was 5.2 × 10 −7 mol cm −2.
Fig. 3 shows the scanning electron micrograph of CPE (Fig. 3a), CR/
CPE (Fig.3b) and Ni/CR/CPE (Fig. 3c). Comparing the SEM of three
electrodes shows that the surface of Ni/CR/CPE was completely cov-
ered with nickel hydroxide micro particles.
Fig. 4 shows the cyclic voltammograms of Ni/CR in 0.1 M NaOH so-
lution at different potential sweep rates in a wide range of
10–400 mV s −1. As it is seen, the peak-to-peak separation potential
(ΔEp = Epa − Epc) of the cyclic voltammograms increased with scan
rate. For ΔEp > 200/n mV, commonly obtained at higher scan rates,
the following relations were proposed by Laviron [34]:
0
Epa ¼ E þ Aln½1−α=m ð1Þ
0
Epc ¼ E þ Bln½α=m ð2Þ
LnKs ¼ αlnð1–α Þ þ ð1–α Þlnα−lnα–lnðRT=nFν Þ–α ð1–α ÞnFΔEp =RT ð3Þ
Fig. 3. Scanning electron micrograph (SEM) of: a) CPE, b) CR/CPE and c) Ni/CR/CPE.
Fig. 4. Main panel: Cyclic voltammograms of Ni/CR/CPE in 0.1 M NaOH solution. Poten-
tial sweep rates from inner to outer are: 10, 20, 30, 40, 50, 80, 100, 150, 200, 300 and
400 mV s−1. Inset: Plot of Ep vs. log ν for cyclic voltammograms depicted in the main
panel.
where A = RT / (1 − α)nF, B = RT / αnF and m = (RT/F)(Ks/nv). Epa and
Epc are the anodic and cathodic peak potentials, respectively, and α,
Ks, and ν are the electron-transfer coefficient, apparent charge-
transfer rate constant, and potential sweep rate, respectively. From
these expressions it is possible to determine the transfer coefficient
(α) by measuring the variation of the peak potentials with scan rate
and Ks can be determined for electron transfer between the electrode
and the surface-deposited layer by measuring the ΔEp values. A plot
of Ep versus log ν yields two straight lines with slopes equal to
2.3RT/αnF and 2.3RT/(1 − α)nF for the cathodic and anodic peaks, re-
spectively. The inset of Fig. 4 shows the plot of Ep versus log ν with
slopes equal to 0.125 and 0.095 for anodic and cathodic peaks.
Using the slopes of plots, the value of α was specified as 0.42. This
value suggests that the activation energy for the reduction and oxida-
tion processes might be the same. Moreover, the mean value of Ks
was determined to be 4.5 s −1. The relatively large value of the elec-
tron transfer rate constant indicates a high ability promoting elec-
trons between Ni(II)–curcumin and the electrode surface [35].
Another point in these voltammograms is that anodic and cathodic
peak currents are linearly proportional to the potential sweep rate at
low values from 10 to 80 mV s−1 (not shown). This can be attributed
to an electrochemical activity of an immobilized redox couple at the
surface. In the higher range of potential sweep rates (100–400)
mV s −1, the peak currents depend on square root of the potential
sweep rate (not shown), signifying the dominance of a diffusion process
as the rate limiting step in the total redox transition of the modifier film.
This limiting diffusion process was also reported for other Ni-modified
electrodes [36].
 R. Ojani et al. / Bioelectrochemistry 85 (2012) 44–49
Fig. 5. Electrochemical responses of CR/CPE: a) 0, b) 0.1 mM amoxicillin and Ni/CR/CPE
to: c) 0 and d) 0.1 mM amoxicillin in 0.1 M NaOH solution, scan rate 10 mV s−1.
3.3. Electrocatalytic oxidation of amoxicillin on the modified electrode
3.3.1. Cyclic voltammetry studies
In this work, the oxidation of amoxicillin was first studied at a CR/
CPE electrode (without the incorporation of nickel) by cyclic voltam-
metric experiments in 0.1 M NaOH. Typical results obtained for a poten-
tial scan from 0.2 to 0.8 V vs. Ag/AgCl at potential scan rate of 10 mVs −1
are displayed in Fig. 5. The electrochemical response of CR/CPE in the
absence of amoxicillin is exhibited in Fig. 5(a); the addition of 0.3 mM
amoxicillin to the alkaline solution causes no effect on the electrochem-
ical response of the CR/CPE (Fig. 5(b)) for analytical. The electrochemi-
cal response of a Ni/CR/CPE in alkaline solution (i.e., 0.1 M NaOH)
exhibits well defined anodic and cathodic peaks (Fig. 5(c)) associated
with the Ni(OH)2/NiOOH redox couple. As it is seen (Fig. 5(d)), after
adding amoxicillin (0.1 mM) there is an increase in the anodic peak cur-
rent and a decrease in the cathodic peak current. This behavior is typical
of that expected for the mediated oxidation (EC′ mechanism) as follows
[37,38]:
The Ni/CR/CPE can catalyze the electrooxidation of amoxicillin due
to the existence of Ni(OH)2 in the curcumin film. Cyclic voltammograms
of the Ni/CR/CPE in the presence of 0.5 mM amoxicillin at various scan
rates were recorded (Fig. 6A). With increasing scan rate, the peak
Fig. 6. (A) cyclic voltammograms of the Ni/CR/CPE in 0.1 M NaOH solution containing 0.5 mM amoxicillin at the scan rates: a)20, b) 40, c) 60, d) 80, and e) 100 mV s−1, respectively.
(B) Variations of Ipa vs. v1/2. (C) Dependence of the peak potential, Ep on log v for the oxidation of amoxicillin at Ni/CR/CPE.
47
Fig. 7. Chronoamperograms obtained at the Ni/CR/CPE in the a) absence and presence
of b) 0.1, c) 0.6, d) 1.1 and e) 2 mM of amoxicillin in 0.1 M NaOH solution, first and sec-
ond potential steps were 0.57 and 0.30 V vs. Ag/AgCl, respectively. Inset (A) depen-
dence of Q (μC) vs. t, (a′) and (e′) respectively derived from the data of
chronoamperograms of (a) and (e). Inset (B): dependence of IC/IL on t1/2 derived
from the data of chronoamperogams of (a) and (e) in the main panel.
potential for the catalytic oxidation of amoxicillin shifts to increasingly
positive potentials, suggesting a kinetic limitation in the reaction be-
tween the redox sites of the Ni/CR/CPE and amoxicillin. Alternatively,
simpler explanation of this shift might be due to ohmic drop,
ΔE = IpaR, where R is the resistance and Ipa is the anodic peak current.
Also, as it can be seen at higher potential scan rates, the cathodic peak
current relating to Ni(III) reduction to Ni(II) appears which confirms
EC′ mechanism. Fig. 6B shows that the oxidation current for amoxicillin
increased linearly with the square root of the scan rate, suggesting that
the reaction is mass transfer controlled.
3.3.2. Chronoamperometric studies
Double potential step chronoamperometry was employed to in-
vestigate the electrochemical processes at Ni/CR/CPE. The main
panel of Fig. 7 represents the current–time profiles obtained by set-
ting the working electrode potential at 0.57 V (first potential step)
and 0.3 V (second potential step) for various concentrations of amox-
icillin. The forward and backward potential step chronoamperometry
of the modified electrode in the blank solution showed an almost
symmetrical chronoamperogram with almost equal charges con-
sumed for the oxidation and reduction of Ni(OH)2/NiOOH sites.
48 R. Ojani et al. / Bioelectrochemistry 85 (2012) 44–49

Fig. 9. Typical amperograms a) 10 mL NaOH solution (0.1 M) and 1 mL of capsule sam-

ples solution, the other amperograms show the current response for the indicated vol-
ume of 10−4 M amoxicillin standard solution added.

was I (μA) = 381.92 C (μM) + 2.408 with correlation coefficient of

Fig. 8. Main panel: Typical amperograms showing the current response for successive
added volumes of 5 mM solution of amoxicillin in 0.1 M NaOH solution. Inset: Varia-
tion of amperometric current vs. amoxicillin concentration.
However, in the presence of amoxicillin, the charge value associated
with the forward chronoamperometry, Q, is greater than that ob-
served for the backward chronoamperometry (Fig. 7, inset A). The
rate constant for the chemical reaction between the amoxicillin and
redox sites of Ni/CR/CPE can be evaluated by chronoamperometry
according to the method described in the literature [39].
h
 i
1=2 1=2 1=2 1=2
IC =I L ¼ γ π erf γ þ expð−γÞ=γ
where IC is the catalytic current of amoxicillin at the surface of Ni/CR/
CPE, IL is the limiting current in the absence of amoxicillin and
γ = kcot (co is the bulk concentration of amoxicillin) is the argument
of the error function. In the cases where γ exceeds 1.5, the error func-
tion is almost equal to 1 and the above equation can be reduced to:
1=2 1=2 1=2 1=2
IC =I L ¼ γ π ¼π ðkco t Þ
where k, co and t are the catalytic rate constant (cm 3 mol −1 s −1),
amoxicillin concentration (mol cm −3) and time elapsed (s), respec-
tively. From the slope of the IC/IL vs. t 1/2 plot we can simply calculate
the value of k for a given concentration of substrate. Inset (B) of Fig. 7
shows one such plot, constructed from the chronoamperogram of the
Ni/CR/CPE in the absence and presence of 2 mM amoxicillin. The
mean value for k was found to be 2.44 × 10 6 cm 3 mol −1 s −1 which is
comparable with k of other catalytic processes [20].
3.3.3. Electrocatalytic determination of amoxicillin
In order to enhance the sensitivity of the method (lowering the
detection limit), constant potential amperometry under hydrody-
namic conditions was used. Typical amperograms obtained at con-
stant potential of 570 mV, by successive addition of a 5 mM
standard amoxicillin solution to 10 ml alkaline media (0.1 M NaOH)
are shown in Fig. 8. As seen in inset Fig. 8, the dynamic range with
this technique was obtained (8 × 10 −6 to 1 × 10 −4 M) and the detec-
tion limit decreased to 5 × 10 −6 M. Equation of calibration curve
0.9991.
The applicability of the proposed amperometric method was ex-
amined by analyzing the capsules and urine sample. The recovery of
amoxicillin was measured by spiking amoxicillin into highly diluted
urine sample and the standard addition method was used to analyze
the prepared samples. The quantity of experimentally determined
amoxicillin was compared to that of the reported amoxicillin in cap-
sules, on the one hand, and to that of the spiking in urine sample.
The results are summarized in Table 1. Typical example of ampero-
grams is shown in Fig. 9 for capsule.
3.3.4. Effect of electroactive interferences
ð6Þ The detection of amoxicillin is an important task in many biologi-
cal studies. The interferences of some electroactive compounds com-
monly present in physiological samples can prevent accurate
determination of amoxicillin concentration. Fig. 10 exhibits the cur-
rent responses of the Ni/CR/CPE to successive additions of 7 μM
amoxicillin (AMO) and 7 μM of common interfering species (ascorbic
acid (AA), uric acid (UA), and dopamine (DA)) under the optimized
experimental condition. Compared to the response for amoxicillin,
ð7Þ the current generated due to the interfering species is negligible, indi-
cating high selectivity of the sensor.
3.3.5. The electrode stability, repeatability and reproducibility
To verify the durability and long-term stability of Ni/CR/CPE, 50
consecutive cyclic voltammograms using this electrode were
recorded in 0.1 M NaOH solution (data not shown). It was found
that the peak currents changed slightly (b5%). In addition, the elec-
trode was stored in 0.1 M NaOH solution when it was not in use
and retained its electroactivity for 4 weeks. To investigate the repeat-
ability of electrode, the Ni/CR/CPE was applied to the 7 parallel deter-
minations of 1.0 × 10 −5 M amoxicillin and the relative standard
deviation (RSD) was calculated as 3.9%. Further, under the same and
independent conditions, it was found that the electrocatalytic oxida-
tion currents of 4.0 × 10 −5 M amoxicillin almost remained the same

Table 1
Determination and recovery of amoxicillin in commercial capsules and urine sample.

Sample Amount Amount Amount Recovery RSD (%)

labeled added found (%) (n = 3 )

Capsule 200 mg – 196 mg 98 1.22

Capsule 500 mg – 515 mg 103 2.10
Fig. 10. Amperometric response of Ni/CR/CPE kept at 0.57 V for the sequential addition
Urine – 20 μM 21.12 μM 105.1 1.51
of 7 μM amoxicillin, AA, UA, DA, and amoxicillin, in 0.1 M NaOH solution.
 R. Ojani et al. / Bioelectrochemistry 85 (2012) 44–49
by seven Ni/CR/CPEs with a R.S.D. of 3.7%, indicating a high
reproducibility.
4. Conclusion
A carbon paste electrode modified with Ni–curcumin complex was
examined for electrooxidation of amoxicillin in alkaline medium.
Using cyclic voltammetry and chronoamperometry techniques, the
kinetical parameters, such as charge-transfer coefficient and catalytic
reaction rate constant, were determined. The value of the rate con-
stant (k) obtained from the chronoamperometric method indicated
that the modified electrode can overcome the kinetic limitations for
amoxicillin oxidation by a catalytic process and can decrease the
overpotential for the oxidation reaction. According to the experimen-
tal results, the catalytic oxidation current of amoxicillin at this elec-
trode can be used to determine amoxicillin in aqueous solution, so
an acceptable linear dynamic range and detection limit can be
obtained. An amperometric method was proposed for the determina-
tion of amoxicillin with good sensitivity and selectivity in pharma-
ceutical preparations and biological media.
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