Analytica Chimica Acta 765 (2013) 7076

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Analytica Chimica Acta

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Sensitive voltammetric determination of paracetamol by poly

(4-vinylpyridine)/multiwalled carbon nanotubes modied glassy
carbon electrode
Hanieh Ghadimi, Ramin M.A.Tehrani, Abdussalam Salhin Mohamed Ali,
Norita Mohamed, Sulaiman Ab Ghani
Pusat Pengajian Sains Kimia, Universiti Sains Malaysia, 11800 USM, Pulau Pinang, Malaysia

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 A P4VP/MWCNT modied glassy car-

bon electrode was fabricated and
characterized.
 The electrode was useful for determi-
nation of paracetamol.
 At optimum conditions, ascorbic acid
and uric acid did not interfere in the
electrode activity.
 The electrode exhibited good sensi-
tivity, reproducibility and stability.
 The electrode was used for the
determination of paracetamol in for-
mulation tablets and urine samples.

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

Article history: A novel glassy carbon electrode (GCE) modied with a composite lm of poly (4-vinylpyridine) (P4VP)
Received 15 October 2012 and multiwalled carbon nanotubes (P4VP/MWCNT GCE) was used for the voltammetric determination
Received in revised form of paracetamol (PCT). This novel electrode displayed a combined effect of P4VP and MWCNT on the
15 December 2012
electro-oxidation of PCT in a solution of phosphate buffer at pH 7. Hence, conducting properties of P4VP
Accepted 20 December 2012
along with the remarkable physical properties of MWCNTs might have combined effects in enhancing
Available online 7 January 2013
the kinetics of PCT oxidation. The P4VP/MWCNT GCE has also demonstrated excellent electrochemical
activity toward PCT oxidation compared to that with bare GCE and MWCNT GCE. The anodic peak currents
Keywords:
Paracetamol
of PCT on the P4VP/MWCNT GCE were about 300 fold higher than that of the non-modied electrodes.
Multiwalled carbon nanotubes By applying differential pulse voltammetry technique under optimized experimental conditions, a good
Poly (4-vinylpyridine) linear ratio of oxidation peak currents and concentrations of PCT over the range of 0.02450 M with
Voltammetric determination a limit of detection of 1.69 nM were achieved. This novel electrode was stable for more than 60 days
and reproducible responses were obtained at 99% of the initial current of PCT without any inuence of
physiologically common interferences such as ascorbic acid and uric acid. The application of this electrode
to determine PCT in tablets and urine samples was proposed.
2012 Elsevier B.V. All rights reserved.

1. Introduction

Drug analysis plays a major role in the quality control of drug

formulations which has great impact on public health. A simple,
sensitive and accurate method to determine the active ingredi-
Corresponding author. Tel.: +60 4 6534030; fax: +60 4 6574854. ents in drugs seems essential [1]. Paracetamol (PCT) is an analgesic
E-mail address: sag@usm.my (S. Ab Ghani). drug which is extensively used to alleviate headaches, backache

0003-2670/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.aca.2012.12.039
 H. Ghadimi et al. / Analytica Chimica Acta 765 (2013) 7076
and postoperative pain [2]. PCT was rst synthesized in the late
nineteenth century and it is considered to possess analgesic and
antipyretic properties [3]. Taking high doses of PCT may cause
adverse effects in the body, although in proper doses it does
not display any side effects. Nowadays, PCT is widely used for
its remarkable therapeutic characteristics thus precise determina-
tion and control of its quality is vital [4]. Various methods have
been used to determine PCT in pharmaceutical formulations and
biological uids comprising electro-analytical [5,6], spectropho-
tometry [7], liquid chromatography [8] capillary electrophoresis,
infra red spectroscopy [9] and HPLC methods [10,11]. Most of these
methods are tedious, troublesome and require pre-treatment of
samples. Development of a new drug essentially requires analyt-
ical chemistry during synthesis as well as in the production stages.
Electroanalytical methods are more preferred mainly because of
their simplicity, low cost, and applicability [1,12]. The selectivi-
ties of these methods are usually high as the analyte can be easily
traced by its standard potential. The features and benets of mod-
ied glassy carbon electrodes (GCE) in the manufacturing of ion
sensors and biosensors and their electro-analytical applications
have been reported [2,13]. However, carbon nanotube (CNTs) elec-
trodes are nowadays more widely used to manufacture ion-sensors
and biosensors [14,15]. This is by virtue of its superior structural
properties as compared to the GCE such as high electrical con-
ductivity, chemical stability, mechanical strength, minimal errors,
overvoltage defects, faster electron transfer properties and higher
sensitivity. But the poor solubility of CNT is a major disadvan-
tage which hinders their applicability. Different types of modied
CNT electrodes such as paste [16], lm-coated [1], and conduct-
ing polymer/CNT [17,18] have been thoroughly investigated. The
non-covalent and covalent methods to prepare conducting poly-
mer/CNT electrodes are performed to enhance CNTs dispersion and
3D orientation in aqueous solutions [19,20]. The simplest route
among the non-covalent methods is polymer wrapping. This has
remarkably improved electrical, thermal, physical, chemical and
conductive properties of the conducting polymer/CNT electrodes
as in the analysis of PCT [2,16]. Poly 4vinylpyridine (P4VP) is a one
of the conducting polymers extensively studied for this purpose
[21,22]. The main advantage of P4VP in the P4VP/CNT nanocom-
posite electrodes is that besides being an electrical conductor, it is
also a redox polymer [23,24].
The objective of the current research is to develop a simple,
highly sensitive and accurate method to determine PCT using
P4VP/MWCNT modied GCE (P4VP/MWCNT GCE) based on the
voltammetric signals of PCT. Favorable electrode performance is
described in the following sections.
2. Experimental
2.1. Instrumentation
Electrochemical measurements were conducted using the elec-
trochemical workstation BAS Epsilon 2000 (Bioanalytical system,
USA). A three-electrode system consisted of a platinum wire as
an auxiliary electrode and an Ag/AgCl (3 M NaCl) as a refer-
ence electrode. The working electrode was either unmodied GCE
or GCE modied with P4VP/MWCNT. Unless otherwise stated,
all potentials were obtained against the reference electrode.
Impedance measurements were performed using EG&G FRD 100
(Princeton Applied Research, USA). The results of electrochemical
impedance spectroscopy (EIS) were analyzed by using Zsimp Win
3.22 software. The surface and quantitative morphologies of the
P4VP/MWCNT GCE were studied using a eld emission scanning
electron microscope (FESEM) model Leo Supra 50 VP (Oxford INCA
400, UK) and the energy-ltering transmission electron microscope
71
(EFTEM) LIBRA 120 equipped with an Olympus SIS ITEM Version 5.0
(build 1243) (Carl Zeiss, Germany).
2.2. Materials
PCT (SigmaAldrich, USA) and MWCNT (Chengdu Organic
Chemicals, China) were used as received. All other chemicals (E.
Merck, Germany) were of analytical grade and used without fur-
ther purication. A stock solution of 0.001 M PCT was prepared by
dissolving PCT in water and stored in a refrigerator until further
use. A 0.1 M phosphate buffer (pH 7) was prepared by mixing stock
solutions of K2 HPO4 and KH2 PO4 .Various standard solutions of PCT
were prepared by dilution of the stock solution with the buffer solu-
tion. All solutions were freshly prepared with pure water (18.2 M
cm) from Milli-Q plus (Millipore, USA). PCT tablets were purchased
from a local pharmacy.
2.3. MWCNTs purication and electrode preparation
The MWCNT was puried using the following procedure: rstly,
it was puried by sonication in 6 M HCl for 4 h. Then, 50 mg of
puried MWCNT was sonicated in a 40 mL mixture of H2 SO4 /HNO3
(V:V = 3:1) in a water bath at 40 C for 6 h. After cooling off to ambi-
ent temperature, the MWCNT was centrifuged, collected and later
washed with pure water until neutral. The nal solid was then dried
to a constant weight. A liquid phase blending method was used
to make a thin lm composite. The modied electrode was fab-
ricated as follows; rst the GCE was polished with alumina then
rinsed thoroughly with water/ethanol (V:V = 2:1), cleaned in an
ultrasonic bath with water and nally rinsed with deionized water.
The clean GCE was then dried in ambient temperature. The mix-
ture of P4VP and MWCNT in a weight ratio of 2: 4 was dispersed
in 1 mL DMF for 3 h in an ultrasonic bath. The P4VP/MWCNT GCE
was prepared by a drop casted method. A 10 L of P4VP/MWCNT
dispersion (1.0 mg mL1 ) was dropped onto the surface of GCE and
dried at 25 5 C. The resulting P4VP/MWCNT GCE was then used
for further experiments.
2.4. Procedure
The experiments were carried out by studying the cyclic voltam-
metric behavior of the reagent in phosphate buffer (pH 7) as
supporting electrolyte and buffer at a potential range of 0.00.8 V.
The cyclic voltammogram (CV) was swept at scan rates between 10
and 300 mV s1 . Electrochemical impedance measurements were
performed in a 0.1 M KCL solution containing 5 mM Fe(CN)6 3/4
and the results were plotted as Nyquist plots with a frequency range
from 100 kHz to 100 mHz and AC voltage amplitude of 5 mV.
The DPV was performed with potentials from 0.0 V to 0.8 V,
a step potential of 2 mV, modulation amplitude of 50 mV and a
scan rate 10 mV s1 . Experiments were conducted at 25 5 C. All
potentials were measured against an Ag/AgCl (3 M NaCl) reference
electrode.
2.4.1. Determination of PCT in formulation tablets
The developed electrode was tested for the determination of PCT
in tablets. The tablets were weighed, ground into a powder, and
then dissolved in 25 mL of distilled water. The solution was trans-
ferred to a 50 mL volumetric ask and diluted with 0.1 M phosphate
buffer (pH 7). A portion of the resulting solution (25 mL) was then
taken out and served as the sample for the determination of PCT
using differential pulse voltammetry.
2.4.2. Determination of PCT in urine samples
The use of P4VP/MWCNT GCE is investigated for the measure-
ment of PCT in three human urine samples. Recovery tests were
72 H. Ghadimi et al. / Analytica Chimica Acta 765 (2013) 7076

Fig. 1. FESEM images of (a) MWCNT, (b) P4VP and P4VP/MWCNT in (c) low-magnication and (d) high-magnication, EFTEM images of P4VP/MWCNT in (e) low-magnication
and (f) high-magnication.

carried out by adding certain amounts of PCT standard solution
into the diluted urine samples of healthy specimens. A urine sam-
ple was collected 4 h after the introduction of a 500 mg PCT tablet.
The non-pretreated samples (250 mL) of the middle part are diluted
30 times with phosphate buffer (pH 7).
3. Results and discussion
The FESEM image of P4VP/MWCNT GCE indicates that the MWCNT
are densely covered by P4VP (Fig. 1c and 1d). The EFTEM images also
conrm these ndings (Fig. 1e and 1f). The P4VP in the nanocom-
posite appear to be distributed homogeneously throughout the
material and are adherent to the CNT surface. The P4VP appear as
dark spots embedded in the MWCNT matrix. These clearly reveal
the co-existence of P4VP along with MWCNT on the GCE.

3.1. Surface morphology studies 3.2. EIS studies

The FESEM images of MWCNT, P4VP and P4VP/MWCNT are The AC impedance spectra of bare GCE, MWCNT GCE,
shown in Fig. 1. The typical morphology of the well-aligned MWCNT P4VP/MWCNT GCE were also looked into. Fig. 2A shows Nyquist
and microspheres of P4VP are shown in Fig. 1a and 1b, respectively. plots of 5 mM Fe(CN)6 3/4 at these electrodes within the frequency
 H. Ghadimi et al. / Analytica Chimica Acta 765 (2013) 7076 73

Fig. 2. Nyquist plots of (a) MWCNT GCE, (b) P4VP/MWCNT GCE, (c) P4VP/GCE and
(d) bare GCE in 0.5 M KCl supporting electrolyte containing 5 mM Fe (CN)6 3/4 (A).
and (B) Randles equivalent circuit for the system.
range of 100 kHz to 100 mHz at the formal potential of the redox
probe. The almost straight line plots obtained implies the low
charge transfer resistance of the redox probe [25,26]. At high fre-
quencies, MWCNT GCE (curve a) experiences a sharp increase of
Zim and behaves closer to an ideal capacitor [27]. The slight vari-
ation from ideal capacitive behavior could be due to the pore size
distribution of MWCNTs [2830]. The P4VP/MWCNT GCE (curve
b) demonstrates a deviation from an ideal capacitor and shows a
much lower impedance than the pure MWNT GCE (curve a), P4VP
GCE (curve c) and bare GCE (curve d). The presence of a small and
depressed semicircle in curves a and b (more pronounced for the
bare GCE than the P4VP/MWNT GCE at higher frequencies) could
be due to the charge-transfer resistance (Rct ) of the electrodes. The
extended semicircle loop in the high to medium frequency region
displayed by the P4VP/GCE indicates the high Rct and Warburg ele-
ment (Zw ) of diffusion limitations as compared to the other two
electrodes. Fig. 2B is the Randles equivalent circuit from data t-
ted in the high frequency region. In this circuit, Rs and Q represent
solution resistance and a constant phase element corresponding
to the double-layer capacitance. It can be summarized that the
sequence of Rct is in the order of P4VP/MWNT GCE (23 ) < MWNT
GCE (25 ) < P4VP GCE (30 ) < GCE (1640 ). The P4VP/MWNT
GCE has a lower Rct which implies that the interfacial resistance has
decreased and the conductivity and the electron transfer process
has improved when P4VP is present in the nanocomposite modi-
ed electrode as compared to the other electrodes. Therefore, it can
be concluded that the nanocomposite P4VP/MWNT GCE benetted
from the synergistic effect of P4VP and MWNT as well as P4VP being
an electron mediator in the electron transfer process.
Fig. 3. CV obtained for the (a) bare GCE, (b) MWCNT and (c) P4VP/MWCNT GCE in
0.1 M phosphate buffer (pH 7) with a scan rate 20 mV s1 .
a sluggish rate of electron transfer. However, the P4VP/MWCNT
GCE displays well-dened redox peaks with Epa at 404 mV and Epc
at 307 mV. The peak separation (Ep ) 97 mV indicates a favorable
quasi-reversible electrode process (Fig. 4c). It is obvious that the
increase in peak currents is due to the huge increment in the area
of the electrode surface modied with P4VP and MWCNT.
Additionally, the composite lms with different mass ratios of
MWCNT and P4VP (at 2:4, 2:3, 1:1, 3:2 and 4:2) were fabricated.
Then the effects of these ratios on voltammetric responses of the
nanocomposite electrodes for the detection of PCT were investi-
gated (see Supplementary le Fig. 1).
3.4. Effects of solution pH
The effect of solution pH on the electrochemical response of
the P4VP/MWCNT GCE towards 100 M PCT was investigated using
CV (see Supplementary le Fig. 2). Variation of peak currents with
respect to pH of the electrolyte in the pH range of 2.58 is shown
in Fig. 5. It can be seen that the Ipa increases with solution pH until
the pH reaches 7. But, in Fig. 4 the Ipa of PCT in phosphate buffer
(pH 7) is higher than the reduction peak current, Ipc , indicating
the electrode process as one of quasi-reversible. Consequently, the
buffering at pH 7, which is near to the physiological pH, will be used
for the rest of the work. A small current was detected when the pH
of the solution was either lower or higher than 7. The broadening of

3.3. Electrochemical behavior of PCT.

At bare GCE (Fig. 3a) and in the absence of PCT only capacitive
current is exhibited and with poor electrochemical response. How-
ever, this current is more noticeable for the MWNT GCE (Fig. 3b)
and particularly for P4VP/MWCNT GCE (Fig. 3c) indicating that the
effective surface area of the P4VP/MWCNT GCE is larger than that
of MWNT GCE.
The electrochemical response of 100 M PCT in 0.1 M phosphate
buffer (pH 7) at three different electrodes have been studied by
using cyclic voltammetry (Fig. 4). The broad redox couple peaks Fig. 4. CV of 100 M PCT at the (a) bare GCE, (b) MWCNT and (c) P4VP/MWCNT GCE
of PCT at the bare GCE and MWCNT (Fig. 4a and b) could indicate in 0.1 M phosphate buffer (pH 7) at a scan rate 20 mV s1 .
74 H. Ghadimi et al. / Analytica Chimica Acta 765 (2013) 7076
Fig. 5. Effect of the pH on the anodic peak currents.
Scheme 1. The expected mechanism for PCT.
oxidation peaks, Epa , and decreasing of Ipa are observed with
increasing basicity, at pH higher than 7, suggesting a kinetically
less favorable reaction at higher pH. The effect of phosphate buffer
pH on Epa has been investigated in the mentioned range. The results
show that the Epa is shifted towards negative potentials with a
slope of 58 mV decade1 . A linear relationship of Epa (V) = 0.058
pH + 771.34 is obtained with (R = 0.994). The slope is very close to
the Nernstian value of 59 mV decade1 . This suggests that the
number of protons and electrons transferred in the redox reaction
of PCT are equal and likely to be two [31,32]. Thus, the mechanism
in Scheme 1 for oxidation of PCT is proposed [3135].
3.5. Effect of scan rate
The scan rate dependence of the modied electrode for 100 M
PCT is also investigated (Fig. 6). It is clear that the redox peak
currents at the P4VP/MWCNT GCE in the PCT solution increase
Fig. 6. (A) CV of 100 M PCT in 0.1 M phosphate buffer (pH 7) at P4VP/MWCNT GCE at scan rates 10, 20, 50, 100, 200, 300 mV s1 and (B) linear relationship of anodic and
cathodic peaks currents for 100 M PCT vs. square root of scan rate.
Fig. 7. Differential pulse voltammogram of 0.02, 0.04, 2, 10, 20, 50, 100, 200, 300,
450 M PCT in 0.1 M phosphate buffer (pH 7) at P4VP/MWCNT GCE. Inset: the cor-
responding calibration curve.
linearly as the scan rate increases from 10 to 300 mV s1 . In addi-
tion, Epa is shifted slightly to positive potentials while Epc is
negatively shifted. This could be due to changes in the electro-
catalytic activity and kinetic effect of P4VP/MWCNT GCE surface
on the oxidation of PCT especially at scan rates higher than
100 mV s1 . In other words, at scan rates higher than 100 mV s1
the time window for the PCT oxidation becomes very nar-
row, avoiding the facile electron transfer between substrate
and catalytic sites. The linear relationship between the peak
current and scan rate can be expressed by the linear regres-
sion equation as: Ipa /A = 26.10X + 211.26 /mV s1 (R = 0.997) and
Ipc /A = 32.76X 91.86 /mV s1 (R = 0.998), respectively. The
results indicate that the electrochemical reaction of PCT on the
P4VP/MWCNT GCE is a surface-controlled process [5,36].
3.6. Determination of PCT by differential pulse voltammetry
Differential pulse voltammetry is superior to cyclic voltammetry
because of its sensitivity, resolution and lower limit of detection.
Fig. 7 shows the differential pulse voltammogram (DPV) of dif-
ferent concentrations of PCT in 0.1 M phosphate buffer (pH 7)
with applied potentials of 00.8 V, step potential of 2.0 mV, mod-
ulation amplitude of 50 mV and a scan rate of 10 mV s1 . The
Ipa is linearly proportional to the concentration of PCT in the
 H. Ghadimi et al. / Analytica Chimica Acta 765 (2013) 7076 75

Table 1
Responses of some of PCT sensors constructed from various materials.

Electrode materials Technique Detection limit Linear range (M) Ref.

Carbon unic liquid electrode DPV 0.3 M 12000 [38]

Gold nanoparticle modied CPE DPV 0.0146 M 0.05270 [39]
Poly(thaurine)/MWCNT modied GCE DPV 0.5 M 1100 [2]
SWNT/DCP modied GCE SWV 0.04 M 0.120 [1]
SPE/PEDOT
DPV 1.39 M 4400 [40]
MWCNTs DPV 39.8 nM 0.074230 [13]
MWCNT BPPGE CV 45 nM 0.125 [41]
MWCNT BPPGE SWASV 10 nM 0.012 [41]
MWCNT/Li+ /Bi2 O3 composite modied GCE CV 0.74 M 0.52000 [33]
Poly (DA)/GC CV 0.0067 M 0.02500 [42]
MWCNT-l-Cys-Au/SAMs-CME Flow injection irreversible 1 M 21000 [43]
biamperometric
ETPG ATSDPV 0.0025 M 0.052.5 [6]
MWCNT/GCE CV 0.02 M 0.11000 [44]
Carbon paste electrode modied with CNT/Poly3(aminophenol) SWV 1.1 M 10100 [16]
GCE/MWCNT Polyhis DPV 32 nM 0.2510 [5]
P4VP/MWCNT GCE DPV 1.69 nM 0.02450 This work

Table 2
Determination of PCT in formulation tablets using P4VP/MWCNT GCE (n = 5).

Sample Content (M) Added (M) Found (M) RSD (%) Recovery (%)

1 81.45 0 80.9 1.42 99.3

2 81.45 10 90.03 1.52 98.4
3 81.45 20 100.66 1.51 99.2

Table 3
Determination of PCT in human urine samples using P4VP/MWCNT GCE (n = 3).

Sample Detected (M) Spike (M) Found (M) RSD% Recovery %

Urine 1 94.4 25 121.0 1.18 101.3

Urine 2 96.7 25 121.6 1.02 99.9
Urine 3 98.4 25 122.3 1.24 99.1

range of 0.02450 M. A linear equation of Ipa (A) = 1.778[PCT] P4VP/MWCNT GCE for oxidation of 100 M PCT in both synthetic
(M) + 75.839 with (R = 0.998), was obtained. The detection limit and real samples have also been studied. Long term stability is
of PCT at P4VP/MWCNT GCE is 1.69 nM which is superior to the obtained when the modied electrode is kept in 0.1 M phosphate
others (Table 1). buffer (pH 7) at 4 C when not in use.
The operational stability is retained at 99% of the initial current
3.7. Analysis of real samples when it is subjected under optimum conditions to approximately
400 cycles and more than 60 days of continuous use.
3.7.1. Determination of PCT in formulation tablets
The developed electrode is tested for the determination of PCT 3.9. Interference studies
in tablets. The recovery was obtained by using DPV to evaluate
the accuracy of the method. The relative standard deviation of this A sensor which is to be used in biological samples must be able to
method, based on ve replicates (n = 5), is presented in Table 2. discriminate between target analytes and interfering species such
Satisfactory recoveries of PCT at P4VP/MWCNT GCE in the range
of 0.02450 M revealed that this method is effective and reli-
able. These ndings indicate that the method is rapid and simple
for the selective and sensitive analysis of PCT in pharmaceutical
preparations.

3.7.2. Determination of PCT in urine samples

P4VP/MWCNT GCE is investigated for the measurement of PCT
in three human urine samples. The percentage of recovery of the
spiked sample is in the range between 99.1 and 101.3 (Table 3).
The results show that the modied electrode is suitable for the
determination of PCT in biological uids.

3.8. Reproducibility and stability of P4VP/MWCNT GCE

The electrode reproducibility was examined using CV over

seven electrodes constructed by the same procedure. A rela-
tive standard deviation (RSD) of the Ipa is 3.66% which indicates Fig. 8. CV of 100 M AA, 100 M UA and 100 M PCT at the (a) bare GCE, (b) MWCNT
good reproducibility. The operational and storage stabilities of the and (c) P4VP/MWCNT GCE in 0.1 M phosphate buffer (pH 7) at a scan rate 20 mV s1 .
76 H. Ghadimi et al. / Analytica Chimica Acta 765 (2013) 7076
as ascorbic acid (AA) and uric acid (UA) commonly present in physi-
ological environments. It is difcult to detect PCT in the presence of
AA and UA by electrochemical methods because they have nearly
the same redox potential ranges and comparable sensitivities on
the unmodied electrode [37]. The effects of AA and UA on the
measurement of PCT were investigated using cyclic voltammetry.
Fig. 8a and b indicates that Epa of a mixture of AA, UA and PCT is
inseparable at the bare GCE and MWCNT GCE. At the P4VP/MWCNT
GCE, the Epa of AA is close to that of UA at the same potential range.
The well-dened wave of PCT was obtained at the P4VP/MWCNT
GCE with good separation from AA and UA. The anodic peak poten-
tials of AA, UA and PCT were 290, 300 and 404 mV respectively. This
indicates that the voltammetric determination of PCT in biological
samples is devoid of any interference from AA and UA.
4. Conclusions
A new electrode based on P4VP/MWCNT GCE is prepared, char-
acterized and utilized for the electrochemical sensing of PCT. The
electrode has a higher electrochemical activity toward the oxi-
dation of PCT as compared with that for either GCE or MWCNT
modied GCE. The incorporation of P4VP into the MWCNT-based
composite has signicantly increased the conductivity and effec-
tive electroactive surface area of the electrode. Additionally, the
P4VP/MWCNT GCE has exhibited a low detection limit, stability
and reproducibility towards PCT without any interference from
common physiological interferences i.e. AA and UA. The proposed
method has been successfully applied for the determination of PCT
in human urine and in pharmaceutical tablets with good precision
and accuracy. This method could be an alternative method for the
analysis of PCT in the future with its high sensitivity, stability, good
reproducibility and it being devoid of interference.
Acknowledgements
Financial support from the Ministry of Higher Educa-
tion (MOHE), Malaysia through a Research University (RU)
grant 1001/PKIMIA/811192 is appreciated. One of us (Ramin
M.A.Tehrani) is thankful to Shahre Rey Branch, Islamic Azad Uni-
versity, Tehran, Iran for permission to be on leave as a post-doctoral
fellow at Universiti Sains Malaysia (USM).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.aca.2012.12.039.
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