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Goyal 2005
Goyal 2005
www.elsevier.com/locate/elecom
a
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee-247 667, India
b
Division of Research Initiatives, International Innovation Center, Kyoto University, Sakyo-ku, Kyoto 606-8501, Japan
Received 20 April 2005; received in revised form 11 May 2005; accepted 11 May 2005
Available online 13 June 2005
Abstract
A nanogold modified indium tin oxide (ITO) electrode was used for the determination of paracetamol at pH 7.2. The electrode
exhibited an effective catalytic response to the oxidation of paracetamol with good reproducibility and stability. Under conditions
of differential pulse voltammetry, the oxidation potential of paracetamol is lowered by approximately 110 mV and current response
is enhanced significantly relative to the situation prevailing when a bare ITO electrode is used. Linear calibration curve is obtained over
the range 2.0 · 107–1.5 · 103 M with a correlation coefficient of 0.997. The detection limit (3r) was estimated to be 1.8 · 107 M. The
physiologically common interferents viz., ascorbic acid, glucose and urea negligibly affected the current response of paracetamol. The
practical analytical utility of the method is illustrated by determination of paracetamol in pharmaceutical preparations.
2005 Elsevier B.V. All rights reserved.
Keywords: Nanogold modified indium tin oxide electrode; Paracetamol; Differential pulse voltammetry; Pharmaceutical preparations
1388-2481/$ - see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.elecom.2005.05.005
804 R.N. Goyal et al. / Electrochemistry Communications 7 (2005) 803–807
[16], Fourier transform infra red spectrometry [17], and tion limit of 0.18 lM is attained which is lower than that
many other methods are proposed for the determination of other electrochemical methods reported.
of paracetamol. Since voltammetric techniques are more
selective, less costly and less time-consuming, they are
widely used for the determination of paracetamol in phar- 2. Experimental
maceutical preparations. Shuyan et al. described a rela-
tively simple and rapid electrochemical method by cyclic 2.1. Reagents
voltammetry using glassy carbon electrode for the detec-
tion of paracetamol in 1.0 M HCl solution [18]. Voltam- Paracetamol was received as a gift from Sri Krishna
metric determination of paracetamol at chemically Pharmaceuticals Ltd. (India) and was used as received.
modified electrodes [19,20], boron doped diamond film Ascorbic acid, glucose and urea were obtained from
electrode [21] and at other electrodes [22–25] have also at- Merck. All other reagents used were of analytical grade.
tracted attention, however, the lowest detection limit of All solutions were prepared in double distilled water.
1.2 lM is reported at nafion/ruthenium oxide pyrochlore Phosphate buffer solutions (l = 1 M) at various pH val-
chemically modified electrode. ues, prepared according to the method of Christian and
Owing to their novel optical, electronic, magnetic and Purdy [33], were used as supporting electrolyte for the
catalytic properties gold nanoparticles are one of the determination of paracetamol.
most intensively studied and one of the most popular
materials to be assembled on electrodes [26]. It has been 2.2. Apparatus and procedure
reported that the small size of gold nanoparticles allow
the conductive materials to come into the vicinity of Differential pulse voltammetric experiments were per-
the active process providing bioelectrocatalytic activity formed on BAS (Bioanalytical Systems, West Lafayette,
that can be utilized in the construction of biosensors IN, USA) CV-50W Voltammetric analyzer. The electro-
[27]. It also provides some important functions for elec- chemical measurements were carried out in a single-
troanalysis [28]. Gold nanoparticles-modified electrodes compartment three-electrode glass cell with a gold
are used increasingly in many electrochemical applica- nanoparticles modified ITO electrode (geometric area
tions since they have the ability to enhance the electrode ca. 0.0314 cm2) as the working electrode, a platinum wire
conductivity and facilitate the electron transfer, thus, as counter electrode and Ag/AgCl electrode as reference
improving the analytical selectivity and sensitivity. Nor- electrode (Model MF-2052 RB-5B). Gold nanoparticles
mally peculiar binding molecules are used to assemble modified ITO electrodes were prepared by the method re-
gold nanoparticles on the electrode surfaces [29,30] but ported in the literature [32]. JEOL JSM-7400F field emis-
this may alter the conducting properties of the modified sion scanning electron microscopy (FE-SEM) instrument
electrode [31]. Recently, Oyama et al. [32] have pre- was used to characterize the growth of the gold nanopar-
sented a new method to fabricate a gold nanoparticles- ticles on the ITO surface. All experiments were carried
attached indium tin oxide (Au/ITO) electrode without out at an ambient temperature of 25 ± 2 C. Stock solu-
using peculiar binding molecules. The present work re- tion of paracetamol (2 mM) was prepared by dissolving
ports the differential pulse voltammetric determination the required amount of the compound in double distilled
of paracetamol at a physiological pH of 7.2 using gold water. The solution was wrapped with black paper and
nanoparticles-modified indium tin oxide (Au/ITO) elec- kept in the dark. Freshly prepared solutions of paraceta-
trode. The modified electrode shows a strong catalytic mol were prepared each day owing to its low stability. To
function towards the oxidation of paracetamol. A detec- record differential pulse voltammograms (DPVs), the
following instrumental parameters were used: pulse
amplitude, 5 mV; sample width, 2 ms; pulse width, 5 ms;
pulse period, 200 ms; scan rate, 20 mV/s; sensitivity,
100 nA/V.
Fig. 2. A typical differential pulse voltammogram for 1.0 mM para- 3.2. Effect of pH
cetamol at pH 7.2 at bare (- - -) and gold nanoparticles modified (—)
ITO electrode.
The pH of the solution has a significant influence on
the peak potential of the catalytic oxidation of paracet-
effectively modified. The catalytic function of the gold amol. Fig. 4 illustrates the dependence of the DPV peak
nanoparticles modified ITO electrode is demonstrated
in Fig. 2 for 1.0 mM paracetamol at pH 7.2 recorded at
a bare ITO electrode and the nanogold particles modified
electrode by DPV. Paracetamol gives a peak response at
about 940 mV vs. Ag/AgCl at the bare ITO electrode,
while the use of gold nanoparticles modified ITO elec-
trode leads to an anodic peak at about 830 mV vs. Ag/
AgCl and the peak current increased greatly. The en-
hanced peak current response is a clear evidence of the
catalytic effect of the gold nanoparticles modified ITO
electrode towards oxidation of paracetamol. Also, a shift
in the oxidation potential of paracetamol by about
110 mV in the cathodic direction was observed at the
modified electrode. The lowering of peak potential is,
again, a good indication of the catalytic effect. Fig. 4. Observed dependence of Ep on pH for 0.1 mM paracetamol.
806 R.N. Goyal et al. / Electrochemistry Communications 7 (2005) 803–807