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Electrochimica Acta
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Article history: Simultaneous determination of ascorbic acid (AA) and caffeine (CAF) in pharmaceutical preparation is
Received 21 December 2012 important and it has been achieved by square wave voltammetry (SWV) using a glassy carbon electrode
Received in revised form 6 January 2013 (GCE) modified with multiwall carbon nanotubes (MWCNT). The oxidation of AA and CAF at MWCNT
Accepted 11 January 2013
occurred at ∼−10 mV and ∼1103 mV at a much lower potential, than that observed (∼202 mV and
Available online 21 January 2013
∼1402 mV) for their oxidation at bare GCE. The mechanistic study has shown that the equal number
of electrons and protons are involved in the oxidation of drugs. The electrodes could be used for the
Keywords:
determination of AA and CAF in a wide concentration range 10–500 M, respectively, whereas the detec-
Ascorbic acid
Caffeine
tion limit has been found to be 1.0 × 10−2 M and 3.52 × 10−3 M respectively. In view of high sensitivity
Square wave voltammetry for the detection of the drugs, the technique has been used for the reliable determination of AA and CAF
Glassy carbon electrode in tea leaves, coffee, cold drink (mountain dew), pharmaceutical preparations and urine samples.
Multiwall carbon nanotubes © 2013 Elsevier Ltd. All rights reserved.
1. Introduction available for the determination of AA and CAF. These techniques are
highly sophisticated, time consuming and expensive [16–20], and
Ascorbic acid (AA) (2(1, 2-dihydroxyethyl)-4,5-dihydroxyfuran- require large infrastructure back up and expert knowledge. Thus
3-one), commonly known as vitamin-C [1], plays an important role they are not very appropriate for the analysis of large number of
in the formation and maintenance of collagen and as a powerful samples. Electrometric methods provide a faster and convenient
antioxidant protecting the body against oxidative stress [2]. Owing route for the determination of drugs. A number of drugs have been
to these properties, it is used for the prevention and treatment accurately determined separately by voltammetric technique using
of common cold, mental illness, infertility, cancer, Alzheimer’s modified glassy carbon electrode (MGCE) [23–28].
disease, atherosclerosis, and AIDS [3,4]. However, at higher con- Simultaneous determination of AA and CAF in many pharma-
centration levels, AA contributes to the formation of kidney stones. ceutical formulations is important as they are widely used for
Caffeine (CAF) (1,3,7-trimethyl-purine-2,6-dione), is an alkaloid treatment of various diseases. It has been attempted by differential
and found in many food products such as coffee, tea, yerbamate, pulse voltammetry using boron doped diamond electrode (BDD)
guarana berries, cola nuts and cacao beans. It promotes many [29] and glassy carbon electrode (GCE) [30]. The detection limit for
physiological functions such as gastric acid secretion, diuresis, and BDD has been found 19 M and 7.0 M for AA and CAF, respectively
stimulation of central nervous system [5,6]. Its other formulations [29] and for MGCE 1.0 × 10−2 M and 3.52 × 10−3 M, respectively
are used for the treatment of migraine and for anti-inflammatory and therefore these methods are not very appropriate for trace
and diuretic action. However, at higher concentration it is toxic and determination of these drugs.
causes cardiovascular disease, depression and hyperactivity [7–9]. In order to determine small concentrations of AA and CAF simul-
In addition to several important applications of AA and CAF taneously, we have attempted the determination by square wave
separately, their combinations are widely used for analgesic and voltammetry (SWV) using both bare GCE and MGCE. As the sensi-
antipyretic effects [10–12]. As a result of widespread use of AA and tivity of bare GCE was found to be poor, the electrode was modified
CAF they are present in many environmental samples. In view their by multiwall carbon nanotubes (MWCNT) to give better results.
adverse effects it is important to determine them in environmental
samples, human body fluids and pharmaceutical preparations. 2. Materials and methods
A number of techniques such as spectrophotometry [13–15],
chromatography [16,17] and solid phase analysis [18–22] are 2.1. Chemicals, reagents and instrumentation
0013-4686/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.electacta.2013.01.065
V.K. Gupta et al. / Electrochimica Acta 93 (2013) 248–253 249
Fig. 3. The square wave voltammograms obtained with blank solution (dotted line)
and with MGCE (solid line) in phosphate buffer solution 7.2 pH; (a) containing con-
stant concentration of AA (80 M) and increasing concentration of CAF: (a) 10, (b)
30, (c) 50, (d) 80, (e) 100, (f) 300 and (g) 500 M. Inset is the plot between peak
current versus concentration of the CAF.
3.2. Effect of pH
Table 1
Calibration characteristics for the determination of AA and CAF by SWV using
MWCNT modified glassy carbon electrode. E p (mV) = −58.98 (pH)
Characteristics AA CAF + 1818.0 versus Ag/AgCl for CAF on bare GCE (pH 4.0–10.0) (B.3)
Calibration range 10–500 M 10–500 M It is seen that the values of dEp /dpH obtained from the linear plots
Detection limit 1.0 × 10−2 M 3.52 × 10−3 M
are ∼58 and ∼55 mV which indicate that equal number of protons
Limit of quantification 3.33 × 10−2 M 11.73 × 10−3 M
Sensitivity 17.17 A M−1 48.54 A M−1 and electrons are involved in the electrochemical oxidation of these
Intercept 2.603 3.219 drugs at the electrode. Further, similar values of ∼55 and ∼59 mV
RSD of slope 2.97 5.35 are obtained for AA and CAF respectively, for bare GCE indicate
RSD of intercept 0.45 0.02 that the equal number of electrons and protons are involved in the
oxidation reaction at this electrode also [29].
V.K. Gupta et al. / Electrochimica Acta 93 (2013) 248–253 251
Table 2
Determination of CAF in tea leaves, coffee and cold drink (mountain dew) by SWV
using MWCNT modified glassy carbon electrode.
The amount of CAF determined in coffee, tea leaves and cold drink
(mountain dew) is reported in Table 2.
2 ml of the cold drink (mountain dew) was taken and volume
made up to 4 ml with PBS (pH 7.2) for the determination of CAF
and subjected to SWV. The peak currents were evaluated from the
voltammograms and used to determine amount of CAF using cali-
bration plot Fig. 4b obtained for the oxidation of CAF separately.
ip (A) = 2.920f 1/2 (Hz) − 1.081 for CAF on bare GCE (B.5)
Table 3
Determination of AA and CAF in pharmaceutical formulations by SWV using MWCNT modified glassy carbon electrode.
Compound Tablet name/company Amount reported mg/gm of the tablets Amount determined mg/gm of the tablets
Table 4
Determination of AA and CAF in human urine sample by SWV using MWCNT modified glassy carbon electrode.
Urine sample Added AA amount (mg/ml) Added CAF amount (mg/ml) Determined AA amount (mg/ml) Determined CAF amount (mg/ml)
not identified. The amount of AA and CAF determined is shown in [8] S. Kerrigan, T. Lindsey, Fatal caffeine overdose: two case reports, Forensic sci-
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4. Conclusion
[10] M. Amiri, A. Bezaatpour, Z. Pakdel, K. Nekoueian, Simultaneous voltammetric
determination of uric acid and ascorbic acid using carbon paste/cobalt Schiff
The studies have shown that the peak potentials, detection base composite electrode, Journal of Solid State Electrochemistry 16 (2012)
2187.
limit for modified glassy carbon electrode for the determination
[11] A.B. Florou, M.I. Prodromidis, S.M. Tzouwara-Karayanni, M.I. Karayannis, Fab-
of AA and CAF are ∼−10 mV and ∼1103 mV, and 1.0 × 10−2 M rication and voltammetric study of lanthanum 2,6-dichlorophenolindophenol
and 3.52 × 10−3 M respectively and for bare glassy carbon chemically modified screen printed electrodes. Application for the determina-
electrode are ∼202 mV and ∼1402 mV and 5.29 × 10−1 M and tion of ascorbic acid, Analytica Chimica Acta 423 (2000) 107.
[12] A.A. Ensafi, H. Karimi-Maleh, S. Mallakpour, Simultaneous determination of
9.41 × 10−2 M, respectively. The lower value shows that the mod- ascorbic acid, acetaminophen, and tryptophan by square wave voltammetry
ified glassy carbon electrode is superior to bare glassy carbon using N-(3,4-Dihydroxyphenethyl)-3,5-Dinitrobenzamide-modified carbon
electrode. Further, it is believed that this alternative approach nanotubes paste electrode, Electroanalysis 24 (2012) 666.
[13] J. Zou, H. Zhang, M. Ding, Z. Shang, Large phase ratio spontaneous extraction
of determining AA and CAF by square wave voltammetry is followed by GC-MS for the determination of caffeine in beverages, Chro-
convenient, faster and accurate. It is thus superior to exist- matographia 71 (2010) 323.
ing spectrophotometric and chromatographic methods which are [14] N.H. Ishler, T.P. Finucane, E. Broker, Rapid spectrophotometric determination
of caffeine, Analytical Chemistry 20 (1948) 1162.
expensive and time consuming. Thus it can be said that this biosen- [15] Y. Yamauchi, A. Nakamura, I. Kohno, M. Kitai, K. Hatanaka, T. Tanimoto, Sim-
sor is a useful addition in the field of analytical chemistry for the ple and rapid UV spectrophotometry of caffeine in tea coupled with sample
determination of drugs. pre-treatment using a cartridge column filled with polyvinylpolypyrrolidone
(PVPP), Chemical and Pharmaceutical Bulletin 56 (2008) 185.
[16] Y. Yamauchi, A. Nakamura, I. Kohno, K. Hatanaka, M. Kitai, T. Tanimoto,
Acknowledgements Quasi-flow injection analysis for rapid determination of caffeine in tea
using the sample pre-treatment method with a cartridge column filled
with polyvinylpolypyrrolidone, Journal of Chromatography A 1177 (2008)
One of the authors (Sudhir Kumar Shoora) is thankful to the 190.
University Grants Commission/Council of Scientific and Industrial [17] S.K. Srivastava, V.K. Gupta, M.K. Dwivedi, S. Jain, Caesium PVC-crown
(dibenzo-24-crown-8) based membrane sensor, Analytical Proceedings includ-
Research, New Delhi for the award of Junior Research Fellowship, ing Analytical Communications 32 (1995) 21.
New Delhi vide Grant No. 6405-13-044. [18] V. Silvestre, V.M. Mboula, C. Jouitteau, S. Akoka, R.J. Robins, G.S. Remaud, Iso-
topic 13C NMR spectrometry to assess counterfeiting of active pharmaceutical
ingredients: site-specific 13C content of aspirin and paracetamol, Journal of
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