Electrooxidation of Indomethacin at Multiwalled Carbon Nanotubes-Modified GCE and Its Determination in Pharmaceutical Dosage Form and Human Biological Fluids
A simple, rapid, selective, and sensitive electrochemical method for the direct determination of indomethacin was developed. The electrochemical behavior of indomethacin was carried at multiwalled carbon nanotube- (MWCNTs-) modified glassy carbon electrode (GCE). The cyclic voltammetric results indicated that MWCNT-modified glassy carbon electrode remarkably enhanced electrocatalytic activity towards the oxidation of indomethacin in slightly acidic solutions. It led to a considerable improvement of the anodic peak current for indomethacin and could effectively accumulate at this electrode and produce two anodic peaks at 0.720?V and 0.991?V, respectively, and one reduction peak at 0.183?V. The electrocatalytic behavior was further exploited as a sensitive detection scheme for the determination of indomethacin by differential-pulse voltammetry (DPV). Under optimized conditions, the concentration range and detection limit were 0.2 to 6.0? M and 13.2?nM, respectively. The proposed method was successfully applied to determination of Indomethacine in pharmaceutical samples. The analytical performance of this sensor has been evaluated for detection of analyte in human serum and urine as real samples. 1. Introduction Indomethacin, (Scheme 1) {1-(p-chlorobenzoyl)-5-methoxy-2-methyl-3-indolylacetic acid} (INM), a nonsteroidal anti-inflammatory drug, is usually regarded as the father figure in the family of nonsteroidal agents. It relieves pain and reduces inflammation and fever. It is slightly more toxic but in certain circumstances more effective than aspirin. INM has two additional modes of actions [1] with clinical importance. It inhibits motility of polymorphonuclear leukocytes and, like salicylates, uncouples oxidative phosphorylation in cartilaginous (and hepatic) mitochondria. These additional effects account as well for the analgesic and the anti-inflammatory properties. Generally, overdose in humans causes drowsiness, dizziness, severe headache, mental confusion, numbness of limbs, nausea and vomiting, severe gastrointestinal bleeding, and cerebral edema and cardiac arrest, its fatal outcome is seen in children. For these reasons, it is important to analyze INM in real samples. Scheme 1: Chemical structure of indomethacin. The widespread use of INM and the need for clinical and pharmacological study require fast and sensitive analytical techniques to determine the presence of INM in pharmaceutical formulations and biological fluids. Until now, the most common techniques for the determination of INM in commercial dosage form were based on
References
[1]
G. W. Bisits, “Preterm labour. The present and future of tocolysis,” Best Practice and Research: Clinical Obstetrics and Gynaecology, vol. 21, pp. 857–868, 2007.
[2]
K.-I. Mawatari, F. Iinuma, and M. Watanabe, “Fluorimetric determination of indomethacin in human serum by high-performance liquid chromatography coupled with post-column photochemical reaction with hydrogen peroxide,” Journal of Chromatography: Biomedical Applications, vol. 491, no. 2, pp. 389–396, 1989.
[3]
A. F. Arruda and A. D. Campiglia, “Phosphorimetric determination of indomethacin in pharmaceutical formulations,” Analyst, vol. 122, no. 6, pp. 559–562, 1997.
[4]
N. Fouzia, A. Tehseen, M. Amina, and N. Saima, “Spectrophotometric determination of indomethacin using partial least square method,” Proceedings of the PAS: Pakistan Academy of Sciences, vol. 44, no. 3, pp. 173–179, 2007.
[5]
H. Kubo, Y. Umiguchi, and T. Kinoshita, “Fluorometric determination of indomethacin in serum by high performance liquid chromatography with in-line alkaline hydrolysis,” Chromatographia, vol. 33, no. 7-8, pp. 321–324, 1992.
[6]
M. Otsuka, H. Tanabe, K. Osaki, K. Otsuka, and Y. Ozaki, “Chemoinformetrical evaluation of dissolution property of indomethacin tablets by near-infrared spectroscopy,” Journal of Pharmaceutical Sciences, vol. 96, no. 4, pp. 788–801, 2007.
[7]
K. M. Jensen, “Determination of indomethacin in serum by an extractive alkylation technique and gas-liquid chromatography,” Journal of Chromatography, vol. 153, no. 1, pp. 195–202, 1978.
[8]
L. Novákova, L. Matysová, L. Havlíková, and P. Solich, “Development and validation of HPLC method for determination of indomethacin and its two degradation products in topical gel,” Journal of Pharmaceutical and Biomedical Analysis, vol. 37, pp. 899–905, 2005.
[9]
A. Merko?i, “Nanobiomaterials in electroanalysis,” Electroanalysis, vol. 19, no. 7-8, pp. 739–741, 2007.
[10]
M. Trojanowicz, “Analytical applications of carbon nanotubes: a review,” TrAC: Trends in Analytical Chemistry, vol. 25, no. 5, pp. 480–489, 2006.
[11]
S. Iijima, “Helical microtubules of graphitic carbon,” Nature, vol. 354, no. 6348, pp. 56–58, 1991.
[12]
P. M. Ajayan, “Nanotubes from Carbon,” Chemical Reviews, vol. 99, no. 7, pp. 1787–1799, 1999.
[13]
J. M. Nugent, K. S. V. Santhanam, A. Rubio, and P. M. Ajayan, “Fast electron transfer kinetics on multiwalled carbon nanotube microbundle electrodes,” Nano Letters, vol. 1, no. 2, pp. 87–91, 2001.
[14]
A. Merkoci, “Carbon nanotubes in analytical sciences,” Microchimica Acta, vol. 152, pp. 157–174, 2006.
[15]
J. J. Gooding, “Nanostructuring electrodes with carbon nanotubes: a review on electrochemistry and applications for sensing,” Electrochimica Acta, vol. 50, no. 15, pp. 3049–3060, 2005.
[16]
C. E. Banks and R. G. Compton, “New electrodes for old: from carbon nanotubes to edge plane pyrolytic graphite,” Analyst, vol. 131, no. 1, pp. 15–21, 2006.
[17]
G.-C. Zhao, Z.-Z. Yin, L. Zhang, and X.-W. Wei, “Direct electrochemistry of cytochrome c on a multi-walled carbon nanotubes modified electrode and its electrocatalytic activity for the reduction of H2O2,” Electrochemistry Communications, vol. 7, no. 3, pp. 256–260, 2005.
[18]
G. D. Christian and W. C. Purdy, “The residual current in orthophosphate medium,” Journal of Electroanalytical Chemistry, vol. 3, no. 6, pp. 363–367, 1962.
[19]
B. Rezaei and S. Damiri, “Voltammetric behavior of multi-walled carbon nanotubes modified electrode-hexacyanoferrate(II) electrocatalyst system as a sensor for determination of captopril,” Sensors and Actuators B: Chemical, vol. 134, no. 1, pp. 324–331, 2008.
[20]
D. K. Gosser, Cyclic Voltammetry: Simulation and Analysis of Reaction Mechanisms, Wiley-VCH, New York, NY, USA, 1993.
[21]
E. Laviron, “General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems,” Journal of Electroanalytical Chemistry, vol. 101, no. 1, pp. 19–28, 1979.
[22]
A. J. Bard and L. R. Faulkner, Electrochemical Methods Fundamentals and Applications, Wiley, 2nd edition, 2004.
[23]
Y. Wu, X. Ji, and S. Hu, “Studies on electrochemical oxidation of azithromycin and its interaction with bovine serum albumin,” Bioelectrochemistry, vol. 64, no. 1, pp. 91–97, 2004.