Boehmite nanoparticle modified carbon paste electrode for determination of piroxicam
Graphical abstract
Introduction
Piroxicam (PXM, 4-hydroxy-2-methyl-N-(pyridine-2-yl)-2H-1,2-benzo-thiazine-3-carboxamide-1,2-dioxide) is a well-known non-steroidal anti-inflammatory and analgesic drug (NSAIDs) for treatment of rheumatoid arthritis, osteoarthritis, ankylosing spondylitis and acute pain [1], [2]. PXM belongs to the oxicam group of a class of enolic acids. Many diverse properties have been exhibited by the oxicam group of drugs, including chemoprevention, chemosupression [3], [4], [5], and UV-induced photosensitization of the skin [6]. Many analytical methods for assay of PXM in pharmaceutical formulations and human body fluids have been reported in the literature. They include spectrophotometry [7], [8], [9], [10], [11], [12], spectrofluorimetry [13], [14], [15], capillary zone electrophoresis [16], liquid chromatography [17], thin-layer chromatography [18], high-performance liquid chromatography [19], [20], [21], and voltammetry at mercury and carbon paste electrodes [22], [23], [24]. However, most of those methods presented insufficient sensitivity and therefore, there is a considerable interest in developing a simple and sensitive method for PXM detection.
Due to the unique properties of nanoparticles, they have been applied in various fields of science and technology [25], [26], [27], [28]. Metal and metal oxide nanoparticles are the most widely employed nanomaterials owing to excellent physical and catalytic properties of these materials. In order to increase the response signal, sensitivity and to achieve a better reproducibility the fabrication of electrodes modified with nanoparticles has been the focus of recent attention [28], [29], [30], [31], [32], [33].
Aluminum oxide is one of the most stable inorganic materials and are generally inexpensive, non-toxic, and resistant to the chemical cleaning agents. Boehmite is an aluminum oxide hydroxide (γ-AlOOH) particle, containing hydroxyl groups attached to its surface. Boehmite has excellent properties such as chemical resistance, good mechanical strength, high hardness, transparency, high abrasive and corrosion resistance [34]. Therefore, the application of the boehmite nanoparticles into the carbon paste as a modifier seems to improve the performance of the electrode toward drug detection. Pharmaceutical analysis is an essential step for drug quality control. Analytical methods may have been used to generate data for acceptance, release, stability, or pharmacokinetic studies of the pharmaceutical material. Due to the accelerated progress in the discovery, synthesis and means of delivery of substances used in the drug industry, there is a great demand for more sensitive, robust and fast procedures of analysis [35], [36]. Different sensors, including a carbon ceramic sensor [37], potentiometric plastic-membrane sensor [38], modified carbon paste electrode [39], modified pyrolytic graphite electrode [40], multi-walled carbon nanotubes electrodes [41], [42] and molecular imprinted polymer-modified carbon paste electrode [43] have also been developed for selective determination of PXM. In present work, a carbon paste electrode modified by BNP was introduced for detection of low level of PXM. The proposed modified electrode was tested by differential pulse anodic stripping and cyclic voltammetric techniques and was directed toward electroanalytical applications for determination of PXM in pharmaceutical and biological fluid samples. The ease and speed of fabrication, simplicity along with wider linear range, higher sensitivity and low detection limit are the main advantageous of this method over the previously reported ones.
Section snippets
Apparatus
Electrochemical data were obtained with a three-electrode system using a potentiostat/galvanostat model PGSTAT30, AUTOLAB. Self-made CPE or modified CPE (with a diameter of 2.0 mm), platinum wire and Ag/AgCl electrodes were used as working, counter and reference electrodes, respectively. Metrohm pH-meter (model 827 pH Lab) was also used for pH measurements. A Hewlett-Packard 8453 diode-array spectrophotometer controlled by a computer and equipped with a 1 cm path length quartz cell was used for
Characterization of boehmite nanoparticles
Boehmite crystallizes as orthorhombic cells and is composed of AlO(OH) sheets piling up with the oxygen ions located either into the sheets (OI) or at their surface (OII). The aluminum ions located in the center of octahedral are surrounded by 4(OI) and 2(OII) [45]. OH groups are binding to the octahedron double layers. In Fig. 1A the XRD pattern, obtained on the synthesized boehmite nanoparticles, shows a good agreement with the reference XRD pattern (21-1307JCPDSfile).
Fig. 1B presents TEM
Conclusion
The results of the present work demonstrate that the carbon paste electrode modified with boehmite nanoparticles is able to accumulate the PXM for performing sensitive voltammetric detections. The electrode showed high stability in repetitive experiments due to the chemical resistance and the low solubility of the boehmite in water. The proposed electrode was used in determination of PXM in real samples such as serum, gel and capsule with satisfactory recovery and without the necessity of
Mohammad Bagher Gholivand was born on 1954 in Kermanshah, Iran. He received his PhD degree in Analytical Chemistry from Shiraz University, Shiraz, Iran in 1993. Currently he works as a Full Professor at Razi University, Kermanshah, Iran. His research interests include electrochemical sensors, optical sensor and biosensors.
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Mohammad Bagher Gholivand was born on 1954 in Kermanshah, Iran. He received his PhD degree in Analytical Chemistry from Shiraz University, Shiraz, Iran in 1993. Currently he works as a Full Professor at Razi University, Kermanshah, Iran. His research interests include electrochemical sensors, optical sensor and biosensors.
Ghodratollah Malekzadeh was born on 1980 in Omidiyeh, Khuzestan, Iran. He received his PhD degree in Applied Chemistry from Razi University, Kermanshah, Iran on 2013. Currently he works as an Assistant Professor at Department of Chemistry, Omidiyeh Branch, Islamic Azad University, Khuzestan, Iran. His research interests include instrumentation, chemometrics and electrochemical sensors.
Ali Ashraf Derakhshan was born on 1982 in Kermanshah, Iran. He received his BS degree in Applied Chemistry from Isfahan University of Technology, Isfahan, Iran on 2008. He received his MSc degree in Organic Chemistry from Razi University, Kermanshah, Iran, on 2011. Now, he is working towards as assistant research at Razi University. His interests are organic synthesis, Nanotechnology and Electrochemistry.