Development of a New Analytical Method for Determination of Veterinary Drug Oxyclozanide by Electrochemical Sensor and Its Application to Pharmaceutical Formulation
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chemosensors Article Development of a New Analytical Method for Determination of Veterinary Drug Oxyclozanide by Electrochemical Sensor and Its Application to Pharmaceutical Formulation Ersin Demir 1 and Hulya Silah 2,* 1 Department of Analytical Chemistry, Faculty of Pharmacy, Afyonkarahisar University of Health Sciences, Afyonkarahisar 03200, Turkey; [email protected] 2 Department of Chemistry, Faculty of Art & Science, Bilecik ¸SeyhEdebali University, Bilecik 11210, Turkey * Correspondence: [email protected]; Tel.: +90-228-214-1484 Received: 25 February 2020; Accepted: 26 March 2020; Published: 30 March 2020 Abstract: A novel highly selective, sensitive and simple analytical technique was recommended for the investigation of anthelmintic veterinary drug oxyclozanide based on square wave anodic stripping voltammetry (SWASV) by using a carbon paste electrode (CPE). According to the cyclic voltammetric data, the oxidation and electron transfer processes of oxyclozanide were found as irreversible and adsorption-controlled, respectively. The voltammetric anodic peak response was characterized with respect to pH, accumulation potential, accumulation time, frequency and pulse amplitude, etc. Under these optimized experimental conditions, the anodic peak density of oxyclozanide was linear to oxyclozanide concentrations in the range from 0.058 to 4.00 mg/L. The described electrochemical method was successfully carried out for the oxyclozanide in pharmaceutical formulation and tap water with mean percentage recovery of 101.5 % and 102.2 %, respectively. The results of pharmaceutical formulation studies were statistically compared to the high-performance liquid chromatographic method. Keywords: carbon paste electrode; determination; oxyclozanide; pharmaceutical formulation; voltammetry 1. Introduction Pharmaceuticals are necessary for human and animal health. They are an important class of emerging contaminants in the environment because, after usage, these compounds and their metabolites are widespread in the environment by several mechanisms. Many drug residues have been detected in the environmental areas such as surface water, groundwater, sewage sludge and manure [1,2]. Therefore, it is very important to the enhancement of some efficient, appropriate and accurate detection methods for these pharmaceuticals in environmental samples. Oxyclozanide is an anthelmintic drug introduced over 50 years ago and its IUPAC name is [2,3,5-trichloro-N-(3,5-dichloro-2-hydroxyphenyl)-6-hydroxybenzamide] [3]. Helminths are the most important group of parasitic infections in livestock and can be classified into three major types; cestodes, trematodes and nematodes [4]. The chemical structure of oxyclozanide is shown in Figure1. It has been widely used to control parasitic flatworms called flukes in livestock fields, primarily for ruminants such as goat, cattle and sheep [5]. Oxyclozanide is also used to treat infections caused by F. gigantic and F. hepatica [6]. Chemosensors 2020, 8, 25; doi:10.3390/chemosensors8020025 www.mdpi.com/journal/chemosensors Chemosensors 2020, 8, 25 2 of 11 Chemosensors 2020, 8, x FOR PEER REVIEW 2 of 11 Cl Cl H O O N H O Cl H Cl Cl Figure 1. MoleMolecularcular structure of oxyclozanide oxyclozanide.. Very fewfew papers,papers, most of themthem areare spectrophotometricspectrophotometric andand chromatographicchromatographic analytical methods, have been reported in the literature for the determination of oxyclozanide in veterinary medicinal productsproducts and biological fluids fluids such as liquid chromatography [7], [7], high high-performance-performance liquid chromatography (HPLC) [[8,9],8,9], high-performancehigh-performance thin-layerthin-layer chromatography [[10],10], HPLC–tandemHPLC–tandem mass spectrometry [11] [11],, liquid chromatography coupled with tandem mass spectrometry [12] [12] and spectrophotometry [13]. [13]. These These methods methods are are widely widely used used in in routine analysis since they are good in sensitivity, stability and repeatability. However, the disadvantage of these methods is that they are timetime-consuming,-consuming, expensive,expensive, require require a largea large sample sample volume volume and needand aneed large a numberlarge number of organic of solventsorganic withsolvents extraction with extraction and separation and separation procedures procedures [14,15]. [14,15]. Electroanalytical Electroanalytical techniques techniques are selective, are selective, rapid, rapid,sensitive sensitive and easy and methods; easy methods; they also they have also low h detectionave low detection and determination and determination limits. So, limits. they have So, beenthey widelyhave been used widely to analyze used organic to analyze molecules organic as molecules pharmaceuticals as pharmaceuticals and pesticides and in food, pesticides environmental in food, environmentalor biological samples or biological and commercial samples and formulations commercial formulations [16–20]. Carbon [16– electrodes,20]. Carbon whichelectrodes, have which great haveadvantages, great advantages such as low, such cost, as lightness, low cost,large lightness, specific large surface specific area, surface light weight,area, light oxidation weight, resistance,oxidation resistance,high corrosion high resistance corrosion and resistance extraordinary and extraordinary porous structure, porous have structure, a dominant have position a dominant in the position analysis inof the drugs, analysis pesticides of drugs, and numerouspesticides organicand numerous molecules organic [21]. molec Therefore,ules [21]. the carbon Therefore, paste the electrode carbon (CPE)paste electrodecan be one (CPE) of the mostcan be suitable one of indicator the most electrodes suitable for indicator the determination electrodes offor oxyclozanide. the determination of oxyclozanide.To our knowledge, there are no published procedures regarding the electrochemical properties of oxyclozanideTo our knowledge, and it is available there are for no determining published procedures by electrochemical regarding methods. the electrochemical This manuscript properties reports ofthe oxyclozanide development and of a newit is analyticalavailable methodfor determining for the sensitive by electrochemical detection of themethods. oxyclozanide This manuscript based on a voltammetricreports the development technique using of a new a carbon analytical paste method electrode for (CPE). the sensitive The principal detection purpose of the of oxyclozanide this work is basedthe development on a voltammetric of a highly technique sensitive using and a selectivity carbon paste electroanalytical electrode (CPE). technique The principal for the detection purpose of thisoxyclozanide work is the and development to implement of thea highly methodology sensitive for and its selectivity quantitative electroanalytical determination technique in environmental for the detectionsamples and of oxyclozanide pharmaceutical and formulation. to implement the methodology for its quantitative determination in environmental samples and pharmaceutical formulation. 2. Materials and Methods 2.2.1. Materials Apparatus and Methods 2.1. ApparatusThe cyclic and square wave stripping voltammetric measurements were carried out by using a Vertex.One/Ivium electrochemical analyzer (Potentiostat/galvanostat, Eindhoven, The Netherlands) controlledThe cyclic with and software. square The wave electrochemical stripping voltammetric cell consisted measurements of three electrodes: were carried the CPE out as by a working using a Vertex.electrode,One an/Ivium Ag/AgCl electrochemical (3 M NaCl) as analyzer a reference (Potentiostat/galvanostat, electrode and a platinum Eindhoven, counter electrode. Netherlands) The pH controlledof the solution with was software. measured The electrochemical using the HANNA cell modelconsisted HI 8521of three digital electrodes pH-meter.: the CPE as a working electrode, an Ag/AgCl (3 M NaCl) as a reference electrode and a platinum counter electrode. The pH of the solution was measured using the HANNA model HI 8521 digital pH-meter. Chemosensors 2020, 8, 25 3 of 11 HPLC analyses were performed as indicated by Jo et al. [8]. The HPLC system (Shimadzu UFLCXR HPLC System, Shimadzu Corp., Kyoto, Japan) consisted of a SIL-20A XR autosampler, C18 column and a model of the SPD-M20A diode array detector. The mobile phase consisting of a mixture of 0.1% phosphoric acid/acetonitrile (6:4 v/v) was degassed by sonication before use. Detection of oxyclozanide was carried out at a wavelength of UV-300 nm. The flow rate was 1.0 mL/min and injected volume was 50.0 µL. Each treatment consisted of three replicates. Mixed graphite powder (<150 µm) and paraffin oil in the ratio 70:30 (w/w) were used to prepare CPE and the obtained carbon paste was packed into the end of the BASi-MF 2010 electrode (3 mm diameter). The procedure for cleaning the electrode surface was done with distilled water. In addition, when not cleaned with pure water, polishing was applied to the electrode surface before the measurements. 2.2. Chemicals and Reagents Oxyclozanide was purchased from Sigma-Aldrich as an analytical standard. Stock oxyclozanide solution of 500 mg/L oxyclozanide was prepared by dissolving the required weight in acetonitrile and storing it in the dark under refrigeration. Further required dilutions for working solutions were performed with acetonitrile. Veterinary drug formulation containing oxyclozanide, Okzan® (Ceva, Istanbul, Turkey), was purchased from local