Electroanalytical performance of a β-cyclodextrin and ionic liquid modified carbon paste electrode for the determination of verapamil in urine and pharmaceutical formulation.

The analytical performance of sensitive and cost-effective electrochemical sensors based on ionic liquids (ILs) with the bis(trifluoromethylsulfonyl)imide anion, [NTf2]-, and the imidazolium cation with different alkyl chain lengths for electrochemical oxidation of verapamil (VER) was investigated. 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf2]), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][NTf2]) and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([HMIM][NTf2]) were studied as possible materials for modification of a carbon paste electrode (CPE) for trace-level determination of VER. The experimental parameters including selection of the working electrode, the pH of working media, and the amount of CPE modifiers were investigated. Among them, the [EMIM][NTf2]-CPE with 4.3 wt% of IL was selected as the most appropriate for the square wave voltammetric (SWV) determination of VER at pH 5.0. Cyclic voltammetric studies showed that the electrochemical oxidation of VER was adsorption controlled. Consequently, the square wave adsorptive stripping voltammetric (SW-AdSV) parameters were optimized with Eacc = -0.4 V and tacc = 180 s as the most suitable for accumulation of VER on the electrode surface. The electroanalytical performance of the [EMIM][NTf2]-CPE was further improved by its in situ electrochemical modification with β-cyclodextrin (β-CD) and the linear concentration range of VER was from 0.006 to 0.129 μg mL-1; the relative standard deviation did not exceed 0.7%, and the evaluated limit of detection in model solution was 0.002 μg mL-1. The β-CD/[EMIM][NTf2]-CPE showed adequate selectivity towards VER in the presence of inorganic ions and interferents usually found in human urine. The proposed sensor was successfully applied for VER determination in a spiked human urine sample and pharmaceutical formulation with good repeatability and recovery.