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In present work, the enzyme cholesterol oxidase (ChOx) was immobilized by Nafion® (Naf) on Pt,Ru-C nanocomposite and an ionic liquid (IL)-modified carbon paste electrode (CPE) in order to create cholesterol biosensor (Naf/ChOx/Pt,Ru-C/IL-CPE). The prepared working electrodes were characterized using scanning electron microscopy-energy-dispersive spectrometry, while their electrochemical performance was evaluated using electrochemical impedance spectroscopic, cyclic voltammetric, and amperometric techniques. Excellent synergism between IL 1-allyl-3-methylimidazolium dicyanamide ([AMIM][DCA]), Pt,Ru-C, and ChOx, as modifiers of CPE, offers the most pronounced analytical performance for improved cholesterol amperometric determination in phosphate buffer solution pH 7.50 at a working potential of 0.60 V. Under optimized experimental conditions, a linear relationship between oxidation current and cholesterol concentration was found for the range from 0.31 to 2.46 µM, with an estimated detection limit of 0.13 µM and relative standard deviation (RSD) below 5.5%. The optimized amperometric method in combination with the developed Naf/ChOx/Pt,Ru-C/IL-CPE biosensor showed good repeatability and high selectivity towards cholesterol biosensing. The proposed biosensor was successfully applied to determine free cholesterol in a human blood serum sample via its enzymatic reaction product hydrogen peroxide despite the presence of possible interferences. The percentage recovery ranged from 99.08 to 102.81%, while RSD was below 2.0% for the unspiked as well as the spiked human blood serum sample. The obtained results indicated excellent accuracy and precision of the method, concluding that the developed biosensor can be a promising alternative to existing commercial cholesterol tests used in medical practice., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

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.

The rapid and sensitive voltammetric determination of organic UV filters benzophenone-3 (BP-3) and avobenzone (AVO) was performed by an ionic liquid carbon paste electrode (IL-CPE). Namely, the synthesized pyridinium-based ILs, 1-butyl-3-methylpyridinium chloride ([ N –C 4 –3C 1 Py]Cl) and 1-ethoxyethyl-3-methylpyridinium chloride ([ N –C 2 OC 2 –3C 1 Py]Cl) were compared as bulk CPE modifiers for BP-3 determination. [ N –C 4 –3C 1 Py]Cl-CPE showed more favorable interactions with the target analyte, and it was tested for AVO determination, too. Cyclic voltammetric (CV) studies suggested that the irreversible electrode reaction is adsorption controlled in the case of both UV filters. Also, the square-wave adsorptive stripping voltammetric (SW-AdSV) method was optimized for quantifying selected UV filters. In the model solutions, the linear calibration curve was obtained by the SW-AdSV method in the concentration range from 0.05 to 0.89 μg mL−1 at pH 3.0 for BP-3 (E acc = −0.7 V, t acc = 100 s), and from 0.05 to 1.77 μg mL−1 at pH 11.98 for AVO (E acc = 0.2 V, t acc = 100 s). The evaluated limit of detection (LOD) was 0.015 μg mL−1 in both cases, while the relative standard deviation (RSD) was lower than 1.5%. The affordable IL-based voltammetric sensor fulfills the main requirements for application in real samples due to an adequate selectivity towards selected analytes in the presence of interferents usually found in swimming pool water. Therefore, the BP-3 and AVO were quantified in a swimming pool water matrix with good repeatability and recovery. The obtained results demonstrate an excellent potential of the IL-CPEs, especially of the [ N –C 4 –3C 1 Py]Cl-CPE, for determining selected UV filters in various real samples. [Display omitted] • Pyridinium-based ionic liquids were used for carbon paste electrode modification. • Simple and reliable SW-AdSV method for selected UV filters sensing was developed. • Achieved LOD for benzophenone-3 (BP-3) and avobenzone (AVO) was 0.015 μg mL−1. • [ N –C 4 –3C 1 Py]Cl-CPE enables determination of BP-3 and AVO in swimming pool water sample. • Good repeatability and high selectivity towards UV filters sensing were obtained. [ABSTRACT FROM AUTHOR]