Application of a Carbon Fiber Microelectrode as a Sensor for Apocynin Electroanalysis.

In this study, a carbon fiber microelectrode (CF) was applied for the investigation of the electrochemical behavior of the natural antioxidant, apocynin (APO). Given the limited solubility of APO in water, a mixture of anhydrous acetic acid (AcH) with 20%, v/v acetonitrile (AN) and 0.1 mol L-1 sodium acetate (AcNa) was used. The electrochemical properties of APO were examined through linear sweep voltammetry (LSV), differential pulse voltammetry (DPV), and cyclic voltammetry (CV). The anodic oxidation of APO, which is the basis of the method used, proved to be diffusion-controlled and proceeded with a two-electron and one proton exchange. Both radicals and radical cations, arising from the first and second step of electrode reactions, respectively, underwent subsequent chemical transformations to yield more stable final products (EqCiEiCi mechanism). Using optimized DPV conditions, the anodic peak current of APO at a potential of 0.925 V vs. Ag/AgCl showed a good linear response within the concentration range of 2.7 × 10-6-2.6 × 10-4 mol L-1. The detection and quantification limits were determined as 8.9 × 10-7 and 2.7 × 10-6 mol L-1, respectively. The developed DPV method enabled the successful determination of APO in herbal extracts and in dietary supplements. It should be noted that this is the first method to be used for voltammetric determination of APO.

Electrochemical Characterization and Voltammetric Determination of Methylisothiazolinone on a Boron-Doped Diamond Electrode.

The electrochemical properties of methylisothiazolinone (MIT), the most widely used preservative, were investigated by cyclic (CV) and differential pulse voltammetry (DPV) to develop a new method for its determination. To our knowledge, this is the first demonstration of a voltammetric procedure for the determination of MIT on a boron-doped diamond electrode (BDDE) in a citrate-phosphate buffer (C-PB) environment. The anodic oxidation process of methylisothiazolinone, which is the basis of this method, proved to be diffusion-controlled and proceeded with an irreversible two-electron exchange. The radical cations, as unstable primary products, were converted in subsequent chemical reactions to sulfoxides and sulfones, and finally to more stable final products. Performed determinations were based on the DPV technique. A linear calibration curve was obtained in the concentration range from 0.7 to 18.7 mg L-1, with a correlation coefficient of 0.9999. The proposed procedure was accurate and precise, allowing the detection of MIT at a concentration level of 0.24 mg L-1. It successfully demonstrated its suitability for the determination of methylisothiazolinone in household products without the need for any separation steps. The proposed method can serve as an alternative to the prevailing chromatographic determinations of MIT in real samples.

Carbon Materials in Electroanalysis of Preservatives: A Review.

Electrochemical sensors in electroanalysis are a particularly useful and relatively simple way to identify electroactive substances. Among the materials used to design sensors, there is a growing interest in different types of carbon. This is mainly due to its non-toxic properties, low cost, good electrical conductivity, wide potential range, and the possibility of using it in both aqueous and nonaqueous media. The electrodes made of carbon, and especially of carbon modified with different materials, are currently most often used in the voltammetric analysis of various compounds, including preservatives. The objective of this paper is to present the characteristics and suitability of different carbon materials for the construction of working electrodes used in the voltammetric analysis. Various carbon materials were considered and briefly discussed. Their analytical application was presented on the example of the preservatives commonly used in food, cosmetic, and pharmaceutical preparations. It was shown that for the electroanalysis of preservatives, mainly carbon electrodes modified with various modifiers are used. These modifications ensure appropriate selectivity, high sensitivity, low limits of detection and quantification, as well as a wide linearity range of voltammetric methods of their identification and determination.

Voltammetric Determination of Isopropylmethylphenols in Herbal Spices.

Thymol and carvacrol-the components of herbal spices-are known for their broad biological activity as antimicrobials and antioxidants. For this reason, it is important to develop new methods for their determination in plant material. A simple, rapid, and sensitive method for determination of total content of these analytes in herbal spices using differential pulse voltammetry (DPV) has been developed. The basis of the research is the oxidation process of isopropylmethylphenols on a platinum microelectrode in glacial acetic acid containing acetonitrile (20%, v/v) and 0.1 mol L-1 sodium perchlorate as the supporting electrolyte. Linear voltammetric responses for thymol and carvacrol were obtained in a wide concentration range from 0.39-1105 and 0.47-640 µg mL-1, with a low detection limit of 0.04 and 0.05 µg mL-1, respectively. The analysis was performed using the multiple standard addition method. The results of the voltammetric determination are in good agreement with the data of the standard chromatographic method. To the best of our knowledge, this is the first presentation of an electrochemical procedure to determine these compounds in these environmental and electrode materials.

Anodic oxidation of 3,4-dihydroxyphenylacetic acid on carbon electrodes in acetic acid solutions.

The electrochemical oxidation of 3,4-dihydroxyphenylacetic acid (DOPAC) on a carbon fiber microelectrode (CF) and a glassy carbon macroelectrode (GC) in glacial acetic acid solutions was investigated using voltammetric techniques. Voltammograms recorded at these electrodes show well-defined single waves or peaks. The proposed mechanism of the anodic oxidation of DOPAC consists of two successive one-electron one-proton steps. The loss of the first electron proceeds irreversibly and determines the overall rate of the electrode process. This stage is accompanied by the generation of an unstable phenoxyl radical in position 4 of the aromatic ring. The second stage of the electrode reaction produces substituted orto-quinone as the final product of the electrode process of DOPAC. DOPAC exhibits more antioxidative power than synthetic BHT and can be useful in food protection against reactive oxygen species. The results presented can help to explain biochemical and antioxidative properties of DOPAC in a living cell and can be useful in determination of this compound in real samples.