Flow-Injection Amperometric Determination of Adrenalin, Melatonin, and Cortisol on an Electrode Modified with a Gold–Palladium Binary System and a Nafion Film

Abstract

The control of the precise concentration of steroid hormones and their synthetic analogs in biomedical objects is a relevant analytical task. A method for selective and highly sensitive simultaneous amperometric determination of adrenaline, melatonin, and cortisol with the use of a two-detector flow-injection system is developed. Screen-printed carbon electrodes (SPE) with one or two working electrodes modified with a gold–palladium binary system that exhibits catalytic activity upon electrooxidation of the organic compounds under consideration are used as detectors. The high sensitivity of determination is attributed to the catalytic properties of the metal modifier: the transition from the metal to the binary system leads to an increase in the catalytic oxidation current of hormones. The selectivity of determination of adrenaline in the presence of melatonin and cortisol is provided by the difference in the oxidation potentials of the hormones on the proposed electrode. For selective determination of melatonin and cortisol, the surface of the modified working electrode is coated with a Nafion film. The difference of potentials of the peaks of oxidation of adrenaline, melatonin, and cortisol on such an electrode is 300 mV. The proposed method is tested in the analysis of urine samples. The flow-injection scheme is supplemented with a dialyzer and a chromatographic minicolumn to eliminate the interfering effect of electrophilic compounds. The linear bilogarithmic dependence of the analytical signal on the concentration of adrenaline, melatonin, and cortisol is observed in the ranges of 5.0 × 10^–10–5.0 × 10^–3, 5.0 × 10^–11–5.0 × 10^–3, and 5.0 × 10^–12–5.0 × 10^–3 mol/L, respectively. Amperometric determination of the hormones in the flow-injection system leads to an increase in the productivity of the analysis and a decrease in the consumption of the sample and makes it possible to automate the process.