Engineering electrode surfaces through the electrodeposition of gold may provide a range of advantages in the context of biosensor development, such as greatly enhanced surface area, improved conductivity and versatile functionalization. In this work we report on the development of an electrochemical biosensor for the laccase-catalyzed assay of two catecholamines—dopamine and L-epinephrine. Variety of electrochemical techniques—cyclic voltammetry, differential pulse voltammetry, electrochemical impedance spectroscopy and constant potential amperometry have been used in its characterization. It has been demonstrated that the laccase electrode is capable of sensing dopamine using two distinct techniques—differential pulse voltammetry and constant potential amperometry, the latter being suitable for the assay of L-epinephrine as well. The biosensor response to both catecholamines, examined by constant potential chronoamperometry over the potential range from 0.2 to −0.1 V (vs. Ag|AgCl, sat KCl) showed the highest electrode sensitivity at 0 and −0.1 V. The dependencies of the current density on either catecholamine’s concentration was found to follow the Michaelis—Menten kinetics with apparent constants KMapp = 0.116 ± 0.015 mM for dopamine and KMapp = 0.245 ± 0.031 mM for L-epinephrine and linear dynamic ranges spanning up to 0.10 mM and 0.20 mM, respectively. Calculated limits of detection for both analytes were found to be within the sub-micromolar concentration range. The biosensor applicability to the assay of dopamine concentration in a pharmaceutical product was demonstrated (with recovery rates between 99% and 106%, n = 3).
Hydroperoxides generated on lipid peroxidation are highly reactive compounds, tend to form free radicals, and their elevated levels indicate the deterioration of lipid samples. A good alternative to the classical methods for hydroperoxide monitoring are the electroanalytical methods (e.g., a catalytic electrode for their redox-transformation). For this purpose, a series of metal oxides—doped graphitic carbon nitride 2D nanomaterials—have been examined under mild conditions (pH = 7, room temperature) as catalysts for the electrochemical reduction of two water-soluble hydroperoxides: hydrogen peroxide and tert-butyl hydroperoxide. Composition of the electrode modifying phase has been optimized with respect to the catalyst load and binding polymer concentration. The resulting catalytic electrode has been characterized by impedance studies, cyclic voltammetry and chronoamperometry. Electrocatalytic effect of the Co-g-C3N4/Nafion modified electrode on the electrochemical reduction of both hydroperoxides has been proved by comparative studies. An optimal range of operating potentials from −0.215 V to −0.415 V (vs. RHE) was selected with the highest sensitivity achieved at −0.415 V (vs. RHE). At this operating potential, a linear dynamic range from 0.4 to 14 mM has been established by means of constant-potential chronoamperometry with a sensitivity, which is two orders of magnitude higher than that obtained with polymer-covered electrode.
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