Biosensing Dopamine and L-Epinephrine with Laccase (Trametes pubescens) Immobilized on a Gold Modified Electrode

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)

Electrocatalytic Reduction of Hydrogen Peroxide on Palladium-Gold Codeposits on Glassy Carbon: Applications to the Design of Interference-Free Glucose Biosensor

Following our previous studies on the catalytic activity electrochemically codeposited on graphite Pd-Pt electrocatalysts for hydrogen peroxide electroreduction, a series of glassy carbon electrodes were modified with Pd or (Pd+Au) deposits aiming at the development of even more efficient electrocatalysts for the same process. The resulting electrodes were found to be very effective at low applied potentials (−100 and −50 mV versus Ag/AgCl, 1 M KCl). The surface topography of the electrode modified with Pd+Au mixed in proportions 90% : 10%, exhibiting optimal combination of sensitivity and linear dynamic range towards hydrogen peroxide electrochemical reduction, was studied with SEM and AFM. The applicability of the same electrode as transducer in an amperometric biosensor for glucose assay was demonstrated. At an applied potential of −50 mV, the following were determined: detection limit (S/N=3) of 6×10−6 M glucose, electrode sensitivity of 0.15 μA μM−1, and strict linearity up to concentration of 3×10−4 M

2D Nanomaterial—Based Electrocatalyst for Water Soluble Hydroperoxide Reduction

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

Pd-Au Electrocatalysts for Hydrogen Evolution Reaction at Neutral pH

Pd-Au codeposits with different ratio of both metals were electrodeposited on carbon felt, characterized by scanning electron microscopy, and investigated as electrocatalysts towards hydrogen evolution reaction in neutral phosphate buffer solution. The quantities of the produced hydrogen gas with different electrocatalysts, estimated from data obtained by chronoamperometry, were confirmed by mass spectrometry analysis. The highest hydrogen evolution rate was achieved with the electrocatalysts, produced from electrolyte with equal Pd and Au content

Duplex Surface Modification of 304-L SS Substrates by an Electron-Beam Treatment and Subsequent Deposition of Diamond-like Carbon Coatings

In this study, we present the results of the effect of duplex surface modification of 304-L stainless steel substrates by an electron-beam treatment (EBT) and subsequent deposition of diamond-like carbon coatings on the surface roughness and corrosion behavior. During the EBT process, the beam power was varied from 1000 to 1500 W. The successful deposition of the DLC coatings was confirmed by FTIR and Raman spectroscopy experiments. The results showed a presence of C–O, C=N, graphite-like sp2, and mixed sp2-sp3 C–C bond vibrations. The surface topography was studied by atomic force microscopy. The rise in the beam power leads to a decrease in the surface roughness of the deposited DLC coatings. The studies on the corrosion resistance of the samples have been performed using three electrochemical techniques: open circuit potential (OCP), cyclic voltammetry (polarization measurements), and non-destructive electrochemical impedance spectroscopy (EIS). The measured corrosion potentials suggest that these samples are corrosion-resistant even in a medium, containing corrosive agents such as chloride ions. It can be concluded that the most corrosion-resistant specimen is DLC coating deposited on electron-beam-treated 304-L SS substrate by a beam power of 1500 W

Direct electron transfer between ligninolytic redox enzymes and electrodes

The electrochemistry of the ligninolytic redox enzymes, which include lignin peroxidase, manganese peroxidase and laccase and possibly also cellobiose dehydrogenase, is reviewed and discussed in conjunction with their basic biochemical characteristics. It is shown that long-range electron transfer between these enzymes and electrodes can be established and their ability to degrade lignin through a direct electron transfer mechanism is discussed