This work presents the development and characterization of a new chemically modified electrode exploiting recordable Au-rewritable compact discs (AuCDs) as substrate for drop casting of a chemically-reduced graphene-oxide slurry focusing on simple and low-cost electrochemical sensors. Increase in electrochemical responses in cyclic voltammetric and amperometric measurements were achieved using the proposed sensor. Both scanning electron microscopy and atomic force microscopy data showed increase in rugosity (about 46% higher) for the chemically reduced graphene oxide (CRGO) AuCD surface while Raman spectroscopy confirmed the presence of structural defects of graphene. The calculated charge transfer resistances (Rct) and heterogeneous electron transfer rate constants (k0) were 1638 Ω and 0.0022 cm s-1 for the bare substrate, and 91 Ω and 0.0027 cm s-1 for the modified electrode, evidencing the facilitated electron transfer of the CRGO-AuCD surface. The dopamine (DP) amperometric detection using CRGO-AuCD provided low detection limit (0.12 µg L-1) compared with other modified electrodes already reported, high precision (relative standard deviation (RSD) < 5%) and analytical frequency (370 h-1). As a proof-of-concept, DP determination in synthetic saliva samples was performed and a satisfactory recovery value (98.6 ± 0.9%) was obtained.
The electrochemical behavior of N-nitrosothiazolidine carboxylic acid (NTAC) on gold and hanging mercury electrodes, using the cyclic and square wave voltammetries, was studied. Whereas NTAC suffer reduction in a single step on the mercury electrode, two peaks appears on the cyclic voltammograms on the gold electrode, one anodic peak overlaying the gold oxide process at 1.2 V and one cathodic peak at -0.41 V vs Ag/AgCl, KCl 3.0 mol L-1. The cathodic peak depends on the previous oxidation of NTAC at the electrode surface, presents irreversible and adsorption controlled characteristics and it is suitable for quantitative purposes.
Canonical Monte Carlo simulations, at 298 K, of the adsorption of phenol in a dilute aqueous solution on gold electrodes, at the potential of zero charge, are presented. The results suggest that the process occurs in two distinct and successive steps. Adsorption starts with the phenol oxygen atom pointing towards the gold surface and the aromatic ring in a quasi-perpendicular orientation relative to the surface. This is followed by the reorientation of the aromatic ring to a parallel configuration. The effect of the solvent is analyzed through the calculation of the potential of mean force acting on phenol. Despite the simplicity of the model and the interaction potentials used in the simulations, the results are in good agreement with experimental observations, giving insight into the microscopic details of the adsorption process of phenol at low concentrations.
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The voltammetric behaviour of glutamate at a gold electrode was studied by means of cyclic voltammetry. From 2.6 to 11.5 pH values, glutamate originated a single cathodic peak. Potential of the peak, Ep, was -0.8 V, and it was independent from pH. The reduction of glutamate was found irreversible and mainly controlled by diffusion. An analytical approach for analysis of glutamate by means of square wave voltammetry was developed. Plots of current versus concentration presented a linear behaviour from 2.5×10-4 to 2.7×10-3 M. The detection limit was 6.3×10-5 M. Interference from compounds co-existing with glutamate in food was negligible, and in favour of an application of the proposed method to the analysis of real samples. Determination of glutamate in pure solutions resulted in acceptable deviation from the stated concentration. Relative errors ranged -2.5 to +1.6 %.