The present paper deals with the reaction of oxidative dimerization of the H[Ru(III)Cl2(H2EDTA)].4.5 H2O complex on the surface of silica gel functionalized (SF) with [3-(2-aminoethyl)aminopropyl]trimethoxysilane (AEATS), generating the dimeric (EDTA)2Ru2(IV,IV) complex immobilized on the surface of this silica through the coordination with amide bonds. The oxidation of water by the anchored dimeric complex proceeded rapidly and was observed by the evolution of O2 and the decrease in pH, yielding the SF-AEATS/(EDTA)2Ru2(III1/2 ,III1/2). This anchored dimer was characterized by electronic, vibrational and EPR spectroscopies. The electrochemical behavior of a modified carbon paste electrode prepared with SF-AEATS/(EDTA)2Ru2(III1/2 ,III1/2) was also studied.

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.

The anodic voltammetric behavior of 4-chlorophenol (4-CF) in aqueous solution has been studied on a Boron-doped diamond electrode using square wave voltammetry (SWV). After optimization of the experimental conditions, 4-CF was analyzed in pure and natural waters using a Britton-Robinson buffer with pH = 6.0 as the supporting electrolyte. Oxidation occurs at 0.80 V vs Ag/AgCl in a two-electron process controlled by adsorption of the species. The detection limits obtained were 6.4 µg L-1 in pure water and 21.5 µg L-1 for polluted water taken from a local creek, respectively. The combination of square wave voltammetry and diamond electrodes is an interesting and desirable alternative for analytical determinations.

The anodic voltammetric behavior of 4-Nitrophenol on a Boron-doped diamond electrode in aqueous solution has been studied using square wave voltammetry. After optimization of the experimental conditions, that model molecule was analyzed in pure water solutions using a Britton-Robinson buffer with pH 6.0 as the supporting electrolyte. Oxidation occurs at 1.0 V vs. Ag/AgCl in an irreversible two-electron process controlled by adsorption of the species. The detection limit (DL) obtained was 2.8 mug L-1. This result was comparable to that obtained from reduction of the molecule at -0.8 V vs. Ag/AgCl under the same experimental conditions (DL = 4.2 mug L-1). Both DL values are within the limits required by the legislation for drinking water (30 mug L-1). The combination of square wave voltammetry and diamond electrodes has proved to be an interesting and desirable alternative for the analytical determination of organic molecules.

The present study aims the development and application of an electrochemical method for simple coumarin determination in aqueous media by using a boron-doped diamond electrode (BDDE). The studies were carried out at pH 8.0 by cyclic voltammetry (CV) and registered an irreversible reduction process controlled by diffusion with the peak potential recorded around -1.6 V. The square wave voltammetry analysis (SWV) showed the reversible behavior of the electrochemical reduction of coumarin at the same pH. Additionally, the reversibility of the process was improved by increasing the solution pH. The chronoamperometry study showed that the coumarin reduction process involves two electrons. From the optimized SWV parameters, the analytical curve was constructed in a linear range between 0.5 × 10-5 and 10.0 × 10-5 mol L-1. The limits of detection and quantification were 1.5 × 10-6 mol L-1 and 4.5 × 10-6 mol L-1, respectively. The coumarin was determined in an aqueous infusion of Mikania glomerata, showing recovery values between 92 and 104%.

Multilayer graphene (G-US) and multilayer graphene muffled (Gm-US) produced by liquid exfoliation ultrasound were used as support for Pd nanoparticles with a load of 20 wt% for application in an alkaline direct ethanol fuel cell (ADEFC) anode. The multilayer graphene–based electrocatalyst (Pd/G-US) exhibited superior current density and less positive onset potential for ethanol oxidation reaction (EOR) than the commercial Pd/C (AA). Also, the Pd/G-US electrocatalyst showed the less positive onset potential for CO oxidation. In ADEFC experiments, the Pd/G-US catalyst exhibited a superior performance with 38 mW cm−2. The findings suggest that the defective graphene structure promotes electron transport, and the presence of oxygenated species increases hydrophilicity facilitating the oxidation of intermediates. Hence, the synthesized material can be considered as promising support for an anode in ADEFC. Graphical abstract: [Figure not available: see fulltext.]

The aim of this work is to discuss some selected applications of square wave voltammetry published in the last five years. The applications focused here cover several electroanalytical fields such as: determination of pesticides; molecules with biological activity; metals and other environmental pollutants. Special attention is given to the work developed in the Grupo de Materiais Eletroquímicos e Métodos Eletroanalíticos - IQSC - USP concerning the utilization of square wave voltammetry, with different kinds of electrodes, for the determination of pesticides in natural waters and active principles in pharmaceutical formulations. The new methodology is simple, fast and sensitive when compared with the traditional ones such as chromatography and spectrophotometry. The satisfactory results obtained provide alternative procedures for the quality control of drugs and the monitoring of pesticides in natural environments.

This work studied the fluorescent and solvatochromic properties of coumarin and its derivatives aiming to contribute in the elucidation of the excited state behavior of the molecule in solvent mixtures. This approach has been developed through a set of measurements involving different solvent ratios, which present distinct dielectric constants. The excitation and fluorescence maxima were largely blue-shifted with increasing participation of the organic solvent and the Stokes shifts were unusually low in mixtures with lower solvent polarity parameter, Δf. The emission intensity of coumarin was extremely sensitive to the polarity and the different structural conformations of solvents. These results influenced the spectroscopic behavior and explain the deviation from the linearity of the Lippert-Mataga relationship. The use of fluorescence spectroscopy makes the understanding of the behavior of the systems studied when in the presence of different environments being extremely important for the identification and characterization of coumarin in different pharmaceutical formulations.

In this study the role of different metal centers (magnesium, zinc and copper) on the enhancement of the hydrophilic character of metallochlorophylls, was evaluated. The solvatochromism as well as the aggregation process for these compounds in water/ethanol mixtures at different volume ratios were evaluated using Fluorescence, and Resonant Light Scattering (RLS) measurements, aiming to characterize the behavior of these compounds. Independently on the studied metallochlorophyll, the presence of at least 60% of water results in a considerable increase in the fluorescence emission, probably a direct consequence of a lower aggregation of these compounds, which is confirmed by the results from RLS measurements. Additionally, the results suggest that magnesium and zinc chlorophyll should be promising phototherapeutic agents for Photodynamic Therapy.