Robson T. S. Oliveira

Voltametria de onda quadrada. Segunda parte: aplicações

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 Eletroquimicos e Metodos Eletroanaliticos - 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.

The Use of Ultrasound for the Analytical Determination of Nitrite on Diamond Electrodes by Square Wave Voltammetry

Abstract This work describes an analytical methodology for the determination of nitrite ions in aqueous solutions using boron‐doped diamond electrodes and square wave voltammetry associated with ultrasound radiation. The nitrite ions were oxidized to nitrate ions in Britton‐Robinson buffer solutions 0.1 M, pH 2.0 at 1.0 V versus Ag/AgCl. The voltammetric response of nitrite in the presence of ultrasound showed a peak current five times higher than the obtained in silent conditions. Thus, the detection limit obtained in the presence of radiation was 17 nM (0.782 µg l−1), a small value if compared with that obtained in the absence of ultrasound: 140 nM (6.44 µg l−1).

Quantificação do pesticida diclorvos por voltametria de onda quadrada em águas puras e naturais

This work reports the use of square wave voltammetry (SWV) to analyse the electrochemical reduction of dichlorvos (2, 2-dichlorovinyl-dimethylphosphate) in spiked pure and natural waters. SWV measurements were carried out in 0.5 mol L-1 Na2SO4 aqueous solutions at pH 5, prepared with water originated from three different sources, namely, one sample of purified water and others from two urban creeks in Sao Carlos County. In all cases, two reduction peaks were observed, at potentials of -0.15 and -1.05 V vs Ag/AgCl, with both current and potential being dependent on pesticide concentration. This allowed the calculation of the following detection limits: 1.0, 2.5 and 3.0x10-8 mol L-1 for purified, Gregorio creek and Monjolinho creek waters, respectively, in a working range between 2.0x10-7 and 1.4x10-6 mol L-1. Recovery measurements found values higher than 80% in all cases, for an added concentration of 4.0 x 10-7 mol L-1 of dichlorvos in each solution. All analytical experiments were performed in triplicate and showed a standard deviation always less than 3%.

Analytical determination of aliskiren in pharmaceutical formulations using boron-doped diamond electrodes

Here, we developed a simple and sensitive electroanalytical methodology and quantified aliskiren in pharmaceutical formulations, as well as in human serum samples by square-wave voltammetry. The analytical signal response was obtained by electrochemical oxidation of the aliskiren drug at a boron-doped diamond (BDD) electrode. The determination was carried out in 0.04 M Britton–Robinson pH 8 buffer solution. Aliskiren oxidation reveals a well-defined irreversible oxidation peak. The analytical curve was obtained in the concentration range from 1.81 × 10−5 to 1.63 × 10−4 M (r = 0.997). Limits of detection and quantification for aliskiren were 2.5 × 10−8 and 8.4 × 10−8 M, respectively. Recovery values were in the range of 98.2–100.2%, indicating no matrix interference effects on the analytical determination of aliskiren in commercial samples. The presence of interferents commonly found in human serum negligibly affects the electroanalytical response of aliskiren yielding good average recoveries of 95.5–97.8% after standard-solution additions. The BDD electrode exhibited a stable, selective and sensitive response to aliskiren in the presence of interferents.

High-Area Ti/Pt Electrodes for the Electrochemically Catalyzed Transesterification of Soybean Oil with Methanol

Biodiesel fuel is a renewable energy source normally produced in industry by using an alkaline homogeneous catalyst to promote the transesterification of oil and methanol to fatty acid methyl ester (FAME). Undesirable side reactions occur when poorly refined oils are used, leading to serious problems of product separation and low FAME yield. Therefore, about 85% of the cost of biodiesel is determined by the cost of the feedstock. Here, we describe the development of high-area Pt films deposited on Ti substrates for the electrolytic synthesis of biodiesel from soybean oil containing water, without the addition of catalyst. The higher both the calcination temperature and the number of layers deposited on the Ti surface, the higher the electrochemically active area of Pt exposed to surface. Conversion into esters in electrolysis is proportional to the increase in the superficial area of the Ti/Pt electrodes. Thus, it is possible to synthesize biodiesel using electrodes containing very low amounts of Pt (<0.441 mg cm−2), an important parameter in the industrial production of biodiesel.

Degradação eletroquímica da vinhaça usando eletrodo de diamante dopado com boro

The degradation of vinasses in aqueous solution from ethanol industry has been investigated by electrochemical oxidation using a boron doped diamond electrode (BDD). Samples of vinasses were electrolyzed in medium of (0.1 mol L-1) Na2SO4 solutions at controlled potentials of +2.4, +3.0 and +4.0 V (vs. Ag/AgCl) and exhibited considerable reduction of total organic carbon. The cyclic voltammetry studies indicate that the vinasses are oxidized irreversibly over the BDD at 2.0 V (vs. Ag/AgCl) in diffusion controlled process. From the experimental results it is clear that the BDD electrode can be a valuable tool to the electrochemical degradation of vinasses in practical applications