Eletrodo de diamante foi usado para avaliar a interação dos nucleotídeos guanosina monofosfato (GMP) e adenosina monofosfato (AMP) com os pesticidas clorpirifós, metamidofós e monocrotofós. Observaram-se alterações nas correntes e potenciais de picos dos voltamogramas dos nucleotídeos na presença dos pesticidas dependendo da concentração de pesticida (de 5,0 × 10-7 a 5,0 × 10-5 mol L-1) e do tempo de interação (de 1 min a 4 h). Isto é provavelmente devido à ligação dos pesticidas às bases nitrogenadas presentes nos nucleotídeos, o que poderia levar a problemas na replicação do DNA e nas funções biológicas de nucleotídeos. Os pesticidas apresentaram maior interação com AMP que com GMP. Estudos sobre a interação de DNA 50 µg mL-1 com os pesticidas (de 30 min até 4 h, e de 1,0 × 10-6 a 6,0 × 10-5 mol L-1) não revelaram picos relativos à abertura da dupla hélice ou desenrolamento do DNA.

Diamond electrode was used to evaluate the interaction of the nucleotides guanosine monophosphate (GMP) and adenosine monophosphate (AMP) with the pesticides chlorpyrifos, methamidophos and monocrotophos. Changes were observed in the currents and peak potentials of the nucleotide voltammograms in the presence of the pesticides, with dependence on the pesticide concentration (from 5.0 × 10-7 to 5.0 × 10-5 mol L-1) and the interaction time (from 1 min to 4 h). This is probably due to binding of the pesticides to the nitrogenous bases present in the nucleotides, which could lead to problems in the DNA replication and biological functions of nucleotides. The pesticides showed stronger interaction with AMP than with GMP. Studies of the interaction of 50 µg mL-1 DNA with the pesticides (from 30 min to 4 h and from 1.0 × 10-6 to 6.0 × 10-5 mol L-1) did not reveal any peaks relating to double helix opening or DNA unwinding.

A espectrofotometria UV-Vis foi utilizada para medir a solubilidade do corante disperso red 1 (DR1) em soluções aquosas, com diferentes solventes e dispersantes. O corante foi quantificado em amostras de águas, e sua interação com o ds-DNA de timo de vitelo foi investigada. Os resultados mostraram que o dispersante comercial Fongranal® FB foi adequado para a preparação das soluções aquosas do DR1. Para a determinação de DR1 em água pura, o limite de detecção foi de 2,47 × 10-6 mol L-1, e o limite de quantificação, 8,22 × 10-6 mol L-1. Porcentagens de recuperação de 91,2 e 103% foram obtidas para as concentrações de DR1 em 3,00 × 10-6 e 40,0 × 10-6 mol L-1, respectivamente. As recuperações alcançadas de DR1 em água de torneira e de rio ficaram na faixa de 85,9-113%. A interação de DR1 com o DNA de timo de vitela foi acompanhada por efeitos de hipocromismo e hipercromismo, que foram relacionados à mudanças conformacionais e lesão na dupla hélice do DNA.

UV-Vis spectrophotometry was used to measure the solubility of disperse red 1 (DR1) dye in aqueous solutions, using different solvents and dispersants. The dye was quantified in water samples, and its interaction with calf thymus ds-DNA was investigated. The results showed that the commercial dispersant Fongranal® FB was suitable for the preparation of aqueous DR1 solutions. For the determination of DR1 in purified water, the limit of detection was 2.47 × 10-6 mol L-1, and the limit of quantification was 8.22 × 10-6 mol L-1. Percentage recoveries of 91.2 and 103% were obtained for DR1 concentrations of 3.00 × 10-6 and 40.0 × 10-6 mol L-1, respectively. The recoveries achieved for DR1 present in tap and river water were in the range 85.9-113%. The interaction of DR1 with calf thymus DNA was accompanied by hypochromic and hyperchromic effects, which were related to conformational changes and damage to the DNA double helix.

A detecção individual e em mistura equimolar dos nucleotídeos de DNA guanosina (GMP), adenosina (AMP), timidina (TMP) e citidina (CMP) 5'-monofosfato, utilizando a voltametria de onda quadrada, foi realizada sobre o eletrodo de diamante dopado com boro (DDB) prétratado catodicamente (Red-DDB) e anodicamente (Oxi-DDB). A oxidação dos nucleotídeos individuais de DNA foi mais sensível sobre o Oxi-DDB. Na detecção simultânea de nucleotídeos, as respostas de GMP, AMP, TMP e CMP foram muito adequadas sobre ambos os eletrodos tratados. Particularmente, picos mais sensíveis e mais separados para TMP e CMP sobre o Oxi-DDB e Red-DDB, respectivamente, foram observados após procedimento de deconvolução. A detecção dos nucleotídeos em soluções aquosas certamente contribuirá para avaliação genotóxica de substâncias e em reações de hibridização por meio da imobilização de ss ou ds-DNA sobre a superfície do DDB.

The individual detection and equimolar mixture of DNA nucleotides guanosine monophosphate (GMP), adenosine monophosphate (AMP), thymidine (TMP) and cytidine (CMP) 5'-monophosphate using square wave voltammetry was performed on boron doped diamond (BDD) electrodes cathodically (Red-DDB) and anodically (Oxi-DDB) pretreated. The oxidation of individual DNA nucleotides was more sensitive on Oxi-BDD electrode. In a simultaneous detection of nucleotides, the responses of GMP, AMP, TMP and CMP were very adequate on both treated electrodes. Particularly, more sensitive and separate peaks for TMP and CMP on Oxi-BDD and Red-BDD electrodes, respectively, were observed after deconvolution procedure. The detection of nucleotides in aqueous solutions will certainly contribute for genotoxic evaluation of substances and hybridization reactions by immobilizing ss or ds-DNA on BDD surface.

The potentiality of the use of ultrasound radiation in association with a boron-doped diamond electrode was evaluated on the voltammetric determination of the pesticide carbaryl. Improvements in the sensitivity, limit of detection and reproducibility of the measurements were observed due to both, the enhancement of mass transport and the cleaning of the electrode surface provided by ultrasound. Satisfactory recovery levels for carbaryl in pure water (96-98%) and pineapple juice (89-92%) for quiescent and sonovoltammetric methodologies were obtained. These methodologies can be alternative tools for the analyses of pesticides in fruit samples, mainly the insonated condition that improve the analytical performance and dispense intermediary cleanings of the electrode surface.

An analytical method for the determination of the anti-inflammatory drug 5-aminosalicylic acid (5-ASA) in pharmaceutical formulations using square wave voltammetry at pencil graphite electrodes was developed. After the optimization of the experimental conditions, calibration curves were obtained in the linear concentration range from 9.78 × 10-7 to 7.25 × 10-5 mol L-1 resulting in a limit of detection of 2.12 ± 0.05 x 10-8 mol L-1. Statistical tests showed that the concentrations of 5-ASA in commercial tablets and enemas obtained with the proposed voltammetric method agreed with HPLC values at a 95% confidence level.

The beneficial effects of the ultrasound (US) like the cleaning of electrode surface and enhancement of mass transport were evaluated in association with potentiostatic electrolyses for the degradation of pentachlorophenol (PCP) at 3.0 V vs. Ag/AgCl, using a boron-doped diamond (BDD) electrode during 270 minutes. Different decay levels of the PCP spectrum bands in 220, 251 and 321 nm, respectively, were observed after application of ultrasound without electrochemical process (18.1, 17.7 and 19.8 %), silent electrolyses (29.3, 71.6 and 70.8 %), pulsed sonoelectrolysis (31.0, 75.1 and 76.3%) and sonoelectrolyses (39.2, 80.0 and 82.6 %). For silent and sonoelectrolyses processes, cleaning/reactivation of the BDD surface by acetonitrile and/or electrochemical treatment was necessary. The pulsed sonolectrolysis were carried out purposely without cleaning/reactivation of the surface. The results showed greater PCP degradation for insonated studies than those obtained for the silent electrolyses, due to the increase of mass transport, minimization of the electrode fouling and the combined generation of hydroxyl radicals by both ultrasound and the polarized BDD surface. These tools (US and BDD), especially the pulsed sonoelectrolysis, can improve the degradation of pesticides and their metabolites in the environment and enable the use of sonoelectrochemistry for wastewater remediation.

The aim of this review is to present and discuss the applications of ultrasound in electrochemical systems such as in sonoelectroanalysis and sonoelectrolysis for the electrochemical combustion of organic compounds. Initially, theoretical and experimental aspects are discussed, particularly those related to the enhancement of mass transport and the surface cleaning effects. Some results are included to illustrate alternative geometries for the experimental measurements and the working electrodes used in these systems. In the sequence, the available publications are presented and discussed to demonstrate that ultrasound combined with electrochemical techniques is a powerful set-up for the detection of analytes such as metals and/or organic compounds in hostile media and for the effective destruction of toxic organic substances. At the end, a table summarizes the results already published in the literature.

A determinação sonovoltamétrica do 4-nitrofenol foi estudada sobre um eletrodo de diamante dopado com boro. Foram observadas melhorias significativas na sensibilidade analítica devido à limpeza da superfície eletródica e ao aumento no transporte de espécies ao eletrodo proporcionados pelo ultra-som. Desta maneira, para os processos de oxidação e redução, os limites de detecção diminuíram de 11.7 para 3.87 e de 6.38 para 2.57 µg L-1, respectivamente.

The sonovoltammetric determination of 4-nitrophenol was studied on a boron-doped diamond electrode. Significant improvements in the analytical sensibility were observed due to electrode surface cleaning and the enhancement in the transport of species to the electrode surface provided by ultrasound. Thus, for the oxidation and reduction process, the limit of detection diminished from 11.7 to 3.87 and from 6.38 to 2.57 µg L-1, respectively.

This work describes the development of electroanalytical methodologies for the determination of atrazine, ametrine and simazine by square wave voltammetry on a mercury electrode. For pure atrazine and pure ametrine, the detection limits (DL) were 3.7 and 4.3 µg L-1, respectively, while they increased to 4.8 and 6.5 µg L-1 in the presence of 3.0 x 10-6 mol L-1 of the other component (a mathematical deconvolution program was used in the mixture cases). The voltammetric response for simazine could not be separated from that of atrazine and measurements were carried out only in pure simazine solutions (DL: 7.5 µg L-1).

The aim of this work is to discuss selected applications of electroanalytical techniques for the detection of pesticides in foods and beverages, published in the last ten years. The applications involved different working electrodes for the electroanalytical determination of pesticides, namely amperometric biosensors, cholinesterase-based biosensors, polymer-modified electrodes, ultramicroelectrodes and hanging mercury drop electrodes. They were used for several voltammetric and amperometric techniques in different analytical procedures for the detection and quantification of different classes of pesticides in different food matrices.