Electrochemical behavior and voltammetric determination of pyrazinamide using a poly-histidine modified electrode

Pyrazinamide (Pyrazinecarboxamide-PZA) is a drug that is used to treatment tuberculosis. In the present work, the voltammetric behavior of PZA was studied using a screen-printed modified electrode (SPCE). The modified electrode was constructed using poly-histidine films, and it showed an electrocatalytic effect, thus promoting a decrease in PZA reduction potential and improving the voltammetric response. Cyclic voltammetry and electrochemical impedance spectroscopy techniques have been employed in order to elucidate of the electrodic reaction. The results allowed the proposal that in the PZA reduction, a further chemical reaction occurs that corresponds to a second-order process which is subsequent to the electrode reaction. In addition, a sensitive voltammetric method was developed, and it was successfully applied for PZA determination in human urine samples. The best response was found using SPCE modified with poly-histidine prepared by histidine monomer electropolymerization (SPCE/EPH). The electroanalytical performance of the SPCE/EPH was investigated by linear sweep (LSV), differential pulse (DPV), and square wave voltammetry (SWV). A linear relationship between peak current and PZA concentrations was obtained from 9.0 × 10-7 to 1.0 × 10-4 mol L-1 by using DPV. The limit of detection at 5.7 × 10 -7 mol L-1 was estimated, and a relative standard deviation of the 5.0 × 10-6 mol L-1 of PZA of 10 measurement was 3.7%. © 2012 Elsevier B.V. All rights reserved.

Produtividade e nutrição em três acessos de Baccharis trimera em função da adubação organo-mineral, em casa de vegetação

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Determination of tetradifon in brazilian green bell pepper by differential pulse voltammetry

Tetradifon, a potentially carcinogenic and mutagenic pesticide, can contribute to environmental and human contamination when applied to green bell pepper crops. In this context, in this work, a reliable and sensitive method for determination of tetradifon in Brazilian green bell pepper samples involving a differential pulse voltammetry (DPV) technique on a glassy carbon electrode is proposed. The electrochemical behavior of tetradifon as followed by cyclic voltammetry (CV) suggests that its reduction occurs via an irreversible five–electron transfer vs. Ag|AgCl, KCl 3 M reference electrode. Very well–resolved diffusion controlled voltammetric peaks have been obtained in a supporting electrolyte solution composed of a mixture of 40% dimethylformamide (DMF), 30% methanol, and 30% NaOH 0.3 mol L−1 at −1.43, −1.57, −1.73, −1.88, and −2.05 V. The proposed DPV method has a good linear response in the 3.00 – 10.0 μmol L−1 range, with a limit of detection (L.O.D) of 0.756 μmol L−1 and 0.831 μmol L−1 in the absence and in the presence of the matrix, respectively. Moreover, improved L.O.D results (0.607 μmol L−1) have been achieved in the absence of DMF from the supporting electrolyte solution. Recovery has been evaluated in five commercial green bell pepper samples, and recovery percentages ranging from 91.0 to 109 have been obtained for tetradifon determinations. The proposed voltammetric method has also been tested for reproducibility, repeatability, and potential interferents, and the results obtained for these three analytical parameters are satisfactory for electroanalytical purposes.

New voltammetry-based technique for the determination of tebuthiuron in crystal and brown sugar samples

Sugar is widely consumed worldwide and Brazil is the largest producer, consumer, and exporter of this product. To guarantee proper development and productivity of sugar cane crops, it is necessary to apply large quantities of agrochemicals, especially herbicides and pesticides. The herbicide tebuthiuron (TBH) prevents pre- and post-emergence of infesting weed in sugarcane cultures. Considering that it is important to ensure food safety for the population, this paper proposes a reliable method to analyse TBH in sugar matrixes (brown and crystal) using square wave voltammetry (SWV) and differential pulse voltammetry (DPV) at bare glassy carbon electrode and investigate the electrochemical behavior of this herbicide by cyclic voltammetry (CV). Our results suggest that TBH or the product of its reaction with a supporting electrolyte is oxidized through irreversible transfer of one electron between the analyte and the working electrode, at a potential close to +1.16 V vs. Ag |AgClsat in 0.10 mol L-1 KOH as supporting electrolyte solution. Both DPV and SWV are satisfactory for the quantitative analysis of the analyte. DPV is more sensitive and selective, with detection limits of 0.902, 0.815 and 0.578 mg kg-1, and quantification limits of 0.009, 0.010 and 0.008 mg kg-1 in the absence of the matrix and in the presence of crystal and brown sugar matrix, respectively. Repeatability lay between 0.53 and 13.8%, precision ranged between 4.14 and 15.0%, and recovery remained between 84.2 and 113% in the case of DPV conducted in the absence of matrix and in the presence of the crystal sugar matrix, respectively.

New voltammetry-based analytical method for indirect determination of procymidone in brazilian apples

Procymidone, a potentially carcinogenic and mutagenic pesticide, can contribute to environmental and human contamination when applied to apple crops. In this work, we propose a reliable and sensitive method to determine procymidone in Brazilian apples. The method involves differential pulse (DPV) and square-wave voltammetry (SWV) techniques on a glassy carbon electrode. In a supporting electrolyte solution of 0.5 mol L−1 NaOH, procymidone undergoes an irreversible one-electron oxidation at +1.42 V by cyclic voltammetric vs. Ag|AgCl, KCl 3 M reference electrode. The proposed DPV and SWV methods have a good linear response in the 8.00–20.0 mg L−1 range, with limits of detection (LOD) of 0.678 and 0.228 mg L−1, respectively, in the absence of the matrix. We obtained improved LOD (0.097 mg L−1) in the presence of apple matrix and the supporting electrolyte solution. We used three commercial apple samples to evaluate recovery, and we achieved recovery percentages ranging from 94.6 to 110 % for procymidone determinations. We also tested the proposed voltammetric method for reproducibility, repeatability, and potential interferents, and the results were satisfactory for electroanalytical purposes.

Cathodic stripping voltammetric determination of arsenic in sugarcane brandy at a modified carbon nanotube paste electrode

We have developed an eletroanalytical method that employs Cu2+ solutions to determine arsenic in sugarcane brandy using an electrode consisting of carbon paste modified with carbon nanotubes (CNTPE) and polymeric resins. We used linear sweep (LSV) and differential-pulse (DPV) voltammetry with cathodic stripping for CNTPE containing mineral oil or silicone as binder. The analytical curves were linear from 30 to 110 μg L−1 and from 10 to 110 μg L−1 for LSV and DPV, respectively. The limits of detection (L.O.D.) and quantification (L.O.Q.) of CNTPE were 10.3 and 34.5 μg L−1 for mineral oil and 3.4 and 11.2 μg L−1 for silicone. We applied this method to determine arsenic in five commercial sugarcane brandy samples. The results agreed well with those obtained by hydride generation combined with atomic absorption spectrometry (HG AAS).

Detecção eletroquímica de furfural e hidroximetilfurfural em bagaço de cana-de-açúcar utilizando cromatografia líquida de alta eficiência

Pós-graduação em Química - IQ

Desenvolvimento de eletrodos modificados para determinação de cálcio e magnésio em biodiesel

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Desenvolvimento de sensores baseados em eletrodos modificados com pentacianonitrosilferratos para determinação de compostos sulfurados em gás natural

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Qualidade fisiológica e desempenho agronômico de soja em função do tamanho das sementes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Variabilidade sazonal da condutância estomática em um ecossistema de manguezal amazônico e suas relações com variáveis meteorológicas

No presente trabalho foram estudadas as variações da condutância estomática (g_s) para o período chuvoso (março) e seco (agosto) do ano de 2003, e suas relações de dependência com algumas variáveis meteorológicas medidas em um ecossistema de manguezal amazônico. As informações utilizadas foram do projeto ECOBIOMA, parte integrante do Experimento de Grande Escala da Biosfera-Atmosfera da Amazônia (LBA). A g_s acompanha a tendência de variação do balanço de radiação, atingindo valores máximos durante o dia e mínimos durante a noite. A condutância apresentou maiores flutuações no período chuvoso, com valor médio de g_s = 0,015 m s^-1, porém com magnitudes inferiores as do período seco. Durante a época seca apresentou um valor médio de g_s = 0,027 m s^-1, com menor amplitude, variando de 0,010 < g_s < 0,042 m s^-1. As variáveis meteorológicas utilizadas para o estabelecimento de relações de dependência com a variabilidade diária de g_s foram déficit de umidade específica (δq), déficit de pressão de vapor (DPV), saldo de radiação (Rn) e velocidade do vento (Vv). O DPV apresentou as melhores correlações com a g_s sendo o R² = 0,99 em ambos os períodos. Apesar de também ser importante nas trocas gasosas entre a vegetação e a atmosfera, a Vv apresentou a menor influência na variação média da g_s, com um R² = 0,44 para época chuvosa e R² =0,51 para o período seco.

Desenvolvimento de métodos eletroanalíticos para determinação de compostos nitrogenados em combustíveis derivados do petróleo

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Desenvolvimento de eletrodos modificados para determinação de compostos sulfurados em gasolina

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

An Electrochemical Sensor for Reducing Sugars Based on a Glassy Carbon Electrode Modified with Electropolymerized Molecularly Imprinted Poly-o-phenylenediamine Film

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Efeito da sazonalidade nos parâmetros ecofisiológicos de Copaifera langsdorffii Desf. (Fabaceae-Caesalpinoideae) em Floresta Estacional Semidecídua

Os fatores ambientais podem causar estresse nas plantas acarretando alterações no metabolismo ou desenvolvimento, consequentemente modifica as condições ótimas que afetam o ciclo de vida e induz respostas em todos os níveis funcionais do organismo. A seca é um fator que tem grande influência nas plantas. Algumas espécies arbóreas desenvolveram mecanismos morfológicos, fisiológicos e bioquímicos para superar eventual suprimento inadequado de água. A espécie estudada, Copaifera langsdorffii Desf. está presente em formações vegetais de transição do cerrado stricto senso para a floresta semidecídua. Essa característica possibilita analisar respostas fisiológicas perante os efeitos sazonais da seca presente nestas formações florestais. O objetivo do trabalho foi comparar as respostas fisiológicas de Copaifera langsdorffii Desf. Em relação ao contraste hídrico característico de floresta estacional semidecídua. Para compreeender os efeitos desta sazonalidade avaliamos alguns parâmetros ecofisiológicos como Condutância Estomática (gs), Conteúdo Relativo de Água (Relative Water Content –RWC), Déficit Pressão de Vapor (DPV), potencial água foliar (Ψw) e fluorescência da clorofila. As avaliações foram feitas ao final da época úmida (FEU), final da época seca (FES) e início da época úmida (IEU) ao longo de 3 períodos do dia 5:00h (Predawn – PD), 12:00h (Midday – MD) e 17:00h (Afternoon – AF). Após as análises observamos queda de gs e aumento do DPV, valores constantes de RWC e Ψw foliar no FES. Mesmo em condições de déficit hídrico as plantas não apresentaram mecanismos de fotoinibição