Determination of glyphosate and AMPA on polyester-toner electrophoresis microchip with contactless conductivity detection.

This paper reports a method for rapid, simple, direct, and reproducible determination of glyphosate and its major metabolite aminomethylphosphonic acid (AMPA). The platform described herein uses polyester-toner microchips incorporating capacitively coupled contactless conductivity detection and electrophoresis separation of the analytes. The polyester-toner microchip presented 150 µm-wide and 12 µm-deep microchannels, with injection and separation lengths of 10 and 40 mm long, respectively. The best results were obtained with 320 kHz frequency, 4.5 Vpp excitation voltage, 80 mmol/L CHES/Tris buffer at pH 8.8, injection in -1.0 kV for 7 s, and separation in -1.5 kV. RSD values related to the peak areas for glyphosate and AMPA were 1.5 and 3.3% and 10.1 and 8.6% for intra- and interchip assays, respectively. The detection limits were 45.1 and 70.5 µmol/L, respectively, without any attempt of preconcentration of the analytes. Finally, the method was applied to river water samples in which glyphosate and AMPA (1.0 mmol/L each) were added. The recovery results were 87.4 and 83.7% for glyphosate and AMPA, respectively. The recovery percentages and LOD values obtained here were similar to others reported in the literature.

Rapid and direct determination of glyphosate and aminomethylphosphonic acid in water using anion-exchange chromatography with coulometric detection.

A simple, rapid, and low-cost coulometric method for direct detection of glyphosate and aminomethylphosphonic acid (AMPA) in water samples using anion-exchange chromatography and coulometric detection with copper electrode is presented. Under optimized conditions, the limits of detection (LODs) (S/N=3) were 0.038microgml(-1) for glyphosate and 0.24microgml(-1) for AMPA, without any preconcentration method. The calibration curves were linear and presented an excellent correlation coefficient. The method was successfully applied to the determination of glyphosate and AMPA in water samples without any kind of extraction, clean-up, or preconcentration step. No interferent was found in the water, like this, the recovery was, practically, 100%.

Simultaneous determination of vitamins C, B6 and PP in pharmaceutics using differential pulse voltammetry with a glassy carbon electrode and multivariate calibration tools.

In this work, the artificial neural networks (ANN) and partial least squares (PLS) were applied to data obtained by differential pulse voltammetry for the determination of vitamins in synthetic and pharmaceutical samples. For calibration purposes, both synthetic and commercial samples were employed as standards. From the results it was possible to verify that ANN is the best method for modeling the data due to the fact that interactions among electro-active components result in non-linear response on the glassy carbon electrode. The results achieved for the determination of vitamins in pharmaceutical samples using ANN method provided a maximum value for relative error of 0.40% for VC, 8.3% for VPP and 9.1% for VB6. The proposed methodology is simple, rapid and can be easily used to control quality laboratories as an alternative analysis method.

Monitoring electrochemical reactions in situ using steady-state free precession (13)C NMR spectroscopy.

All attempts to use in situ(13)C NMR in spectroelectrochemical studies, using static cells and unlabeled substrates, have failed due to the very long average time (several hours). In this paper, we demonstrated that steady-state free precession (SSFP) pulse sequence can enhance signal to noise ratio and reduces the average time of (13)C NMR signals by more than one order of magnitude. The results showed that each (13)C NMR spectrum during the electrochemical reduction of 9-chloroanthracene, in a static cell, can be acquired in eleven minutes. This short averaging time allowed the analysis of the reaction every 30min during 3h. The phase and truncation anomalies present in SSFP spectra were minimized using Traff apodization function and Krylov basis diagonalization method (KBDM).

DFT and electrochemical studies on nortriptyline oxidation sites.

A study on the possible sites of oxidation and epoxidation of nortriptyline was performed using electrochemical and quantum chemical methods; these sites are involved in the biological responses (for example, hepatotoxicity) of nortriptyline and other similar antidepressants. Quantum chemical studies and electrochemical experiments demonstrated that the oxidation and epoxidation sites are located on the apolar region of nortriptyline, which will useful for understanding the molecule's activity. Also, for the determination of the compound in biological fluids or in pharmaceutical formulations, we propose a useful analytical methodology using a graphite-polyurethane composite electrode, which exhibited the best performance when compared with boron-doped diamond or glassy carbon surfaces.

Direct determination of glyphosate using hydrophilic interaction chromatography with coulometric detection at copper microelectrode.

A simple, rapid, and low-cost coulometric method for direct detection of glyphosate using hydrophilic interaction chromatography is presented. The principle of detection is based on the enhancement of the anodic current of copper microelectrode in the presence of complexing agents, such as glyphosate, with the formation of a soluble Cu(II) complex. Under optimized conditions, the limit of detection (S/R=3) for glyphosate was 0.1 mg L(-1) (0.59 microM) without any preconcentration method. The calibration curve has been found linear in all concentration range tested (from limit of detection to 34 mg L(-1)) with an excellent correlation coefficient (0.9999). The present method was successfully applied for the determination of glyphosate in fruit juices without any kind of extraction, clean-up, or preconcentration step, with recoveries of 92 and 90% for apple and grape juice, respectively.

Determination of triazine herbicides: development of an electroanalytical method utilizing a solid amalgam electrode that minimizes toxic waste residues, and a comparative study between voltammetric and chromatographic techniques.

The use of a copper solid amalgam electrode (CuSAE) for the analytical determination of triazine herbicides (atrazine and ametryne) instead of the conventional hanging mercury drop electrode (HMDE) is reported. The results obtained using electroanalytical methods utilizing each of these electrodes were also compared with those provided by the HPLC technique. The results indicated that the CuSAE electrode can be used to detect the herbicides studied, since the detection limits reached using the electrode (3.06 microg L-1 and 3.78 microg L-1 for atrazine and ametryne, respectively) are lower than the maximum values permitted by CONAMA (Brazilian National Council for the Environment) for wastewaters (50 microg L-1) and by the US EPA (Environmental Protection Agency of the United States) in natural water samples (10.00 microg L-1). An electroanalytical methodology employing CuSAE and square wave voltammetry (SWV) was successfully applied to the determination of atrazine and ametryne in natural water samples, yielding good recoveries (70.30%-79.40%). This indicates that the CuSAE provides a convenient substitute for the HMDE, particularly since the CuSAE minimizes the toxic waste residues produced by the use of mercury in HDME-based analyses.

Electrophoresis microchip fabricated by a direct-printing process with end-channel amperometric detection.

We describe the development of an electrophoresis microchip fabricated by a direct-printing process, based on lamination of printed polyester films with end-channel amperometric detection. The channel structures are defined by polyester (base and cover) and by a toner layer (walls). The polyester-toner devices presented an electroosmotic flow (EOF) magnitude of approximately 10(-5) cm2 V(-1) s(-1), which is generated by a polymeric mixture of the toner and polyester composition. The microelectrodes used for detection were produced combining this laser-printer technology to compact discs. The performance of this device was evaluated by amperometric detection of iodide and ascorbate. The detection limits found were 500 nmol.L(-1) (135 amol) and 1.8 micromol.L(-1) (486 amol) for iodide and ascorbate, respectively.

Estudo voltamétrico e espectrofotométrico do complexo Cu(II)-glifosato / Voltammetric and spectrophotometric study of Cu(II)-Glyphosate complex

O objetivo deste trabalho foi estudar o comportamento voltamétrico e espectrofotométrico do complexo Cu(II)-glifosato em solução. Esse complexo apresentou duas bandas de absorção na região ultravioleta-visível (200 a 1000nm); uma em 231 nm (transferência de carga) e outra em 732 nm (transição d-d). No estudo voltamétrico, utilizando a voltametria de onda quadrada (SWV), observou-se que a presença de glifosato deslocou o potencial de pico do Cu(II) de +0,034 V para valor de potencial mais negativo (-0,200V). A partir desses valores de potencial pode-se estimar a constante de estabilidade condicional do complexo igual a log K=7,9. Os resultados obtidos neste artigo mostraram que o glifosato pode ser detectado na forma de complexo metálico, sem derivação. O uso de metodologias de análise direta é muito interessante, devido a economia de reagentes e de tempo no preparo das amostras. A habilidade do glifosato em complexar grande variedade de metais pode ser utilizada com propósitos analíticos como o desenvolvimento de metodologias de análise (voltametria e espectrofotométrica) desse herbicida em amostras de solo e água.

Pesticidas: mecanismo de ação, degradação e toxidez / Pesticides: action mechanism, degradation and toxicity

Este artigo apresenta breve revisão sobre pesticidas muito utilizados no Brasil em culturas de soja, milho e cana-de-açúcar. Foram abordados o mecanismo de ação, a degradação e a toxidez dos herbicidas glifosato, pendimetalina e atrazina e dos inseticidas fenitrotion e fipronil. Verificou-se que o modo de ação desses pesticidas ocorre por meio da inibição de enzimas específicas como a enolpipuvil shikimato-3-fosfato sintase (glifosato0 e a colinesterase (fenitrotion), de proteínas como as tubulinas (pendimetalina), de receptores do sistema nervoso como o ácido gama aminibutírico (fipronil) e da inibição da fotossíntese (atrazina). Em relação à degradação, a rota mais importante para o desaparecimento dos herbicidas glifosato e atrazina e do inseticida fenitrotion é a biodegradação. Fipronil, moderadamente persistente no ambiente é degradado pela luz (fotodegradação). Para a pendimetalina, tanto os microorganismos quanto a luz são responsáveis pelo desaparecimento desse composto. A toxidez dos pesticidas varia de acordo com o grupo químico em que se enquadram, sendo o efeito tóxico mais agudo para os seres humanos e outros mamíferos apresentado pelo fenitrotion (organofosforado)