A simple and sensitive detection of diquat herbicide using a dental amalgam electrode A comparison using the chromatographic technique

This paper describes the use of a dental amalgam electrode (DAE) to evaluate the electrochemical behaviour and to develop an electroanalytical procedure for determination of diquat herbicide in natural water and potato samples. The work was based on the square wave voltammetry responses of diquat, which presented two well-defined and reversible reduction peaks, at -0.56 V (peak 1) and -1.00V (peak 2). The experimental and voltammetric parameters were optimised, and the analytical curves were constructed and compared to similar curves performed by high performance liquid chromatography coupled to ultraviolet-visible spectrophotometric detector (HPLC/UV-vis). The responses were directly proportional to diquat concentration in a large interval of concentration, and the calculated detection limits were very similar, around 10 mu g L(-1) (10 ppb) for voltammetric and chromatographic experiments. These values were lower than the maximum residue limit established for natural water by the Brazilian Environmental Agency. The recovery percentages in pure electrolyte, natural water and potato samples showed values from 70% to 130%, demonstrating that the voltammetric methodology proposed is suitable for determining any contamination by diquat in different samples, minimising the toxic residues due to the use of liquid mercury or the adsorptive process relative to use of other solid surfaces. (C) 2009 Published by Elsevier B.V.

Development of impedimetric and optical calcium biosensor by using modified gold electrode with porcine S100A12 protein

We describe the development of a label free method to analyze the interactions between Ca(2+) and the porcine S100A12 protein immobilized on polyvinyl butyral (PVB). The modified gold electrodes were characterized using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) and surface plasmon resonance (SPR) techniques. SEM analyses of PVB and PVB-S100A12 showed a heterogeneous distribution of PVB spherules on gold surface. EIS and CV measurements have shown that redox probe reactions on the modified gold electrodes were partially blocked due the adsorption of PVB-S100A12, and confirm the existence of a positive response of the immobilized S100Al2 to the presence of calcium ions. The biosensor exhibited a wide linear response to Ca(2+) concentrations ranging from 12.5 to 200 mM. The PVB-S100A12 seems to be bound to the gold electrode surface by physical adsorption: we observed an increase of 1184.32 m degrees in the SPR angle after the adsorption of the protein on the PVB surface (in an indication that 9.84 ng of S100A12 are adsorbed per mm(2) of the Au-PVB electrode), followed by a further increase of 581.66 m degrees after attachment of the Ca(2+) ions. In addition, no SPR response is obtained for non-specific ions. These studies might be useful as a platform for the design of new reusable and sensitive biosensing devices that could find use in the clinical applications. (C) 2010 Elsevier B.V. All rights reserved.

A renewable copper electrode as an amperometric flow detector for nitrate determination in mineral water and soft drink samples

A novel approach was developed for nitrate analysis in a FIA configuration with amperometric detection (E=-0.48 V). Sensitive and reproducible current measurements were achieved by using a copper electrode activated with a controlled potential protocol. The response of the FIA amperometric method was linear over the range from 0.1 to 2.5 mmol L(-1) nitrate with a detection limit of 4.2 mu mol L(-1) (S/N = 3). The repeatability of measurements was determined as 4.7% (n=9) at the best conditions (flow rate: 3.0 mL min(-1), sample volume: 150 mu L and nitrate concentration: 0.5 mmol L(-1)) with a sampling rate of 60 samples h(-1). The method was employed for the determination of nitrate in mineral water and soft drink samples and the results were in agreement with those obtained by using a recommended procedure. Studies towards a selective monitoring of nitrite were also performed in samples containing nitrate by carrying out measurements at a less negative potential (-0.20 V). (C) 2009 Elsevier B.V. All rights reserved.

Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 nanostructured silica in the simultaneous determination of divalent lead, copper and mercury ions

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol in the simultaneous determination of Pb(II), Cu(II) and Hg(II) ions in natural water and sugar cane spirit (cachaca) is described. Pb(II), Cu(II) and Hg(II) were pre-concentrated on the surface of the modified electrode by complexing with 2-benzothiazolethiol and reduced at a negative potential (-0.80 V). Then the reduced products were oxidised by DPASV procedure. The fact that three stripping peaks appeared on the voltammograms at the potentials of -0.48 V (Pb2+), -0.03 V (Cu2+) and +0.36 V (Hg2+) in relation to the SCE, demonstrates the possibility of simultaneous determination of Pb2+, Cu2+ and Hg2+. The best results were obtained under the following optimised conditions: 100 mV pulse amplitude, 3 min accumulation time, 25 mV s(-1) scan rate in phosphate solution pH 3.0. Using such parameters, calibration graphs were linear in the concentration ranges of 3.00-70.0 x 10(-7) mol L-1 (Pb2+), 8.00-100.0 X 10(-7) mol L-1 (Cu2+) and 2.00-10.0 x 10(-6) mol L-1 (Hg2+). Detection limits of 4.0 x 10(-8) mol L-1 (Pb2+), 2.0 x 10(-7) mol L-1 (Cu2+) and 4.0 x 10(-7) mol L-1 (Hg2+) were obtained at the signal noise ratio (SNR) of 3. The results indicate that this electrode is sensitive and effective for simultaneous determination of Pb2+, Cu2+ and Hg2+ in the analysed samples. (C) 2008 Published by Elsevier B.V.

Use of copper and gold electrodes as sensitive elements for fabrication of an electronic tongue: Discrimination of wines and whiskies

A low-cost method is proposed to classify wine and whisky samples using a disposable voltammetric electronic tongue that was fabricated using gold and copper substrates and a pattern recognition technique (Principal Component Analysis). The proposed device was successfully used to discriminate between expensive and cheap whisky samples and to detect adulteration processes using only a copper electrode. For wines, the electronic tongue was composed of copper and gold working electrodes and was able to classify three different brands of wine and to make distinctions regarding the wine type, i.e., dry red, soft red, dry white and soft white brands. Crown Copyright (C) 2011 Published by Elsevier B.V. All rights reserved.