Non-purged voltammetry explored with AGNES.

The reduction of oxygen increases pH in the surroundings of an electrode. A theoretical model estimates the steady-state pH profile from the surface of the electrode up to the bulk solution. A very simple formula predicts that, in non-deaerated solutions, for bulk pH-values between 4.0 and 10.0, the corresponding surface pH could be as high as 10.3, regardless of the thickness of the diffusion layer and composition of the sample (except if it has a buffering capacity). For bulk pH lower than 3.0 or higher than 10, pH increases are negligible. Less steep pH-profiles are obtained using buffers (such as MOPS 0.01 M or MES 0.01 M). The change in surface pH modifies the local speciation and hinders the standard interpretation of voltammetric responses. The electroanalytical technique Absence of Gradients and Nernstian Equilibrium Stripping (AGNES), implemented with Screen Printed Electrodes (SPE), provides experimental insights into this phenomenon. AGNES probes the free metal concentration at the electrode surface, from which the surface pH can be estimated for systems of known composition. These estimations agree with the theoretical model for the assayed systems. Additionally, the quantification of the bulk free Zn(2+) and Cd(2+) concentrations with specific modifications of AGNES for non-purged synthetic solutions is discussed. In general, more accurate determinations of the bulk free metal concentrations in non-purged solutions are expected: (i) when the calibration is performed in a medium where the pH increase induces similar changes in the surface free metal concentration and in the sample solution and (ii) when the system is more buffered.

Direct determination of free metal concentration by implementing stripping chronopotentiometry as the second stage of AGNES.

The electroanalytical technique Absence of Gradients and Nernstian Equilibrium Stripping (AGNES) has been extended by applying stripping chronopotentiometry (SCP) as the re-oxidation stage in the determination of the free concentration of Zn(2+), Cd(2+) and Pb(2+). This new approach, called AGNES-SCP, has been implemented with screen-printed electrodes (SPE) and the standard Hanging Mercury Drop Electrode (HMDE). Clear advantages of this variant have been shown: (i) the easy resolution of the peaks of different metals present in mixtures and (ii) the sparing of blanks. A rigorous computation of the faradaic charge along the SCP stage takes into account the contribution of other oxidants, which can be efficiently measured at the end of the deposition stage of AGNES. The free Cd concentration determined in an oxalate solution at pH 6 with an HMDE as the working electrode agreed well with values obtained with a Cd Ion Selective Electrode. The free metal concentration measured using an SPE for the system Cd and nitrilotriacetic acid (NTA) at pH = 4.8 also conformed well with Visual MINTEQ results.

Improved synthesis of a protected 11-oxoestrone.

An improved synthesis of 11-oxoestrone-3-acetate-17-ethyleneketal is reported. Adjustments are proposed for the oxidation of estrone by 2,3-dichloro-5,6-dicyano-1,4-benzoquinone into 9(11)-dehydroestrone. A complete hydroboration-oxidation of the resulting ketal, by means of borane-methylsulfide complex, gives the corresponding 11-hydroxy derivative. This latter compound is then acetylated for successful oxidation with pyridinium chlorochromate on alumina. The overall yield is 30%.

Cadmium speciation assessed by voltammetry, ion exchange and geochemical calculation in soil solutions collected after soil rewetting.

Analytical techniques and speciation models have been developed to characterize the speciation of Cd in soil solution. They provide an estimate of operationally defined species of Cd that need to be compared, especially for soil solutions highly concentrated in organic matter as are the solutions collected after soil rewetting. This work deals with the comparison between the speciation of Cd measured by anodic stripping voltammetry (ASV) and ion exchange and the speciation of Cd calculated using Visual MINTEQ. The aim of this study was to quantify and explain the differences in Cd speciation observed between the three approaches. Cd speciation was assessed in soil solutions collected 4, 8, 24, 48, 96 and 144h after the rewetting of an air-dried contaminated soil. To optimize the computed speciation of Cd, other physico-chemical parameters were followed (e.g. pH, ionic strength and the concentrations of major anions, major cations and dissolved organic carbon) and a brief characterisation of dissolved organic matter (DOM) was performed. The discrepancy between model predictions and analytical measurements highlighted the need for caution in the interpretation of geochemical speciated data for Cd. The major result of this study was that a characterization of DOM based on its specific UV-absorbance at 254 nm improved the accuracy of model predictions. Another finding is that labile Cd complexes, even organic, may have been included in the electrochemically labile fraction of Cd measured by ASV.

Comparison of two experimental speciation methods with a theoretical approach to monitor free and labile Cd fractions in soil solutions.

This work focused on the suitability of two techniques to monitor cadmium speciation in soil solutions collected during a 7-day incubation of a contaminated soil. Anodic stripping voltammetry (ASV) and ion exchange were performed on soil solutions collected daily and results were compared with calculations obtained with the speciation software Visual MINTEQ. The electrochemically labile Cd fraction was greater than the exchange-estimated free Cd fraction during the first 6 days, after which it decreased sharply during the last 2 days to reach values close to the exchange-estimated free Cd fraction. Further investigations showed that the increase in pH was mainly responsible for the reduction. However, calculations performed with Visual MINTEQ software clearly demonstrated that a change in the nature of organic matter and/or its complexing capacity also needed to be taken into consideration.

Gold nanoparticle-based quantitative electrochemical detection of amplified human cytomegalovirus DNA using disposable microband electrodes.

An electrochemical DNA detection method has been developed for the sensitive quantification of an amplified 406-base pair human cytomegalovirus DNA sequence (HCMV DNA). The assay relies on (i) the hybridization of the single-stranded target HCMV DNA with an oligonucleotide-modified Au nanoparticle probe, (ii) followed by the release of the gold metal atoms anchored on the hybrids by oxidative metal dissolution, and (iii) the indirect determination of the solubilized AuIII ions by anodic stripping voltammetry at a sandwich-type screen-printed microband electrode (SPMBE). Due to the enhancement of the AuIII mass transfer by nonlinear diffusion during the electrodeposition time, the SPMBE allows the sensitive determination of AuIII in a small volume of quiescent solution. The combination of the sensitive AuIII determination at a SPMBE with the large number of AuIII released from each gold nanoparticle probe allows detection of as low as 5 pM amplified HCMV DNA fragment.