in Situ X-ray Photoelectron Spectroscopic and Electrochemical Studies of the Bromide Anions Dissolved in 1-Ethyl-3-Methyl Imidazolium Tetrafluoroborate.

Influence of electrode potential on the electrochemical behavior of a 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) solution containing 5 wt % 1-ethyl-3-methylimidazolium bromide (EMImBr) has been investigated using electrochemical and synchrotron-initiated high-resolution in situ X-ray photoelectron spectroscopy (XPS) methods. Observation of the Br 3d5/2 in situ XPS signal, collected in a 5 wt % EMImBr solution at an EMImBF4⁻vacuum interface, enabled the detection of the start of the electrooxidation process of the Br⁻ anion to Br3⁻ anion and thereafter to the Br2 at the micro-mesoporous carbon electrode, polarized continuously at the high fixed positive potentials. A new photoelectron peak, corresponding to B⁻O bond formation in the B 1s in situ XPS spectra at E ≤ ⁻1.17 V, parallel to the start of the electroreduction of the residual water at the micro-mesoporous carbon electrode, was observed and is discussed. The electroreduction of the residual water caused a reduction in the absolute value of binding energy vs. potential plot slope twice to ca. dBE dE-1 = ⁻0.5 eV V-1 at E ≤ ⁻1.17 V for C 1s, N 1s, B 1s, F 1s, and Br 3d5/2 photoelectrons.

An introduction to thiol redox proteins in the endoplasmic reticulum and a review of current electrochemical methods of detection of thiols.

This aim of this paper is to expound the complexity of thiol redox systems in the endoplasmic reticulum of eukaryotic cells to the electroanalytical community. A summary of the state of the art in electrochemical methods for detection of thiols gives an insight into the challenges that need to be addressed to bridge the disparity between current analytical techniques and applications in a 'real' biological scenario.

Modular assembly of a preorganised, ditopic receptor for dicarboxylates.

Two types of calix[4]arene derived hosts for anions with, respectively, 1,3-alternate and cone conformations have been prepared; the 1,3-alternate system binds dicarboxylate anions in a ditopic manner while the cone compounds are deprotonated by carboxylates.

Manganese detection in marine sediments: anodic vs. cathodic stripping voltammetry.

Three different electroanalytical techniques for the detection of manganese in marine sediments are evaluated. The anodic stripping voltammetry of manganese at an in situ bismuth-film-modified boron-doped diamond electrode and cathodic stripping voltammetry at a carbon paste electrode are shown to lack the required sensitivity and reproducibility whereas cathodic stripping voltammetry at a bare boron-doped diamond electrode is shown to be reliable and selective with a limit of detection, from applying a 60s accumulation period of 7.4 x 10(-7)M and a sensitivity of 0.24AM(-1). The method was used to evaluate the manganese content of marine sediments taken from Sibenik, Croatia.

Mercury-free sono-electroanalytical detection of lead in human blood by use of bismuth-film-modified boron-doped diamond electrodes.

We report the electroanalytical determination of lead by anodic stripping voltammetry at in-situ-formed, bismuth-film-modified, boron-doped diamond electrodes. Detection limits in 0.1 mol L(-1) nitric acid solution of 9.6 x 10(-8) mol L(-1) (0.2 ppb) and 1.1 x 10(-8) mol L(-1) (2.3 ppb) were obtained after 60 and 300 s deposition times, respectively. An acoustically assisted deposition procedure was also investigated and found to result in improved limits of detection of 2.6 x 10(-8) mol L(-1) (5.4 ppb) and 8.5 x 10(-10) mol L(-1) (0.18 ppb) for 60 and 300 s accumulation times, respectively. Furthermore, the sensitivity obtained under quiescent and insonated conditions increased from 5.5 (quiescent) to 76.7 A mol(-1) L (insonated) for 60 s accumulation and from 25.8 (quiescent) to 317.6 A mol(-1) L (insonated) for 300 s accumulation. Investigation of the use of ultrasound with diluted blood revealed detection limits of the order of 10(-8) mol L(-1) were achievable with excellent inter- and intra-reproducibility and sensitivity of 411.9 A mol(-1) L. For the first time, electroanalytical detection of lead in diluted blood is shown to be possible by use of insonated in-situ-formed bismuth-film-modified boron-doped diamond electrodes. This method is a rapid, sensitive, and non-toxic means of clinical sensing of lead in whole human blood.

Sonoelectroanalysis: investigation of bismuth-film-modified glassy carbon electrodes.

Bismuth-modified glassy carbon electrodes have been investigated for their suitability in sonoelectroanalysis. The stability of the bismuth film to the application of ultrasound was assessed via voltammetric and atomic force microscopy (AFM) studies which revealed little ablation at powers up to an intensity of 130 W cm(-2) delivered from a 25-kHz sonic horn. Furthermore, bismuth-film-modified glassy carbon electrodes were evaluated for the sonoelectroanalytical quantification of zinc and cadmium. Detection limits of 2 x 10(-7) M and 6 x 10(-9) M respectively were found after a 60-s deposition time via an acoustically assisted deposition protocol.