Electrochemical studies of chalcogen-containing species under aqueous conditions are often hindered by unwanted oxidation and surface adsorption. Disulfides, diselenides, thiols, and selenols react readily with metallic electrodes to form self-assembled monolayers and films. We have shown that the intrinsic reactivity between selenium and gold yields a stable and reproducible electrode surface modification that makes the reduction of selenocystine to selenocysteine accessible at neutral pH. The adsorbate can be removed via oxidative stripping and subsequently regenerated, displaying high recyclability with little to no loss in signal restoration. X-ray photoelectron spectroscopy confirms the presence of selenium on surfaces that have been reductively cycled in the presence of a diselenide source. Voltammetric studies on the modified electrodes have extended to the cysteine / cystine redox couple and to physiologically relevant chalcogenone ligands. Electrochemical and spectroscopic characterization of these systems will be presented and biosensing applications of the selenium-modified electrodes will be discussed.

Selenium redox chemistry: From surface reactivity to biological applications

255th National Meeting (2018)

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