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Issue 11, 2016
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[RuIII(EDTA)(H2O)] mediated oxidation of cellular thiols by HSO5

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Abstract

The [RuIII(EDTA)(H2O)] (EDTA4− = ethylenediaminetetraacetate) complex is shown to mediate the oxidation of thiols, RSH (RSH = cysteine, glutathione, N-acetylcysteine, and penicillamine), with peroxomonosulfate ion (HSO5). The kinetics of the catalytic oxidation process were studied using stopped-flow and rapid scan spectrophotometry as a function of [RuIII(EDTA)(H2O)], [HSO5], and [RSH] at a constant pH (6.2). Spectral analyses and kinetic data are suggestive of a catalytic pathway in which the RSH reacts with the [RuIII(EDTA)] catalyst complex to form [RuIII(EDTA)(SR)]2− intermediate species. In a subsequent step the HSO5 ion reacts directly with the coordinated S-atom of [RuIII(EDTA)(SR)]2− yielding the disulfido species, RSSR, as a major oxidation product (as identified using HPLC and ESI-MS analyses) under the employed conditions. Based on the experimental data, a working mechanism is proposed for the [RuIII(EDTA)] catalyzed oxidation of thiols.

Graphical abstract: [RuIII(EDTA)(H2O)]− mediated oxidation of cellular thiols by HSO5−

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Publication details

The article was received on 15 May 2016, accepted on 14 Sep 2016 and first published on 15 Sep 2016


Article type: Paper
DOI: 10.1039/C6NJ01540A
Citation: New J. Chem., 2016,40, 9380-9384
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    [RuIII(EDTA)(H2O)] mediated oxidation of cellular thiols by HSO5

    P. Sarkar, A. Saha and D. Chatterjee, New J. Chem., 2016, 40, 9380
    DOI: 10.1039/C6NJ01540A

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