Thiolate-disulfide exchange is a fundamental biochemical process with roles in structure, regulation, and redox processes. Results suggest that at the early stages of inflammation (e.g. oxidative stress), metal homeostasis may be altered, making some metals, such as zinc, more bioavailable. We have been interested in exploring how metals, such as Zn and Au, alter the thiolate-disulfide exchange mechanism. 2D (<sup>1</sup>H-<sup>1</sup>H) ROESY NMR spectroscopy has been used to explore the association and exchange reactions involving a metal thiolate (M-SR') and disulfide (R''SSR''). NMR results indicate that during metal-mediated thiolate-disulfide exchange, association between the metal-thiolate (M-SR') and disulfide (R''SSR'') occurs via a square arrangement of the M-S and S-S atoms, suggesting a metathesis-like mechanism. Kinetic and solvent effects, whose trends appear significantly different than the non-metal thiolate-disulfide exchange reaction, will be also discussed.

Metal-assisted (Zn, Au) thiolate-disulfide exchange: Explorations of the mechanism using 2D NMR

251st National Meeting (2016)

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