title: On the Reactions of Thiols, Sulfenic Acids, and Sulfinic Acids with Hydrogen Peroxide.
abstract: The reaction of thiols with H2O2is central to many processes essential to life, from protein folding to redox signaling. The initial products are assumed to be sulfenic acids, but their observation, and the kinetic and mechanistic characterization of their subsequent reactions, has proven challenging. The introduction of a 9-fluorotriptycene substituent enabled the use of19F NMR to directly monitor the reaction of a thiol with H2O2to yield a sulfenic acid, and its subsequent oxidation to sulfinic and sulfonic acids. The oxidations are specific base catalyzed, as revealed by the lack of isotope effects and the dependence of the kinetics on pH but not buffer concentration.
authors.affiliation: Department of Chemistry & Biomolecular Sciences, University of Ottawa, 10 Marie Curie Pvt., Ottawa, Ontario, K1N 6N5, Canada.
authors.forename: Jean-Philippe R
authors.identifier: 0000-0001-8771-7968
authors.initials: JR
authors.lastname: Chauvin
authors.affiliation: Department of Chemistry & Biomolecular Sciences, University of Ottawa, 10 Marie Curie Pvt., Ottawa, Ontario, K1N 6N5, Canada.
authors.forename: Derek A
authors.identifier: 0000-0002-7305-745X
authors.initials: DA
authors.lastname: Pratt
keywords: hydrogen peroxide; oxidation; sulfenic acid; sulfinic acid; thiols