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A possible biological pathway of HNO formation is the S\u2010thiolation reaction between thiols and <jats:italic>S\u2010<\/jats:italic>nitrosothiols (RSNOs). Our density functional theory (DFT) calculations suggested that S\u2010thiolation proceeds through a proton transfer from the thiol to the RSNO nitrogen atom, which increases electrophilicity of the RSNO sulfur, followed by nucleophilic attack by thiol, yielding a charge\u2010separated zwitterionic intermediate structure RSS<jats:sup>+<\/jats:sup>(R)N(H)O<jats:sup>\u2212<\/jats:sup> (<jats:bold>Zi<\/jats:bold>), which decomposes to yield HNO and disulfide RSSR. In the gas phase, the proton transfer and the S\u2212S bond formation are asynchronous, resulting in a high activation barrier (&gt;40\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>), making the reaction infeasible. However, the barrier can decrease below the S\u2212N bond dissociation energy in RSNOs (\u224830\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup>) upon transition into an aqueous environment that stabilizes <jats:bold>Zi<\/jats:bold> and provides a proton shuttle to synchronize the proton transfer and the S\u2212S bond formation. These mechanistic features suggest that S\u2010thiolation can easily lend itself to enzymatic catalysis and thus can be a possible route of endogenous HNO production.<\/jats:p>","DOI":"10.1002\/cbic.201600556","type":"journal-article","created":{"date-parts":[[2017,2,7]],"date-time":"2017-02-07T22:30:57Z","timestamp":1486506657000},"page":"726-738","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":23,"title":["Modeling of <i>S<\/i>\u2010Nitrosothiol\u2013Thiol Reactions of Biological Significance: HNO Production by S\u2010Thiolation Requires a Proton Shuttle and Stabilization of Polar Intermediates"],"prefix":"10.1002","volume":"18","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-9327-6679","authenticated-orcid":false,"given":"Lena V.","family":"Ivanova","sequence":"first","affiliation":[{"name":"Department of Chemistry Marquette University  535 N. 14th Street Milwaukee WI 53233 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