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Utilizing infrared multiple\u2010photon dissociation (IRMPD) spectroscopy, electron\u2010activated dissociation (EAD), and quantum\u2010chemical calculations, we characterize the gas\u2010phase structure of the complex [(Et\n                    <jats:sub>3<\/jats:sub>\n                    P)AuGSH]\n                    <jats:sup>+<\/jats:sup>\n                    . Our results reveal that in the gas phase, the NH\n                    <jats:sub>2<\/jats:sub>\n                    group of the N\u2010terminal glutamate residue of GSH serves as a competitive coordination site, challenging coordination by the canonical cysteine thiol, with both isomers coexisting in comparable abundances. This finding suggests that in microenvironments characterized by a reduced dielectric constant, the GSH\u2013Au(I) complex might also exist as an N\u2010bound isomer with a free thiol, which may significantly affect its biological reactivity and functions. Moreover, considering that the dielectric constant within buried protein active sites is substantially lower than that of bulk water, this N\u2010binding motif identifies the unprotonated N\u2010terminus as a plausible target for metalation, even in the presence of free thiols. These insights offer a broader perspective on the competitive binding landscape of gold(I) drugs. As a future direction, we hypothesize potential implications for the inhibition of enzymes with N\u2010terminal catalytic groups, which are crucial for tumor progression, such as nucleophile (Ntn) hydrolases.\n                  <\/jats:p>","DOI":"10.1155\/bca\/5944632","type":"journal-article","created":{"date-parts":[[2026,10,20]],"date-time":"2026-10-20T06:23:08Z","timestamp":1792477388000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Reevaluating Gold(I) Thiophilicity in Reduced Dielectric Environments: IRMPD Spectroscopy and Theoretical Investigation of Auranofin\u2013Glutathione Complexes"],"prefix":"10.1155","volume":"2026","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5325-9452","authenticated-orcid":false,"given":"Roberto","family":"Paciotti","sequence":"first","affiliation":[{"name":"Dipartimento di Farmacia Universit\u00e0 G. 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