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Because exposure to malodorants may lead to irritation of the respiratory system, choking, and coma, bioanalytical verification of poisoning might be required in a medical and forensic context. We herein present the detection and identification of novel biomarkers of exposure to ethyl mercaptan, <jats:italic>n<\/jats:italic>\u2010butyl mercaptan, <jats:italic>tert<\/jats:italic>\u2010butyl mercaptan, and <jats:italic>iso<\/jats:italic>\u2010amyl mercaptan. These alkyl thiol compounds were found to form disulfide adducts in human serum albumin (HSA) in plasma in vitro with the only non\u2010disulfide\u2010bridged Cys<jats:sup>34<\/jats:sup> residue and with other residues being part of the disulfide\u2010bridged pattern in HSA. After proteinase K\u2010catalyzed proteolysis, adducts of all mercaptans were detected simultaneously as the tripeptide Cys<jats:sup>34<\/jats:sup>*ProPhe and the dipeptides Cys<jats:sup>369<\/jats:sup>*Tyr, ValCys<jats:sup>316<\/jats:sup>*, and Cys<jats:sup>x<\/jats:sup>*Ala (x denominates either Positions 91, 200, 253, 361, and\/or 448) by a sensitive micro\u2010liquid chromatography\u2013electrospray ionization tandem mass spectrometry (\u03bcLC\u2010ESI MS\/MS) method working in the scheduled multiple reaction monitoring (sMRM) mode. Time\u2010 and concentration\u2010dependent adduct formations while exposure and proteolysis were investigated and the suitability of adducts as biomarkers of exposure was elaborated. Adducts at Cys<jats:sup>34<\/jats:sup> showed the lowest limits of identification (LOIs, 6\u00a0nM to 1.2\u00a0\u03bcM mercaptan in plasma) and superior stability in plasma at 37\u00b0C. Therefore, Cys<jats:sup>34<\/jats:sup>*ProPhe appears as the most promising target to prove exposure to mercaptans at least in vitro.<\/jats:p>","DOI":"10.1002\/dta.3776","type":"journal-article","created":{"date-parts":[[2024,7,25]],"date-time":"2024-07-25T06:29:39Z","timestamp":1721888979000},"page":"722-734","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Mercaptans in malodorants break disulfide bridges in human serum albumin and form adducts suitable as biomarkers of exposure in vitro"],"prefix":"10.1002","volume":"17","author":[{"ORCID":"https:\/\/orcid.org\/0009-0000-1977-9091","authenticated-orcid":false,"given":"Paula Helena","family":"Sieber","sequence":"first","affiliation":[{"name":"Bundeswehr Institute of Pharmacology and Toxicology  Munich Germany"},{"name":"Walther\u2010Straub\u2010Institute of Pharmacology and Toxicology LMU Munich  Munich Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dirk","family":"Steinritz","sequence":"additional","affiliation":[{"name":"Bundeswehr Institute of Pharmacology and Toxicology  Munich Germany"},{"name":"Walther\u2010Straub\u2010Institute of Pharmacology and Toxicology LMU Munich  Munich Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Franz","family":"Worek","sequence":"additional","affiliation":[{"name":"Bundeswehr Institute of Pharmacology and Toxicology  Munich Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7126-6709","authenticated-orcid":false,"given":"Harald","family":"John","sequence":"additional","affiliation":[{"name":"Bundeswehr Institute of Pharmacology and Toxicology  Munich Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,7,25]]},"reference":[{"key":"e_1_2_6_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/0471238961.2008091518150205.a01"},{"key":"e_1_2_6_3_1","doi-asserted-by":"publisher","DOI":"10.3390\/toxins6061761"},{"issue":"3","key":"e_1_2_6_4_1","first-page":"227","article-title":"Science that stinks. 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