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Here, the photo<jats:italic>sulfoxidation<\/jats:italic> process was studied by mass spectrometry (MS) and discussed in the context of photodemethylation processes which both contribute to TBO consumption over time. Analysis of solvent effects with D<jats:sub>2<\/jats:sub>O, H<jats:sub>2<\/jats:sub>O, and CH<jats:sub>3<\/jats:sub>CN along with product yields and MS fragmentation patterns provided mechanistic insight into TBO sulfoxide's formation. The formation of TBO sulfoxide is minor and detectable up to 12% after irradiation of 3\u2009h. The photosulfoxidation process is dependent on oxygen wherein instead of a type II (singlet oxygen, <jats:sup>1<\/jats:sup>O<jats:sub>2<\/jats:sub>) reaction, a type I reaction involving TBO to reach the TBO sulfoxide is consistent with the results. Density functional theory results point to the formation of the TBO sulfoxide by the oxidation of TBO via transiently formed peroxyl radical or thiadioxirane intermediates. We discover that the TBO photosulfoxidation arises competitively with TBO photodemethylation with the latter leading to formaldehyde formation.<\/jats:p>","DOI":"10.1111\/php.13882","type":"journal-article","created":{"date-parts":[[2023,12,15]],"date-time":"2023-12-15T18:38:30Z","timestamp":1702665510000},"page":"772-781","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["On the mechanism of visible\u2010light sensitized photosulfoxidation of toluidine blue O"],"prefix":"10.1111","volume":"100","author":[{"given":"Jennifer","family":"Otero\u2010Gonz\u00e1lez","sequence":"first","affiliation":[{"name":"Universidad de Panam\u00e1, Facultad de Ciencias Naturales, Exactas y Tecnolog\u00eda, Departamento de Bioqu\u00edmica  Panam\u00e1 Panama"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Whitney","family":"Querini\u2010Sanguill\u00e9n","sequence":"additional","affiliation":[{"name":"Universidad de 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