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Following electronic excitation with UV\u2010A light, some of these pterins degrade, producing hydrogen peroxide as the main side product. This process, which is known to take place in\u2005vivo, contributes to oxidative stress and melanocyte destruction in vitiligo. In this work, we present for the first time mechanistic insight into the formation of transient triplet species that simultaneously trigger Type I and Type II photosensitizing processes and the initiation of degradation processes. Our calculations reveal that photodegradation of 6\u2010biopterin, which accumulates in the skin of vitiligo patients, leads to 6\u2010formylpterin through a retro\u2010aldol reaction, and subsequently to 6\u2010carboxypterin through a water\u2010mediated aldehyde oxidation. Additionally, we show that the changes in the photosensitizing potential of these systems with pH come from the modulation of their excited\u2010state redox potentials.<\/jats:p>","DOI":"10.1002\/chem.202300519","type":"journal-article","created":{"date-parts":[[2023,3,17]],"date-time":"2023-03-17T07:40:08Z","timestamp":1679038808000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Unveiling Photodegradation and Photosensitization Mechanisms of Unconjugated Pterins"],"prefix":"10.1002","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1288-6059","authenticated-orcid":false,"given":"Enrique M.","family":"Arpa","sequence":"first","affiliation":[{"name":"Department of Physics, Chemistry and Biology (IFM) Link\u00f6ping University  58183 Link\u00f6ping Sweden"},{"name":"Departamento de Qu\u00edmica Universidad Aut\u00f3noma de Madrid  C\/ Francisco Tom\u00e1s y Valiente, 7 28049 Madrid Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9455-4906","authenticated-orcid":false,"given":"In\u00e9s","family":"Corral","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica Universidad Aut\u00f3noma de Madrid  C\/ Francisco Tom\u00e1s y Valiente, 7 28049 Madrid Spain"},{"name":"Institute for Advanced Research in Chemical Sciences (IAdChem) Universidad Aut\u00f3noma de Madrid  28049 Madrid Spain"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,4,13]]},"reference":[{"key":"e_1_2_7_1_1","doi-asserted-by":"publisher","DOI":"10.1515\/pterid-2016-0012"},{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1006\/mgme.2000.3027"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1093\/ajcn\/77.6.1352"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0021-9258(19)50001-1"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.2174\/1389200024605082"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1042\/BJ20110293"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jinsphys.2007.06.016"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1586\/1744666X.2014.962996"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1751-1097.1981.tb05470.x"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar050151c"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1039\/b202114e"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1039\/b209993d"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jpap.2021.100045"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1007\/s43630-022-00248-6"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1111\/php.12099"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.freeradbiomed.2013.05.044"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jphotobiol.2015.10.026"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1515\/pterid-2017-0013"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1515\/pteridines.2000.11.3.100"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/b707312g"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja075367j"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cp41476g"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1010-6030(00)00304-X"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1111\/j.1751-1097.2008.00450.x"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.solener.2014.08.025"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)83082-3"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2009.12.008"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1016\/S1010-6030(99)00224-5"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CP01574G"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp0727502"},{"key":"e_1_2_7_31_1","volume-title":"Autoimmune Diseases of the Skin: Pathogenesis, Diagnosis, Management","author":"Schallreuter K. 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