{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,25]],"date-time":"2025-10-25T12:45:04Z","timestamp":1761396304666,"version":"build-2065373602"},"reference-count":43,"publisher":"MDPI AG","issue":"12","license":[{"start":{"date-parts":[[2022,6,16]],"date-time":"2022-06-16T00:00:00Z","timestamp":1655337600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Funda\u00e7\u00e3o para a Ci\u00eancia e Tecnologia","award":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"],"award-info":[{"award-number":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"]}]},{"DOI":"10.13039\/501100001871","name":"R&amp;D Units CIQUP","doi-asserted-by":"publisher","award":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"],"award-info":[{"award-number":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"name":"GreenUPorto","award":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"],"award-info":[{"award-number":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"]}]},{"DOI":"10.13039\/501100001871","name":"Associated Laboratory IMS","doi-asserted-by":"publisher","award":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"],"award-info":[{"award-number":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"FCT under the Scientific Employment Stimulus","doi-asserted-by":"publisher","award":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"],"award-info":[{"award-number":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001871","name":"FCT","doi-asserted-by":"publisher","award":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"],"award-info":[{"award-number":["PTDC\/QUI-QFI\/2870\/2020","UIDB\/00081\/2020","UIDB\/05748\/2020","LA\/P\/0056\/2020","2021.00768.CEECIND","SRFH\/BD\/143211\/2019"]}],"id":[{"id":"10.13039\/501100001871","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The intramolecular chemiexcitation of high-energy peroxide intermediates, such as dioxetanones, is an essential step in different chemi- and bioluminescent reactions. Here, we employed the Time-Dependent Density Functional Theory (TD-DFT) methodology to evaluate if and how external stimuli tune the intramolecular chemiexcitation of model dioxetanones. More specifically, we evaluated whether the strategic placement of ionic species near a neutral dioxetanone model could tune its thermolysis and chemiexcitation profile. We found that these ionic species allow for the \u201cdark\u201d catalysis of the thermolysis reaction by reducing the activation barrier to values low enough to be compatible with efficient chemi- and bioluminescent reactions. Furthermore, while the inclusion of these species negatively affected the chemiexcitation profile compared with neutral dioxetanones, these profiles appear to be at least as efficient as anionic dioxetanones. Thus, our results demonstrated that the intramolecular chemiexcitation of neutral dioxetanones can be tuned by external stimuli in such a way that their activation barriers are decreased. Thus, these results could help to reconcile findings that neutral dioxetanones could be responsible for efficient chemi-\/bioluminescence, while being typically associated with high activation parameters.<\/jats:p>","DOI":"10.3390\/molecules27123861","type":"journal-article","created":{"date-parts":[[2022,6,17]],"date-time":"2022-06-17T05:25:11Z","timestamp":1655443511000},"page":"3861","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":4,"title":["Tuning the Intramolecular Chemiexcitation of Neutral Dioxetanones by Interaction with Ionic Species"],"prefix":"10.3390","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9152-7865","authenticated-orcid":false,"given":"Carla M.","family":"Magalh\u00e3es","sequence":"first","affiliation":[{"name":"Centro de Investiga\u00e7\u00e3o em Qu\u00edmica (CIQUP), Instituto de Ci\u00eancias Moleculares (IMS), Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre s\/n, 4169-007 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8478-3441","authenticated-orcid":false,"given":"Joaquim C. G.","family":"Esteves da Silva","sequence":"additional","affiliation":[{"name":"Centro de Investiga\u00e7\u00e3o em Qu\u00edmica (CIQUP), Instituto de Ci\u00eancias Moleculares (IMS), Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre s\/n, 4169-007 Porto, Portugal"},{"name":"LACOMEPHI, GreenUPorto, Departamento de Geoci\u00eancias, Ambiente e Ordenamento do Territ\u00f3rio, Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre s\/n, 4169-007 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5647-8455","authenticated-orcid":false,"given":"Lu\u00eds","family":"Pinto da Silva","sequence":"additional","affiliation":[{"name":"Centro de Investiga\u00e7\u00e3o em Qu\u00edmica (CIQUP), Instituto de Ci\u00eancias Moleculares (IMS), Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre s\/n, 4169-007 Porto, Portugal"},{"name":"LACOMEPHI, GreenUPorto, Departamento de Geoci\u00eancias, Ambiente e Ordenamento do Territ\u00f3rio, Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre s\/n, 4169-007 Porto, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2022,6,16]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"2257","DOI":"10.1002\/cphc.201200195","article-title":"Firefly Chemiluminescence and Bioluminescence: Efficient Generation of Excited States","volume":"13","year":"2012","journal-title":"ChemPhyschem"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"6927","DOI":"10.1021\/acs.chemrev.7b00649","article-title":"Chemi- and Bioluminescence of Cyclic Peroxides","volume":"118","author":"Vacher","year":"2018","journal-title":"Chem. 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