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dc.contributor.author | Navarrete-Miguel, Miriam | es_ES |
dc.contributor.author | Francés-Monerris, Antonio | es_ES |
dc.contributor.author | Miranda Alonso, Miguel Ángel | es_ES |
dc.contributor.author | Lhiaubet, Virginie Lyria | es_ES |
dc.contributor.author | Roca-Sanjuan, Daniel | es_ES |
dc.date.accessioned | 2022-10-13T18:07:37Z | |
dc.date.available | 2022-10-13T18:07:37Z | |
dc.date.issued | 2021-05 | es_ES |
dc.identifier.uri | http://hdl.handle.net/10251/187701 | |
dc.description.abstract | [EN] Photocycloreversion plays a central role in the study of the repair of DNA lesions, reverting them into the original pyrimidine nucleobases. Particularly, among the proposed mechanisms for the repair of DNA (6-4) photoproducts by photolyases, it has been suggested that it takes place through an intermediate characterized by a four-membered heterocyclic oxetane or azetidine ring, whose opening requires the reduction of the fused nucleobases. The specific role of this electron transfer step and its impact on the ring opening energetics remain to be understood. These processes are studied herein by means of quantum-chemical calculations on the two azetidine stereoisomers obtained from photocycloaddition between 6-azauracil and cyclohexene. First, we analyze the efficiency of the electron-transfer processes by computing the redox properties of the azetidine isomers as well as those of a series of aromatic photosensitizers acting as photoreductants and photo-oxidants. We find certain stereodifferentiation favoring oxidation of the cis-isomer, in agreement with previous experimental data. Second, we determine the reaction profiles of the ring-opening mechanism of the cationic, neutral, and anionic systems and assess their feasibility based on their energy barrier heights and the stability of the reactants and products. Results show that oxidation largely decreases the ring-opening energy barrier for both stereoisomers, even though the process is forecast as too slow to be competitive. Conversely, one-electron reduction dramatically facilitates the ring opening of the azetidine heterocycle. Considering the overall quantum-chemistry findings, N,N-dimethylaniline is proposed as an efficient photosensitizer to trigger the photoinduced cycloreversion of the DNA lesion model. | es_ES |
dc.description.sponsorship | This work has been funded by the Generalitat Valenciana and the European Social Fund through the postdoctoral contract APOSTD/2019/149 and the project GV/2020/226. It also was funded by the Spanish Ministerio de Ciencia e Innovacion (MICINN), projects CTQ2017-87054-C2-2-P and PGC2018-096684-B-I00, and a 2019 Leonardo Grant for Researchers and Cultural Creators, BBVA Foundation. The Foundation takes no responsibility for the opinions, statements, and contents of this project, which are entirely the responsibility of its authors. D.R.-S. is grateful to the Spanish MICINN for the "Ramon y Cajal" grant (Ref. RYC-2015-19234). M.N.-M. acknowledges the Generalitat Valenciana for the predoctoral grant (Ref. ACIF/2020/075). | es_ES |
dc.language | Inglés | es_ES |
dc.publisher | MDPI AG | es_ES |
dc.relation.ispartof | Molecules | es_ES |
dc.rights | Reconocimiento (by) | es_ES |
dc.subject | Azetidine | es_ES |
dc.subject | DNA repair | es_ES |
dc.subject | Electron transfer | es_ES |
dc.subject | Density functional theory | es_ES |
dc.subject | Photochemistry | es_ES |
dc.subject | Ring opening | es_ES |
dc.subject | Redox properties | es_ES |
dc.subject.classification | QUIMICA ORGANICA | es_ES |
dc.title | Theoretical Study on the Photo-Oxidation and Photoreduction of an Azetidine Derivative as a Model of DNA Repair | es_ES |
dc.type | Artículo | es_ES |
dc.identifier.doi | 10.3390/molecules26102911 | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-87054-C2-2-P/ES/FOTOFISICA DE SISTEMAS ORGANICOS DE TRANSFERENCIA DE CARGA INNOVADORES/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/GVA//ACIF%2F2020%2F075/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-096684-B-I00/ES/REPARACION DEL ADN POR PROCESOS MULTIFOTONICOS/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/MINECO//RYC-2015-19234//RYC-2015-19234/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/MINECO//RYC-2015-19234/ES/RYC-2015-19234/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/GVA//APOSTD%2F2019%2F149/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/GVA//GV%2F2020%2F226/ | es_ES |
dc.rights.accessRights | Abierto | es_ES |
dc.contributor.affiliation | Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química | es_ES |
dc.description.bibliographicCitation | Navarrete-Miguel, M.; Francés-Monerris, A.; Miranda Alonso, MÁ.; Lhiaubet, VL.; Roca-Sanjuan, D. (2021). Theoretical Study on the Photo-Oxidation and Photoreduction of an Azetidine Derivative as a Model of DNA Repair. Molecules. 26(10):1-14. https://doi.org/10.3390/molecules26102911 | es_ES |
dc.description.accrualMethod | S | es_ES |
dc.relation.publisherversion | https://doi.org/10.3390/molecules26102911 | es_ES |
dc.description.upvformatpinicio | 1 | es_ES |
dc.description.upvformatpfin | 14 | es_ES |
dc.type.version | info:eu-repo/semantics/publishedVersion | es_ES |
dc.description.volume | 26 | es_ES |
dc.description.issue | 10 | es_ES |
dc.identifier.eissn | 1420-3049 | es_ES |
dc.identifier.pmid | 34068908 | es_ES |
dc.identifier.pmcid | PMC8157190 | es_ES |
dc.relation.pasarela | S\461466 | es_ES |
dc.contributor.funder | Fundación BBVA | es_ES |
dc.contributor.funder | European Social Fund | es_ES |
dc.contributor.funder | Generalitat Valenciana | es_ES |
dc.contributor.funder | Agencia Estatal de Investigación | es_ES |
dc.contributor.funder | Ministerio de Economía y Competitividad | es_ES |
dc.contributor.funder | Ministerio de Ciencia, Innovación y Universidades | es_ES |