Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization

[EN] Polymethylene-linked bipyrimidine models have been designed with different C5 substitutions and bridge lengths. Selective irradiation of 2'-methoxyacetophenone (2M) with the bipyrimidine models affords cyclobutane pyrimidine dimers, even in the presence of bulky substituents. Substitut...

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Detalles Bibliográficos
Autores: Rodriguez-Alzueta, Ofelia, Cuquerella Alabort, Maria Consuelo, Miranda Alonso, Miguel Ángel
Tipo de recurso: artículo
Fecha de publicación:2019
País:España
Institución:Universitat Politècnica de València (UPV)
Repositorio:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
Idioma:inglés
OAI Identifier:oai:riunet.upv.es:10251/156029
Acceso en línea:https://riunet.upv.es/handle/10251/156029
Access Level:acceso abierto
Palabra clave:Pyrimidine dimer formation
DNA
Thymine
Benzophenone
Damage
QUIMICA ORGANICA
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spelling Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine DimerizationRodriguez-Alzueta, OfeliaCuquerella Alabort, Maria ConsueloMiranda Alonso, Miguel ÁngelPyrimidine dimer formationDNAThymineBenzophenoneDamageQUIMICA ORGANICA[EN] Polymethylene-linked bipyrimidine models have been designed with different C5 substitutions and bridge lengths. Selective irradiation of 2'-methoxyacetophenone (2M) with the bipyrimidine models affords cyclobutane pyrimidine dimers, even in the presence of bulky substituents. Substitution at CS affects both the relative triplet energies (E-T(rel)) of the pyrimidines (Pyr) and the steric hindrance toward intermolecular energy transfer and intramolecular triplet Pyr* quenching. Photophysical studies showed that alkyl substitution resulted in a significant decrease in the E-T(rel) value. Quenching of the triplet excited state of 2M by the Pyr derivatives was proven and established their quenching rate constants (k(q)). As a general trend, the thymine-containing compounds showed k(q) values higher than 10(9) M(-1)s(-1), while in the uracil and tert-butyluracil analogues, k(q) was markedly lower. These data are explained considering three different scenarios: (a) triplet energy transfer is the rate controlling step, (b) excited state cyclization is the rate controlling step, and (c) the rate controlling step switches along the reaction. Thus, by introducing variations in the substitution at C5, the length of the linking bridge, or the substrate concentration, it is possible to switch from a process governed by the intrinsic dimerization step to an energy transfer-controlled process.Financial support by the Spanish Government (PGC2018-096684 and O.R.A. for FPU14/05294) and Generalitat Valenciana (PROMETEO/2017/075) is gratefully acknowledged.American Chemical SocietyGeneralitat ValencianaMinisterio de EducaciónAgencia Estatal de InvestigaciónRepositorio Institucional de la Universitat Politècnica de València Riunet20192019-11-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfapplication/pdfhttps://riunet.upv.es/handle/10251/156029reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengAgencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PGC2018-096684-B-I00 REPARACION DEL ADN POR PROCESOS MULTIFOTONICOSMinisterio de Educación y Cultura http://dx.doi.org/10.13039/501100003176 FPU14%2F05294 FPU14%2F05294Generalitat Valenciana https://doi.org/10.13039/501100003359 PROMETEO%2F2017%2F075 Reacciones fotoquímicas de biomoléculasopen accesshttp://purl.org/coar/access_right/c_abf2Reserva de todos los derechoshttp://rightsstatements.org/vocab/InC/1.0/info:eu-repo/semantics/openAccessoai:riunet.upv.es:10251/1560292026-06-13T07:49:27Z
dc.title.none.fl_str_mv Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization
title Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization
spellingShingle Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization
Rodriguez-Alzueta, Ofelia
Pyrimidine dimer formation
DNA
Thymine
Benzophenone
Damage
QUIMICA ORGANICA
title_short Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization
title_full Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization
title_fullStr Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization
title_full_unstemmed Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization
title_sort Triplet Energy Transfer versus Excited State Cyclization as the Controlling Step in Photosensitized Bipyrimidine Dimerization
dc.creator.none.fl_str_mv Rodriguez-Alzueta, Ofelia
Cuquerella Alabort, Maria Consuelo
Miranda Alonso, Miguel Ángel
author Rodriguez-Alzueta, Ofelia
author_facet Rodriguez-Alzueta, Ofelia
Cuquerella Alabort, Maria Consuelo
Miranda Alonso, Miguel Ángel
author_role author
author2 Cuquerella Alabort, Maria Consuelo
Miranda Alonso, Miguel Ángel
author2_role author
author
dc.contributor.none.fl_str_mv Generalitat Valenciana
Ministerio de Educación
Agencia Estatal de Investigación
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv Pyrimidine dimer formation
DNA
Thymine
Benzophenone
Damage
QUIMICA ORGANICA
topic Pyrimidine dimer formation
DNA
Thymine
Benzophenone
Damage
QUIMICA ORGANICA
description [EN] Polymethylene-linked bipyrimidine models have been designed with different C5 substitutions and bridge lengths. Selective irradiation of 2'-methoxyacetophenone (2M) with the bipyrimidine models affords cyclobutane pyrimidine dimers, even in the presence of bulky substituents. Substitution at CS affects both the relative triplet energies (E-T(rel)) of the pyrimidines (Pyr) and the steric hindrance toward intermolecular energy transfer and intramolecular triplet Pyr* quenching. Photophysical studies showed that alkyl substitution resulted in a significant decrease in the E-T(rel) value. Quenching of the triplet excited state of 2M by the Pyr derivatives was proven and established their quenching rate constants (k(q)). As a general trend, the thymine-containing compounds showed k(q) values higher than 10(9) M(-1)s(-1), while in the uracil and tert-butyluracil analogues, k(q) was markedly lower. These data are explained considering three different scenarios: (a) triplet energy transfer is the rate controlling step, (b) excited state cyclization is the rate controlling step, and (c) the rate controlling step switches along the reaction. Thus, by introducing variations in the substitution at C5, the length of the linking bridge, or the substrate concentration, it is possible to switch from a process governed by the intrinsic dimerization step to an energy transfer-controlled process.
publishDate 2019
dc.date.none.fl_str_mv 2019
2019-11-01
dc.type.none.fl_str_mv journal article
http://purl.org/coar/resource_type/c_6501
VoR
http://purl.org/coar/version/c_970fb48d4fbd8a85
dc.type.openaire.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv https://riunet.upv.es/handle/10251/156029
url https://riunet.upv.es/handle/10251/156029
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Agencia Estatal de Investigación http://dx.doi.org/10.13039/501100011033 Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020 PGC2018-096684-B-I00 REPARACION DEL ADN POR PROCESOS MULTIFOTONICOS
Ministerio de Educación y Cultura http://dx.doi.org/10.13039/501100003176 FPU14%2F05294 FPU14%2F05294
Generalitat Valenciana https://doi.org/10.13039/501100003359 PROMETEO%2F2017%2F075 Reacciones fotoquímicas de biomoléculas
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reserva de todos los derechos
http://rightsstatements.org/vocab/InC/1.0/
dc.rights.openaire.fl_str_mv info:eu-repo/semantics/openAccess
rights_invalid_str_mv open access
http://purl.org/coar/access_right/c_abf2
Reserva de todos los derechos
http://rightsstatements.org/vocab/InC/1.0/
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
instname:Universitat Politècnica de València (UPV)
instname_str Universitat Politècnica de València (UPV)
reponame_str RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
collection RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300724

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