The origin of efficient triplet state population in sulfur-substituted nucleobases

Elucidating the photophysical mechanisms in sulfur-substituted nucleobases (thiobases) is essential for designing prospective drugs for photo-and chemotherapeutic applications. Although it has long been established that the phototherapeutic activity of thiobases is intimately linked to efficient int...

Descripción completa

Detalles Bibliográficos
Autores: Mai, Sebastian, Pollum, Marvin, Martínez-Fernández, Lara, Dunn, Nicholas, Marquetand, Philipp, Corral Pérez, Inés, Crespo-Hernández, Carlos E., González, Leticia
Tipo de recurso: artículo
Fecha de publicación:2016
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/676911
Acceso en línea:http://hdl.handle.net/10486/676911
https://dx.doi.org/10.1038/ncomms13077
Access Level:acceso abierto
Palabra clave:Sulfur-substituted
Nucleobases
Química
id ES_3fdf7bfc53734d389489b2febaccbe4e
oai_identifier_str oai:repositorio.uam.es:10486/676911
network_acronym_str ES
network_name_str España
repository_id_str
spelling The origin of efficient triplet state population in sulfur-substituted nucleobasesMai, SebastianPollum, MarvinMartínez-Fernández, LaraDunn, NicholasMarquetand, PhilippCorral Pérez, InésCrespo-Hernández, Carlos E.González, LeticiaSulfur-substitutedNucleobasesQuímicaElucidating the photophysical mechanisms in sulfur-substituted nucleobases (thiobases) is essential for designing prospective drugs for photo-and chemotherapeutic applications. Although it has long been established that the phototherapeutic activity of thiobases is intimately linked to efficient intersystem crossing into reactive triplet states, the molecular factors underlying this efficiency are poorly understood. Herein we combine femtosecond transient absorption experiments with quantum chemistry and nonadiabatic dynamics simulations to investigate 2-thiocytosine as a necessary step to unravel the electronic and structural elements that lead to ultrafast and near-unity triplet-state population in thiobases in general. We show that different parts of the potential energy surfaces are stabilized to different extents via thionation, quenching the intrinsic photostability of canonical DNA and RNA nucleobases. These findings satisfactorily explain why thiobases exhibit the fastest intersystem crossing lifetimes measured to date among bio-organic molecules and have near-unity triplet yields, whereas the triplet yields of canonical nucleobases are nearly zeroS.M., P.M. and L.G. thank the Austrian Science Fund (FWF) through project P25827, the COST action CM1204 (XLIC) and the Vienna Scientific Cluster (VSC) for the allocation of computational time. We also thank F. Plasser for assistance with the TheoDORE program. I.C. and L.M.-F. thank the Comunidad Autónoma de Madrid, the Ministerio de Economía y Competitividad (Spain) for an FPU (L.M.-F.) grant, the Projects FOTOCARBON-CM S2013/MIT-2841 and No. CTQ2015-63997-C2, and the ERA-Chemistry Project PIM2010EEC-00751 for financial support, as well as the Centro de Computación Científica UAM for generous allocation of computational time. M.P., N.D. and C.E.C.-H. acknowledge the CAREER program of the National Science Foundation (Grant No. CHE-1255084) for financial supportNature Publishing GroupDepartamento de QuímicaFacultad de Ciencias20162016-10-05research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/676911https://dx.doi.org/10.1038/ncomms13077reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengopen accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/6769112026-06-23T12:46:27Z
dc.title.none.fl_str_mv The origin of efficient triplet state population in sulfur-substituted nucleobases
title The origin of efficient triplet state population in sulfur-substituted nucleobases
spellingShingle The origin of efficient triplet state population in sulfur-substituted nucleobases
Mai, Sebastian
Sulfur-substituted
Nucleobases
Química
title_short The origin of efficient triplet state population in sulfur-substituted nucleobases
title_full The origin of efficient triplet state population in sulfur-substituted nucleobases
title_fullStr The origin of efficient triplet state population in sulfur-substituted nucleobases
title_full_unstemmed The origin of efficient triplet state population in sulfur-substituted nucleobases
title_sort The origin of efficient triplet state population in sulfur-substituted nucleobases
dc.creator.none.fl_str_mv Mai, Sebastian
Pollum, Marvin
Martínez-Fernández, Lara
Dunn, Nicholas
Marquetand, Philipp
Corral Pérez, Inés
Crespo-Hernández, Carlos E.
González, Leticia
author Mai, Sebastian
author_facet Mai, Sebastian
Pollum, Marvin
Martínez-Fernández, Lara
Dunn, Nicholas
Marquetand, Philipp
Corral Pérez, Inés
Crespo-Hernández, Carlos E.
González, Leticia
author_role author
author2 Pollum, Marvin
Martínez-Fernández, Lara
Dunn, Nicholas
Marquetand, Philipp
Corral Pérez, Inés
Crespo-Hernández, Carlos E.
González, Leticia
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv Departamento de Química
Facultad de Ciencias
dc.subject.none.fl_str_mv Sulfur-substituted
Nucleobases
Química
topic Sulfur-substituted
Nucleobases
Química
description Elucidating the photophysical mechanisms in sulfur-substituted nucleobases (thiobases) is essential for designing prospective drugs for photo-and chemotherapeutic applications. Although it has long been established that the phototherapeutic activity of thiobases is intimately linked to efficient intersystem crossing into reactive triplet states, the molecular factors underlying this efficiency are poorly understood. Herein we combine femtosecond transient absorption experiments with quantum chemistry and nonadiabatic dynamics simulations to investigate 2-thiocytosine as a necessary step to unravel the electronic and structural elements that lead to ultrafast and near-unity triplet-state population in thiobases in general. We show that different parts of the potential energy surfaces are stabilized to different extents via thionation, quenching the intrinsic photostability of canonical DNA and RNA nucleobases. These findings satisfactorily explain why thiobases exhibit the fastest intersystem crossing lifetimes measured to date among bio-organic molecules and have near-unity triplet yields, whereas the triplet yields of canonical nucleobases are nearly zero
publishDate 2016
dc.date.none.fl_str_mv 2016
2016-10-05
dc.type.none.fl_str_mv research article
http://purl.org/coar/resource_type/c_2df8fbb1
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 http://hdl.handle.net/10486/676911
https://dx.doi.org/10.1038/ncomms13077
url http://hdl.handle.net/10486/676911
https://dx.doi.org/10.1038/ncomms13077
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.rights.none.fl_str_mv open access
http://purl.org/coar/access_right/c_abf2
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
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Nature Publishing Group
publisher.none.fl_str_mv Nature Publishing Group
dc.source.none.fl_str_mv reponame:Biblos-e Archivo. Repositorio Institucional de la UAM
instname:Universidad Autónoma de Madrid
instname_str Universidad Autónoma de Madrid
reponame_str Biblos-e Archivo. Repositorio Institucional de la UAM
collection Biblos-e Archivo. Repositorio Institucional de la UAM
repository.name.fl_str_mv
repository.mail.fl_str_mv
_version_ 1869406690588229632
score 15,300724

Similares en LA Referencia