Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy

[EN] Guanine-cytosine hairpins, containing a hexaethylene glycol bridge, are studied by steady-state fluorescence spectroscopy and time-correlated single photon counting; their properties are compared to those of duplexes with the same sequence. It is shown that, both in hairpins and in duplexes, ba...

Descripción completa

Detalles Bibliográficos
Autores: Brazard, J., Thazhathveetil, A.K., Lewis, F.D., Gustavsson, T., Markovitsi, D., Vayá Pérez, Ignacio|||0000-0003-1682-9342
Tipo de recurso: artículo
Fecha de publicación:2013
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:10251/60361
Acceso en línea:https://riunet.upv.es/handle/10251/60361
Access Level:acceso abierto
Palabra clave:QUIMICA ANALITICA
QUIMICA ORGANICA
id ES_e9efe391b1a10cae5a209e345dcf7bfa
oai_identifier_str oai:riunet.upv.es:10251/60361
network_acronym_str ES
network_name_str España
repository_id_str
spelling Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopyBrazard, J.Thazhathveetil, A.K.Lewis, F.D.Gustavsson, T.Markovitsi, D.Vayá Pérez, Ignacio|||0000-0003-1682-9342QUIMICA ANALITICAQUIMICA ORGANICA[EN] Guanine-cytosine hairpins, containing a hexaethylene glycol bridge, are studied by steady-state fluorescence spectroscopy and time-correlated single photon counting; their properties are compared to those of duplexes with the same sequence. It is shown that, both in hairpins and in duplexes, base pairing induces quenching of the pi pi(star) fluorescence, the quantum yield decreasing by at least two orders of magnitude. When the size of the systems increases from two to ten base pairs, a fluorescent component decaying on the nanosecond time-scale appears at energy higher than that stemming from the bright states of non-interacting mono-nucleotides (ca. 330 nm). For ten base pairs, this new fluorescence forms a well-defined band peaking at 305 nm. Its intensity is about 20% higher for the hairpin compared to the duplex. Its position (red-shifted by 1600 cm(-1)) and width (broader by 1800 cm(-1) FWHM) differ from those observed for large duplexes containing 1000 base pairs, suggesting the involvement of electronic coupling. Fluorescence anisotropy reveals that the excited states responsible for high energy emission are not populated directly upon photon absorption but are reached during a relaxation process. They are assigned to charge transfer states. According to the emerging picture, the amplitude of conformational motions determines whether instantaneous deactivation to the ground state or emission from charge transfer states will take place, while pi pi(star) fluorescence is associated to imperfect base-pairing.The French Agency for Research (ANR-10-BLAN-0809-01), the Conselleria de Educacion-Generalitat Valenciana (VALi+D program to I.V., N° 2010033) and the US Department of Energy, Office of Basic Energy Sciences (grant no. DE-FG02-96ER14604 to F.D.L.) are acknowledged for financial support.Royal Society of ChemistryInstituto Universitario Mixto de Tecnología QuímicaDepartamento de QuímicaEscuela Técnica Superior de Ingeniería IndustrialAgence Nationale de la Recherche, FranciaGeneralitat ValencianaU.S. Department of EnergyRepositorio Institucional de la Universitat Politècnica de València Riunet20132013-01-01journal articlehttp://purl.org/coar/resource_type/c_6501VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttps://riunet.upv.es/handle/10251/60361reponame:RiuNet. Repositorio Institucional de la Universitat Politécnica de Valénciainstname:Universitat Politècnica de València (UPV)InglésengGeneralitat Valenciana https://doi.org/10.13039/501100003359 APOSTD%2F2010%2F033Agence Nationale de la Recherche, Francia https://doi.org/10.13039/501100001665 ANR-10-BLAN-0809 Photo-induced energy transfer in methylated DNA helices and its relevance to UV damage : an interactive theoretical-experimental studyU.S. Department of Energy https://doi.org/10.13039/100000015 DE-FG02-96ER14604open 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:10251/603612026-06-13T07:49:27Z
dc.title.none.fl_str_mv Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy
title Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy
spellingShingle Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy
Brazard, J.
QUIMICA ANALITICA
QUIMICA ORGANICA
title_short Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy
title_full Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy
title_fullStr Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy
title_full_unstemmed Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy
title_sort Electronic excited states of guanine-cytosine hairpins and duplexes studied by fluorescence spectroscopy
dc.creator.none.fl_str_mv Brazard, J.
Thazhathveetil, A.K.
Lewis, F.D.
Gustavsson, T.
Markovitsi, D.
Vayá Pérez, Ignacio|||0000-0003-1682-9342
author Brazard, J.
author_facet Brazard, J.
Thazhathveetil, A.K.
Lewis, F.D.
Gustavsson, T.
Markovitsi, D.
Vayá Pérez, Ignacio|||0000-0003-1682-9342
author_role author
author2 Thazhathveetil, A.K.
Lewis, F.D.
Gustavsson, T.
Markovitsi, D.
Vayá Pérez, Ignacio|||0000-0003-1682-9342
author2_role author
author
author
author
author
dc.contributor.none.fl_str_mv Instituto Universitario Mixto de Tecnología Química
Departamento de Química
Escuela Técnica Superior de Ingeniería Industrial
Agence Nationale de la Recherche, Francia
Generalitat Valenciana
U.S. Department of Energy
Repositorio Institucional de la Universitat Politècnica de València Riunet
dc.subject.none.fl_str_mv QUIMICA ANALITICA
QUIMICA ORGANICA
topic QUIMICA ANALITICA
QUIMICA ORGANICA
description [EN] Guanine-cytosine hairpins, containing a hexaethylene glycol bridge, are studied by steady-state fluorescence spectroscopy and time-correlated single photon counting; their properties are compared to those of duplexes with the same sequence. It is shown that, both in hairpins and in duplexes, base pairing induces quenching of the pi pi(star) fluorescence, the quantum yield decreasing by at least two orders of magnitude. When the size of the systems increases from two to ten base pairs, a fluorescent component decaying on the nanosecond time-scale appears at energy higher than that stemming from the bright states of non-interacting mono-nucleotides (ca. 330 nm). For ten base pairs, this new fluorescence forms a well-defined band peaking at 305 nm. Its intensity is about 20% higher for the hairpin compared to the duplex. Its position (red-shifted by 1600 cm(-1)) and width (broader by 1800 cm(-1) FWHM) differ from those observed for large duplexes containing 1000 base pairs, suggesting the involvement of electronic coupling. Fluorescence anisotropy reveals that the excited states responsible for high energy emission are not populated directly upon photon absorption but are reached during a relaxation process. They are assigned to charge transfer states. According to the emerging picture, the amplitude of conformational motions determines whether instantaneous deactivation to the ground state or emission from charge transfer states will take place, while pi pi(star) fluorescence is associated to imperfect base-pairing.
publishDate 2013
dc.date.none.fl_str_mv 2013
2013-01-01
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/10251/60361
url https://riunet.upv.es/handle/10251/60361
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv Generalitat Valenciana https://doi.org/10.13039/501100003359 APOSTD%2F2010%2F033
Agence Nationale de la Recherche, Francia https://doi.org/10.13039/501100001665 ANR-10-BLAN-0809 Photo-induced energy transfer in methylated DNA helices and its relevance to UV damage : an interactive theoretical-experimental study
U.S. Department of Energy https://doi.org/10.13039/100000015 DE-FG02-96ER14604
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
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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
_version_ 1869423095482155008
score 15,301603

Similares en LA Referencia