Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculations

The fluorescent base guanine analog, 8‐vinyl‐deoxyguanosine (8vdG), is studied in solution using a combination of optical spectroscopies, notably femtosecond fluorescence upconversion and quantum chemical calculations, based on time‐dependent density functional theory (TD‐DFT) and including solvent...

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Detalles Bibliográficos
Autores: Martinez‐Fernandez, Lara, Gustavsson, Thomas, Diederichsen, Ulf, Improta, Roberto
Tipo de recurso: artículo
Fecha de publicación:2020
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/694544
Acceso en línea:http://hdl.handle.net/10486/694544
https://dx.doi.org/10.3390/molecules25040824
Access Level:acceso abierto
Palabra clave:DNA
Fluorescent probe
Solvent effect
TD‐DFT
Química
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spelling Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculationsMartinez‐Fernandez, LaraGustavsson, ThomasDiederichsen, UlfImprota, RobertoDNAFluorescent probeSolvent effectTD‐DFTQuímicaThe fluorescent base guanine analog, 8‐vinyl‐deoxyguanosine (8vdG), is studied in solution using a combination of optical spectroscopies, notably femtosecond fluorescence upconversion and quantum chemical calculations, based on time‐dependent density functional theory (TD‐DFT) and including solvent effect by using a mixed discrete‐continuum model. In all investigated solvents, the fluorescence is very long lived (3¥4 ns), emanating from a stable excited state minimum with pronounced intramolecular charge‐transfer character. The main non‐radiative decay channel features a sizeable energy barrier and it is affected by the polarity and the H‐bonding properties of the solvent. Calculations provide a picture of dynamical solvation effects fully consistent with the experimental results and show that the photophysical properties of 8vdG are modulated by the orientation of the vinyl group with respect to the purine ring, which in turn depends on the solvent. These findings may have importance for the understanding of the fluorescence properties of 8vdG when incorporated in a DNA helixThis work has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skodowska-Curie grant agreement No 765266 (LightDyNAmics) and the French CNRS-CNR PICS project (N86827-2015)MDPIDepartamento de QuímicaFacultad de Ciencias20202020-02-13research articlehttp://purl.org/coar/resource_type/c_2df8fbb1VoRhttp://purl.org/coar/version/c_970fb48d4fbd8a85info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10486/694544https://dx.doi.org/10.3390/molecules25040824reponame:Biblos-e Archivo. Repositorio Institucional de la UAMinstname:Universidad Autónoma de MadridInglésengEuropean Commission http://dx.doi.org/10.13039/501100000780 Horizon 2020 Framework Programme 765266open accesshttp://purl.org/coar/access_right/c_abf2info:eu-repo/semantics/openAccessoai:repositorio.uam.es:10486/6945442026-06-23T12:46:27Z
dc.title.none.fl_str_mv Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculations
title Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculations
spellingShingle Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculations
Martinez‐Fernandez, Lara
DNA
Fluorescent probe
Solvent effect
TD‐DFT
Química
title_short Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculations
title_full Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculations
title_fullStr Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculations
title_full_unstemmed Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculations
title_sort Excited state dynamics of 8‐vinyldeoxyguanosine in aqueous solution studied by time‐resolved fluorescence spectroscopy and quantum mechanical calculations
dc.creator.none.fl_str_mv Martinez‐Fernandez, Lara
Gustavsson, Thomas
Diederichsen, Ulf
Improta, Roberto
author Martinez‐Fernandez, Lara
author_facet Martinez‐Fernandez, Lara
Gustavsson, Thomas
Diederichsen, Ulf
Improta, Roberto
author_role author
author2 Gustavsson, Thomas
Diederichsen, Ulf
Improta, Roberto
author2_role author
author
author
dc.contributor.none.fl_str_mv Departamento de Química
Facultad de Ciencias
dc.subject.none.fl_str_mv DNA
Fluorescent probe
Solvent effect
TD‐DFT
Química
topic DNA
Fluorescent probe
Solvent effect
TD‐DFT
Química
description The fluorescent base guanine analog, 8‐vinyl‐deoxyguanosine (8vdG), is studied in solution using a combination of optical spectroscopies, notably femtosecond fluorescence upconversion and quantum chemical calculations, based on time‐dependent density functional theory (TD‐DFT) and including solvent effect by using a mixed discrete‐continuum model. In all investigated solvents, the fluorescence is very long lived (3¥4 ns), emanating from a stable excited state minimum with pronounced intramolecular charge‐transfer character. The main non‐radiative decay channel features a sizeable energy barrier and it is affected by the polarity and the H‐bonding properties of the solvent. Calculations provide a picture of dynamical solvation effects fully consistent with the experimental results and show that the photophysical properties of 8vdG are modulated by the orientation of the vinyl group with respect to the purine ring, which in turn depends on the solvent. These findings may have importance for the understanding of the fluorescence properties of 8vdG when incorporated in a DNA helix
publishDate 2020
dc.date.none.fl_str_mv 2020
2020-02-13
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/10486/694544
https://dx.doi.org/10.3390/molecules25040824
url http://hdl.handle.net/10486/694544
https://dx.doi.org/10.3390/molecules25040824
dc.language.none.fl_str_mv Inglés
eng
language_invalid_str_mv Inglés
language eng
dc.relation.none.fl_str_mv European Commission http://dx.doi.org/10.13039/501100000780 Horizon 2020 Framework Programme 765266
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 MDPI
publisher.none.fl_str_mv MDPI
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
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