Photophysics and reductive quenching reactivity of gadusol in solution

Autores
Arbeloa, Ernesto Maximiliano; Bertolotti, Sonia Graciela; Churio, Maria Sandra
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The photostability and photophysics of gadusol in aqueous solution has been studied. The photodecomposition quantum yields (ca. 4 × 10-2 and 1 × 10-4 at acidic and neutral pH, respectively) confirm the high photostability of the metabolite, independently of the presence of oxygen, under physiological conditions. The nature of the electronic transition of gadusol has been assigned as π → π* on the basis of the solvatochromic shifts of the UV absorption spectrum and the time-dependent density functional theory calculation of the vertical transition energies. The results from the photoacoustic calorimetry point to the rapid non-radiative decay as the dominant relaxation pathway of the excited species at pH 7, which is consistent with the proposed UV-sunscreening role of the molecule in the early atmosphere. Laser flash photolysis experiments probed that the ground state of the enolate form (gadusolate) undergoes electron transfer reactions with some triplet sensitizers in water or methanol solution. A rate constant of 2 × 108 M-1 s-1 has been determined for the quenching of rose bengal triplet state in water at pH 7. This reductive quenching reactivity may be considered as one of the underlying mechanisms that support the antioxidant capacity of gadusol in biological environments. © The Royal Society of Chemistry and Owner Societies 2011.
Fil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Churio, Maria Sandra. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Grupo de Investigación del Departamento de Química de la Unmdp | Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata. Grupo de Investigación del Departamento de Química de la Unmdp; Argentina
Materia
GADUSOL
PHOTOPHYSICS
REACTIVE QUENCHING
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/189137
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/189137
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Photophysics and reductive quenching reactivity of gadusol in solutionArbeloa, Ernesto MaximilianoBertolotti, Sonia GracielaChurio, Maria SandraGADUSOLPHOTOPHYSICSREACTIVE QUENCHINGhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The photostability and photophysics of gadusol in aqueous solution has been studied. The photodecomposition quantum yields (ca. 4 × 10-2 and 1 × 10-4 at acidic and neutral pH, respectively) confirm the high photostability of the metabolite, independently of the presence of oxygen, under physiological conditions. The nature of the electronic transition of gadusol has been assigned as π → π* on the basis of the solvatochromic shifts of the UV absorption spectrum and the time-dependent density functional theory calculation of the vertical transition energies. The results from the photoacoustic calorimetry point to the rapid non-radiative decay as the dominant relaxation pathway of the excited species at pH 7, which is consistent with the proposed UV-sunscreening role of the molecule in the early atmosphere. Laser flash photolysis experiments probed that the ground state of the enolate form (gadusolate) undergoes electron transfer reactions with some triplet sensitizers in water or methanol solution. A rate constant of 2 × 108 M-1 s-1 has been determined for the quenching of rose bengal triplet state in water at pH 7. This reductive quenching reactivity may be considered as one of the underlying mechanisms that support the antioxidant capacity of gadusol in biological environments. © The Royal Society of Chemistry and Owner Societies 2011.Fil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; ArgentinaFil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Churio, Maria Sandra. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Grupo de Investigación del Departamento de Química de la Unmdp | Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata. Grupo de Investigación del Departamento de Química de la Unmdp; ArgentinaRoyal Society of Chemistry2010-11-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/189137Arbeloa, Ernesto Maximiliano; Bertolotti, Sonia Graciela; Churio, Maria Sandra; Photophysics and reductive quenching reactivity of gadusol in solution; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 10; 1; 12-11-2010; 133-1421474-905XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlelanding/2011/pp/c0pp00250jinfo:eu-repo/semantics/altIdentifier/doi/10.1039/C0PP00250Jinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T10:06:38Zoai:ri.conicet.gov.ar:11336/189137instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-03 10:06:38.542CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Photophysics and reductive quenching reactivity of gadusol in solution
title Photophysics and reductive quenching reactivity of gadusol in solution
spellingShingle Photophysics and reductive quenching reactivity of gadusol in solution
Arbeloa, Ernesto Maximiliano
GADUSOL
PHOTOPHYSICS
REACTIVE QUENCHING
title_short Photophysics and reductive quenching reactivity of gadusol in solution
title_full Photophysics and reductive quenching reactivity of gadusol in solution
title_fullStr Photophysics and reductive quenching reactivity of gadusol in solution
title_full_unstemmed Photophysics and reductive quenching reactivity of gadusol in solution
title_sort Photophysics and reductive quenching reactivity of gadusol in solution
dc.creator.none.fl_str_mv Arbeloa, Ernesto Maximiliano
Bertolotti, Sonia Graciela
Churio, Maria Sandra
author Arbeloa, Ernesto Maximiliano
author_facet Arbeloa, Ernesto Maximiliano
Bertolotti, Sonia Graciela
Churio, Maria Sandra
author_role author
author2 Bertolotti, Sonia Graciela
Churio, Maria Sandra
author2_role author
author
dc.subject.none.fl_str_mv GADUSOL
PHOTOPHYSICS
REACTIVE QUENCHING
topic GADUSOL
PHOTOPHYSICS
REACTIVE QUENCHING
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The photostability and photophysics of gadusol in aqueous solution has been studied. The photodecomposition quantum yields (ca. 4 × 10-2 and 1 × 10-4 at acidic and neutral pH, respectively) confirm the high photostability of the metabolite, independently of the presence of oxygen, under physiological conditions. The nature of the electronic transition of gadusol has been assigned as π → π* on the basis of the solvatochromic shifts of the UV absorption spectrum and the time-dependent density functional theory calculation of the vertical transition energies. The results from the photoacoustic calorimetry point to the rapid non-radiative decay as the dominant relaxation pathway of the excited species at pH 7, which is consistent with the proposed UV-sunscreening role of the molecule in the early atmosphere. Laser flash photolysis experiments probed that the ground state of the enolate form (gadusolate) undergoes electron transfer reactions with some triplet sensitizers in water or methanol solution. A rate constant of 2 × 108 M-1 s-1 has been determined for the quenching of rose bengal triplet state in water at pH 7. This reductive quenching reactivity may be considered as one of the underlying mechanisms that support the antioxidant capacity of gadusol in biological environments. © The Royal Society of Chemistry and Owner Societies 2011.
Fil: Arbeloa, Ernesto Maximiliano. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina
Fil: Bertolotti, Sonia Graciela. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Churio, Maria Sandra. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Físicas de Mar del Plata. Grupo de Investigación del Departamento de Química de la Unmdp | Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Físicas de Mar del Plata. Grupo de Investigación del Departamento de Química de la Unmdp; Argentina
description The photostability and photophysics of gadusol in aqueous solution has been studied. The photodecomposition quantum yields (ca. 4 × 10-2 and 1 × 10-4 at acidic and neutral pH, respectively) confirm the high photostability of the metabolite, independently of the presence of oxygen, under physiological conditions. The nature of the electronic transition of gadusol has been assigned as π → π* on the basis of the solvatochromic shifts of the UV absorption spectrum and the time-dependent density functional theory calculation of the vertical transition energies. The results from the photoacoustic calorimetry point to the rapid non-radiative decay as the dominant relaxation pathway of the excited species at pH 7, which is consistent with the proposed UV-sunscreening role of the molecule in the early atmosphere. Laser flash photolysis experiments probed that the ground state of the enolate form (gadusolate) undergoes electron transfer reactions with some triplet sensitizers in water or methanol solution. A rate constant of 2 × 108 M-1 s-1 has been determined for the quenching of rose bengal triplet state in water at pH 7. This reductive quenching reactivity may be considered as one of the underlying mechanisms that support the antioxidant capacity of gadusol in biological environments. © The Royal Society of Chemistry and Owner Societies 2011.
publishDate 2010
dc.date.none.fl_str_mv 2010-11-12
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/189137
Arbeloa, Ernesto Maximiliano; Bertolotti, Sonia Graciela; Churio, Maria Sandra; Photophysics and reductive quenching reactivity of gadusol in solution; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 10; 1; 12-11-2010; 133-142
1474-905X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/189137
identifier_str_mv Arbeloa, Ernesto Maximiliano; Bertolotti, Sonia Graciela; Churio, Maria Sandra; Photophysics and reductive quenching reactivity of gadusol in solution; Royal Society of Chemistry; Photochemical and Photobiological Sciences; 10; 1; 12-11-2010; 133-142
1474-905X
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.rsc.org/en/content/articlelanding/2011/pp/c0pp00250j
info:eu-repo/semantics/altIdentifier/doi/10.1039/C0PP00250J
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
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eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
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:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 13.13397

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