Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan

Autores
Haggi, Ernesto; Blasich, Néstor; Montaña, Maria Paulina; Ferrari, Gabriela Verónica; Muñoz, Vanesa Alejandra; Challier, Cecilia; Criado, Susana Noemi; Natera, Jose Eduardo; Miskoski, Sandra; Garcia, Norman Andino
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Within the frame of the frequently invoked correlation between antioxidant contents and potential antioxidative protection, the stability of the amino acid (AA) tryptophan (trp), taken as a prototype of photooxidizable-relevant biological target, was evaluated in the presence of the known antioxidant ascorbic acid (AsA). The peptide glutathione (GSH) was also included in order to eliminate thermal decomposition of AsA. Riboflavin (Rf, vitamin B2), endogenous in most biological environments, was employed as a photosensitizer. A systematic kinetic and mechanistic study was conducted under aerobic conditions in pH 7 aqueous medium. The evaluation of oxygen uptake rates (OUR) in the photoirradiated mixtures, taken as an overall indicator of the total oxidation degree of the mixture components, constitutes an interesting and useful tool in this case. In the presence of Rf, the isolated AA and AsA undergo photodegradation under conditions currently found in natural media. The photodegradations occur in a non-simple reaction, mediated by reactive oxygen species (ROS) such as singlet molecular oxygen (O2(1g)), superoxide radical anion, and hydrogen peroxide and hydroxyl-radical. All ROS are photogenerated from triplet excited Rf after interaction with the ground state of AsA and trp. The photoirradiation also triggers an already described parallel thermally-driven and dark reaction on AsA which is stopped by the addition of GSH. The global outcome can be interpreted as a sort of conjunctive antioxidant protection exerted on the system AsA + trp + GSH upon Rf-photosensitization, a result that cannot be predicted from the individual behavior of the mixture components.
Fil: Haggi, Ernesto. Universidad Nacional de la Patagonia Austral; Argentina
Fil: Blasich, Néstor. Universidad Nacional de la Patagonia Austral; Argentina
Fil: Montaña, Maria Paulina. Universidad Nacional de San Luis. Departamento de Quiâ­mica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ferrari, Gabriela Verónica. Universidad Nacional de San Luis. Departamento de Quiâ­mica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Muñoz, Vanesa Alejandra. Universidad Nacional de San Luis. Departamento de Quiâ­mica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Challier, Cecilia. 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: Criado, Susana Noemi. 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: Natera, Jose Eduardo. 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: Miskoski, Sandra. 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: Garcia, Norman Andino. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
Ascorbate
Glutathione
Photodegradation
Photooxidation
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:11336/7515

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network_name_str CONICET Digital (CONICET)
spelling Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophanHaggi, ErnestoBlasich, NéstorMontaña, Maria PaulinaFerrari, Gabriela VerónicaMuñoz, Vanesa AlejandraChallier, CeciliaCriado, Susana NoemiNatera, Jose EduardoMiskoski, SandraGarcia, Norman AndinoAscorbateGlutathionePhotodegradationPhotooxidationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Within the frame of the frequently invoked correlation between antioxidant contents and potential antioxidative protection, the stability of the amino acid (AA) tryptophan (trp), taken as a prototype of photooxidizable-relevant biological target, was evaluated in the presence of the known antioxidant ascorbic acid (AsA). The peptide glutathione (GSH) was also included in order to eliminate thermal decomposition of AsA. Riboflavin (Rf, vitamin B2), endogenous in most biological environments, was employed as a photosensitizer. A systematic kinetic and mechanistic study was conducted under aerobic conditions in pH 7 aqueous medium. The evaluation of oxygen uptake rates (OUR) in the photoirradiated mixtures, taken as an overall indicator of the total oxidation degree of the mixture components, constitutes an interesting and useful tool in this case. In the presence of Rf, the isolated AA and AsA undergo photodegradation under conditions currently found in natural media. The photodegradations occur in a non-simple reaction, mediated by reactive oxygen species (ROS) such as singlet molecular oxygen (O2(1g)), superoxide radical anion, and hydrogen peroxide and hydroxyl-radical. All ROS are photogenerated from triplet excited Rf after interaction with the ground state of AsA and trp. The photoirradiation also triggers an already described parallel thermally-driven and dark reaction on AsA which is stopped by the addition of GSH. The global outcome can be interpreted as a sort of conjunctive antioxidant protection exerted on the system AsA + trp + GSH upon Rf-photosensitization, a result that cannot be predicted from the individual behavior of the mixture components.Fil: Haggi, Ernesto. Universidad Nacional de la Patagonia Austral; ArgentinaFil: Blasich, Néstor. Universidad Nacional de la Patagonia Austral; ArgentinaFil: Montaña, Maria Paulina. Universidad Nacional de San Luis. Departamento de Quiâ­mica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Ferrari, Gabriela Verónica. Universidad Nacional de San Luis. Departamento de Quiâ­mica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Muñoz, Vanesa Alejandra. Universidad Nacional de San Luis. Departamento de Quiâ­mica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Challier, Cecilia. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Criado, Susana Noemi. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Natera, Jose Eduardo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Miskoski, Sandra. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Garcia, Norman Andino. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaResearch Trends2013-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/7515Haggi, Ernesto; Blasich, Néstor; Montaña, Maria Paulina; Ferrari, Gabriela Verónica; Muñoz, Vanesa Alejandra; et al.; Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan; Research Trends; Current topics in peptide & protein research; 14; 12-2013; 57-650972-4524enginfo:eu-repo/semantics/altIdentifier/url/http://www.researchtrends.net/tia/abstract.asp?in=0&vn=14&tid=26&aid=5362&pub=2013&type=3info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:59:40Zoai:ri.conicet.gov.ar:11336/7515instacron: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:34982025-10-15 14:59:40.607CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan
title Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan
spellingShingle Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan
Haggi, Ernesto
Ascorbate
Glutathione
Photodegradation
Photooxidation
title_short Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan
title_full Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan
title_fullStr Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan
title_full_unstemmed Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan
title_sort Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan
dc.creator.none.fl_str_mv Haggi, Ernesto
Blasich, Néstor
Montaña, Maria Paulina
Ferrari, Gabriela Verónica
Muñoz, Vanesa Alejandra
Challier, Cecilia
Criado, Susana Noemi
Natera, Jose Eduardo
Miskoski, Sandra
Garcia, Norman Andino
author Haggi, Ernesto
author_facet Haggi, Ernesto
Blasich, Néstor
Montaña, Maria Paulina
Ferrari, Gabriela Verónica
Muñoz, Vanesa Alejandra
Challier, Cecilia
Criado, Susana Noemi
Natera, Jose Eduardo
Miskoski, Sandra
Garcia, Norman Andino
author_role author
author2 Blasich, Néstor
Montaña, Maria Paulina
Ferrari, Gabriela Verónica
Muñoz, Vanesa Alejandra
Challier, Cecilia
Criado, Susana Noemi
Natera, Jose Eduardo
Miskoski, Sandra
Garcia, Norman Andino
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Ascorbate
Glutathione
Photodegradation
Photooxidation
topic Ascorbate
Glutathione
Photodegradation
Photooxidation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Within the frame of the frequently invoked correlation between antioxidant contents and potential antioxidative protection, the stability of the amino acid (AA) tryptophan (trp), taken as a prototype of photooxidizable-relevant biological target, was evaluated in the presence of the known antioxidant ascorbic acid (AsA). The peptide glutathione (GSH) was also included in order to eliminate thermal decomposition of AsA. Riboflavin (Rf, vitamin B2), endogenous in most biological environments, was employed as a photosensitizer. A systematic kinetic and mechanistic study was conducted under aerobic conditions in pH 7 aqueous medium. The evaluation of oxygen uptake rates (OUR) in the photoirradiated mixtures, taken as an overall indicator of the total oxidation degree of the mixture components, constitutes an interesting and useful tool in this case. In the presence of Rf, the isolated AA and AsA undergo photodegradation under conditions currently found in natural media. The photodegradations occur in a non-simple reaction, mediated by reactive oxygen species (ROS) such as singlet molecular oxygen (O2(1g)), superoxide radical anion, and hydrogen peroxide and hydroxyl-radical. All ROS are photogenerated from triplet excited Rf after interaction with the ground state of AsA and trp. The photoirradiation also triggers an already described parallel thermally-driven and dark reaction on AsA which is stopped by the addition of GSH. The global outcome can be interpreted as a sort of conjunctive antioxidant protection exerted on the system AsA + trp + GSH upon Rf-photosensitization, a result that cannot be predicted from the individual behavior of the mixture components.
Fil: Haggi, Ernesto. Universidad Nacional de la Patagonia Austral; Argentina
Fil: Blasich, Néstor. Universidad Nacional de la Patagonia Austral; Argentina
Fil: Montaña, Maria Paulina. Universidad Nacional de San Luis. Departamento de Quiâ­mica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Ferrari, Gabriela Verónica. Universidad Nacional de San Luis. Departamento de Quiâ­mica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Muñoz, Vanesa Alejandra. Universidad Nacional de San Luis. Departamento de Quiâ­mica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Challier, Cecilia. 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: Criado, Susana Noemi. 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: Natera, Jose Eduardo. 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: Miskoski, Sandra. 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: Garcia, Norman Andino. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Departamento de Química; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description Within the frame of the frequently invoked correlation between antioxidant contents and potential antioxidative protection, the stability of the amino acid (AA) tryptophan (trp), taken as a prototype of photooxidizable-relevant biological target, was evaluated in the presence of the known antioxidant ascorbic acid (AsA). The peptide glutathione (GSH) was also included in order to eliminate thermal decomposition of AsA. Riboflavin (Rf, vitamin B2), endogenous in most biological environments, was employed as a photosensitizer. A systematic kinetic and mechanistic study was conducted under aerobic conditions in pH 7 aqueous medium. The evaluation of oxygen uptake rates (OUR) in the photoirradiated mixtures, taken as an overall indicator of the total oxidation degree of the mixture components, constitutes an interesting and useful tool in this case. In the presence of Rf, the isolated AA and AsA undergo photodegradation under conditions currently found in natural media. The photodegradations occur in a non-simple reaction, mediated by reactive oxygen species (ROS) such as singlet molecular oxygen (O2(1g)), superoxide radical anion, and hydrogen peroxide and hydroxyl-radical. All ROS are photogenerated from triplet excited Rf after interaction with the ground state of AsA and trp. The photoirradiation also triggers an already described parallel thermally-driven and dark reaction on AsA which is stopped by the addition of GSH. The global outcome can be interpreted as a sort of conjunctive antioxidant protection exerted on the system AsA + trp + GSH upon Rf-photosensitization, a result that cannot be predicted from the individual behavior of the mixture components.
publishDate 2013
dc.date.none.fl_str_mv 2013-12
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/11336/7515
Haggi, Ernesto; Blasich, Néstor; Montaña, Maria Paulina; Ferrari, Gabriela Verónica; Muñoz, Vanesa Alejandra; et al.; Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan; Research Trends; Current topics in peptide & protein research; 14; 12-2013; 57-65
0972-4524
url http://hdl.handle.net/11336/7515
identifier_str_mv Haggi, Ernesto; Blasich, Néstor; Montaña, Maria Paulina; Ferrari, Gabriela Verónica; Muñoz, Vanesa Alejandra; et al.; Kinetic and mechanistic behavior of the ascorbate ion-glutathione mixture in the visible-light-mediated oxidation of tryptophan; Research Trends; Current topics in peptide & protein research; 14; 12-2013; 57-65
0972-4524
dc.language.none.fl_str_mv eng
language eng
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dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
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dc.publisher.none.fl_str_mv Research Trends
publisher.none.fl_str_mv Research Trends
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repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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