Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions

Autores
Miskoski, Sandra; Soltermann, Arnaldo Teseo; Molina, Patricia Gabriela; Günther, Mauricio German; Zanocco, Antonio L.; Garcia, Norman Andino
Año de publicación
2005
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Thyronine derivatives are essential indicators of thyroid gland diseases in clinical diagnosis and are currently used as standards for developing ordinary biochemical assays. Photo-oxidation of gland hormones of the thyronine (TN) family and structurally related compounds (TN, 3,5-dliodothyronine,3,3′,5- triiodothyronine and 3,3′,5,5′-tetraiodothyronine or thyroxine) was studied using rose bengal, eosin and perinaphthenone (PN) as dye sensitizers. Tyrosine (Tyr) and two iodinated derivatives (3-iodotyrosine and 3,5-diiodotyrosine) were also included in the study for comparative purposes. Irradiation of aqueous solutions of substrates containing xanthene dyes with visible light triggers a complex series of competitive interactions, which include the triplet excited state of the dye (3Xdye*) and singlet molecular oxygen [O2(1Δg,)]- mediated and superoxide ion-mediated reactions. Rate constants for interaction with the 3Xdye*, attributed to an electron transfer process, are in the order of 108-109 M-1 s-1 depending on the dye and the particular substrate. The photosensitization using PN follows a pure Type-II (O2(1Δg) mediated) mechanism. The presence of the phenolic group in Tyr, TN and iodinated derivatives dominates the kinetics of photooxidation of these compounds. The reactive rate constants, kγ, and the quotient between reactive and overall rate constants (kγ/kt, values, in the range of 0.7-0.06) behave in an opposite fashion compared with the overall rate constants and oxidation potentials. This apparent inconsistency was interpreted on the basis of an internal heavy atom effect, favoring the intersystem-crossrag deactivation route within the encounter complex with the concomitant reduction of effective photooxidation.
Fil: Miskoski, Sandra. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; Argentina
Fil: Soltermann, Arnaldo Teseo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Molina, Patricia Gabriela. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; Argentina
Fil: Günther, Mauricio German. Universidad de Chile; Chile
Fil: Zanocco, Antonio L.. Universidad de Chile; Chile
Fil: Garcia, Norman Andino. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Materia
Thyronine
Sensitized 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:11336/115572
Acceder
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network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactionsMiskoski, SandraSoltermann, Arnaldo TeseoMolina, Patricia GabrielaGünther, Mauricio GermanZanocco, Antonio L.Garcia, Norman AndinoThyronineSensitized Photooxidationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Thyronine derivatives are essential indicators of thyroid gland diseases in clinical diagnosis and are currently used as standards for developing ordinary biochemical assays. Photo-oxidation of gland hormones of the thyronine (TN) family and structurally related compounds (TN, 3,5-dliodothyronine,3,3′,5- triiodothyronine and 3,3′,5,5′-tetraiodothyronine or thyroxine) was studied using rose bengal, eosin and perinaphthenone (PN) as dye sensitizers. Tyrosine (Tyr) and two iodinated derivatives (3-iodotyrosine and 3,5-diiodotyrosine) were also included in the study for comparative purposes. Irradiation of aqueous solutions of substrates containing xanthene dyes with visible light triggers a complex series of competitive interactions, which include the triplet excited state of the dye (3Xdye*) and singlet molecular oxygen [O2(1Δg,)]- mediated and superoxide ion-mediated reactions. Rate constants for interaction with the 3Xdye*, attributed to an electron transfer process, are in the order of 108-109 M-1 s-1 depending on the dye and the particular substrate. The photosensitization using PN follows a pure Type-II (O2(1Δg) mediated) mechanism. The presence of the phenolic group in Tyr, TN and iodinated derivatives dominates the kinetics of photooxidation of these compounds. The reactive rate constants, kγ, and the quotient between reactive and overall rate constants (kγ/kt, values, in the range of 0.7-0.06) behave in an opposite fashion compared with the overall rate constants and oxidation potentials. This apparent inconsistency was interpreted on the basis of an internal heavy atom effect, favoring the intersystem-crossrag deactivation route within the encounter complex with the concomitant reduction of effective photooxidation.Fil: Miskoski, Sandra. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; ArgentinaFil: Soltermann, Arnaldo Teseo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Molina, Patricia Gabriela. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; ArgentinaFil: Günther, Mauricio German. Universidad de Chile; ChileFil: Zanocco, Antonio L.. Universidad de Chile; ChileFil: Garcia, Norman Andino. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaWiley Blackwell Publishing, Inc2005-03info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/115572Miskoski, Sandra; Soltermann, Arnaldo Teseo; Molina, Patricia Gabriela; Günther, Mauricio German; Zanocco, Antonio L.; et al.; Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions; Wiley Blackwell Publishing, Inc; Photochemistry and Photobiology; 81; 2; 3-2005; 325-3320031-86551751-1097CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1562/2004-10-27-RA-352.1info:eu-repo/semantics/altIdentifier/url/https://bioone.org/journals/photochemistry-and-photobiology/volume-81/issue-2/2004-10-27-RA-352.1info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T10:32:23Zoai:ri.conicet.gov.ar:11336/115572instacron: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:34982025-09-29 10:32:24.157CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions
title Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions
spellingShingle Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions
Miskoski, Sandra
Thyronine
Sensitized Photooxidation
title_short Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions
title_full Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions
title_fullStr Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions
title_full_unstemmed Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions
title_sort Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions
dc.creator.none.fl_str_mv Miskoski, Sandra
Soltermann, Arnaldo Teseo
Molina, Patricia Gabriela
Günther, Mauricio German
Zanocco, Antonio L.
Garcia, Norman Andino
author Miskoski, Sandra
author_facet Miskoski, Sandra
Soltermann, Arnaldo Teseo
Molina, Patricia Gabriela
Günther, Mauricio German
Zanocco, Antonio L.
Garcia, Norman Andino
author_role author
author2 Soltermann, Arnaldo Teseo
Molina, Patricia Gabriela
Günther, Mauricio German
Zanocco, Antonio L.
Garcia, Norman Andino
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Thyronine
Sensitized Photooxidation
topic Thyronine
Sensitized 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 Thyronine derivatives are essential indicators of thyroid gland diseases in clinical diagnosis and are currently used as standards for developing ordinary biochemical assays. Photo-oxidation of gland hormones of the thyronine (TN) family and structurally related compounds (TN, 3,5-dliodothyronine,3,3′,5- triiodothyronine and 3,3′,5,5′-tetraiodothyronine or thyroxine) was studied using rose bengal, eosin and perinaphthenone (PN) as dye sensitizers. Tyrosine (Tyr) and two iodinated derivatives (3-iodotyrosine and 3,5-diiodotyrosine) were also included in the study for comparative purposes. Irradiation of aqueous solutions of substrates containing xanthene dyes with visible light triggers a complex series of competitive interactions, which include the triplet excited state of the dye (3Xdye*) and singlet molecular oxygen [O2(1Δg,)]- mediated and superoxide ion-mediated reactions. Rate constants for interaction with the 3Xdye*, attributed to an electron transfer process, are in the order of 108-109 M-1 s-1 depending on the dye and the particular substrate. The photosensitization using PN follows a pure Type-II (O2(1Δg) mediated) mechanism. The presence of the phenolic group in Tyr, TN and iodinated derivatives dominates the kinetics of photooxidation of these compounds. The reactive rate constants, kγ, and the quotient between reactive and overall rate constants (kγ/kt, values, in the range of 0.7-0.06) behave in an opposite fashion compared with the overall rate constants and oxidation potentials. This apparent inconsistency was interpreted on the basis of an internal heavy atom effect, favoring the intersystem-crossrag deactivation route within the encounter complex with the concomitant reduction of effective photooxidation.
Fil: Miskoski, Sandra. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; Argentina
Fil: Soltermann, Arnaldo Teseo. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Molina, Patricia Gabriela. Universidad Nacional de Río Cuarto. Instituto para el Desarrollo Agroindustrial y de la Salud. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto para el Desarrollo Agroindustrial y de la Salud; Argentina
Fil: Günther, Mauricio German. Universidad de Chile; Chile
Fil: Zanocco, Antonio L.. Universidad de Chile; Chile
Fil: Garcia, Norman Andino. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
description Thyronine derivatives are essential indicators of thyroid gland diseases in clinical diagnosis and are currently used as standards for developing ordinary biochemical assays. Photo-oxidation of gland hormones of the thyronine (TN) family and structurally related compounds (TN, 3,5-dliodothyronine,3,3′,5- triiodothyronine and 3,3′,5,5′-tetraiodothyronine or thyroxine) was studied using rose bengal, eosin and perinaphthenone (PN) as dye sensitizers. Tyrosine (Tyr) and two iodinated derivatives (3-iodotyrosine and 3,5-diiodotyrosine) were also included in the study for comparative purposes. Irradiation of aqueous solutions of substrates containing xanthene dyes with visible light triggers a complex series of competitive interactions, which include the triplet excited state of the dye (3Xdye*) and singlet molecular oxygen [O2(1Δg,)]- mediated and superoxide ion-mediated reactions. Rate constants for interaction with the 3Xdye*, attributed to an electron transfer process, are in the order of 108-109 M-1 s-1 depending on the dye and the particular substrate. The photosensitization using PN follows a pure Type-II (O2(1Δg) mediated) mechanism. The presence of the phenolic group in Tyr, TN and iodinated derivatives dominates the kinetics of photooxidation of these compounds. The reactive rate constants, kγ, and the quotient between reactive and overall rate constants (kγ/kt, values, in the range of 0.7-0.06) behave in an opposite fashion compared with the overall rate constants and oxidation potentials. This apparent inconsistency was interpreted on the basis of an internal heavy atom effect, favoring the intersystem-crossrag deactivation route within the encounter complex with the concomitant reduction of effective photooxidation.
publishDate 2005
dc.date.none.fl_str_mv 2005-03
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/11336/115572
Miskoski, Sandra; Soltermann, Arnaldo Teseo; Molina, Patricia Gabriela; Günther, Mauricio German; Zanocco, Antonio L.; et al.; Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions; Wiley Blackwell Publishing, Inc; Photochemistry and Photobiology; 81; 2; 3-2005; 325-332
0031-8655
1751-1097
CONICET Digital
CONICET
url http://hdl.handle.net/11336/115572
identifier_str_mv Miskoski, Sandra; Soltermann, Arnaldo Teseo; Molina, Patricia Gabriela; Günther, Mauricio German; Zanocco, Antonio L.; et al.; Sensitized photooxidation of thyroidal hormones. Evidence for heavy atom effect on singlet molecular oxygen [O2(1Δ g)]-mediated photoreactions; Wiley Blackwell Publishing, Inc; Photochemistry and Photobiology; 81; 2; 3-2005; 325-332
0031-8655
1751-1097
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1562/2004-10-27-RA-352.1
info:eu-repo/semantics/altIdentifier/url/https://bioone.org/journals/photochemistry-and-photobiology/volume-81/issue-2/2004-10-27-RA-352.1
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
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Wiley Blackwell Publishing, Inc
publisher.none.fl_str_mv Wiley Blackwell Publishing, Inc
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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