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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/115572
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oai:ri.conicet.gov.ar:11336/115572 |
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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 Técnicas2025-09-03T10:07:07Zoai: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:34982025-09-03 10:07:07.857CONICET 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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1842269990542114816 |
score |
13.13397 |