ESR characterization of thallium(III)-mediated nitrones oxidation

Autores
Verstraeten, Sandra Viviana; Lucangioli, Silvia Edith; Galleano, Mónica Liliana
Año de publicación
2009
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
We characterized the reactions between Tl (III) and the usual nitrone spin traps (DMPO, POBN, and PBN). The ESR signal obtained with DMPO corresponded to DMPOX which was avoided neither by the enzymes superoxide dismutase or catalase, nor by the hydroxyl radical scavengers´ mannitol, ethanol, or methanol. Only when methanol concentration rose to 90% (v/v), a significant decrease in DMPOX formation was observed while no detectable DMPOX signal was present at 100% methanol solution. POBN rendered an unexpected adduct, while no oxidation products were obtained with PBN. Together, the experimental evidence demonstrates that Tl(III)-supported DMPO oxidation is not mediated by oxygen reactive species. Instead, we propose that Tl(III) interacts with the probe, favoring the addition of water. The intermediate is susceptible to be further oxidized by Tl(III) yielding a keto group. Kinetic studies showed that Tl(III) disappearance rate was higher (1.6 times) than DMPOX formation rate, and equal to Tl(I) formation rate, suggesting a stoichiometry 1.5:1 for Tl(III):DMPOX and 1:1 for Tl(III):Tl(I). The process, an example of the Forrester-Hepburn´s mechanism, was demonstrated for DMPO while the reactions of Tl(III) with POBN and PBN are still under elucidation.
Fil: Verstraeten, Sandra Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas "Prof. Alejandro C. Paladini". Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Físico-Química Biológicas; Argentina
Fil: Lucangioli, Silvia Edith. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Tecnología Farmacéutica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Galleano, Mónica Liliana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Programa de Radicales Libres; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Bioquímica y Medicina Molecular. Universidad de Buenos Aires. Facultad Medicina. Instituto de Bioquímica y Medicina Molecular; Argentina
Materia
THALLIUM
NITRONES
ESR
FORRESTER-HEPBURN MECHANISM
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:11336/103314
Acceder
id CONICETDig_f64accde7903c30ce5097e5bde810e7a
oai_identifier_str oai:ri.conicet.gov.ar:11336/103314
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling ESR characterization of thallium(III)-mediated nitrones oxidationVerstraeten, Sandra VivianaLucangioli, Silvia EdithGalleano, Mónica LilianaTHALLIUMNITRONESESRFORRESTER-HEPBURN MECHANISMhttps://purl.org/becyt/ford/1.6https://purl.org/becyt/ford/1We characterized the reactions between Tl (III) and the usual nitrone spin traps (DMPO, POBN, and PBN). The ESR signal obtained with DMPO corresponded to DMPOX which was avoided neither by the enzymes superoxide dismutase or catalase, nor by the hydroxyl radical scavengers´ mannitol, ethanol, or methanol. Only when methanol concentration rose to 90% (v/v), a significant decrease in DMPOX formation was observed while no detectable DMPOX signal was present at 100% methanol solution. POBN rendered an unexpected adduct, while no oxidation products were obtained with PBN. Together, the experimental evidence demonstrates that Tl(III)-supported DMPO oxidation is not mediated by oxygen reactive species. Instead, we propose that Tl(III) interacts with the probe, favoring the addition of water. The intermediate is susceptible to be further oxidized by Tl(III) yielding a keto group. Kinetic studies showed that Tl(III) disappearance rate was higher (1.6 times) than DMPOX formation rate, and equal to Tl(I) formation rate, suggesting a stoichiometry 1.5:1 for Tl(III):DMPOX and 1:1 for Tl(III):Tl(I). The process, an example of the Forrester-Hepburn´s mechanism, was demonstrated for DMPO while the reactions of Tl(III) with POBN and PBN are still under elucidation.Fil: Verstraeten, Sandra Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas "Prof. Alejandro C. Paladini". Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Físico-Química Biológicas; ArgentinaFil: Lucangioli, Silvia Edith. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Tecnología Farmacéutica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Galleano, Mónica Liliana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Programa de Radicales Libres; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Bioquímica y Medicina Molecular. Universidad de Buenos Aires. Facultad Medicina. Instituto de Bioquímica y Medicina Molecular; ArgentinaElsevier Science Sa2009-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/103314Verstraeten, Sandra Viviana; Lucangioli, Silvia Edith; Galleano, Mónica Liliana; ESR characterization of thallium(III)-mediated nitrones oxidation; Elsevier Science Sa; Inorganica Chimica Acta; 362; 7; 5-2009; 2305-23100020-1693CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0020169308006385info:eu-repo/semantics/altIdentifier/doi/10.1016/j.ica.2008.10.013info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:46:50Zoai:ri.conicet.gov.ar:11336/103314instacron: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 09:46:50.955CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv ESR characterization of thallium(III)-mediated nitrones oxidation
title ESR characterization of thallium(III)-mediated nitrones oxidation
spellingShingle ESR characterization of thallium(III)-mediated nitrones oxidation
Verstraeten, Sandra Viviana
THALLIUM
NITRONES
ESR
FORRESTER-HEPBURN MECHANISM
title_short ESR characterization of thallium(III)-mediated nitrones oxidation
title_full ESR characterization of thallium(III)-mediated nitrones oxidation
title_fullStr ESR characterization of thallium(III)-mediated nitrones oxidation
title_full_unstemmed ESR characterization of thallium(III)-mediated nitrones oxidation
title_sort ESR characterization of thallium(III)-mediated nitrones oxidation
dc.creator.none.fl_str_mv Verstraeten, Sandra Viviana
Lucangioli, Silvia Edith
Galleano, Mónica Liliana
author Verstraeten, Sandra Viviana
author_facet Verstraeten, Sandra Viviana
Lucangioli, Silvia Edith
Galleano, Mónica Liliana
author_role author
author2 Lucangioli, Silvia Edith
Galleano, Mónica Liliana
author2_role author
author
dc.subject.none.fl_str_mv THALLIUM
NITRONES
ESR
FORRESTER-HEPBURN MECHANISM
topic THALLIUM
NITRONES
ESR
FORRESTER-HEPBURN MECHANISM
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.6
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv We characterized the reactions between Tl (III) and the usual nitrone spin traps (DMPO, POBN, and PBN). The ESR signal obtained with DMPO corresponded to DMPOX which was avoided neither by the enzymes superoxide dismutase or catalase, nor by the hydroxyl radical scavengers´ mannitol, ethanol, or methanol. Only when methanol concentration rose to 90% (v/v), a significant decrease in DMPOX formation was observed while no detectable DMPOX signal was present at 100% methanol solution. POBN rendered an unexpected adduct, while no oxidation products were obtained with PBN. Together, the experimental evidence demonstrates that Tl(III)-supported DMPO oxidation is not mediated by oxygen reactive species. Instead, we propose that Tl(III) interacts with the probe, favoring the addition of water. The intermediate is susceptible to be further oxidized by Tl(III) yielding a keto group. Kinetic studies showed that Tl(III) disappearance rate was higher (1.6 times) than DMPOX formation rate, and equal to Tl(I) formation rate, suggesting a stoichiometry 1.5:1 for Tl(III):DMPOX and 1:1 for Tl(III):Tl(I). The process, an example of the Forrester-Hepburn´s mechanism, was demonstrated for DMPO while the reactions of Tl(III) with POBN and PBN are still under elucidation.
Fil: Verstraeten, Sandra Viviana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Química y Físico-Química Biológicas "Prof. Alejandro C. Paladini". Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Instituto de Química y Físico-Química Biológicas; Argentina
Fil: Lucangioli, Silvia Edith. Universidad de Buenos Aires. Facultad de Farmacia y Bioquímica. Departamento de Tecnología Farmacéutica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Galleano, Mónica Liliana. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Programa de Radicales Libres; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Bioquímica y Medicina Molecular. Universidad de Buenos Aires. Facultad Medicina. Instituto de Bioquímica y Medicina Molecular; Argentina
description We characterized the reactions between Tl (III) and the usual nitrone spin traps (DMPO, POBN, and PBN). The ESR signal obtained with DMPO corresponded to DMPOX which was avoided neither by the enzymes superoxide dismutase or catalase, nor by the hydroxyl radical scavengers´ mannitol, ethanol, or methanol. Only when methanol concentration rose to 90% (v/v), a significant decrease in DMPOX formation was observed while no detectable DMPOX signal was present at 100% methanol solution. POBN rendered an unexpected adduct, while no oxidation products were obtained with PBN. Together, the experimental evidence demonstrates that Tl(III)-supported DMPO oxidation is not mediated by oxygen reactive species. Instead, we propose that Tl(III) interacts with the probe, favoring the addition of water. The intermediate is susceptible to be further oxidized by Tl(III) yielding a keto group. Kinetic studies showed that Tl(III) disappearance rate was higher (1.6 times) than DMPOX formation rate, and equal to Tl(I) formation rate, suggesting a stoichiometry 1.5:1 for Tl(III):DMPOX and 1:1 for Tl(III):Tl(I). The process, an example of the Forrester-Hepburn´s mechanism, was demonstrated for DMPO while the reactions of Tl(III) with POBN and PBN are still under elucidation.
publishDate 2009
dc.date.none.fl_str_mv 2009-05
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/11336/103314
Verstraeten, Sandra Viviana; Lucangioli, Silvia Edith; Galleano, Mónica Liliana; ESR characterization of thallium(III)-mediated nitrones oxidation; Elsevier Science Sa; Inorganica Chimica Acta; 362; 7; 5-2009; 2305-2310
0020-1693
CONICET Digital
CONICET
url http://hdl.handle.net/11336/103314
identifier_str_mv Verstraeten, Sandra Viviana; Lucangioli, Silvia Edith; Galleano, Mónica Liliana; ESR characterization of thallium(III)-mediated nitrones oxidation; Elsevier Science Sa; Inorganica Chimica Acta; 362; 7; 5-2009; 2305-2310
0020-1693
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0020169308006385
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.ica.2008.10.013
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
dc.publisher.none.fl_str_mv Elsevier Science Sa
publisher.none.fl_str_mv Elsevier Science Sa
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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