Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite

Autores
Cuevasanta, Ernesto; Zeida Camacho, Ari Fernando; Carballal, Sebastián; Wedmann, Rudolf; Morzan, Uriel N.; Trujillo, Madia; Radi, Rafael; Estrin, Dario Ariel; Filipovic, Milos R.; Alvarez, Beatriz
Año de publicación
2015
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Hydrogen sulfide and peroxynitrite are endogenously generated molecules that participate in biologically relevant pathways. A revision of the kinetic features of the reaction between peroxynitrite and hydrogen sulfide revealed a complex process. The rate constant of peroxynitrite decay, (6.65 ± 0.08) × 103 M-1 s-1 in 0.05 M sodium phosphate buffer (pH 7.4, 37 °C), was affected by the concentration of buffer. Theoretical modeling suggested that, as in the case of thiols, the reaction is initiated by the nucleophilic attack of HS- on the peroxide group of ONOOH by a typical bimolecular nucleophilic substitution, yielding HSOH and NO2 -. In contrast to thiols, the reaction then proceeds to the formation of distinct products that absorb near 408 nm. Experiments in the presence of scavengers and carbon dioxide showed that free radicals are unlikely to be involved in the formation of these products. The results are consistent with product formation involving the reactive intermediate HSSH and its fast reaction with a second peroxynitrite molecule. Mass spectrometry and UV-Vis absorption spectra predictions suggest that at least one of the products is HSNO2 or its isomer HSONO.
Fil: Cuevasanta, Ernesto. Universidad de la República; Uruguay
Fil: Zeida Camacho, Ari Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Carballal, Sebastián. Universidad de la República; Uruguay
Fil: Wedmann, Rudolf. Universitat Erlangen-Nuremberg; Alemania
Fil: Morzan, Uriel N.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Trujillo, Madia. Universidad de la República; Uruguay
Fil: Radi, Rafael. Universidad de la República; Uruguay
Fil: Estrin, Dario Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Filipovic, Milos R.. Universitat Erlangen-Nuremberg; Alemania
Fil: Alvarez, Beatriz. Universidad de la República; Uruguay
Materia
Hydrogen Sulfide
Peroxynitrite
Kinetics
Oxidation
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:11336/38044
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/38044
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitriteCuevasanta, ErnestoZeida Camacho, Ari FernandoCarballal, SebastiánWedmann, RudolfMorzan, Uriel N.Trujillo, MadiaRadi, RafaelEstrin, Dario ArielFilipovic, Milos R.Alvarez, BeatrizHydrogen SulfidePeroxynitriteKineticsOxidationhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1https://purl.org/becyt/ford/1.6https://purl.org/becyt/ford/1Hydrogen sulfide and peroxynitrite are endogenously generated molecules that participate in biologically relevant pathways. A revision of the kinetic features of the reaction between peroxynitrite and hydrogen sulfide revealed a complex process. The rate constant of peroxynitrite decay, (6.65 ± 0.08) × 103 M-1 s-1 in 0.05 M sodium phosphate buffer (pH 7.4, 37 °C), was affected by the concentration of buffer. Theoretical modeling suggested that, as in the case of thiols, the reaction is initiated by the nucleophilic attack of HS- on the peroxide group of ONOOH by a typical bimolecular nucleophilic substitution, yielding HSOH and NO2 -. In contrast to thiols, the reaction then proceeds to the formation of distinct products that absorb near 408 nm. Experiments in the presence of scavengers and carbon dioxide showed that free radicals are unlikely to be involved in the formation of these products. The results are consistent with product formation involving the reactive intermediate HSSH and its fast reaction with a second peroxynitrite molecule. Mass spectrometry and UV-Vis absorption spectra predictions suggest that at least one of the products is HSNO2 or its isomer HSONO.Fil: Cuevasanta, Ernesto. Universidad de la República; UruguayFil: Zeida Camacho, Ari Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Carballal, Sebastián. Universidad de la República; UruguayFil: Wedmann, Rudolf. Universitat Erlangen-Nuremberg; AlemaniaFil: Morzan, Uriel N.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Trujillo, Madia. Universidad de la República; UruguayFil: Radi, Rafael. Universidad de la República; UruguayFil: Estrin, Dario Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Filipovic, Milos R.. Universitat Erlangen-Nuremberg; AlemaniaFil: Alvarez, Beatriz. Universidad de la República; UruguayElsevier Science Inc2015-01info: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/11336/38044Cuevasanta, Ernesto; Zeida Camacho, Ari Fernando; Carballal, Sebastián; Wedmann, Rudolf; Morzan, Uriel N.; et al.; Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite; Elsevier Science Inc; Free Radical Biology and Medicine; 80; 1-2015; 93-1000891-5849CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.freeradbiomed.2014.12.017info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T15:31:51Zoai:ri.conicet.gov.ar:11336/38044instacron: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 15:31:51.368CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
title Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
spellingShingle Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
Cuevasanta, Ernesto
Hydrogen Sulfide
Peroxynitrite
Kinetics
Oxidation
title_short Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
title_full Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
title_fullStr Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
title_full_unstemmed Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
title_sort Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
dc.creator.none.fl_str_mv Cuevasanta, Ernesto
Zeida Camacho, Ari Fernando
Carballal, Sebastián
Wedmann, Rudolf
Morzan, Uriel N.
Trujillo, Madia
Radi, Rafael
Estrin, Dario Ariel
Filipovic, Milos R.
Alvarez, Beatriz
author Cuevasanta, Ernesto
author_facet Cuevasanta, Ernesto
Zeida Camacho, Ari Fernando
Carballal, Sebastián
Wedmann, Rudolf
Morzan, Uriel N.
Trujillo, Madia
Radi, Rafael
Estrin, Dario Ariel
Filipovic, Milos R.
Alvarez, Beatriz
author_role author
author2 Zeida Camacho, Ari Fernando
Carballal, Sebastián
Wedmann, Rudolf
Morzan, Uriel N.
Trujillo, Madia
Radi, Rafael
Estrin, Dario Ariel
Filipovic, Milos R.
Alvarez, Beatriz
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Hydrogen Sulfide
Peroxynitrite
Kinetics
Oxidation
topic Hydrogen Sulfide
Peroxynitrite
Kinetics
Oxidation
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
https://purl.org/becyt/ford/1.6
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Hydrogen sulfide and peroxynitrite are endogenously generated molecules that participate in biologically relevant pathways. A revision of the kinetic features of the reaction between peroxynitrite and hydrogen sulfide revealed a complex process. The rate constant of peroxynitrite decay, (6.65 ± 0.08) × 103 M-1 s-1 in 0.05 M sodium phosphate buffer (pH 7.4, 37 °C), was affected by the concentration of buffer. Theoretical modeling suggested that, as in the case of thiols, the reaction is initiated by the nucleophilic attack of HS- on the peroxide group of ONOOH by a typical bimolecular nucleophilic substitution, yielding HSOH and NO2 -. In contrast to thiols, the reaction then proceeds to the formation of distinct products that absorb near 408 nm. Experiments in the presence of scavengers and carbon dioxide showed that free radicals are unlikely to be involved in the formation of these products. The results are consistent with product formation involving the reactive intermediate HSSH and its fast reaction with a second peroxynitrite molecule. Mass spectrometry and UV-Vis absorption spectra predictions suggest that at least one of the products is HSNO2 or its isomer HSONO.
Fil: Cuevasanta, Ernesto. Universidad de la República; Uruguay
Fil: Zeida Camacho, Ari Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Carballal, Sebastián. Universidad de la República; Uruguay
Fil: Wedmann, Rudolf. Universitat Erlangen-Nuremberg; Alemania
Fil: Morzan, Uriel N.. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Trujillo, Madia. Universidad de la República; Uruguay
Fil: Radi, Rafael. Universidad de la República; Uruguay
Fil: Estrin, Dario Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Filipovic, Milos R.. Universitat Erlangen-Nuremberg; Alemania
Fil: Alvarez, Beatriz. Universidad de la República; Uruguay
description Hydrogen sulfide and peroxynitrite are endogenously generated molecules that participate in biologically relevant pathways. A revision of the kinetic features of the reaction between peroxynitrite and hydrogen sulfide revealed a complex process. The rate constant of peroxynitrite decay, (6.65 ± 0.08) × 103 M-1 s-1 in 0.05 M sodium phosphate buffer (pH 7.4, 37 °C), was affected by the concentration of buffer. Theoretical modeling suggested that, as in the case of thiols, the reaction is initiated by the nucleophilic attack of HS- on the peroxide group of ONOOH by a typical bimolecular nucleophilic substitution, yielding HSOH and NO2 -. In contrast to thiols, the reaction then proceeds to the formation of distinct products that absorb near 408 nm. Experiments in the presence of scavengers and carbon dioxide showed that free radicals are unlikely to be involved in the formation of these products. The results are consistent with product formation involving the reactive intermediate HSSH and its fast reaction with a second peroxynitrite molecule. Mass spectrometry and UV-Vis absorption spectra predictions suggest that at least one of the products is HSNO2 or its isomer HSONO.
publishDate 2015
dc.date.none.fl_str_mv 2015-01
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/11336/38044
Cuevasanta, Ernesto; Zeida Camacho, Ari Fernando; Carballal, Sebastián; Wedmann, Rudolf; Morzan, Uriel N.; et al.; Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite; Elsevier Science Inc; Free Radical Biology and Medicine; 80; 1-2015; 93-100
0891-5849
CONICET Digital
CONICET
url http://hdl.handle.net/11336/38044
identifier_str_mv Cuevasanta, Ernesto; Zeida Camacho, Ari Fernando; Carballal, Sebastián; Wedmann, Rudolf; Morzan, Uriel N.; et al.; Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite; Elsevier Science Inc; Free Radical Biology and Medicine; 80; 1-2015; 93-100
0891-5849
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.freeradbiomed.2014.12.017
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 Elsevier Science Inc
publisher.none.fl_str_mv Elsevier Science 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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score 13.22299

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