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

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...

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Autores principales:	Morzan, Uriel Nicolas, Estrin, Dario Ariel
Publicado:	2015
Materias:	Free radicals Hydrogen sulfide Kinetics Peroxynitrite Persulfides carbon dioxide hydrogen sulfide peroxynitrite sodium dihydrogen phosphate thiol derivative buffer peroxynitrous acid persulfides sulfide Article chemical reaction chemical reaction kinetics mass spectrometry priority journal reaction analysis ultraviolet spectroscopy chemical model chemistry kinetics pH thermodynamics Buffers Hydrogen Sulfide Hydrogen-Ion Concentration Models, Chemical Peroxynitrous Acid Sulfides Thermodynamics
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08915849_v80_n_p93_Cuevasanta http://hdl.handle.net/20.500.12110/paper_08915849_v80_n_p93_Cuevasanta
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_08915849_v80_n_p93_Cuevasanta
record_format	dspace
spelling	paper:paper_08915849_v80_n_p93_Cuevasanta2023-06-08T15:47:13Z Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite Morzan, Uriel Nicolas Estrin, Dario Ariel Free radicals Hydrogen sulfide Kinetics Peroxynitrite Persulfides carbon dioxide hydrogen sulfide peroxynitrite sodium dihydrogen phosphate thiol derivative buffer hydrogen sulfide peroxynitrous acid persulfides sulfide Article chemical reaction chemical reaction kinetics mass spectrometry priority journal reaction analysis ultraviolet spectroscopy chemical model chemistry kinetics pH thermodynamics Buffers Hydrogen Sulfide Hydrogen-Ion Concentration Kinetics Models, Chemical Peroxynitrous Acid Sulfides Thermodynamics 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. © 2014 Elsevier Inc. All rights reserved. Fil:Morzan, U.N. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Estrin, D.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2015 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08915849_v80_n_p93_Cuevasanta http://hdl.handle.net/20.500.12110/paper_08915849_v80_n_p93_Cuevasanta
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	Free radicals Hydrogen sulfide Kinetics Peroxynitrite Persulfides carbon dioxide hydrogen sulfide peroxynitrite sodium dihydrogen phosphate thiol derivative buffer hydrogen sulfide peroxynitrous acid persulfides sulfide Article chemical reaction chemical reaction kinetics mass spectrometry priority journal reaction analysis ultraviolet spectroscopy chemical model chemistry kinetics pH thermodynamics Buffers Hydrogen Sulfide Hydrogen-Ion Concentration Kinetics Models, Chemical Peroxynitrous Acid Sulfides Thermodynamics
spellingShingle	Free radicals Hydrogen sulfide Kinetics Peroxynitrite Persulfides carbon dioxide hydrogen sulfide peroxynitrite sodium dihydrogen phosphate thiol derivative buffer hydrogen sulfide peroxynitrous acid persulfides sulfide Article chemical reaction chemical reaction kinetics mass spectrometry priority journal reaction analysis ultraviolet spectroscopy chemical model chemistry kinetics pH thermodynamics Buffers Hydrogen Sulfide Hydrogen-Ion Concentration Kinetics Models, Chemical Peroxynitrous Acid Sulfides Thermodynamics Morzan, Uriel Nicolas Estrin, Dario Ariel Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
topic_facet	Free radicals Hydrogen sulfide Kinetics Peroxynitrite Persulfides carbon dioxide hydrogen sulfide peroxynitrite sodium dihydrogen phosphate thiol derivative buffer hydrogen sulfide peroxynitrous acid persulfides sulfide Article chemical reaction chemical reaction kinetics mass spectrometry priority journal reaction analysis ultraviolet spectroscopy chemical model chemistry kinetics pH thermodynamics Buffers Hydrogen Sulfide Hydrogen-Ion Concentration Kinetics Models, Chemical Peroxynitrous Acid Sulfides Thermodynamics
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. © 2014 Elsevier Inc. All rights reserved.
author	Morzan, Uriel Nicolas Estrin, Dario Ariel
author_facet	Morzan, Uriel Nicolas Estrin, Dario Ariel
author_sort	Morzan, Uriel Nicolas
title	Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite
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
publishDate	2015
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_08915849_v80_n_p93_Cuevasanta http://hdl.handle.net/20.500.12110/paper_08915849_v80_n_p93_Cuevasanta
work_keys_str_mv	AT morzanurielnicolas insightsintothemechanismofthereactionbetweenhydrogensulfideandperoxynitrite AT estrindarioariel insightsintothemechanismofthereactionbetweenhydrogensulfideandperoxynitrite
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Insights into the mechanism of the reaction between hydrogen sulfide and peroxynitrite

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