Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps

Azanone (1HNO, nitroxyl) is a highly reactive molecule with interesting chemical and biological properties. Like nitric oxide (NO), its main biologically related targets are oxygen, thiols, and metalloproteins, particularly heme proteins. As HNO dimerizes with a rate constant between 106 and 107 M-1...

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Autores principales:	Suarez, Sebastian, Bikiel, Damian Ezequiel, Martí, Marcelo Adrián, Doctorovich, Fabio Ariel
Publicado:	2014
Materias:	iron manganese nitrogen oxide nitroxyl porphyrin chemistry kinetics oxidation reduction reaction Iron Kinetics Manganese Nitrogen Oxides Oxidation-Reduction Porphyrins
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v53_n14_p7351_Alvarez http://hdl.handle.net/20.500.12110/paper_00201669_v53_n14_p7351_Alvarez
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_00201669_v53_n14_p7351_Alvarez
record_format	dspace
spelling	paper:paper_00201669_v53_n14_p7351_Alvarez2023-06-08T14:40:42Z Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps Suarez, Sebastian Bikiel, Damian Ezequiel Martí, Marcelo Adrián Doctorovich, Fabio Ariel iron manganese nitrogen oxide nitroxyl porphyrin chemistry kinetics oxidation reduction reaction Iron Kinetics Manganese Nitrogen Oxides Oxidation-Reduction Porphyrins Azanone (1HNO, nitroxyl) is a highly reactive molecule with interesting chemical and biological properties. Like nitric oxide (NO), its main biologically related targets are oxygen, thiols, and metalloproteins, particularly heme proteins. As HNO dimerizes with a rate constant between 106 and 107 M-1 s-1, reactive studies are performed using donors, which are compounds that spontaneously release HNO in solution. In the present work, we studied the reaction mechanism and kinetics of two azanone donors Angelís Salt and toluene sulfohydroxamic acid (TSHA) with eight different Mn porphyrins as trapping agents. These porphyrins differ in their total peripheral charge (positively or negatively charged) and in their MnIII/MnII reduction potential, showing for each case positive (oxidizing) and negative (reducing) values. Our results show that the reduction potential determines the azanone donor reaction mechanism. While oxidizing porphyrins accelerate decomposition of the donor, reducing porphyrins react with free HNO. Our results also shed light into the donor decomposition mechanism using ab initio methods and provide a thorough analysis of which MnP are the best candidates for azanone trapping and quantification experiments. © 2014 American Chemical Society. Fil:Suarez, S.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Bikiel, D.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Martí, M.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Doctorovich, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2014 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v53_n14_p7351_Alvarez http://hdl.handle.net/20.500.12110/paper_00201669_v53_n14_p7351_Alvarez
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	iron manganese nitrogen oxide nitroxyl porphyrin chemistry kinetics oxidation reduction reaction Iron Kinetics Manganese Nitrogen Oxides Oxidation-Reduction Porphyrins
spellingShingle	iron manganese nitrogen oxide nitroxyl porphyrin chemistry kinetics oxidation reduction reaction Iron Kinetics Manganese Nitrogen Oxides Oxidation-Reduction Porphyrins Suarez, Sebastian Bikiel, Damian Ezequiel Martí, Marcelo Adrián Doctorovich, Fabio Ariel Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps
topic_facet	iron manganese nitrogen oxide nitroxyl porphyrin chemistry kinetics oxidation reduction reaction Iron Kinetics Manganese Nitrogen Oxides Oxidation-Reduction Porphyrins
description	Azanone (1HNO, nitroxyl) is a highly reactive molecule with interesting chemical and biological properties. Like nitric oxide (NO), its main biologically related targets are oxygen, thiols, and metalloproteins, particularly heme proteins. As HNO dimerizes with a rate constant between 106 and 107 M-1 s-1, reactive studies are performed using donors, which are compounds that spontaneously release HNO in solution. In the present work, we studied the reaction mechanism and kinetics of two azanone donors Angelís Salt and toluene sulfohydroxamic acid (TSHA) with eight different Mn porphyrins as trapping agents. These porphyrins differ in their total peripheral charge (positively or negatively charged) and in their MnIII/MnII reduction potential, showing for each case positive (oxidizing) and negative (reducing) values. Our results show that the reduction potential determines the azanone donor reaction mechanism. While oxidizing porphyrins accelerate decomposition of the donor, reducing porphyrins react with free HNO. Our results also shed light into the donor decomposition mechanism using ab initio methods and provide a thorough analysis of which MnP are the best candidates for azanone trapping and quantification experiments. © 2014 American Chemical Society.
author	Suarez, Sebastian Bikiel, Damian Ezequiel Martí, Marcelo Adrián Doctorovich, Fabio Ariel
author_facet	Suarez, Sebastian Bikiel, Damian Ezequiel Martí, Marcelo Adrián Doctorovich, Fabio Ariel
author_sort	Suarez, Sebastian
title	Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps
title_short	Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps
title_full	Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps
title_fullStr	Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps
title_full_unstemmed	Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps
title_sort	redox potential determines the reaction mechanism of hno donors with mn and fe porphyrins: defining the better traps
publishDate	2014
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v53_n14_p7351_Alvarez http://hdl.handle.net/20.500.12110/paper_00201669_v53_n14_p7351_Alvarez
work_keys_str_mv	AT suarezsebastian redoxpotentialdeterminesthereactionmechanismofhnodonorswithmnandfeporphyrinsdefiningthebettertraps AT bikieldamianezequiel redoxpotentialdeterminesthereactionmechanismofhnodonorswithmnandfeporphyrinsdefiningthebettertraps AT martimarceloadrian redoxpotentialdeterminesthereactionmechanismofhnodonorswithmnandfeporphyrinsdefiningthebettertraps AT doctorovichfabioariel redoxpotentialdeterminesthereactionmechanismofhnodonorswithmnandfeporphyrinsdefiningthebettertraps
_version_	1768543735343218688

Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps

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