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: Álvarez, L., Suarez, S.A., Bikiel, D.E., Reboucas, J.S., Batinić-Haberle, I., Martí, M.A., Doctorovich, F.
Formato: JOUR
Materias:
iron
manganese
nitrogen oxide
nitroxyl
porphyrin
chemistry
kinetics
oxidation reduction reaction
Iron
Kinetics
Manganese
Nitrogen Oxides
Oxidation-Reduction
Porphyrins
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00201669_v53_n14_p7351_Alvarez
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
id todo:paper_00201669_v53_n14_p7351_Alvarez
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spelling todo:paper_00201669_v53_n14_p7351_Alvarez2023-10-03T14:17:07Z Redox potential determines the reaction mechanism of HNO donors with Mn and Fe porphyrins: Defining the better traps Álvarez, L. Suarez, S.A. Bikiel, D.E. Reboucas, J.S. Batinić-Haberle, I. Martí, M.A. Doctorovich, F. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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
Álvarez, L.
Suarez, S.A.
Bikiel, D.E.
Reboucas, J.S.
Batinić-Haberle, I.
Martí, M.A.
Doctorovich, F.
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.
format JOUR
author Álvarez, L.
Suarez, S.A.
Bikiel, D.E.
Reboucas, J.S.
Batinić-Haberle, I.
Martí, M.A.
Doctorovich, F.
author_facet Álvarez, L.
Suarez, S.A.
Bikiel, D.E.
Reboucas, J.S.
Batinić-Haberle, I.
Martí, M.A.
Doctorovich, F.
author_sort Álvarez, L.
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
url http://hdl.handle.net/20.500.12110/paper_00201669_v53_n14_p7351_Alvarez
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