Nitrite reduction mediated by heme models. Routes to NO and HNO?
The water-soluble ferriheme model Fe III (TPPS) mediates oxygen atom transfer from inorganic nitrite to a water-soluble phosphine (tppts), dimethyl sulfide, and the biological thiols cysteine (CysSH) and glutathione (GSH). The products with the latter reductant are the respective sulfenic acids CysS...
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2013
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Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v135_n10_p4007_Heinecke http://hdl.handle.net/20.500.12110/paper_00027863_v135_n10_p4007_Heinecke |
Aporte de: |
id |
paper:paper_00027863_v135_n10_p4007_Heinecke |
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record_format |
dspace |
institution |
Universidad de Buenos Aires |
institution_str |
I-28 |
repository_str |
R-134 |
collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
topic |
Biological thiols Dimethyl sulfide Ischemia/reperfusion Nitrite reduction Oxygen atom transfer Potential mechanism Reactive intermediate Redox transformations Amino acids Iron compounds Linear transformations Phosphorus compounds Reduction cysteine dimethyl sulfide glutathione hematin heme nitric acid nitric oxide nitrite oxygen phosphine sulfenic acid derivative thiol aqueous solution article electrochemistry ischemia nitrosylation oxidation reduction reaction reperfusion injury Hemeproteins Nitric Oxide Nitrites Nitrogen Oxides Oxidation-Reduction |
spellingShingle |
Biological thiols Dimethyl sulfide Ischemia/reperfusion Nitrite reduction Oxygen atom transfer Potential mechanism Reactive intermediate Redox transformations Amino acids Iron compounds Linear transformations Phosphorus compounds Reduction cysteine dimethyl sulfide glutathione hematin heme nitric acid nitric oxide nitrite oxygen phosphine sulfenic acid derivative thiol aqueous solution article electrochemistry ischemia nitrosylation oxidation reduction reaction reperfusion injury Hemeproteins Nitric Oxide Nitrites Nitrogen Oxides Oxidation-Reduction Suarez, Sebastian Doctorovich, Fabio Ariel Nitrite reduction mediated by heme models. Routes to NO and HNO? |
topic_facet |
Biological thiols Dimethyl sulfide Ischemia/reperfusion Nitrite reduction Oxygen atom transfer Potential mechanism Reactive intermediate Redox transformations Amino acids Iron compounds Linear transformations Phosphorus compounds Reduction cysteine dimethyl sulfide glutathione hematin heme nitric acid nitric oxide nitrite oxygen phosphine sulfenic acid derivative thiol aqueous solution article electrochemistry ischemia nitrosylation oxidation reduction reaction reperfusion injury Hemeproteins Nitric Oxide Nitrites Nitrogen Oxides Oxidation-Reduction |
description |
The water-soluble ferriheme model Fe III (TPPS) mediates oxygen atom transfer from inorganic nitrite to a water-soluble phosphine (tppts), dimethyl sulfide, and the biological thiols cysteine (CysSH) and glutathione (GSH). The products with the latter reductant are the respective sulfenic acids CysS(O)H and GS(O)H, although these reactive intermediates are rapidly trapped by reaction with excess thiol. The nitrosyl complex Fe II (TPPS)(NO) is the dominant iron species while excess substrate is present. However, in slightly acidic media (pH ≈ 6), the system does not terminate at this very stable ferrous nitrosyl. Instead, it displays a matrix of redox transformations linking spontaneous regeneration of Fe III (TPPS) to the formation of both N 2 O and NO. Electrochemical sensor and trapping experiments demonstrate that HNO (nitroxyl) is formed, at least when tppts is the reductant. HNO is the likely predecessor of the N 2 O. A key pathway to NO formation is nitrite reduction by Fe II (TPPS), and the kinetics of this iron-mediated transformation are described. Given that inorganic nitrite has protective roles during ischemia/reperfusion (I/R) injury to organs, attributed in part to NO formation, and that HNO may also reduce net damage from I/R, the present studies are relevant to potential mechanisms of such nitrite protection. © 2013 American Chemical Society. |
author |
Suarez, Sebastian Doctorovich, Fabio Ariel |
author_facet |
Suarez, Sebastian Doctorovich, Fabio Ariel |
author_sort |
Suarez, Sebastian |
title |
Nitrite reduction mediated by heme models. Routes to NO and HNO? |
title_short |
Nitrite reduction mediated by heme models. Routes to NO and HNO? |
title_full |
Nitrite reduction mediated by heme models. Routes to NO and HNO? |
title_fullStr |
Nitrite reduction mediated by heme models. Routes to NO and HNO? |
title_full_unstemmed |
Nitrite reduction mediated by heme models. Routes to NO and HNO? |
title_sort |
nitrite reduction mediated by heme models. routes to no and hno? |
publishDate |
2013 |
url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00027863_v135_n10_p4007_Heinecke http://hdl.handle.net/20.500.12110/paper_00027863_v135_n10_p4007_Heinecke |
work_keys_str_mv |
AT suarezsebastian nitritereductionmediatedbyhememodelsroutestonoandhno AT doctorovichfabioariel nitritereductionmediatedbyhememodelsroutestonoandhno |
bdutipo_str |
Repositorios |
_version_ |
1764820555506122755 |