The HNO donor ability of hydroxamic acids upon oxidation with cyanoferrates(III)

The hydroxamic acids (RC(O)NHOH, HA) exhibit diverse biological activity, including hypotensive properties associated with formation of nitroxyl (HNO) or nitric oxide (NO). Oxidation of two HAs, benzohydroxamic and acetohydroxamic acids (BHA, AHA) by [Fe(CN)5NH3]2- or [Fe(CN)6]3- was analyzed by spe...

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Autores principales: Bari, Sara Elizabeth, Olabe Iparraguirre, Jose Antonio
Publicado: 2015
Materias:
Acylnitroso species
Hydroxamic acids
Nitroxyl
Nitroxyl donor
Pentacyano(L)ferrate(III) oxidants
Acceso en línea:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00958972_v68_n17-18_p3236_Gutierrez
http://hdl.handle.net/20.500.12110/paper_00958972_v68_n17-18_p3236_Gutierrez
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling paper:paper_00958972_v68_n17-18_p3236_Gutierrez2023-06-08T15:09:42Z The HNO donor ability of hydroxamic acids upon oxidation with cyanoferrates(III) Bari, Sara Elizabeth Olabe Iparraguirre, Jose Antonio Acylnitroso species Hydroxamic acids Nitroxyl Nitroxyl donor Pentacyano(L)ferrate(III) oxidants The hydroxamic acids (RC(O)NHOH, HA) exhibit diverse biological activity, including hypotensive properties associated with formation of nitroxyl (HNO) or nitric oxide (NO). Oxidation of two HAs, benzohydroxamic and acetohydroxamic acids (BHA, AHA) by [Fe(CN)5NH3]2- or [Fe(CN)6]3- was analyzed by spectroscopic, mass spectrometric techniques, and flow EPR measurements. Mixing BHA with both Fe(III) reactants at pH 11 allowed detecting the hydroxamate radical, (C6H5)C(O)NO-, as a one-electron oxidation product, as well as N2O as a final product. Successive UV-vis spectra of mixtures containing [Fe(CN)5NH3]2- (though not [Fe(CN)6]3-) at pH 11 and 7 revealed an intermediate acylnitroso-complex, [Fe(CN)5NOC(O)(C6H5)]3- (max, 465 nm, very stable at pH 7), formed through ligand interchange in the initially formed reduction product, [Fe(CN)5NH3]3-, and characterized by FTIR spectra through the stretching vibrations (CN), (CO), and (NO). Free acylnitroso derivatives, formed by alternative reaction paths of the hydroxamate radicals, hydrolyze forming RC(O)OH and HNO, postulated as precursor of N2O. Minor quantities of NO are formed only with an excess of oxidant. The intermediacy of HNO was confirmed through its identification as [Fe(CN)5(HNO)]3- (max, 445 nm) as a result of hydrolysis of [Fe(CN)5(NOC(O)(C6H5)]3- at pH 11. The results demonstrate that hydroxamic acids behave predominantly as HNO donors. © 2015 Taylor and Francis. Fil:Bari, S.E. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Olabe, J.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2015 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00958972_v68_n17-18_p3236_Gutierrez http://hdl.handle.net/20.500.12110/paper_00958972_v68_n17-18_p3236_Gutierrez
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Acylnitroso species
Hydroxamic acids
Nitroxyl
Nitroxyl donor
Pentacyano(L)ferrate(III) oxidants
spellingShingle Acylnitroso species
Hydroxamic acids
Nitroxyl
Nitroxyl donor
Pentacyano(L)ferrate(III) oxidants
Bari, Sara Elizabeth
Olabe Iparraguirre, Jose Antonio
The HNO donor ability of hydroxamic acids upon oxidation with cyanoferrates(III)
topic_facet Acylnitroso species
Hydroxamic acids
Nitroxyl
Nitroxyl donor
Pentacyano(L)ferrate(III) oxidants
description The hydroxamic acids (RC(O)NHOH, HA) exhibit diverse biological activity, including hypotensive properties associated with formation of nitroxyl (HNO) or nitric oxide (NO). Oxidation of two HAs, benzohydroxamic and acetohydroxamic acids (BHA, AHA) by [Fe(CN)5NH3]2- or [Fe(CN)6]3- was analyzed by spectroscopic, mass spectrometric techniques, and flow EPR measurements. Mixing BHA with both Fe(III) reactants at pH 11 allowed detecting the hydroxamate radical, (C6H5)C(O)NO-, as a one-electron oxidation product, as well as N2O as a final product. Successive UV-vis spectra of mixtures containing [Fe(CN)5NH3]2- (though not [Fe(CN)6]3-) at pH 11 and 7 revealed an intermediate acylnitroso-complex, [Fe(CN)5NOC(O)(C6H5)]3- (max, 465 nm, very stable at pH 7), formed through ligand interchange in the initially formed reduction product, [Fe(CN)5NH3]3-, and characterized by FTIR spectra through the stretching vibrations (CN), (CO), and (NO). Free acylnitroso derivatives, formed by alternative reaction paths of the hydroxamate radicals, hydrolyze forming RC(O)OH and HNO, postulated as precursor of N2O. Minor quantities of NO are formed only with an excess of oxidant. The intermediacy of HNO was confirmed through its identification as [Fe(CN)5(HNO)]3- (max, 445 nm) as a result of hydrolysis of [Fe(CN)5(NOC(O)(C6H5)]3- at pH 11. The results demonstrate that hydroxamic acids behave predominantly as HNO donors. © 2015 Taylor and Francis.
author Bari, Sara Elizabeth
Olabe Iparraguirre, Jose Antonio
author_facet Bari, Sara Elizabeth
Olabe Iparraguirre, Jose Antonio
author_sort Bari, Sara Elizabeth
title The HNO donor ability of hydroxamic acids upon oxidation with cyanoferrates(III)
title_short The HNO donor ability of hydroxamic acids upon oxidation with cyanoferrates(III)
title_full The HNO donor ability of hydroxamic acids upon oxidation with cyanoferrates(III)
title_fullStr The HNO donor ability of hydroxamic acids upon oxidation with cyanoferrates(III)
title_full_unstemmed The HNO donor ability of hydroxamic acids upon oxidation with cyanoferrates(III)
title_sort hno donor ability of hydroxamic acids upon oxidation with cyanoferrates(iii)
publishDate 2015
url https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00958972_v68_n17-18_p3236_Gutierrez
http://hdl.handle.net/20.500.12110/paper_00958972_v68_n17-18_p3236_Gutierrez
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AT barisaraelizabeth hnodonorabilityofhydroxamicacidsuponoxidationwithcyanoferratesiii
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