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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todo:paper_00958972_v68_n17-18_p3236_Gutierrez2023-10-03T14:56:41Z The HNO donor ability of hydroxamic acids upon oxidation with cyanoferrates(III) Gutiérrez, M.M. Almaraz, A.E. Bari, S.E. Olabe, J.A. Amorebieta, V.T. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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 Gutiérrez, M.M. Almaraz, A.E. Bari, S.E. Olabe, J.A. Amorebieta, V.T. 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. |
| format |
JOUR |
| author |
Gutiérrez, M.M. Almaraz, A.E. Bari, S.E. Olabe, J.A. Amorebieta, V.T. |
| author_facet |
Gutiérrez, M.M. Almaraz, A.E. Bari, S.E. Olabe, J.A. Amorebieta, V.T. |
| author_sort |
Gutiérrez, M.M. |
| 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) |
| url |
http://hdl.handle.net/20.500.12110/paper_00958972_v68_n17-18_p3236_Gutierrez |
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