Stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces

Nitroxyl (HNO/NO-) is a small short-lived molecule that has been suggested to be produced by nitric oxide (NO) synthases under certain conditions. As for NO, biologically relevant targets of HNO are mainly heme-proteins and therefore, it has been difficult to discriminate the physio-pathological rol...

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Autores principales: Doctorovich, F., Bikiel, D., Pellegrino, J., Suárez, S.A., Martí, M.A.
Formato: JOUR
Materias:
Angeli's salt
Co
electrochemistry
heme
HNO
metalloporphyrins
Mn
nitrosyl complex
nitroxyl
NO
Piloty's acid
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_10884246_v14_n12_p1012_Doctorovich
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_10884246_v14_n12_p1012_Doctorovich2023-10-03T16:04:23Z Stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces Doctorovich, F. Bikiel, D. Pellegrino, J. Suárez, S.A. Martí, M.A. Angeli's salt Co electrochemistry heme HNO metalloporphyrins Mn nitrosyl complex nitroxyl NO Piloty's acid Nitroxyl (HNO/NO-) is a small short-lived molecule that has been suggested to be produced by nitric oxide (NO) synthases under certain conditions. As for NO, biologically relevant targets of HNO are mainly heme-proteins and therefore, it has been difficult to discriminate the physio-pathological role of each molecule conclusively. Therefore, accurate discrimination between them is still an unresolved matter. On the other hand, there is only scarce information about nitroxyl-metalloporphyrin complexes. Hence, there is growing interest in obtaining and characterizing stable heme model nitroxyl complexes. In this review we show how HNO and NO can be discriminated electrochemically by a Co porphyrin attached to a gold surface, and how nitroxyl can be stabilized by coordination to an electron-poor Fe porphyrin. The Co porphyrin with four anchors, cobalt(II)-5,10,15,20-tetrakis[3- (p-acetylthio-propoxy)phenyl]porphyrin [Co(P)] was covalently attached to gold electrodes, and its reactions with NO and HNO donors were studied electrochemically. By fixing the potential to values that oxidize Co III(P)NO-, HNO can be selectively detected by amperometric techniques. On the other hand, the one-electron chemical reduction of Fe II(TFPPBr8)NO (TFPPBr8 = 2,3,7,8,12,13,17,18- octa-β-bromo-5,10,15,20-[tetrakis-(pentafluorophenyl)]porphyrin) with cobaltocene yields the significantly stable {FeNO}8 nitroxyl anion complex, [Co(C5H5)2]+[Fe(TFPPBr 8)NO]-, which was isolated and characterized by several spectroscopies and DFT calculations. This species is intermediate between FeIINO- and FeINO, which is contrasted with the predominant FeIINO- character of known non-heme {FeNO}8 complexes. © 2010 World Scientific Publishing Company. Fil:Doctorovich, F. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Bikiel, D. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Pellegrino, J. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:Suárez, S.A. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_10884246_v14_n12_p1012_Doctorovich
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic Angeli's salt
Co
electrochemistry
heme
HNO
metalloporphyrins
Mn
nitrosyl complex
nitroxyl
NO
Piloty's acid
spellingShingle Angeli's salt
Co
electrochemistry
heme
HNO
metalloporphyrins
Mn
nitrosyl complex
nitroxyl
NO
Piloty's acid
Doctorovich, F.
Bikiel, D.
Pellegrino, J.
Suárez, S.A.
Martí, M.A.
Stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces
topic_facet Angeli's salt
Co
electrochemistry
heme
HNO
metalloporphyrins
Mn
nitrosyl complex
nitroxyl
NO
Piloty's acid
description Nitroxyl (HNO/NO-) is a small short-lived molecule that has been suggested to be produced by nitric oxide (NO) synthases under certain conditions. As for NO, biologically relevant targets of HNO are mainly heme-proteins and therefore, it has been difficult to discriminate the physio-pathological role of each molecule conclusively. Therefore, accurate discrimination between them is still an unresolved matter. On the other hand, there is only scarce information about nitroxyl-metalloporphyrin complexes. Hence, there is growing interest in obtaining and characterizing stable heme model nitroxyl complexes. In this review we show how HNO and NO can be discriminated electrochemically by a Co porphyrin attached to a gold surface, and how nitroxyl can be stabilized by coordination to an electron-poor Fe porphyrin. The Co porphyrin with four anchors, cobalt(II)-5,10,15,20-tetrakis[3- (p-acetylthio-propoxy)phenyl]porphyrin [Co(P)] was covalently attached to gold electrodes, and its reactions with NO and HNO donors were studied electrochemically. By fixing the potential to values that oxidize Co III(P)NO-, HNO can be selectively detected by amperometric techniques. On the other hand, the one-electron chemical reduction of Fe II(TFPPBr8)NO (TFPPBr8 = 2,3,7,8,12,13,17,18- octa-β-bromo-5,10,15,20-[tetrakis-(pentafluorophenyl)]porphyrin) with cobaltocene yields the significantly stable {FeNO}8 nitroxyl anion complex, [Co(C5H5)2]+[Fe(TFPPBr 8)NO]-, which was isolated and characterized by several spectroscopies and DFT calculations. This species is intermediate between FeIINO- and FeINO, which is contrasted with the predominant FeIINO- character of known non-heme {FeNO}8 complexes. © 2010 World Scientific Publishing Company.
format JOUR
author Doctorovich, F.
Bikiel, D.
Pellegrino, J.
Suárez, S.A.
Martí, M.A.
author_facet Doctorovich, F.
Bikiel, D.
Pellegrino, J.
Suárez, S.A.
Martí, M.A.
author_sort Doctorovich, F.
title Stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces
title_short Stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces
title_full Stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces
title_fullStr Stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces
title_full_unstemmed Stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces
title_sort stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces
url http://hdl.handle.net/20.500.12110/paper_10884246_v14_n12_p1012_Doctorovich
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