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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2010
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10884246_v14_n12_p1012_Doctorovich http://hdl.handle.net/20.500.12110/paper_10884246_v14_n12_p1012_Doctorovich |
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paper:paper_10884246_v14_n12_p1012_Doctorovich2023-06-08T16:06:12Z Stabilization and detection of nitroxyl by iron and cobalt porphyrins in solution and on surfaces Doctorovich, Fabio Ariel Bikiel, Damian Ezequiel Pellegrino, Juan Suarez, Sebastian Martí, Marcelo Adrián 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. 2010 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10884246_v14_n12_p1012_Doctorovich 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, Fabio Ariel Bikiel, Damian Ezequiel Pellegrino, Juan Suarez, Sebastian Martí, Marcelo Adrián 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. |
| author |
Doctorovich, Fabio Ariel Bikiel, Damian Ezequiel Pellegrino, Juan Suarez, Sebastian Martí, Marcelo Adrián |
| author_facet |
Doctorovich, Fabio Ariel Bikiel, Damian Ezequiel Pellegrino, Juan Suarez, Sebastian Martí, Marcelo Adrián |
| author_sort |
Doctorovich, Fabio Ariel |
| 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 |
| publishDate |
2010 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10884246_v14_n12_p1012_Doctorovich http://hdl.handle.net/20.500.12110/paper_10884246_v14_n12_p1012_Doctorovich |
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