A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold
Nitroxyl (HNO) is a small short-lived molecule for which it has been suggested that it could be produced, under certain cofactors conditions, by nitric oxide (NO) synthases. Biologically relevant targets of HNO are heme proteins, thiols, molecular oxygen, NO, and HNO itself. Given the overlap of the...
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todo:paper_00201669_v49_n15_p6955_Suarez2023-10-03T14:17:02Z A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold Suárez, S.A. Fonticelli, M.H. Rubert, A.A. De La Llave, E. Scherlis, D. Salvarezza, R.C. Martí, M.A. Doctorovich, F. cobalt dichloromethane gold hydroxamic acid metalloporphyrin nitric oxide nitrogen oxide nitroxyl polyphosphate triphosphoric acid article chemical structure chemistry conformation electrochemistry electrode quantum theory scanning electron microscopy surface property X ray photoelectron spectroscopy Cobalt Electrochemistry Electrodes Gold Hydroxamic Acids Metalloporphyrins Methylene Chloride Microscopy, Electron, Scanning Models, Molecular Molecular Conformation Nitric Oxide Nitrogen Oxides Photoelectron Spectroscopy Polyphosphates Quantum Theory Surface Properties Nitroxyl (HNO) is a small short-lived molecule for which it has been suggested that it could be produced, under certain cofactors conditions, by nitric oxide (NO) synthases. Biologically relevant targets of HNO are heme proteins, thiols, molecular oxygen, NO, and HNO itself. Given the overlap of the targets and reactivity between NO and HNO, it is very difficult to discriminate their physiopathological role conclusively, and accurate discrimination between them still remains critical for interpretation of the ongoing research in this field. The high reactivity and stability of cobalt(II) porphyrins toward NO and the easy and efficient way of covalently joining porphyrins to electrodes through S-Au bonds prompted us to test cobalt(II) 5,10,15,20-tetrakis[3-(p- acetylthiopropoxy)phenyl]porphyrin [Co(P)], as a possible candidate for the electrochemical discrimination of both species. For this purpose, first, we studied the reaction between NO, NO donors, and commonly used HNO donors, with Co II(P) and Co III(P). Second, we covalently attached Co II(P) to gold electrodes and characterized its redox and structural properties by electrochemical techniques as well as scanning tunneling microscopy, X-ray photoelectron spectroscopy, and solid-state density functional theory calculations. Finally, we studied electrochemically the NO and HNO donor reactions with the electrode-bound Co(P). Our results show that Co(P) is positioned over the gold surface in a lying-down configuration, and a surface effect is observed that decreases the Co III(P) (but not Co III(P)NO -) redox potential by 0.4 V. Using this information and when the potential is fixed to values that oxidize Co III(P)NO - (0.8 V vs SCE), HNO can be detected by amperometric techniques. Under these conditions, Co(P) is able to discriminate between HNO and NO donors, reacting with the former in a fast, efficient, and selective manner with concomitant formation of the Co III(P)NO - complex, while it is inert or reacts very slowly with NO donors. © 2010 American Chemical Society. Fil:Suárez, S.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. Fil:De La Llave, E. 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. Fil:Doctorovich, F. 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_00201669_v49_n15_p6955_Suarez |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
cobalt dichloromethane gold hydroxamic acid metalloporphyrin nitric oxide nitrogen oxide nitroxyl polyphosphate triphosphoric acid article chemical structure chemistry conformation electrochemistry electrode quantum theory scanning electron microscopy surface property X ray photoelectron spectroscopy Cobalt Electrochemistry Electrodes Gold Hydroxamic Acids Metalloporphyrins Methylene Chloride Microscopy, Electron, Scanning Models, Molecular Molecular Conformation Nitric Oxide Nitrogen Oxides Photoelectron Spectroscopy Polyphosphates Quantum Theory Surface Properties |
| spellingShingle |
cobalt dichloromethane gold hydroxamic acid metalloporphyrin nitric oxide nitrogen oxide nitroxyl polyphosphate triphosphoric acid article chemical structure chemistry conformation electrochemistry electrode quantum theory scanning electron microscopy surface property X ray photoelectron spectroscopy Cobalt Electrochemistry Electrodes Gold Hydroxamic Acids Metalloporphyrins Methylene Chloride Microscopy, Electron, Scanning Models, Molecular Molecular Conformation Nitric Oxide Nitrogen Oxides Photoelectron Spectroscopy Polyphosphates Quantum Theory Surface Properties Suárez, S.A. Fonticelli, M.H. Rubert, A.A. De La Llave, E. Scherlis, D. Salvarezza, R.C. Martí, M.A. Doctorovich, F. A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold |
| topic_facet |
cobalt dichloromethane gold hydroxamic acid metalloporphyrin nitric oxide nitrogen oxide nitroxyl polyphosphate triphosphoric acid article chemical structure chemistry conformation electrochemistry electrode quantum theory scanning electron microscopy surface property X ray photoelectron spectroscopy Cobalt Electrochemistry Electrodes Gold Hydroxamic Acids Metalloporphyrins Methylene Chloride Microscopy, Electron, Scanning Models, Molecular Molecular Conformation Nitric Oxide Nitrogen Oxides Photoelectron Spectroscopy Polyphosphates Quantum Theory Surface Properties |
| description |
Nitroxyl (HNO) is a small short-lived molecule for which it has been suggested that it could be produced, under certain cofactors conditions, by nitric oxide (NO) synthases. Biologically relevant targets of HNO are heme proteins, thiols, molecular oxygen, NO, and HNO itself. Given the overlap of the targets and reactivity between NO and HNO, it is very difficult to discriminate their physiopathological role conclusively, and accurate discrimination between them still remains critical for interpretation of the ongoing research in this field. The high reactivity and stability of cobalt(II) porphyrins toward NO and the easy and efficient way of covalently joining porphyrins to electrodes through S-Au bonds prompted us to test cobalt(II) 5,10,15,20-tetrakis[3-(p- acetylthiopropoxy)phenyl]porphyrin [Co(P)], as a possible candidate for the electrochemical discrimination of both species. For this purpose, first, we studied the reaction between NO, NO donors, and commonly used HNO donors, with Co II(P) and Co III(P). Second, we covalently attached Co II(P) to gold electrodes and characterized its redox and structural properties by electrochemical techniques as well as scanning tunneling microscopy, X-ray photoelectron spectroscopy, and solid-state density functional theory calculations. Finally, we studied electrochemically the NO and HNO donor reactions with the electrode-bound Co(P). Our results show that Co(P) is positioned over the gold surface in a lying-down configuration, and a surface effect is observed that decreases the Co III(P) (but not Co III(P)NO -) redox potential by 0.4 V. Using this information and when the potential is fixed to values that oxidize Co III(P)NO - (0.8 V vs SCE), HNO can be detected by amperometric techniques. Under these conditions, Co(P) is able to discriminate between HNO and NO donors, reacting with the former in a fast, efficient, and selective manner with concomitant formation of the Co III(P)NO - complex, while it is inert or reacts very slowly with NO donors. © 2010 American Chemical Society. |
| format |
JOUR |
| author |
Suárez, S.A. Fonticelli, M.H. Rubert, A.A. De La Llave, E. Scherlis, D. Salvarezza, R.C. Martí, M.A. Doctorovich, F. |
| author_facet |
Suárez, S.A. Fonticelli, M.H. Rubert, A.A. De La Llave, E. Scherlis, D. Salvarezza, R.C. Martí, M.A. Doctorovich, F. |
| author_sort |
Suárez, S.A. |
| title |
A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold |
| title_short |
A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold |
| title_full |
A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold |
| title_fullStr |
A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold |
| title_full_unstemmed |
A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold |
| title_sort |
surface effect allows hno/no discrimination by a cobalt porphyrin bound to gold |
| url |
http://hdl.handle.net/20.500.12110/paper_00201669_v49_n15_p6955_Suarez |
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