Artículo

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" (2010) Inorganic Chemistry. 49(15):6955-6966
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Abstract:

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.

Registro:

Documento: Artículo
Título:A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold
Autor:Suárez, S.A.; Fonticelli, M.H.; Rubert, A.A.; De La Llave, E.; Scherlis, D.; Salvarezza, R.C.; Martí, M.A.; Doctorovich, F.
Filiación:Departamento de Química Inorgánica, Analítica y Química Física, Ciudad Universitaria, Pabellón II, Buenos Aires C1428EHA, Argentina
Departamento de Química Biologica, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, Pab. II, (1428), Buenos Aires, Argentina
Instituto de Investigaciones Fisicoquímicas, Teóricas y Aplicadas (INIFTA), Universidad Nacional de la Plata-CONICET, Sucursal 4 Casilla de Correo 16, 1900 La Plata, Argentina
Palabras clave: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
Año:2010
Volumen:49
Número:15
Página de inicio:6955
Página de fin:6966
DOI: http://dx.doi.org/10.1021/ic1007022
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
CAS:cobalt, 7440-48-4; dichloromethane, 75-09-2; gold, 7440-57-5; nitric oxide, 10102-43-9; nitrogen oxide, 11104-93-1; polyphosphate, 13813-62-2, 8017-16-1; triphosphoric acid, 10380-08-2; Cobalt, 7440-48-4; Gold, 7440-57-5; Hydroxamic Acids; Metalloporphyrins; Methylene Chloride, 75-09-2; Nitric Oxide, 10102-43-9; Nitrogen Oxides; Polyphosphates; nitroxyl, 14332-28-6; triphosphoric acid, 10380-08-2
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v49_n15_p6955_Suarez

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Citas:

---------- APA ----------
Suárez, S.A., Fonticelli, M.H., Rubert, A.A., De La Llave, E., Scherlis, D., Salvarezza, R.C., Martí, M.A.,..., Doctorovich, F. (2010) . A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold. Inorganic Chemistry, 49(15), 6955-6966.
http://dx.doi.org/10.1021/ic1007022
---------- CHICAGO ----------
Suárez, S.A., Fonticelli, M.H., Rubert, A.A., De La Llave, E., Scherlis, D., Salvarezza, R.C., et al. "A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold" . Inorganic Chemistry 49, no. 15 (2010) : 6955-6966.
http://dx.doi.org/10.1021/ic1007022
---------- MLA ----------
Suárez, S.A., Fonticelli, M.H., Rubert, A.A., De La Llave, E., Scherlis, D., Salvarezza, R.C., et al. "A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold" . Inorganic Chemistry, vol. 49, no. 15, 2010, pp. 6955-6966.
http://dx.doi.org/10.1021/ic1007022
---------- VANCOUVER ----------
Suárez, S.A., Fonticelli, M.H., Rubert, A.A., De La Llave, E., Scherlis, D., Salvarezza, R.C., et al. A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold. Inorg. Chem. 2010;49(15):6955-6966.
http://dx.doi.org/10.1021/ic1007022