title: A surface effect allows HNO/NO discrimination by a cobalt porphyrin bound to gold.
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.
authors.affiliation: Departamento de Química Inorgánica, Analítica y Química Física/INQUIMAE-CONICET, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Buenos Aires C1428EHA, Argentina.
authors.forename: Sebastián A
authors.initials: SA
authors.lastname: Suárez
authors.forename: Mariano H
authors.initials: MH
authors.lastname: Fonticelli
authors.forename: Aldo A
authors.initials: AA
authors.lastname: Rubert
authors.forename: Ezequiel
authors.initials: E
authors.lastname: de la Llave
authors.forename: Damián
authors.initials: D
authors.lastname: Scherlis
authors.forename: Roberto C
authors.initials: RC
authors.lastname: Salvarezza
authors.forename: Marcelo A
authors.initials: MA
authors.lastname: Martí
authors.forename: Fabio
authors.initials: F
authors.lastname: Doctorovich
mesh_terms: D003035:Cobalt / Q000737:chemistry*; D004563:Electrochemistry; D004566:Electrodes; D006046:Gold / Q000737:chemistry*; D006877:Hydroxamic Acids / Q000737:chemistry; D008665:Metalloporphyrins / Q000737:chemistry*; D008752:Methylene Chloride / Q000737:chemistry; D008855:Microscopy, Electron, Scanning; D008958:Models, Molecular; D008968:Molecular Conformation; D009569:Nitric Oxide / Q000032:analysis* / Q000737:chemistry*; D009589:Nitrogen Oxides / Q000032:analysis* / Q000737:chemistry*; D056951:Photoelectron Spectroscopy; D011122:Polyphosphates / Q000737:chemistry; D011789:Quantum Theory; D013499:Surface Properties
chemical_list: D006877:Hydroxamic Acids; D008665:Metalloporphyrins; D009589:Nitrogen Oxides; D011122:Polyphosphates; D009569:Nitric Oxide; D003035:Cobalt; D008752:Methylene Chloride; D006046:Gold; C039900:nitroxyl; C005692:triphosphoric acid