ascorbic-acid and oxyhyponitrite

1. This study made use of a nitric oxide-sensitive electrode to examine possible means of generating nitric oxide from nitroxyl anion (NO(-)) released upon the decomposition of Angeli's salt. 2. Our results show that copper ions (from CuSO(4)) catalyze the rapid and efficient oxidation of nitroxyl to nitric oxide. Indeed, the concentrations of copper required to do so (0.1 - 100 microM) are roughly 100-times lower than those required to generate equivalent amounts of nitric oxide from S-nitroso-N-acetyl-D,L-penicillamine (SNAP). 3. Experiments with ascorbate (1 mM), which reduces Cu(2+) ions to Cu(+), and with the Cu(2+) chelators, EDTA and cuprizone, and the Cu(+) chelator, neocuproine, each at 1 mM, suggest that the oxidation is catalyzed by copper ions in both valency states. 4. Some compounds containing other transition metals, i.e. methaemoglobin, ferricytochrome c and Mn(III)TMPyP, were much less efficient than CuSO(4) in catalyzing the formation of nitric oxide from nitroxyl, while FeSO(4), FeCl(3), MnCl(2), and ZnSO(4) were inactive. 5. Of the copper containing enzymes examined, Cu-Zn superoxide dismutase and ceruloplasmin were weak generators of nitric oxide from nitroxyl, even at concentrations (2500 and 30 u ml(-1), respectively) vastly greater than are present endogenously. Two others, ascorbate oxidase (10 u ml(-1)) and tyrosinase (250 u ml(-1)) were inactive. 6. Our findings suggest that a copper-containing enzyme may be responsible for the rapid oxidation of nitroxyl to nitric oxide by cells, but the identity of such an enzyme remains elusive.

Topics: Analysis of Variance; Ascorbic Acid; Chelating Agents; Copper; Enzymes; Iron Compounds; Manganese Compounds; Nitric Oxide; Nitrites; Nitrogen Oxides; Oxidation-Reduction; Zinc Compounds

The reaction of nitrite ion with ascorbic acid and its effect on the rate of nitrosation of secondary amines have been investigated by differential pulse polarography in aqueous acidic solution. Ascorbic acid shows nonuniform behavior: it accelerates the nitrosation of N-methylaniline between pH 1.00 and 1.95, allows the nitrosation of diphenylamine and iminodiacetonitrile, but inhibits the nitrosation of secondary amines, such as dimethylamine, diethylamine, proline, hydroxyproline, N-methylaminoacetonitrile, N-methylaminopropionitrile, and sarcosine. The nitrosating agent generated by the reaction between ascorbic acid and nitrite ion appears to be oxyhyponitrite ion (N2O3-2).

Topics: Ascorbic Acid; Chemical Phenomena; Chemistry; Hydrogen-Ion Concentration; Indicators and Reagents; Kinetics; Nitrites; Nitrosamines; Polarography