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M108079200v1
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Papers In Press, published online ahead of print January 17, 2002
J. Biol. Chem, 10.1074/jbc.M108079200
Submitted on August 22, 2001
Revised on January 17, 2002
Accepted on January 17, 2002

Formation of peroxynitrite from reaction of nitroxyl anion with molecular oxygen

Michael Kirsch and Herbert de Groot

Uni-Klinikum Essen, Inst. f. Physiologische Chemie, Essen 45122

Corresponding Author: michael.kirsch{at}uni-essen.de

Peroxynitrite (ONOO—/ONOOH) is generally expected to be formed in vivo from the diffusion-controlled reaction between superoxide and nitric oxide. In the present paper we show that under aerobic conditions the nitroxyl anion (NO—), released from Angeli´s salt (disodium diazen-1-ium-1,2,2-triolate, —ON=NO2—), generated peroxynitrite with a yield of about 65%. Simultaneously, hydroxyl radicals are formed from the nitroxyl anion with a yield of about 3% via a minor, peroxynitrite-independent pathway. Further experiments clearly underline that the chemistry of NO— in the presence of oxygen is mainly characterized by peroxynitrite and not by HO-radicals. Quantum-chemical calculations predict that peroxynitrite formation should proceed via intermediary formation of nitric oxide and superoxide, probably by an electron-transfer mechanism. This prediction is supported by the fact that H2O2 is formed during the decay of NO— in the presence of superoxide dismutase (Cu(II),Zn-SOD). Since the nitroxyl anion may be released endogenously by a variety of biomolecules, substantial amounts of peroxynitrite might be formed in vivo via NO— in addition to the "pure” nitric oxide + superoxide pathway.


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