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Originally published In Press as doi:10.1074/jbc.M108079200 on January 17, 2002

J. Biol. Chem., Vol. 277, Issue 16, 13379-13388, April 19, 2002
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Formation of Peroxynitrite from Reaction of Nitroxyl Anion with Molecular Oxygen*

Michael KirschDagger and Herbert de Groot

From the Institut für Physiologische Chemie, Universitätsklinikum, Hufelandstrasse 55, D-45122 Essen, Germany

Peroxynitrite (ONOO-/ONOOH) is generally expected to be formed in vivo from the diffusion-controlled reaction between superoxide (O<UP><SUB>2</SUB><SUP>&cjs1138;</SUP></UP>) and nitric oxide (·NO). 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=NO<UP><SUB>2</SUB><SUP>−</SUP></UP>), 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 ·NO and O<UP><SUB>2</SUB><SUP>&cjs1138;</SUP></UP>, 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 "classical" ·NO + O<UP><SUB>2</SUB><SUP>&cjs1138;</SUP></UP> pathway.


* This work was supported by the Stiftung VERUM.The costs of publication of this article were defrayed in part by the payment of page charges. The article must therefore be hereby marked "advertisement" in accordance with 18 U.S.C. Section 1734 solely to indicate this fact.

Dagger To whom correspondence should be addressed: Institut für Physiologische Chemie, Universitätsklinikum Essen, Hufelandstr. 55, D-45122 Essen, Germany. Tel.: 49-201-723-4107; Fax: 49-201-723-5943; E-mail: michael.kirsch@uni-essen.de.


Copyright © 2002 by The American Society for Biochemistry and Molecular Biology, Inc.
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