Reactions of peroxynitrite with aldehydes as probes for the reactive intermediates responsible for biological nitration

Chemical Research in Toxicology
Rao M UppuW A Pryor

Abstract

We have examined the reactions of peroxynitrite with short-chain aliphatic aldehydes to model the reaction of the peroxynitrite anion (ONOO-) with CO2. Aldehydes, like CO2, react rapidly with peroxynitrite and catalyze its decomposition. The pH dependence of the reaction is consistent with the addition of ONOO- (not ONOOH) to the carbonyl carbon atom of the free aldehyde forming a 1-hydroxyalkylperoxynitrite anion adduct (5), which structurally resembles the nitrosoperoxycarbonate adduct (1) formed from the reaction of ONOO- with CO2. Intermediate 5, or the secondary products derived from it, decays to give NO3- and regenerated aldehyde, with small but significant yields of H2O2, organic acids, and organic nitrates. In analogy with the peroxynitrite/CO2 system, it is suggested that 5 undergoes homolytic or heterolytic cleavage at the O-O bond, giving a caged radical pair [RCH(OH)O./ .NO2] (7) or intimate ion pair [RCH(OH)O -/+ NO2] (8). The radicals and ions in intermediates 7 and 8 can recombine within the solvent cage to form 1-hydroxyalkylnitrate [RCH(OH)ONO2] (6), which can then dissociate to give nitrate and regenerate the aldehyde. The aldehyde/ peroxynitrite adducts 5-8 mediate the oxidation of 2,2'-azinobis(3-ethylbenzt...Continue Reading

Citations

Apr 25, 2000·Archives of Biochemistry and Biophysics·C X SantosO Augusto
Mar 8, 2020·Free Radical Biology & Medicine·Leticia C P GonçalvesEtelvino J H Bechara
Mar 18, 2021·Antioxidants & Redox Signaling·Marilene DemasiLeonor Thomson
Jul 31, 1998·Archives of Biochemistry and Biophysics·H Ischiropoulos
Sep 29, 1998·Archives of Biochemistry and Biophysics·R M UppuW A Pryor
Oct 7, 2010·Chemical Research in Toxicology·Júlio MassariEtelvino José Henriques Bechara
Feb 6, 2018·Chemical Reviews·Gerardo Ferrer-SuetaRafael Radi
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Feb 6, 2019·Chemical Reviews·Paolo Di MascioJean Cadet
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