The complex chemistry of peroxynitrite decomposition: New insights

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DOIResolve DOI: http://doi.org/10.1021/ja980871x
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume120
Issue29
Pages72117219; # of pages: 9
Subjectdimethyl sulfoxide; hydroxyl radical; peroxynitrite; article; decomposition; oxidation; proton nuclear magnetic resonance; thermodynamics
AbstractThe yield of hydroxyl radicals produced in the decomposition of peroxynitrous acid (HOONO) at room temperature in deoxygenated and bicarbonate free water at pH ~6.8 has been determined to be roughly 10%. This value rests on a detailed study of the decomposition of peroxynitrous acid in the presence of dimethyl sulfoxide with stopped-flow kinetics and product analyses by unequivocal methods. The HO·/DMSO reaction is known to yield methane sulfinic acid (MSA) and CH3· radicals with 91% efficiency. MSA was quantified by 1H NMR and its measured yield was corrected to allow for its extensive further oxidation to methane sulfonic acid. Methyl radicals were quantified by trapping with a water-soluble, stable nitroxide. At low peroxynitrite concentrations these two techniques gave HO· yields of ca. 8% and ca. 13%, respectively. We conclude that in water the main (ca. 90%) decomposition pathway for peroxynitrite involves a rearrangement to nitric acid via an in-cage collapse of the singlet HO·/·NO2 radical pair which may, in part, be preceded by electron transfer to form an HO-/+NO2 intimate ion pair. We emphasize that, in contrast to many earlier reports, a distinct pathway to hydroxyl radicals is present, which implies that a significant portion of the oxidative nature of peroxynitrite can stem from hydroxyl radical-induced chemistry.
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276561
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Record identifier99f1c503-7b33-4462-94b8-0ea25526ddd9
Record created2015-10-13
Record modified2016-05-09
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