Cage-escape of geminate radical pairs can produce peroxynitrate from peroxynitrite under a wide variety of experimental conditions

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DOIResolve DOI: http://doi.org/10.1021/ja991077u
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TypeArticle
Journal titleJournal of the American Chemical Society
ISSN0002-7863
Volume121
Issue46
Pages1069510701; # of pages: 7
Subjectperoxynitrite; radical; superoxide; tetranitromethane; article; catalysis; chemical analysis; chemical modification; chemical reaction; decomposition; optical density; reaction analysis; reaction time
AbstractThe spontaneous and CO2-catalyzed decomposition of peroxynitrite yields HO· and -CO3· radicals, respectively, together with ·NO2. The geminate HO·/·NO2 and -CO3·/·NO2 pairs undergo competitive in-cage collapse to nitrate and diffusive separation. Free HO· and -CO3· radicals react with H2O2 and, in the presence of O2, suitable alcohols or formate to produce superoxide, which is trapped by the ·NO2 to form peroxynitrate. The formation of peroxynitrate may influence the rate of change in optical density at 302 nm, the wavelength normally employed to monitor peroxynitrite decay, leading to misleading kinetic traces. Tetranitromethane (TNM) was used as a colorimetric probe for superoxide to quantify the yield of free HO· (27-28%) and free -CO3· (32-33%). The yields of both of these free radicals are in excellent agreement with other recent estimates. Superoxide was also detected in some oxygenated aldehyde-catalyzed peroxynitrite decompositions both by peroxynitrate formation and by its reaction with TNM. Superoxide yields, measured with TNM, were aldehyde (RCHO) dependent (R = - O2CC6H4, CH3, CH3CH2, (CH3)3C and HOCH2CHOH; yields were 15, 9, 0.8, 0, and 30%, respectively).
Publication date
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC)
Peer reviewedYes
NPARC number21276516
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Record identifier31012dfe-72d6-4095-bfbb-80a81c6bcbe3
Record created2015-10-13
Record modified2016-05-09
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