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The decomposition of peroxynitrite does not yield nitroxyl anion and singlet oxygen
KTH, Superseded Departments, Chemistry.
KTH, Superseded Departments, Chemistry.
2000 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 97, no 15, 8216-8218 p.Article in journal (Refereed) Published
Abstract [en]

In a recent article [Khan, A. U., Kovacic, D., Kolbanovsky, A., Desai, M., Frenkel, K. & Geacintov, N, E. (2000) Proc. Natl. Acad. Sci. USA 97, 2984-2989], the authors claimed that ONOO-, after protonation to ONOOH, decomposes into (HNO)-H-1 and O-1(2) according to a spin-conserved unimolecular mechanism. This claim was based partially on their observation that nitrosylhemoglobin is formed via the reaction of peroxynitrite with methemoglobin at neutral pH. However, thermochemical considerations show that the yields of O-1(2) and (HNO)-H-1 are about 23 orders of magnitude lower than those of (NO2)-N-. and (OH)-O-., which are formed via the homolysis of ONOOH. We also show that methemoglobin does not form with peroxynitrite any spectrally detectable product, but with contaminations of nitrite and H2O2 present in the peroxynitrite sample. Thus, there is no need to modify the present view of the mechanism of ONOOH decomposition, according to which initial homolysis into a radical pair, [(ONOOH)-O-..](cage), is followed by the diffusion of about 30% of the radicals out of the cage, while the rest recombines to nitric acid in the solvent cage.

Place, publisher, year, edition, pages
2000. Vol. 97, no 15, 8216-8218 p.
Keyword [en]
nitric-oxide, biological-activity, radical formation, acid, oxidations, superoxide, mechanism, water, co2
URN: urn:nbn:se:kth:diva-19911ISI: 000088273900007OAI: diva2:338603
QC 20100525Available from: 2010-08-10 Created: 2010-08-10Bibliographically approved

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