The decomposition of peroxynitrite does not yield nitroxyl anion and singlet oxygen

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, 2984-2 989], the authors claimed that ONOO-, after protonation to ONOOH, decompose s into (HNO)-H-1 and O-1(2) according to a spin-conserved unimolecular mech anism. This claim was based partially on their observation that nitrosylhem oglobin is formed via the reaction of peroxynitrite with methemoglobin at n eutral 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 (N O2)-N-. and (OH)-O-., which are formed via the homolysis of ONOOH. We also show that methemoglobin does not form with peroxynitrite any spectrally det ectable 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 ni tric acid in the solvent cage.