Formation of peroxynitrate from the reaction of peroxynitrite with CO2:: Evidence for carbonate radical production

The decomposition of peroxynitrite in the presence of bicarbonate and various substrates was studied using the stopped-flow technique. We have shown that peroxynitrite (ONOOH/ONOO-) reacts with excess of CO2 to form peroxynitrate (O2NOOH/O2NOO-) in aerated solutions containing HCO2-, H2O2, CH3OH, or (CH3)(2)CHOH. The yield of peroxynitrate increased with the increase in these substrate concentrations approaching 30-33% of added peroxynitrite. Competition kinetics study yields rate constants which are similar to those determined directly for the reactions of these substrates with the carbonate radical anion. We therefore suggest that the formation of peroxynitrate takes place via the following steps: (i) the rapid reaction of peroxynitrite with CO2 to form ONOOCO2-; (ii) the homolytic cleavage of 30-33% of ONOOCO2- into (NO2)-N-. and CO3.-; (iii) the reaction of CO3.- with the various substrates, yielding ultimately superoxide in aerated solutions: and (iv) the fast reaction of superoxide with (NO2)-N-. to form O2NOO-.