Quantitative generation of singlet (1 delta g) oxygen from acidified aqueous peroxynitrite produced by the reaction of nitric oxide and superoxide anion.

Simple acidification of aqueous alkaline peroxynitrite quantitatively generates singlet (1 delta g) molecular oxygen, detected and quantitated spectroscopically (1270 nm). This observation provides a chemical basis for physiological cytotoxicity of ONOO- generated in the diffusion - controlled reaction of cellular NO. and O2-. The experiments consist of (i) chemical generation of ONOO- from NO. gas and KO2 powder in alkaline aqueous solution; (ii) absorption spectral identification of ONOO- in the near-UV with maximum at 301 nm; (iii) spectroscopic identification of 1O2 by its emission band at 1200-1340 nm with maximum at 1275 nm; and (i.v.) quantification of 1O2 generated in ONOO-/H+ reaction by comparison of the chemiluminescence intensity at 1270 nm with that from H2O2/OCI- reaction that generates 1O2 with unit efficiency at alkaline pH. 1O2 was generated with unit efficiency with respect to ONOO- concentration by the ONOO-/H+ reaction.