Glutathiyl radical as an intermediate in glutathione nitrosation.

Nitrosation of thiols is thought to be mediated by dinitrogen trioxide (N(2)O(3)) or by nitrogen dioxide radical (()NO(2)). A kinetic study of glutathione (GSH) nitrosation by NO donors in aerated buffered solutions was undertaken. S-nitrosoglutathione (GSNO) formation was assessed spectrophotometrically and by chemiluminescence. The results suggest an increase in the rate of GSNO formation with an increase in GSH with a half-maximum constant EC(50) that depends on NO concentration. Our observed increase in EC(50) with NO concentration suggests a significant contribution of ()NO(2)-mediated nitrosation with the glutathiyl radical as an intermediate in the production of GSNO.