Facile reaction of gangliosides with hydroxyl radical.

: The reactivity of gangliosides with superoxide anion (O2(•-)) and hydroxyl radical (HO(•)) was evaluated by ESR spin-trapping using 5,5-dimethyl-1-pyrroline-N-oxide under physiological conditions (1/15 M phosphate buffer, pH 7.4). Gangliosides proved to react with HO(•) but not with O2(•-). The second order rate constants for various gangliosides with HO(•) ranged from 5 × 10(9) M(-1)s(-1) to 16 × 10(9) M(-1)s(-1). The rate constant for tetrasialoganglioside, GQ1b, was about three times higher than that of monosialoganglioside, GM1. The reactivity of gangliosides and asialo-GM1 with HO(•) was in the order: GQ1b >GT1b >GD1a >GD1b = GM1 ≫ asialo-GM1. The observed high reactivity of gangliosides probably involves the sialyl residues, since sialic acid was shown to be more reactive with HO(•) than d-glucose under the same conditions.