Laser flash photolysis study on the retinol radical cation in polar solvents

Laser flash photolysis (LFP) of retinol in argon-saturated methanol gives rise to a transient at 580 nm (transient A). Formation of transient A is accompanied by a transient growth at 370 nm. The rate of this growth is retinol concentration-dependent. The transient growth at 370 nm was removed in the presence of N2O, which is known to scavenge solvated electrons. These results can be interpreted by formation of retinol(center dot+) (lambda(max) = 580 nm) and solvated electrons following LFP of retinol. Subsequently, the solvated electrons are rapidly scavenged by retinol to form retinol center dot (lambda(max) = 370 nm in methanol). On the other hand, transient A is not ascribed to the retinyl cation, as was previously proposed, because the retinyl cation, generated from LFP of retinyl acetate, and transient A show different reactivities towards halide ions (e.g. k(Br) = 1.7 x 10(9) and 1.51 x 10(10) M-1 s(-1) respectively, in acetonitrile). After demonstrating the identity of transient A as retinol center dot(+), its reactions with carotenoids were examined in air-saturated polar solvents. In the presence of carotenoids, an enhancement in the decay of retinol(center dot+) was observed and was accompanied by formation of the corresponding carotenoid radical cations via electron transfer from carotenoids to retinol(center dot+). Furthermore, the reactivity of retinol(center dot+) towards pyridine derivatives was investigated in air-saturated polar solvents. It was found that the decay of retinol(center dot+) was accelerated with concomitant formation, with the same rate, of a transient at 370 nm. Similar observations were obtained with increasing pH of air-saturated aqueous 2% Triton X-100 of retinol(center dot+). The 370 nm (or 380 nm in the case of Triton X-100) transient is attributed to the base adducts or deprotonated neutral radicals. On the basis of these results, the reactivities of the retinyl cation and retinol(center dot+) are compared and the consequences of retinol(center dot+) formation within biological environments are discussed.