Singlet Fission Reaction of Light-Exposed β-Carotene Bound to Bovine Serum Albumin. A Novel Mechanism in Protection of Light-Exposed Tissue by Dietary Carotenoids.

We have attempted to investigate the role of carotenoids (Car) in protecting pigment-protein complexes against light-induced degradation. Upon direct photoexcitation of β-carotene (β-Car), nanosecond flash photolysis and femtosecond time-resolved spectroscopy detected a substantial population of triplet states for β-Car aggregates associated with bovine serum albumin (BSA) or dispersed in aqueous phase with 10% tetrahydrofuran (THF), but none were observed for monomeric β-Car in neat THF. The direct photogeneration of triplet states was on the time scale of <1 ps, indicating that the underlying reaction mechanism was singlet fission (SF). Efficient triplet-triplet annihilation in the time regime from picoseconds to microseconds resulted in a <1 μs triplet lifetime for β-Car aggregates, in contrast to a 20 μs lifetime for monomeric β-Car as determined by anthracene-sensitized flash photolysis. The short-lived triplet excitations of β-Car aggregates associated with BSA or dispersed in aqueous phase were found to be insensitive to the presence of oxygen, which are considered to be important for the protection of both protein and carotenoid against light-induced degradation via reaction with oxidative species.