On the generation and quenching of reactive-oxygen-species by aqueous vitamin B2 and serotonin under visible-light irradiation

It is well known that endogenous daylight-absorbing compounds produce the sensitized photodegradation of biologically relevant substrates. In this context the photostability of a mixture of the indole neurotransmitter serotonin (Sero) and vitamin B2 (riboflavin, Rf) upon visible-light irradiation and the possible role of Sero and related compounds as generators or deactivators of reactive oxygen species (ROS) was investigated through a kinetic and mechanistic study. The work was done at pH 7 and under experimental conditions in which only the vitamin absorbs photoirradiation. Tryptamine (Trpa) and 5-hydroxyindole (OHIn) were included in the study as model compounds for the neurotransmitter. The visible light irradiation of aqueous Rf in the individual presence of Sero, Trpa and 5-OHIn, under aerobic conditions, induce degradative processes on the indole derivatives (In-der). At least two different mechanisms operate. Our analysis shows that the main reaction pathway is an electron-transfer-mediated quenching of triplet excited Rf (3Rf*) by the In-der. It produces the species Rf−/RfH and the In-der radical cation that could react to form phenoxy and α-amino radicals. In a further reaction step the species O2- and OH could be produced. In parallel, energy transfer from 3Rf* to dissolved oxygen would generate O2(1Δg).Within the frame of the proposed mechanism, results suggest that Rf-sensitized degradation of Sero occurs via the mentioned ROS and non-oxygenated radical-mediated processes.The indole compound quenches O2(1Δg) in a dominant physical fashion. This fact constitutes a desirable property in antioxidants, provided that the quenching process practically does not eliminate the scavenger.Sero exerts a photoprotective effect towards tryptophan through the combined quenching of O2(1Δg) and 3Rf*, the latter excited species responsible for the generation of ROS. The amino acid can be taken as a target model of oxidizable biological substrates, particularly proteins.

► The photostability of a mixture serotonin–riboflavin (Rf) was studied.
► Electron-transfer quenching of triplet Rf by serotonin produces O2- and OH.
► Energy transfer from triplet Rf to dissolved oxygen produces O2(1Δg).
► The photogenerated ROS are quenched by serotonin.
► Serotonin acts as a photoprotector towards photooxidation of tryptophan.