Singlet Oxygen (O2(1Δg)) Quenching by Dihydropterins

Abstract

Pterins belong to a class of heterocyclic compounds present in a wide range of living systems. They participate in relevant biological functions and are involved in different photobiological processes. Dihydropterins are one of the biologically active forms of pterins. The photoinduced production and quenching of singlet oxygen (1O2) by a series of dihydropterins (7,8-dihydrobiopterin (DHBPT), 7,8-dihydroneopterin (DHNPT), 6-formyl-7,8-dihydropterin (FDHPT), sepiapterin (SPT), 7,8-dihydrofolic acid (DHFA), and 7,8-dihydroxanthopterin (DHXPT)) in aqueous solution at physiological pH ( approximately 7) were investigated, and the quantum yields of 1O2 production (PhiDelta) and rate constants of total quenching (kt) of 1O2 were determined. Studied compounds do not produce 1O2 under UV-A irradiation and are very efficient 1O2 quenchers. The chemical reactions between 1O2 and dihydropterin derivatives were investigated, and the corresponding rate constants (kr) were found to be particularly high. The oxidized pterin derivatives, biopterin (BPT), neopterin (NPT), 6-formylpterin (FPT), and folic acid (FA), were identified and quantified during the reaction of 1O2 with DHBPT, DHNPT, FDHPT, and DHFA, respectively. Besides the oxidation of the dihydropyrazine ring to yield the corresponding oxidized pterins, a second oxidation pathway, leading to fragmentation of the dihydropterin and formation of non-pterinic products, was identified. Mechanisms and biological implications are discussed.