Photooxidation of tetrahydrobiopterin under UV irradiation: possible pathways and mechanisms.
Tetrahydrobiopterin (H4 Bip) is a cofactor for several key enzymes, including NO synthases and aromatic amino acid hydroxylases (AAHs). Normal functioning of the H4 Bip regeneration cycle is extremely important for the work of AAHs. Oxidized pterins may accumulate if the H4 Bip regeneration cycle is disrupted or if H4 Bip autoxidation occurs. These oxidized pterins can photosensitize the production of singlet molecular oxygen (1)O2 and thus cause oxidative stress. In this context, we studied the photooxidation of H4 Bip in phosphate buffer at pH 7.2. We found that UV irradiation of H4 Bip affected its oxidation rate (quantum yield Φ300 = (2.7 ± 0.4) × 10(-3)). The effect of UV irradiation at λ = 350 nm on H4 Bip oxidation was stronger, especially in the presence of biopterin (Bip) (Φ350 = (9.7 ± 1.5) × 10(-3)). We showed that the rate of H4 Bip oxidation linearly depends on Bip concentration. Experiments with KI, a selective quencher of triplet pterins at micromolar concentrations, demonstrated that the oxidation is sensitized by the triplet state biopterin (3) Bip. Apparently, electron transfer sensitization (Type-I mechanism) is dominant. Energy transfer (Type-II mechanism) and singlet oxygen generation play only a secondary role. The mechanisms of H4 Bip photooxidation and their biological meaning are discussed.
A. N. Bach Institute of Biochemistry, Russian Academy of Sciences, Moscow, Russia.
Andrey A
AA
Buglak
Taisiya A
TA
Telegina
Tamara A
TA
Lyudnikova
Yulia L
YL
Vechtomova
Mikhail S
MS
Kritsky
D001708:Biopterins / Q000031:analogs & derivatives* / Q000737:chemistry*; D002021:Buffers; D004579:Electron Transport; D004583:Electrons; D004735:Energy Transfer; D006863:Hydrogen-Ion Concentration; D010084:Oxidation-Reduction; D055668:Photochemical Processes; D017319:Photosensitizing Agents / Q000737:chemistry*; D011789:Quantum Theory; D026082:Singlet Oxygen / Q000737:chemistry*; D012996:Solutions / Q000528:radiation effects; D014466:Ultraviolet Rays
D002021:Buffers; D017319:Photosensitizing Agents; D012996:Solutions; D026082:Singlet Oxygen; D001708:Biopterins; C003402:sapropterin