Model studies of the (6–4) photoproduct photoreactivation: efficient photosensitized splitting of thymine oxetane units by covalently linked tryptophan in high polarity solvents

Abstract

Three covalently linked tryptophan–thymine oxetane compounds used as a model of the (6–4) photolyase–substrate complex have been prepared. Under 290 nm light, efficient splitting of the thymine oxetane with aromatic carbonyl compounds gives the thymine monomer and the corresponding carbonyl compounds by the covalently linked tryptophan via an intramolecular electron transfer, and exhibits a strong solvent dependence: the quantum yield (Φ) is ca. 0.1 in dioxane, and near 0.3 in water. Electron transfer from the excited tryptophan residue to the oxetane unit is the origin of fluorescence quenching of the tryptophan residue, and is more efficient in strong polar solvents. The splitting efficiency of the oxetane radical anion within the tryptophan˙⁺–oxetane˙⁻ species is also solvent-dependent, ranging from ca. 0.2 in dioxane to near 0.35 in water. Thus, the back electron transfer reaction in the charge-separated species would be suppressed in water, but is still a main factor causing low splitting efficiencies in the tryptophan–oxetane systems. In contrast to the tryptophan–oxetane system, fast nonradiation processes are the main causes of low efficiency in the flavin–oxetane system. Hence, nonradiative processes of the excited FADH⁻, rather than electron transfer to oxetane, may be an important factor for the low repair efficiency of (6–4) photolyase.