Photogeneration of singlet oxygen (1O2) and free radicals (Sen·-, O·-2) by tetra-brominated hypocrellin B derivative

Abstract

To improve photodynamic activity of the parent hypocrellin B (HB), a tetra-brominated HB derivative (compound 1) was synthesized in high yield. Compared with HB, compound 1 has enhanced red absorption and high molar extinction coefficients. The photodynamic action of compound 1, especially the generation mechanism and efficiencies of active species (Sen·-, O·-2 and 1O2) were studied using electron paramagnetic resonance (EPR) and spectrophotometric methods. In the deoxygenated DMSO solution of compound 1, the semiquinone anion radical of compound 1 is photogenerated via the self-electron transfer between the excited and ground state species. The presence of electron donor significantly promotes the reduction of compound 1. When oxygen is present, superoxide anion radical (O·-2) is formed via the electron transfer from Sens·- to the ground state molecular oxygen. The efficiencies of Sens·- and O·-2 generation by compound 1 are about three and two times as much as that of HB, respectively. Singlet oxygen (1O2) can be produced via the energy transfer from triplet compound 1 to ground state oxygen molecules. The quantum yield of singlet oxygen (1O2) is 0.54 in CHCl3 similar to that of HB. Furthermore, it was found that the accumulation of Sens·- would replace that of O·-2 or 1O2 with the depletion of oxygen in the sealed system.