Embelin's Versatile Photochemistry Makes It a Potent Photosensitizer for Photodynamic Therapy.

Embelin, a natural product isolated from Embelia ribes, is a promising small-molecular drug for photodynamic anticancer therapy. Using modern quantum chemical methodology, embelin is shown to possess a versatile photochemistry comprising the capability of singlet oxygen generation, excited-state proton transfer, and oxidation. In particular, the detailed molecular mechanisms of singlet oxygen generation and proton transfer upon excitation are studied in great detail. While excited-state proton transfer can damage the protein itself, it also mediates intersystem crossing along its reaction pathway, thus facilitating singlet oxygen generation. When embelin is bound to proteins, all these processes can lead to protein damage and the desired phototoxicity.