Photosensitized Generation of Singlet Oxygen ( 1 O 2 ) from Pyropheophorbide a Specifically Bound to All Parallel-Stranded G-Quadruplex DNAs.

Pyropheophorbide a (Pyro- a ), a chlorophyll metabolite, is a potential photosensitizer for photodynamic therapy (PDT), but little is known about its interaction with the target molecules for PDT, e.g., nucleic acids. Elucidation of the interaction between photosensitizers and nucleic acids will help us understand the initial process of PDT at the molecular level and hence to develop photosensitizing agents. We found that pyro- a forms a 1:1 complex with an all parallel-stranded G-quadruplex DNA and that pyro- a in the complex exhibits a quantum yield for singlet oxygen generation, with excitation at 664 nm, higher by a factor of ∼10 than that of pyro- a in an aqueous solution. These findings provided novel insights into molecular design of pyro- a -based photosensitizers to enhance their PDT efficacy.