title: Charge separation in acridine- and phenothiazine-modified DNA.
abstract: The formation of the long-lived, charge-separated state in DNA upon visible light irradiation is of particular interest in molecular-scale optoelectronics, sensor design, and other areas of nanotechnology. However, the efficient generation of the charge-separated state is hampered by fast charge recombination within a contact ion pair, which limits the application of DNA for photoelectrochemical sensors and devices. In this study, a series of protonated 9-alkylamino-6-chloro-2-methoxyacridine (Acr+)- and phenothiazine (Ptz)-modified DNAs were synthesized for the further understanding of the mechanism of charge separation in DNA to generate a long-lived, charge-separated state with a high quantum yield (Phi). The Acr+ serves as a photosensitizer to produce a hole on guanine (G), and the G-C base pairs were used as a hole-transporting pathway to separate a hole from Acr* (the one-electron-reduced form of Acr+) to be trapped at Ptz. Since Acr+ oxides only G upon photoexcitation, the A-T base pair can be used as a spacer between Acr+ and the G-C base pair to avoid the formation of a contact ion pair. The charge injection dynamics was investigated by steady-state fluorescence spectra and fluorescence lifetime measurements, and the Phi and the lifetime of the charge-separated state produced upon photoirradiation were assessed by nanosecond laser flash photolysis of the Acr+- and Ptz-modified DNA. A long-lived, charge-separated state was successfully formed upon visible-light irradiation, and the Phi was the highest for the DNA having a single intervening A-T base pair between Acr+ and the G-C base pair. These results clearly demonstrated that the charge separation process in DNA can be refined by putting a redox-inactive intervening base pair as a spacer between a photosensitizer and the nucleobase to be oxidized to slow down the charge recombination rate.
authors.affiliation: The Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan. kiyohiko@sanken.osaka-u.ac.jp
authors.forename: Kiyohiko
authors.initials: K
authors.lastname: Kawai
authors.forename: Yasuko
authors.initials: Y
authors.lastname: Osakada
authors.forename: Mamoru
authors.initials: M
authors.lastname: Fujitsuka
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Majima
mesh_terms: D000166:Acridines / Q000737:chemistry*; D020029:Base Pairing / Q000528:radiation effects; D004247:DNA / Q000737:chemistry* / Q000528:radiation effects*; D007477:Ions; D010084:Oxidation-Reduction; D010640:Phenothiazines / Q000737:chemistry*; D010777:Photochemistry; D017319:Photosensitizing Agents; D013050:Spectrometry, Fluorescence; D055672:Static Electricity
chemical_list: D000166:Acridines; D007477:Ions; D010640:Phenothiazines; D017319:Photosensitizing Agents; D004247:DNA; C031637:phenothiazine