title: Direct observation of hole transfer through double-helical DNA over 100 A.
abstract: Mechanism of photo-induced electron transfer and the subsequent hole transfer in DNA has been studied extensively, but so far we are not aware of any reliable report of the observation of the long-distance hole-transfer process. In this article, we demonstrate the results of direct observation for the long-distance hole transfer in double-helical DNA over 100 A with time-resolved transient absorption measurements. DNA conjugated with naphthalimide (NI) and phenothiazine (PTZ) (which worked as electron-acceptor and donor molecules, respectively) at both 5' ends was synthesized to observe the hole-transfer process. Site-selective charge injection into G by means of the adenine-hopping process was accomplished by excitation of NI with a 355-nm laser flash. Transient absorption around 400 nm, which was assigned to the NI radical anion, was observed immediately after the irradiation of a laser flash, indicating that the charge separation between NI and the nearest G occurred. Then, the transient absorption of the PTZ radical cation (PTZ(*+)) at 520 nm was emerged, which was attributed to the hole transfer through DNA to the PTZ site. By monitoring the time profiles of the transient absorption of PTZ(*+) for NI-A(6)-(GA)(n)-PTZ and NI-A(6)-(GT)(n)-PTZ (n = 2, 3, 4, 6, 8, 12) (base sequences correspond to those for DNA modified with NI), the long-distance hole-transfer process from G to PTZ, which occurred in the time scale of microsecond to millisecond, was observed directly. By assuming an average distance of 3.4 A between base-pairs, total distance reaches 100 A for n = 12 sequences. Our results clearly show the direct observation of the long-distance hole transfer over 100 A.
authors.affiliation: Institute of Scientific and Industrial Research (SANKEN), Osaka University, Mihogaoka 8-1, Ibaraki, Osaka 567-0047, Japan.
authors.forename: Tadao
authors.initials: T
authors.lastname: Takada
authors.forename: Kiyohiko
authors.initials: K
authors.lastname: Kawai
authors.forename: Mamoru
authors.initials: M
authors.lastname: Fujitsuka
authors.forename: Tetsuro
authors.initials: T
authors.lastname: Majima
mesh_terms: D001483:Base Sequence; D004247:DNA / Q000737:chemistry* / Q000235:genetics / Q000528:radiation effects; D004579:Electron Transport; D007700:Kinetics; D008958:Models, Molecular; D009281:Naphthalenes / Q000737:chemistry; D009690:Nucleic Acid Conformation; D010640:Phenothiazines / Q000737:chemistry; D010782:Photolysis; D017319:Photosensitizing Agents / Q000737:chemistry; D013057:Spectrum Analysis
chemical_list: D009281:Naphthalenes; D010640:Phenothiazines; D017319:Photosensitizing Agents; D004247:DNA