As a structural analogue of adenine, 2-aminopurine (2Ap) is often used as a fluorescent probe to study the intramolecular charge transfer reaction in DNA. We have designed and synthesized a series of model DNA helix with the variation in the distance between the 2Ap probe and the GGG sequence, and have investigated, by means of picosecond time-resolved fluorescence spectroscopy, the effect of the length of the bridge (consisting of a number of inosines, I) separating the electron donor (???GGG???) and the acceptor (2Ap) on the charge transfer dynamics. The fluorescence dynamics of 2Ap exhibited three exponential decay components, the one with a time constant of a few hundred picoseconds is assigned to the intramolecular charge transfer from GGG to 2Ap. Within 2.4 nm of the donor-acceptor separation, the rate of charge transfer decreased exponentially upon increasing the separation, from which the decay factor β is determined to be 1.3 nrrf-1. Beyond 2.4 nm, however, the rate started toincrease, this abnormal behavior of charge transfer is interpreted in terms of the match of elec- tronic energies between the l-bridge and the donor/acceptor couple.
ZHANG Huijuan WANG Peng WANG Xuefei FENG Juan XU Sichuan AI Xicheng ZHANG Xingkang ZHANG Jianping
The photophysical properties of the polyamide PyPyPyβDp (PPP) were investigated by means of steady-state absorption and fluorescence spectroscopies, as well as time-resolved fluo-rescence spectroscopy. It was found that the excited-state properties of PPP are very sensitive to solvents. In TKMC buffer PPP exhibited weak fluorescence with a decay time constant of 16 ps, while with the decrease of the solvent polarity PPP showed the blue-shifted peak position, increased inten-sity and lengthened life-time for its fluorescence behavior. In the presence of calf thymus DNA, it was observed that the fluorescence intensity was enhanced and the fluorescence lifetime increased from 16 to 32 ps for PPP, which verified that PPP bound into the minor groove of DNA duplex.
ZHANG Huijuan1,2, WANG Jin3, WU Yishi1, YUAN Gu3, AI Xicheng1, WANG Li4 & ZHANG Jianping1 1. State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China
