화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.138, No.23, 7395-7401, 2016
UV-Induced Proton-Coupled Electron Transfer in Cyclic DNA Miniduplexes
The excited-state dynamics of two cyclic DNA miniduplexes, each containing just two base pairs, are investigated using time-resolved infrared spectroscopy. As in longer DNA duplexes, intrastrand electron transfer induced by "UV excitation triggers interstrand proton transfer in the alternating miniduplex containing two out-of-phase G center dot C base pairs. The resulting excited state decays on a time scale of several tens of picoseconds. This state is absent when one of the two G residues is substituted by 8-oxo-7,8-dihydroguanine, a modification that is suggested to disrupt base stacking, while maintaining base pairing. These findings demonstrate that a nucleobase tetramer arranged as two stacked base pairs accurately captures the interplay between intrastrand and interstrand decay channels. The similar signals seen in the miniduplexes and longer sequences suggest that excited states in the latter rapidly localize on two adjacent base pairs.