Sequence Dependent Long Range Hole Transport in DNA

Abstract

A guanine radical cation (G+•) was site-selectively generated in double stranded DNA and the charge transfer in different oligonucleotide sequences was investigated. The method is based on the competition between a charge transfer from G+• through the DNA and its trapping reaction with H2O. We analyzed the hole transfer from this G+• to a GGG unit through one, two, three, and four AT base pairs and found that the rate decreases by about 1 order of magnitude with each intervening AT base pair. This strong distance dependence led to a β-value of 0.7 ± 0.1 A-1. Within the time scale of this assay the charge transfer nearly vanished when the G+• was separated by four AT base pairs from the GGG unit. However, if the second or the third of the four intervening AT base pairs was exchanged by a GC base pair, the rate of the hole transfer from the G+• to the GGG unit increased by 2 orders of magnitude. In addition, a long-range charge transfer over 15 base pairs could be observed in a mixed strand that contained A...