long-range charge transport in duplex DNA: anthraquinone sensitization results are independent of terminal ionic...

Irradiation of an anthraquinone (AQ) derivative linked to a 5'-terminus of duplex DNA results in the formation of a base radical cation ("hole") that can migrate through the DNA. Reaction of the radical cation occurs primarily at the 5'-G of GG sequences. This reaction results in the formation of strand breaks when the irradiated DNA is treated with piperidine. The strand breaks are detected by polyacrylamide gel electrophoresis of samples that are labeled at the 3'- or 5'-terminus with (32)P. In contrast to a previous report in which a linked rhodium metallointercalator is used as the sensitizer to oxidize the DNA (Williams, T. T.; Barton, J. K. J. Am. Chem. Soc. 2002, 124, 1840-1841), we find that the position of the label does not affect the relative reactivity of the GG steps when AQ is the sensitizer.