Delaney, Sarah and Yoo, Jae and Stemp, Eric D. A. and Barton, Jacqueline K. (2004) Charge equilibration between two distinct sites in double helical DNA. Proceedings of the National Academy of Sciences of the United States of America, 101 (29). pp. 10511-10516. ISSN 0027-8424 http://resolver.caltech.edu/CaltechAUTHORS:DELpnas04
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DNA assemblies containing a pendant dipyridophenazine complex of Ru(II) along with two oxidative traps, a site containing the nucleoside analog methylindole (5'-GMG-3') and a 5'-GGG-3' site, have been constructed to explore long-range charge transport through the base pair stack. With these chemically well defined assemblies, in combination with the flash/quench technique, formation of the methylindole cation radical and the neutral guanine radical is monitored directly by using transient absorption spectroscopy, and yields of oxidative damage are quantitated biochemically by gel electrophoresis. In these assemblies the base radicals form with a rate of ≥107 s–1. The rate of base radical formation does not change upon the addition of a second radical trap, the 5'-GGG-3' site; however, the yield of methylindole oxidation is significantly lower. This observation indicates that the 5'-GGG-3' site is effective in competing for the migrating charge and provides a second trapping site. Switching the orientation of the two trapping sites does not affect the yield of oxidized products at either site. Therefore, in DNA both forward and reverse charge transport occur so as to provide equilibration across the duplex on a timescale that is fast compared with trapping at a particular site. Further evidence of charge equilibration results from incorporating an intervening base-stacking perturbation and monitoring the fate of the injected charge. These experiments underscore the dynamic nature of DNA charge transport and reveal the importance of considering radical propagation in both directions along the DNA duplex.
|Additional Information:||© 2004 by The National Academy of Sciences of the USA Contributed by Jacqueline K. Barton, May 28, 2004. This study was supported by the National Institutes of Health.|
|Subject Keywords:||CT, charge transport; dppz, dipyridophenazine; 4-methylindole; BT, back electron transfer; bpy’, 4-methylbypyridine-4-butyric acid|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Archive Administrator|
|Deposited On:||21 Sep 2005|
|Last Modified:||26 Dec 2012 08:41|
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