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Oxidative DNA damage through long-range electron transfer

Hall, Daniel B. and Holmlin, R. Erik and Barton, Jacqueline K. (1996) Oxidative DNA damage through long-range electron transfer. Nature, 382 (6593). pp. 731-735. ISSN 0028-0836. doi:10.1038/382731a0.

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THE possibility has been considered for almost forty years that the DNA double helix, which contains a π-stacked array of heterocyclic base pairs, could be a suitable medium for the migration of charge over long molecular distances. This notion of high charge mobility is a critical consideration with respect to DNA damage. We have previously found that the DNA double helix can serve as a molecular bridge for photo-induced electron transfer between metallointercalators, with fast rates (≥10^(10) S^(−1))^(10) and with quenching over a long distance (>40Å)^8. Here we use a metallointercalator to introduce a photoexcited hole into the DNA π-stack at a specific site in order to evaluate oxidative damage to DNA from a distance. Oligomeric DNA duplexes were prepared with a rhodium inter-calator covalently attached to one end and separated spatially from 5′-GG-3′ doublet sites of oxidation. Rhodium-induced photo-oxidation occurs specifically at the 5′-G in the 5′-GG-3′ doublets and is observed up to 37 Å away from the site of rhodium intercalation. We find that the yield of oxidative damage depends sensitively upon oxidation potential and π-stacking, but not on distance. These results demonstrate directly that oxidative damage to DNA may be promoted from a remote site as a result of hole migration through the DNA π-stack.

Item Type:Article
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Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 1996 Nature Publishing Group. Received 20 February; accepted 25 June 1996. We are grateful to the NIH for financial support. We also thank the NIH for an NRSA for D.B.H., the NSF for a predoctoral fellowship for R.E.H. and the NFCR for additional funds.
Funding AgencyGrant Number
NIH National Research Service AwardUNSPECIFIED
NSF Predoctoral FellowshipUNSPECIFIED
National Foundation for Cancer ResearchUNSPECIFIED
Issue or Number:6593
Record Number:CaltechAUTHORS:20150617-092516497
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Official Citation:Oxidative DNA damage through long-range electron transfer 731 Daniel B. Hall, R. Erik Holmlin & Jacqueline K. Barton doi:10.1038/382731a0
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58310
Deposited By: Ruth Sustaita
Deposited On:17 Jun 2015 16:45
Last Modified:10 Nov 2021 22:03

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