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Oxidative DNA damage through long-range electron transfer.
Nature 1996; 382(6593):731-5Nat

Abstract

The possibility has been considered for almost forty years that the DNA double helix, which contains a pi-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 (> or = 10(10)s-1) and with quenching over a long distance (>40 A). Here we use a metallointercalator to introduce a photoexcited hole into the DNA pi-stack at a specific site in order to evaluate oxidative damage to DNA from a distance. Oligomeric DNA duplexes were prepared with a rhodium intercalator 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 A away from the site of rhodium intercalation. We find that the yield of oxidative damage depends sensitively upon oxidation potential and pi-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 pi-stack.

Authors+Show Affiliations

Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena 91125, USA.No affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, P.H.S.

Language

eng

PubMed ID

8751447

Citation

Hall, D B., et al. "Oxidative DNA Damage Through Long-range Electron Transfer." Nature, vol. 382, no. 6593, 1996, pp. 731-5.
Hall DB, Holmlin RE, Barton JK. Oxidative DNA damage through long-range electron transfer. Nature. 1996;382(6593):731-5.
Hall, D. B., Holmlin, R. E., & Barton, J. K. (1996). Oxidative DNA damage through long-range electron transfer. Nature, 382(6593), pp. 731-5.
Hall DB, Holmlin RE, Barton JK. Oxidative DNA Damage Through Long-range Electron Transfer. Nature. 1996 Aug 22;382(6593):731-5. PubMed PMID: 8751447.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Oxidative DNA damage through long-range electron transfer. AU - Hall,D B, AU - Holmlin,R E, AU - Barton,J K, PY - 1996/8/22/pubmed PY - 1996/8/22/medline PY - 1996/8/22/entrez SP - 731 EP - 5 JF - Nature JO - Nature VL - 382 IS - 6593 N2 - The possibility has been considered for almost forty years that the DNA double helix, which contains a pi-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 (> or = 10(10)s-1) and with quenching over a long distance (>40 A). Here we use a metallointercalator to introduce a photoexcited hole into the DNA pi-stack at a specific site in order to evaluate oxidative damage to DNA from a distance. Oligomeric DNA duplexes were prepared with a rhodium intercalator 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 A away from the site of rhodium intercalation. We find that the yield of oxidative damage depends sensitively upon oxidation potential and pi-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 pi-stack. SN - 0028-0836 UR - https://www.unboundmedicine.com/medline/citation/8751447/Oxidative_DNA_damage_through_long_range_electron_transfer_ L2 - https://doi.org/10.1038/382731a0 DB - PRIME DP - Unbound Medicine ER -