DNA-mediated electron transfer from a modified base to ethidium: π-stacking as a modulator of reactivity
- Creators
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Kelley, Shana O.
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Barton, Jacqueline K.
Abstract
Background: The DNA double helix is composed of an array of aromatic heterocyclic base pairs and, as a molecular π-stack, represents a novel system for studying long-range electron transfer. Because many base damage and repair processes result from electron-transfer reactions, the ability of DNA to mediate charge transport holds important biological implications. Seemingly contradictory conclusions have been drawn about electron transfer in DNA from the many different studies that have been carried out. These studies must be reconciled so that this phenomenon can be understood both at a fundamental level and in the context of biological systems. Results: The photoinduced oxidation of a modified base, 7-deazaguanine, has been examined as a function of distance, sequence, and base stacking in DNA duplexes covalently modified with ethidium. Over ethidium/deazaguanine separations of 6–27 Å, the photooxidation reaction proceeded on a subnanosecond time scale, and the quenching yield exhibited a shallow distance dependence. The efficiency of the reaction was highly sensitive to small changes in base composition. Moreover, the overall distance-dependence of the reaction is sensitive to sequence, despite the constancy of photoexcited ethidium as acceptor. Conclusions: The remarkable efficiency of deazaguanine photooxidation by intercalated ethidium over long distances provides new evidence for fast electron-transfer pathways through DNA. By varying sequence as well as reactant separation, this work provides the first experimental demonstration of the importance of reactant stacking in the modulation of long-range DNA-mediated electron transfer.
Additional Information
© 1998 Current Biology Publications. Received: 5 May 1998. Revisions requested: 1 June 1998. Revisions received: 5 June 1998. Accepted: 9 June 1998. Published: 21 July 1998. We are grateful to NIH (GM49216) for financial support of this research. We also thank the NIH for a predoctoral traineeship to S.O.K. In addition, we thank R.E. Holmlin for assistance in carrying out the single photon counting experiments.Additional details
- Eprint ID
- 65763
- Resolver ID
- CaltechAUTHORS:20160330-112529738
- NIH
- GM49216
- NIH Predoctoral Fellowship
- Created
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2016-03-30Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field