Electron transfer in DNA: predictions of exponential growth and decay of coupling with donor-acceptor distance
Abstract
Experimental and theoretical work indicates the importance of protein structure in controlling electron-transfer (ET) reactions. Recently, great interest has been shown in exploring electronic coupling interactions in DNA. We report here that the electronic coupling calculated for a recently synthesized class of DNA oligomers with rigidly attached donors and acceptors displays a remarkable dependence on the nucleic acid structure. Indeed, a reversal in the sign of the exponential decay parameter is found in some cases if the donor-acceptor couplings are fit to a single exponential expression. The sign reversal reflects the inadequacy of single exponential models for describing bridge-mediated electron-transfer reaction rates. These effects in DNA oligomers arise from the three-dimensional structure of the double helix. The couplings do decay monotonically with the tunneling pathway length between donor and acceptor, σl (estimated from tunneling pathway analysis), but not with the direct through-space donor-acceptor separation distance.
Additional Information
© 1993 American Chemical Society. Received November 19, 1992. Support of this research by the Department of Energy's Advanced Industrial Concepts Division (D.N.B.), a National Science Foundation National Young Investigator Award (D.N.B.), and an award from Research Corporation (T.J.M.) is gratefully acknowledged. We also thank the Biological Imaging Center of the Beckman Institute, California Institute of Technology, for generous support.Additional details
- Eprint ID
- 86166
- Resolver ID
- CaltechAUTHORS:20180501-151528555
- Department of Energy (DOE)
- NSF
- Research Corporation
- Caltech Beckman Institute
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2018-05-01Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field