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DNA is not a molecular wire: Protein-like electron-transfer predicted for an extended π-electron system

Publication ,  Journal Article
Priyadarshy, S; Risser, SM; Beratan, DN
Published in: Journal of Physical Chemistry
October 31, 1996

The earliest studies of electron-transfer proteins1 raised the question of whether or not π-electron residues might facilitate electron transport.2 Three recent long-range electron-transfer experiments utilizing DNA bridges revisit this provocative, yet unresolved, question.3,4,5 The distance dependence of electron transfer in DNA is not a matter of purely academic concern; it controls the mechanism of DNA damage and repair in cells and is being exploited in new molecular probes of DNA sequence. We present a theoretical analysis based upon very large scale self-consistent-field quantum calculation of all valence electrons (as many as ∼3300) in these three systems This computation is the first performed on such large macromolecules and also the first to extract long-range electronic interactions at this level of theory. DNA electron transfer is found to be mediated by through-space interactions between the π-electron-containing base pairs, but the magnitude of the coupling facilitated by this channel drops rapidly with distance, as a consequence of the ∼3.4 Å noncovalent gap between base pairs. These, predictions are in agreement with most of the experimental data. The rapid decay of electron-transfer rates with distance computed here suggests that biologically controlled DNA electron-transfer events, of importance in DNA repair,6 must function over relatively short range. Moreover, the predicted distance dependence of electron transfer in DNA is strikingly close to that found in proteins. © 1996 American Chemical Society.

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Published In

Journal of Physical Chemistry

DOI

ISSN

0022-3654

Publication Date

October 31, 1996

Volume

100

Issue

44

Start / End Page

17678 / 17682
 

Citation

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Priyadarshy, S., Risser, S. M., & Beratan, D. N. (1996). DNA is not a molecular wire: Protein-like electron-transfer predicted for an extended π-electron system. Journal of Physical Chemistry, 100(44), 17678–17682. https://doi.org/10.1021/jp961731h
Priyadarshy, S., S. M. Risser, and D. N. Beratan. “DNA is not a molecular wire: Protein-like electron-transfer predicted for an extended π-electron system.” Journal of Physical Chemistry 100, no. 44 (October 31, 1996): 17678–82. https://doi.org/10.1021/jp961731h.
Priyadarshy S, Risser SM, Beratan DN. DNA is not a molecular wire: Protein-like electron-transfer predicted for an extended π-electron system. Journal of Physical Chemistry. 1996 Oct 31;100(44):17678–82.
Priyadarshy, S., et al. “DNA is not a molecular wire: Protein-like electron-transfer predicted for an extended π-electron system.” Journal of Physical Chemistry, vol. 100, no. 44, Oct. 1996, pp. 17678–82. Scopus, doi:10.1021/jp961731h.
Priyadarshy S, Risser SM, Beratan DN. DNA is not a molecular wire: Protein-like electron-transfer predicted for an extended π-electron system. Journal of Physical Chemistry. 1996 Oct 31;100(44):17678–17682.

Published In

Journal of Physical Chemistry

DOI

ISSN

0022-3654

Publication Date

October 31, 1996

Volume

100

Issue

44

Start / End Page

17678 / 17682