DNA-Mediated Charge Transport Requires Conformational Motion of the DNA Bases: Elimination of Charge Transport in Rigid Glasses at 77 K
- Creators
- O'Neill, Melanie A.
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Barton, Jacqueline K.
Abstract
We have proposed that DNA-mediated charge transport (CT) is gated by base motions, with only certain base conformations being CT-active; a CT-active conformation can be described as a domain, a transiently extended π-orbital defined dynamically by DNA sequence. Here, to explore these CT-active conformations, we examine the yield of base-base CT between photoexcited 2-aminopurine (Ap*) and guanine in DNA in rigid LiCl glasses at 77 K, where conformational rearrangement is effectively eliminated. Duplex DNA assemblies (35-mers) were constructed containing adenine bridges Ap(A)_nG (n = 0−4). The yield of CT was monitored through fluorescence quenching of Ap* by G. We find, first, that the emission intensity of Ap* in all DNA duplexes increases dramatically upon cooling and becomes comparable to free Ap*. This indicates that all quenching of Ap* in duplex DNA is a dynamic process that requires conformational motion of the DNA bases. Second, DNA-mediated CT between Ap* and G is not observed at 77 K; rather than hindering the ability of DNA to transport charge, conformational motion is required. Moreover, the lack of DNA-mediated CT at 77 K, even through the shortest bridge, suggests that the static structures adopted upon cooling do not represent optimum CT-active conformations. These observations are consistent with our model of conformationally gated CT. Through conformational motion of the DNA bases, CT-active domains form and break-up transiently, both facilitating and limiting CT.
Additional Information
© 2004 American Chemical Society. Received July 22, 2004. Publication Date (Web): September 25, 2004. We acknowledge the NIH and NFCR. M.A.O. thanks NSERC for a postdoctoral fellowship.Attached Files
Supplemental Material - ja0455897si20040722_115211.pdf
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Additional details
- Eprint ID
- 76802
- DOI
- 10.1021/ja0455897
- Resolver ID
- CaltechAUTHORS:20170421-084130900
- NIH
- National Foundation for Cancer Research
- Natural Sciences and Engineering Research Council of Canada (NSERC)
- Created
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2017-04-21Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field