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Direct measurement of hole transport dynamics in DNA

Nature volume 406, pages 51–53 (2000)Cite this article

Abstract

Our understanding of oxidative damage to double helical DNA and the design of DNA-based devices for molecular electronics is crucially dependent upon elucidation of the mechanism and dynamics of electron and hole transport in DNA1,2,3,4. Electrons and holes can migrate from the locus of formation to trap sites1,5, and such migration can occur through either a single-step “superexchange” mechanism or a multistep charge transport “hopping” mechanism6,7,8,9,10,11,12,13,14,15,16,17. The rates of single-step charge separation and charge recombination processes are found to decrease rapidly with increasing transfer distances6,7,8,9, whereas multistep hole transport processes are only weakly distance dependent10,11,12,13. However, the dynamics of hole transport has not yet been directly determined. Here we report spectroscopic measurements of photoinduced electron transfer in synthetic DNA that yield rate constants of ∼ 5 × 107 s-1 and 5 × 106 s-1, respectively, for the forward and return hole transport from a single guanine base to a double guanine base step across a single adenine. These rates are faster than processes leading to strand cleavage, such as the reaction of guanine cation radical with water2, thus permitting holes to migrate over long distances in DNA. However, they are too slow to compete with charge recombination in contact ion pairs6,7, a process which protects DNA from photochemical damage.

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Figure 1: Structures of the stilbene linker and synthetic hairpins.
Figure 2: Structures for the hairpins 3G (panel a) and 3G3 (panel b).
Figure 3: Decay of the transient absorption spectrum of 3G3 probed at 575 nm.
Figure 4: Kinetic scheme for processes occurring in a hairpin containing a single guanine proximal to the stilbene linker and a GG step distal from the stilbene linker.

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Acknowledgements

We thank R. L. Letsinger for discussions. This work was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, US Department of Energy.

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  1. Department of Chemistry, Northwestern University, Evanston , 60208-3113, Illinois, USA

    Frederick D. Lewis, Xiaoyang Liu, Jianqin Liu, Scott E. Miller, Ryan T. Hayes & Michael R. Wasielewski

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  1. Frederick D. Lewis
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Correspondence to Frederick D. Lewis.

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Lewis, F., Liu, X., Liu, J. et al. Direct measurement of hole transport dynamics in DNA. Nature 406, 51–53 (2000). https://doi.org/10.1038/35017524

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