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Rapid Radical Formation by DNA Charge Transport through Sequences Lacking Intervening Guanines

Yoo, Jae and Delaney, Sarah and Stemp, Eric D. A. and Barton, Jacqueline K. (2003) Rapid Radical Formation by DNA Charge Transport through Sequences Lacking Intervening Guanines. Journal of the American Chemical Society, 125 (22). pp. 6640-6641. ISSN 0002-7863. doi:10.1021/ja034326u.

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Using the flash-quench technique to probe DNA charge transport in assemblies containing a tethered ruthenium intercalator, the kinetics and yield of methylindole radical formation as a function of DNA sequence were studied by laser spectroscopy and biochemical methods. In these assemblies, the methylindole moiety serves as an artificial base of low oxidation potential. Hole injection and subsequent formation of the methylindole radical cation were observed at a distance of over 30 Å at rates ≥10^7 s^(-1) in assemblies containing no guanine bases intervening the ruthenium intercalator and GMG oxidation site. Radical yield was, however, strikingly sensitive to an intervening base mismatch; no significant methylindole radical formation was evident with an intervening AA mismatch. Also critical is the sequence at the injection site; this sequence determines initial hole localization and hence the probability of hole propagation. With guanine rather than inosine near the site of hole injection, decreased yields of radicals and long-range oxidative damage are observed. The presence of the low-energy guanine site in this case serves to localize the hole and therefore diminish charge transport through the base pair stack.

Item Type:Article
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Stemp, Eric D. A.0000-0003-2098-4214
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2003 American Chemical Society. Received January 24, 2003. Publication Date (Web): May 10, 2003. We are grateful to the NIH for financial support (GM49216).
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Issue or Number:22
Record Number:CaltechAUTHORS:20160208-152837570
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Official Citation:Rapid Radical Formation by DNA Charge Transport through Sequences Lacking Intervening Guanines Jae Yoo, Sarah Delaney, Eric D. A. Stemp, and Jacqueline K. Barton Journal of the American Chemical Society 2003 125 (22), 6640-6641 DOI: 10.1021/ja034326u
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:64317
Deposited By: George Porter
Deposited On:09 Feb 2016 00:01
Last Modified:10 Nov 2021 23:29

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