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Long-range oxidation of guanine by Ru(III) in duplex DNA

Arkin, Michelle R. and Stemp, Eric D. A. and Pulver, Sabine Coates and Barton, Jacqueline K. (1997) Long-range oxidation of guanine by Ru(III) in duplex DNA. Chemistry and Biology, 4 (5). pp. 389-400. ISSN 1074-5521. doi:10.1016/S1074-5521(97)90129-0.

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Background: Theoretical and experimental studies have demonstrated that 5′-GG-3′ sequences in DNA are ‘hot spots’ for oxidative damage, but few studies have definitively addressed whether oxidative damage to DNA may arise from a distance via long-range charge migration. Towards this end, we have prepared tethered ruthenium (Ru)-oligonucleotide duplexes and used a flash—quench strategy to demonstrate long-range charge transport through the DNA double helix. Results: DNA assemblies containing a tethered Ru(II) intercalator have been synthesized. Ru(III), generated in situ in the presence of externally bound electron-transfer quenchers, promotes base damage selectively at the 5′-G of a 5′-GG-3′ doublet located ∼ 37 Å from the binding site of the oxidant. In the absence of a guanine doublet, oxidative damage occurs equally at all guanine bases in the strand. Oxidative damage is also observed at long range for guanine in a G·A mismatch but not in a G·T mismatch. Conclusions: The present study expands the scope of long-range electron-transfer chemistry in terms of experiments, applications, and possible reactions within the cell. Here we demonstrate oxidative damage to DNA occurring with a high quantum yield over a distance of ∼37 Å using a ground-state oxidant. These results point to the equilibration of the radical across the DNA duplex to the sites of lowest energy. In addition, this charge migration is sensitive to the intervening π-stack formed by DNA base pairs and hence may be useful for the detection of mismatches.

Item Type:Article
Related URLs:
URLURL TypeDescription
Stemp, Eric D. A.0000-0003-2098-4214
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 1997 Current Biology Ltd. Received: 19 February 1997. Revisions requested: 20 March 1997. Revisions received: 24 April 1997. Accepted: 28 April 1997. We are grateful to the NIH (GM 49216) for their financial support of this work. In addition, we thank the NIH for predoctoral trainee support (M.R.A.) and a postdoctoral fellowship (S.C.P.). and the American Cancer Society for postdoctoral support (E.D.A.S.). We also thank J. Winkler for helpful discussions.
Funding AgencyGrant Number
NIHGM 49216
NIH Predoctoral FellowshipUNSPECIFIED
American Cancer SocietyUNSPECIFIED
Subject Keywords:base mismatch; electron transfer; metallointercalator; oxidative DNA repair; radical migration
Issue or Number:5
Record Number:CaltechAUTHORS:20160330-112529436
Persistent URL:
Official Citation:Michelle R. Arkin, Eric D.A. Stemp, Sabine Coates Pulver, Jacqueline K. Barton, Long-range oxidation of guanine by Ru(III) in duplex DNA, Chemistry & Biology, Volume 4, Issue 5, May 1997, Pages 389-400, ISSN 1074-5521, (
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:65762
Deposited By: Ruth Sustaita
Deposited On:30 Mar 2016 21:24
Last Modified:10 Nov 2021 23:49

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