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Metal complexes for DNA-mediated charge transport

Barton, Jacqueline K. and Olmon, Eric D. and Sontz, Pamela A. (2011) Metal complexes for DNA-mediated charge transport. Coordination Chemistry Reviews, 255 (7-8). pp. 619-634. ISSN 0010-8545. PMCID PMC3105778. doi:10.1016/j.ccr.2010.09.002.

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In all organisms, oxidation threatens the integrity of the genome. DNA-mediated charge transport (CT) may play an important role in the generation and repair of this oxidative damage. In studies involving long-range CT from intercalating Ru and Rh complexes to 5′-GG-3′ sites, we have examined the efficiency of CT as a function of distance, temperature, and the electronic coupling of metal oxidants bound to the base stack. Most striking is the shallow distance dependence and the sensitivity of DNA CT to how the metal complexes are stacked in the helix. Experiments with cyclopropylamine-modified bases have revealed that charge occupation occurs at all sites along the bridge. Using Ir complexes, we have seen that the process of DNA-mediated reduction is very similar to that of DNA-mediated oxidation. Studies involving metalloproteins have, furthermore, shown that their redox activity is DNA-dependent and can be DNA-mediated. Long range DNA-mediated CT can facilitate the oxidation of DNA-bound base excision repair proteins to initiate a redox-active search for DNA lesions. DNA CT can also activate the transcription factor SoxR, triggering a cellular response to oxidative stress. Indeed, these studies show that within the cell, redox-active proteins may utilize the same chemistry as that of synthetic metal complexes in vitro, and these proteins may harness DNA-mediated CT to reduce damage to the genome and regulate cellular processes.

Item Type:Article
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URLURL TypeDescription CentralArticle
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2010 Elsevier B.V. Received 21 June 2010; accepted 5 September 2010. Available online 7 October 2010. We are grateful to NIH for their support of this research. We also thank our many colleagues for their efforts and insights, especially Harry Gray, whose seminal work on protein electron transfer, especially that using our favorite flash-quench methodology, inspired many experiments.
Funding AgencyGrant Number
Subject Keywords:DNA electron transfer; Oxidative damage; DNA repair; Iron-sulfur clusters
Issue or Number:7-8
PubMed Central ID:PMC3105778
Record Number:CaltechAUTHORS:20110506-101158648
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Official Citation:Jacqueline K. Barton, Eric D. Olmon, Pamela A. Sontz, Metal complexes for DNA-mediated charge transport, Coordination Chemistry Reviews, Volume 255, Issues 7-8, A Celebration of Harry B. Gray's 75th Birthday, April 2011, Pages 619-634, ISSN 0010-8545, DOI: 10.1016/j.ccr.2010.09.002.
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:23570
Deposited By: Tony Diaz
Deposited On:22 Jun 2011 21:38
Last Modified:09 Nov 2021 16:16

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