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Luminescent Properties of Ruthenium(II) Complexes with Sterically Expansive Ligands Bound to DNA Defects

McConnell, Anna J. and Lim, Mi Hee and Olmon, Eric D. and Song, Hang and Dervan, Elizabeth E. and Barton, Jacqueline K. (2012) Luminescent Properties of Ruthenium(II) Complexes with Sterically Expansive Ligands Bound to DNA Defects. Inorganic Chemistry, 51 (22). pp. 12511-12520. ISSN 0020-1669. PMCID PMC3622160. doi:10.1021/ic3019524.

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A new family of ruthenium(II) complexes with sterically expansive ligands for targeting DNA defects was prepared, and their luminescent responses to base pair mismatches and/or abasic sites were investigated. Design of the complexes sought to combine the mismatch specificity of sterically expansive metalloinsertors, such as [Rh(bpy)_2(chrysi)]^(3+) (chrysi = chrysene-5,6-quinone diimine), and the light switch behavior of [Ru(bpy)_2(dppz)]^(2+) (dppz = dipyrido[3,2-ɑ:2′,3′c]phenazine). In one approach, complexes bearing analogues of chrysi incorporating hydrogen-bonding functionality similar to dppz were synthesized. While the complexes show luminescence only at low temperatures (77 K), competition experiments with [Ru(bpy)_2(dppz)]^(2+) at ambient temperatures reveal that the chrysi derivatives preferentially bind DNA mismatches. In another approach, various substituents were introduced onto the dppz ligand to increase its steric bulk for mismatch binding while maintaining planarity. Steady state luminescence and luminescence lifetime measurements reveal that these dppz derivative complexes behave as DNA “light switches” but that the selectivity in binding and luminescence with mismatched/abasic versus well-matched DNA is not high. In all cases, luminescence depends sensitively upon structural perturbations to the dppz ligand.

Item Type:Article
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URLURL TypeDescription CentralArticle
McConnell, Anna J.0000-0001-7329-4319
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2012 American Chemical Society. Received: September 6, 2012. Published: October 31, 2012. We thank the NIH (GM33309 to J.K.B.) for their financial support, the Lindemann Trust for a postdoctoral fellowship to A.J.M., the Tobacco-Related Disease Research Program (TRDRP) for a postdoctoral fellowship to M.H.L., and a Dissertation Research Award to H.S. We also thank Dr. Eva Rüba for developing the synthesis of [Ru(bpy)2(chrysi)]2+ and Jessica Yeung for carrying out preliminary studies. We are grateful to the Beckman Institute Laser Resource Center (BILRC) at Caltech for facilities.
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Lindemann TrustUNSPECIFIED
California Tobacco-Related Disease Research ProgramUNSPECIFIED
Issue or Number:22
PubMed Central ID:PMC3622160
Record Number:CaltechAUTHORS:20130116-113416623
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Official Citation:Luminescent Properties of Ruthenium(II) Complexes with Sterically Expansive Ligands Bound to DNA Defects Anna J. McConnell, Mi Hee Lim, Eric D. Olmon, Hang Song, Elizabeth E. Dervan, and Jacqueline K. Barton Inorganic Chemistry 2012 51 (22), 12511-12520
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:36428
Deposited By: Ruth Sustaita
Deposited On:16 Jan 2013 21:05
Last Modified:09 Nov 2021 23:22

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