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[Ru(bpy)_2(L)]Cl_2: Luminescent Metal Complexes That Bind DNA Base Mismatches

Ruba, Eva and Hart, Jonathan R. and Barton, Jacqueline K. (2004) [Ru(bpy)_2(L)]Cl_2: Luminescent Metal Complexes That Bind DNA Base Mismatches. Inorganic Chemistry, 43 (15). pp. 4570-4578. ISSN 0020-1669. doi:10.1021/ic0499291. https://resolver.caltech.edu/CaltechAUTHORS:20160229-120833802

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Abstract

Here we report the synthesis of luminescent ruthenium complexes that bind DNA base pair mismatches. [Ru(bpy)_2(tpqp)]Cl_2 (tpqp = 7,8,13,14-tetrahydro-6-phenylquino[8,7-k][1,8]phenanthroline), [Ru(bpy)_2(pqp)]Cl_2 (pqp = 6-phenylquino[8,7-k][1,8]phenanthroline), and [Ru(bpy)_2(tactp)]Cl_2 [tactp = 4,5,9,18-tetraazachryseno[9,10-b]triphenylene] have been synthesized, and their spectroscopic properties in the absence and presence of DNA have been examined. While [Ru(bpy)_2(pqp)]^(2+) shows no detectable luminescence, [Ru(bpy)_2(tpqp)]^(2+) is luminescent in the absence and presence of DNA with an excited-state lifetime of 10 ns and a quantum yield of 0.002. Although no increase in emission intensity is associated with binding to mismatch-containing DNA, luminescence quenching experiments and measurements of steady-state fluorescence polarization provide evidence for preferential binding to oligonucleotides containing a CC mismatch. Furthermore, by marking the site of binding through singlet oxygen sensitized damage, the complex has been shown to target a CC mismatch site directly with a specific binding affinity, K_b = 4 × 10^6 M^(-1). [Ru(bpy)_2(tactp)]^(2+), an analogue of [Ru(bpy)_2(dppz)]^(2+) containing a bulky intercalating ligand, is luminescent in aqueous solution at micromolar concentrations and exhibits a 12-fold enhancement in luminescence in the presence of DNA. The complex, however, tends to aggregate in aqueous solution; we find a dimerization constant of 9.8 × 10^5 M^(-1). Again, by singlet oxygen sensitization it is apparent that [Ru(bpy)_2(tactp)]^(2+) binds preferentially to a CC mismatch; using a DNase I footprinting assay, a binding constant to a CC mismatch of 8 × 10^5 M^(-1) is found. Hence results with these novel luminescent complexes support the concept of using a structurally demanding ligand to obtain selectivity in targeting single base mismatches in DNA. The challenge is coupling the differential binding we can obtain to differential luminescence.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ic0499291DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic0499291PublisherArticle
ORCID:
AuthorORCID
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2004 American Chemical Society. Received January 16, 2004. Publication Date (Web): May 26, 2004. We gratefully acknowledge the NIH (GM33309) for financial support of this work. E.R. also thanks the FWF for a postdoctoral fellowship.
Funders:
Funding AgencyGrant Number
NIHGM33309
FWF Der WissenschaftsfondsUNSPECIFIED
Issue or Number:15
DOI:10.1021/ic0499291
Record Number:CaltechAUTHORS:20160229-120833802
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20160229-120833802
Official Citation:[Ru(bpy)2(L)]Cl2: Luminescent Metal Complexes That Bind DNA Base Mismatches Eva Rüba,Jonathan R. Hart, and Jacqueline K. Barton Inorganic Chemistry 2004 43 (15), 4570-4578 DOI: 10.1021/ic0499291
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:64854
Collection:CaltechAUTHORS
Deposited By:INVALID USER
Deposited On:29 Feb 2016 20:35
Last Modified:10 Nov 2021 23:36

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