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Paper
Dalton Trans., 2007, 4333 - 4342, DOI: 10.1039/b706747j
Dinuclear ruthenium(II) complexes with flexible bridges as non-duplex DNA binding agents
Joy L. Morgan, Caitriona B. Spillane, Jayden A. Smith, Damian P. Buck, J. Grant Collins and F. Richard Keene
The stereoisomers of a series of dinuclear ruthenium(II) complexes [{Ru(phen)2}2(µ-BL)]4+ (phen = 1,10-phenanthroline) with flexible bridging ligands (BL) bb2 {1,2-bis[4(4
-methyl-2,2-bipyridyl)]ethane}, bb5 {1,5-bis[4(4-methyl-2,2-bipyridyl)]pentane}, bb7 {1,7-bis[4(4-methyl-2,2-bipyridyl)]heptane}, and bb10 {1,10-bis[4(4-methyl-2,2-bipyridyl)]decane} have been synthesised. Their binding to a control dodecanucleotide, d(CCGGAATTCCGG)2, and a tridecanucleotide, d(CCGAGAATTCCGG)2, which contains a single adenine bulge have been studied using fluorescence displacement assays involving intercalating and groove-binding dyes, equilibrium dialysis and binding affinity chromatography. The fluorescence intercalator displacement (FID) assay indicated that 
-[{Ru(phen)2}2(µ-bb7)]4+ had the greatest binding affinity with all the oligonucleotides, whereas an analogous fluorescence technique using a minor-groove binding dye, equilibrium dialysis and affinity binding chromatography showed that 
-[{Ru(phen)2}2(µ-bb7)]4+ had the strongest binding. An 1H NMR study of the binding of the -enantiomer of [{Ru(phen)2}2(µ-bb7)]4+ to d(CCGAGAATTCCGG)2 confirmed the selectivity of the metal complex for the bulge site and provided the basis for an energy-minimised binding model of the dinuclear ruthenium complex with the single adenine bulge containing trinucleotide. The binding model demonstrated the ability of the flexibly-linked complex to follow the curvature of the DNA minor groove.
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