Morgan, Joy L., Spillane, Caitriona B., Smith, Jayden A., Buck, Damian P., Collins, J. Grant, and Keene, F. Richard (2007) Dinuclear ruthenium(II) complexes with flexible bridges as non-duplex DNA binding agents. Dalton Transactions, 38. pp. 4333-4342.

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Abstract

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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