A study of the interactions of some polypyridylruthenium(II) complexes with DNA using fluorescence spectroscopy, topoisomerisation and thermal denaturation

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Abstract
The nature of binding of Ru(phen)32+ (I), Ru(bipy) 32+. (II), Ru(terpy) 22+ (III) (phen = 1,10-phenanthroline, bipy = 2,2′-bipyridyl, terpy = 2,2′2,′′ −terpyridyl) to DNA, poly[d(G−C)] and poly[d(A-T)] has been compared by absorption, fluorescence, DNA melting and DNA unwinding techniques. I binds intercalatively to DNA in low ionic strength solutions. Topoisomerisation shows that it unwinds DNA by 22°±1 per residue and that it thermally stabilizes poly[d(A-T)] in a manner closely resembling ethidium. Poly[d(A-T)] induces greater spectral changes on I than poly[d(G-C)] and a preference for A−T rich regions is indicated. I binding is very sensitive to Mg2+ concentration. In contrast to I the binding of II and III appears to be mainly electrostatic in nature, and causes no unwinding. There is no evidence for the binding of the neutral Ru(phen)2(CN)2 or Ru(bipy)2(CN)2 complexes. DNA is cleaved, upon visible irradiation of aerated solutions, in the presence of either I or II.