The interaction of native DNA with Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine

The interaction of native calf thymus DNA with the Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene ortophenylendiimine (ZnL2+ and CuL2+), in 1 mM Tris-HCl aqueous solutions at neutral pH, has been monitored as a function of the metal complex-DNA molar ratio by UV absorption spectro photometry, circular dichroism (CD) and fluorescence spectroscopy. The results support for an intercalative interaction of both ZnL2+ and CuL2+ with DNA, showing CuL2+ an affinity of approximately 10 times higher than ZnL2+. In particular, the values of the binding constant, determined by UV spectrophotometric titration, equal to 7.3 x 10(4) and 1.3 x 10(6) M-1. for ZnL2+ and CuL2+, respectively, indicate the occurrence of a marked interaction with a binding size of about 0.7 in base pairs. The temperature dependence of the absorbance at 258 nm suggests that both complexes strongly increase the DNA melting temperature (Tm) already at metal complex-DNA molar ratios equal to 0.1. As evidenced by the quenching of the fluorescence of ethidium bromide-DNA solutions in the presence of increasing amounts of metal complex, ZnL2+ and CuL2+ are able to displace the ethidium cation intercalated into DNA. A tight ZnL2+-DNA and CuL2+-DNA binding has been also proven by the appearance, in both metal complex-DNA solutions, of a broad induced CD band in the range 350-450 nm. In the case of the CuL2+-DNA system, the shape of the CD spectrum, at high CuL2+ content, is similar to that observed for psi-DNA solutions. Such result allowed us to hypothesize that CuL2+ induces the formation of supramolecular aggregates of DNA in aqueous solutions.