Molecular Recognition of Metal Complexes by DNA: A Comparative Study of the Interactions of the Parent Complexes [PtCl(TERPY)]Cl and [AuCl(TERPY)]Cl2with Double Stranded DNA

Abstract

The interactions of the parent complexes [AuCl(Terpy)]Cl2and [PtCl(Terpy)]Cl with DNA were analysed by various physicochemical methods. Surprisingly, these metal complexes produce different interaction patterns with DNA in spite of their profound structural similarity. Indeed, important modifications are detected in the characteristic UV-Vis bands of [PtCl(Terpy)]Cl upon addition ofct-DNA, while the spectrum of [AuCl(Terpy)]Cl2is almost unaffected. Gel electrophoresis studies confirm these findings: [PtCl(Terpy)]Cl — but not [AuCl(Terpy)]Cl2— retards significantly the mobility of the supercoiled form of the pHV14 plasmid after a short incubation time. Ultrafiltration studies indicate that the affinity of [PtCl(Terpy)]Cl forct-DNA is significantly greater than that of [AuCl(Terpy)]Cl2. On the other hand, both [AuCl(Terpy)]Cl2and [PtCl(Terpy)]Cl induce important changes in the CD spectrum ofct-DNA, at high concentration, and increase its Tmvalue. Remarkably, the analysed metal-complex/DNA interaction patterns depend critically on the incubation times. We propose that [PtCl(Terpy)]Cl quickly intercalates DNA; then, formation of coordinative bonds progressively takes place with time. At variance, [AuCl(Terpy)]Cl2first interacts electrostatically with the DNA surface, with subsequent slow formation of some coordinative bonds.