Synthesis, characterization, DNA-binding and cleavage studies of polypyridyl copper(II) complexes

Abstract

Six new mixed-ligand copper(II) complexes were synthesized namely [Cu(phen)2OAc]ClO4⋅H2O(1), [Cu(bpy)2OAc]ClO4⋅H2O(2), [Cu(o-ampacac)(phen)]ClO4(3), [Cu(o-ampbzac)(phen)]ClO4(4), [Cu(o-ampacac)(bpy)]ClO4(5), and [Cu(o-ampbzac)(bpy)]ClO4(6) (phen=1,10-phenanthroline, bpy=2, 2′-bipyridine, o-ampacac=(Z)-4-(2-hydroxylamino)pent-3-ene-2-one,o-ampbzac=(Z)-4-(2-hydroxylamino)-4-phenylbut-3-ene-2-one)and characterized by UV–Vis, IR, EPR and cyclic voltammetry. Ligands were characterized by NMR spectra. Single crystal X-ray studies of the complex 1 shows Cu(II) ions are located in a highly distorted octahedral environment. Absorption spectral studies reveal that the complexes 1–6 exhibit hypochromicity during the interaction with DNA and binding constant values derived from spectral and electrochemical studies indicate that complexes 1, 2 and 3 bind strongly with DNA possibly by an intercalative mode. Electrochemical studies reveal that the complexes 1–4 prefer to bind with DNA in Cu(I) rather than Cu(II) form. The shift in the formal potentials E1/2 and CD spectral studies suggest groove or electrostatic binding mode for the complexes 4–6. Complex 1 can cleave supercoiled (SC) pUC18 DNA efficiently into nicked form II under photolytic conditions and into an open circular form (form II) and linear form (form III) in the presence of H2O2 at pH 8.0 and 37°C, while the complex 2 does not cleave DNA under similar conditions.