Synthesis, structure and nuclease activity of copper complexes of disubstituted 2,2′-bipyridine ligands bearing ammonium groups

A series of Cu(II) complexes of disubstituted 2,2′-bipyridine bearing ammonium groups [Cu(L1−4)2Br]5+ (1–4, L1 = [5,5′-(Me2NHCH2)2-bpy]2+, L2 = [5,5′-(Me3NCH2)2-bpy]2+, L3 = [4,4′-(Me2NHCH2)2-bpy]2+, L4 = [4,4′-(Me3NCH2)2-bpy]2+ and bpy = 2,2′-bipyridyl) were synthesized, of which complexes 1 and 4 were structurally characterized. Both coordination configurations of Cu(II) ions can be described as distorted trigonal bipyramid. The interaction between all complexes and CT-DNA was evaluated by thermal-denaturation experiments and CD spectroscopy. Results show that the complexes interact with CT-DNA via outside electrostatic interactions and their binding ability follows the order: 1 > 2 > 3 > 4. In the absence of any reducing agents, the cleavage of plasmid pBR322 DNA by these complexes was investigated and the hydrolysis kinetics of DNA was studied in Tris buffer (pH 7.5) at 37 °C. Obtained pseudo-Michaelis–Menten kinetic parameters: 15.0, 13.6, 2.01 and 1.69 h−1 for 1, 2, 3 and 4, respectively, indicate that complexes 1 and 2 exhibit very high DNA cleavage activities. According to their crystal data, the high nuclease activity may be attributed to the strong interaction of the metal moiety and two ammonium groups with phosphate groups of DNA.

Graphical abstractA series of Cu(II) complexes of disubstituted 2,2′-bipyridine bearing ammonium groups at 5,5′- and 4,4′-positions were synthesized. All complexes, especially the two with 5,5′-ammonium groups, exhibit strong DNA cleavage abilities. The high nuclease activity may be attributed to the strong interaction of the metal moiety and two ammonium groups with three adjacent phosphate groups of DNA.Figure optionsDownload full-size imageDownload as PowerPoint slide