Mixed-ligand complexes of copper(II) ions with AMP and CMP in the systems with polyamines and non-covalent interaction between bioligands.

The occurrence of non-covalent interactions and formation of molecular complexes between adenosine 5'-monophosphate (AMP) or cytidine 5'-monophosphate (CMP) and the polyamines, putrescine, 1,7-diamino-4-azaheptane (3,3-tri), spermidine and 1,11-diamino-4,8-diazaundecane (3,3,3-tet), were detected in metal-free systems. The stoichiometric composition of the adducts and their stability constants were determined on the basis of computer analysis of the titration data, taking into account the fact that the acid-base properties of the system change as a result of these interactions. Spectral analysis allowed an identification of the interaction centers in the adducts as protonated amine groups of polyamines, phosphate groups as well as nitrogen atoms of high electron density from nucleotides. Unexpectedly, no participation of the phosphate group from AMP in the formation of molecular complexes with tetramine-3,3,3-tet was detected. The stoichiometric composition and stability constants of mixed-ligand complexes in the systems of Cu(II) with AMP or CMP and polyamines were obtained. Analysis of the results of equilibrium studies and 13C, 31PNMR, UV-Vis, IR and EPR data permitted determination of the mode of coordination. In the systems with metal ions, the formation of molecular complexes Cu(CMP)H4(3,3-tri) was found, apart from heteroligand complexes of the MLL' and MLL'Hx type. In protonated complexes the occurrence of non-covalent interactions leading to stabilization of the coordination compounds was observed. The differences in the character of coordination biogenic amines and their biologically inactive analogs were identified.