Synthesis, Characterization And Biological Activities Of Macrocyclic Polyamine Complexes

Polyamines and macrocyclic complexes were used as research objects, and the synthesis, characterization and biological activities of them were studied in this dissertation. And four new complexes, [Cu(4,4'-bipy)LO]·ClO₄ 1 , [Ni₂L¹(OAc)]·ClO₄·H₂O 2 , [Ni₂L²(OAc)]·ClO₄ 3 , [Co₂L¹(OAc)]·1.5(ClO₄)·0.5Na·2(CH₃OH) 4 have been synthesized and characterized by infrared spectra, elemental analysis, ES-MS spectrum and X-ray single crystal diffraction, where L = N,N-bis(3-aminopropyl)-4-methoxybenzylamine, and the ligand L¹ and L² are [2+2] condensation products between N,N-bis(3-aminopropyl)-4-methoxybenzylamine and 2,6-diformyl -4-methyl (bromine)phenol in the presence of metal ions. The interactions of the complexes with CT-DNA have been measured by spectroscopy, viscosity and electrochemical measurements. The agarose gel electrophoresis studies were also did.The work is composed of:1. N,N-bis(3-aminopropyl)-4-methoxybenzylamine has been prepared from 4-methoxybenzylamine and characterized by infrared spectra and 1HNMR. A new mononuclear copper polyamine complex has been synthesized and the X-ray crystallographic analysis shows the coordination of Cu2+ is five-coordinated square pyramid. The interactions of complex 1 with DNA have been measured by spectroscopy, viscosity and electrochemical measurements, and a mode of electrostatic was deduced. The agarose gel electrophoresis studies show a low cleavage activity of complex 1 to pBR 322 DNA.2. Complex 2,3,4 have been synthesized by [2+2] cyclo-condensation between N, N - bis (3-aminopropyl)-4-methoxybenz ylamine and 2,6-diformyl-4-methyl(bromine)phenol, and the X-ray crystallographic analysis show the similar crystal structures of the three complexes. All the two metal ions are bridged byμ2-OAc in the three complexes, and 4-methoxyphenoethyl groups are situated in the same side of the convexity of the distorted macrocycle. The ES-MS spectra of complex 2, 3, 4 show that all the three complexes are stable in methanol solution.3. Complex 2, 3, 4 have different binding mode with DNA. The UV absorption, fluorescence spectroscopy, CD spectra and viscosity measurements show that complex 2, 3 may be have a moderate intercalation mode, and the binding affinity of complex 2 is stronger than complex 3. Different from complex 2, 3, the UV absorption of complex 4 have a hyperchromicity, and the viscosity of CT-DNA binding with complex 4 is decreased. These phenomenons show a groove binding of complex 4 with DNA. The agarose gel electrophoresis studies show a cleavage activity of complex 2, 3, 4, and a hydrolytic pathway cleavage was proposed.