Synthesis, Characterization And Biological Activities Of Polyamine Complexes With Phenoxide Groups

This dissertation mainly synthesis two kinds of metal complexes:one are open chain complexes, the other are unsymmetrical macrocyclecomplexes, which are fully characterized by Elemental analyses, IRspectra, Electrospray mass spectrum, X-ray single crystal diffraction.The interactions of the complexes with CT-DNA have been measured byUV-Vis spectra, fluorescence spectra（competitive between complexesand EB）, viscosity and cyclic voltammogram. Part of their hydrolysisactivities when simulate the phosphatase enzymes also have beenstudied.The work is composed of:1. Open-loop complex [Cu₂L1（OAc）（CH₃OH）]·CH₃OH1has beenprepared from the condensation reaction of2-hydroxyl-1,3-propanediamine with5-Methylsalicylaldehyde.（?） is dinuclear copper （Ⅱ）complexes bridging by mono molar phenoloxide and one molar OAc-,copper （II） ions can be described as a tetrahedron and a planequadrilateral, UV-Vis spectras exhibit the binding constants of[Cu₂L1（OAc）（CH₃OH）]·CH₃OH （?） is1.16×105M^-1, and suggest that thecompounds bind to DNA via the intercalation mode. Fluorescencespectras show Stern-Volmer quenching constants of （?） is4.89×102M^-1.The two center copper ions with distances of3.306. The cleavageactivity of complex [Cu₂¹L（OAc）（CH₃OH）]·CH₃OH （?） to pBR322DNAis via hydrolytic mode.2. Another two unsymmetrical macrocyclic complexes are asfllowed:[CuNiL²]·（ClO₄）₂（?）,[Cu₂L²]·（OAc）（?）, in this paper asymmetricsynthesis method was taken out, firstly two molar2,6-Diformyl-4-CH₃-phenol react with1molar ethanediamine to get asymmetric semi-ring N,N-bis（3-formyl-5-CH₃-salicylidene）ethylene-diimine, the coordinationpolyhedrons of nickel ion and copper ion in complex [CuNiL²]·（ClO₄）₂（?）can be described as a plane quadrilateral and a octahedron. BNPP istaken as substrate, research their activity of hydrolysis, the results indicate the complexes [CuNiL²]·（ClO24）₂（?） and [Cu₂L]·（OAc）（?） enhancethe hydrolysis affinity by10⁹times compared to its self-hydrolysis.3. Open-loop schiff base complexes [NiL³]·H₂O（?）,[Ni（L⁴）]（?） havebeen prepared from the condensation reation of5-chlorosalicylaldehydewith ethylenediami or N,N-bis（3-aminopropyl）-4-methoxybenzylamine.Both of the complex [NiL³]·H₂O （?） and complex [Ni（L⁴）]（?） aremononuclear nickel complexes whose metal coordination environmentcan be described as a six-coordinated distorted octahedron. UV-Visspectras exhibit the binding constants of [NiL³]·H₂O （?）,[Ni（L⁴）]（?） are0.71×10²M^-1，0.2310²M^-1, and suggest that the compounds bind toDNA via the electrostatic binding mode. Fluorescence spectras showStern-Volmer quenching constants of [NiL³]·H₂O （?）,[Ni（L⁴）]（?） are5.72×10²M^-1，1.46×10³M^-1. The two center copper ions with distances of3.306. The cleavage activity of complex [NiL³]·H₂O （?）,[Ni（L⁴）]（?） topBR322DNA are via hydrolytic mode, and [NiL³]·H₂O （?） has higherthan that of [Ni（L⁴）]（?）.