Synthesis, Characterization And Properties Of Polyamine And Pantent Macrocyclic Complexes

This dissertation uses polyamines and macrocyclic complexes asresearch o ctions of the complexes with calf thymus （CT） DNA and nucleaseactivities of the complexes. Four novel metal complexes,[CuL¹Cl₂]（?）,[MnL²]（ClO₄）₂2,[Ni₂2L（OAc）]（ClO₄）CH₃CN₃,[MnL³]（ClO₄）₂0.25（H₂O）（?）have been synthesized and characterized by infrared spectra, elementalanalysis, ES-MS spectrum and X-ray single crystal diffraction. Theinteractions of the complexes with CT-DNA have been measured byspectroscopy, viscosity and electrochemical measurements. In the end, thehydrolysis of（?）-nitrophenyl phosphate catalyzed by complex（?）have been alsoinvestigated.The work is composed of:1. A new mononuclear copper polyamine complex has been preparedfrom N,N-bis（3-aminopropyl）-4-methoxybenzylamine, and characterized byelemental analysis and ES-MS spectrum. X-ray single crystal diffractiontechniques indicate that the copper atom was five-coordinated displaying asquare-pyramidal configuration. The interactions of the complexes withCT-DNA have been systematically analysed by spectroscopy, viscosity andelectrochemical measurements. The UV absorption of complex （?）have ahyperchromicity under the influence of the solution of the CT-DNA,considering the the calculated binding constants （Kb） values and Stern-Volmerquenching constants, and a mode of electrostatic was deduced. The agarosegel electrophoresis studies show an efficient cleavage activity of complex（?）,and the complex cleaves pBR32（?）DNA via a hydrolytic pathway.2. N,N′-bis（2-thiophene）-N,N′-bis（3-formyl-5-methyl-salicylaldehyde）ethylenediamine （H₂L²） was obtained from N,N′-bis（2-thiophene）-1,2-diaminoethane and3-bromomethyl-5-methyl-salicyladehyde. Two newmacrocyclic complexes were synthesized from the ligand H₂L². The ES-MS spectrum show that complex （?）and（?）are stable enough in methanol solution.3. Binding modes of the complexes （?）and（?）with CT-DNA wereinvestigated via UV-vis absorption, respectively. The results of theexperiments show the two complexes interact with DNA may be intercalativemodes, and the binding affinity of complex（?）is stronger than that of complex（?）. The agarose gel electrophoresis studies show that both the complexes cantransform the supercoiled （SC） to nicked circular （NC） DNA form, and thecleavage activity both increases with increasing the concentration of the twocomplexes, respectively. Hydrolysis of（?）-nitrophenyl phosphate catalyzed bythe complex （?）and（?）were investigated by UV absorption spectroscopy.Complex（?）exhibits a more efficient catalysis than that of（?）, which can beconfirmed as an excellent enzyme reagent for phosphate hydrolysis.4. N,N′-bis（2-pyridin）-N,N′-bis（3-formyl-5-methyl-salicylaldehyde）ethylenediamine （H2L3） was obtained fromN,N′-bis（2-pyridin）-1,2-diaminoethane and3-bromomethyl-5-methyl-salicyladehyde. The macrocyclic complex（?） was synthesized from the ligandH32L, and were characterized by X-ray single crystal diffraction. Theinteraction between the complex and the CT-DNA was monitored by theexperiment, and the cleavage activity of complex（?） was studied by agarosegel electrophoresis.