Study On The Polyamine Complexes As Nitric Oxide Scavenger

Novel type of macrocyclic polyamine complexes were chosen as the research target of the thesis, and the synthesis, characterizations, properties and theoretical analyses of the ligand predecessors and macrocyclic complexes were the research contents. The special attentions were focused on the synthesis of the macrocyclic polyamine complexes with heterocyclic(pyridine ring, furan ring and thiophene ring)pendant-arms, and scavengers of small molecules in biological condition. In order to study the effects of different combination of metal ions in polynuclear complexes, the cavity size of the macrocycle and the peripheral pendants of the ligands on the crystal structures and biological activity of the complexes, six new such type of complexes have been prepared and characterized by X-ray diffractions techniques. NO bounding,DNA cleavage activity have been studied by UV-Vis, gel electrophoresis, respectively.The major works include the following aspects:Through two step reactions, such as addition and hydrogenation catalysts,N,N?-bis(3-aminopropyl)-3-pyridylmethylamine was synthesized in present of 3-pyridylmethylamine. In accordance with this method, N,N?-bis(3-aminopropyl)-2- furanylmethylpolyamines and N,N?-bis(3-aminopropyl)-2-thienylethylpolyamines were prepared.Six unreported asymmetrical mononuclear copper(II) complexes heterocyclic cantilever were synthesized in present of branched polyamines, 2,6-diformyl-4-X(CH3, Cl, F)phenol and ethylene diamine or 1,2-propanediamine. The X-ray diffraction results of the complexes reveal that a square-pyramidal was constituted with one copper(II) ion, two imine N and two protonated phenol O. The nitrogen atom in the pyridine ring coordinated with metal ion in the neighboring macrocyclic complex to form an one-dimensional coordination polymer in complexes 1 and 2.Each unit was surrounded with a free perchlorate and a water molecule. Three asymmetrical mononuclear macrocyclic complexes 3-5 with pendant arm containing thiophene group were obtained by cyclocondensation between 2,6-diformyl-4-X(CH3,Cl, F)phenol, 1,2-diaminopropane and N,N?-bis(3-aminopropyl)-2-thienylethylpoly-amines. The X-ray diffraction results reveal that complex 3 was a dimer by Cu-Oph between two adjacent units. Complex 6 was synthesized in present of N,N?-bis(3-aminopropyl)-2-furanylmethylpolyamines, 1,2-propanediamine and 2,6- diformyl-4-methylphenol.Complexes 1-6 and 7-9 which were preliminary synthesized to bind NO were studied by UV/Vis spectrophotometry, the results show that those complexes can bind with NO, and the binding is irreversible. The gel electrophoresis diagram show that the complexes 1-6 exhibit weak DNA cleavage activity.Branched-chain polyamines and mononuclear unsymmetrical complexes were synthesized. The interaction of complexes with DNA or small molecules was researched to seek good complexes those can eliminate harmful small molecules without hurting biomolecules as nitric oxide scavengers in vivo. Experimental data was provided as the basis of the research and development of drug design,as well as new analog design and synthesis of enzymes provide alternative pathways.