Dissertation
Dissertation > Mathematical sciences and chemical > Chemistry > Physical Chemistry ( theoretical chemistry ),chemical physics > Structural Chemistry > Complex chemistry ( coordination chemistry )

Structure, Bioactivity and Initial Interaction Research with DNA of Complexes with Aryl-acylhydrazone Containing Carboxylic Acid

Author WuWangZuo
Tutor WangYaoYu;HeShuiYang
School Northwestern University
Course Inorganic Chemistry
Keywords acylhydrazone complexes polypyridyl crystal structure bioactivity DNA
CLC O641.4
Type PhD thesis
Year 2007
Downloads 499
Quotes 2
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The main organic ligands are aryl-acylhydrazones in the paper. On the base of reading abundant literature and analyzing development state, four series-fifty compounds about aryl-acylhydrazones and their mono- and binuclear complexes were synthesized, and characterized by elemental analysis, IR, UV-Vis, FS,1H NMR, thermoanalysis and XRD. At the same time, the bioactivity of some compounds against several plant and animal bacteria has been tested and gained the virulence recursive equation. The active mechanism and intensity of the compounds with CT-DNA were analyzed by UV, FS and fluorescence quench titration. The concrete content is following:1. The synthesis of organic ligands: Three organic aryl-acylhydrazone ligands have been synthesized with different carboxyl group which was mono- and di-hydrazones firstly. They are bi-[N-(propionic acid)] terephthalal diacylhydrazone (C14H14H4O6, L2), bi(2-ketoglutaric acid) terephthalal diacylhydrazone (C18H18N4O10, L3) and (2-ketoglutaric acid)-salicyloyl hydrazone(C12H12N2O6, L4), and obtained the crystal structures of two ligands Ll(N-(2-propionic acid)-salicyloyl hydrazone, C10H10N2O4) and L2. Four ligands determined by elemental analysis, IR, 1H NMR, MS, UV, FS and thermoanalysis.2. The binary complexes of rare earth or transition metal with L1: In mixed solution, Five unreported complexes of N-(2-propionic acid)-salicyloyl hydrazone with RE(NO33·nH2O(RE= La、Pr、Gd、Er) and CuCl2·2H2O respectively were synthesized, And the crystal structures were determined by X-ray single crystal diffraction. The complex structures are different. Two negative univalent tridentate ligands were coordinated viaμ2- bridging mode in the binuclear praseodymium(III) complex. The coordination number is decrease with rare earth ion radius decrease. The coordination modes and valence states are variety in the complexes. And the fluorescent properties were discussed.3. The ternary supermolecule complexes of rare earth or transition metal with L1 and polypyridyl (bipy/phen): In mixed solution, sixteen complexes of N-(2-propionic acid)-salicyloyl hydrazone with rare earth nitrate(RE= La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Yb、Lu and Y) and transition metal(Ni2+,Cd2+)were synthesized firstly. The component and structure of all rare earth complexes are similar except the crystal lattice waters. The crystal structures of three representative complexes(RE = Nd、Eu、Dy) were determined. RE(III) is 9-coordinated by carboxyl O and acyl O atoms and azomethine N atoms of two ligands (H2L and HL forms) and O atom from three water molecules. The coordination polyhedron around RE(III) was described as a monocapped square antiprism. One free 2, 2-dipyridyl and two lattice waters connecting with coordinated water and ligands by hydrogen bonds lie in the crystal cell. The complexes formed a three-dimensional super molecule in space through hydrogen bonds. The structures of [NiHL(bipy)H2O] and [NiHL(phen)H2O]H2O are similar where HL is the tridentate ligand the N-(2-propionic acid)-salicyloyl hydrazone, bipy/phen a bidentate 2, 2-dipyridyl/1,10- and one water, thus generating a distorted octahedral coordination for Ni(II). To binuclear complex [CdHL(bipy)(H2O)2]2·2H2O, Two center ions Cd(II) are connected by twoμ2-bridging carboxyl oxygen. The Cd(II) is seven-coordinated via one water, one tridentate ligand and one bidentate bipy. The coordination polyhedron of Cd(II) can be described as a distorted quadrilateral- triangle underside. The strongπ-πstacking interaction exist between two adjacent bipys.4. The binary complexes of rare earth or transition metal with L2: Fifteen unreported binucleus complexes of bi[N-(propionic acid)] terephthalal diacylhydrazone with rare earth nitrate(RE= La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Yb、Lu and Y)and transition metal(Cu2+, Zn2+)were synthesized. The component and structure of all rare earth complexes are similar except the crystal lattice waters by several characterization. The crystal structure of binuclear Cu complex was determined.5. The binary complexes of rare earth with L4: Thirteen unreported complexes of (2-ketoglutaric acid)-salicyloyl hydrazone with RE(NO33·nH2O (RE= La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Er、Yb、Lu and Y) were synthesized. The component and structure of all rare earth complexes are same but the crystal lattice waters in which are different by several characterization and discussed the bonding feature and spectral properties.6. The biologic activity: The bioactivity of some compounds against three plant bacteria(Botrytis cirerea Pers.ex Tris., Alternaria alternata (Fries) keissler and Wheat rust). The animal bacteria are Gram-positive bacteria (Staphylococcin aureus), Gram-negative bacteria (Coliforms and Salmonella typhimurium) and leukemia K562. The result showed that all compounds possessed a certain bacteriostasis activity against three plant bacteria and Coliforms. By relativity analyses, the virulence regress equations were obtained for L2 and Dy (H2L)(HL)·0.5bipy5H2O. And the compounds are no palpable effect against Staphylococcin aureus, Salmonella typhimurium and leukemia K562.7. The binding mechanism and intensity with CT-DNA were analyzed by UV, FS and fluorescence quench titration which can offer theoretical foundation for further study of bacteriostatic mechanism.

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