| This dissertation consists of three partsIn the first chapter, the nitrogen heterocycle compounds are summarized briefly, On the basis of summing up the biological groundwork of Deoxyribo Nucleic Acid (DNA), introduce the advances in biological activities (DNA-binding, Cytoxic activities) and optical properties of nitrogen heterocycle compounds and their metal complexes. Additionally, develop thoroughly the study in biology,optics and catalysis field of magnetic Fe3O4nanoparticles, and introduce the preparation methods of Fe3O4nanoparticles.In the second chapter, acetanilid as raw material, quinoline-2-one-3-carbaldehyde is synthesized by Vilsmeier-Haack reaction and dechlorine reaction under70%acetic acid condition. Then by two phase reaction (Insoluble materials:quinoline-2-one-3-carbaldehyde and Soluble materials:hydrazine or amine derivates), nine new quinoline-2-one-3-carbaldehyde derived Schiff-base ligands are synthesized. They are quinoline-2-one-3-carbaldehyde-thiosemicarbazone (L1), quinoline-2-one-3-carbaldehyde-4'-hydroxybenzoylhydrazone (L2), quinoline-2-one-3-carbaldehyde-benzoylhydrazone (L3), quinoline-2-one-3-carbaldehyde-2'-hydroxybenzoyl-hydrazone (L4), quinoline-2-one-3-carbaldehyde-3',4'-dimethylpyrryl-2'-carboxylic acid hydrazone (L5), quinoline-2-one-3-carbaldehyde-4'-aminoantipyrine (L6), quinoline-2-one-3-carbaldehyde-isonicotinyl hydrazone (L7), quinoline-2-one-3-carbaldehyde-ethylenediamine (L8), quinoline-2-one-3-carbaldehyde-lH-benzotriazol-l-acetic acid hydrazone (L9), and their transition metal and rare earth complexes are also synthesized. The structures of the Schiff-base ligands and complexes are characterized by1H-NMR, ESI-MS, FT-IR and X-ray single crystal diffraction. X-ray single crystal diffraction demonstrate the structures of CuL2, CuL3, CuL4and CuL5are interesting five-coordinative framework, and CuL1is four-coordinative framework. All the coordination ratio between Cu(Ⅱ) and ligand are1:1. The side chain (-C=O bond) of hydrazone from ligand are enloic and the coordination of oxygen atom with Cu(Ⅱ) lead to one five ring and one six ring configuration and excellent planar structure, in the Cu(Ⅱ) complexes, there are some methanol, H2O or nitrate molecules which take part in coordination with Cu(Ⅱ)The binding modes of Cu(Ⅱ) complex with CT-DNA are investigated by Un-vis spectrum, fluorescence spectrum, viscosity experiment and EB-DNA displace experiment. The experiments demonstrate the Cu(Ⅱ) complexes can bind to CT-DNA by intercalation, and show high binding constant. In addition, the anti-oxidative activities (OH· and O2-) of CuL1, CuL2, CuL6, ZnL6and NiL6are studied by in vitro radical scavenging experiments. The data demonstrate CuL1and CuL2exhibit stronger scavenging effect than traditional anti-oxidative product mannitol. And CuL1has strongest anti-superoxide radical activities among the metal complexes. The cytoxic activities against HeLa cells and HL-60cells tests of CuL3,CuL4and CuL5demonstrate that the Cu(Ⅱ) complexes exhibit more effective cell viability than corresponding ligands. And compared with CuL3and CuL4, the Cu(II) complex CuL5, which contains terminal functional group3,4-dimethylpyrryl heterocycle, shows highest cytoxic activity. The Cu(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) complexes of L6are synthesized and their DNA binding are investigated systemically. The results show that the compounds can interact with CT-DNA by intercalation, and CuL6exhibits higher binding affinity than ZnL6and NiL6. The ligand L7and its Sm(Ⅲ) complex are prepared. The crystal structure confirmed that the complex formed a distorted bicapped square-antiprism polyhedron. Through the fluorescence investigation, SmL7shows no characteristic luminescence of samarium ion due to the unsuitable energy gap between the triplet excited state energy of ligand and the lowest excited state of samarium ion. Interestingly, after the coordinated nitrate from SmL7was substituted with1,10-phenanthrolin which is an excellent chromophore to lanthanide ion, the compounds exhibited characteristic emission of Sm(Ⅲ) ion. Last, the selective properties toward various metal ions of L8and L9are also studied. The results demonstrate that L8exhibits high selectivity and sensitivity toward Zn(Ⅱ) in CH3CN solution. The coordination ration between Zn(II) and L8is demonstrated by X-ray diffraction and exhibits1:1coordinative configuration. Additionally, the fluorescence experiments show the ligand quinoline-2-one-3-carbaldehyde-1H-benzotriazol-1-acetic acid hydrazone (L9) exhibits more excellent fluorescence quenching activity toward Cu(Ⅱ) ions comparing with other metal ions in aqueous condition. Furthermore the coordination between Cu(Ⅱ) and the organic molecule sensor fabricated an interesting ID chain coordination polymer framework (1:1) by the bridge nitrogen atom from the ligand.In the third chapter, uniform particle diameter and excellent dispersed superparamagnetic Fe3O4nanoparticles are synthesized by descomposing the ferric acetylacetonate under high temperature condition. Then the modified water-soluble polyethylene glycol molecules coordinate with Fe3O4NPs by ligand exchange interaction. Water-soluble, excellent dispersed and biocompatible Fe3O4NPs materials (Fe3O4NPs-DBI-PEG-NH) are prepared. According to chemical bond reaction, modified diethylenetriamine pentaacetic acid (DTPA) rare earth (Eu3+and Gd3+) complexes by decorating antenna group,7-amino-4-methyl-coumarin (AMC) conjugates with biocompatible Fe3O4NPs materials (Fe3O4NPs-DBI-PEG-NH). Multifunctional magnetic materials (Fe3O4NPs-DBI-PEG-NH-DTPA-AMC-Eu3+and Fe3O4NPs-DBI-PEG-NH-DTPA-AMC-Gd3+) are synthesized and their cell fluorescence labelling and magnetic resonance imaging properties are investigated. The experiments in vitro demonstrates that the water-soluble Fe3O4NPs-DBI-PEG-NH-DTPA-AMC-Eu3+shows good cell imaging activity. Moreover, Fe3O4NPs-DBI-PEG-NH-DTPA-AMC-Gd3+shows higher T1relaxation effect than traditional MR agent DTPA-Gd3+, and according to liver MRI in vivo, the liver organ with addition to Fe3O4NPs-DBI-PEG-NH-DTPA-AMC-Gd3+has better contrast.
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