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4-甲酰基吡唑啉酮类席夫碱配合物的合成表征及其生物活性研究
Syntheses, Characterization and DNA-binding Study on Metal-complexes with4-formyl Pyrazolone Schiff-base Ligand
【作者】 王明芳;
【导师】 杨正银;
【作者基本信息】 兰州大学 , 无机化学, 2012, 硕士
【摘要】 Schiff碱类化合物具有较强的配位能力和灵活的配位方式,在生物应用、催化、医药、材料等领域表现出新颖的性能。本论文设计合成了4-甲酰基吡唑啉酮类的五个席夫碱配体和二十四个稀土和过渡金属配合物。本论文共有六章:第一章简要综述了席夫碱结构、吡唑啉酮类席夫碱的研究进展以及小分子金属配合物与DNA的相互作用等。第二章设计合成了三种配体及其稀土金属配合物,并用核磁共振、元素分析、摩尔电导、红外光谱等检测手段对其结构进行了分析表征。配体L1:1-苯基-3-甲基-5-羟基吡唑-4-甲醛(安替比林基)腙;配体L2:1-苯基-3-甲基-5-羟基吡唑-4-甲醛(1,2,3-苯并三唑酰基)腙;配体L3:1-苯基-3-甲基-5-羟基吡唑-4-甲醛(3,4-二甲基吡咯酰基)腙。第三章通过荧光光谱法、紫外光谱法和粘度法研究了4-甲酰基吡唑啉酮腙类席夫碱配体L1、L2、L3及其稀土金属配合物与DNA的作用方式。第四章设计合成了另外两种配体,并合成包括L’在内的三个配体的过渡金属配合物,并用核磁共振、元素分析、摩尔电导、红外光谱等检测手段对其结构进行分析表征。配体L4:1-苯基-3-甲基-5-羟基吡唑-4-甲醛(氨基硫脲基)腙;配体L5:1-苯基-3-甲基-5-羟基吡唑-4-甲醛(2-氨甲基吡啶基)腙。第五章运用第三章中方法继续探讨了L1、L4、L5及其过渡金属配合物与DNA的作用方式。第六章研究了配体L1、L4、L5及其金属配合物清除羟基自由基的活性。
【Abstract】 Schiff-bases and their coordination complexes have attracted great attention over the past decades not only due to their facile syntheses, their wide application and the accessibility of diverse structural modifications, but also due to their biological applications, catalysis, design of molecular ferromagnets and materials chemistry. In this paper, we have reported synthesis and characterization of4-formyl pyrazolone Schiff-bases ligand and their metal complexes. This paper is composed of six chapters:In the first chapter, we summarize the structure of Schiff-base, progress of pyrazolone Schiff-bases and interaction mechanism between small molecular compounds with DNA.In the second chapter, three Schiff-base ligands derived from1-phenyl-3-methyl-5-hydroxypyrazole-4-carbaldhyde Schiff-Base ligand and their rare earth complexes have been synthesized and characterized on the basis of1H NMR spectra, elemental analysis, molar conductivities, IR spectra and so on.L1:1-phenyl-3-methyl-5-hydroxypyrazole-4-carbaldhydemethyleneiminophenazone,L2:1-phenyl-3-methyl-5-hydroxypyrazol-4-carbaldehyde-(3’,4’-dimethylpyrrole-2’-formyl)h ydrazine,L3:1-phenyl-3-methyl-5-hydroxypyrazol-4-carbaldehyde-(benzo[1’,2’,3’]triazol-1’-formyl)hy drazoneIn the third chapter, we studied interaction mechanism by spectroscopic methods such as electronic absorption spectroscopy, fluorescence spectra and viscostity measurements between the three ligands and their rare earth complexes with DNA. In the fourth chapter, another two Schiff-base ligands derived from1-phenyl-3-methyl-5-hydroxypyrazole-4-carbaldhyde Schiff-Base and transition metal complexes of L1, L4, L5have been synthesized and characterized.L4:1-phenyl-3-methyl-5-hydroxypyrazole-4-carbaldhyde-(thiosemicarbazide)hydrazie,L5:1-phenyl-3-methyl-5-hydroxypyrazol-4-carbaldehyde-((pyridine-2’-yl)methylimin.In the fifth chapter, the interaction mechanism of the ligands and transition metal complexes with DNA were studied by the same methods.In the sixth chapter, scavenger effects on hydroxyl radical of L1, L4, L5and their metal complexes were investigated in detail.
【Key words】 Pyrazole ketone Schiff base; Rare earth metal complexes; Transition metalcomplexes; DNA binding; Anti-hydroxyl radical;