【作者】 王芳；

【导师】 谭黎峰；

【作者基本信息】 湘潭大学 ， 无机化学， 2008， 硕士

【摘要】 DNA对于生命遗传密码的翻译、转录、复制起着非常重要的作用。研究金属配合物与DNA相互作用的键合机理将有助于人们从分子水平上了解生命现象的本质,在生命科学上具有重要的理论意义和潜在的应用价值。近年来,由于钌(II)多吡啶配合物在光化学、光物理及生物化学等领域的广泛应用,对这类配合物的研究已经引起了人们广泛的关注,特别是它们在生物无机领域的重要应用。例如:充当识别DNA结构的探针;DNA介导的电子转移;金属足迹试剂;DNA切割试剂。本研究工作的重点是设计对DNA有较大亲和力和识别能力的配合物,并探索影响其结合DNA能力的各种因素。因此我们不但合成了一系列有代表性的新型配体及其钌(II)多吡啶配合物,而且深入研究了配合物与CT-DNA相互作用的机理。主要工作如下:首先,合成了含有柔性链的BPIP多吡啶配体,利用这个配体进一步合成了配合物[Ru(bpy)2(BPIP)](ClO4)2·H2O和[Ru(phen)2(BPIP)](ClO4)2·H2O (bpy = 2,2’-联吡啶,phen = 1,10-邻菲咯啉)。并用紫外光谱、核磁和质谱对它们进行了表征。采用电子吸收光谱、稳态荧光、圆二色谱和粘度测定研究了配合物与CT-DNA的相互作用。结果表明亚甲基的存在对配合物与CT-DNA键合与相互作用机理有很大影响。其次,对新型含S原子的多吡啶配体btip及其配合物[Ru(bpy)2(btip)](ClO4)2·2H2O和[Ru(dmb)2(btip)](ClO4)2·nH2O(dmb = 4,4’-二甲基联吡啶)进行了合成及表征,研究了配合物与CT-DNA的相互作用,并用紫外光谱和荧光光谱研究了铜离子对配合物与DNA相互作用的影响。另外,在配体dppz的基础上,合成了新的配体tbtc及其配合物。通过紫外可见光谱、稳态荧光、圆二色谱和粘度测定研究了配合物与CT-DNA的相互作用。结果发现配合物[Ru(bpy)2(tbtc)](ClO4)2·2H2O是一良好的分子光开关。更多还原

【Abstract】 DNA is the most important substance in the inherited password’s translation, convey, reproduction for the life. Studying the interactions and mechanism of metal complexes binding with DNA may be a more complete understanding of the origin of life on a molecular level, which have great theoretical significance and potential applied values in biological science. Ruthenium(II) polypyridyl complexes have aroused intense interest because of their extensive applications in the fields of photochemistry, photophysics and biochemistry. In particular, their important application for probes of DNA structure, DNA mediated electron transfer, DNA footprinting and sequence-specific cleaving agents are well known.The aim of this paper is the design complexes with high affinity and specific recognition to DNA, as well as the understanding of factors, which might influence the DNA-binding affinity of the complexes. In order to investigate and explore the DNA-binding mechanism, a series of novel polypyridyl ligands and their ruthenium(II) complexes have been synthesized. The major contents as follows:First, a new flexible ligand BPIP and its Ru(II) complexes [Ru(bpy)2(BPIP)](ClO4)2·H2O and [Ru(phen)2(BPIP)](ClO4)2·H2O (bpy = 2,2’-bipyridine, phen = 1,10-phenanthroline) have been synthesized and characterized by UV-vis, 1H NMR, and mass spectra. The binding of the two complexes with calf thymus DNA has been investigated by absorption, steady-state luminescence, CD spectra and viscosity measurements. The experimental results indicate that methene group existence or not have a significant effect on the DNA-binding and cleavage mechanism of these complexes.Secondly, a new polypyridyl ligand btip (btip = 2-benzo[b]thiophenimidazo [4,5-f]1,10-phenan-throline) which contain S atom and its ruthenium(II) complexes, [Ru(bpy)2(btip)]2+ and [Ru(dmb)2(btip)]2+ (dmb = 4,4’-dimethyl-2,2’-bipyridine) have been synthesized and characterized. The interactions of these complexes with DNA have been investigated. The effect of Cu2+ on the DNA interaction of the two complexes was studied by electronic absorption and emission methods.Otherwise, a new polypyridyl ligand tbtc and its ruthenium(II) complexes have been synthesized and characterized. The binding of the two complexes with calf thymus DNA has been investigated by absorption, steady-state luminescence, CD spectra and viscosity measurements. The results suggest that the complex [Ru(bpy)2(tbtc)](ClO4)2·2H2O was a good molecular“light switch”.更多还原