【作者】 谭年元；

【导师】 肖小明；

【作者基本信息】 湖南师范大学 ， 有机化学， 2003， 硕士

【摘要】 本文简要介绍了微波辐射作用机理和特点，以及微波辐射技术在有机和无机合成中的应用，并对近年来多吡啶配合物的电化学与光谱性质的研究，和多吡啶配合物与DNA的键合模式及其影响因素作了简要评述，还介绍了紫外光谱、荧光光谱、核磁共振谱及电化学测定等一些常用的研究配合物和DNA作用机制的实验方法。 通过微波辐射加热方式，快速合成了[Co（H₂bzimpy）₂]（ClO₄）₂{H₂bzimpy=2，6-bis（benzimidazol-2-yl）pyridine，2，6-二（苯并咪唑-2）吡啶}和[Co（5-NO₂-phen）₂dppz]（ClO₄）₃{5-NO₂-phen=5-Nitro-1，10-phenanthroline，5-硝基-1，10-菲咯啉；dppz=dipyrido[3，2-a；2，3-c]phenazine，二吡啶吩嗪}两种新型多吡啶钴功能配合物，利用循环伏安法和微分脉冲伏安法等电化学方法测定了配合物的电化学行为，并用紫外可见和荧光光谱法研究了配合物的谱学性质。络果表明，配合物[Co（H₂bzimpy）₂]（ClO₄）₂的中心离子由+3价还原为+2价的半波电位为E_1/2=0.601V（vs SCE），对应的电极反应为准可逆过程，由+2价还原为+1价的半波电位为E_1/2=-0.908V（vs SCE），对应的电极反应为可逆过程，此外，配合物在-1.593V和-1.978V有两个明显的不可逆还原峰，对应的电极反应可能是配体H₂bzimpy的还原反应；配合物[Co（H₂bzimpy）₂]（ClO₄）₂在乙腈溶液中于308nm和345nm处有两个吸收峰，而在N-N-二甲基甲酰胺（DMF）溶液中只有334nm处一个吸收峰；配合物在乙腈溶液中能产生荧光，其最大发射波长为443nm。 配合物[Co（5-NO₂-phen）₂dppz]（ClO₄）₃的中心离子由+3价还原为+2价的半波电位为E_1/2=0.567V（vs SCE），对应的电极反应为准可逆过程，此外，配合物在-0.551V有一个不可逆还原峰，对应的电极反应可能是+2价离子被还原为0价金属；配合物在甲醇溶液中于232，271，341，357，375nm（logε4.77，4.83，3.94，3.90，3.86）处有五个吸收峰；并在甲醇溶液中能产生荧光，其最大发射波长分别为476nm和538nm。 采用紫外光谱法和荧光光谱法考察了这两种新型多吡啶钴配合物[Co（5-NO₂-phen）₂dppz]（ClO₄）₃和[Co（H₂bzimpy）₂]（ClO₄）₂与DNA的相互作用。研究发现，两种配合物与DNA作用时吸收强度都减小，且吸收峰红移，表明两种配合物都能以插入方式与DNA结合。更多还原

【Abstract】 In this paper, the mechanism and properties of microwave irradiation and its applications in both organic and inorganic synthesizing field were introduced. Studies on the electrochemical and spectral characteristics of polypyridly complexes, binding-modes of polypyridly complexes binding to DNA and factors affecting the binding of complexes to DNA are reviewed. Experimental methods forstudying mechanisms of complexes binding to DNA are introduced, including UV, Fluorescence, NMR and Electrochemistry.Two novel functional polypyridly cobalt complexes of [Co（H2bzimpy）2]（ClO4）2 （ H2bzimpy = 2,6-bis（benzimidazol-2-yl） pyridine） and [Co（5-NO2-phen）2dppz]（ClO4）3 （5-NO2-phen = 5-Nitro-1.10-phenanthroline, dppz = dipyrido[3,2-a;2 , 3 -cjphenazine） was synthesized by microwave irradiation method. The electrochemical behaviors of the complexes have been investigated by cyclic voltammetry and differential pulse voltammetry techniques, and theelectronic absorption spectroscopy and fluorescence spectroscopy ofthe complexes were determined at room temperatu e.The cyclic voltammpgram of the complex [Co（H2bzimpy）2]2+ have shown a quasi-reversible Co（III）/ Co（II） redox couple at 0.601V vs SCE and a reversible Co（II）/Co（ I ） redox couple at -0.908V vs SCE. In addition, the complex [Co（H2bzimpy）2]2+ displayed two irreversible reduction waves for its H₂bzimpy ligands at -1.593V and -1.978V, respectively. The two maxima of adsorption of the complex in acetonitrile occur respectively at 308nm and 345nm, and that of adsorption of it in DMF does at 334nm. That of emission of the complex in acetonitrile occurs at 443nm.The cyclic voltammogram of the complex [Co（5-NO2-phen）2 dppz]3+ have shown a quasi-reversible Co（III）/Co（ II） redox couple at 0.567V vs SCE, and a irreversible Co（II）/Co（0） reduction reaction at -0.551V vs SCE. The five maxima of adsorption of the complex inCH3OH occur respectively at 232, 271, 341, 357nm and 375nm, and those of emission of the complex in CHsOH occur at 476nm and 538nm, respectively.The interaction of the complexes [Co（H2bzimpy）2](CIO₄)2 and [Co（5-NO2-phen）2dppz]（ClO4）₃ with DNA have been studied by absorption spectra and fluorescence spectra. The results indicate that both of the new polypyridly cobalt complexes interact with DNA by intercalative binding.更多还原