含磷多功能配体及其铕配合物合成与性质研究

发布时间：2018-06-29 12:41

本文选题：稀土铕配合物 + BSA　；参考：《宁夏大学》2017年硕士论文

【摘要】：设计合成了四种含磷多功能配体及稀土铕配合物,采用核磁共振、红外光谱、元素分析、差热-热重、摩尔比法及计算化学进行辅助的一系列方法对合成的配体及相应配合物的结构与组成进行了表征和分析,结果表明,四种配体与铕离子均以1:1形式结合。分别使用紫外可见光谱法和荧光光谱法研究了四种铕配合物与牛血清白蛋白在不同温度下的相互作用。由紫外光谱可知:合成的四种铕配合物与牛血清白蛋白之间均有较强的结合能力,其结合力大小为:Eu(pic)3L3-BSAEu(pic)3L2-BSAEu(pic)3L1-BSAEuL4-BSA;由荧光光谱可知:合成的四种铕配合物与牛血清白蛋白内源荧光猝灭是以静态猝灭的方式进行的,并计算了在不同温度下四种铕配合物与牛血清白蛋白相关的热力学参数(AH,δS,AG)、结合常数K和结合位点n。结果表明,四种铕配合物均可以自发进行(δG0),且均为放热反应(δH0),体系的作用力类型是范德华力和氢键(AS0、AH0)。使用荧光光谱法研究了 Cu2+和Fe3+在不同温度下对合成的四种铕配合物与牛血清白蛋白之间相互作用的影响。研究结果表明:在Cu2+和Fe3+的作用下,大大增强了铕配合物与牛血清白蛋白的结合能力,说明两种金属离子参与且对铕配合物与牛血清白蛋白的结合有一定的影响。分别通过紫外光谱法与荧光光谱法对四种铕配合物与DNA的相互作用模式进行了研究。紫外光谱表明:加入DNA探针后,铕配合物的紫外吸收光谱图的最大吸收峰均出现了一定的减色效应且其最大吸收波长轻微的蓝移,其结合常数分别为5.34×105 L mol-1、2.15×105 L·mol-1、2.57×105 L·mol-1和2.28×105 L·ol-1与报道中的数值接近,我们初步推测四种铕配合物均插入DNA与其发生嵌插作用。荧光光谱表明:四种铕配合物与DNA的结合常数分别为4.11×105 L·mol-1、4.50×105 L·mol-1、9.39×105L·mol-1 和 5.0×105L·mol-1 与文献报道的数值接近,我们判断四种铕配合物对EB-DNA复合体系的荧光猝灭可能为静态猝灭,进一步推测四种铕配合物均可以与DNA以经典嵌插进行结合。使用抑菌圈法研究了四种铕配合物对大肠杆菌和金黄色葡萄球菌的抑菌活性,结果表明四种合成的铕配合物对大肠杆菌和金黄色葡萄球菌均有一定的抑菌性能。
[Abstract]:Four kinds of phosphorus-containing multifunctional ligands and rare earth europium complexes were designed and synthesized. Nuclear magnetic resonance (NMR), infrared spectroscopy (IR), elemental analysis, differential thermogravimetry (DTA) were used. The structure and composition of the synthesized ligands and their corresponding complexes were characterized and analyzed by molar ratio method and a series of methods assisted by computational chemistry. The results showed that the four ligands combined with europium ions in the form of 1:1. The interaction of four europium complexes with bovine serum albumin at different temperatures was studied by UV-Vis and fluorescence spectra. The UV spectra show that the four europium complexes have strong binding ability to bovine serum albumin (BSA). The binding force of EU (pic) 3L3-BSAEu (pic) 3L2-BSAEu (pic) 3L1-BSAEuL4-BSA-BSA-BSA-BSA-BSA-BSA-BSA-BSA-BSA-BSA-BSA.The fluorescence spectra show that the four europium complexes have been quenched with bovine serum albumin (BSA) by static quenching. The thermodynamic parameters of four europium complexes related to bovine serum albumin (AH, 未 Szag), binding constant K and binding site n were calculated at different temperatures. The results show that all of the four europium complexes can spontaneously proceed (未 G _ 0), and all of them are exothermic reactions (未 H _ 0). The interaction forces of the system are van der Waals force and hydrogen bond (as _ 0C _ 0 AH _ 0). The effects of Cu _ 2 and Fe _ 3 on the interaction of four europium complexes with bovine serum albumin (BSA) at different temperatures were studied by fluorescence spectroscopy. The results show that the binding ability of europium complexes with bovine serum albumin is greatly enhanced by Cu _ 2 and Fe _ 3, indicating that two kinds of metal ions are involved and have certain influence on the binding of europium complexes to bovine serum albumin. The interaction modes of four europium complexes with DNA were studied by UV and fluorescence spectra respectively. UV spectra showed that the maximum absorption peaks of europium complexes showed a decreasing color effect and a slight blue shift of the maximum absorption wavelength after the addition of DNA probe. The binding constants are 5.34 脳 105L mol-1C 2.15 脳 105L mol-1C 2.57 脳 105L mol-1 and 2.28 脳 105L ol-1, respectively. We preliminarily speculate that the four europium complexes are intercalated. The fluorescence spectra showed that the binding constants of the four europium complexes were 4.11 脳 105L mol-1 (4.50 脳 105L mol ~ (-1) mol-1 and 5.0 脳 105L mol-1 respectively, which were close to those reported in the literature. We concluded that the fluorescence quenching of EB-DNA complex by four europium complexes might be static quenching. It is further speculated that the four europium complexes can bind to DNA by classical intercalation. The bacteriostatic activity of four europium complexes against Escherichia coli and Staphylococcus aureus was studied by using bacteriostasis method. The results showed that the four synthesized europium complexes had certain bacteriostasis to Escherichia coli and Staphylococcus aureus.
【学位授予单位】：宁夏大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.4

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