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手性M2L3型金属有机配合物笼子的合成与性能研究
Synthesis and Application of Chiral M2L3-type Metal-organic Coordination Cage
【作者】 赵晓慧;
【导师】 卞证;
【作者基本信息】 东北师范大学 , 无机化学, 2021, 硕士
【摘要】 以非共价键为主导相互作用的金属有机超分子组装体系往往存在动态可逆、稳定性较差但是具有结构有序,特定功能的特点。本论文以配位键导向的自组装为基础,设计合成了三角双锥结构的超分子金属有机自组装笼子,并探索其在分子识别与分离方面的应用。第一章简单介绍了超分子化学领域的发展,以及以配位键导向的自组装体系的理论基础、研究进展和其在各个领域的应用。第二章首先合成了含有手性联萘基团以及联吡啶基团的配体L1-L3,进一步通过一锅法将配体与二价铁离子(FeII)配位,合成了三种三角双锥结构的Fe2L3型超分子金属有机配合物笼子(Cage 1-3),并对合成的配合物笼子进行了元素分析、红外光谱、质谱、核磁共振、紫外可见光谱、圆二色光谱及电镜等多方面的结构表征第三章探索了所合成配合物笼子的潜在应用,结果发现Cage 1对赖氨酸有特别的分子识别分离作用。核磁共振氢谱清楚表明,Cage 1对赖氨酸有响应,而对其他十九种天然结构氨基酸没有响应,等当量配合物笼子与赖氨酸混合溶液的DOSY核磁共振二维谱图证明它们具有相近的溶液扩散系数。质谱也给出配合物笼子与一个或几个赖氨酸结合的信号。最后将Cage 1固体粉末放入赖氨酸和其他氨基酸的混合溶液中室温静置,高效液相色谱分析表明Cage 1能选择性吸附分离赖氨酸。第四章介绍了各部分实验的条件、方法以及使用的实验药品规格,采用的测试仪器规格、测试手段等实验细节。
【Abstract】 Metal-organic coordination cages dominated by non-covalent bonds often have dynamic reversibility,poor stability,but are characteristic of orderly structure and specific functions.Based on the coordination bond-oriented self-assembly,this thesis designed and synthesized the supramolecular metal-organic cages with triangular bipyramid structure,and further explored its application in molecular recognition and separation.Chapter 1 briefly introduced the development of supramolecular chemistry,as well as theoretical basis,research progress and applications in various fields of self-assembly systems oriented by coordination bonds.Chapter 2 chapter,three chiral binaphtylbipiridine ligands L1-L3 first were prepared.Then,using the one-pot method,the resulting ligands were coordinated to ferrous ions to afford three Fe2L3-type metal organic coordination cages,Cage 1-3,with a trigonal bipyramidal structure,respectively.The coordination cages were fully characterized by elemental analyses,IR,NMR,MS,UV-vis,circular dichroism spectrum and transmission electron microscopy techniques.Chapter 3 explored the potential application of these metal-organic coordination cages.The results showed that Cage 1 exhibited the special ability in molecular recognition and separation.NMR measurements showed that Cage 1 can selectively respond to lysine,but not to other nineteen natural amino acids.MS data also indicated that Cage 1 can combine with one or several lysine molecules.The DOSY 2D NMR experiments of the mixed solution of Cage 1 and lysine confirmed that both them had similar diffusion coefficients.Moreover,Cage1 as powder can selectively absorb the lysine in the mixed amino acid aqueous solution.Chapter 4 introduced all the experimental methods,as well as the specifications of experimental drugs and the specifications of test instruments.
- 【网络出版投稿人】 东北师范大学 【网络出版年期】2021年 12期
- 【分类号】O641.4
- 【下载频次】86