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中文题名:

 新颖的寡聚脲折叠体的合成及折叠性质研究    

姓名:

 王霄    

保密级别:

 公开    

论文语种:

 中文    

学科代码:

 070303    

学科专业:

 有机化学    

学生类型:

 硕士    

学位:

 理学硕士    

学位类型:

 学术学位    

学位年度:

 2018    

校区:

 北京校区培养    

学院:

 化学学院    

第一导师姓名:

 龚兵    

第一导师单位:

 北京师范大学化学学院    

提交日期:

 2018-06-06    

答辩日期:

 2018-05-30    

外文题名:

 The Synthesis and Folding Propensity of Novel Aromatic Oligoureas    

中文关键词:

 寡聚芳香脲 ; 分子内氢键 ; 折叠体 ; 螺旋结构    

中文摘要:
构筑非天然折叠分子并探索其在人工离子通道上的应用前景是当前化学家关注的研究领域之一。本文利用易修饰的苯环为骨架构成的基本单元,以脲键为连接基团,设计并合成了一系列具有不同链长度的寡聚芳香脲类化合物,并进一步研究了它们的折叠性质。研究成果总结如下: (1)本文成功制备出一类新颖的长链寡聚芳香脲类化合物。通过芳香胺与芳香异氰酸酯结构单元的缩合反应,凭借逐步偶联法分别制备了两类分子结构:不对称且链长度可调节的寡聚物中间体。然后对芳香脲低聚物中的官能团进行转换,合成出对应的含有异氰酸酯的芳香脲片段。最后通过片段对接法将高活性的1,5-二烷氧基-2,4-二氨基苯与含异氰酸酯的芳香脲进行反应,从而快速得到了链长度从三聚到十三聚的芳香脲寡聚物。本部分共得到关键中间体和寡聚物53个,化合物的结构都已通过核磁共振氢谱、核磁共振碳谱、红外和质谱等手段表征。 (2)本文凭借圆二色谱、紫外光谱、核磁共振及X-射线单晶衍射等多种分析手段,较为系统地研究了寡聚芳香脲目标分子在溶液和固态下的折叠行为。实验结果表明:1)寡聚芳香脲在MeCN中发生折叠能力最强,在CHCl3中折叠能力较弱,而在其他测试的溶剂体系中没有观察到折叠现象。2)寡聚芳香脲的折叠性质与温度,链长度有关。3)通过圆二色谱对比实验证明,在乙腈中,本论文制备的一系列寡聚体的折叠能力优于已有文献报道的寡聚体这一现象说明增强骨架的刚性的确有利于骨架发生折叠。
外文摘要:
Constructing unnatural folded molecules and studying on their potential application of artificial ion channels is one of charming research highlights to chemists. In this thesis, a series of aromatic urea oligomers compounds with different chain lengths were designed and synthesized, using modified phenyl ring as the basic building blocks that is connected through urea bond. Besides synthesis work, folding properties of aromatic oligourea were studied. The results of the thesis were listed as followed: (1) A series of aryl urea oligomers with variable chain length have been successfully prepared. Two types of asymmetric oligourea motifs with variable chain length were obtained through step by step coupling strategy, and then functional group of the motif was converted to isocyanate derivatives, which reacted with highly reactive 1,5-dialkoxy-2,4-diaminobenzene, leading to the formation of aryl oligoureas that had a range from trimer to 13mer. In this part, 53 key intermediates and oligomers were characterized by 1H NMR, 13C NMR, IR and MS. (2) The folding behaviors of these aromatic oligoureas both in solution and solid state were studied by cicular dichroism, UV, NMR and XRD methods. The collected results indicated:1)The aromatic oligoureas prefer to fold MeCN, and fold weakly in CHCl3. Folding propensity fails to be observed in other tested solvents, such as toluene, tetrahydrofuran, DMF and DMSO. 2)Their folding behavior depends on the temperature and chain length of the oligourea. (3) The cicular dichroism spectra support that the new generation of oligomers has a stronger folding preference than the reported oligourea analogs in MeCN. This observation suggests that increasing backbone rigidity leads to a improved folding behavior of oligoureas.
参考文献总数:

 0    

馆藏号:

 硕070303/18006    

开放日期:

 2019-07-09    

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