【作者】 季衍卿；

【导师】 杨发福；

【作者基本信息】 福建师范大学 ， 高分子化学与物理， 2006， 硕士

【摘要】 杯芳烃是一类由取代苯酚和甲醛缩合而成的大环化合物。它具有独特的空腔结构和丰富的反应点，可制备具有各种官能团、构象确定、π空腔大小可调的衍生物，在分子识别、模拟酶催化、物质的检测和分离等方面都显示出其作为超分子化学中的一类重要的受体化合物的特殊价值，引起了人们的关注，被誉为继冠醚和环糊精之后的“第三代超分子主体化合物”。本文设计并合成了多重氮杂杯[4]芳烃衍生物和杯[6]冠醚接枝纤维素螯合树脂，并研究了新衍生物的阳离子吸附性能。 首先，我们合成了首例杯[6]冠醚接枝纤维素螯合树脂，通过对其阳离子吸附性能的研究，发现该树脂结合了纤维素和杯芳冠醚的各自优势，不仅具有较大的吸附容量，而且对Na⁺和Ag⁺表现出较高的吸附选择性。 其次，设计并合成了一系列具有桥联或开链结构的新型多重氮杂杯[4]芳烃衍生物：通过阳离子萃取实验发现，与只含有酰胺或席夫碱单元的杯芳烃衍生物相比，新型杯芳烃衍生物对软金属离子具有更好的配合能力，而且对Ni²⁺和Cs⁺有较好的萃取选择性；氨基酸萃取实验发现，新型杯芳烃衍生物对氨基酸分子，尤其是芳香族氨基酸有较好的配合能力，它们的氨基酸萃取性能相似，都对色氨酸具有较高的萃取率；通过对新化合物的紫外吸收光谱研究发现，过渡金属和重金属离子的加入均能使其紫外最大吸收波长发生红移；对新化合物的荧光光谱研究发现，几种常见金属离子的加入能够不同程度的改变新型杯[4]多重氮杂冠醚的荧光峰的强度，而Cu²⁺的加入不仅使得其荧光强度发生了变化，连荧光峰也发生了红移，另一方面，我们发现几种金属离子的加入也均引起具有开链结构的多重氮杂杯[4]芳烃衍生物发生荧光猝灭。更多还原

【Abstract】 Calixarenee are macrocylic compounds generally formed by condensation of aldehydes and substituted phenols. Because calixarenes have a calix-shaped, hydrophobic cavity and several reactable positions, they have attracted considerable attentions. And they are broadly used as building blocks to construct well preorganized host molecules which have widely applying potential in the field of molecular recognition, enzyme mimics, etc. So they are considered as the third host molecule after crown ethers and cyclodextrins in supramolecular chemistry. The design, syntheses, properties of novel calix[6]-crown-g-cellulose chelating resins and calix[4]arene derivatives containing polyaza groups are described.Firstly, a series of novel calix[6]-crown-g-cellulose chelating resins are synthesized. The chelating resins not only keep high adsorption capacities but also exhibit excellent adsorption selectivity to Na⁺ and Ag⁺ due to the synergetic effect of cellulose derivatives and calixarene polymers.Secondly, a series of novel ringopening or bridged calix[4]arene derivatives containing polyaza groups are synthesized. It is found that the extraction percentage of these new calix[4]arene derivatives for soft cations are higher than that of calixarene derivatives only containing amide groups or Shiff-base groups, and they exhibit a good extraction selectivity towards Cs⁺ and Ni²⁺. Amino acids extracting experiments showed that the novel compounds exhibite outstanding extractabilities towards amino acids, especially towards aromatic amino acids. Ringopening or bridged calix[4]arene derivatives containing polyaza groups show similar extractabilities with a good selectivity toward tryptophane. Their UV/vis spectra show a red shift upon the addition of the transition or heavy metal ions. From the fluorescence spectra of the bridged calix[4]crown containing polyaza groups, it is found that the fluorescence intensity of emission spectrum changes upon the addition of the metal ions, while it could form a complex with copper ion to cause its peak of fluorescence emission spectrum shift. On the other hand, the addition of these metal ions causes the ringopening calix[4]arene derivatives’ fluorescence quenching.更多还原