【作者】 黄翠玉；

【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， 2007， 硕士

【摘要】 以杯芳烃为平台构筑对客体具有良好识别能力的新型主体分子一直颇受瞩目。其中，杂原子桥联的杯芳烃，特别是硫杂杯芳烃的研究近几年受到了人们的广泛关注，是杯芳烃化学新的研究热点。对叔丁基硫杂杯[4]芳烃是以4个S原子取代桥联的亚甲基基团（-CH₂），从而展现出与普通杯芳烃不同的特性，对它的研究方兴未艾。本文以硫杂杯[4]芳烃为平台，设计并合成了硫杂杯[4]芳烃的一系列衍生物和聚合物，并研究了它们对金属阳离子和氨基酸的配合性能。首先合成了一系列具有桥联或开链结构的硫杂杯芳烃氮杂冠醚及其相关衍生物，包括酯基、酰胺基、席夫碱基、硫脲基衍生物。金属阳离子萃取实验表明，含酰胺基和硫脲基的硫杂杯[4]芳烃衍生物对软金属离子Ag⁺和Hg²⁺表现出更好的萃取性能。氨基酸萃取实验表明，它对所测的氨基酸表现出良好的萃取能力。UV-vis光谱法和¹H NMR谱研究了硫杂杯芳氮杂冠醚与系列α—氨基酸的识别配合性能并计算出它们的配合常数，结果表明它对所测试的α—氨基酸有较好的配合作用，主客体分子形成1：1的配合物。本论文还合成了首例具有立体网状结构的含席夫碱基的硫杂杯芳烃聚合物。这种聚合物不仅结构新颖，官能团丰富，而且对阳离子的吸附性能较好，对Cd²⁺和Hg²⁺展现出吸附选择性。更多还原

【Abstract】 Calixarenes are utilized as building blocks to construct the novel host moleculeswith good recognition abilities towards the guests, which have attracted considerableattention for researchers. Recently, people have paid much attention to calixarenesbridged by heteroatom, especially the study of thiacalixarene, which becomes a newhot molecule in calixarenes chemistry. Because its four S atoms substitute for bridging-CH₂, thiacalix[4]arenes exhibit different properties from "classical" calixarenes,therefore, studies on their derivation and recognition properties are in the ascendant.In this paper, thiacalixarene is used as a building block, and a series ofthiacalix[4]arene derivatives and polymers are designed and synthesized, and theirbinding properties towards metal cations and amino acids are studied.In this thesis, we first synthesize a series of thiacalixarene aza-crown ether and itsrelative derivatives with the structure of bridging or open-chain, such as ester, amide,schiff base and thiourea derivatives. Metal cation extraction experiments demonstratethat thiacalix[4]arene derivatives containing amide and thiourea units shows betterextraction property towards soft metal ions Ag⁺ and Hg²⁺. And amino acid extractionexperiments suggest that this derivative exhibits excellent extractability towardsamino acids. UV-vis and ¹H NMR are used to study the binding property ofthiacalixarene aza crown ether towards a series ofα—amino acids, and their bindingconstants are calculated. The results show that it possesses good complexationabilities towardsα—amino acids, and complex compound of 1:1 is formed betweenhost and guest molecules.First example of thiacalixarene polymer that contains schiff base unit and possessesthe stereo and netted structure has been synthesized. This polymer possesses novelstructure and N- and S- functional group, and exhibit outstanding adsorption propertytowards cations, expecially for Cd²⁺ and Hg²⁺.更多还原