复杂含水体系中选择性识别和分离特定离子的超分子功能材料的设计合成及性能

Recognition and separation of specific ions with single selectivity in complicated aqueous solution is an difficult problem faced by host-guest recognition researches. In order to resolve this problem, this project introduced hydrophilic groups into host molecule to improve the poor water solubility of host. On the other hand, classical organic host molecule couldn't separate the guest molecules although it could recognize the guest ion. In order to overcome this difficulty, we introduced hydrophilic hyperbranched polymer into the host molecule, design and synthesized a series of supramolecular functional materials based on hydrophilic hyperbranched polymer as framework, fluorescent groups or chromophoric groups as signal groups and the groups which could selectively binding specific ions as binding site. These materials could dissolve or swelling in water, when these hosts meet the specific ions in water, the hosts molecule could binding the ions selectively and report the binding process by color or fluorescence changes. The swelling host-guest complex could filtrated out from solution, accordingly, achieved selectively recognition and separation. These materials shows an wide application prospect in the fields of detection and separation of heavy metal ions or noxious anions, sewage disposal or precious metal extraction. Moreover, in this project, we will carefully investigate the influence of the water soluble groups on the soubilities of host, the influence of the binding sites on the selectivities and the influence of signal groups on the colorimetric recognition abilities. Therefor, this project possesses some theoretical value.

为解决在水相和复杂竞争体系中对特定离子进行单一选择性识别和分离这一主客体识别研究中的难题，本项目在主体分子设计中针对性的引入了亲水基团来解决有机主体分子水溶性差的问题；同时，为了解决传统有机主体分子只能识别客体离子而无法分离客体的难题，本项目将超支化材料引入到主体分子中，设计合成一系列以亲水性超支化材料为骨架，以对特定客体有选择性结合能力的官能团为结合位点，以发色基团或荧光基团为信号报告基团的超分子功能材料。这种材料可在水溶液中溶解或溶胀，遇到特定客体时可选择性结合该客体并产生荧光或颜色变化来指示选择性结合过程。在水中溶胀的超分子功能材料选择性结合特定客体后可从水中滤出，从而实现选择性分离。这种材料在重金属离子和有毒阴离子的检测、分离以及水处理和贵金属提取等领域有广泛的应用前景。本项目还将详细研究超分子功能材料选择性识别和分离特定客体的原理和构效关系，因此该项目还具有一定的理论研究价值。

为解决在水相和复杂竞争体系中对特定离子进行单一选择性识别和分离这一主客体识别研究中的难题，本项目在主体分子设计中针对性的引入了亲水基团来解决有机主体分子水溶性差的问题。同时，为了解决有机主体分子对特定离子的专一响应，我们又设计在主体分子中引入对特定客体有选择性结合能力的官能团为结合位点，以发色基团或荧光基团为信号报告基团的超分子功能材料。这种材料可在遇到特定客体时可选择性结合该客体并产生荧光或颜色变化来指示选择性结合过程。基于上述思路，本项目设计合成了多个系列的超分子传感器分子和超分子功能材料，实现了在有机-水体系、纯水相中的离子识别和分离。另外还制备了基于超分子凝胶材料离子识别传感器和离子识别、分离材料。这些超分子传感器和超分子离子识别材料主要有以下三种类型：（1）含水介质中对离子的专一响应；（2）基于有机凝胶的阴阳离子专一选择性识别；（3）基于柱芳烃的离子识别受体的设计与合成。这些材料在重金属离子和有毒阴离子的检测、分离以及水处理和贵金属提取等领域有一定的应用前景。本项目还详细研究了超分子离子识别和超分子功能材料的组装、刺激响应机理。并提出了多种控制超分子刺激响应的新机理。为丰富和拓展超分子刺激响应和离子识别范围提供了一些新思路，因此该项目还具有一定的理论研究价值。