基于冠醚和柱芳烃主客体识别的超分子聚合物材料

Supramolecular Polymer Materials Based on Crown Ether and Pillararene Host-Guest Recognition Motifs

超分子聚合物材料是高分子科学、超分子化学和材料科学3个学科相结合的产物.通过精妙的设计,我们不仅可以赋予它传统高分子材料所拥有的光学、电学以及力学等性能,同时还可以使其具有超分子材料的动态可逆性和刺激响应性.已用于构筑超分子聚合物材料的主客体识别体系有很多,从识别体系中的主体来说,包括基于冠醚、环糊精、杯芳烃、葫芦脲、柱芳烃等大环的主客体体系.其中,冠醚作为第一代大环主体,它的模板合成直接开辟了超分子化学这一领域,而柱芳烃是最近发展起来的一类新的大环主体,它具有刚性的骨架,并且制备简单,容易功能化,同样也受到超分子化学家们的广泛关注.本文着重综述了我们课题组基于冠醚和柱芳烃主客体识别所构筑的超分子聚合物材料.在这些材料的制备中,我们利用了主客体识别的刺激响应性、可逆性和选择性,来实现对这类材料的组装结构以及功能的精确调控.

Supramolecular polymer materials, which have emerged as the marriage of polymer science, supramolecular chemistry and materials science, have gained considerable interest in recent years as excellent materials not only due to their properties similar to traditional polymers which are built by covalent bonds, but also because of the reversibility and stimuli-responsiveness of noncovalent bonds. As a result, the reversibility and responsiveness to external stimuli may further provide a range of potential applications, including those as superabsorbers, as matrices in analytical chemistry or biology, and as storage and delivery systems for active substances in the biomedical field. Various kinds of noncovalent interactions can be introduced into polymer materials, such as hydrogen bonding, aromatic stacking interactions, metal coordination, and host-guest interactions. Among them, host-guest interactions have been widely used in the construction of functional supramolecular polymer materials, because they usually combine multiple noncovalent interactions, such as hydrogen bonding, aromatic stacking interactions, charge transfer, and hydrophobic interactions between two complementary compounds, making them not only show good binding affinity, but also form complexes with fixed host-guest geometry and directionality. Moreover, macrocycle-based supramolecular polymer materials can response to abundant external stimuli, such as pH change, photo irradition, anions, cations, temperature, and solvent. Furthermore, macrocycle-based supramolecular polymer materials can be prepared under different conditions, namely in solution, in gel, and in the solid state. Macrocyclic hosts, including crown ethers, cyclodextrins, calixarenes, cucurbiturils, and pillararenes, are the most commonly used building blocks in the fabrication of supramolecular polymer materials. Crown ethers, the first generation of artificial supramolecular hosts, have been utilized to construct various supramolecular polymer materials. Moreover, pillararenes, a kind of novel supramolecular hosts, have shown novel properties and functionalities. In this paper, we stated the utilization of crown ether and pillararene host-guest recognition motifs to control the self-assembly of traditional polymers in order to fabricate supramolecular polymer materials.