Guest-Responsive Covalent Frameworks by the Cross-Linking of Liquid-Crystalline Salts: Tuning of Lattice Flexibility by the Design of Polymerizable Units
作者:Yasuhiro Ishida、Hiroaki Sakata、Ammathnadu S. Achalkumar、Kuniyo Yamada、Yuki Matsuoka、Nobutaka Iwahashi、Sayaka Amano、Kazuhiko Saigo
DOI:10.1002/chem.201102422
日期:2011.12.23
liquid‐crystalline salts were found to work as solid‐state hosts with a flexible framework. As a component of such hosts, four kinds of polymerizable amphiphilic carboxylic acids bearing alkyl chains with acryloyloxy (A), dienyl (D), and/or nonreactive (N) chain ends (monomeric carboxylic acids; MAAA, MANA, MDDD, and MDND) were used. The carboxylic acids were mixed with an equimolar amount of a template unit, (1R
发现通过液晶盐原位聚合制备的交联聚合物可作为具有柔性骨架的固态基质发挥作用。作为这类主体的组分,带有烷基链的四种可聚合的两亲羧酸具有丙烯酰氧基(A),二烯基(D)和/或非反应性(N)链端(单体羧酸;M AAA,M ANA,M DDD,和M DND)。将羧酸与等摩尔量的模板单元(1 R,2 S)-去氧麻黄碱(客体胺; G RS),形成相应的盐。每种盐在室温下均呈矩形柱状LC相,可通过60 Coγ射线诱导的聚合反应成功聚合,而不会发生严重的结构紊乱,从而得到交联羧酸(聚合羧酸;P AAA,P ANA,P DDD和P DND)和G RS。由于聚合物骨架P和模板G RS之间的相互作用不具有共价性,因此交联的聚合物可以可逆地释放并捕获大量的G RS。响应于G RS的解吸和吸附,交联的聚合物极大地改变了其纳米级结构顺序。对聚合物的系统比较显示,可聚合基团的选择对所得聚合物骨架作为固态主体的性能有重大影