Construction of Tailormade Sugar Host Molecules Bearing High Polymer Recognition Ability

在生物系统中，核酸和抗体等生物聚合物有效地发挥宿主分子的作用，以准确识别特定的客体聚合物。开发对聚合物客体具有如此精确识别能力的人工主体聚合物是非常重要的，因为这些主体聚合物可以用于构建新型识别装置。本研究研究了骨架修饰的环糊精(CD)衍生物、部分2，3-O-甲基化淀粉和γ-环糊精(γ-CD)三种主体分子与不同聚合物的包合物，以开发一种能够与特定聚合物选择性络合的主体分子。骨架修饰的CD衍生物不仅与传统的聚合物客体如聚四氢呋喃(PTHF)和聚(ε-己内酯)(PCL)形成包合物，而且还与聚丙烯酸(PAA)形成新型的拟…更多的岩藻烷。这是第一个CD-PAA包合物的例子，骨架修饰的CD衍生物可以有效地与主链上带有取代基的聚合物客体形成包合物，而不是与线性聚合物形成包合物。部分2，3-O-甲基化的淀粉与PTHF和PCL形成包合物的方法是简单地将它们混合在DMSO-H_2O(1：9)溶液中。γ-CD与等规聚甲基丙烯酸甲酯(it-PMMA)形成包合物比与间规聚甲基丙烯酸甲酯(St-PMMA)形成包合物更有效。γ-CD与St-PMMA包合物的形成受γ-CD加入量的影响较大，需要过量的γ-CD才能形成γ-Cd_st-PMMA包合物。较少

In biological systems, biopolymers such as nucleic acids and antibodies effectively function as host molecules to precisely recognize particular guest polymers. The development of artificial host polymers possessing such precise recognition ability towards polymeric guests is of great importance, since these host polymers can be useful for the construction of novel recognition devices. In this study, we examined the inclusion complex formation of three kinds of host molecules, a skeleton-modified cyclodextrin (CD) derivative, partially 2,3-O-methylated amyloses, and γ-cyclodextrin (γ-CD), with various kinds of polymers in order to develop a host molecule capable of selectively complexing with a specific polymer.The skeleton-modified CD derivative, which bears a β-(1,4) glucosidic bond, formed an inclusion complex with not only conventional polymeric guests such as polytetrahydrofuran (PTHF) and poly(ε-caprolactone) (PCL), but also with poly(acrylic acid) PAA to generate novel pseudo-po … More lyrotaxanes. This is the first example of a CD-PAA inclusion complex.The skeleton-modified CD derivative was found to effectively form inclusion complexes with polymeric guests with substituents on the main chain rather than with the linear polymer.Partially 2,3-O-methylated amyloses efficiently formed inclusion complexes with PTHF and PCL by simply mixing them in DMSO-H_2O (1:9) solution. The degree of methylation of amylose affected the inclusion ability towards PTHF and PCL: MAs with 8 and 20% methylation formed inclusion complexes with these guest polymers, while MAs with more than 33% methylation formed few inclusion complexes with the guest polymers.γ-CD was found to form inclusion complexes with isotactic poly(methyl methacrylate) (it-PMMA) more effectively than with syndiotactic poly(methyl methacrylate) (st-PMMA). The formation of an inclusion complex between γ-CD and st-PMMA was strongly influenced by the amount of γ-CD added, and the addition of an excess amount of γ-CD was required for γ-CD_st-PMMA complex formation. Less