Construction of Tailormade Sugar Host Molecules Bearing High Polymer Recognition Ability

在生物系统中，生物聚合物如核酸和抗体有效地充当主体分子以精确地识别特定的客体聚合物。开发具有这种对聚合物客体的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用于构建新型识别装置。为了开发一种能够选择性地与特定聚合物形成包合物的主体分子，本研究考察了三种主体分子--环糊精（CD）衍生物、部分2，3-O-甲基化的直链淀粉和γ-环糊精（γ-CD）与不同聚合物的包合物形成情况。以聚四氢呋喃（PTHF）和聚己内酯（PCL）为客体，以聚丙烯酸（PAA）为客体，制备了新型的准分子包合物 关于我们 lyrotaxanes。这是第一个用环糊精修饰的环糊精与聚丙烯酸形成包合物的例子，发现环糊精修饰的环糊精能有效地与主链上有取代基的高分子客体形成包合物，而不是与线性聚合物形成包合物，部分2，3-O-甲基化的直链淀粉与PTHF和PCL在DMSO-H_2 O（1：9）溶液中简单混合就能有效地形成包合物。直链淀粉的甲基化程度影响对PTHF和PCL的包合能力：具有8%和20%甲基化的MA与这些客体聚合物形成包合物，甲基化程度大于33%的MA与客体聚合物形成的包合物较少，而γ-CD与等规聚苯乙烯形成的包合物较少（甲基丙烯酸甲酯）（it-PMMA）比间同立构聚（甲基丙烯酸甲酯）（st-PMMA）更有效。γ-CD的加入量对γ-CD与st-PMMA形成包合物的影响很大，过量的γ-CD加入才能形成包合物。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