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Approach toward Artificial Enzyme Models Using Water-soluble Cyclophanes with Hyrophobic Cavities

使用具有疏水空腔的水溶性环芳的人工酶模型的方法

基本信息

批准号：
05557096
负责人：
KOGA Kenji
金额：
$ 3.9万
依托单位：
University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1994
项目状态：
已结题

项目摘要

Studies aiming at application of cyclophanes having diphenylmethane units to artificial enzyme models in aqueous solutions and at membrane surfaces were carried out, and the following results were obtained.1. Catalytic cyclophanes in which an imidazolyl or thiol group as a catalytic functional group was introduced to a cyclophane macrocycle having diphenylmethane units were synthesized, and their abilities to accelerate ester docomposition were compared in aqueous solution (pH 8.65). Although 3.8-fold acceleration was observed for a cyclophane having an imidazolyl group, control experiments with addition of a nonreactive guest or 4-methyl-imidazole without a cyclophane ring showed that the acceleration by the imidazolyl cyclophane was not due to the reaction with a guest included in the cyclophane cavity. These results manifested the necessity of the design of catalytic cylophanes in which the catalytic group is located in close proximity to the reactive site of the included guest.2. An optically active, anionic cyclophane having a C_2-symmetrical structure with two OH groups was synthesized as a new type of chiral hydrophobic cavity that is capable of introducing catalytic functional groups. This cyclophane showed strong complexation to cationic aromatic guests (K_3-10^3M^<-1>) in aqueous solution (pD12.8).3. A series of lipophilic cyclophanes having long alkyl chains were synthesized to achieve molecular recognition at a membrane surface, evaluated as guest-induced changes in membrane potential by using PVC-supported liquid membrane systems. A cyclophane having a definite charged group on one side and a lipophilic alkyl chain on the other side of the benzene rings gave greatest potential changes, indicating an important principle for designing interfacial receptors.

针对具有二苯基甲烷单元的环烷在水溶液和膜表面人工酶模型中的应用进行了研究，得到了以下结果：在pH为8.65的水溶液中，以咪唑基或巯基为催化官能团，合成了具有二苯基甲烷单元的环烷大环，并比较了它们加速酯合成的能力。虽然对含有咪唑基的环双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲双亲。这些结果表明了设计催化环烷的必要性，其中催化基团位于靠近所含客体的反应位点2。合成了一种具有光学活性的阴离子环烷，该环烷具有c_2对称结构和两个OH基团，是一种能够引入催化官能团的新型手性疏水腔。该环烷在水溶液（pD12.8）中与阳离子芳香客体（K_3-10^3M^<-1>）有较强的络合作用。合成了一系列具有长烷基链的亲脂环烷，在膜表面实现分子识别，并利用pvc支撑的液膜系统评价了客体诱导的膜电位变化。苯环的一侧有一个确定的带电基团，另一侧有亲脂烷基链的环烷具有最大的潜在变化，这表明了设计界面受体的一个重要原则。