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CONSTRUCTION OF COMPOUNDS WITH SPECIFIC STRUCTURES AND FUNCTIONS BY SELF-ASSEMBLIES

通过自组装构建具有特定结构和功能的化合物

基本信息

批准号：
07555292
负责人：
HARADA Akira
金额：
$ 8.9万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555292/
关键词：
SELF-ASSEMBLY CYCLODEXTIN INCLUSION MOLECULAR RECOGNITION SUPRAMOLECULE ポリロタキサン

项目摘要

We found that alpha-cyclodextrin forms complexes with poly (ethylene glycol) (PEG) of various molecular weights to give crystalline compounds in high yields, although beta-cyclodextrin did not form complexes with PEG.However, beta-cyclodextrin formed complexes with poly (propylene glycol) (PPG) to give stoichiometric compounds in high yields, though alpha-cyclodextrin did not form complexes with PPG of any molecular weights. gamma-Cyclodextrin formed complexes with poly (methyl vinyl ether) (PMVE), though alpha- and beta-cyclodextrin did not form complexes with PMVE.Spectroscopic studies of the complexes show that polymer chains are included in the cavities of cyclodextrins. Recently we found that cyclodextrins form complexes not only with hydrophilic polymers but also with hydrophobic polymers. alpha-Cyclodextrin, for example, formed complexes with oligoethylenes (OE) selectively. In contrast, gamma-cyclodextrin formed complexes with poly (isobutylene) (PIB) efficiently, although a-cyclodextrin did not form complexes with PIB.We have prepared polyrotaxanes in which many cyclodextrins are threaded on a polymer chain by capping the polymer chain ends with bulky substituents, such as 2,4-dinitrophenyl groups and 3,5-dinitrobenzoyl groups. The products were characterized by IR,UV,X-ray diffraction (powder), 1H NMR,13C NMR,13C-CP/MAS,and 2D NOESY NMR spectra.

我们发现α-环糊精与不同分子量的聚乙二醇（PEG）形成复合物，以高产率得到结晶化合物，尽管β-环糊精不与PEG形成复合物;然而，β-环糊精与聚丙二醇（PPG）形成复合物，以高产率得到化学计量的化合物，尽管α-环糊精不与任何分子量的PPG形成复合物。γ-环糊精与聚甲基乙烯基醚（PMVE）形成复合物，而α-环糊精和β-环糊精与PMVE不形成复合物，光谱研究表明聚合物链被包含在环糊精的空腔中。最近我们发现环糊精不仅与亲水性聚合物形成复合物，而且与疏水性聚合物形成复合物。例如，α-环糊精选择性地与低聚乙烯（OE）形成复合物。相比之下，γ-环糊精与聚（异丁烯）（PIB）有效地形成复合物，虽然α-环糊精没有与PIB形成复合物。我们已经制备了聚轮烷，其中许多环糊精是线程上的聚合物链的大体积取代基，如2，4-二硝基苯基和3，5-二硝基苯甲酰基的聚合物链端。产物经IR、UV、X射线粉末衍射、1H NMR、13 C NMR、13 C-CP/MAS和2D NOESY NMR表征。