Synthesis Of Chiral Calix[4]arenes With Long-chain Alkyl At The Upper Rim And Micro/nano-meter Vesicles Formed By Their Self-assemblies

Supramolecular self-assemblies have potential application in drug delivery, nanomaterial preparation, selective catalysis, or cell mimicry and so on. So supramolecular self-assemblies have attracted great attention by chemists and they are one of topic current interests. Calixarenes can include guest molecules and have much dominance in the fields of self-assembly because of their hydrophobic cavities and easy chemical modification. The synthesis and self-assembly based on a series of calix[4]arenes derivatives have been studied in this thesis. The results conclude the following main points:1. According to the theories of molecular recognition and self-assembly, a series of new calix[4]arenes derivatives with long chain alkyl at the upper rim and chiral amines substituted in 1, 3 position at the lower rim were synthesized, and characterized by 1HNMR, MS and IR spectroscopy.2. L/D-2, 3-dibenzoyl tartaric acid (10L/D) could be recognized with calix[4]arenes derivatives. The gelation behaviors of the complexes were tested in various organic solvents. The two components of 5a~5c and 10L/D could form gels in cyclohexane but 5d, 5e not. Transparent gel could occur in high temperature and gel could transform to sol by cooling in 5a-10D system.3. The morphologies of these two-components were examined by electro devices. Indeed decreasing the length of long chain alkyl from 5a to 5c reduced, micro-fibers structures changed to micro/nano-capsules in cyclohexane by 5a-5c/10L system. The complexes between 5a and 10L could self-assemble into vesicles in low temperature and fibers formed by heating in cyclohexane. The system of 5d-10L could form bone like fibers in 1, 2-dichloroethane. The information of self-assembly from vesicles to fibers could be controlled by changing the molar ratio of 5b-10L from 1:2 to 1:1. Moreover, these tiny fibers could be led to large fibers by decreasing concentration and increasing sample standing time. So these results indicated that we could manipulate supramecular self-assemlby by changing different conditions.4. A new amphiphilic calix[4]arene-sulphonate was synthesized, and the properties of concluding ferrocene molecule and self-assembly were preliminary studied.