Preparation Of Supramolecular Soft Materials Based On Pillar [5] Arene Macrocycle

As a new class of macrocyclic host molecule after crown ethers,cyclodextrins,calixarenes and cucurbiturils,pillararene has a highly symmetrical columnar structure and rich electron cavities and advantages of easily preparation and derivative compared to other host molecules.Pillararene have a wide range of application in the biological,energy storage,medicine and material science.Supramolecular gels and vesicles are two representative supramolecular soft materials that self-assembled by structure units by means of weakly noncovalent interactions,which have characteristics of morphological variability,self-healing,and reversible responsiveness to the outside.Therefore,embed pillararene into these soft matters is expected to give the materials more abilities.Recent strategy is using the host and guest interaction to prepare these soft matters,but this strategy had used the cavities of pillararene.The reports of introducing pillararene into the soft matters as functional groups in order to give the special properties of these assembly are seldom.Therefore,it is urgent to construct supramolecular soft materials containing the cavities of the pillararene.The contents of this thesis are as follows:1.A novel C3-symmetric disc molecule decorated benzene-1,3,5-tricarboxamide(BTAs)with three identical pillar[5]arene tails was designed and synthesized.It has been shown that the compound can gelate acetonitrile at very low concentration(0.2 wt%)upon sonication at room temperature,but obtained precipitate by conventional heating-cooling process,and found that both gel and precipitate were constructed by entangled,high-aspect ratio flexible bundles of nanofibrils,what more the fibrous structure in the gel was composed of the chiral helix structure.UV-vis,CD,IR and XRD showed that the compound form chiral helical,elongated,columnar aggregates with nanofiber morphology by the combination of intermolecular hydrogen bonding between N-H and C=O of amide,?-? stacking(H-aggregate)and hydrophobic interaction and stereo-hindrance effect of peripheral group.2.A amphiphilic compound containing two cholic acid based on the pillar[5]arene skeleton was designed and prepared.Since the cholic acid has a special amphiphilic structure with a hydrophilic side and a hydrophobic side,the compound can self-assembled into a homogeneous vesicle through H-bonding of the hydroxyl hydrogen and hydrophobic interaction of the hydrophobic alkyl chain of the cholic acid.DLS,SEM and TEM showed that the diameter of the vesicles can be adjusted by change the proportion of water,and the vesicle wall was constructed by parallel stacking of compound ?.The cholic acid molecules can form cavities similar to the macrocycle hosts with host and guest interaction through the hydrophilic and hydrophobic parts.These cavities in the wall of the vesicles can encapsulate the dyes.When the proportion of water in the system increased,most of the vesicles fused with each other,and further cracked and stacked into lamellar structure.