Column Of Aromatic Hydrocarbons Derived And Its Performance Study

Macrocycles, such as cyclodextrins, crown ethers, calixarenes and cucurbiturils, have been well studied and play an important role in supramolecular chemistry. Pillararenes, as new kind of macrocycles, have also reached broad interests in supramolecular chemistry for their symmetrical cylindrical structure and the electron rich cavity. Modification of the hydroxyl groups at both ends of the pillararene would generate tubular structures. In this dissertation, construction of organic nanotubes from pillararene is described. The molecular recognition and transmembrane transport properties of the organic nanotubes are also studied. The following three main research works are included:In the first part, a water-soluble pillar[5]arene decaamine has been synthesized. It has been revealed that pillar[5]arene decaamine bind with linear diacids of six to twenty carbons in a broad pH range in aqueous solution to form pseudo[2]rotanxanes, which was confirmed by NMR, ESI-MS spectroscopy, and X-ray crystal structure analysis. The formation of pseudo[2]rotanxanes is mainly driven by hydrophobic and electrostatic interactions. The pseudo[2]rotanxanes further undergo self-assembly with triethylamine to form ion pair-stopped [2]rotaxanes. The construction of rotaxane by attaching stoppers with non-covalent bonding represents a new strategy for self-assembly of rotaxane.In the second part, hydrazide-appended pillar[5]arene derivatives are synthesized. X-ray crystal structure analysis and1H NMR studies reveal that the molecules adopt unique tubular conformations. Inserting the molecules into the lipid membranes of vesicles leads to the transportation of water through the channels produced by single molecules, which are supported by dynamic light scattering and cryo-SEM experiments. The channels exhibit the transport activity at very low channel to lipid ratio and the water permeability of8.6x10-10cm s-1is realized. In addition, like natural water channel proteins, the artificial systems also block the transport of proton. The hydrazide-appended pillar[5]arene derivatives represent a new type of organic nanotubes. By using these simple models, the mimicking water transmembrane transport properties of natural water channel proteins is realized. The artificial system display potential applications in medical and water purification.In the third part, a new series of pillar[n]arenes (n=7-10) are prepared and their conformation and recognition properties are studied. X-ray crystal structure analysis reveals that pillar[n]arenes (n=8-10) possess two cavities like double pillar in their solid state. The complexing properties of these pillararenes for octyltrimethyl ammonium are further investigated by1H NMR experiments. The results demonstrate that pillar[7]arene and pillar[8]arene exhibit no bonding while pillar[9]arene and pillar[10]arene can form1:1and1:2complex with octyltrimethyl ammonium respectively. These pillar[n]arenes (n=7-10) provide good modules to constructure new supramolecular architectures and also provide new motifs for us to build new transmembrane channels.