Supramolecular Self-assembly And Properties Of Cucurbital Ring And Cyclic Organic Amine Molecules

Supramolecular self-assembly based on Cucurbit[n]uril（Q[n]）has attracted increasing attention because of their application in fabricating novel molecular device and supramolecular materials.In previous studies,the alkyl group and the aromatic group were usually chosen as guest molecules.From a structural viewpoint,the cyclohexyl moiety has a similar structure that is more reminiscent of an aromatic molecule rather than an alkyl group.Our interest in this thesis is mainly focused on the supramolecular interactions between Q[6],Q[8]and cyclohexylamine derivatives.A series of supramolecular self-assembly based on cucurbit-cyclicamine has been successfully constructed.The main content in this thesis as following:（1）Cyclohexylamine derivatives,namely cyclohexylamine（CyA）,cyclohexane-1,4-diamine（CyDA）,N-ethylcyclohexylamine（NECyA）,N-cyclohexylethanolamine（NCyEA）,and N-（3-aminopropyl）cyclohexylamine（N3ACyA）,were selected as the guests for binding to the Q[8]host.The interaction between Q[8]and cyclohexylamine derivatives was investigated by nuclear magnetic resonance spectroscopy and ITC.The results showed that Q[8]and cyclohexylamine derivatives formed an inclusion complex with molar ratio of 1:2.The binding constant（Ka）for the complexation of Q[8]with N3ACyA and NECyA was determined to be 10⁷ M^-1 at298.15 K,which is much larger than that of previously reported ternary complexes involving alkyl groups inside the Q[8]cavity(Ka on the order of 10⁵ M^-1).The X-ray structure revealed that two cycloalkane moieties can be simultaneously encapsulated in the hydrophobic cavity of the Q[8]host.（2）A series of supramolecular self-assembly based on cucurbit-cyclohexylamine derivatives has been successfully constructed,and the interaction between Q[6]and cyclohexylamine derivatives was characterized by single-crystal X-ray diffraction and XRD.The results are as follows:Q[6]and cyclohexylamine derivatives formed an inclusion complex with molar ratio of 1:1.Encouraged by their pores structure,we employed these supramolecular self-assembly to control drug delivery in vitro.Ibuprofen（IBU）was chosen as a model drug and the results showed that Q[6]·NCyEA·ZnCl₂ exhibited excellent ability of sustained/controlled release in IBU.（3）The supramolecular interactions between Q[5],Cy₅Q[5]and Amantadine,1,2-Diaminocyclohexane,p-Xylyenediamine was investigated by single-crystal X-ray diffraction.