The Investigation Of Molecular Selectively Binding And Construction Of Functional Aggregates Based On Several Hydrophobic Macrocyclic Receptors

The synthesis,molecular recognition and assembly of cyclodextrin and other macrocycle receptors such as cucurbit[n]uril(CB[n]),nanocarbon tube(CNT) et al.are the most popular topics of supramolecular chemistry.To reveal the molecular recognition and assembly mechanisms of cyclodextrins,especially the per-methylated cyclodextrin(PMCD) and their derivatives,we prepared a series of novel per-methylated cyclodextrins and investigated their binding modes and molecular recognition behaviors and assembly arrangements for special guest molecules such as bile slats,oligopeptides and azo benzene derivatives.On the other hand,we successfully acquired two polymeric pseudorotaxanes constructed from CB[7] /PMCD and aniline.Moreover,a water-soluble CNT composite wrapped by PMCD/polyaniline polymeric pseudorotaxane were synthesized.All of these novel assemblies were further employed to explore their properties for the potential applications on chemistry and material fields.The major contents of this thesis are as follows:(1) Two novel PM-β-CD derivatives(1 and 2) appended with naphthalene and quinoline fluorophores,and further investigated their molecular binding ability and selectivity for bile salts.Complex-induced fluorescent behaviors,binding ability and selectivity for bile salts were checked by using the circular dichroism,2D NMR, steady-state and time-resolved fluorescent spectra.It is our special interest to compare the binding mechanisms betweenβ-CD and PM-β-CD with bile salts,and further discuss that how the substituted fluorescent groups affect the inclusion behaviors of PM-β-CD derivatives,and explore closely their photophysical/photochemical behaviors upon complexation with guests.(2) Two naphthalene fluorescence moiety linked amino-β-CD derivatives were prepared and their fluorescence behavior and binding mode with six oligopeptides by using fluorescence,circle dichroism and 2D NMR.The experimental results reveal that the different influence on the oligopeptide recognition behavior with different cavity. (3) Two inclusion complexes of PM-β-CD with 4-HAB and 4-AAB were obtained and their binding and assembly behaviors were studied by means of X-ray crystallography,circular dichroism and 2D NMR spectra,and isothermal titration calorimetry(ITC).To give more deep insight on the respective characteristics of CD and PMCD,their complexation structures and binding thermodynamics were systemically analyzed and discussed.Moreover,it is also our interest to explore how the disparities of substituents of azobenzene guests affect the inclusion complexation and aggregate behavior of PMCD(4) We constructed a polypseudorotaxane by capsulizing a PANI chain with numerous CB[7]cavities and the sufficient investigation on its morphology and stabilization effect to PANI radical cations by microscopy,EPR and cyclic voltammetry were investigated.(5) We constructed a polypseudorotaxane by capsulizing a PANI chain with numerous PM-β-CD cavities.The water solubility and photo-modulation controllability were investigated.The introduction of PM-β-CD enhance the water solubility of parent PANI.Moreover,the reversible redox properties of PANI chain remains after the treatment of PM-β-CDs.Furthermore,the proton transfer process of the polypseudorotaxane could be photo-modulated by the spiropyran(SP) even in aqueous solution.(6) We employed PANI/PM-β-CD polypseudorotaxane to regularly wrap onto the surface of the MWCNT to yield a novel polypseudorotaxane wrapped MWCNT composite.The assembly was characterized by using thermogravimetric analysis,Raman spectroscopy,XPS,TEM and AFM.Moreover,this composite shows an improved solubility and can be stably dispersed in water.