| As a third-generation supramolecular host compound,calixarene has unique cavity structure,is easy to be chemically modified and has good biocompatibility,and is an ideal molecular platform for constructing a special structure and function.The amphiphilic aromatic derivatives obtained by specific modification not only have better water solubility,but also have a remarkable enhancement of aggregation stability.With the non-covalent bond as the driving force,the amphiphilic calixarene derivatives can selectively recognize the metal ions,anions,neutral molecules and bioactive active molecules,and at the same time,it is easy to self-assemble with itself or guest molecules into a variety of specific functional aggregates.The isoquinoline ionic liquid consists of the hydrophilic cationic isoquinoline ring head and the hydrophobic alkyl tail chain.The special chemical structure makes it possible to identify with calixarene by a variety of possible ways,and there are different aggregation behavior under different conditions.Based on the above background,this paper has designed and synthesized the calixarene derivatives of the upper marginal carboxylic acid group modification and the lower edge alkyl chain modification,and studied its surface activity and aggregation behavior.Based on this,further explored the identification and aggregation behavior of the calixarene derivatives and isoquinoline ionic liquids under different influence factors.This article mainly includes the following aspects:1.Synthesized amphiphilic calix[4]arene modified by the upper marginal hydrophilic carboxylic acid group and the lower marginal hydrophobic alkyl chain.The structure and purity of the compounds were determined by nuclear magnetic resonance spectroscopy,Fourier transform infrared spectroscopy,and elemental analysis.The structural characteristics and aggregation behavior of amphiphilic calix[4]arene in the gas-liquid interface were studied by means of traditional surfactant.The results showed that at the same pH,the critical micelle concentration(CMC)of the amphiphilic calix[4]arene gradually decreased with the increase of the hydrophobic alkyl chain length of the lower margin,and the value of ?cmc also decreased gradually.When the hydrophobic tails were the same,the critical micelle concentration under alkaline conditions was much larger than that under weak acid conditions.The aggregation behavior of amphiphilic calix[4]arene is influenced by concentration and pH,and has nothing to do with temperature.The collective size increased with the increase of solution concentration and pH.2.Firstly,the identification ratio of amphiphilic calix[4]arene and isoquinoline ionic liquid was preliminarily determined by using the electrical conductivity method.Then,the identification and mechanism between amphiphilic calix[4]arene and isoquinoline ionic liquids were revealed by isothermal titration microcalorimetry,static fluorescence,time-resolved fluorescence and NMR.Finally,the formation of self-assembled aggregates and their morphology were observed through dynamic light scattering and frozen etching transmission electron microscopy.The results showed that the recognition ratio of both of them is 1:1,and the increase of the alkyl chain and iso-quinoline ionic liquid alkyl chains in the amphiphilic calix[4]arene is beneficial to the identification,and the driving force is C-H…? action.The aggregates of the static host-guest complexes produced in the solution are identified as vesicles,and its size is affected by the alkyl chain length of the lower margin of amphiphilic calix[4]arene.3.The amphiphilic calix[4]arene was used as an anionic surfactant to study its compounding behavior with cationic isoquinoline ionic liquid surfactants,and compared with amphiphilic calix[4]arene and quaternary ammonium surfactant complex systems,this paper emphatically studied the adhesive behavior of the compound system and explored the critical gel concentration.Through rheology and fluorescence probe technology,the mechanism of gelation and the influence of concentration,pH,temperature,alkyl chain and hydrophilic head group on the complex system gel were explored.The results showed that the formation of gels was due to the formation of wormlike micelles in the system compound cross-linking winding form a three-dimensional network structure.The longer the hydrophobic alkyl chain,the smaller the hydrophilic head group is beneficial to the generation of the complex system gel.The increase of temperature and concentration leads to the transformation of the complex system from gel to sol,which is not conducive to the formation of gel. |
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