Study Of Self-assemblies And Functional Materials Of Anthracene Containing Amphiphilic Molecules

For the past few years,self-assembly of amphiphilic molecules has attracted more and more attention,and based on which thousands of regular structures have been constructed.With more and more thorough understandings,researches on self-assemblies have involved various aspects ranging from molecular design,self-assembly mechanism,to the construction of functionalized structures.By means of introducing functional groups into the amphiphilic molecules,not only the regular selfassembled structures could be obtained,but the molecules with special properties could be to acquired for implementing a specific function.Anthracene is one of the best functional group in self-assembly and material design systems due to its hydrophobic conjugate plate,blue-violet fluorescence and reversible photodimerization.Herein,anthracene was introduced for preparing a series of anthracene containing amphiphilic molecules to conduct the studies from molecular design,self-assembly and assembly mechanism,to functional material construction.Specifically,anthracene was first used to adjust the hydrophobicity of amphiphilic molecules to fabricate the amphiphilic self-assemblies,and then to photocrosslink the self-assembly structures for the probe into assembly mechanism.Meanwhile,based on the anthracene containing amphiphilic molecular assemblies,we have developed and fabricated a functional material to achieve dye adsorption and separation.Anthracene was first introduced into β-cyclodextrin molecules to obtain anthracene-functionalized β-cyclodextrin(CD-AN).The obtained CD-AN amphiphiles could self-assemble in water from primary core-shell micelles with the hydrophobic anthracene parts interiorly and the hydrophilic cyclodextrin sections peripherally to strong and regular secondary aggregates with the diameter of around 600-700 nm via a multimicelle aggregation(MMA)process,followed by the further crosslinking through photodimerization of anthracene.Such photo-crosslinked selfassemblies were able to disaggregate reversibly into the primary micelles when changing the solution conditions,benefiting from the designed regular structure of the CD-AN and the rigid ranging of anthracene in the core during assembly.In solvents on the contrary,the amphiphilic CD-AN could assemble into reverse aggregates but cannot disaggregate after photocrosslinking.The design of CD-AN molecules made it possible to let the CD-AN primary nanoparticles capable of being crosslinked intrananoparticle exactly,therefore providing a new way of the oriented design and self-assembly of functionalized amphiphilic macromolecules in the process of MMA.Then,we introduced anthracene into amphiphilic hyperbranched poly(ether amine)system,using the regular self-assembly of molecules,to fabricate a novel anthracene-containing hyperbranched poly(ether amine)/carbon nanotube ultrathin membrane(hPEA-AN@CNT UTM),which could implement not only efficient selective adsorption but also separation and recycling of dye molecules with similar backbones and the same charge states.Taking advantage of the π-π stacking interactions between anthracene and CNT sidewalls,the anthracene and CNT could self-assemble to form the fibrous hPEA-AN@CNT complex with the hPEA-AN tightly coating on the CNT.Then,a simple filtration process was applied to prepare the smooth hPEA-AN@CNT UTM.It is the synergy of the host hPEA-AN molecules and the CNT components and the fibrous nano-scale network structure of the UTM that contribute to the superior adsorption performance of hPEA-AN@CNT UTM,which could be further crosslinked through anthracene photodimerization to make sure the UTM would be steady.Hydrophobic interactions instead of electrostatic interactions might be the primary origin of the adsorption forces,and the adsorption process of the dyes accorded well with the pseudo-second-order kinetic model and the Langmuir isotherm model.Meanwhile,the hPEA-AN@CNT UTM could present the long-term stability in the adsorption/desorption cycles,making it a potential candidate for use in wastewater treatment,especially for the removal and simultaneous separation of hydrophilic dyes with similar properties.