Construction Of Branched Block Copolymers Based On Living Supramolecular Polymers And Its Application In Chiral Recognition

Living supramolecular block copolymers(LSCP)are an emerging class of materials capable of combining different monomeric units to obtain complex functions beyond the monomers.Their potential has been widely demonstrated over the past few years.However,since this research is in the early stage of development,there are still many challenges:(1)How to realize living supramolecular block copolymerization with simple small-molecule monomers.Most of the current research is based on complex synthesis to meet the matching of structure and interaction,and its functional similarity also limits its development;(2)How to prepare complex high-level structures to obtain controllable life-like active materials.Among them,controlled branching has been fully demonstrated in biological systems,but the study of LSCP based entirely on non-covalently interacting branched structures is very limited due to the need for well-directed molecular design;(3)How to transfer the research object from microscopic research Zoom in to the macro,magnify small differences on the monomer scale for visualization with the naked eye.The research contents of this paper are as follows:1.A simple aromatic acid molecule,p-hydroxyphenylpropionic acid(HPA),was selected.After using the confinement effect of layered double hydroxide(LDH)nanomaterials to obtain intercalated hydrotalcite,the LDH laminate was dissolved and added with a suitable solution.Metastable assemblies of simple monomers are assembled into long-range anisotropic structures to obtain living supramolecular polymers(LSP)prepared from simple small molecules.Due to the existence of active ends,try to use other small molecule melamine(MM)as co-assembly molecules and provide branch points to participate in active supramolecular polymerization,thus obtaining a scheme for preparing active LSCP with complex branched structure and assembling by slow evaporation The unique macroscopic morphology of thermodynamically stable state is obtained.To explore the versatility of this scheme,the effect of intercalated molecules with different alkyl chain lengths(HPA;p-hydroxyphenylacetic acid,HAA;p-hydroxybenzoic acid,HBA)on the formation of LSP and the difference of LSCP after co-assembly with MM;MM homologous The effects of MM homologues(methylguanamine,MGA)and MM structural analogs(cyanuric acid,CA)as co-assembled molecules on LSCP;2.On the basis of the dynamic controllability of LSP,the dynamic controllability of LSCP was explored by changing the size of the LDH confinement space,the ultrasonic time and the time of adding the co-assembled molecule MM control preparation;similarly,freshly prepared LSCP as a seed-induced living supramolecular block copolymer(SSCP)also has excellent tunability;3.In the step-by-step assembly of chiral enantiomer molecules,the weak energy difference will gradually enlarge.Macroscopic morphology of thermodynamically stable state prepared by LSP,active LSCP,and evaporative assembly step-by-step amplifies the energy difference between small molecules(L-tyrosine,L-Tyr;D-tyrosine,D-Tyr),which also Provides the possibility for naked-eye visualization of chiral recognition.