Chiral Pillararene:"Light-Initiated Click" Systhsis Assembled On The Surface And Recognition

The pillar[n]arenes have been a popular family of macrocyclic arene hosts due to their accessible one-step synthesis,convenient functionalization,symmetrical prism structures and perfect cavity host-guest properties since they were reported in 2008.The pillar[5,6]arenes have been synthesized as platform moleculars and the chiral functional pillar[5,6]arenes have been synthesized via 'light-initiated click' reaction.The functional surface was fabicated based on the chiral pillar[5,6]arenes.The chiral recognition of functional surface to durg and protein was researched and chiral induction based on pillar[5]arenes and chiral guest interaction also discussed.Based on this point,research contents can be divided into seven sections around how to design and synthesize the receptors and how to fabricate the chiral surface towards chiral guest.1.The properties and applications of reponsive surface were reviewed.The novel structure,recognition properties and planar chirality of pillar[n]arene were introduced.The applications of 'light-initiated click' reaction on polymer material and supramolecular chemistry were discussed.Based on the above review,the design strategy and research contents of dissertation were proposed.2.The water soluble pillar[5,6]arenes were designed and synthesized by'light-initiated click' reaction.This kind of pillar[5,6]arenes were modified by carboxyl group or amino group.And then,the N-acetyl-D-/L-Cysteine modified pillar[5,6]arenes were designed and synthesized by 'light-initiated click' reaction.Above compounds were characterized by 1H NMR,13C NMR,MS and CD spectrum.3.N-acetyl-D-?L-Cysteine modified pillar[6]arenes(D-/L-NACP6)were designed and synthesized as receptor for R-adrenaline.And they were modified to fabricated chiral Si-surface via condensation reaction.The surface shown an efficient chiral discrimination for R-adrenaline.Notably,taking both advantages of functional pillar[6]arenes and Si-surface,the proposed D-/L-NACP6 not only shown high chiral recognition ability toward R-adrenaline in solution,but also a chiral visible macroscopic wettability change on surface was found out in the system.4.The planar chirality of pillar[5]arenes is caused by the substitution position of the alkoxy groups.The units can rotate around the methylene bridges,meaning that pillar[5]arene has two equivalent most stable conformations(pS and pR).Interconversion between pS and pR occurs by rotation of these units at 25? in solution.It is diffidult to separating the pS and pR conformation.We have introduced host-guest interaction to obtain the pS and pR based on CD study.The possible mechanism of chiral inducution was proposed and confirmed based on 1H NMR,Gaussian simulation.5.Based on the pS and pR planar chiral pillar[5]arene,and in order to achieve the application of planar chirality.The planar chiral pillar[5]arene was introduced on Au-surface.The pS and pR surface adsorption of lysozyme were researched.The proposed pR pillar[5]arenes not only demonstrates extremely high bonding ability and chiral selectivity toward recognition of lysozyme in solution,but a visible macroscopic chiral-responsive wettability of pR surface based on it adsorpted more lysozyme than pS surface.The chiral selectivity was also realized by electrochemical impedance in the system.6.The chiral memory surface based on pillar[5]arene was fabricated.The chiral inducution surface based on pillar[5]arene planar chirality was fabricated on Si-surface.And the ionic liquid was used as achiral guest to replace chiral guest R-and Sphenylethylamineon surface.The planar chirality signal of pillar[5]arene could be kept even when the chiral guest was removed.7.This dissertation have been designed and synthesized the chiral functional pillar[5,6]arenes via 'light-initiated click' reaction.And the chiral surface was fabricated to recognize drug and protein.The chiral memory surface based on pillar[5]arene was fabricated.