基于纳米材料的拆分体系构建及其微调控机制研究

Due to their ability of improving chiral separation effects,this project is planning to a molecular design of carbon nanotubes (CNTs). Chiral recognition groups will be introduced to CNTs by covalent grafting or noncovalent coating,thus they can recognize enantiomers. Simultaneously, polar molecules and micro-environmental regulation molecules will be grafted onto aforementioned CNTs, and chiral CNT composites with different dispersibility and desirable chiral recognition are expected, that is, the chiral recognition adaptability of CNTs will be formed and enhanced. Chial CNT solid membranes will be prepared by using previous chiral CNT composites and used to enantioseparate amino acid enantiomers. The effects of grafted molecules, CNT prototype structures and preparation conditions and so on to the physical and chemical properties of the solid membranes will be discussed. The relationship among chiral CNT composites and amino acid enantiomers, including the effects of external environment will be investigated in a deep analysis from molecular levels. The correlation of "CNTs - chiral ligands - chiral recognition" will be found. The mechanism of enantioseparation and the regulation mechanism in the chiral separation systems are to be resoluted, thus control technologies of the chiral separation systems will be established. The project will provide the molecular design of chiral CNT composites and the regulation of chiral separation system with theoretical supporting and experimental basis.

基于将纳米材料用于拆分对映体可显著改善拆分效果这一特点，本项目拟针对碳纳米管进行分子设计，采用共价键接枝或非共价键包覆两种方式引入手性识别基团，使其具备手性识别功能。同时，以极性分子和微环境调节分子对其进行双修饰/多修饰，以期得到分散性能各异、手性识别功能优良的碳纳米管手性复合材料，改善其手性识别普适性。将上述具有手性识别功能的碳纳米管复合物制备成固膜拆分氨基酸对映体，探讨引入分子种类、碳纳米管本身结构、成膜条件等对固膜理化性质的影响。从分子水平深入分析碳纳米管手性复合材料与氨基酸对映体之间的各种作用及外部环境条件的影响，建立"碳纳米管-手性配基-拆分功能"的相关性，解析拆分机理和拆分体系的调控机制，实现拆分体系的可调控，为碳纳米管手性复合材料的分子设计及其拆分体系的调控提供理论支持和实验基础。

纳米材料可用于对映体拆分，显著改善拆分效果。项目针对碳纳米管进行分子设计，采用共价键接枝或非共价键包覆两种方式引入了手性识别基团，使其具备手性识别功能。较高立体选择性地合成了手性胺类化合物，制备了两种光学纯胺类化合物(R)-1-(1H-吲哚-3-基)丙-2-胺（e.e. > 99%）；采用双氧水（H2O2）氧化MWCNTs 引入羟基与羧基，将其与D-(-)-酒石酸（D-(-)-tartaric acid, DTA）偶联制得DTA 修饰的MWCNTs（MWCNTs-DTA）；制备了二碘卡宾偶联的多壁碳纳米管复合材料，探讨了其手性识别性能；制备了分散性能较好的羟丙基-β-环糊精修饰的氧化多壁碳纳米管（多壁碳纳米管-羟丙基-β-环糊精）复合材料，研究了其手性识别性能；制备了水溶液中稳定分散的聚乙二醇接枝的多壁碳纳米管；探究了氧化多壁碳纳米管对苏丹红I / II 的吸附性能；将羟丙基-β-环糊精、甲基-β-环糊精、羧甲基-β-环糊精、氨基-β-环糊精、巯基-β-环糊精、磺丁基-β-环糊精等修饰的单壁/多壁碳纳米管分散，以戊二醛作交联剂制备了多种新型基于碳纳米管的纳米手性固膜，将其用于拆分氨基酸对映体；以壳聚糖修饰了碳纳米管，将其用于修饰玻碳电极，在峰电流及峰电位差别上实现了氨基酸对映体的手性识别；构筑了基于碳纳米管的固相萃取柱，实现了水溶液中有机成分的分离富集及分析。从分子水平分析了碳纳米管手性复合材料与氨基酸对映体之间的各种相互作用，解析了拆分机理，实现拆分体系的可调控。