全手性金属有机框架色谱固定相的手性拆分性能及机理

It is very important to use chiral stationary phases for the separation and analysis of chiral compounds. Novel homochiral metal organic frameworks(HMOFs) based on animo acid are used as chiral stationary phases for enantiomeric resolution. A multitude of racemic oxygen-, nitrogen- and sulfur-containing selectands can be separated without prior derivatization into enantiomers by complexation GC. Moreover, One of the most prominent advantages of using HMOFs as CSPs is their high column capacity,which is made possible by their highly porous frameworks.Based on the earlier research,the project will embarked upon chiral separation of HMOFs on gas chromatogaraphy for chiral compounds,in order to estabish an analysis system based on HMOFs chiral station phases for GC.The Chiral Discrimination and Interaction Mechanism Between Enantiomers and HMOFs will be studied. At the same time, other questions such as structure-activity relationship, analysis categories, qualitative and quantitative basis, influence factors and so on, will be studied.Moreover,high resolution and rapid separation of the racemic oxygen-, nitrogen- and sulfur-containing selectands will be investigated using HMOFs-based chiral stationary phases for GC.The further study of the subject will provide better technical support for the application of MOFs in the field of chiral separation and give new impetus for the progress of chromatographic stationary phase materials.

手性色谱固定相在手性化合物的分离及检测方面非常重要。课题以研制新型高效氨基酸类全手性金属有机框架化合物（HMOFs)作为手性分离材料。作为手性气相色谱固定相，一是能够分离大量无需衍生化的含氧（如醇、酸）、含N及含S的外消旋化合物，二是具有高孔隙率的手性金属有机框架化合物作固定相可获得高的柱容量。在此前期研究基础上，课题首次将基于光学纯氨基酸（缬氨酸等）类全手性金属框架化合物作为气相色谱固定相，分离旋光异构体，创建全手性金属有机框架化合物固定相分析检测旋光异构体的分析及分离体系。重点研究该固定相的手性分离机理、材料的构效关系、分析类别、定性定量依据及影响因素等，实现对含O、N及S等的手性异构体的高效快速检测及制备分离。课题深入研究将为MOFs材料在手性分离中的应用提供技术支持，为分析复杂手性体系提高技术和理论支持,为手性色谱材料技术进步提供新的动力。

采用含N及羧基的配体合成了不同结构的全手性有机框架化合物和非手性有机框架化合物，通过动态法将上述全手性有机框架化合物和非手性有机框架化合物沉积到毛细管内表面，制备得到基于全手性有机框架化合物和非手性有机框架化合物的色谱毛细管柱，考察该固定相的分离性能，并在线监测手性分子与全手性有机框架化合物结合的热力学过程，推算出识别的异构体时的焓变和熵变，对识别机理进行了初步探讨。获得的全手性有机框架化合物对对芳烃异构体、烷烃异构体表现出较好的选择性，并且对手性分子特别是α-蒎烯表现出较好的识别能力及选择性；而非手性有机框架化合物对芳烃异构体、烷烃异构体表现出较好的选择性。识别过程由焓变和熵变共同控制。此外课题还进行了相关的研究，合成制备了环糊精衍生缬氨酸固定相及层状纳米g-C3N4，并对环糊精衍生缬氨酸拆分手性异构体及层状纳米g-C3N4分离异构体性能进行了研究，环糊精衍生缬氨酸对手性异构体如柠檬烯、乳酸甲酯、樟脑及1-苯乙醇等显示出了一定的选择性和分离能力。