基于手性金属-有机骨架材料的高效液相色谱手性柱的研究

Currently, chiral analytical methods mainly include high performance liquid chromatography, capillary gas chromatography, and high performance capillary electrophoresis.However, the high performance liquid chromatography is the most widely used. Metal-Organic Frameworks (MOFs) is relatively a new class of multi-functional materials with uniform structured cavities, high surface areas (more than 10000 m2/g), as well as excellent chemical and thermal stability. In recent years, there are only three attempts of chiral MOFs used in the liquid chromatographic enantioseparation, which have been published in JACS and CC.However, they have the shortcomings of low chiral selectivity and column efficiency.This project includes: (A) synthesis and optimization of many chiral MOFs for obtaining high selectivity chiral MOFs; (B) further enhancing chiral selectivity of chiral MOFs by post-synthetic modification; (C)preparation of chiral column with high column efficiency by immobilizing some chiral MOFs on silica sphere particles; (D)the structures of chiral stationary phases are characterized by IR,UV,elemental analysis,SEM,TEM,single crystal and powder XRD for exploring the chiral recognition mechanism. This research will develop a new type of HPLC CSP with high selectivity, column efficiency and practicality, and open a new door for the development of a new generation of HPLC CSP with independent intellectual property rights.

目前手性分析方法主要有高效液相色谱、毛细管气相色谱和高效毛细管电泳等，而高效液相色谱应用最为广泛。金属-有机骨架材料（MOFs）是一类新型多功能材料，具有有序的孔穴结构、高比表面积（可超过10000平方米/克）及良好的化学和热稳定性。近年来已有3篇关于手性MOFs用于液相色谱对映体分离的研究发表在JACS和CC上，但它们都存在着手性选择性不足和手性柱效较低的缺点。本项目将：A、手性MOFs进行合成及大量筛选以获得高手性选择性的MOFs手性固定相；B、对一些手性MOFs进行后修饰进一步提高其手性选择性；C、将手性MOFs固载于硅球颗粒上制备高柱效手性柱；D、通过红外、紫外、元素分析、扫描和透射电镜、单晶和粉末X-射线衍射等表征手性固定相的结构特征，探索其手性识别机理。研究具有高选择性，高柱效和实用性广的高效液相色谱手性固定相，为开发具有自主知识产权的新一代高效液相色谱手性固定相开辟新的途径。

目前，手性分析方法主要有高效液相色谱、毛细管气相色谱和高效毛细管电泳等，而高效液相色谱应用最为广泛。近年来，手性金属-有机骨架材料（metal-organic frameworks, MOFs）因其优异的手性功能性而被广泛应用于不对称催化和手性分离。本项目将手性金属-有机骨架材料作为固定相开发成为新型的高效液相色谱手性柱。项目主要研究内容：（1）首先按文献合成及表征了39种手性MOFs；（2）将化学稳定性良好、孔尺寸合适的手性MOFs材料用作固定相制备成高效液相色谱手性柱。成功制备了多种手性MOFs液相色谱柱并用于外消旋化合物的拆分，研究结果表明有些手性MOFs柱具有较好的手性拆分能力；（3）为了提高手性MOFs柱的柱效和拆分能力，将具有较好手性识别性能的手性MOFs制备成手性MOFs@SiO2核壳复合材料，并将其制备成液相色谱手性柱用于外消旋化合物的拆分。制备的手性MOFs@SiO2柱的柱效和手性拆分能力相对于纯手性MOFs液相色谱柱有明显的提高，同时大大缩短了手性样品的分析时间。结果表明通过制备手性MOFs@SiO2核壳复合材料能够很好的提高手性MOFs液相色谱柱的柱效和分离性能，为手性MOFs材料更广泛的用作HPLC固定相拆分外消旋化合物提供了一条新的途径；（4）初步考察了手性MOFs的结构与手性拆分能力的关系。.在该项目的资助下，共发表学术论文10篇，其中SCI论文7篇、核心期刊论文3篇；申请发明专利1项（实质审查中）。培养硕士生3名，其中1名已经取得硕士学位，2名在读。