Salen金属配合物的液相色谱手性固定相的合成及特性研究

Chirality is one of the basic phenomena in nature, and enantiomeric drugs can have entirely different medicinal properties. At present, there are three main chiral analysis methods for separating chiral compounds. These are high performance liquid chromatography, capillary gas chromatography and high performance capillary electrophoresis. However the use of these analysis methods is rather constricted due to the limitation of selectivity of the chiral separation column. Salen is a famous chiral catalyst and chiral extractant. It also has a high chiral recognition. This study investigated the synthetic method of Salen ligands, and also, the selectivity and synthesis of Salen metal complexes with better chiral molecular recognition. To investigate the method of the separation of chiral liquid chromatography and explore the chiral resolution mechanism of various Salen metal complexes in various Salen ligands, with different optical size of complexes, bonding arms and solute molecules, the study operated by bonding the Salen metal complex bone with silica gel in a self-made chiral separation column. The study discovered new Salen metal complexes for use in a type of high performance liquid chromatography with chiral stationary phase, which has significant application prospects and the prospect of proprietary intellectual property rights. It provided a new solution for chiral separation and detection in natural products, and for the separation of chiral drugs. The use of chromatographic separation and the development of chiral drugs and natural products in Yunnan are also improved in this study.

手性是自然界的基本属性之一,对映体药物常有截然不同的药性。目前对手性化合物的分离主要使用高效液相色谱、毛细管气相色谱、高效毛细管电泳三大手性分析方法，它们所使用的手性分离柱选择性仍比较有限，使其应用仍受到一定限制。Salen是著名的手性催化剂以及手性萃取剂，具有显著的手性识别性能。本项目将研究Salen配体的合成方法、选取和合成具有较好手性分子识别性能的Salen金属配合物，将Salen型金属配合物键合到硅胶上自制手性分离柱，考察Salen型配体种类、不同的金属配合物、配合物旋光性大小、键合臂、溶质分子等对液相色谱手性分离的影响，探索手性Salen型金属配合物的手性拆分机理。研究出拥有自主知识产权、具有明显应用前景的新型Salen型金属配合物高效液相色谱手性固定相，为手性药物分离、天然产物中手性化合物的分离检测提供新的方法，促进色谱分离科学、手性药物以及云南天然产物的发展。

高效液相色谱（HPLC）是一种新型高效的固-液分配色谱技术，也是分离和测定药物对映体的常用方法。手性HPLC拆分法是以现代HPLC技术为基础，引入手性环境使对映异构体间呈现物理特征的差异而进行分离。手性Salen金属配合物、手性冠醚、手性介孔硅等具有显著的手性识别性能。本项目合成和选取了具有较好手性选择性能的Salen型金属配合物，并将其键合到硅胶上作为液相色谱固定相自制了HPLC手性分离柱，对大量的手性样品及异构体样品进行了拆分实验研究，同时考察和探索了一些因素对液相色谱手性分离的影响。项目还合成了具有手性表面的SBA-15、手性冠醚R-(3,3'-二溴基-1,1'-二萘基)-20-冠-6，手性介孔硅等手性识别材料，也将他们作为液相色谱固定相自制了HPLC手性分离柱，对大量的手性样品进行了拆分实验研究。以上自制色谱手性柱对不同的手性化合物和异构体表现出了不同程度的分离效果。该研究工作为手性药物分离、天然产物中手性化合物的分离检测提供了新的方法。