手性碳纳米复合材料的新组装策略及在毛细管气相色谱手性识别中的应用研究

The separation of chiral enantiomers is one of the most attractive tasks in analysis chemistry field. Currently, there are limit types of chiral stationary phase (CSP) used for gas chromatographic (GC) enantioseparation. With increasing number of enantiomers, some of racemates cannot be effectively enantioseparated. The project will focus on the design and synthesis of a series of amino acid ionic liquids (AAILs) as chiral center, incorporation with carbon nanomaterials which have abundant pore structures, high surface area and excellent thermal stability as the novel CSP in GC. The AAILs/carbon nanomaterial-based chiral composites will be first prepared by the self-polymerization-composite of dopamine and then statically coated onto fused silica capillary columns. The separation properties of these stationary phases will be evaluated by separating numbers of racemic compounds. In addition, the chiral recognition ability of these stationary phases for GC enantioseparation will be further improved by the selection and optimization of chiral composites with excellent enantioselectivity. The structure-activity relationship between the assembly, structure and properties of chiral composites and their chiral discrimination properties will also be studied. The results will be expected to reveal the chiral recognition mechanism of the chiral composites as the novel GC stationary phases. This study can provide theoretical and experimental basis to explore the chiral composites as novel chiral stationary phase for GC enantioseparation.

手性对映体的分离是分析化学领域的重要任务之一。目前用于手性对映体分离的气相色谱手性固定相种类较少，而且随着需分离的对映体数目不断增加，部分外消旋体不能有效拆分。针对这些问题，本项目拟设计合成一系列氨基酸离子液体（AAILs）作为手性中心，与具有大比表面积，丰富孔隙结构和良好热稳定性的碳纳米材料复合组装作为新型的气相色谱手性固定相，采用多巴胺自聚-复合技术构筑-组装手性碳纳米复合材料，并通过静态法将其制备成毛细管气相色谱手性柱。以多种外消旋体作为分析物考察复合材料固定相的手性选择性，遴选出具有优良手性选择性的碳纳米复合材料，并通过优化设计，进一步提高其手性识别能力。通过研究手性碳纳米复合材料的组装、结构、性质与其手性识别性能的构效关系，阐明手性碳纳米复合材料作为气相色谱手性固定相的手性识别机制，为探索新型的手性碳纳米复合材料在气相色谱手性拆分领域的应用提供理论和实验依据。

本项目利用多巴胺自聚-复合技术，制备了新型的手性碳纳米复合材料。这些复合材料作为固定相首次应用于毛细管气相色谱分析。由于碳纳米材料的熔点较高，所制备的色谱柱的柱效不高，未能实现对手性化合物的高效分离。此外，本项目合成和表征了新型的氨基酸离子液体、杯芳烃和聚己内酯。本项目深入研究了氨基酸离子液体、杯芳烃、聚己内酯，离子液体/杯芳烃，离子液体/聚己内酯的色谱分离性能。以上研究工作为制备新型的毛细管气相色谱固定相提供了重要的实验基础和可行性策略。氨基酸离子液体易于功能化，具有较好的化学稳定性和热稳定性，在常见的有机溶剂中溶解性较好，适合用作毛细管气相色谱固定相的研究。更重要的是氨基酸离子液体固定相具有较高的色谱选择性，能够分离多种在气相色谱领域难分离的对映异构体，在芳香类环境污染物的分离检测方面具有较好的应用前景。