Study On Novel Chromatographic Stationary Phases Based On Chiral Metal-organic Framework Materials And Their Applications

Metal-Organic Frameworks(MOFs) constructed by metal ions and organic ligands, which has potential applications in gas storage, gas separation, catalysis, imaging, and separation. In several cases, unwanted side effects or even toxic effects may occur with the inactive enantiomer. The administration of pure, pharmacologically active enantiomers is therefore of great importance. Emerging chiral MOFs have great potential applications in enantioseparation, drug discovery for chiral analyses and preparation due to their chiral channels and the resolved molecules, large specific surface areas, controllable synthesis and flexibility, high adsorption affinity, diverse structures and pore topologies, accessible cages, and tunnels. Numerous MOFs have been synthesized and some of them have already demonstrated great potential in such breakthrough type separations, both in the liquid and in the gas phase. Despite the many pioneering works on chromatographic separation, only a few chiral MOFs have been studied in the High-Performance Liquid Chromatography(HPLC) chiral separation. This dissertation mainly composed of three parts:1. A Planar-Tetracoordinated-Oxygen(pt O) containing three-dimensional chiral channel framework Mn4O(D-Cam)4(Me2NH2)3(H2O)5 has been synthesized and characterized, which can be used as a new chiral stationary phase on high-performance liquid chromatography(HPLC) to efficiently separate racemates. Mn4O(D-Cam)4(Me2NH2)3(H2O)5 is the first Mn4 O cluster-based 3D homochiral framework constructed by a planner tetra-coordinated oxygen(pt O) and enantiopure D-camphoric acid, which was used as a new stationary phase on HPLC. Due to its chiral condition, we used it on HPLC separations of chiral compounds, including racemates, positional isomers, alcohols and so on. The experiment shows that Mn4 O stationary phase possessed outstanding chiral recognition ability toward isomers, alcohols etc, especially for chiral racemates. Five chiral compounds include pharmaceutically important(±)-ibuprofen and(±)-1-phenyl-1, 2-ethanediol were separated at least 85% baseline resolution. It demonstrated that the unique feature of shape selectivity and multiple active sites provide MOF packed columns a greater potential for HPLC separation. The chiral MOFs explored as a novel chiral stationary phase for HPLC enantioseparation are practicable.2. Enantiopure L-Lac acid as chiral source, porous-framework material which [Zn2(bdc)(L-Lac)(dmf)](DMF)(1·DMF) has a three-dimensional channel with intrinsic chiral topology was synthesized according to literature, and packed into four stainless steel empty columns to investigate its chromatographic activities. Our investigation was mainly about separation of racemates and sulfoxide. The result shows chiral MOF showed a narrow range of chiral compounds, especially chiral recognition ability towards sulfoxides.3. Three-dimensional chiral MOF [Mn3(HCOO)2(D-Cam)2(DMF)2]n has been synthesized under hydrothermal condition via enantiopure D-Cam as started material according to the literature. Using this chiral MOF as stationary phase on HPLC to investigate separation of chiral compounds, results shows that this chiral MOF has good chiral separation ability to organic acid and alcohol, indicating the chiral stationary phase has good stability and separation ability. We believe convenient selectivity on the naturally chiral MOF column can promote the application of chiral MOFs used as stationary phase on HPLC on certain degree.