Dong Qing, Guo Xinyu, Qu Xinran, Bai Siqi, You Xingyu, Cui Hongshou, Qin Shili, Gao Lidi
College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar, 161006, China.
College of Chemistry and Chemical Engineering, Qiqihar University, Qiqihar, 161006, China.
Talanta. 2023 Jun 1;258:124415. doi: 10.1016/j.talanta.2023.124415. Epub 2023 Mar 8.
A novel chiral covalent organic framework (CCOF) was synthesized with an imine covalent organic framework TpBD (synthesized via Schiff-base reaction between phloroglucinol (Tp) and benzidine (BD)) modified using (1S)-(+)-10-camphorsulfonyl chloride as chiral ligand by chemical bonding method for the first time, and was characterized by X-ray diffraction, Fourier-transform infrared spectra, X-ray photoelectron spectroscopy, nitrogen adsorption/desorption, thermogravimetry analysis, and zeta-potential. The results revealed that the CCOF had good crystallinity, high specific surface area and good thermal stability. Then, the CCOF was employed as stationary phase in open-tubular capillary electrochromatography (OT-CEC) column (the CCOF-bonded OT-CEC column) for enantioseparation of 21 single chiral compounds (12 natural amino acids including acidic, neutral and basic, 9 pesticides including herbicides, insecticides and fungicides) and simultaneous enantioseparation of mixture amino acids and pesticides with similar structures or properties. Under the optimized CEC conditions, all the analytes reached the baseline separation with high resolutions of 1.67-25.93 and selectivity factors of 1.06-3.49 in 8 min. Finally, the reproducibility and stability of the CCOF-bonded OT-CEC column were measured. Relative standard deviations (RSDs) of retention time and separation efficiency were 0.58-4.57% and 1.85-4.98%, and not obviously changed after 150 runs. These results demonstrate that COFs-modified OT-CEC explore a promising method to separate chiral compounds.
首次通过化学键合法，以（1S）-（+）-10-樟脑磺酰氯为手性配体，对通过间苯三酚（Tp）与联苯胺（BD）之间的席夫碱反应合成的亚胺共价有机框架TpBD进行修饰，合成了一种新型手性共价有机框架（CCOF），并通过X射线衍射、傅里叶变换红外光谱、X射线光电子能谱、氮吸附/脱附、热重分析和zeta电位对其进行了表征。结果表明，该CCOF具有良好的结晶性、高比表面积和良好的热稳定性。然后，将CCOF用作开管毛细管电色谱（OT-CEC）柱（CCOF键合OT-CEC柱）的固定相，用于21种单一手性化合物（包括酸性、中性和碱性的12种天然氨基酸、包括除草剂、杀虫剂和杀菌剂的9种农药）的对映体分离，以及结构或性质相似的混合氨基酸和农药的同时对映体分离。在优化的CEC条件下，所有分析物在8分钟内实现了基线分离，分辨率高达1.67-25.93，选择性因子为1.06-3.49。最后，测定了CCOF键合OT-CEC柱的重现性和稳定性。保留时间和分离效率的相对标准偏差（RSD）分别为0.58-4.57%和1.85-4.98%，在150次运行后没有明显变化。这些结果表明，COF修饰的OT-CEC为手性化合物的分离探索了一种有前景的方法。
