高等学校化学学报2025，Vol.46Issue(11)：50-59,10.DOI:10.7503/cjcu20250102
巯基-烯点击反应制备手性多亚胺大环键合手性固定相用于高效液相色谱对映体分离
Preparation of a Chiral Polyimine Macrocycle Bonded Chiral Stationary Phase via Thiol-ene Click Reaction for Enantioseparation in High-performance Liquid Chromatography
摘要
Abstract
In this study,a chiral polyimine macrocycle,BINOL-CPM,was synthesized via a one-step condensation of(S)-2,2′-dihydroxy-[1,1′-binaphthalene]-3,3′-dialdehyde and 1,2-phenylenediamine.After modification,it was bonded to the surface of thiolated silica via thiol-ene click reaction to fabricate a chiral stationary phase(CSP)for high-performance liquid chromatography(HPLC).The CSP-packed column exhibits good chiral separation performance in both normal-phase(NP)and reversed-phase(RP)elution modes,with 12 racemates resolved in the NP mode and 6 racemates resolved in the RP mode.The chiral separation performance of this column for these resolved racemates was compared with two commonly used commercial columns,Chiralpak AD-H and Chiralcel OD-H.Among the 12 racemates resolved in the NP mode,4 racemates,[1-(3-fluorophenyl)ethanol,1-phenyletha-nol,3-hydroxy-2-butanone and 1-(4-fluorophenyl)ethanol],could not be resolved on the Chiralpak AD-H column,and 3 racemates,[1-(3-fluorophenyl)ethanol,3-hydroxy-2-butanone and 1-(4-fluorophenyl)ethanol],could not be resolved on the Chiralcel OD-H column.Among the 6 racemates resolved in the RP mode,one racemate(1-phenyleth-anol),could not be resolved on the Chiralpak AD-H column.Moreover,the resolution values(Rs)of some racemates on this column were higher than those on the two commercial columns.Therefore,this prepared column demonstrates good complementarity in chiral separation,enabling the separation of some chiral compounds that cannot be resolved or be well resolved by these two commercial columns.In addition,the column also demonstrates excellent reproducibility and stability in chiral separation.After hundreds of injections,the retention time(tR)and Rs of the two enantiomeric peaks for the separation of ethyl mandelate show no significant changes compared to the initial use of the column.The relative standard deviation(RSD,n=5)of tR for the chromatographic peaks of the two enantiomers was less than 0.49%,and the RSD of Rs(n=5)was less than 2.88%.Moreover,the column-to-column reproducibility was also good,with the RSD(n=3)of tR and Rs for the two enantiomeric peaks of ethyl mandelate separation on columns prepared from different batches being less than 1.09%and 5.75%,respectively.This study indicates that BINOL-CPM is a promising chiral separation material for HPLC and has good research significance and value.It also provides a reference for the development of novel HPLC CSP.关键词
高效液相色谱/手性分离/手性固定相/手性多亚胺大环Key words
High-performance liquid chromatography/Chiral separation/Chiral stationary phase/Chiral polyimide macrocycle分类
化学引用本文复制引用
吴嘉蕾,俞力琴,谢生明,王帮进,章俊辉,袁黎明..巯基-烯点击反应制备手性多亚胺大环键合手性固定相用于高效液相色谱对映体分离[J].高等学校化学学报,2025,46(11):50-59,10.基金项目
国家自然科学基金(批准号:22064020,22364022,22174125)资助. Supported by the National Natural Science Foundation of China(Nos.22064020,22364022,22174125). （批准号:22064020,22364022,22174125）
