色谱2024，Vol.42Issue(9)：891-902,12.DOI:10.3724/SP.J.1123.2024.01025
手性多孔有机笼用作气相色谱固定相分离手性和非手性化合物
Chiral porous organic cage used as stationary phase for gas chromatographic separation of chiral and achiral compounds
摘要
Abstract
Porous organic cages(POCs)are a new type of molecular material.The well-defined cavities,abundant host-guest recognition ability,and good solubility of POCs render them attractive for use in various fields such as molecular recognition,gas adsorption,molecu-lar containers,sensing,catalysis,chromatographic separation.In this study,a chiral POC(CPOC)was synthesized via the Schiff base condensation of 4,4′,4″,4″′-(ethene-1,1,2,2-tetrayl)tetrabenzaldehyde with(R,R)-1,2-cyclohexanediamine.CPOC was characterized using nuclear magnetic resonance(NMR)spectroscopy,Fourier transform-infrared(FT-IR)spec-troscopy,mass spectroscopy(MS),and thermogravimetric analysis(TGA).The FT-IR spec-trum of CPOC showed a strong peak at 1 638 cm-1,which was attributed to imine(-C=N-)absorption,as well as absorption peaks at 2 928 and 2 856 cm-1,which were attributed to the stretching vibrations of-CH2-and-CH-,respectively.MS analysis of CPOC revealed peaks at m/z=1 801.9 797,m/z=901.991 4,and m/z=601.663 1,corresponding to[M+H]+,[M+2H]2+,and[M+3H]3+,respectively,and indicating a molecular formula of CPOC(C126 H120 N12).The TGA curve of CPOC indicated high thermal stability up to 360℃;thus,the material is suitable for use as a stationary phase for gas chromatography(GC).CPOC was coa-ted on the inner wall of a capillary column using the static coating method to prepare a GC col-umn.Scanning electron microscopy(SEM)was used to characterize the coating condition of the fabricated column.The SEM images showed that the column had a uniform coating with a thickness of approximately 200 nm.Column efficiency was determined to be 3 500 plates/m using n-dodecane as a target at 120℃.The polarity of the CPOC stationary phase was evaluated using McReynolds constants,which were measured using benzene,1-nitropropane,2-pen-tanone,pyridine,and 1-butanol as probe molecules at 120℃.The average McReynolds con-stant was 152,indicating that CPOC is a moderately polar stationary phase.The ability of the column to separate organic mixtures,isomers,and chiral compounds was subsequently investi-gated.All components of the four organic mixtures(n-alkanes,aromatics,n-alcohols,and Grob mixtures)tested achieved baseline separation on the column.In addition,nine positional isomers of disubstituted benzenes were well separated,and seven(o,m,p-nitrotoluene,o,m,p-nitrochlorobenzene,o,m,p-nitrobromobenzene,o,m,p-bromotoluene,o,m,p-dichlo-robenzene,o,m,p-chloroaniline,and o,m,p-bromoaniline)achieved baseline separation.Some polar and apolar structural isomers,such as pentanol,dimethylphenol,dimethylaniline,butanol,and C9 aromatic hydrocarbon isomers,were also well separated on the column.Five cis/trans-isomers(nerol/geraniol,cis/trans-1,3-dichloropropene,cis/trans-1,2,3-trichloro-propene,cis/trans-citral,and cis/trans-decahydronaphthalene)were baseline-separated on the column.More importantly,the column successfully separated 12 chiral compounds,indica-ting good chiral separation ability.Among these chiral compounds,five(ethyl 3-hydroxybu-tyrate,a valine derivative,a glutamic acid derivative,1,2-butanediol diacetate,and 1,2-epoxy-butane)achieved baseline separation.Six of these chiral compounds(ethyl 3-hydroxybutyrate,the valine derivative,the glutamic acid derivative,1,2-epoxybutane,epichlorohydrin,and epi-bromohydrin)could not be separated on a β-DEX 120 column but were well separated on the developed column.Moreover,the separation efficiency of 1,2-butanediol diacetate and the iso-leucine derivative on this column was better than that on the β-DEX 120 column.Separation of the glutamic acid derivative and o,m,p-nitrotoluene was performed before and after the column was used for repeated injections to explore its repeatability.The retention times and selectivity observed after 80,160,and 500 injections were nearly unchanged compared with those ob-tained following the first use of the column,indicating that the column has good repeatability.The column was conditioned at 280℃for a certain period to examine its thermal stability.Sep-aration of 3-hydroxybutyrate and o,m,p-nitrochlorobenzene after the column was conditioned at 280℃for 2,4,or 8 h revealed no obvious changes compared with the first use of the col-umn,indicating that the column had good thermal stability.Thus,CPOC is a stationary phase with good application potential for GC.关键词
气相色谱/固定相/手性分离/多孔有机笼Key words
gas chromatography(GC)/stationary phase/chiral separation/porous organic cage(POC)分类
化学引用本文复制引用
黄斌,陈娟,王帮进,章俊辉,谢生明,袁黎明..手性多孔有机笼用作气相色谱固定相分离手性和非手性化合物[J].色谱,2024,42(9):891-902,12.基金项目
国家自然科学基金项目(22064020,21964021) （22064020,21964021）
云南省基础研究计划面上项目(202101AT070101,202201AT070029).National Natural Science Foundation of China(Nos.22064020,21964021) （202101AT070101,202201AT070029）
Applied Basic Research Founda-tion of Yunnan Province(Nos.202101AT070101,202201AT070029). （Nos.202101AT070101,202201AT070029）
