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

作　　者：黄斌 陈娟 王帮进[1] 章俊辉 谢生明[1] 袁黎明[1] HUANG Bin;CHEN Juan;WANG Bangjin;ZHANG Junhui;XIE Shengming;YUAN Liming(School of Chemistry and Chemical Engineering,Yunnan Normal University,Kunming 650500,China)

机构地区：[1]云南师范大学化学化工学院,云南昆明650500

出　　处：《色谱》2024年第9期891-902,共12页Chinese Journal of Chromatography

基　　金：国家自然科学基金项目(22064020,21964021);云南省基础研究计划面上项目(202101AT070101,202201AT070029).

摘　　要：多孔有机笼(POCs)是一种新型的多孔分子材料,具有明确的分子内腔结构、丰富的主客体识别能力和良好的溶解性,因而在分子识别、气体吸附、传感、催化、色谱分离等多个领域受到广泛关注。本文由四(4-醛基苯基)乙烯和(R,R)-1,2-环己二胺通过席夫碱缩合反应合成了一种手性多孔有机笼(CPOC),采用静态涂敷法将其涂敷于毛细管柱内表面制备了气相色谱柱,测试了该柱对有机混合物、异构体以及手性化合物的分离能力。结果显示,该柱可以实现4种有机混合物(正构烷烃、芳香烃、正构醇和Grob混合物)中所有组分的基线分离;同时有9种二取代苯位置异构体以及包括结构异构和顺反异构在内的16种有机异构体在该柱上也获得了较好的分离。更重要的是,该柱还具有优秀的手性拆分性能,有12种手性化合物在该柱上得到了拆分,其中5种手性化合物(3-羟基丁酸乙酯、缬氨酸衍生物、谷氨酸衍生物、1,2-丁二醇二乙酸酯和1,2-环氧丁烷)获得了基线分离。将该柱与商品β-DEX 120柱的拆分效果相比,该柱可以拆分β-DEX 120柱不能拆分的3-羟基丁酸乙酯、缬氨酸衍生物、谷氨酸衍生物、1,2-环氧丁烷、环氧氯丙烷和环氧溴丙烷等6种手性化合物,说明其与β-DEX 120柱具有手性拆分互补性。研究表明,CPOC制备的毛细管柱对手性和非手性化合物都具有良好的分离能力。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 1638 cm-1,which was attributed to imine(-C=N-)absorption,as well as absorption peaks at 2928 and 2856 cm-1,which were attributed to the stretching vibrations of-CH2-and-CH-,respectively.MS analysis of CPOC revealed peaks at m/z=18019797,m/z=9019914,and m/z=6016631,corresponding to[M+H]^(+),[M+2H]^(2+),and[M+3H]^(3+),respectively,and indicating a molecular formula of CPOC(C_(126)H_(120)N_(12)).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 3500 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,isomer

关 键 词：气相色谱 固定相 手性分离 多孔有机笼 

分 类 号：O658[理学—分析化学]