多孔有机笼的制备及其用作毛细管电色谱手性固定相  

Preparation of porous organic cage and its use as chiral stationary phase for capillary electrochromatography

作　　者：郑康妮 秦该照 蒋雪菲 章俊辉 袁黎明[1] ZHENG Kangni;QIN Gaizhao;JIANG Xuefei;ZHANG Junhui;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》2023年第10期929-936,共8页Chinese Journal of Chromatography

基　　金：国家自然科学基金(22174125).

摘　　要：多孔有机笼(POCs)是具有一类内在的、客体可及的空腔的离散分子,是一类独特的微孔材料。本文根据席夫碱反应原理,用(1 R,2R)-二氨基环己烷和3,3′,5,5′-四醛基-4,4′-联苯二酚缩合成一种孔径均匀、高比表面积、热化学稳定性良好的棱柱形手性多孔有机笼(POCs)。采用核磁共振氢谱仪、红外光谱、热重分析和扫描电子显微镜对该材料进行表征。将该材料溶解在二氯甲烷中,用动态涂覆法将溶液均匀地涂覆在石英毛细管内壁上,制成毛细管电色谱柱。结果表明,该手性电色谱柱不仅能拆分氧氟沙星、特罗格尔碱、2-氨基-1-丁醇和1-苯基-1-戊醇4种手性药物,还能拆分o,m,p-甲苯胺和o,m,p-氯苯胺2种位置异构体,说明该手性柱具有良好的手性分离能力。通过研究氧氟沙星、特罗格尔碱、2-氨基-1-丁醇和1-苯基-1-戊醇的最佳拆分条件,得出电压、缓冲溶液浓度和pH值对组分分离度有显著影响,其中,氧氟沙星、特罗格尔碱、2-氨基-1-丁醇的最优分离电压均为15 kV,1-苯基-1-戊醇的最佳分离电压为17 kV;氧氟沙星、特罗格尔碱、2-氨基-1-丁醇、1-苯基-1-戊醇的最佳缓冲液浓度均为0.100 mol/L,pH为7.5。在最佳的分离条件下,该电色谱柱拆分氧氟沙星、特罗格尔碱、2-氨基-1-丁醇和1-苯基-1-戊醇的分离度分别为1.80、3.33、1.69、1.18,都获得了较好的分离效果。可见,POCs是一种良好的手性毛细管电色谱固定相,有一定的手性拆分能力,在色谱分离中具有良好的应用前景。Porous organic cages(POCs)are a unique type of microporous materials composed of discrete molecules with internal cavities that are accessible to various compounds.In this study,a prismatic chiral POC with good thermochemical stability was synthesized by condensing(1 R,2R)-diaminocyclohexane and 3,3′,5,5′-teturonic-4,4′-biphenediol via the Schiff base reaction and characterized by proton nuclear magnetic resonance spectroscopy,infrared(IR)spectroscopy,thermogravimetric analysis(TGA),and scanning electron microscopy.The IR spectrum of the POC revealed a strong characteristic absorption peak at 1635 cm-1,indicating that it formed imine bonds(C=N).The absorption peak at 3425 cm-1 was attributed to the stretching vibrations of-OH,the absorption peaks at 2925 and 2858 cm-1 were attributed to the stretching vibrations of N=C-H and C-H,and the absorption peaks at 1446 and 1383 cm-1 were attributed to the stretching vibrations of C=C-H and C=C in the benzene ring.High-resolution mass spectral analysis of the POC showed a molecular ion peak at m/z 1363.7228,indicating its successful synthesis.TGA was performed from 25 to 800℃at a rate of 10℃/min,and the results of this analysis showed that the POC was stable up to approximately 300℃.The POC was dissolved in dichloromethane and uniformly coated on the inner wall of a quartz capillary via the dynamic coating method to prepare a capillary electrochromatographic column.The experimental results revealed that the chiral electrochromatographic column could not only resolve ofloxacin,Troger’s base,2-amino-1-butanol,and 1-phenyl-1-amyl alcohol but also separate the isomers of o-,m-,and p-toluidine and o-,m-,and p-chloroaniline,indicating its good chiral separation ability.Investigation of the optimal separation conditions for ofloxacin,Troger’s base,2-amino-1-butanol,and 1-phenyl-1-amyl alcohol revealed that the voltage,buffer solution concentration,and pH significantly affected their separation degree.In particular,the optimal separation voltage for ofloxacin,Trog

关 键 词：毛细管电色谱 多孔有机笼 手性分离 手性药物 

分 类 号：O658[理学—分析化学]