基于Co-BDC-NH_(2)的二维手性金属有机框架纳米片用作气相色谱固定相  

Two-dimensional chiral metal-organic-framework nanosheets based on Co-BDC-NH_(2)used as stationary phases for gas chromatography

作　　者：杨梅芳 郑康妮 龙怡幸 李毅洁 王雪萍 章俊辉 袁黎明[1] YANG Meifang;ZHENG Kangni;LONG Yixing;LI Yijie;WANG Xueping;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》2025年第4期335-344,共10页Chinese Journal of Chromatography

基　　金：国家自然科学基金项目(22174125).

摘　　要：二维金属有机框架材料(2D-MOFs)具有易于衍生化、孔隙率高、活性位点充足等特点,目前,鲜有将2D-MOFs应用于色谱分离的研究报道,在气相色谱手性分离分析领域的报道更为罕见。本文通过表面活性剂辅助溶剂热法制备了2D-MOFs纳米片,即Co-BDC-NH_(2),采用扫描电子显微镜、X射线粉末衍射对其进行表征。通过后修饰法分别将手性配体甘氨酰-L-天冬氨酸、甘氨酰-L-谷氨酸引入到Co-BDC-NH_(2)中,得到两种具有手性的2D-MOFs纳米片材料,采用傅里叶红外光谱(FT-IR)、圆二色谱(CD)、热重分析(TGA)对其进行表征。将两种2D-MOFs纳米片材料用作气相色谱手性固定相,采用动态涂覆法分别将其涂覆到石英毛细管柱中,通过扫描电子显微镜分析,确定制备得到两根手性柱,并进行气相色谱分离测试。结果表明:两根色谱柱的理论塔板数各为3538和3108 N/m,柱效优良;两根柱子的麦氏常数依次为181与208,说明两种手性2D-MOFs纳米片是中等极性。两根色谱柱对位置异构体、外消旋化合物(尤其是氨基酸衍生物类)表现出较好的分离能力,其中,Co-BDC-NH_(2)-甘氨酰-L-天冬氨酸与Co-BDC-NH_(2)-甘氨酰-L-谷氨酸色谱柱分别对7种与8种外消旋化合物表现出手性识别能力。此外,Co-BDC-NH_(2)-甘氨酰-L-天冬氨酸色谱柱对正构烷烃混合物、正构醇混合物及Grob试剂也表现出较好的分离效果。本研究在2D-MOFs纳米片上引入了手性功能团,验证其作为气相色谱固定相的可行性,也拓展了其在手性分离分析领域的应用。Two-dimensional metal-organic-framework(2D-MOF)materials have emerged as a new class of functional 2D material.Compared to bulk crystals,2D-MOFs are easily derivatized,highly porous,and have sufficient active sites.While 2D-MOFs are of considerable research interest,they are also efficient candidates for multiple applications in a variety of fields owing to their numerous advantages.The ability to separate and analyze chiral compounds is greatly significant for progressing human society,and chromatographic separation is widely used in this regard owing to its high resolution and sensitivity.Few reports on the use of 2D-MOFs in chromatographic-separation applications currently exist,and those use gas chromatography to analyze and separate enantiomers are even rarer.Unsurprisingly,the development of novel stationary phases has become a popular topic in the chiral-chromatography field.In this study,2D-MOF nanosheets(Co-BDC-NH_(2))were synthesized using a surfactant-assisted solvothermal method.The nanosheets were subsequently characterized by scanning electron microscopy and X-ray diffractometry.MOFs can be post-synthetically modified without affecting their frameworks,and such modifications can lead to the construction of chiral MOFs.Accordingly,Co-BDC-NH_(2)was post-synthetically modified with glycyl-L-aspartic acid and glycyl-L-glutamic acid as chiral ligands to afford two chiral 2D-MOF nanosheets,namely Co-BDC-NH_(2)-glycyl-L-aspartic acid and Co-BDC-NH_(2)-glycyl-L-glutamic acid.These chiral 2D-MOF nanosheets were characterized by Fourier-transform infrared spectroscopy,circular dichroism,and thermogravimetric analysis.The two 2D-MOF nanosheet materials were used as chiral stationary phases in gas chromatography by coating them onto prepared capillary columns using a dynamic coating method;this process leaves a homogeneous coating layer on the inner wall of the column.Scanning electron microscopy confirmed that the two chiral columns had been successfully prepared.The columns were finally tested through gas-chr

关 键 词：二维手性金属有机框架纳米片 手性固定相 气相色谱 手性分离 

分 类 号：O658[理学—分析化学]