色谱2026，Vol.44Issue(6)：639-649,11.DOI:10.3724/SP.J.1123.2025.09020
介孔共价有机骨架核壳固定相的制备及其用于黄芪中黄芪甲苷含量的分析
Preparation of mesoporous covalent organic framework core-shell stationary phase and its application in the analysis of astragaloside Ⅳ content in Astragalus
摘要
Abstract
Quality control of traditional Chinese medicine(TCM)has always been a key and challenging issue in the field of its modernization research.This has posed a high demand for advanced separation materials due to the complex compositions.Covalent organic framework materials(COFs)are a new class of porous crystalline materials composed of multidentate organic units connected by covalent bonds.They have demonstrated significant application value in areas such as catalysis and chromatographic analysis.This study focused on developing a novel core-shell-type chromatographic stationary phase using 2,4,6-tris(4-aminophenyl)-1,3,5-triazine(TAPT)and 1,4-benzenedicarboxaldehyde(TA)as building units.The TAPT-TA-COF@SiO2 core-shell composite materials were successfully prepared on the surface of silica microspheres using a multi-step po-lymerization strategy,in which the SiO2 cores were fabricated using the polymerization-induced colloidal aggregation(PICA)method.The imine-linked TAPT-TA-COF@SiO2 core-shell stationary phase was subjected to comprehensive physicochemical characterization and chromatographic evaluation experiments.The analytical techniques employed included scanning electron microscopy(SEM),transmission electron microscopy(TEM),energy dispersive spectroscopy analysis(EDS),nitrogen adsorption-desorption isotherms,Fourier transform infrared spectroscopy(FT-IR),and powder X-ray diffraction(PXRD).The systematic characterization results clearly indicate that the prepared stationary phase exhibits excellent monodispersity,and the COF layer is uniformly coated on the surface of the SiO2 core.TEM characterization demonstrated that the thickness of the COF materials on the surface of SiO2 is approximately 110 nm.Furthermore,FT-IR spectra were collected and the results demonstrated that the characteristic stretching vibrations at 3 209,2 927,and 1 515 cm-1,attributed to N-H,C-H,and C=N stretching,confirm the condensation reaction between TAPT and TA.In the XRD pattern,the peaks observed at 16.6°,18.9°,25.2° and 27.5° were attributed to the COF material and were consistent with previous reports,thereby confirming the successful synthesis of this derivative.The N2 adsorption-desorption isotherm analysis confirmed that the material possesses a typical mesoporous structure.Its specific surface area and pore size distribution are similar to those of the original porous SiO2 microspheres,subsequently providing a structural basis for efficient chromatographic mass transfer kinetics.In addition,the chromatographic per-formance was investigated.And it was confirmed that the stationary phase was effectively used for the separation of representative neutral polar or non-polar compounds such as benzenes,alkyl-benzenes,phthalate esters,formamides,and aniline mixtures.These compounds are separated due to hydrophobic interactions,π-π interactions,and the unique mesoporous structure in the reversed-phase chromatography mode.ACN-water(30:80 or 40:60,volume ratio)was selected as the mobile phase at a flow rate of 1 mL/min.The results of the methodological validation indicate that the intra-batch relative standard deviations(RSDs)of one TAPT-TA-COF@SiO2 packed chromatographic column were less than 1.6％,demonstrating excellent preparation reproducibility.Furthermore,this stationary phase was applied to the quality control of traditional Chinese medicine.Specifically,it was used to determine the content of astragaloside Ⅳ in Astragalus according to pharmacopoeial records.The measured result met the pharmacopoeia standard of≥0.08％.This research work not only provides new opportunities for advancing fundamental and applied research on novel COF stationary phases,but also helps to further promote in-depth research on the application of COF materials at the intersection of separation science and pharmaceutical sciences.关键词
介孔/共价有机骨架/固定相/黄芪甲苷Key words
mesoporous/covalent organic framework(COF)/stationary phase/astragalo-side Ⅳ分类
化学化工引用本文复制引用
赵兴云,靳疆燕,刘肖剑,闫丽娟,杨思羽,张振伟,张莉芸,吴荣芳..介孔共价有机骨架核壳固定相的制备及其用于黄芪中黄芪甲苷含量的分析[J].色谱,2026,44(6):639-649,11.基金项目
国家自然科学基金(22304108) （22304108）
山西大学文瀛青年学者人才计划 （）
山西省中医药科研课题(2025ZYYA023,2025ZYYB040).National Natural Science Foundation of China(No.22304108) （2025ZYYA023,2025ZYYB040）
Program for Young Scholar Talents of Wenying in Shanxi University （）
Traditional Chinese Medicine Research Project of Shanxi Province(Nos.2025ZYYA023,2025ZYYB040). （Nos.2025ZYYA023,2025ZYYB040）
