色谱 ›› 2023, Vol. 41 ›› Issue (10): 843-852.DOI: 10.3724/SP.J.1123.2023.04021

• 专论与综述 • 上一篇    下一篇

基于共价有机框架的色谱固定相制备及其应用研究进展

刘锦, 吴帆, 甘霖, 金乐怡, 林子俺*()   

  1. 食品安全与生物分析教育部重点实验室, 福建省食品安全分析与检测重点实验室, 福州大学化学学院, 福建 福州 350108
  • 收稿日期:2023-04-23 出版日期:2023-10-08 发布日期:2023-10-23
  • 通讯作者: *E-mail: zianlin@fzu.edu.cn.
  • 基金资助:
    国家自然科学基金(22274021);国家自然科学基金(21974021);国家自然科学基金(22036001)

Research progress on preparation and applications of covalent organic framework-based chromatographic stationary phases

LIU Jin, WU Fan, GAN Lin, JIN Leyi, LIN Zian*()   

  1. Ministry of Education Key Laboratory of Analytical Science for Food Safety and Biology, Fujian Provincial Key Laboratory of Analysis and Detection Technology for Food Safety, College of Chemistry, Fuzhou University, Fuzhou 350108, China
  • Received:2023-04-23 Online:2023-10-08 Published:2023-10-23
  • Supported by:
    National Natural Science Foundation of China(22274021);National Natural Science Foundation of China(21974021);National Natural Science Foundation of China(22036001)

摘要:

工业领域与科学研究的不断发展,使得复杂体系的高灵敏、高通量和高选择性分离分析面临新的挑战。色谱法在分离科学中发挥着不可替代的作用,已被广泛应用于环境监测、药物分析和食品安全等领域。由于载样量高、定量分析精确和重现性好等突出优势,基于多种保留机制的色谱分离技术已被应用于不同分析物的检测。固定相作为色谱柱的核心,对色谱的分离性能有着极其重要的影响。分离的选择性和效率极大程度上取决于所采用的固定相。然而,传统固定相如硅胶基质制备工艺复杂、pH适用范围窄,聚合物基质机械稳定性较差且易溶胀等缺点限制了其在分离领域的进一步应用。因此,开发高效的新型色谱固定相以满足不同情况下的分离要求是提高色谱分离效率的关键。共价有机框架(COFs)是一类由共价键连接而成的多孔晶体聚合物,具有低密度、高孔隙率、大比表面积和性质稳定等优点。这些突出优势使得COFs材料在分离分析领域具有潜在应用价值,且被认为是新型色谱固定相的理想材料。本文综述了最近5年基于COFs的色谱固定相的制备及其应用的最新研究进展,简要介绍了基于COFs的色谱固定相的制备,详细总结了基于COFs的固定相在色谱分离领域方面的最新应用,展望了基于COFs的色谱固定相的未来发展前景与趋势。

关键词: 共价有机框架, 色谱固定相, 有机化合物, 异构体, 手性化合物

Abstract:

Given continuous developments in industrial and scientific research, the separation and analysis of complex systems with high sensitivity, throughput, and selectivity is facing new challenges. Chromatography plays an irreplaceable role in separation science and is widely applied in environmental monitoring, pharmaceutical analysis, and food safety. Owing to their outstanding advantages, such as high loading capacity, precise quantification, and good reproducibility, chromatographic separation techniques based on various retention mechanisms have been utilized to detect different analytes. The stationary phase is the core material of chromatographic columns and has an extremely important influence on their separation performance. The selectivity and efficiency of separation largely depend on the chromatographic stationary phase. However, traditional stationary phases, such as silicon-based matrices, are characterized by complex preparation processes, poor permeability, large mass transfer resistance, and a narrow pH range. In addition, polymer matrices show poor mechanical stability and susceptibility to swelling, which limit their applications in the field of separation. Therefore, the development of novel stationary phases with the advantages of traditional stationary phases has become a research emphasis in the field of analytical science in efforts to meet separation requirements under different environments. Various stationary phases based on novel porous materials, such as metal organic frameworks (MOFs), porous organic cages (POCs), and covalent organic frameworks (COFs), are used for chromatographic separation. As mesh crystalline porous materials, MOFs have the advantages of a large surface area, adjustable structure, and easy functionalization; thus, they are widely used as chromatographic stationary phases in reverse-phase chromatography, hydrophilic-mode chromatography, mixed-mode chromatography, and other separation modes. However, because the pore size of MOFs is small and most MOFs demonstrate poor chemical stability under acidic or alkaline conditions, their applications in chromatographic separation are greatly limited. COFs are porous, crystalline polymer materials composed of light elements (H, O, C, N, B, and Si) connected via covalent bonds. Their advantages include a low density, large specific surface area, high porosity, good chemical and thermal stability, regular pores, and adjustable pore sizes. Because of their unique structures and properties, COFs are widely used in many fields such as catalysis, enrichment, gas capture, and sensing. COF materials are also suitable for separation analysis and considered ideal materials for novel chromatographic stationary phases. This review summarizes the latest research progress on the preparation and applications of COF-based chromatographic stationary phases over the past five years. First, the preparation of COF-based stationary phases (SiO2@COFs stationary phase, COFs monolithic stationary phase, pure COFs stationary phase and COFs-coated stationary phase) is introduced. The latest applications of COF-based stationary phases in the separation of organic compounds, isomers, and chiral compounds are then described in detail. Finally, the future development trends and challenges of chromatographic stationary phases based on COFs are discussed to provide new ideas for the future design and development of novel chromatographic stationary phases based on COFs.

Key words: covalent organic frameworks (COFs), chromatographic stationary phase, organic compounds, isomers, chiral compounds

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