Cheng Ying-Chao, Gao Yi-Yang, Li Xiao-Min, Chen Lu-Yu, DU Fang, Guo Jie, Meng Yi-Tong, Sun Min, Feng Juan-Juan
School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China.
Se Pu. 2025 Feb;43(2):120-130. doi: 10.3724/SP.J.1123.2024.01002.
Solid-phase microextraction (SPME) is a fast and simple sample preparation technique that enables the enrichment of analytes, and it is used in combination with other detection techniques to provide accurate and sensitive analytical methods. SPME is widely used in environmental monitoring, food safety, life analysis, biomedicine, and other applications. The extractive coating is the core of the SPME technique, and the properties of the extractive coating greatly influence extraction selectivity and efficiency, as well as the enrichment effect. Therefore, the development of new and efficient extractive coating materials remains a hot topic in the analytical chemistry and sample preparation fields. Covalent organic frameworks (COFs) are a kind of porous crystalline network polymer materials formed by covalent bonds. Owing to the advantages of large specific surface area, high porosity, good stability, high designability, simple synthesis and post-modification, etc., it has been widely used in gas adsorption, catalysis, sensing and drug delivery. In recent years, COFs have attracted much attention in the field of sample preparation. A variety of novel COF-based SPME materials had been developed for extracting and enriching various types of analytes through - interaction, hydrophilic/hydrophobic interaction, electrostatic adsorption, and hydrogen-bonding, as well as pore effects. In this paper, the research advances of COFs for using in fiber-, in tube-, and membrane-based SPME over the past three years were discussed. Fiber surfaces had been modified with functionalized COFs or COF-hybrid materials for use in SPME through physical coating, in-situ growth, and chemical-bonding approaches. The combination of SPME fiber and chromatographic analysis can be used to detect a variety of analytes such as polycyclic aromatic hydrocarbons, phthalates, polychlorinated biphenyls, and pesticides in environmental and food samples, with good enrichment effects, wide linear ranges, and high sensitivity. Based on in tube-SPME, COFs-based monolithic column and fiber-filled tube as the extraction tubes were combined with high performance liquid chromatography online to develop highly sensitive detection methods for synthetic phenolic antioxidants and bisphenol compounds, respectively. In addition, COFs had also been used in membrane SPME technique, showing high efficiency in the extraction of trace polychlorinated biphenyls in environmental water. Finally, the development trends of COFs in the field of SPME was prospected.
固相微萃取（SPME）是一种快速简便的样品制备技术，能够实现分析物的富集，它与其他检测技术结合使用，以提供准确且灵敏的分析方法。SPME广泛应用于环境监测、食品安全、生命分析、生物医药等领域。萃取涂层是SPME技术的核心，萃取涂层的性质极大地影响萃取的选择性和效率以及富集效果。因此，开发新型高效的萃取涂层材料仍然是分析化学和样品制备领域的热点话题。共价有机框架（COFs）是一类通过共价键形成的多孔晶体网络聚合物材料。由于具有比表面积大、孔隙率高、稳定性好、可设计性强、合成及后修饰简单等优点，它已被广泛应用于气体吸附、催化、传感及药物递送等领域。近年来，COFs在样品制备领域备受关注。已经开发出多种基于COF的SPME材料，通过 - 相互作用、亲水/疏水相互作用、静电吸附、氢键作用以及孔隙效应来萃取和富集各类分析物。本文讨论了过去三年COFs在基于纤维、管内和膜的SPME中的研究进展。通过物理涂覆、原位生长和化学键合方法，用功能化的COFs或COF杂化材料对纤维表面进行修饰，用于SPME。SPME纤维与色谱分析相结合，可用于检测环境和食品样品中的多种分析物，如多环芳烃、邻苯二甲酸酯、多氯联苯和农药等，具有良好的富集效果、宽线性范围和高灵敏度。基于管内SPME，分别将基于COFs的整体柱和填充纤维管作为萃取管与高效液相色谱在线联用，开发了合成酚类抗氧化剂和双酚类化合物的高灵敏度检测方法。此外，COFs还被用于膜SPME技术，在环境水中痕量多氯联苯的萃取方面显示出高效性。最后，对COFs在SPME领域的发展趋势进行了展望。
