色谱 ›› 2025, Vol. 43 ›› Issue (2): 120-130.DOI: 10.3724/SP.J.1123.2024.01002

• 专论与综述 • 上一篇    下一篇

基于共价有机框架材料的固相微萃取研究进展

程颖超, 高祎阳, 李小敏, 陈鲁玉, 杜芳, 郭洁, 孟弋童, 孙敏*(), 冯娟娟*()   

  1. 济南大学化学化工学院, 山东 济南 250022
  • 收稿日期:2024-01-02 出版日期:2025-02-08 发布日期:2025-01-23
  • 通讯作者: *Tel:(0531)82765475,E-mail:chm_sunm@ujn.edu.cn(孙敏);
    Tel:(0531)82765475,E-mail:chm_fengjuanjuan@ujn.edu.cn(冯娟娟).
  • 基金资助:
    2023年山东省大学生创新创业训练计划项目(202310427292);山东省自然科学基金(ZR2023MB006);山东省自然科学基金(ZR2023MB154);国家自然科学基金(21777054);国家自然科学基金(21405061)

Research advance of solid-phase microextraction based on covalent organic framework materials

CHENG Yingchao, GAO Yiyang, LI Xiaomin, CHEN Luyu, DU Fang, GUO Jie, MENG Yitong, SUN Min*(), FENG Juanjuan*()   

  1. School of Chemistry and Chemical Engineering, University of Jinan, Jinan 250022, China
  • Received:2024-01-02 Online:2025-02-08 Published:2025-01-23
  • Supported by:
    2023 Shandong College Students Innovation and Entrepreneurship Training Program Project(202310427292);Natural Science Foundation of Shandong Province(ZR2023MB006);Natural Science Foundation of Shandong Province(ZR2023MB154);National Natural Science Foundation of China(21777054);National Natural Science Foundation of China(21405061)

摘要:

固相微萃取(SPME)是一种快速、简便的样品前处理技术,能够实现分析物的富集,并便于与其他检测技术联用,从而建立准确、灵敏的分析方法。SPME技术已被广泛应用于环境监测、食品安全、生命分析、生物医药等诸多领域。SPME技术的核心是萃取涂层,萃取涂层的性能直接决定着萃取选择性、萃取效率和富集效应等,因此新型、高性能萃取涂层材料的开发一直是分析化学及样品前处理领域的热点。共价有机框架(COFs)是一种通过共价键连接形成的多孔结晶性网状高分子材料,具有比表面积大、孔隙率高、稳定性好、可设计性强、合成及后修饰简便等优点,已广泛应用于气体吸附、催化、传感和药物输送等领域。近年来,COFs在样品前处理领域引起了广泛关注,多种基于COFs的新型SPME材料被开发出来,并应用于不同类型样品中多种分析物的萃取和富集。本文主要总结了近三年COFs在纤维SPME、管内SPME以及膜SPME等方面的研究进展。通过物理涂覆、原位合成以及化学键合的方法,将功能化COFs或COFs杂化材料修饰于纤维表面,制备出SPME纤维;将SPME纤维与色谱分析技术联用,可用于环境和食品样品中多环芳烃、邻苯二甲酸酯类化合物、多氯联苯类化合物和农药等多种分析物的检测,并能够展现出良好的富集能力、较宽的线性范围和较高的灵敏度。基于管内SPME技术,COFs基整体柱型萃取管和纤维填充型萃取管能够与高效液相色谱在线联用,分别开发出针对合成酚类抗氧化剂和双酚类化合物的高灵敏检测方法。此外,COFs也被应用于膜SPME技术,并能够实现环境水中痕量多氯联苯的高效萃取。最后,本文展望了COFs在SPME领域的发展趋势。

关键词: 共价有机框架, 固相微萃取, 色谱分析, 环境分析, 食品分析, 生物分析, 综述

Abstract:

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 π-π 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.

Key words: covalent organic frameworks (COFs), solid-phase microextraction (SPME), chromatographic analysis, environmental analysis, food analysis, bioanalysis, review

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