色谱 ›› 2021, Vol. 39 ›› Issue (3): 241-259.DOI: 10.3724/SP.J.1123.2020.08002

• 专论与综述 • 上一篇    下一篇

离子液体固定化材料在固相萃取中的应用研究进展

王艺聪, 刘磊磊*()   

  1. 吉首大学, 林产化工工程湖南省重点实验室, 湖南 张家界 427000
  • 收稿日期:2020-08-05 出版日期:2021-03-08 发布日期:2021-02-03
  • 通讯作者: 刘磊磊
  • 作者简介:*Tel:(0744)8231386,E-mail: liull126@126.com.
  • 基金资助:
    国家自然科学基金项目(21864012);林产化工实验室开放课题(JDZ201801)

Research progress in application of immobilized ionic liquid materials to separation by solid-phase extraction

WANG Yicong, LIU Leilei*()   

  1. Key Laboratory of Hunan Forest Products and Chemical Industry Engineering, Jishou University, Zhangjiajie 427000, China
  • Received:2020-08-05 Online:2021-03-08 Published:2021-02-03
  • Contact: LIU Leilei
  • Supported by:
    National Natural Science Foundation of China(21864012);Forest Products Chemical Laboratory Open Item(JDZ201801)

摘要:

离子液体是由阴、阳离子组成的低温熔融盐,几乎没有蒸汽压,具有稳定性好、溶解能力强、结构可设计、导电性好等优良性能。离子液体作为一种广受关注的新型“绿色溶剂”,具有代替传统有机溶剂的潜力,其制备方法和应用范围研究日趋完善和多样,已广泛应用于催化化学、光电化学、材料化学和分析化学等领域。离子液体通过功能化导向设计后,可以将羟基、氨基、羧基、氰基等活性基团键合在离子液体结构上,促使其更加易于与目标分子通过生成π-π键、氢键、离子键和范德华力等而产生相互作用,更加易于发生固定化反应。将离子液体负载到固体载体材料进行固定化后,新型材料既可以减少离子液体的流失,同时保留了离子液体和固体载体的独特性能,具有富集效率高、吸附容量高、稳定性好、识别位点多、萃取选择性强、离子液体利用率高等特点,近年来,在有机小分子固相萃取分离研究中应用广泛。该文从离子液体与硅胶、分子筛、分子印迹聚合物、氧化石墨烯、磁性材料等固体载体的固定化研究情况入手,综述了离子液体固定化材料在固相萃取分离中的应用情况,涉及的目标分离物质包括生物碱类、黄酮类、多酚类等天然活性成分,以及常见药物分子、有机农药等有机小分子化合物,系统地介绍了离子液体与多种载体固定化的性质、应用和分离机制。离子液体的引入,增加了复合材料的活性位点分布和吸附容量,离子液体固定化材料的吸附效率与离子液体种类、吸附材料用量、样品溶液浓度、吸附温度、pH值、洗脱溶剂类型、用量及流速等因素有关。该文探讨了离子液体结构相对单一、相关基础理论研究相对薄弱、复杂基质萃取程度不理想等问题,并提出相应的解决思路,以期为离子液体固定化材料在复杂基质中目标分子分离分析方面的应用提供借鉴和参考。

关键词: 离子液体, 固定化, 固相萃取, 分子印迹聚合物, 综述

Abstract:

Ionic liquids are low-temperature molten salts with almost no vapor pressure, and they are composed of organic cations and inorganic anions. Ionic liquids are characterized by the properties of good chemical stability, high solubility, designable structure, high conductivity and so on. The physicochemical properties of an ionic liquid depend on the nature and size of the cation and anion, which confer unique characteristics; hence, these reagents are also termed “designed extractants.” As a new class of green solvents, ionic liquids are potential replacements to traditional volatile organic solvents used for extraction; for this reason, ionic liquids have attracted the attention of scientists. Research on the methods of preparation and applications of ionic liquids is being diversified, and they are extensively used in catalytic chemistry, photoelectron chemistry, materials chemistry, analytical chemistry, etc. By functional guiding design, the structures of ionic liquids, especially the imidazole ring cations, can be easily grafted with active groups such as hydroxyl, amino, carboxyl, and cyano groups, so that interactions between the ionic liquids and target molecules can be promoted via the formation of π-π bonds, hydrogen bonds, ionic bonds, and van der Waals forces. In addition, ionic liquids can be readily immobilized on solid carriers by physical or chemical means in order to obtain a new solid material with ionic liquids embedded internally or decorated on the surface. Furthermore, ionic liquids could be converted into ionic liquid-immobilized composite materials by impregnation, grafting, etc. The resulting composites not only suffer minimal loss of ionic liquids but also retain the typical characteristics of the ionic liquids and solid materials, thus showing improved mass transfer performance and better adsorption performance. Immobilized materials are characterized by high enrichment efficiency, high adsorption capacity, good stability, and strong extraction selectivity, as well as the presence of numerous recognition sites and high utilization rate of ionic liquids. In recent years, they have been widely used as solid-phase extraction adsorption materials for the separation of small organic molecules. This review introduces common immobilization methods and the characteristics of ionic liquid-immobilized materials, as well as their application in solid-phase extraction. In this paper, methods for the immobilization of ionic liquids with solid carriers such as silica gel, molecular sieves, molecularly imprinted polymers, graphene oxide, and magnetic nanomaterials are summarized, and the application of ionic liquid-immobilized materials in solid-phase extraction is reviewed. The target substances include alkaloids, flavonoids, polyphenols, and other natural active components as well as common drug molecules, organic pesticides, and other organic small molecular compounds. The properties, applications, and separation mechanisms of ionic liquids immobilized with various carriers are systematically introduced. Literature survey shows that the distribution of the binding active sites of ionic liquid-immobilized materials to the target molecules is more uniform, which increases the adsorption capacity of the materials. The adsorption efficiency of ionic liquid-immobilized materials is related to the type of ionic liquid, amount of adsorption material, concentration of the sample solution, adsorption temperature, solution pH, flow rate of the eluent, and type and amount of the eluting solvent. The existing disadvantages of ionic liquids, such as simple structures, insufficient basic theoretical research, and unsatisfactory extraction degree in complex matrixes would also be discussed. The corresponding solutions would be presented with the aim of providing guidance for the application of ionic liquid-immobilized materials in the separation and analysis of targets in complex matrices, thus paving the way for a new direction in the field of extraction and separation.

Key words: ionic liquid (IL), immobilization, solid phase extraction (SPE), molecularly imprinted polymer (MIP), review

中图分类号: