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

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.