基于低共熔溶剂的萃取分离技术及其应用研究进展

随着绿色化学的发展,开发和应用符合绿色化学要求的溶剂和方法备受关注。作为离子液体类似物,低共熔溶剂(deep eutectic solvent, DES)是通过氢键受体(hydrogen bond acceptor, HBA)和氢键供体(hydrogen bond donator, HBD)的氢键作用而形成的一种混合物,具有环境友好、制备简单、成本低、可生物降解等优点,在很多领域均有越来越广泛的应用。DES可以从不同样品中萃取和分离不同的目标化合物,其作为萃取溶剂具有独特的优势,可以获得较高的萃取效率且样品基质对分析过程的影响较小。在分散液液微萃取(dispersive liquid-liquid micro-extraction, DLLME)程序中,DES可以萃取复杂基质中的残留药物、金属离子和生物活性成分;与传统的萃取方法相比,该方法具有对有机试剂需求少,萃取效率更高等明显优势。而且,在DLLME中加入DES作为分散剂,能够加速萃取剂在样品溶液中的扩散,具有小型化、成本低等优点。相比于传统分散剂甲醇、乙腈的高挥发性、易燃性,DES的高稳定性、低毒性使其在绿色化学领域中更具有优势,应用更广。因此,DES与DLLME的结合近年来发展迅速。不仅如此,DES与固相萃取联合应用也具有广泛的应用前景,在与固相萃取小柱和搅拌棒联合应用时,DES可以作为洗脱剂,氢键供体及氢键给体的用量之比是洗脱效率的重要考察因素之一。在与磁性材料联用时,DES能与磁性多壁碳纳米管、磁性氧化石墨烯等纳米复合材料结合,通过氢键、π-π作用力和静电作用力等特异性吸附目标分析物。并且能够参与磁性凝胶和分子印迹聚合物的合成,推动磁性材料向绿色化学的方向发展,进一步拓展DES的应用。作为一类新兴的绿色溶剂,DES在化合物的萃取分离技术方面受到广泛关注,在不同的萃取技术中扮演了不同的角色,并表现出良好的性能,因此逐渐成为绿色化学领域的研究重点。该文整合了DES在萃取分离技术中的研究进展,介绍了DES的制备、性质和分类,对DES在DLLME和固相萃取中的应用进行了总结和归类,并展望了DES在萃取分离技术中的应用前景,为DES未来的应用提供参考。

Progress in the application of deep eutectic solvents to extraction and separation technology

With the rapid development of green chemistry, the design and application of the related methods and requisite solvents have received increasing attention in recent years. Deep eutectic solvents (DESs) are mixtures formed from a hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD). Generally, ionic liquids (ILs) and DESs have similar physical and chemical properties, and hence, find application in the same fields. However, DESs have many advantages over ILs, such as non-toxicity, environmental friendliness, low cost, and biodegradability. Thus, there are many areas where DESs play a key role and act as new, efficient green extraction solvents. DESs can aid the extraction and separation of different target compounds from a variety of samples, thus promoting the rapid development of sample pretreatment technology. As extraction solvents, DESs offer unique advantages. In dispersive liquid-liquid microextraction (DLLME), DESs show incredible ability to extract residual drugs, metal ions, and bioactive components from complex matrices, which would require complicated sample preparation steps when using traditional organic extraction solvents. Compared with traditional organic extraction solvents, DESs have considerable merits of greenness, hypotoxicity, higher extraction efficiency, etc. Moreover, as a dispersant, a DES can accelerate the diffusion of the extractant in the sample solution during DLLME, owing to its benefits of miniaturization and low cost. Traditional dispersants such as methanol and acetonitrile have many disadvantages, including high volatility, flammability, and toxicity, while DESs are environmentally friendly. Therefore, the combination of DES and DLLME has recently gained prominence in the field of sample preparation. Additionally, the combination of DES and solid-phase extraction (SPE) has broad application prospects. By virtue of their diverse functions, DESs have been used as eluents, in combination with a solid-phase extraction column and a stir bar, to elute analytes from the sorbent surface. The molar ratio of the HBA and HBD is one of the important factors influencing the elution efficiency. DESs can be combined with magnetic multiwalled carbon nanotubes, magnetic graphene oxide, and other nanocomposites to specifically adsorb target analytes through hydrogen bonding, π-π forces, and electrostatic forces. In addition, the DES can be used in the synthesis of magnetic nanocomposites and molecularly imprinted polymers when combined with magnetic materials. Magnetic nanocomposites functionalized with DES show excellent performance and high efficiency in the extraction process. The combination of DES and magnetic materials would promote the development of magnetic materials for green chemistry and expand the application of DES to several other fields. However, to the best of our knowledge, research on the microstructure, physical and chemical properties, and extraction mechanism of DESs is still in its nascent stage. Therefore, exploring the theoretical mechanism and applications of new DESs with special functions would be an essential future research direction. This article integrates the research progress of DESs in extraction separation technology; introduces the preparation, properties, and classification of DESs; and summarizes the applications of DESs in DLLME and SPE.