Liu Qiaoling, Wei Wanjiao, Liu Yanjuan, Zhang Yuefei, Chen Wei, Tang Sheng
School of Chemistry and Environmental Engineering, Hubei Key Laboratory of Novel Reactor and Green Chemical Technology, Wuhan Institute of Technology, Wuhan, 430205, China.
College of Medicine, Linyi University, Linyi, 276000, Shandong, China.
Anal Chim Acta. 2024 Nov 22;1330:343268. doi: 10.1016/j.aca.2024.343268. Epub 2024 Sep 20.
Deep eutectic solvents (DESs) have been widely and significantly applied in various fields due to their outstanding features such as low cost, easy preparation and good biodegradability. As novel derivatives of DESs, deep eutectic supramolecular polymers (DESPs) combine the macroscopic state of DESs with the covalent interactions of supramolecular polymers, which also possess the properties of DESs as multifunctional materials. Therefore, DESPs are believed to be promising candidates for separation science. However, there are no studies on the application of DESPs as stationary phases for HPLC analysis.
In this work, a novel DESP based HPLC stationary phase (Poly(DES)@SiO) was developed for the first time through a green synthesis method by using DES as the polymerization monomer as well as the reaction medium. The results manifest that this novel Poly(DES)@SiO column can well interact with analytes through various mechanisms, and realize selective separation of a wide range of structurally similar hydrophilic/hydrophobic substances. More importantly, the separation of hydrophobic analytes on the Poly(DES)@SiO column is less time-consuming with fewer organic eluent, although the column efficiency is slightly lower than that of commercial C18 column. Furthermore, the Poly(DES)@SiO column exhibits excellent mechanical stability and satisfactory separation repeatability for steroid hormones. Therefore, a reliable method was established for detecting steroid hormones in actual samples with the recoveries ranging from 94.56 % to 103.84 %, which can meet the detection needs of commonly seen steroid hormones in food and the environment.
In summary, this work provides some valuable theoretical references for the synthesis of new DESP based stationary phases through a green and facile strategy, and meanwhile, verifies the feasibility of DESP for effective HPLC separations. In addition, the promising application prospect of DESP based stationary phases in the analysis of complex samples has also been demonstrated, expanding the potential application of DES in separation science.
由于具有低成本、易于制备和良好的生物降解性等突出特性，深共熔溶剂（DESs）已在各个领域得到广泛且重要的应用。作为DESs的新型衍生物，深共熔超分子聚合物（DESPs）将DESs的宏观状态与超分子聚合物的共价相互作用相结合，作为多功能材料也具备DESs的性质。因此，DESPs被认为是分离科学领域有前景的候选材料。然而，尚无关于将DESPs用作高效液相色谱（HPLC）分析固定相的应用研究。
在本工作中，首次通过绿色合成方法，以DES作为聚合单体及反应介质，开发出一种新型的基于DESP的HPLC固定相（聚（DES）@SiO）。结果表明，这种新型的聚（DES）@SiO柱能够通过多种机制与分析物良好相互作用，并实现对多种结构相似的亲水/疏水物质的选择性分离。更重要的是，尽管该柱效略低于商用C18柱，但在聚（DES）@SiO柱上分离疏水分析物耗时更短且有机洗脱剂用量更少。此外，聚（DES）@SiO柱对甾体激素表现出优异的机械稳定性和令人满意的分离重复性。因此，建立了一种可靠的方法用于检测实际样品中的甾体激素，回收率在94.56%至103.84%之间，能够满足食品和环境中常见甾体激素的检测需求。
综上所述，本工作通过绿色简便策略为新型基于DESP的固定相合成提供了一些有价值的理论参考，同时验证了DESP用于高效HPLC分离的可行性。此外，还展示了基于DESP的固定相在复杂样品分析中广阔的应用前景，拓展了DES在分离科学中的潜在应用。
