左旋肉碱基低共熔溶剂双水相的相行为及萃取性能

Phase Behavior and Extraction Performance of Aqueous Two-phase System ComprisingL-Carnitine-based Deep Eutectic Solvents and Polyethylene Glycol

摘要

离子液体双水相体系（IL-ATPS）是一种温和且高效的液-液分离体系，但常用的咪唑和吡啶基离子液体因毒性大而应用受限.低共熔溶剂（DES）具有离子液体（IL）的优点且生物降解好，已被用来替代IL构建双水相体系（ATPS）.本文以左旋肉碱和两种常见有机酸（L-乳酸和DL-苹果酸）制备两种生物相容性DES，通过红外光谱和核磁共振氢谱确认了DES结构.以左旋肉碱基DES与聚乙二醇（PEG）构筑低共熔溶剂双水相体系（DES-ATPS），研究了该DES-ATPS的相行为，考察了影响DES-ATPS成相能力的主要因素.结果表明，该DES-ATPS表现出典型的下临界溶解温度（LCST）型相行为.PEG平均分子量增大、DES的氢键供体亲水性减弱以及氢键受体摩尔占比增大均会增大DES与PEG的亲/疏水性差异，从而促进ATPS的形成，符合形成ATPS的组分亲/疏水差异越大成相能力越强的规律.以香兰素为萃取模型物，探究该DES-ATPS的萃取性能，发现在最佳萃取条件下该ATPS对香兰素的萃取率可以达到93.6%，验证了其用于萃取体系的可能性.

Abstract

Ionic liquid-based aqueous two-phase system (IL-ATPS), a type of mild and efficient liquid-liquid extraction system, has attracted wide-ranging attention. However, the practical application of imidazolium- and pyridinium-based ionic liquids are severely restricted because of their high toxicity. Deep eutectic solvents (DES), which inherit the advantages of IL and exhibit biodegradability, have been used as substitutes for IL to construct ATPS. In this study, two biocompatible DES were synthesized usingL-carnitine and two common organic acids (L-lactic acid and DL-malic acid). The structures of the two DESs were confirmed by FTIR and ¹H NMR. DES-based ATPS (DES-ATPS) was constructed using L-carnitine-based DES and polyethylene glycol (PEG). The liquid-liquid phase behavior of the DES-ATPS was investigated, and the main factors influencing its phase-forming ability were examined. The results indicate that the DES-ATPS exhibits typical low critical solution temperature (LCST) phase transition behavior. The increase in the average molecular weight of PEG, the decreased hydrophilicity of the hydrogen bond donor in the DES, and the increased molar ratio of the hydrogen bond acceptor all contribute to enlarging the hydrophilic/hydrophobic difference between the DES and PEG, thereby promoting the formation of the ATPS. These align with the principle that the greater the difference in hydrophilicity/hydrophobicity between components forming ATPS, the stronger the phase-forming ability exists. Vanillin was selected as the model extraction compound to systematically investigate the extraction performance and potential of the DES-ATPS. The experimental results demonstrate that under the optimized conditions, the system achieves a notably high extraction efficiency, with the recovery rate of vanillin reaching up to 93.6%, which verifies the possibility of its application in extraction systems.

关键词

低共熔溶剂 / 双水相 / 相行为 / 萃取 / 香兰素

Key words

Deep eutectic solvent (DES) / Aqueous two-phase system (ATPS) / Phase behavior / Extraction / Vanillin

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基金资助

国家自然科学基金(21606107)