低共熔溶剂在分子印迹技术中的应用研究进展

doi:10.3969/j.issn.0253-2417.2022.06.017

摘要/Abstract

摘要：

以低共熔溶剂(DES)在分子印迹聚合物(MIP)中所发挥的作用为主线, 综述了低共熔溶剂在分子印迹聚合物制备过程中以不同组成部分而存在所发挥的作用，主要包括：低共熔溶剂作为修饰模板分子, 增强其水溶性, 使合成的分子印迹聚合物具有良好的选择性；作为功能单体或辅助功能单体, 增加与模板分子的结合位点, 有效改善对目标物的亲和力；作为致孔剂, 降低对环境的污染, 提高孔的通透性；作为洗脱剂, 实现环境友好, 且低成本分离；低共熔溶剂还可以修饰表面印迹分子的载体, 使载体表面负载低共熔溶剂后获得所需功能基团, 有利于分子印迹聚合物的制备也可以提高分子印迹聚合物的吸附性能，并为低共熔溶剂应用于未来分子印迹技术的绿色分离提供理论依据和发展方向。

关键词: 低共熔溶剂, 分子印迹技术, 绿色化学, 天然产物分离

Abstract:

Using the roles of deep eutectic solvents(DES) in the molecularly imprinted polymers(MIP) as the main line, the roles of different components of DES in the preparation process of MIP were summarized. DES was used as the template molecule to enhance its water solubility, and make the synthesized MIP with good selectivity. DES could be used as the functional monomer or auxiliary functional monomer to increase the binding site with template molecules and effectively improve the affinity of the target. As the pore-forming agent, DES could reduce environmental pollution and improve pore permeability. DES was used as eluent to realize the advantages of environmental friendliness and low cost separation. DES could also modify the support of imprinted molecules on the surface, so that the required functional groups could be obtained after the support surface was loaded with DES, which was conducive to the preparation of molecule-imprinted polymers and could improve the adsorption performance of molecule-imprinted polymers. Meanwhile, a theoretical basis and development direction for the application of DES in the future green separation of molecular imprinting technology(MIT) was prospected.

Key words: deep eutectic solvent(DES), molecular imprinting technology(MIT), green chemistry, separation of natural products

中图分类号:

TQ35

马春慧, 王晓静, 孙莉寒, 李伟, 罗沙, 刘守新. 低共熔溶剂在分子印迹技术中的应用研究进展[J]. 林产化学与工业, 2022, 42(6): 123-135.

Chunhui MA, Xiaojing WANG, Lihan SUN, Wei LI, Sha LUO, Shouxin LIU. Application of Deep Eutectic Solvents in Molecular Imprinting Separation Technology[J]. Chemistry and Industry of Forest Products, 2022, 42(6): 123-135.

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参考文献 81

1	田海圆. 低共熔溶剂中天然产物分离方法研究[D]. 南京: 南京师范大学, 2020.
	TIAN H Y. Study on separation method of natural products in low eutectic solvent[D]. Nanjing: Nanjing Normal University, 2020.
2	郝翠, 翟立海, 陈立宗, 等. 新型绿色溶剂在天然产物提取中的应用研究进展[J]. 西南民族大学学报(自然科学版), 2020, 46 (5): 464- 470.
	HAO C , ZHAI L H , CHEN L Z , et al. Research progress on the application of new green solvents in the extraction of natural products[J]. Journal of Southwest University for Nationalities(Natural Science Edition), 2020, 46 (5): 464- 470.
3	ABBOTT A P , CAPPER G , DAVIES D L , et al. Novel solvent properties of choline chloride/urea mixtures[J]. Chemical communications(Cambridge, England), 2003, 9 (1): 70- 71.
4	唐为扬. 新型杂化分子印迹聚合物与低共熔溶剂的合成及在固相萃取中的应用研究[D]. 天津: 天津理工大学, 2017.
	TANG W Y. Synthesis of novel hybrid molecularly imprinted polymers and eutectic solvents and their application in solid phase extraction[D]. Tianjin: Tianjin University of Technology, 2017.
5	LI X X , DAI Y L , ROW K H . Purification of antibiotics from the millet extract using hybrid molecularly imprinted polymers based on deep eutectic solvents[J]. RSC Advances, 2017, 7 (28): 16997- 17004. doi: 10.1039/C7RA01059A
6	LI G Z , ROW K H . Magnetic hybrid imprinted polymers with three-templates modified by DESs for the rapid purification of monosaccharide from seaweed[J]. Journal of Liquid Chromatography & Related Technologies, 2017, 40 (20): 1037- 1046.
7	王聪慧, 任娜, 魏微, 等. 天然产物分离纯化新技术[J]. 应用化工, 2019, 48 (8): 1940- 1943. doi: 10.3969/j.issn.1671-3206.2019.08.039
	WANG C H , REN N , WEI W , et al. New technology for separation and purification of natural products[J]. Application of Chemical, 2019, 48 (8): 1940- 1943. doi: 10.3969/j.issn.1671-3206.2019.08.039
8	LIANG C L, ZHANG Z Y, ZHANG H D, et al. Ordered macroporous molecularly imprinted polymers prepared by a surface imprinting method and their applications to the direct extraction of flavonoids from Gingko leaves[J/OL]. Food Chemistry, 2020, 309: 125680[2021-06-20]. https://doi.org/10.1016/j.foodchem.2019.125680.
9	ABU-ALSOUD G F, BOTTARO C S. Porous thin-film molecularly imprinted polymer device for simultaneous determination of phenol, alkylphenol and chlorophenol compounds in water[J/OL]. Talanta, 2021, 223: 121727[2021-06-20]. https://doi.org/10.1016/j.talanta.2020.121727.
10	DUAN L K , ZHAO Y . Zwitterionic molecularly imprinted cross-linked micelles for alkaloid recognition in water[J]. The Journal of Organic Chemistry, 2019, 84 (21): 13457- 13464. doi: 10.1021/acs.joc.9b01629
11	KARTAL F, DENIZLI A. Molecularly imprinted cryogel beads for cholesterol removal from milk samples[J/OL]. Colloids and Surfaces B: Biointerfaces, 2020, 190: 110860[2021-06-20]. https://doi.org/10.1016/j.colsurfb.2020.110860.
12	管习文, 李欣怡, 周琪, 等. 分子印迹聚合物的制备与应用进展[J]. 胶体与聚合物, 2015, 33 (2): 88- 92.
	GUAN X W , LI X Y , ZHOU Q , et al. Progress in preparation and application of molecularly imprinted polymers[J]. Colloids and Polymers, 2015, 33 (2): 88- 92.
13	TAN L, ZHOU L D, JIANG Z F, et al. Selective separation and inexpensive purification of paclitaxel based on molecularly imprinted polymers modified with ternary deep eutectic solvents[J/OL]. Journal of Pharmaceutical and Biomedical Analysis, 2021, 192: 113661[2021-06-20]. https://doi.org/10.1016/j.jpba.2020.113661.
14	GAO L , QIN D L , CHEN Z X , et al. Determination of sulfonamide antibiotics in fish and shrimp samples based on magnetic carbon nanotube dummy molecularly imprinted polymer extraction followed by UPLC-MS/MS[J]. Electrophoresis, 2021, 42 (6): 725- 734. doi: 10.1002/elps.202000243
15	REBELO P, COSTA-RAMA E, SEGURO I, et al. Molecularly imprinted polymer-based electrochemical sensors for environmental analysis[J/OL]. Biosensors and Bioelectronics, 2021, 172: 112719[2021-06-20]. https://doi.org/10.1016/j.bios.2020.112719.
16	TIAN L X, GUO H Q, LI J, et al. Fabrication of a near-infrared excitation surface molecular imprinting ratiometric fluorescent probe for sensitive and rapid detecting perfluorooctane sulfonate in complex matrix[J/OL]. Journal of Hazardous Materials, 2021, 413(1): 125353[2021-06-20]. https://doi.org/10.1016/j.jhazmat.2021.125353.
17	焦琳娟, 张映珊, 宋彩玲. 甲基对硫磷磁性印迹复合光催化剂的制备及其光催化性能研究[J]. 化工新型材料, 2020, 48 (10): 226- 231.
	JIAO L J , ZHANG Y S , SONG C L . Preparation and photocatalytic performance of methyl parathion magnetically imprinted composite photocatalyst[J]. New Chemical Materials, 2020, 48 (10): 226- 231.
18	LIU B H , HAN M Y , GUAN G J , et al. Highly-controllable molecular imprinting at superparamagnetic iron oxide nanoparticles for ultrafast enrichment and separation[J]. Journal of Physical Chemistry C, 2011, 115 (35): 17320- 17327. doi: 10.1021/jp205327q
19	黄健祥, 胡玉斐, 潘加亮, 等. 分子印迹样品前处理技术的研究进展[J]. 中国科学(B辑: 化学), 2009, 39 (8): 733- 746.
	HUANG J X , HU Y F , PAN J L , et al. Research progress on pretreatment technology of molecularly imprinted samples[J]. Science in China(Series B: Chemistry), 2009, 39 (8): 733- 746.
20	ZHANG Z J, LIU B W, LIU J W. Molecular imprinting for substrate selectivity and enhanced activity of enzyme mimics[J/OL]. Small, 2017, 13(7): 1602730[2021-06-20]. https://doi.org/10.1002/smll.201602730.
21	徐玮, 毛乐宝, 陈苗苗, 等. 新型分子印迹电化学传感器的构建及其对11种β-2-兴奋剂的检测[J]. 分析科学学报, 2020, 36 (5): 734- 740.
	XU W , MAO L B , CHEN M M , et al. Construction of a novel molecular Imprinted electrochemical sensor and its detection of 11 kinds of β-2-stimulants[J]. Journal of Analytical Science, 2020, 36 (5): 734- 740.
22	谢静, 王甜甜, 熊静, 等. 分子印迹聚合物的制备及其在临床药物分析中的应用进展[J]. 中国医院药学杂志, 2019, 39 (4): 407- 411.
	XIE J , WANG T T , XIONG J , et al. Preparation of molecularly imprinted polymers and their application in clinical drug analysis[J]. Chinese Journal of Hospital Pharmacy, 2019, 39 (4): 407- 411.
23	史瑞雪, 郭成海, 邹小红, 等. 分子印迹技术研究进展[J]. 化学进展, 2002, (3): 182- 191. doi: 10.3321/j.issn:1005-281X.2002.03.004
	SHI R X , GUO C H , ZOU X H , et al. Advances in molecular imprinting techniques[J]. Progress in Chemistry, 2002, (3): 182- 191. doi: 10.3321/j.issn:1005-281X.2002.03.004
24	SREENIVASAN K , SIVAKUMAR R . Imparting recognition sites in poly(HEMA) for two compounds through molecular imprinting[J]. Journal of Applied Polymer Science, 1999, 71 (11): 1823- 1826. doi: 10.1002/(SICI)1097-4628(19990314)71:11<1823::AID-APP12>3.0.CO;2-E
25	迟大民, 苏立强, 邓茜珊, 等. 分子印迹功能单体选择方法研究进展[J]. 化工时刊, 2009, 23 (12): 55- 57. doi: 10.3969/j.issn.1002-154X.2009.12.016
	CHI D M , SU L Q , DENG Q S ,et al. Research progress of functional monomer selection for molecular imprinting[J]. Journal of Chemical Industry Times, 2009, 23 (12): 55- 57. doi: 10.3969/j.issn.1002-154X.2009.12.016
26	胡小刚, 汤又文. 分子印迹聚合物制备技术研究进展[J]. 华南师范大学学报, 2003, (3): 152- 159.
	HU X G , TANG Y W . Progress in preparation of molecularly imprinted polymers[J]. Journal of South China Normal University, 2003, (3): 152- 159.
27	刘俊秋, 罗贵民, 沈家骢. 分子印迹聚合物及其应用[J]. 功能高分子学报, 1998, 11 (4): 561- 565.
	LIU J Q , LUO G M , SHEN J C . Molecularly imprinted polymers and their applications[J]. Journal of Functional Polymers, 1998, 11 (4): 561- 565.
28	CHEN L X, WANG X Y, LU W H, et al. Molecular imprinting: Perspectives and applications[J/OL]. Chemical Society Reviews, 2016, 45(8): 2137-2211.
29	钟海艺, 杨舒悦, 黄凤玲. 槲皮素表面分子印迹聚合物的合成及性能研究[J]. 广州化工, 2020, 48 (11): 54- 55.54-55, 73 doi: 10.3969/j.issn.1001-9677.2020.11.017
	ZHONG H L , YANG S Y , HUANG F L . Synthesis and properties of quercetin surface molecularly imprinted polymers[J]. Guangzhou Chemical Industry, 2020, 48 (11): 54- 55.54-55, 73 doi: 10.3969/j.issn.1001-9677.2020.11.017
30	LI C Y, YANG Q, WANG X Y, et al. Facile approach to the synthesis of molecularly imprinted ratiometric fluorescence nanosensor for the visual detection of folic acid[J/OL]. Food Chemistry, 2020, 319(2): 126575[2021-06-20]. https://doi.org/10.1016/j.foodchem.2020.126575.
31	XIA Y Y, WANG Y, ZHANG M, et al. A highly selective electrochemical sensor based on surface molecularly imprinted copolymer for the detection of 5-hydroxytryptamine[J/OL]. Microchemical Journal, 2020, 160: 105748[2021-06-20]. https://doi.org/10.1016/j.microc.2020.105748.
32	LI W , JIANG Z F , TAN L , et al. Rapid measurements of curcumin from complex samples coupled with magnetic biocompatibility molecularly imprinted polymer using electrochemical detection[J]. Journal of Separation Science, 2020, 43 (6): 1173- 1182. doi: 10.1002/jssc.201900884
33	GORNIK T, SHINDE S, LAMOVSEK L, et al. Molecularly imprinted polymers for the removal of antide-pressants from contaminated wastewater[J/OL]. Polymers, 2020, 13(1): 13010120[2021-06-20]. https://doi.org/10.3390/polym13010120.
34	DAS D , CHATTERJEE T N , ROY R B , et al. Titanium oxide nanocubes embedded molecularly imprinted polymer based electrode for selective detection of caffeine in green tea[J]. IEEE Sensors Journal, 2020, 20 (12): 6240- 6247. doi: 10.1109/JSEN.2020.2972773
35	FU N J , LI L T , LIU X , et al. Specific recognition of polyphenols by molecularly imprinted polymers based on a ternary deep eutectic solvent[J]. Journal of Chromatography A, 2017, 1530, 23- 34. doi: 10.1016/j.chroma.2017.11.011
36	许威. 基于绿色溶剂的磁性分子印迹聚合物的制备及用于蛋白质的识别研究[D]. 长沙: 湖南大学, 2019.
	XU W. Preparation of magnetic molecularly imprinted polymer based on green solvent and its application in protein recognition[D]. Changsha: Hunan University, 2019.
37	LIU Y J , WANG Y Z , DAI Q Z , et al. Magnetic deep eutectic solvents molecularly imprinted polymers for the selective recognition and separation of protein[J]. Analytica Chimica Acta, 2016, 936, 168- 178. doi: 10.1016/j.aca.2016.07.003
38	LI X X , ROW K H . Application of novel ternary deep eutectic solvents as a functional monomer in molecularly imprinted polymers for purification of levofloxacin[J]. Journal of Chromatography B, 2017, 1068, 56- 63.
39	RANDAZZO W , FALCO I , AZNAR R , et al. Effect of green tea extract on enteric viruses and its application as natural sanitizer[J]. Food Microbiology, 2017, 66, 150- 156. doi: 10.1016/j.fm.2017.04.018
40	XU K J, WANG Y Z, WEI X X, et al. Preparation of magnetic molecularly imprinted polymers based on a deep eutectic solvent as the functional monomer for specific recognition of lysozyme[J/OL]. Mikrochimica acta, 2018, 185(2): 146[2021-06-20]. https://doi.org/10.1007/s00604-018-2707-8.
41	WANG Y H , DUAN H M , LI L L , et al. A chemiluminescence sensor for determination of lysozyme using magnetic graphene oxide multi-walled carbon nanotube surface molecularly imprinted polymers[J]. RSC Advances, 2016, 6 (15): 12391- 12397. doi: 10.1039/C5RA20845A
42	WANG X J , DONG S H , BAI Q . Preparation of lysozyme molecularly imprinted polymers and purification of lysozyme from egg white[J]. Biomedical Chromatography, 2014, 28 (6): 907- 912. doi: 10.1002/bmc.3207
43	JI S L , LI N , SHEN Y , et al. Poly(amino acid)-based thermoresponsive molecularly imprinted magnetic nanoparticles for specific recognition and release of lysozyme[J]. Analytica Chimica Acta, 2016, 909, 60- 66. doi: 10.1016/j.aca.2016.01.005
44	LI X X , ROW K H . Preparation of levofloxacin-imprinted nanoparticles using designed deep eutectic solvents for the selective removal of levofloxacin pollutants from environmental waste water[J]. The Analyst, 2020, 145 (8): 2958- 2965. doi: 10.1039/C9AN02556A
45	ZHANG Y D , CAO H W , HUANG Q W , et al. Isolation of transferrin by imprinted nanoparticles with magnetic deep eutectic solvents as monomer[J]. Analytical and Bioanalytical Chemistry, 2018, 410 (24): 6237- 6245. doi: 10.1007/s00216-018-1232-2
46	XU W , WANG Y Z , WEI X X , et al. Fabrication of magnetic polymers based on deep eutectic solvent for separation of bovine hemoglobin via molecular imprinting technology[J]. Analytica Chimica Acta, 2019, 1048, 1- 11. doi: 10.1016/j.aca.2018.10.044
47	WANG D D, LUO X X, HUANG Y K, et al. Combined magnetic molecularly imprinted polymers with a ternary deep eutectic solvent to purify baicalein from the Scutellaria baicalensis Georgi by magnetic separation[J/OL]. Microchemical Journal, 2020, 157: 105109[2021-06-20]. https://doi.org/10.1016/j.microc.2020.105109.
48	MA W W, ROWK H. Solid-phase extraction of catechins from green tea with deep eutectic solvent immobilized magnetic molybdenum disulfide molecularly imprinted polymer[J/OL]. Molecules, 2020, 25(2): 280[2021-06-20]. https://doi.org/10.3390/molecules25020280.
49	张家维. 分子印迹技术在三种天然活性成分研究中的应用[D]. 重庆: 重庆大学, 2019.
	ZHANG J W. Application of molecular imprinting technology in the study of three natural active ingredients[D]. Chongqing: Chongqing University, 2019.
50	LI X X , DAI Y L , ROW K H . Preparation of two-dimensional magnetic molecularly imprinted polymers based on boron nitride and a deep eutectic solvent for the selective recognition of flavonoids[J]. The Analyst, 2019, 144 (5): 1777- 1788. doi: 10.1039/C8AN02258E
51	LI G Z , WANG W , WANG Q , et al. Deep eutectic solvents modified molecular imprinted polymers for optimized purification of chlorogenic acid from honeysuckle[J]. Journal of Chromatographic Science, 2016, 54 (2): 271- 279.
52	LI G Z , WANG X Q , ROW K H . Magnetic molecularly imprinted polymers based on silica modified by deep eutectic solvents for the rapid simultaneous magnetic-based solid-phase extraction of Salvia miltiorrhiza bunge, Glycine max(Linn.) Merr and green tea[J]. Electrophoresis, 2018, 39 (8): 1111- 1118. doi: 10.1002/elps.201700474
53	LI G Z , ZHU T , ROW K H . Deep eutectic solvents for the purification of chloromycetin and thiamphenicol from milk[J]. Journal of Separation Science, 2017, 40 (3): 625- 634. doi: 10.1002/jssc.201600771
54	LI G Z , AHN W S , ROW K H . Hybrid molecularly imprinted polymers modified by deep eutectic solvents and ionic liquids with three templates for the rapid simultaneous purification of rutin, scoparone, and quercetin from Herba Artemisiae Scopariae[J]. Journal of Separation Science, 2016, 39 (23): 4465- 4473.
55	FU N J , LIU X , LI L T , et al. Ternary choline chloride/caffeic acid/ethylene glycol deep eutectic solvent as both a monomer and template in a molecularly imprinted polymer[J]. Journal of Separation Science, 2017, 40 (10): 2286- 2291. doi: 10.1002/jssc.201700146
56	LI G Z , ROW K H . Hydrophilic molecularly imprinted chitosan based on deep eutectic solvents for the enrichment of gallic acid in red ginseng tea[J]. Polymers, 2019, 11 (9): 1434.
57	MA W W , TANG B K , AND ROW K H . Exploration of a ternary deep eutectic solvent of methyltriphenylphosphonium bromide/chalcone/formic acid for the selective recognition of rutin and quercetin in Herba Artemisiae Scopariae[J]. Journal of Separation Science, 2017, 40 (16): 3248- 3256.
58	LI G Z , ROW K H . Deep eutectic solvents crosslinked molecularly imprinted chitosan microsphere for the micro-solid phase extraction of p-hydroxybenzoic acid from pear rind[J]. Journal of Separation Science, 2021, 44 (2): 549- 556.
59	LIU X J , WU F J , AU C T , et al. Synthesis of molecularly imprinted polymer by suspension polymerization for selective extraction of p-hydroxybenzoic acid from water[J]. Applied Polymer Science, 2019, 136 (3): 46984- 46992.
60	LI H , LONG R Q , TONG C Y , et al. Shell thickness controlled hydrophilic magnetic molecularly imprinted resins for high-efficient extraction of benzoic acids in aqueous samples[J]. Talanta, 2019, 194, 969- 976.
61	LIU Z W , WANG Y Z , XU F T , et al. A new magnetic molecularly imprinted polymer based on deep eutectic solvents as functional monomer and cross-linker for specific recognition of bovine hemoglobin[J]. Analytica Chimica Acta, 2020, 1129, 49- 59.
62	LIU Y J , WANG Y Z , DAI Q Z , et al. Magnetic deep eutectic solvents molecularly imprinted polymers for the selective recognition and separation of protein[J]. Analytica Chimica Acta, 2016, 936, 168- 178.
63	XU W , WANG Y Z , WEI X X , et al. Fabrication of magnetic polymers based on deep eutectic solvent for separation of bovine hemoglobin via molecular imprinting technology-ScienceDirect[J]. Analytica Chimica Acta, 2019, 1048, 1- 11.
64	GUO T , DENG Q L , FANG G Z , et al. Upconversion fluorescence metal-organic frameworks thermo-sensitive imprinted polymer for enrichment and sensing protein[J]. Biosensors & Bioelectronics, 2016, 79, 341- 346.
65	王涎桦, 应玲玲, 黄艳萍, 等. 以绿色溶剂为致孔剂制备亲水性分子印迹聚合物[C]//中国化学会第十一届全国生物医药色谱及相关技术学术交流会(材料分析与其它分会). 井冈山: [出版者不详], 2016: 1.
	WANG Y H, YING L L, HUANG Y P, et al. Hydrophilic molecular imprinted polymer was prepared with green solvent as pore-forming agent[C]//Abstract collection of the 11th National Symposium on Biomedical Chromatography and Related Technologies(Material Analysis and Other Chapters). Jinggangshan: [s. n. ], 2016: 1
66	王涎桦, 应玲玲, 黄艳萍, 等. 以低共熔溶剂为致孔剂制备分子印迹整体柱[C]//第二十届全国色谱学术报告会及仪器展览会. 西安: [出版者不详], 2015: 2.
	WANG Y H, YING L L, HUANG Y P, et al. The molecular imprinted monolith column was prepared with low eutectic solvent as pore-forming agent[C]//Proceedings of the 20th National Chromatographic Symposium and Instrument Exhibition. Xi'an: [s. n. ], 2015: 2.
67	MA W W , AN Y N , R OW , K H . Preparation and evaluation of a green solvent-based molecularly imprinted monolithic column for the recognition of proteins by high-performance liquid chromatography[J]. The Analyst, 2019, 144 (21): 6327- 6333.
68	ZHANG D D , LAN D D , PANG X M , et al. Separation of proteins from complex bio-matrix samples using a double-functionalized polymer monolithic column[J]. Analyst, 2018, 143 (1): 280- 288.
69	LI X X , ZHANG L S , HUANG Y P , et al. Green synthesis of monolithic column incorporated with graphene oxide using room temperature ionic liquid and eutectic solvents for capillary electrochromatography[J]. Talanta, 2018, 178, 763- 771.
70	MA W W , ROW K H . Solid-phase extraction of chlorophenols in seawater using a magnetic ionic liquid molecularly imprinted polymer with incorporated silicon dioxide as a sorbent[J]. Journal of Chromatography A, 2018, 1559, 78- 85.
71	WEI Z H , SUN X , MU L N , et al. Improving affinity of imprinted monolithic polymer prepared in deep eutectic solvent by metallic pivot[J]. Journal of Chromatography A, 2019, 1602, 48- 55.
72	金磊, 牟丽娜, 卫泽辉. 基于低共融溶剂的离子介导印迹整体柱对绿原酸保留行为研究[J]. 广东化工, 2019, 46 (6): 45- 46.
	JIN L , MOU L N , WEI Z H . Study on the retention behavior of chlorogenic acid by ion-mediated imprinting monolith column based on low solvent[J]. Guangdong Chemical, 2019, 46 (6): 45- 46.
73	LEE Y R , ROW K H . Comparison of ionic liquids and deep eutectic solvents as additives for the ultrasonic extraction of astaxanthin from marine plants[J]. Journal of Industrial and Engineering Chemistry, 2016, 39, 87- 92.
74	LI G Z , TANG W Y , CAO W M , et al. Molecularly imprinted polymers combination with deep eutectic solvents for solid-phase extraction of caffeic acid from hawthorn[J]. Chinese Journal of Chromatography, 2015, 33 (8): 792- 798.
75	GE Y H , SHU H , XU X Y , et al. Combined magnetic porous molecularly imprinted polymers and deep eutectic solvents for efficient and selective extraction of aristolochic acid Ⅰ and Ⅱ from rat urine[J]. Materials Science & Engineering: C, 2019, 97, 650- 657.
76	DAI Q Z , WANG Y Z , XU W , et al. Adsorption and specific recognition of DNA by using imprinted polymer layers grafted onto ionic liquid functionalized magnetic microspheres[J]. Microchimica Acta, 2017, 184 (11): 4433- 4441.
77	XU K J , WANG Y Z , DING X Q , et al. Magnetic solid-phase extraction of protein with deep eutectic solvent immobilized magnetic graphene oxide nanoparticles[J]. Talanta, 2016, 148, 153- 162.
78	徐凯佳, 低共熔溶剂应用于生物大分子的分离分析研究[D]. 长沙: 湖南大学, 2018.
	XU K J. Separation and analysis of biological macromolecules with low eutectic solvents[D]. Changsha: Hunan University, 2018.
79	KHASRAGHI M M , SEFIDKOUHI M A G , VALIPOUR M . Simulation of open- and closed-end border irrigation systems using SIRMOD[J]. Archives of Agronomy and Soil Science, 2015, 61 (7): 929- 941.
80	CHEN W Y , LIU Z C , LIN P H , et al. The hydrophobic interactions of the ion-exchanger resin ligands with proteins at high salt concentrations by adsorption isotherms and isothermal titration calorimetry[J]. Separation & Purification Technology, 2007, 54 (2): 212- 219.
81	LIU H F, JIANG L H, LU M, et al. Magnetic solid-phase extraction of pyrethroid pesticides from environmental water samples using deep eutectic solvent-type surfactant modified magnetic zeolitic imidazolate framework-8[J/OL]. Molecules, 2019, 24(22): 4038[2021-06-20]. https://doi.org/10.3390/molecules24224038.

功能单体(n∶n)¹⁾ functional monomer	模板分子 template molecule	MIP性能参数²⁾ molecularly imprinted polymers	文献 ref.
ChCl/AA(1∶2)	转铁蛋白transferrin(TrF)	IF 3.50	[45]
3-ATLC/U(1∶2)	牛血红蛋白bovine hemoglobin(BHb)	IF 4.93	[46]
ChCl/OA/1, 2-PG(1∶1∶2)	黄芩苷baicalin	Q 7.06 mg/g	[47]
VP/MA(1∶1)	儿茶素catechins	IF 9.23	[48]
CA/ChCl/FA(1∶6∶3)	槲皮素quercetin, 五味子乙素schisandrin B	Q_q23.58 mg/g, Q_s41.64 mg/g	[49]
CA/ChCl/EG(1∶5∶5)	黄酮类化合物flavonoids	Y_q96.8%, Y_i93.6%, Y_k94.8%	[50]

DES组成(n∶n)¹⁾ composition of DES	功能单体 functional monomer	目标产物 target product	产物回收率/% recovery rate of product	文献 ref.
ChCl/GL(1∶2)	丙烯酰胺 acrylamide(AM)	绿原酸chlorogenic acid	72.56	^[51]
ChCl/U(1∶2)	甲基丙烯酸 methacrylic acid(MAA)	丹参酮Ⅰ tanshinone Ⅰ 丹参酮ⅡA tanshinone ⅡA 隐丹参酮cryptotanshinone	85.57 80.58 92.12	^[52]
		大豆素glycitein 染料木素genistein 甘油素daidzein	92.24 87.72 81.65
		表儿茶素epicatechin 表没食子儿茶素没食子酸酯epigallocatechin gallate 表儿茶素没食子酸酯epicatechin gallate	86.43 80.92 93.64
ChCl/GL(1∶2)	AM	氯霉素chloromycetin 甲砜霉素thiamphenicol	91.23 87.02	^[53]
ChCl/GL(1∶3)	MAA	芦丁rutin 东莨菪酮scoparone 槲皮素quercetin	92.27 87.51 80.02	^[54]

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