Preparation of a Hybrid Organic-inorganic Monolith for Extraction and Purification of Quercetin and Myricetin from Chamaecyparis obtusa

A new hybrid organic-inorganic monolithic cartridge was synthesized and used as the selective sorbent for the extraction and purification of quercetin and myricetin from Chamaecyparis obtusa via a solid-phase extraction method.The morphology of the monolithic material was examined by field emission-scanning electron microscopy and a Brunauer-Emmett-Teller（BET） test.The adsorption capacity of the obtained material for quercetin and myricetin was investigated by fitting the adsorption data to four different adsorption equations,of which the LangmuirFreundlich isotherm was selected as the most suitable model.Under optimized conditions,good calibration curves were observed at nine concentrations ranged from 0.5 μg/mL to 100.0 μg/mL of quercetin and myricetin.The extraction recovery ranged from 74.5％ to 84.6％ and the inter-and intra-day relative standard deviations were ＜6％.This type of hybrid monolith has potential for the separation and purification of bioactive compounds from natural plant extracts.     

Effective Extraction of Limonene and Hibaene from Hinoki (Chamaecyparis obtusa) Using Ionic Liquid and Deep Eutectic Solvent

The essential oils of hinoki (Chamaecyparis obtusa) leaves have anti-bacterial, anti-fungal, and relaxation properties that are likely associated with the major components such as sabinene, α-terpinyl acetate, limonene, elemol, myrcene, and hibaene. The present study describes the use of a cellulose-dissolving ionic liquid (IL) [C₂mim][(MeO)(H)PO₂] and low-toxicity solvents called betaine-based deep eutectic solvents (DESs) for the efficient extraction of hinoki essential oils. As a control method, organic solvent extraction was performed using either hexane, ethyl acetate (EtOAc), or acetone at 30 °C for 1 h. Both the experimental and control methods were conducted under the same conditions, which relied on partial dissolution of the leaves using the IL and DESs before partitioning the hinoki oils into the organic solvent for analysis. Quantitative analysis was performed using gas chromatography–mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The results indicated that extraction using the [C₂mim][(MeO)(H)PO₂]/acetone bilayer system improved the yields of limonene and hibaene, 1.5- and 1.9-fold, respectively, when compared with the control method. In addition, extraction using betaine/l-lactic acid (molar ratio 1:1) gave the greatest yields for both limonene and hibaene, 1.3-fold and 1.5-fold greater, respectively, than when using an organic solvent. These results demonstrate the effective extraction of essential oils from plant leaves under conditions milder than those needed for the conventional method. The less toxic and environmentally begin DESs for the extraction are also applicable to the food and cosmetic industries.     

Highly Efficient Diglycolamide‐Based Task‐Specific Ionic Liquids: Synthesis,Unusual Extraction Behaviour,Irradiation, and Fluorescence Studies

Two new diglycolamide‐based task‐specific ionic liquids (DGA? TSILs) were evaluated for the extraction of actinides and lanthanides from acidic feed solutions. These DGA? TSILs were capable of exceptionally high extraction of trivalent actinide ions, such as Am³⁺, and even higher extraction of the lanthanide ion, Eu³⁺ (about 5–10 fold). Dilution of the DGA? TSILs in an ionic liquid, C₄mim⁺ ? NTf₂^?, afforded reasonably high extraction ability, faster mass transfer, and more efficient stripping of the metal ion. The nature of the extracted species was studied by slope analysis, which showed that the extracted species contained one NO₃^? anion, along with the participation of two DGA? TSIL molecules. Time‐resolved laser fluorescence spectroscopy (TRLFS) analysis showed a strong complexation with no inner‐sphere water molecule in the Eu^III? DGA? TSIL complexes in the presence and absence of C₄mim⁺ ? NTf₂^? as the diluent. The very high radiolytic stability of DGA? TSIL 6 makes it one of the most‐efficient solvent systems for the extraction of actinides under acidic feed conditions.     

Insights into the Mechanism of Extraction of Uranium (VI) from Nitric Acid Solution into an Ionic Liquid by using Tri‐n‐butyl phosphate

We present new results on the liquid–liquid extraction of uranium (VI) from a nitric acid aqueous phase into a tri‐n‐butyl phosphate/1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (TBP/[C₄mim][Tf₂N]) phase. The individual solubilities of the ionic‐liquid ions in the upper part of the biphasic system are measured over the whole acidic range and as a function of the TBP concentration. New insights into the extraction mechanism are obtained through the in situ characterization of the extracted uranyl complexes by coupling UV/Vis and extended X‐ray absorption fine structure (EXAFS) spectroscopy. We propose a chemical model to explain uranium (VI) extraction that describes the data through a fit of the uranyl distribution ratio D_U. In this model, at low acid concentrations uranium (VI) is extracted as the cationic complex [UO₂(TBP)₂]²⁺, by an exchange with one proton and one C₄mim⁺. At high acid concentrations, the extraction proceeds through a cationic exchange between [UO₂(NO₃)(HNO₃)(TBP)₂]⁺ and one C₄mim⁺. As a consequence of this mechanism, the variation of D_U as a function of TBP concentration depends on the C₄mim⁺ concentration in the aqueous phase. This explains why noninteger values are often derived by analysis of D_U versus [TBP] plots to determine the number of TBP molecules involved in the extraction of uranyl in an ionic‐liquid phase.     

基于整体材料的固相萃取与毛细管电泳技术联合分离检测桑叶中的多酚类物质

采用甲基丙烯酸丁酯(BMA)为单体、乙二醇二甲基丙烯酸酯(EDMA)为交联剂,合成了聚甲基丙烯酸丁酯-乙二醇二甲基丙烯酸酯(poly(BMA-co-EDMA))整体柱,并将其作为固相萃取整体柱与毛细管电泳联用,建立了桑叶中芦丁、绿原酸、槲皮素等多酚物质的分离检测方法。考察了固相萃取条件如淋洗液种类、淋洗液流速和体积、洗脱液种类对萃取效率的影响,并采用毛细管电泳进行分离分析。结果显示,芦丁、绿原酸、槲皮素均在10～160μg/mL范围内线性关系良好,相关系数分别为0.995 5、0.998 5、0.999 5,检出限分别为4.65、1.12、3.49μg/mL,相对标准偏差分别为2.4%、0.98%、2.8%,平均回收率分别为94.7%、98.9%、102%。该固相萃取柱能有效富集和纯化桑叶中3种多酚物质。方法简便、快速、灵敏,适用于桑叶中3种多酚类物质的分离分析。     

Green and Efficient Processing of Cinnamomum cassia Bark by Using Ionic Liquids: Extraction of Essential Oil and Construction of UV‐Resistant Composite Films from Residual Biomass

There is significant interest in the development of a sustainable and integrated process for the extraction of essential oils and separation of biopolymers by using novel and efficient solvent systems. Herein, cassia essential oil enriched in coumarin is extracted from Cinnamomum cassia bark by using a protic ionic liquid (IL), ethylammonium nitrate (EAN), through dissolution and the creation of a biphasic system with the help of diethyl ether. The process has been perfected, in terms of higher biomass dissolution ability and essential oil yield through the addition of aprotic ILs (based on the 1‐butyl‐3‐methylimidazolium (C₄mim) cation and chloride or acetate anions) to EAN. After extraction of oil, cellulose‐rich material and free lignin were regenerated from biomass–IL solutions by using a 1:1 mixture of acetone–water. The purity of the extracted essential oil and biopolymers were ascertained by means of FTIR spectroscopy, NMR spectroscopy, and GC‐MS techniques. Because lignin contains UV‐blocking chromophores, the oil‐free residual lignocellulosic material has been directly utilized to construct UV‐light‐resistant composite materials in conjunction with the biopolymer chitosan. Composite material thus obtained was processed to form biodegradable films, which were characterized for mechanical and optical properties. The films showed excellent UV‐light resistance and mechanical properties, thereby making it a material suitable for packaging and light‐sensitive applications.     

功能性离子液体萃取水溶液中Cu2+:实验与理论

本工作针对含硫脲基咪唑憎水功能离子液体在溶液中Cu²⁺萃取方面的应用及其机理进行研究. 考察了萃取两相体积比、金属离子浓度、时间、无机盐NaCl、溶液pH及离子液体烷基链长等因素的影响. 结果表明: 室温条件下, 0.1 mL离子液体[C_nMPSM][PF₆] (n=4、6、8)与5 mL 21.94 mg/L的氯化铜溶液室温条件下超声混合30 min, 溶液中Cu²⁺的去除率即超过95%; 且此类离子液体对金属离子的萃取效果顺序为: n=4≈n=6>n=8. 以[HMPSM][PF₆]为研究对象, 发现溶液中无机盐NaCl的含量以及溶液pH 对金属离子的萃取效果影响不明显. 与传统离子液体[C_nbim][PF₆] (n=6、8)相比, 硫脲基的引入使其萃取率由20%左右提高到99%, 且有效避免因阳离子交换而引起水中咪唑阳离子含量增加问题. 通过理论计算发现, 功能离子液体对金属离子的萃取依赖于官能团中的S元素与Cu²⁺之间较强的静电及路易斯酸碱作用, 与萃取实验中离子液体未和Cu²⁺发生阳离子交换作用相吻合.     

功能性离子液体在金属萃取分离中的研究进展

近年来,离子液体在金属萃取领域的研究受到广泛关注,主要集中在两个方面,一是疏水性离子液体作为“绿色”溶剂用于金属离子萃取;二是带有官能团的功能性离子液体作为萃取剂用于金属离子萃取,其中,后者是目前研究的热点。 本文主要对近年来功能性离子液体萃取分离放射性金属、重金属和稀土金属等研究进行综述,并对其未来发展进行了展望。     

Recovery of Metals from Electronic Waste-Printed Circuit Boards by Ionic Liquids,DESs and Organophosphorous-Based Acid Extraction

The extraction of metals from waste printed circuit boards (WPCBs) with ionic liquids (ILs), Deep Eutectic Solvents (DESs) and organophosphorous-based acid (Cyanex 272) has been presented. The study was undertaken to assess the effectiveness of the application of the new leaching liquids, and the new method of extraction of metals from the leachate and the solid phase with or without the leaching process. Solvent extraction from the liquid leachate phase has been studied in detail with popular ILs, such as tetraoctylphosphonium bromide, {[P_8,8,8,8][Br] and tributyltetradecylphosphonium chloride, [P_4,4,4,14][Cl] using Aqueous Biphasic Systems (ABS) method. Trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate, [P_6,6,6,14][Cyanex272], ([P_6,6,6,14][BTMPP]), trihexyltetradecylphosphonium thiocyanate, [P_6,6,6,14][SCN], methyltrioctylammonium chloride (Aliquat 336), as well as bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272) were also used in the extraction of metals from the leachate. Two DESs (1) {choline chloride + lactic acid, 1:2} and (2) {choline chloride + malonic acid, 1:1} were used in the extraction of metals from the solid phase. The extraction behavior of metals with DESs was compared with that performed with three new bi-functional ILs: didecyldimethylammonium salicylate, [N_10,10,1,1][Sal], didecyldimethylammonium bis(2-ethylhexyl) phosphate, [N_10,10,1,1][D2EHPA], and didecyldimethylammonium bis(2,4,4-trimethylpentyl) phosphinate, [N_10,10,1,1][Cyanex272]. The [P_6,6,6,14][Cyanex272]/toluene and (Cyanex 272 + diethyl phosphite ester) mixtures exhibited a high extraction efficiency of about 50–90% for different metal ions from the leachate. High extraction efficiency of about 90–100 wt% with the ABS method using the mixture {[P_8,8,8,8][Br], or [P_4,4,4,14][Cl] + NaCl + H₂O₂ + post-leaching liquid phase} was obtained. The DES 2 revealed the efficiency of copper extraction, E_Cu = 15.8 wt% and silver, E_Ag = 20.1 wt% at pH = 5 from the solid phase after the thermal pre-treatment and acid leaching. The solid phase extraction efficiency after thermal pre-treatment only was (E_Cu = 9.6 wt% and E_Ag = 14.2 wt%). The use of new bi-functional ILs did not improve the efficiency of the extraction of metal ions from the solid phase. Process factors such as solvent concentration, extraction additives, stripping and leaching methods, temperature, pH and liquid/solid as well as organic/water ratios were under control. For all the systems, the selectivity and distribution ratios were described. The proposed extraction processes can represent alternative paths in new technologies for recovering metals from electronic secondary waste.     

Fabrication of an ionic‐liquid‐based polymer monolithic column and its application in the fractionation of proteins from complex biosamples

An ionic‐liquid‐based polymer monolithic column was synthesized by free radical polymerization within the confines of a stainless‐steel column (50 mm × 4.6 mm id). In the processes, ionic liquid and stearyl methacrylate were used as dual monomers, ethylene glycol dimethacrylate as the cross‐linking agent, and polyethylene glycol 200 and isopropanol as co‐porogens. Effects of the prepolymerization solution components on the properties of the resulting monoliths were studied in detail. Scanning electron microscopy, nitrogen adsorption–desorption measurements, and mercury intrusion porosimetry were used to investigate the morphology and pore size distribution of the prepared monoliths, which showed that the homemade ionic‐liquid‐based monolith column possessed a relatively uniform macropore structure with a total macropore specific surface area of 44.72 m²/g. Compared to a non‐ionic‐liquid‐based monolith prepared under the same conditions, the ionic‐liquid‐based monolith exhibited excellent selectivity and high performance for separating proteins from complex biosamples, such as egg white, snailase, bovine serum albumin digest solution, human plasma, etc., indicating promising applications in the fractionation and analysis of proteins from the complex biosamples in proteomics research.     

A Specific Interaction between Ionic Liquids’ Cations and Reichardt’s Dye

Solvatochromic probes are often used to understand solvation environments at the molecular scale. In the case of ionic liquids constituted by an anion and a cation, which are designed and paired in order to obtain a low melting point and other desirable physicochemical properties, these two indivisible components can interact in a very different way with the probe. This is the case with one of the most common probes: Reichardt’s Dye. In the cases where the positive charge of the cation is delocalized on an aromatic ring such as imidazolium, the antibonding orbitals of the positively charged aromatic system are very similar in nature and energy to the LUMO of Reichardt’s Dye. This leads to an interesting, specific cation-probe interaction that can be used to elucidate the nature of the ionic liquids’ cations. Parallel computational and experimental investigations have been conducted to elucidate the nature of this interaction with respect to the molecular structure of the cation.     

咪唑离子液体及其萃取体系的辐射效应研究

离子液体因其低挥发性,高热稳定性及在萃取金属离子方面的优良表现被认为是乏燃料后处理中萃取分离放射性核素的新一代绿色溶剂。但从乏燃料后处理强辐射的应用环境来看,需要首先对离子液体及其萃取体系的辐射效应进行系统研究和评估。本文以两种常见的憎水性咪唑离子液体1-丁基-3-甲基咪唑六氟磷酸盐( )和1-丁基-3-甲基咪唑三氟甲基磺酰亚胺酸盐( )为例,综述了我们在离子液体及其萃取体系的γ辐射效应方面的最新研究进展,内容包括纯离子液体在氮气气氛下的辐射效应,硝酸对离子液体辐射效应的影响,离子液体辐解产物的分离分析及γ辐照对离子液体体系萃取金属离子的影响等。基于以上研究对离子液体用于乏燃料后处理的可行性进行了评估,同时对离子液体及其萃取体系的辐射效应研究进行了展望。     

Selective Extraction of Metal Ions from Aqueous Phase to Ionic Liquids: A Novel Thermodynamic Approach to Separations

The selective extraction of metals from aqueous mixtures has generally relied on the use of selective ionophores. We present an alternative strategy that exploits a recently developed approach to extraction into an ionic liquid phase, and show that a high degree of control over selectivity can be obtained by tuning the relative concentrations of extraction agents. A thermodynamic model for the approach is presented, and an experimental separation of strontium and potassium ions is performed. It is shown that tuning the concentrations of the species involved can shift the ratio of potassium to strontium in the ionic liquid phase from 4:1 to 3:4. This extraction is performed under mild conditions with relatively common reagents. The result is a proof‐of‐concept for a novel separations scheme that could have great importance in a wide range of technological applications.     

An Efficient Ionic Liquid-Mediated Extraction and Enrichment of Isoimperatorin from Ostericum koreanum (Max.) Kitagawa

Ionic liquids (ILs) have attracted significant interest because of their desirable properties. These characteristics have improved their application to overcome the shortcomings of conventional separation techniques for phytochemicals. In this study, several ILs were investigated for their capacity to extract isoimperatorin, a bioactive furanocoumarin, from the roots of Ostericum koreanum. Herein, 1-Butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF₄]) was selected as a promising IL for separating isoimperatorin. A central composite design was applied to optimize the extraction conditions. Under the optimal conditions, the yield of isoimperatorin reached 97.17 ± 1.84%. Additionally, the recovery of isoimperatorin from the [Bmim][BF₄] solution was successfully achieved (87.73 ± 2.37%) by crystallization using water as an antisolvent. The purity of the isoimperatorin was greatly enhanced, from 0.26 ± 0.28% in the raw material to 26.94 ± 1.26% in the product, in a one-step crystallization process. Namely, an enhancement of approximately 103-folds was reached. The developed approach overcomes the shortcomings of conventional separation methods applied for gaining isoimperatorin by significantly reducing the laboriousness of the process and the consumption of volatile organic solvents. Moreover, the simplicity and effectiveness of the method are assumed to be valuable for producing isoimperatorin-enriched products and for promoting its purification. This work also confirms the efficiency of ILs as a promising material for the separation of phytochemicals.     

离子液体在萃取分离中的应用研究进展

室温离子液体作为一种新型绿色溶剂,具有液程宽、几乎不挥发、溶解能力强及结构可调等独特的物理化学性质,近年来逐渐被人们认识了解,它在各个领域的应用也得到了初步的发展.本文重点概述了离子液体在萃取分离金属离子方面的研究进展,并对离子液体萃取分离有机物和生物分子的研究作了简要介绍.引用文献54篇.     

Magnetic graphene oxide modified by imidazole‐based ionic liquids for the magnetic‐based solid‐phase extraction of polysaccharides from brown alga

Magnetic graphene oxide was modified by four imidazole‐based ionic liquids to synthesize materials for the extraction of polysaccharides by magnetic solid‐phase extraction. Fucoidan and laminarin were chosen as the representative polysaccharides owing to their excellent pharmaceutical value and availability. Fourier transform infrared spectroscopy, field‐emission scanning electron microscopy, and thermogravimetric analysis were applied to characterize the synthesized materials. Single‐factor experiments showed that the extraction efficiency of polysaccharides was affected by the amount of ionic liquids for modification, solid–liquid ratio of brown alga and ethanol, the stirring time of brown alga and ionic liquid‐modified magnetic graphene oxide materials, and amount of 1‐(3‐aminopropyl)imidazole chloride modified magnetic graphene oxide materials added to the brown alga sample solution. The results indicated that 1‐(3‐aminopropyl)imidazole chloride modified magnetic graphene oxide possessed better extraction ability than graphene oxide, magnetic graphene oxide, and other three ionic‐liquid‐modified magnetic graphene oxide materials. The highest extraction recoveries of fucoidan and laminarin extracted by 1‐(3‐aminopropyl)imidazole chloride modified magnetic graphene oxide were 93.3 and 87.2%, respectively. In addition, solid materials could be separated and reused easily owing to their magnetic properties.     

Ionic liquid‐based ultrasound‐assisted extraction of fangchinoline and tetrandrine from Stephaniae tetrandrae

An ionic liquid‐based ultrasound‐assisted extraction method has been developed for the effective extraction of fangchinoline and tetrandrine from Stephaniae tetrandrae. The effects of some ultrasound‐assisted extraction parameters including the concentration of [BMIM][BF₄], pH, ultrasonic power and time were investigated to optimize the ultrasound‐assisted extraction conditions. Compared to the regular ultrasound‐assisted extraction and traditional refluent extraction, the proposed [BMIM][BF₄]‐based ultrasound‐assisted extraction offered shorter extraction times (from 6 h to 40 min) and remarkable higher efficiencies (approximately 30% improved), which supported the suitability of the proposed approach. In addition, the proposed approach was confirmed by the good correlation coefficient (R²), recovery and reproducibility (RSD, n = 5), which were in the range of 0.9992–0.9995, 85.5–101.1%, and 1.87–4.33%, respectively.     

Copper(II)‐Specific Fluorogenic Task‐Specific Ionic Liquids as Selective Fluorescence Probes and Recyclable Extractants

The designed synthesis of a series of copper(II) specific fluorogenic hydrophobic task‐specific ionic liquids (TSILs) from a new naphthalene‐based tetradentate ligand is reported. Absorption and fluorescence spectral studies reveal both the ligand and its derivative TSILs show exclusive selectivity towards copper(II) ions. The Stern–Volmer method for calculation of the detection limit for ligand and TSIL_1–3 shows values of 0.12, 20, 17, and 15 μM , respectively. Extraction and striping studies by doping these TSILs in [bmim][NTf₂] demonstrated that these TSILs are recyclable extractants for the selective recovery of Cu^II ions from a mixture of 14 relevant metal chloride aqueous solutions in biphasic liquid–liquid extraction with approximately 95 % recovery.