Green solvents from ionic liquids and deep eutectic solvents to natural deep eutectic solvents

Natural deep eutectic solvents (NADESs) are defined as mixtures of certain molar ratios of natural compounds such as sugars, organic acids, amino acids, and organic bases that are abundant in organisms. The melting points of these mixtures are considerably lower than those of their individual ingredients and far below ambient temperature. The first publications on the NADES concept in 2011 created a great expectation regarding their potential as green solvents that could replace conventional organic solvents in a wide range of applications. This was largely because many of the drawbacks of conventional synthetic ionic liquids (ILs) and deep eutectic solvents (DESs), particularly their toxicity and environmental hazards, could be solved using NADESs. Throughout the last 7 years, the interest in NADESs has increased enormously as reflected by the exponential growth of the number of related publications. The research on NADESs has rapidly expanded particularly into the evaluation of the feasibility of their application in diverse fields such as the extraction of (targeted) bioactive compounds from natural sources, as media for enzymatic or chemical reactions, preservatives of labile compounds, or as vehicles of non–water-soluble compounds for pharmaceutical purposes. Along with the exploration of these potential applications, there have been a large number of other studies related to their physicochemical features, the search for new NADESs, the research into the interactions between NADES components or with solutes, the recovery of solutes from NADES solutions, and the ways of circumventing inherent problems of NADESs such as their high viscosity and the consequent difficulties in handling them. This article contains a review of the applications of NADESs as extraction solvents, reaction media, and preservative, providing also a perspective of their future.     

Natural Deep Eutectic Solvents for the Extraction of Bioactive Steroidal Saponins from Dioscoreae Nipponicae Rhizoma

In the present study, a simple and environmentally friendly extraction method based on natural deep eutectic solvents (NADESs) was established to extract four bioactive steroidal saponins from Dioscoreae Nipponicae Rhizoma (DNR). A total of twenty-one types of choline chloride, betaine, and L-proline based NADESs were tailored, and the NADES composed of 1:1 molar ratio of choline chloride and malonic acid showed the best extraction efficiency for the four steroidal saponins compared with other NADESs. Then, the extraction parameters for extraction of steroidal saponins by selected tailor-made NADES were optimized using response surface methodology and the optimal extraction conditions are extraction time, 23.5 min; liquid–solid ratio, 57.5 mL/g; and water content, 54%. The microstructure of the DNR powder before and after ultrasonic extraction by conventional solvents (water and methanol) and the selected NADES were observed using field emission scanning electron microscope. In addition, the four steroidal saponins were recovered from NADESs by D101 macroporous resin with a satisfactory recovery yield between 67.27% and 79.90%. The present research demonstrates that NADESs are a suitable green media for the extraction of the bioactive steroidal saponins from DNR, and have a great potential as possible alternatives to organic solvents for efficiently extracting bioactive compounds from natural products.     

深共熔溶剂及其生物催化应用

在绿色化学研究领域,溶剂占据着重要的位置。作为一个绿色溶剂必须满足廉价易得、可生物降解、无毒、可循环使用、无挥发性等标准的要求。但是至今能满足这些要求的溶剂仍然非常有限。近年来,深共熔溶剂（Deep Eutectic Solvents,DESs）被认为可以作为绿色溶剂替代传统的有机溶剂而受到广泛关注。DESs是由两个或多个成分在特定比例下形成的凝固点大大降低室温液态混合物。与离子液体相比,DESs具有廉价、低毒、可生物降解等特点,在许多领域成为研究热点。本文综述了DESs的生物降解性、毒性/细胞毒性及其作为生物催化反应介质的研究现状。基于对研究现状的认识,对DESs未来研究、应用需要解决的问题进行了讨论。作者期望对DESs生物催化应用研究现状的综述更进一步促进DESs研究、应用的发展。     

Optimization of the extraction process of flavonoids from Trollius ledebouri with natural deep eutectic solvents

In recent years, natural deep eutectic solvents have been favored greatly due to their environment friendly, mild biological toxicity and simple biodegradability. Natural deep eutectic solvents gradually applied for the extracting bioactive compounds from natural products efficiently. In this study, 20 natural deep eutectic solvents were prepared and their physical and chemical properties were tested. The ultrasonic-assisted extraction method was used to extract flavonoids from Trollius ledebouri and high-performance liquid chromatography-ultraviolet was applied to examine two main bioactive flavonoids (orientin and vitexin). Compared with traditional solvents (water and 60% ethanol solution), natural deep eutectic solvents composed of L(-)-proline and levulinic acid (molar ratio 1:2) show a super extraction efficiency. On this basis, the response surface method was used to optimize the extraction temperature, extraction time, water contents, and solid–liquid ratio. As a consequence, the extraction temperature 60℃, extraction time 18 min, water content 14% (v/v), and the solid–liquid ratio 48 mL·g⁻¹ were chosen as the best extraction process. This study shows that natural deep eutectic solvents can effectively extract flavonoids from T. ledebouri, laying a foundation for the further application of natural deep eutectic solvents to extract bioactive compounds from natural products.     

Low‐Transition‐Temperature Mixtures (LTTMs): A New Generation of Designer Solvents

A new generation of designer solvents emerged in the last decade as promising green media for multiple applications, including separation processes: the low‐transition‐temperature mixtures (LTTMs). They can be prepared by mixing natural high‐melting‐point starting materials, which form a liquid by hydrogen‐bond interactions. Among them, deep‐eutectic solvents (DESs) were presented as promising alternatives to conventional ionic liquids (ILs). Some limitations of ILs are overcome by LTTMs, which are cheap and easy to prepare from natural and readily available starting materials, biodegradable, and renewable.     

Development of deep eutectic solvents applied in extraction and separation

Deep eutectic solvents, as an alternative to ionic liquids, have greener credentials than ionic liquids, and have attracted considerable attention in related chemical research. Deep eutectic solvents have attracted increasing attention in chemistry for the extraction and separation of various target compounds from natural products. This review highlights the preparation of deep eutectic solvents, unique properties of deep eutectic solvents, and synthesis of deep‐eutectic‐solvent‐based materials. On the other hand, application in the extraction and separation of deep eutectic solvents is also included in this report. In this paper, the available data and references in this field are reviewed to summarize the applications and developments of deep eutectic solvents. Based on the development of deep eutectic solvents, an exploitation of new deep eutectic solvents and deep eutectic solvents‐based materials is expected to diversify into extraction and separation.     

Solubility and Stability of Some Pharmaceuticals in Natural Deep Eutectic Solvents-Based Formulations

Some medicines are poorly soluble in water. For tube feeding and parenteral administration, liquid formulations are required. The discovery of natural deep eutectic solvents (NADES) opened the way to potential applications for liquid drug formulations. NADES consists of a mixture of two or more simple natural products such as sugars, amino acids, organic acids, choline/betaine, and poly-alcohols in certain molar ratios. A series of NADES with a water content of 0–30% (w/w) was screened for the ability to solubilize (in a stable way) some poorly water-soluble pharmaceuticals at a concentration of 5 mg/mL. The results showed that NADES selectively dissolved the tested drugs. Some mixtures of choline-based NADES, acid-neutral or sugars-based NADES could dissolve chloral hydrate (dissociated in water), ranitidine·HCl (polymorphism), and methylphenidate (water insoluble), at a concentration of up to 250 mg/mL, the highest concentration tested. Whereas a mixture of lactic-acid–propyleneglycol could dissolve spironolacton and trimethoprim at a concentration up to 50 and 100 mg/mL, respectively. The results showed that NADES are promising solvents for formulation of poorly water-soluble medicines for the development of parenteral and tube feeding administration of non-water-soluble medicines. The chemical stability and bioavailability of these drug in NADES needs further studies.     

低共熔溶剂在萃取分离中的应用

随着绿色化学的不断发展,如何在分析过程中应用和体现绿色化学特点,避免分析过程对环境产生二次污染及对人员造成危害也得到了关注。开发和使用具有绿色化学特点的溶剂和方法是分析工作者努力的方向之一。在已经出现的新溶剂中,低共熔溶剂(DES)与离子液体(ILs)物理性质相似,并具有环境友好、不可燃、生物降解、价廉、易制备等特点,因而近几年来获得了迅速发展。该文总结了低共熔溶剂的制备、性质及分类,综述了近年来其在萃取和分离中的应用进展。     

New eutectic ionic liquids for lipase activation and enzymatic preparation of biodiesel

The enzymatic preparation of biodiesel has been hampered by the lack of suitable solvents with desirable properties such as high lipase compatibility, low cost, low viscosity, high biodegradability, and ease of product separation. Recent interest in using ionic liquids (ILs) as advanced reaction media has led to fast reaction rates and high yields in the enzymatic synthesis of biodiesel. However, conventional (i.e., cation-anion paired) ILs based on imidazolium and other quaternary ammonium salts remain too expensive for wide application at industrial scales. In this study, we report on newly-synthesized eutectic ILs derived from choline acetate or choline chloride coupled with biocompatible hydrogen-bond donors, such as glycerol. These eutectic solvents have favorable properties including low viscosity, high biodegradability, and excellent compatibility with Novozym(?) 435, a commercial immobilized Candida antarctica lipase B. Furthermore, in a model biodiesel synthesis system, we demonstrate high reaction rates for the enzymatic transesterification of Miglyol(?) oil 812 with methanol, catalyzed by Novozym(?) 435 in choline acetate/glycerol (1:1.5 molar ratio). The high conversion (97%) of the triglyceride obtained within 3 h, under optimal conditions, suggests that these novel eutectic solvents warrant further exploration as potential media in the enzymatic production of biodiesel.     

A mini review on synthesis,properties and applications of deep eutectic solvents

Organic solvents have been of great importance for many chemical synthesis, storage and separation processes. The industries and research laboratories are heavily dependent on organic solvents in bulk; are highly volatile, lipophilic, toxic and causes a number of issues to the human health and the environmental fitness. Neoteric solvents have been proposed as a better substitute to these harmful organic solvents, and scientists have come up with several neoteric solvents in the last three decades, to name a few: ionic liquids (ILs), switchable solvents, bio-based solvents and deep eutectic solvents (DESs). These neoteric solvents attract a great deal of interest from the scientific community due to plenty of possibilities, therefore, they have huge impact and novel studies are reported quite frequently on the same. In this review, we intend to focus to brief on deep eutectic solvents, about their properties, synthesis, promising applications, and how they gradually emerged from ILs and later stood out as a different class of neoteric solvent, which overcomes many shortcomings of ILs. DESs are possibly receptive synthetic compounds and their relationship based on the hydrogen bond donor or acceptor restricts their reactivity and allow to explore in different disciplines of science.     

Molecularly Imprinted Polymers Modified by Deep Eutectic Solvents and Ionic Liquids with Two Templates for the Simultaneous Solid-Phase Extraction of Fucoidan and Laminarin from Marine Kelp

Molecularly imprinted polymers modified by deep eutectic solvents and ionic liquids (ILs) were prepared as packing materials for the solid-phase extraction (SPE) of fucoidan and laminarin. The prepared materials were characterized by field emission scanning electron microscopy and Fourier transform infrared spectroscopy. The polymers modified by the deep eutectic solvent prepared by choline chloride and urea had the best extraction efficiencies for fucoidan and laminarin (95.5% and 87.6%, respectively) from marine kelp. The relative standard deviations for intraday and interday determination were less than 4.23%. The molecularly imprinted polymers modified by deep eutectic solvents and ILs showed outstanding applications for SPE and may offer novel sample pretreatment for other analytes.     

Interactions of 1-butyl-3-methylimidazolium carboxylate ionic liquids with glucose in water: a study of volumetric properties, viscosity, conductivity and NMR

Extensive applications of ionic liquids (ILs) may result in their accumulation in the ecological environment and organisms. Although ILs are popularly called "green solvents", their toxicity, in fact, has been exhibited. Therefore the interaction of ILs with biomolecules is a cutting-edge research subject. Herein, the interactions of 1-butyl-3-methylimidazolium carboxylate ionic liquids ([C(4)mim][HCOO], [C(4)mim][CH(3)COO] and [C(4)mim][CH(3)CH(2)COO]) with glucose in water were studied for their volumetric properties, viscosity, conductivity and NMR spectra. Limiting apparent molar volumes (V(Φ, IL)(0)), viscosity B-coefficients, limiting molar conductivities (Λ(0)) and Walden products (Λ(0)η(0)) were evaluated for the ILs in glucose + water solutions. Volumetric interaction parameters were also obtained from the transfer volumes of the ionic liquids. The contributions of the solvent properties (B(1)) and the ionic liquid-solvent interactions (B(2)) to the B-coefficient were extracted, together with molar activation energies (Δμ(IL)(0≠)) of the ionic liquids for viscous flow of the aqueous glucose + IL solution. In addition, the (13)C and (1)H NMR spectra of methyl β-D-glucopyranoside and ILs in β-D-glucopyranoside + IL + D(2)O were studied. The NMR results show that no special and strong interactions were observed between glucopyranoside and the ILs. However, it was confirmed that the H2 on the imidazolium ring has more activity (acidity) than atoms H4 and H5. The macro-properties and their changes were also discussed in terms of the size, structure and solvation of the ILs and glucose.     

离子液体的辐射效应研究进展

离子液体(ILs)具有低挥发性和化学稳定性,在萃取金属离子方面有着优异的表现,被认为是乏燃料后处理中的新一代绿色溶剂.然而在萃取放射性核素过程中,离子液体将处于强辐射场,因此离子液体辐射效应研究是其实际应用的前提.本文综述了国内外关于离子液体的辐射效应研究进展,包括辐照对离子液体结构和性质的影响,离子液体的脉冲辐解和激光光解研究,离子液体辐解产物的分析及其对核素萃取的影响等研究进展,并对今后该领域的研究方向进行了展望.     

离子液体的辐射效应研究进展

离子液体（ILs）具有低挥发性和化学稳定性,在萃取金属离子方面有着优异的表现,被认为是乏燃料后处理中的新一代绿色溶剂. 然而在萃取放射性核素过程中,离子液体将处于强辐射场,因此离子液体辐射效应研究是其实际应用的前提. 本文综述了国内外关于离子液体的辐射效应研究进展,包括辐照对离子液体结构和性质的影响,离子液体的脉冲辐解和激光光解研究,离子液体辐解产物的分析及其对核素萃取的影响等研究进展,并对今后该领域的研究方向进行了展望.     

A Green Deep Eutectic Solvent-Based Ultrasound-Assisted Method to Extract Astaxanthin from Shrimp Byproducts

The extraction of valuable compounds from waste products using green and inexpensive solvents is a significant strategy for sample preparation. Accordingly, in the present study, the use of deep eutectic solvents, an emerging green approach, was used to extract astaxanthin, a well-known and widely-used antioxidant, from shrimp byproducts. After evaluating different combinations of extraction conditions and deep eutectic solvents, an ultrasonication method was established and optimized by a systematic investigation of the influencing factors. A comparison of the amount of astaxanthin (102 μg g^{? 1} ) extracted using a traditional organic solvent, ethanol, showed that more astaxanthin (146 μg g^{? 1} ) was obtained using the reported eco-friendly method. The excellent properties of deep eutectic solvents highlight their advantages as promising inexpensive green solvents for the extraction and determination of a range of bioactive compounds from natural products.     

含CO2/离子液体系统相行为及其在反应与分离中的应用进展

目前已知的绿色溶剂主要包括超临界流体（Supercritical fluids,SCFs）、离子液体（Ionic liquids,ILs）、二氧化碳膨胀液体（CO₂ expanded liquids, CXLs）、水以及上述溶剂的混合物等。其中,由超临界CO₂（Supercritical CO₂,SCCO₂）与ILs混合而构成的新兴溶剂,因为化学热力学方面的特性,成为近年来研究的热点,未来很有发展前景。本文回顾了目前为止在该领域所开展的工作,总结了影响SCCO₂与IL相行为的主要因素。包括温度、压力、ILs的含水量、ILs的阴离子、ILs的阳离子、ILs的摩尔体积以及助溶剂等。同时分析了ILs/SCCO₂与溶质形成的多元混合物相行为的成因。介绍了ILs/CO₂在萃取、反萃取、膜分离、反胶束、萃取与反应耦合等分离方面的应用。由于传统的单元操作很难满足无污染和对过程集成的要求,因而含有ILs/ SCCO₂的分离反应耦合过程将是未来是实现清洁生产的发展方向。     

低共熔溶剂及其应用研究进展

作为一类新型的绿色溶剂,低共熔溶剂具有蒸汽压低、无毒性、可生物降解、溶解性和导电性优良、电化学稳定窗口宽等独特的物理化学性质,并且可以通过选择合适的组成和配比来调节其性能,在很多领域中有着诱人的应用前景.本文从低共熔溶剂的组成、性质及其应用等3个方面综述了近年来低共熔溶剂的研究进展,并对目前研究中存在的问题进行了讨论.     

Pipette‐tip solid‐phase extraction based on deep eutectic solvent modified graphene for the determination of sulfamerazine in river water

A green and novel deep eutectic solvent modified graphene was prepared and used as a neutral adsorbent for the rapid determination of sulfamerazine in a river water sample by pipette‐tip solid‐phase extraction. Compared with conventional graphene, deep eutectic solvent modified graphene can change the surface of graphene with wrinkled structure and higher selective extraction ability. The properties of deep eutectic solvent modified graphene and graphene were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Static adsorption showed deep eutectic solvent modified graphene had a higher adsorption ability (18.62 mg/g) than graphene. Under the optimum conditions, factors such as kinds of washing solvents and elution solvents and volume of elution solvent were evaluated. The limits of detection and quantification were 0.01 and 0.03 μg/mL, respectively. The method recoveries of sulfamerazine were in the range of 91.01–96.82% with associated intraday relative standard deviations ranging from 1.63 to 3.46% and interday relative standard deviations ranging from 0.68 to 3.84%. Deep eutectic solvent modified graphene showed satisfactory results (recovery was 95.38%) and potential for rapid purification of sulfamerazine in river water sample in combination with the pipette‐tip solid‐phase extraction method.     

Optimized extraction of bioactive compounds from Herba Artemisiae Scopariae with ionic liquids and deep eutectic solvents

Ionic liquids with length of alkyl chain and different anions, deep eutectic solvents with choline chloride and 7 different hydrogen bond donors were applied as extraction additives after optimizing the extraction conditions to increase the extraction amounts of rutin, quercetin, and scoparone from Herba Artemisiae Scopariae. The extraction conditions were optimized as follows: refluxing with methanol with a solid/liquid ratio of 1:120 under 60°C for 60 min after changing the different extraction conditions of: extraction methods (dipping, ultrasonic, reflux and soxlet), extraction solvents (methanol, water and ethanol), extraction temperature (30, 40, 50, 60, 70 and 80°C), extraction time (30, 60, 80, 100 and 120 min), extraction ratio of solid to liquid (1:5, 1:10, 1:20, 1:50, 1:100, 1:120 and 1:150). Under these optimal conditions, the best preformed extraction additive among the 7 kinds of ionic liquids and 7 kinds of deep eutectic solvents extraction additives were selected and optimized with its contraction of 0.5mg/mL. Using the most effective extraction additive, [BMIM][Br], 10275.92 µg/g rutin, 899.73 µg/g quercetin, and 554.32 µg/g scoparone were obtained. Overall, ionic liquids and deep eutectic solvents have potential applications as extraction additives for the extraction of bioactive compounds from nature plants.     

Electrodeposition in Ionic Liquids

Due to their attractive physico‐chemical properties, ionic liquids (ILs) are increasingly used as deposition electrolytes. This review summarizes recent advances in electrodeposition in ILs and focuses on its similarities and differences with that in aqueous solutions. The electrodeposition in ILs is divided into direct and template‐assisted deposition. We detail the direct deposition of metals, alloys and semiconductors in five types of ILs, including halometallate ILs, air‐ and water‐stable ILs, deep eutectic solvents (DESs), ILs with metal‐containing cations, and protic ILs. Template‐assisted deposition of nanostructures and macroporous structures in ILs is also presented. The effects of modulating factors such as deposition conditions (current density, current density mode, deposition time, temperature) and electrolyte components (cation, anion, metal salts, additives, water content) on the morphology, compositions, microstructures and properties of the prepared materials are highlighted.