Ionic liquids: solvents and sorbents in sample preparation

The applications of ionic liquids (ILs) and IL‐derived sorbents are rapidly expanding. By careful selection of the cation and anion components, the physicochemical properties of ILs can be altered to meet the requirements of specific applications. Reports of IL solvents possessing high selectivity for specific analytes are numerous and continue to motivate the development of new IL‐based sample preparation methods that are faster, more selective, and environmentally benign compared to conventional organic solvents. The advantages of ILs have also been exploited in solid/polymer formats in which ordinarily nonspecific sorbents are functionalized with IL moieties in order to impart selectivity for an analyte or analyte class. Furthermore, new ILs that incorporate a paramagnetic component into the IL structure, known as magnetic ionic liquids (MILs), have emerged as useful solvents for bioanalytical applications. In this rapidly changing field, this Review focuses on the applications of ILs and IL‐based sorbents in sample preparation with a special emphasis on liquid phase extraction techniques using ILs and MILs, IL‐based solid‐phase extraction, ILs in mass spectrometry, and biological applications.     

离子液体表/界面性质与结构

离子液体与气体、溶剂等物质组成的多相体系为吸收、萃取、两相催化等技术的发展提供了新的平台。离子液体的表/界面性质与结构是含离子液体多相体系的重要科学问题,可在介观尺度下显著影响多相体系反应和分离过程的效率。近年来,离子液体表/界面性质和结构的研究得到了广泛的关注。本文综述了离子液体及其与水、有机溶剂组成的混合物的表/界面张力及结构研究进展,介绍了现有的研究方法、研究对象与研究成果,归纳了离子液体及其混合物表/界面张力及结构的变化规律,分析了表/界面结构与表/界面张力之间的关系,探讨了离子液体表/界面研究存在的问题和未来的发展方向。     

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.     

Analytical developments and applications of ionic liquids for environmental studies

Ionic liquids (ILs) are considered advanced solvents with interesting properties that have led to remarkable improvements in the performance of analytical methods and their practical application. Analytical chemistry has profited from the evolution of ILs in diverse contexts, ranging from their applications in microextractions to uses as matrices for mass spectrometric determinations. Their use in sample preparation has meant significant improvements in terms of miniaturization and analytical performance, and given place to new techniques based on liquid-liquid and solid-phase extractions; the latter greatly driven forward by the combination of ILs with nanomaterials. Furthermore, electrodes have been prepared by combining ILs with different modern materials, significantly improving the sensitivity and selectivity of electroanalytical methods. Moreover, the implementation of ILs as additives to mobile and stationary phases in separation techniques has been proved to improve liquid and gas chromatography, as well as capillary electrophoresis, in terms of the number of analytes that can be efficiently separated and of the useful life of columns, representing also a promising alternative to environmentally dangerous organic solvents. Additionally, their application as matrix modifiers and as ion-pairing additives has introduced their use in mass spectrometry. In this review, the design and implementation of innovative and highly efficient analytical methods based on ILs for the sensitive and selective determination of diverse analytes in environmental matrices is described. Critical issues that have arisen from their application and future challenges in electrochemical, separation and preconcentration techniques based on these solvents are also presented.     

Ionic liquids in sample preparation

Due to their unique properties, their good extractabilities for various target analytes, and the fact that many compounds are highly soluble in them, room-temperature ionic liquids (ILs) are used as promising alternatives to the traditional organic solvents employed in sample preparation. ILs have been used as extraction solvents for a wide range of analytes, from environmental contaminates to biomacromolecules and nanomaterials, and as dissolution solvents for various detection techniques. In this paper, the main applications of ILs in sample preparation are reviewed, and the problems and challenges in this area are described.     

Ionic liquid assisted synthesis of S-heterocycles

Some organic solvents are highly toxic, flammable, and even explosive. In particular, high vapor pressures and toxicity of certain volatile organic solvents may cause significant environmental problems. Therefore, alternative solvents or media with tunable and versatile solvation properties for conducting chemical reactions and materials synthesis have been actively sought. Ionic liquids have numerous applications not only as environmentally benign reaction media, but also as catalysts and reagents. Due to the increase of environmental consciousness in chemical research and industry, the challenge for a sustainable environment calls for clean procedures that avoid the use of harmful organic solvents. Due to the special properties of ILs (ionic liquids) such as wide liquid range, good solvating ability, negligible vapor pressure, non-inflammability, non-volatility, environment friendly medium, high thermal stability, good stability in air and moisture, easy recycling and rate promoters etc. they are used in organic synthesis. Therefore, ionic liquids have attracted the attention of chemists and act as catalyst and reaction medium in organic reactions with high activity. Highly efficient methods are explored for the preparation of S-heterocycles with the application of ILs as catalyst and reaction medium.     

Deep Eutectic Solvents Application in Food Analysis

Current trends in Analytical Chemistry are focused on the development of more sustainable and environmentally friendly procedures. However, and despite technological advances at the instrumental level having played a very important role in the greenness of the new methods, there is still work to be done regarding the sample preparation stage. In this sense, the implementation of new materials and solvents has been a great step towards the development of “greener” analytical methodologies. In particular, the application of deep eutectic solvents (DESs) has aroused great interest in recent years in this regard, as a consequence of their excellent physicochemical properties, general low toxicity, and high biodegradability if they are compared with classical organic solvents. Furthermore, the inclusion of DESs based on natural products (natural DESs, NADESs) has led to a notable increase in the popularity of this new generation of solvents in extraction techniques. This review article focuses on providing an overview of the applications and limitations of DESs in solvent-based extraction techniques for food analysis, paying especial attention to their hydrophobic or hydrophilic nature, which is one of the main factors affecting the extraction procedure, becoming even more important when such complex matrices are studied.     

Application of ionic liquid in liquid phase microextraction technology

Ionic liquids (ILs) are novel nonmolecular solvents. Their unique properties, such as high thermal stability, tunable viscosity, negligible vapor pressure, nonflammability, and good solubility for inorganic and organic compounds, make them excellent candidates as extraction media for a range of microextraction techniques. Many physical properties of ILs can be varied, and the structural design can be tuned to impart the desired functionality and enhance the analyte extraction selectivity, efficiency, and sensitivity. This paper provides an overview of the applications of ILs in liquid phase microextraction technology, such as single‐drop microextraction, hollow fiber based liquid phase microextraction, and dispersive liquid–liquid microextraction. The sensitivity, linear calibration range, and detection limits for a range of target analytes in the methods were analyzed to determine the advantages of ILs in liquid phase microextraction.     

Modern microextraction techniques for natural products

Natural product analysis has gained wide attention in recent years, especially for herbal medicines, which contain complex ingredients and play a significant clinical role in the therapy of numerous diseases. The constituents of natural products are usually found at low concentrations, and the matrices are complex. Thus, the extraction of target compounds from natural products before analysis by analytical instruments is very significant for human health and its wide application. The commonly used traditional extraction methods are time-consuming, using large amounts of sample and organic solvents, as well as expensive and inefficient. Recently, microextraction techniques have been used for natural product extraction to overcome the disadvantages of conventional extraction methods. In this paper, the successful applications of and recent developments in microextraction techniques including solvent-based and sorbent-based microextraction methods, in natural product analysis in recent years, especially in the last 5 years, are reviewed for the first time. Their features, advantages, disadvantages, and future development trends are also discussed.     

Task-specific microextractions using ionic liquids

Ionic liquids (ILs) have been the focus of many scientific investigations including the field of analytical microextractions. ILs have many advantages over traditional organic solvents making them excellent candidates as extraction media for a variety of microextraction techniques. Many physical properties of ILs can be varied, and the structural design and make-up can be tuned to impart desired functionality for enhancement of analyte extraction selectivity, efficiency, and sensitivity. This paper provides a brief overview of ionic liquids and highlights trends in three important sample-preparation techniques, namely, single drop microextraction, solid-phase microextraction, and dispersive liquid–liquid microextraction in terms of performing task-specific extractions using these highly versatile solvents.     

基于低共熔溶剂的萃取分离技术及其应用研究进展

随着绿色化学的发展,开发和应用符合绿色化学要求的溶剂和方法备受关注。作为离子液体类似物,低共熔溶剂(deep eutectic solvent, DES)是通过氢键受体(hydrogen bond acceptor, HBA)和氢键供体(hydrogen bond donator, HBD)的氢键作用而形成的一种混合物,具有环境友好、制备简单、成本低、可生物降解等优点,在很多领域均有越来越广泛的应用。DES可以从不同样品中萃取和分离不同的目标化合物,其作为萃取溶剂具有独特的优势,可以获得较高的萃取效率且样品基质对分析过程的影响较小。在分散液液微萃取(dispersive liquid-liquid micro-extraction, DLLME)程序中,DES可以萃取复杂基质中的残留药物、金属离子和生物活性成分;与传统的萃取方法相比,该方法具有对有机试剂需求少,萃取效率更高等明显优势。而且,在DLLME中加入DES作为分散剂,能够加速萃取剂在样品溶液中的扩散,具有小型化、成本低等优点。相比于传统分散剂甲醇、乙腈的高挥发性、易燃性,DES的高稳定性、低毒性使其在绿色化学领域中更具有优势,应用更广。因此,DES与DLLME的结合近年来发展迅速。不仅如此,DES与固相萃取联合应用也具有广泛的应用前景,在与固相萃取小柱和搅拌棒联合应用时,DES可以作为洗脱剂,氢键供体及氢键给体的用量之比是洗脱效率的重要考察因素之一。在与磁性材料联用时,DES能与磁性多壁碳纳米管、磁性氧化石墨烯等纳米复合材料结合,通过氢键、π-π作用力和静电作用力等特异性吸附目标分析物。并且能够参与磁性凝胶和分子印迹聚合物的合成,推动磁性材料向绿色化学的方向发展,进一步拓展DES的应用。作为一类新兴的绿色溶剂,DES在化合物的萃取分离技术方面受到广泛关注,在不同的萃取技术中扮演了不同的角色,并表现出良好的性能,因此逐渐成为绿色化学领域的研究重点。该文整合了DES在萃取分离技术中的研究进展,介绍了DES的制备、性质和分类,对DES在DLLME和固相萃取中的应用进行了总结和归类,并展望了DES在萃取分离技术中的应用前景,为DES未来的应用提供参考。     

用于食品安全分析样品前处理的共价有机聚合物的制备及应用进展

食品安全关系身体健康和生命安全,是全球关注的热点之一。食品基质复杂,痕量有毒有害物质分析之前必须经过有效的前处理。目前发展的前处理技术如固相萃取、磁固相萃取、固相微萃取等,其关键是吸附介质。共价有机聚合物是一类通过共价键连接而成的有机多孔材料,具有质轻、稳定性好、比表面积大、结构可控、易于修饰等特性,是一类优异的新型吸附材料。该文综述了近年来共价有机聚合物(COPs)在食品安全分析前处理中的应用进展。共价有机聚合物及其功能化复合材料通过简单的装填、聚合反应或化学键合固定到小柱或毛细管柱中用作固相萃取的吸附介质;通过一锅法、原位还原法、原位生长法或共沉淀法生成具有磁性的固相萃取吸附介质;或者通过物理涂覆、化学键合、溶胶凝胶法及原位生长法制备固相微萃取纤维。基于以上高吸附容量共价有机聚合物的样品前处理技术,食品中农残兽残、添加剂、环境污染物及生物毒素等得到了有效富集。最后,展望了COPs在食品分析样品前处理应用中的发展方向:简单高效绿色制备方法的开发,功能化COPs的设计合成;萃取机理的研究;高通量、高灵敏度分析方法研究。这些研究将促进COPs在样品前处理领域获得更广泛的应用。     

Ionic liquids in separation techniques

The growing interest in ionic liquids (ILs) has resulted in an exponentially increasing production of analytical applications. The potential of ILs in chemistry is related to their unique properties as non-molecular solvents: a negligible vapor pressure associated to a high thermal stability. ILs found uses in different sub-disciplines of analytical chemistry. After drawing a rapid picture of the physicochemical properties of selected ILs, this review focuses on their use in separation techniques: gas chromatography (GC), liquid chromatography (LC) and electrophoretic methods (CE). In LC and CE, ILs are not used as pure solvents, but rather diluted in aqueous solutions. In this situation ILs are just salts. They are dual in nature. Too often the properties of the cations are taken as the properties of the IL itself. The lyotropic theory is recalled and the effects of a chaotropic anion are pointed out. Many results can be explained considering all ions present in the solution. Ion-pairing and ion-exchange mechanisms are always present, associated with hydrophobic interactions, when dealing with IL in diluted solutions. Chromatographic and electrophoretic methods are also mainly employed for the control and monitoring of ILs. These methods are also considered. ILs will soon be produced on an industrial scale and it will be necessary to develop reliable analytical procedures for their analysis and control.     

Bioanalytical separation and preconcentration using ionic liquids

Ionic liquids (ILs) are novel solvents that display a number of unique properties, such as negligible vapor pressure, thermal stability (even at high temperatures), favorable viscosity, and miscibility with water and organic solvents. These properties make them attractive alternatives to environmentally unfriendly solvents that produce volatile organic compounds. In this article, a critical review of state-of-the-art developments in the use of ILs for the separation and preconcentration of bioanalytes in biological samples is presented. Special attention is paid to the determination of various organic and inorganic analytes—including contaminants (e.g., pesticides, nicotine, opioids, gold, arsenic, lead, etc.) and functional biomolecules (e.g., testosterone, vitamin B₁₂, hemoglobin)—in urine, blood, saliva, hair, and nail samples. A brief introduction to modern microextraction techniques based on ILs, such as dispersive liquid–liquid microextraction (DLLME) and single-drop microextraction (SDME), is provided. A comparison of IL-based methods in terms of their limits of detection and environmental compatibilities is also made. Finally, critical issues and challenges that have arisen from the use of ILs in separation and preconcentration techniques are also discussed.

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。     

Recent Advances in Sample Preparation for Cosmetics and Personal Care Products Analysis

The use of cosmetics and personal care products is increasing worldwide. Their high matrix complexity, together with the wide range of products currently marketed under different forms imply a challenge for their analysis, most of them requiring a sample pre-treatment step before analysis. Classical sample preparation methodologies involve large amounts of organic solvents as well as multiple steps resulting in large time consumption. Therefore, in recent years, the trends have been moved towards the development of simple, sustainable, and environmentally friendly methodologies in two ways: (i) the miniaturization of conventional procedures allowing a reduction in the consumption of solvents and reagents; and (ii) the development and application of sorbent- and liquid-based microextraction technologies to obtain a high analyte enrichment, avoiding or significantly reducing the use of organic solvents. This review provides an overview of analytical methodology during the last ten years, placing special emphasis on sample preparation to analyse cosmetics and personal care products. The use of liquid–liquid and solid–liquid extraction (LLE, SLE), ultrasound-assisted extraction (UAE), solid-phase extraction (SPE), pressurized liquid extraction (PLE), matrix solid-phase extraction (MSPD), and liquid- and sorbent-based microextraction techniques will be reviewed. The most recent advances and future trends including the development of new materials and green solvents will be also addressed.     

Organic polymer‐based monolithic capillary columns and their applications in food analysis

In recent years, the use of organic polymer monolithic capillary columns in separation science has gained popularity due to the fact that they are easy to fabricate and do not require retaining frits. These materials have been applied in different fields including foods, proteomics, and pharmaceuticals. The interest in food analysis still needs to develop in order to increase the sensitivity towards micro/nano‐scale food applications for food samples of < 5 μg (e.g., foodomics). In this regard, polymer monolithic capillary columns offer great separation capability in the food analytical separation science. We review the most important applications in food analysis using polymer monolithic capillary columns. In addition, several examples of the use of capillary separation methods combined with mass spectrometry detection in food analysis are summarized.     

Green analytical chemistry approaches on environmental analysis

Green analytical chemistry is a comprehensive perspective that aims to reduce or eliminate the toxic and harmful solvents, reagents, and techniques in the preparation, pre-treatment, and determination steps of an analysis process. With the increase in environmental pollution in recent years, awareness has been increasing in terms of both the contamination analysis of environmental sources and the more environmentally friendly analysis methods. This review evaluates the solvents such as bio-based solvents and deep eutectic solvents, nanomaterials synthesized by non-toxic methods, the greener changes in the extraction methods, and chromatographic techniques considering the most recent studies. In particular, trying to make the methods used to analyze environmental samples safer and less toxic is an important point that overlaps with the green approach, which aims to minimize environmental pollution. In this context, this review provides information on green analytical chemistry-based environmental applications covering the last ten years so that the applications of this approach can be examined and understood in more detail and can be applied by other researchers.     

离子液体在分离领域的研究进展

室温离子液体,又称离子液体,是一种在室温及接近室温的环境中完全以离子状态存在的液态物质.由于其具有不可燃、蒸汽压极低、黏度大、导电性和溶解能力好、高温稳定等特点,已被广泛应用于有机合成、催化、电化学、分析化学等领域.本文侧重介绍离子液体在样品预处理、毛细管电泳、高效液相色谱、气相色谱、质谱等分离领域的最新研究进展,并对其发展方向进行了展望.