On the critical temperature, normal boiling point, and vapor pressure of ionic liquids

One-stage, reduced-pressure distillations at moderate temperature of 1-decyl- and 1-dodecyl-3-methylimidazolium bistriflilamide ([Ntf(2)](-)) ionic liquids (ILs) have been performed. These liquid-vapor equilibria can be understood in light of predictions for normal boiling points of ILs. The predictions are based on experimental surface tension and density data, which are used to estimate the critical points of several ILs and their corresponding normal boiling temperatures. In contrast to the situation found for relatively unstable ILs at high-temperature such as those containing [BF(4)](-) or [PF(6)](-) anions, [Ntf(2)](-)-based ILs constitute a promising class in which reliable, accurate vapor pressure measurements can in principle be performed. This property is paramount for assisting in the development and testing of accurate molecular models.     

离子液体在乙烯/乙烷和乙烯/乙炔分离中的应用

乙烯,作为石油化工行业的龙头原料,其高效回收分离具有重要的战略意义。离子液体作为一种结构可调控的新型绿色溶剂,在乙烯的回收分离中展现出巨大的应用前景。本文总结了近年来离子液体在乙烯/乙烷和乙烯/乙炔分离方面的研究进展,从溶剂吸收、膜吸收和与多孔材料相结合的吸附分离法等角度展开,系统地阐述了常规离子液体、功能化离子液体、聚离子液体等纯组分体系及多组分体系在不同分离方法中的研究现状,展望了离子液体在乙烯回收分离方面的应用前景和发展趋势。     

Optimization of Ultrasonic-Assisted Extraction of Active Components and Antioxidant Activity from Polygala tenuifolia: A Comparative Study of the Response Surface Methodology and Least Squares Support Vector Machine

Dried roots of Polygala tenuifolia (YuanZhi in Chinese) are widely used in Chinese herbal medicine. These components in YuanZhi have significant anti-oxidation properties owing to high levels of 3,6’-disinapoylsucrose (DISS) and Polygalaxanthone III (PolyIII). In order to efficiently extract natural medicines, response surface methodology (RSM) and least squares support vector machine (LSSVM) were used for the modeling and optimization of ultrasound-assisted extraction of DISS and PolyIII together to determine the antioxidant activity of the extracts obtained from YuanZhi. For the optimal combination of the comprehensive yield of DISS and PolyIII (Y), the Box-Behnken design (BBD) was used to improve extraction time (X₁), extraction temperature (X₂), liquid–solid ratio (X₃), and ethanol concentration (X₄). The optimal process parameters were determined to be as follows: extraction time, 93 min; liquid–solid ratio, 40 mL/g; extraction temperature, 48 °C; and ethanol concentration, 67%. With these conditions, the predictive optimal combination comprehensive evaluation value is 13.0217. It was clear that the LS-SVM model had higher accuracy in predictive and optimization capabilities, with higher antioxidant activity and lower relative deviations values, than did RSM. Hence, the LS-SVM model proved to be more effective for the analysis and improvement of the extraction process.     

Experimental densities,dynamic viscosities and surface tensions of the ionic liquids series 1-ethyl-3-methylimidazolium acetate and dicyanamide and their binary and ternary mixtures with water and ethanol at T = (298.15 to 343.15 K)

In this paper, experimental densities and dynamic viscosities of 1-ethyl-3-methylimidazolium based ionic liquids (ILs) with the anions acetate and dicyanamide are presented in a wide temperature range (298.15 to 343.15 K) at atmospheric pressure. Surface tension of these ILs was measured at T = 298.15 K. The effect of water and/or ethanol compositions on densities and dynamic viscosities of these ILs are studied in binary and ternary mixtures. A quadratic mixing rule was used to correlate binary and ternary liquid densities. The Eyring–Patel–Teja model, which is recommended for polar and aqueous systems, is used to correlate dynamic viscosity data over the whole range of compositions and temperatures in binary and ternary mixtures. Temperature-dependent interaction parameters are introduced here to account for the changes of viscosities with temperature showing good agreements with experimental data.     

HS–SPME–GC–MS and Electronic Nose Reveal Differences in the Volatile Profiles of Hedychium Flowers

Floral fragrance is one of the most important characteristics of ornamental plants and plays a pivotal role in plant lifespan such as pollinator attraction, pest repelling, and protection against abiotic and biotic stresses. However, the precise determination of floral fragrance is limited. In the present study, the floral volatile compounds of six Hedychium accessions exhibiting from faint to highly fragrant were comparatively analyzed via gas chromatography–mass spectrometry (GC–MS) and Electronic nose (E-nose). A total of 42 volatile compounds were identified through GC–MS analysis, including monoterpenoids (18 compounds), sesquiterpenoids (12), benzenoids/phenylpropanoids (8), fatty acid derivatives (2), and others (2). In Hedychium coronarium ‘ZS’, H. forrestii ‘Gaoling’, H. ‘Jin’, H. ‘Caixia’, and H. ‘Zhaoxia’, monoterpenoids were abundant, while sesquiterpenoids were found in large quantities in H. coccineum ‘KMH’. Hierarchical clustering analysis (HCA) divided the 42 volatile compounds into four different groups (I, II, III, IV), and Spearman correlation analysis showed these compounds to have different degrees of correlation. The E-nose was able to group the different accessions in the principal component analysis (PCA) corresponding to scent intensity. Furthermore, the pattern-recognition findings confirmed that the E-nose data validated the GC–MS results. The partial least squares (PLS) analysis between floral volatile compounds and sensors suggested that specific sensors were highly sensitive to terpenoids. In short, the E-nose is proficient in discriminating Hedychium accessions of different volatile profiles in both quantitative and qualitative aspects, offering an accurate and rapid reference technique for future applications.     

Synthesis and Thermophysical Properties of Ether‐Functionalized Sulfonium Ionic Liquids as Potential Electrolytes for Electrochemical Applications

During this work, a novel series of hydrophobic room temperature ionic liquids (ILs) based on five ether functionalized sulfonium cations bearing the bis{(trifluoromethyl)sulfonyl}imide, [NTf₂]^? anion were synthesized and characterized. Their physicochemical properties, such as density, viscosity and ionic conductivity, electrochemical window, along with thermal properties including phase transition behavior and decomposition temperature, have been measured. All of these ILs showed large liquid range temperature, low viscosity, and good conductivity. Additionally, by combining DFT calculations along with electrochemical characterization it appears that these novel ILs show good electrochemical stability windows, suitable for the potential application as electrolyte materials in electrochemical energy storage devices.     

Tetrahaloindate(III)-based ionic liquids in the coupling reaction of carbon dioxide and epoxides to generate cyclic carbonates: H-bonding and mechanistic studies

The microwave reactions of InX3 with [Q]Y produce a series of tetrahaloindate(III)-based ionic liquids (ILs) with a general formula of [Q][InX3Y] (Q = imidazolium, phosphonium, ammonium, and pyridinium; X = Cl, Br, I; Y = Cl, Br). The reaction of CO2 with a variety of epoxides has been examined in the presence of these ILs wherein tetrahaloindate(III)-based ILs are found to exhibit high catalytic activities and evidence is presented that supports the significant role of H-bonding interactions in the [Q][InX3Y]-catalyzed coupling reactions. The effects of various parameters such as temperature, pressure, and molar ratio of propylene oxide to catalyst have been investigated, and the plausible reaction mechanism based on the 1H and 13C NMR studies is presented for the formation of propylene carbonate.     

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.

Hybrid Bis-Histidine Phenanthroline-Based Ligands to Lessen Aβ-Bound Cu ROS Production: An Illustration of Cu(I) Significance

We here report the synthesis of three new hybrid ligands built around the phenanthroline scaffold and encompassing two histidine-like moieties: phenHH, phenHGH and H’phenH’, where H correspond to histidine and H’ to histamine. These ligands were designed to capture Cu(I/II) from the amyloid-β peptide and to prevent the formation of reactive oxygen species produced by amyloid-β bound copper in presence of physiological reductant (e.g., ascorbate) and dioxygen. The amyloid-β peptide is a well-known key player in Alzheimer’s disease, a debilitating and devasting neurological disorder the mankind has to fight against. The Cu-Aβ complex does participate in the oxidative stress observed in the disease, due to the redox ability of the Cu(I/II) ions. The complete characterization of the copper complexes made with phenHH, phenHGH and H’phenH’ is reported, along with the ability of ligands to remove Cu from Aβ, and to prevent the formation of reactive oxygen species catalyzed by Cu and Cu-Aβ, including in presence of zinc, the second metal ions important in the etiology of Alzheimer’s disease. The importance of the reduced state of copper, Cu(I), in the prevention and arrest of ROS is mechanistically described with the help of cyclic voltammetry experiments.     

Prediction of Density,Surface Tension,and Viscosity of Quaternary Ammonium-Based Ionic Liquids ([N222(n)]Tf2N) by Means of Artificial Intelligence Techniques

In this work, thermophysical properties of quaternary ammonium-based ionic liquids (ILs) including density, surface tension, and viscosity are produced by two powerful artificial intelligence techniques: genetic function approximation (GFA) and artificial neural network (ANN). In proposed GFA and ANN models, the critical temperature and water content of studied ILs ([N_222(n)]Tf₂N with n = 5, 6, 8, 10, and 12) as well as operation temperature were given as the input parameters and the density, surface tension, and viscosity were predicted as the output results. The obtained results reveal that the selected input parameters are appropriate for prediction of thermophysical properties of quaternary ammonium-based ILs. In addition, the high statistical quality represented by various criteria and the low prediction errors of the presented models indicate that they can accurately predict the density, surface tension, and viscosity of new ILs without recourse to experimental data.     

Effect of temperature on the physical properties of two ionic liquids

Density, speed of sound, refractive index, and dynamic viscosity of the ionic liquids (ILs) 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, BMpyr NTf₂, and trihexyl(tetradecyl) phosphonium dicyanamide, P₆₆₆₁₄ dca, were studied as a function of temperature at atmospheric pressure. Thermal expansion coefficient, α_p, molecular volumes, and standard entropies of these ILs were calculated from the experimental density values. The solubility of three aromatic components (benzene, toluene, and ethylbenzene) in the selected ILs was carried out at T = 298.15 K and atmospheric pressure and compared with literature values for sulfolane.     

The molecular characteristics dominating the solubility of gases in ionic liquids

This critical review provides a critical discussion of the current state of knowledge of the key factors influencing the solubility of gases in ionic liquids (ILs), including sample purity, experimental methodology, "molecular" characteristics of ILs, temperature and pressure. The review starts with a brief introduction to the current developments and the existing problems in the studies of the gas solubility in ILs. Then, the experimental, computational and theoretical developments in conformational equilibria of ions, in nanosegregated polar and nonpolar domains in ILs, and in the mechanisms for dissolution of gases in ILs are discussed and subsequently collaborated together with our freeze-fracture transmission electron microscopic and Raman measurements to propose the new microscopic mechanism for dissolving the gases in ILs. Next, a critical and quantitative analysis of the influences of the sample purity and the experimental methodology on the gas solubility is made so that the "real" relationships between structure and solubility property can be revealed. In addition, a systematic and deeper understanding of how the "molecular" features of the ILs, the temperature, and the pressure influence the gas solubility is provided at the molecular level. In the section of concluding remarks, the comments are made on the molecular criteria for the future design of the ILs to enhance the gas solubility by specifically optimizing the molecular characteristics of the ILs (265 references).     

The Removal of Time–Concentration Data Points from Progress Curves Improves the Determination of Km: The Example of Paraoxonase 1

Several approaches for determining an enzyme’s kinetic parameter K_m (Michaelis constant) from progress curves have been developed in recent decades. In the present article, we compare different approaches on a set of experimental measurements of lactonase activity of paraoxonase 1 (PON1): (1) a differential-equation-based Michaelis–Menten (MM) reaction model in the program Dynafit; (2) an integrated MM rate equation, based on an approximation of the Lambert W function, in the program GraphPad Prism; (3) various techniques based on initial rates; and (4) the novel program “iFIT”, based on a method that removes data points outside the area of maximum curvature from the progress curve, before analysis with the integrated MM rate equation. We concluded that the integrated MM rate equation alone does not determine kinetic parameters precisely enough; however, when coupled with a method that removes data points (e.g., iFIT), it is highly precise. The results of iFIT are comparable to the results of Dynafit and outperform those of the approach with initial rates or with fitting the entire progress curve in GraphPad Prism; however, iFIT is simpler to use and does not require inputting a reaction mechanism. Removing unnecessary points from progress curves and focusing on the area around the maximum curvature is highly advised for all researchers determining K_m values from progress curves.     

基于离子交换跃迁模型和实验法对离子液体Walden乘积的研究

提出了关于离子液体的新理论——离子交换跃迁模型,通过理论推导得出1：1型离子液体的Walden乘积仅取决于离子对和离子簇直径的统计平均值,即离子液体的阴阳离子结构不同,Walden乘积不同。为了验证模型的正确性,本文合成8种N-烷基-吡啶二氰胺类和N-烷基-咪唑丝氨酸类离子液体,利用上述离子液体的电导率和动力粘度的实验值及文献数据,计算了33种离子液体的Walden乘积。通过比较发现,不同离子液体的Walden乘积不同,即对于离子液体来说,Walden乘积是它的特征物理量。     

基于离子液的超声辅助萃取小蓼叶中的精油及真实溶剂似导体屏蔽模型研究（英文）

Ionic liquids (ILs) based ultrasonic-assisted extract has been applied for the extraction of essential oil from Persicaria minor leaves. The effects of temperature, sonication time, and particle size of the plant material on the yield of essential oil were investigated. Among the different ILs employed, 1-ethyl-3-methylimidazolium acetate was the most effective, providing a 9.55% yield of the essential oil under optimum conditions (70 ℃, 25 min, IL:hexane ratio of 7:10 (v/v), particle size 60-80 mesh). The performance of 1-ethyl-3-methylimidazolium acetate in the extraction was attributed to its low viscosity and ability to disintegrate the structural matrix of the plant material. The ability of 1-ethyl-3-methylimidazolium acetate was also confirmed using the conductor like-screening model for realistic solvents. This research proves that ILs can be used to extract essential oils from lignocellulosic biomass.     

Viscosity of n-alkyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)amide ionic liquids saturated with compressed CO2

The viscosity of imidazolium-based ionic liquids (ILs) saturated with gaseous, liquid and supercritical carbon dioxide (CO₂) was measured by a high-pressure viscometer at three different temperatures (25, 50, and 70 °C). The high-pressure viscosity of 1-ethyl-3-methylimidazolium ([EMIm]), 1-n-hexyl-3-methylimidazolium ([HMIm]), and 1-n-decyl-3-methylimidazolium ([DMIm]) cations with a common anion, bis(trifluoromethylsulfonyl)amide ([Tf₂N]), saturated with CO₂ was measured up to a maximum of 287 bar. As CO₂ pressure is increased the viscosity of the IL mixture dramatically decreases. While, the ambient pressure viscosity of 1-alkyl-3-methyl-imidazolium [Tf₂N] ILs increases significantly with increasing chain length, the viscosity of all the CO₂-saturated ILs becomes very similar at high CO₂ pressures. From previous vapor–liquid equilibrium data, the viscosity with concentration was determined and found to be the primary factor to describe the fractional viscosity reduction. Several predictive and correlative methods were investigated for the mixture viscosity given pure component properties and include arithmetic mixing rules, the Irving (Predictive Arrhenius) model, Grunberg equation, etc. The modified Grunberg model with one adjustable parameter provided an adequate fit to the data.     

Effect of Cation Structure in Quinolinium-Based Ionic Liquids on the Solubility in Aromatic Sulfur Compounds or Heptane: Thermodynamic Study on Phase Diagrams

Experimental and theoretical studies on thermodynamic properties of quinolinium-based ionic liquids (ILs) based on bis(trifluoromethylsulfonyl)imide anion (namely N-butyl-quinoloinium bis(trifluoromethylsulfonyl)imide, [BQuin][NTf₂], N-hexylquinoloinium bis(trifluoromethyl-sulfonyl)imide, [HQuin][NTf₂], and N-octylquinoloinium bis(trifluoromethyl-sulfonyl)imide, [OQuin][NTf₂]) with aromatic sulfur compounds and heptane, as a model compound of fuel were examined in order to assess the applicability of the studied ionic liquids for desulfurization of fuels. With this aim, the temperature-composition phase diagrams of 13 binary mixtures composed of organic sulfur compounds (thiophene, benzothiophene, or 2-methylthiophene) or heptane and ionic liquid (IL) were investigated at ambient pressure. A dynamic method was used to determine the (solid–liquid) equilibrium phase diagrams in binary systems over a wide composition range and temperature range from T = 255.15 to 365.15 K up to the fusion temperature of ILs. The immiscibility gap with an upper critical solution temperature (UCST) was observed for each binary system under study. The influence of the alkane chain length of the substituent on the IL cation and of the sulfur compounds (the aromaticity of the solvent) was described. The experimental (solid + liquid) phase equilibrium dataset were successfully correlated using the well-known NRTL equation.     

Experimental Research on NO2 Viscosity and Absorption for (1-Ethyl-3-methylimidazolium Trifluoroacetate + Triethanolamine) Binary Mixtures

The viscosity (9.34–405.92 mPa·s) and absorption capacity (0.4394–1.0562 g·g⁻¹) of (1-ethyl-3-methylidazolium trifluoroacetate + triethanolamine) binary blends atmospheric pressure in the temperature range of 303.15–343.15 K and at different mole fractions of [EMIM] [TFA] have been carried out. The molar fraction of [EMIM] [TFA] dependence of the viscosity and absorption capacity was demonstrated. The addition of a small amount of [EMIM] [TFA] into TEA led to rapidly decreased rates of binary blends’ viscosity and absorption capacity. However, the viscosity and absorption of binary blends did not decrease significantly when [EMIM] [TFA] was increased to a specific value. Compared with the molar fraction of the solution, the temperature had no obvious effect on viscosity and absorption capacity. By modeling and optimizing the ratio of viscosity and absorption capacity of ([EMIM] [TFA] + TEA), it is proven that when the mole fraction of [EMIM] [TFA] is 0.58, ([EMIM] [TFA] + TEA) has the best viscosity and absorption capacity at the same time. In addition, at 303.15 K, ([EMIM] [TFA] + TEA) was absorbed and desorbed six times, the absorption slightly decreased, and the desorption increased.     

Recent Advances in Crystalline Oxidopolyborate Complexes of d-Block or p-Block Metals: Structural Aspects,Syntheses, and Physical Properties

Crystalline materials containing hybrid inorganic–organic metal borates (complexes with oxidoborate ligands) display a variety of novel framework building blocks. The structural aspects of these hybrid metallaoxidoborates containing Cd^(II), Co^(II), Cu^(II), Ga^(III), In^(III), Mn^(II), Ni^(II) or Zn^(II) metal centers are discussed in this review. The review describes synthetic approaches to these hybrid materials, their physical properties, their spectroscopic properties and their potential applications.