不同咪唑类离子液体对纤维素酶降解小麦秸秆的影响

分别合成四种离子液体:1-乙基-3-甲基咪唑磷酸二乙酯盐、1,3-二甲基咪唑磷酸二甲酯盐、氯化1-丁基-3-甲基咪唑以及1-丁基-3-甲基咪唑磺胺醋酰盐,考察其对纤维素酶降解小麦秸秆的影响。结果表明:小麦秸秆在1-乙基-3-甲基咪唑磷酸二乙酯盐中溶解度最高;随着温度的升高,小麦秸秆的溶解时间缩短,但再生得率有所下降;将再生的小麦秸秆用纤维素酶进行降解,使用1-乙基-3-甲基咪唑磷酸二乙酯盐预处理得到的再生小麦秸秆还原糖产率最高,为3.45%。     

咪唑类离子液体合成及其应用研究

介绍了咪唑类离子液体的一般性质和合成方法,及其作为一种新型的化学溶剂广泛应用于化学合成、分离过程和电化学等方面,具有良好的发展前景。     

咪唑类离子液体溶解纤维素的研究进展

综述了1-丁基-3-甲基咪唑氯盐、1-烯丙基-3-甲基咪唑氯盐、1-(2-羟乙基)-3-甲基咪唑氯盐等咪唑类离子液体对纤维素的溶解性能,咪唑类离子液体/纤维素溶液的流变性能以及咪唑类离子液体在纤维素纤维及薄膜加工中的应用;咪唑类离子液体均能较好地溶解纤维素,咪唑类离子液体/纤维素溶液均为切力变稀流体;指出选择合适的阴、...     

长链烷基咪唑类离子液体型表面活性剂的聚集行为

采用微波辐射法合成了咪唑类离子液体1-烷基-3-甲基咪唑氯盐[C_nMim]Cl (n=12,14,16),测定了[C_nMim]Cl的电导率及表面张力。结果表明,随着烷基链长度的增加,临界胶束浓度(CMC)与最小表面张力(γCMC)减小,[C_(16)Mim]Cl的表面活性最好。胶束化热力学参数(ΔG_(mic)⁰、ΔH_(mic)0、ΔH_(mic)⁰、ΔS_(mic)0、ΔS_(mic)⁰)表明,[C_(12)Mim]Cl的胶束化是熵驱动;而对于[C_(14)Mim]Cl与[C_(16)Mim]Cl的胶束化而言,25℃为焓驱动,超过35℃为熵驱动。     

咪唑类离子液体的合成与表征

通过两步法合成了阳离子含亲水性咪唑离子基和疏水烷基链结构、阴离子相同的1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)、1-丁基-3-甲基咪唑醋酸盐([Bmim]Ac)、1-己基-3-甲基咪唑醋酸盐([Hmim]Ac)3种离子液体。利用红外光谱对其进行结构表征,并探究温度对pH的影响;考察温度、离子液体质量浓度、有机溶剂对电导率的影响;测定临界胶束浓度和溶解性。结果表明,[Emim]Ac、[Bmim]Ac、[Hmim]Ac碱性递减,其在不同溶剂中的电导率随温度(28～60℃)的升高、离子液体质量浓度(6～20 g/L)的增加而增大,且受溶剂性质影响;临界胶束浓度分别为11.46、9.92 g/L和9.72 g/L;其溶解性随溶剂极性的增强、侧链烷基的伸长而增大。     

咪唑类离子液体高效吸收二氯甲烷

合成了一系列常规离子液体1-丁基-3-甲基咪唑四氟硼酸盐([Bmim][BF4])、1-丁基-3-甲基咪唑六氟磷酸盐([Bmim][PF6])、1-丁基-3-甲基咪唑双三氟甲磺酰亚胺盐([Bmim][NTf2])、1-丁基-3-甲基咪唑双氰胺盐([Bmim][DCA])、1-丁基-3-甲基咪唑硫氰酸盐([Bmim][SCN])、1-乙基-3-甲基咪唑硫氰酸盐([Emim][SCN])和N-丁基吡啶硫氰酸盐([BPy][SCN]),用智能重量分析仪(IGA)测定不同温度和分压下离子液体吸收二氯甲烷(DCM)的容量。结果表明,[Bmim][SCN]具有最高的二氯甲烷吸收容量(1.46 g/g, 303.15 K, 60 kPa),5次循环后吸收能力无明显下降,[Bmim][SCN]基本可完全再生,能循环使用。量化计算结果表明[SCN]?可与二氯甲烷形成氢键,增强其对二氯甲烷的吸收能力。     

绿色催化剂咪唑类离子液体在甲基化反应中的研究

本文以碳酸二甲酯（DMC）为甲基化试剂,以四种咪唑类离子液体作为催化剂,进行6,7-二羟基香豆素甲基化得到目标产物6,7-二甲氧基香豆素的研究,研究表明用咪唑类离子液体作催化剂,不但选择性高,可以很好地提高反应收率,而且还可以在较低温度下进行反应,能够重复利用。通过实验分析四种咪唑类离子液体中[BMIm]Cl的催化效果最好。     

咪唑类离子液体合成及其应用研究

离子液体（ionic liquid）作为一种新型的有机溶剂，自从20世纪40年代以来，由于其特殊的性质被化学家重视，取得了长足的发展。现在离子液体已经被广泛应用到化学合成、化学分离和电化学等方面，并且得到了很好的结果。离子液体为化学提供了一个崭新的反应环境，具有良好的发展前景。本文介绍了离子液体的一般性质、制备方法与应用方面的内容。     

咪唑类室温离子液体中有序聚集体的组装及应用

综述了近五年来国内外有关咪唑类室温离子液体作溶剂组装有序聚集体(如胶束、溶致液晶、微乳液等)的研究新进展,对比分析了离子型、非离子型和聚合物表面活性剂在离子液体和传统水溶液中组装聚集体的形态、结构、尺寸及机理方面的异同。同时,简要介绍了新型聚集体特别是离子液体微乳液的应用,并展望了这一研究的发展趋势。     

咪唑类[PF_6]^-型离子液体萃取苯胺

研究了以咪唑类[PF6]-型室温离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[Bmim][PF6]）、1-己基-3-甲基咪唑六氟磷酸盐（[Hmim][PF6]）和1-辛基-3-甲基咪唑六氟磷酸盐（[Omim][PF6]）对苯胺水溶液的萃取平衡。实验结果表明：pH值对分配系数的影响很大,在碱性条件下,分配系数较高;萃取过程属于吸热过程;经过四级错流萃取,废水可达到排放标准,萃取相中的苯胺回收率在90%左右,离子液体回收率〉90%,离子液体可以循环利用。     

Thermodynamic Modeling of Imidazolium-Based Ionic Liquids with the [PF6]− Anion for Separation Purposes

There is an increased interest in developing accurate tools to relate the physicochemical properties of ionic liquids (ILs) to their microscopic structure as this information is needed to speed up the design of new ionic liquids for chemical and industrial processes. Molecular models can be used for this purpose. We explore here the extended capabilities of a model previously developed in the context of soft-SAFT, by Andreu and Vega in 2007 to reproduce the thermodynamic behavior of imidazolium hexafluorophosphate-based ([C_nmim][PF₆]) ionic liquids. The molecular parameters optimized in the previous work have been used here in a transferable manner; some new members of the [C_nmim][PF₆] family have also been added, as new recent experimental data has been published. The interfacial tensions have been calculated using a Density Gradient Approach and the results have been compared with available experimental data. The solubility of carbon monoxide and hydrogen in those ILs has been studied in the range of temperatures and pressures of application for separation processes. Binary mixtures with other imidazolium ionic liquids with different anions have been calculated, in a predictive manner. Finally, calculations of mixtures of ionic liquids with water also show very good agreement with experimental data. This work highlights the importance of using a simple but robust thermodynamic model, including the right level of interactions, to accurately describe the properties of these highly non-ideal systems.     

Study on Dissolution and Regeneration of Poplar Wood in Imidazolium-Based Ionic Liquids

Abstract

We tested dissolution and regeneration of poplar wood using 1-butyl-3-methylimidazolium chloride ([C₄mim]Cl) and 1-butyl-3-methylimidazolium acetate ([C₄mim]OAc). When 5wt% of poplar sawdust in [C₄mim]OAc was stirred at 130°C, 96wt% of added poplar was dissolved in [C₄mim]OAc, whereas 25.3wt% of poplar dissolved in [C₄mim]Cl at the same reaction condition. Fourier transform infrared spectroscopy (FT-IR) and lignin content analysis revealed that poplar was partially delignified during the dissolution and regeneration processes. X-ray diffraction (XRD), thermal gravimetric analysis (TGA), and microscopy were used to characterize raw poplar sawdust, undissolved poplar, and regenerated wood from the poplar-ionic liquid solution. The direct acetylation of poplar-[C₄mim]OAc solution using acetyl chloride was also performed in the absence of any organic solvent. FT-IR analysis of the resulting wood sample revealed the formation of partially delignified acetylated-poplar.     

Synthesis and Aggregation Behavior of Trisiloxane Ionic Liquids in Aqueous Solution

Trisiloxane ionic liquids with polyether groups (Si₃pyCl-EO₃) were synthesized via thiol-ene reaction between 1-methyl-1-[bis(vinyldimethylsiloxy)methyl]silylpropylpyrrolidinium chloride (Vi-Si₃pyCl) and tri(ethylene glycol) methyl ether thiol. The aggregation behavior of the trisiloxane ionic liquids, Si₃pyCl-EO₃ and Vi-Si₃pyCl, in aqueous solution was investigated using surface tension, electrical conductivity, dynamic light scattering, and transmission electron microscopy. The structures of trisiloxane ionic liquids can obviously influence their aggregation behavior. Vi-Si₃pyCl has excellent surface activity (22.3 mN m⁻¹). However, Si₃pyCl-EO₃ can only reduce the surface tension of water to 33.5 mN m⁻¹. In comparison with Vi-Si₃PyCl, Si₃PyCl-EO₃ has a bulkier hydrophobic group and a higher Α_min value (127.8 Ų) caused by the introduction of the tri(ethylene glycol) methyl ether groups by thiol-ene reaction. The micellization of Vi-Si₃PyCl is entropy driven, while the aggregation process of Si₃PyCl-EO₃ in aqueous solution is enthalpy driven.     

Exploring the Absorption Mechanisms of Imidazolium-Based Ionic Liquids to Epigallocatechin Gallate

Imidazolium-based ionic liquids are wildly used in natural product adsorption and purification. In this work, one typical polymeric ionic liquid (PIL) was synthesized by using L-proline as the anion, which exhibited excellent adsorption capacity toward tea polyphenol epigallocatechin gallate (EGCG). The adsorption conditions were optimized with the response surface method (RSM). Under the optimum conditions, the adsorption capacity of the PIL for EGCG can reach as high as 552 mg/g. Dynamics and isothermal research shows that the adsorption process of EGCG by the PIL particularly meets the quasi-second-order kinetic equation and monolayer adsorption mechanism. According to thermodynamic parameter analysis, the adsorption process is endothermic and spontaneous. The results of theoretical calculation by molecular docking also demonstrated the interaction mechanisms between EGCG and the ionic liquid. Considering the wide application of imidazolium-based ionic liquids in component adsorption and purification, the present study can not only be extended to other similar experimental mechanism validation, but also be representative for guiding the synthesis of PIL and optimization of adsorption conditions.     

Modeling of CO2 Solubility in Selected Imidazolium-Based Ionic Liquids

This study explores the use of COSMO-RS model and Peng-Robinson (PR) equation of state (EoS) to predict the solubility of carbon dioxide (CO₂) in specific ionic liquids (ILs). COSMO-RS was employed to estimate of CO₂ solubility at atmospheric pressure in eight imidazolium-based ILs resulting from the combination of ethyl, butyl, hexyl, and octyl-imidazolium cations with two anions: bis(trifluoromethylsulfonyl)imide ([Tf₂N]) and Trifluoromethanesulfonate ([TFO]). The results indicated relatively acceptable qualitative consistency between the experimental and predicted values. The PR EoS was employed at high pressure by tuning the interaction parameters to fit the experimental data reported in the literature. The model demonstrated excellent accuracy in predicting the solubility of CO₂ at pressure values less than the critical pressure of CO₂; however, at higher pressures, the calculated solubility diverged from the experimental values. Furthermore, the type of anion and cation used in the IL affected the performance of the PR EoS.     

Aggregation Behavior of Imidazolium-Based Amino Acid Ionic Liquid Surfactants in Aqueous Solution: The Effect of Amino Acid Counterions

Three kinds of imidazolium-based amino acid ionic liquid surfactants (AAILS), 1-tetradecyl-3-methylimidazolium _L-aminopropionic acid salt ([C₁₄mim][Ala]), 1-tetradecyl-3-methylimidazolium _L-2-pyrrolidinecarboxylic acid salt ([C₁₄mim][Pro]), and 1-tetradecyl-3-methylimidazolium _L-aminohydrocinnamic acid salt ([C₁₄mim][Phe]), were synthesized by employing natural amino acids as counterions. Their adsorption and self-aggregation behaviors in aqueous solution were investigated systematically by means of surface tension and electrical conductivity measurements. Surface tension results indicate that surface properties and micellization behavior of AAILS are significantly affected by counterions. The micellization of [C₁₄mim][Pro] and [C₁₄mim][Phe] is entropy-driven at low temperatures but enthalpy-driven at high temperatures, whereas [C₁₄mim][Ala] is enthalpy-driven throughout the whole temperature range, owing to the variation in hydrophobicity and size of amino acid counterions. The surface activity of [C₁₄mim][Phe] is superior to that of conventional imidazolium-based ionic liquid surfactants with the same hydrocarbon chain length, 1-tetradecyl-3-methylimidazolium bromide (C₁₄mimBr), indicating that the aromatic counterion can promote the micellar formation process.     

Evaluation of Anion Effect on the Solubility of Hydrogen Sulfide in Ionic Liquids Using Molecular Dynamics Simulation

Theoretical Foundations of Chemical Engineering - In this study the solubility of Hydrogen Sulfide (H2S) in four ionic liquids: 1-Ethyl-3-methylimidazoliom Hexafluorophosphate [Emim][PF6],...     

Aggregation Behavior of Mixed Micellar System of Dodecyl Sulfate-Based Surface-Active Ionic Liquids and Anionic Surfactant in Aqueous Media

Mixed micellization behavior of dodecyl sulfate-based ionic liquids, i.e., 1-propyl-3-methylimidazolium dodecyl sulfate [C₃mim][DS] and 1-hexyl-3-methylimidazolium dodecyl sulfate [C₆mim][DS] with sodium dodecyl sulfate (SDS), is investigated at (298.15, 308.15, and 318.15) K in aqueous medium. For this, the conductometric measurements are carried out to evaluate the critical micelle concentrations (cmc ), ideal critical micelle concentration (cmc* ), degree of counterion dissociation (g ), thermodynamic parameters, micellar mole fraction of ionic liquids, and interaction parameter (β) of the mixed system based on the different proposed models given in the literature. Further surface tension measurements have been carried out to confirm the value of cmc obtained via a conductivity study for all the studied systems at 298.15 K. Other surface parameters, such as surface tension at cmc (γ_cmc ), surface pressure (ᴨ_cmc ), surface excess (Γ_max ), and minimum area per molecule (A_min), have also been evaluated for both the systems.     

Effect of 1-Ethyl-3-methylimidazolium Tetrafluoroborate and Acetate Ionic Liquids on Stability and Amyloid Aggregation of Lysozyme

Amyloid fibrils draw attention as potential novel biomaterials due to their high stability, strength, elasticity or resistance against degradation. Therefore, the controlled and fast fibrillization process is of great interest, which raises the demand for effective tools capable of regulating amyloid fibrillization. Ionic liquids (ILs) were identified as effective modulators of amyloid aggregation. The present work is focused on the study of the effect of 1-ethyl-3-methyl imidazolium-based ILs with kosmotropic anion acetate (EMIM-ac) and chaotropic cation tetrafluoroborate (EMIM-BF₄) on the kinetics of lysozyme amyloid aggregation and morphology of formed fibrils using fluorescence and CD spectroscopy, differential scanning calorimetry, AFM with statistical image analysis and docking calculations. We have found that both ILs decrease the thermal stability of lysozyme and significantly accelerate amyloid fibrillization in a dose-dependent manner at concentrations of 0.5%, 1% and 5% (v/v) in conditions and time-frames when no fibrils are formed in ILs-free solvent. The effect of EMIM-BF₄ is more prominent than EMIM-ac due to the different specific interactions of the anionic part with the protein surface. Although both ILs induced formation of amyloid fibrils with typical needle-like morphology, a higher variability of fibril morphology consisting of a different number of intertwining protofilaments was identified for EMIM-BF_4.     

First Studies on the Rheological Behavior of Suspensions in Ionic Liquids

The suspension rheology of hematite in the ionic liquid Ecoeng^TM.212 was studied in detail and compared to the pure ionic liquid. This is the first report on the rheological behavior of suspensions in ionic liquids, and it is postulated that colloidal stability and rheology must be considered to understand these results, and to overcome limitations on the production of nanosized particles in industrial applications. Concentrated suspensions of particles in the nanometer range show non‐Newtonian flow behavior including shear thinning and shear thickening. These phenomena are mainly caused by particle‐particle interactions in the suspension, and control of these interactions is critical. The influences of temperature and solid concentration on flow behavior were shown for the pure liquid and the suspensions. It is seen that the ionic liquid follows the Arrhenius equation for non‐associating electrolytes. It is possible to shift all hematite suspension curves to a master curve according to the model of Gleißle and Baloch. Furthermore, the flow behavior of the suspensions can be modeled with the well‐known Herschel‐Bulkley plot. A 10 wt % suspension of Fe₂O₃ follows Newtonian behavior over the entire range, similar to the pure ionic liquid. It is believed that the ionic liquid has an influence on the stability of the particles, leading to a decrease of attractive particle‐particle forces.