Temperature-Dependent Surface-Enrichment Effects of Imidazolium-Based Ionic Liquids

We present the first systematic study of the influence of temperature on the degree of surface enrichment of 1-alkyl-3-methylimidazolium-based ionic liquids (ILs). Using angle-resolved X-ray photoelectron spectroscopy, we demonstrate that the degree of surface enrichment strongly decreases with increasing temperature for all the studied ILs. For ILs with the same cation, but different anions, [C₈C₁Im]Br, [C₈C₁Im][TfO] and [C₈C₁Im][Tf₂N], no significant differences of the temperature-induced partial loss of surface enrichment are found. Measurements for [C₄C₁Im][TfO], [C₈C₁Im][TfO] and [C₁₈C₁Im][TfO] indicate a small effect of the chain length. For [C₁₈C₁Im][TfO], a continuous decrease of alkyl surface enrichment is found with increasing temperature, with no abrupt changes at the phase-transition temperature from the smectic A to the isotropic phase, indicating that the surface enrichment is not affected by this phase transition.     

Antimicrobial and Cytotoxic Activity of Novel Imidazolium-Based Ionic Liquids

In this study, a series of 10 novel 1-methyl-3-octyloxymethylimidazolium derivatives carrying various anionic moieties (4-hydroxybenzenesulfonate, benzenesulfonate, carvacroloxyacetate, chloride, formate, propionate, thymoloxyacetate, vanillinoxyacetate, eugenoloxyacetate and trimethylacetate) were synthesized. Compounds were tested for their antimicrobial activity against six microbe strains (Staph-ylococcus aureus, Pseudomonas aeruginosa, Klebsiella pneumoniae, Escherichia coli, Enterococcus faecalis, and Candida albicans), cytotoxic activity against the mouse melanoma cell line (B16 F10), and surface active properties. All synthesized compounds exhibited antimicrobial activity (expressed as minimum inhibitory concentration; in range of 0.10–27.82 mM/L), especially against Gram-positive bacteria and fungi. In addition, all compounds demonstrated cytotoxicity on B16 F10 cells (IC50 values 0.0101–0.0197 mM/L). Surface properties defined as CMC values, ranged from 0.72 to 32.35 mmol L-1. The obtained results provide an insight into the promising activity of a novel group of quaternary imidazolium derivatives having ionic liquid properties. The most potent compounds, containing a thymoloxyacetate and eugenoloxyacetate moiety, could be candidates for new antimicrobial agents or surfactants.     

Structure Effect of Imidazolium-Based Dicationic Ionic Liquids on Claisen Rearrangement

A large group of imidazolium-based dicationic ionic liquids (DILs) has been prepared in good yields. Thermal stability of all DILs has been determined. The effects of the reaction time, cation, imidazolium C₂–H acidity, and anion on the Claisen rearrangement of allyl phenyl ether have been investigated. Type of anion and the presence of the acidic C₂–H bond in the imidazolium moieties have proven to be essential for this reaction. The simple procedure and the possibility of avoiding the use catalysts and volatile organic solvents make this synthetic method environmentally benign and adaptable for large-scale applications.     

咪唑基离子液体的物理化学性质估算及预测(英文)

根据经验和半经验方程及空隙模型理论,可以估算及预测离子液体在298.15K的物理化学性质.本文讨论了离子液体的分子体积,密度,标准熵,晶格能,表面张力,等张比容,摩尔蒸发焓,空隙体积,空隙率和热膨胀系数.通过实验测得的三种离子液体1-乙基-3-甲基咪唑硫酸乙酯([C2mim][EtSO4)]),1-丁基-3-甲基咪唑硫酸辛酯([C4mim][OcSO4])和1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐([C2mim][NTf2])的密度和表面张力估算了它们的其它物理化学性质.由这三种离子液体的分子体积及等张比容预测了同系列中其它离子液体[Cnmim][EtSO4],[Cnmim][OcSO4]和[Cnmim][NTf2](n=1-6)的分子体积及等张比容,由此计算出它们的密度及表面张力.进而预测了它们的物理化学性质.将预测的离子液体[C4mim][NTf2]和[C2mim][OcSO4]的密度值与文献报导的实验值进行比较,其偏差在实验误差范围内.最后,将由Kabo经验方程计算的七个离子液体[C2mim][EtSO4]、[C4mim][OcSO4]、[C2mim][NTf2]、[C4mim][NTf2]、丁基三甲基铵双三氟甲磺酰亚胺盐([N4111][NTf2])、甲基三辛基铵双三氟甲磺酰亚胺盐([N8881][NTf2])和1-辛基-3-甲基吡啶四氟硼酸盐([m3opy][BF4])的摩尔蒸发焓与由Verevkin简单规则预测的摩尔蒸发焓进行比较,发现两者符合很好.因此,在缺乏密度和表面张力实验数据的情况下,可以用Verevkin简单规则来预测离子液体的摩尔蒸发焓.     

分子动力学模拟研究外电场对咪唑类离子液体振动谱的影响

本文利用分子动力学模拟研究了外电场对咪唑类离子液体1-乙基-3-甲基咪唑六氟磷酸盐(EMIMPF₆)从0到4000 cm⁻¹范围内振动谱的影响。研究结果表明,在没有外电场时利用分子动力学模拟计算得到的从400到4000 cm⁻¹的振动带可以重现实验测得的谱。当外电场从0到9 V·nm⁻¹变化时,在50.0和199.8 cm⁻¹处的振动带强度持续增强然后趋于饱和,而从400到4000 cm⁻¹的振动带强度明显减弱并最终消失。此外,在外电场从0变到2 V·nm⁻¹时,50.0 cm⁻¹的振动带红移了16.7 cm⁻¹,然后当外电场变化到3 V·nm⁻¹及更大时,该振动带红移增大到33.3 cm⁻¹。在外电场从0变到3 V·nm⁻¹时,3396.6 cm⁻¹的振动带红移大约16.7 cm⁻¹,然后当外电场增大到4 V·nm⁻¹甚至更大时,该振动带红移33.3 cm⁻¹,但是从0到4000 cm⁻¹的其他振动带的位置几乎没有变化。基于对模拟结果和先前报道文献的进一步分析,对于50.0 cm⁻¹的振动带,增加的外电场增强了阳离子和阴离子之间的极性使阳离子和阴离子间的偶极矩增大,因此该振动带的强度不断增大然后达到饱和。对于199.8 cm⁻¹的振动带增加的外电场增强了乙基链的扭转,使该振动带的强度增大并达到饱和。对于从400到4000 cm⁻¹的其他振动带,增加的外电场使EMIMPF₆中的阳离子和阴离子的取向更一致,并且可以推测这种更一致的取向可能会削弱振动带的强度甚至使它们消失。50.0 cm⁻¹处振动带的红移可能是由于外电场破坏了EMIMPF₆内部的静电场分布进而减弱了阳离子和阴离子间的相互作用。3396.6 cm⁻¹处振动带的红移可归功于外电场减弱了氮原子与阳离子咪唑环上酸性氢原子间形成的氢键的拉伸振动。对于其他的振动带,由于官能团固有的拉伸、弯曲、转动振动不受外电场的影响,外电场没有改变振动带的位置。     

Reactivity and Controlled Redox Reactions of Salt-like Intermetallic Compounds in Imidazolium-Based Ionic Liquids

Substituted imidazolium ionic liquids (ILs) were investigated for their reactivity towards Na₁₂Ge₁₇ as a model system containing redox-sensitive Zintl cluster anions. The ILs proved widely inert for imidazolium cations with a 1,2,3-trisubstitution at least by alkyl groups, and for the anion bis(trifluoromethylsulfonyl)azanide (TFSI). A minute conversion of Na₁₂Ge₁₇ observed on long-time contact with such ILs was not caused by dissolution of the salt-like compound, and did thus not provide dissolved Ge clusters. Rather, a cation exchange led to the transfer of Na⁺ ions into solution. In contrast, by using benzophenone as an oxidizer, heterogeneous redox reactions of Na₁₂Ge₁₇ were initiated, transferring a considerable part of Na⁺ into solution. At optimized conditions, an X-ray amorphous product NaGe_6.25 was obtained, which was thermally convertible to the crystalline type-II clathrate Na_24–δGe₁₃₆ with almost completely Na-filled polyhedral cages, and α-Ge. The presented method thus provides unexpected access to Na_24–δGe₁₃₆ in bulk quantities.     

Solvent Effects on the NMR Chemical Shifts of Imidazolium-Based Ionic Liquids and Cellulose Therein

The interactions of ionic liquids (IL) with solvents usually used in liquid-state nuclear magnetic resonance (NMR) spectroscopy are studied. The ¹H- and ¹³C-NMR chemical shift values of 1-n-butyl-3-methyl (BM)- and 1-ethyl-3-methyl (EM)-substituted imidazolium (IM) -chlorides (Cl) and -acetates (Ac) are determined before and after diluting with deuterated solvents (DMSO-d₆, D₂O, CD₃OD, and CDCl₃). The dilution offers structural modifications of the IL due to the solvents capacity to ionization. For further investigation of highly viscous cellulose dopes made of imidazolium-based IL, solid-state NMR spectroscopy enables the reproducibility of liquid-state NMR data of pure IL. The correlation of liquid- and solid-state NMR is shown on EMIM-Ac and cellulose/EMIM-Ac dope (10 wt %).     

Study of Imidazolium Ionic Liquids:Temperature-dependent Fluorescence and Molecular Dynamics Simulation

The steady-state fluorescence spectra and molecular dynamics simulations were explored to investigate the temperature dependent organization in some imidazolium ionic liquids:1-butyl-3-methylimidazolium hexafluo-rophosphate([bmim][PF6]),1-ethyl-3-methylimidazolium ethylsulfate([emim][EtSO4]) and 1-butyl-3-methylimida-zolium tetrafluoroborate([bmim][BF4]).The pure room temperature ionic liquids(ILs) exhibit a large red shift at more than an excitation wavelength of around 340 nm,which demonstrates the hetero...     

离子液中溶剂化电子的结构及其演化动力学

本文综述了离子型液体介质中过剩电子的结构、存在状态及其时间演化动力学特征。基于从头算分子动力学模拟及计算结果,重点阐述了咪唑型、吡啶型、碱金属离子型熔盐氯化物离子液中与过剩电子溶剂化密切相关的溶剂化能量学、结构特征、可能的存在状态以及态-态转化稳态动力学机制,分析了此类离子型介质中电子高效传导的内在本质及离子液组成离子的重要作用。阳离子的最低未占轨道组成的导带结构是离子液中过剩电子的溶剂化态及其稳定性的决定因素,任何能影响或改变其导带结构的因素均能显著影响过剩电子溶剂化。但快速的态-态转化及电子迁移并不明显取决于其组成离子扩散动力学,而是敏感地受离子液涨落所控制。这种基于溶剂化电子的迁移模式构成了此类离子型介质甚至其它液态介质中电子转移的新途径。     

n-Butane,iso-Butane and 1-Butene Adsorption on Imidazolium-Based Ionic Liquids Studied with Molecular Beam Techniques

The interaction of molecules, especially hydrocarbons, at the gas/ionic liquid (IL) surface plays a crucial role in supported IL catalysis. The dynamics of this process is investigated by measuring the trapping probabilities of n-butane, iso-butane and 1-butene on a set of frozen 1-alkyl-3-methylimidazolium-based ILs [C_nC₁Im]X, where n=4, 8 and X⁻=Cl⁻, Br⁻, [PF₆]⁻ and [Tf₂N]⁻. The decrease of the initial trapping probability with increasing surface temperature is used to determine the desorption energy of the hydrocarbons at the IL surfaces. It increases with increasing alkyl chain length n and decreasing anion size for the ILs studied. We attribute these effects to different degrees of alkyl chain surface enrichment, while interactions between the adsorbate and the anion do not play a significant role. The adsorption energy also depends on the adsorbing molecule: It decreases in the order n-butane>1-butene>iso-butane, which can be explained by different dispersion interactions.     

Temperature Dependence of the Dielectric Properties and Dynamics of Ionic Liquids

No solo dancers: The temperature dependence of dielectric spectra suggests that the lower‐frequency relaxation dominating the dynamics of imidazolium‐based room temperature ionic liquids cannot be solely due to independent rotational diffusion of the cations (see picture), but must also include cooperative motions of the surrounding particles.

     

分子模拟研究气体在室温离子液体中的溶解度

在作者先前建立的分子力场基础上, 采用Widom粒子插入法预测了CO₂、N₂、O₂、Ar及CH₄等5种气体在多种咪唑类离子液体中的溶解度, 包括2种侧链长度的阳离子和3种阴离子. 首先考察了256个离子对组成的体系中溶质分子插入次数对计算结果的影响, 在此基础上计算了不同温度下气体在1-丁基-3-甲基咪唑的四氟化硼盐([bmim][BF₄])和六氟化磷盐([bmim][PF₆])中的溶解度. 计算结果正确反映了CO₂气体溶解度的变化趋势, 在[bmim][BF₄]中溶解度的模拟结果与实验值符合很好, 且明显优于Pádua等的模拟结果；在[bmim][PF₆]中的溶解度较实验值偏高, 精度与文献模拟结果相当；并预测了较高温度下CO₂气体在[bmim][BF₄]和[bmim][PF₆]中的溶解度. 计算结果也正确地反映了5种气体在[bmim][PF₆]中溶解度实验值的相对大小. 另外考察了常温下几种气体在不同室温离子液体中的溶解度, 模拟结果表明气体在含有较长碳链和双-三氟甲基磺酰胺阴离子(Tf₂N^－)的离子液体中溶解度较大.     

离子液体在纤维素研究中的应用

离子液体是一种新型的绿色溶剂,纤维素是一种可再生的生物资源,作为非衍生化纤维素溶剂,离子液体在纤维素研究中呈现出了良好的发展态势。本文综述了纤维素在离子液体溶解、再生、衍生化反应及其在生物酶催化等方面的一些研究成果。     

An imaging pH optode for cell studies based on covalent attachment of 8-hydroxypyrene-1,3,6-trisulfonate to amino cellulose acetate films

The objective of this study was to create a thin film optode for fast pH measurements that meets the requirements for imaging pH-responses from cells as well as for a future hybrid design for detection of multiple analytes simultaneously. The sensor is based on the covalent attachment of 8-hydroxypyrene-1,3,6-trisulfonate (HPTS) to a film forming cellulose acetate material through a sulfonamide linkage. The synthesis routes of the cellulose material and regio-specific covalent attachment of the dye are described in detail. The sensor was sterilized in two different ways and showed excellent biocompatibility with Chinese hamster ovary cells. Imprints from cells and μm thin cell extensions were visualized when altering pH of the surrounding solution. The sensor was tested together with time-dependent sigmoidal calibrations giving pH determinations with an exceptional precision and accuracy during measurement within pH 6-8. The precision of the optode, calculated as pooled S.D. (n = 8) according to IUPAC recommendations between pH 6.641 and 7.742 was 0.0029. The accuracy was significantly better than the electrode used as reference during the measurements. The response time (0-95%) was 100 s between pH 6.641 and 7.742 and the reverse response (95-0%) was 80 s. The sensor shows great potential for extra-cellular pH determination over time during cell growth and pharmacological exposure.     

Effects of Cationic Structure on Cellulose Dissolution in Ionic Liquids: A Molecular Dynamics Study

In recent years, great progress has been made in the dissolution of cellulose with ionic liquids (ILs). However, the mechanism of cellulose dissolution, especially the role the IL cation played in the dissolution process, has not been clearly understood. Herein, the mixtures of cellulose with a series of imidazolium‐based chloride ionic liquids and 1‐butyl‐3‐methyl pyridinium chloride ([C₄mpy]Cl) were simulated to study the effect that varying the heterocyclic structure and alkyl chain length of the IL cation has on the dissolution of cellulose. It was shown that the dissolution of cellulose in [C₄mpy]Cl is better than that in [C₄mim]Cl. For imidazolium‐based ILs, the shorter the alkyl chain is, the higher the solubility will be. In addition, an all‐atom force field for 1‐allyl‐3‐methyl imidazolium cation ([Amim]⁺) was developed, for the first time, to investigate the effect the electron‐withdrawing group within the alkyl chain of the IL cation has on the dissolution of cellulose. It was found that the interaction energy between [Amim]⁺ and cellulose was greater than that between [C₃mim]⁺ and cellulose, indicating that the presence of electron‐withdrawing group in alkyl chain of the cation enhanced the interaction between the cation and cellulose due to the increase of electronegativity of the cations. These findings are used to assess the cationic effect on the dissolution of cellulose in ILs. They are also expected to be important for rational design of novel ILs for efficient dissolution of cellulose.     

Broadband NMR Relaxometry as a Powerful Technique to Study Molecular Dynamics of Ionic Liquids

Fast field cycling nuclear magnetic resonance (FFC NMR) relaxometry technique has been demonstrated to be a useful analytical tool to investigate molecular dynamics in very diverse systems during the last decades. Of particular importance has been its application in studying ionic liquids, upon which this review article is based. Some of the research carried out on ionic liquids during the last ten years using this technique is highlighted in this article with the aim of promoting the favorable features of FFC NMR applied toward understanding dynamics of complex systems.