聚合离子液体用作毛细管电泳背景电解质添加剂快速高效分离5种核苷类化合物

将聚乙烯基-3-乙基咪唑溴盐离子液体用作毛细管电泳背景电解质添加剂,利用聚合离子液体的阳离子聚合物性质静电吸附到毛细管内表面,成功实现电渗流的有效反转,建立了共电渗流模式下5种核苷类化合物分离的新方法。考察了聚合离子液体浓度、pH值等因素对电渗流的影响。在优化实验条件下,3.1 min内实现了对5种核苷类化合物的快速高效分离;将该方法分别与不加添加剂和加入离子液体单体后的体系进行对比,结果表明,该方法大大缩短了5种核苷类化合物的分析时间,提高了分析效率,最高柱效达95万/m塔板数,分析物的迁移时间RSD均不高于0.38%。该方法简单、快速、重复性好,具有很好的应用前景。     

Light‐Controllable Ionic Conductivity in a Polymeric Ionic Liquid

Polymeric ionic liquids (PILs) have attracted considerable attention as electrolytes with high stability and mechanical durability. Light‐responsive materials are enabling for a variety of future technologies owing to their remote and noninvasive manipulation, spatiotemporal control, and low environmental impact. To address this potential, responsive PIL materials based on diarylethene units were designed to undergo light‐mediated conductivity changes. Key to this modulation is tuning of the cationic character of the imidazolium bridging unit upon photoswitching. Irradiation of these materials with UV light triggers a circa 70 % drop in conductivity in the solid state that can be recovered upon subsequent irradiation with visible light. This light‐responsive ionic conductivity enables spatiotemporal and reversible patterning of PIL films using light. This modulation of ionic conductivity allows for the development of light‐controlled electrical circuits and wearable photodetectors.     

氯化锂为添加剂制得的疏水聚偏氟乙烯不对称微孔膜的形态结构及其膜蒸馏性能

结合膜的形态结构研究了以 LiCl为添加剂制得的疏水 PVDF膜的膜蒸馏性能。与来用水溶液高分子添加剂制得的PVDF微孔膜相比,膜蒸馏性能有了较大提高,尤其具有更高的截留率。制得的微孔膜的蒸馏通量已接近商品膜的膜蒸馏通量,表明以LiCl为添加剂制得的PVDF疏水微孔膜是一种适用于膜蒸馏的较理想的疏水微孔膜。     

一种可高温运行的离子液体电解质燃料电池

本文采用N-甲基咪唑为原料通过溴盐的中间步骤合成了1-乙基-3甲基咪唑磷酸二氢盐([Emim]H₂PO₄)离子液体。首先利用元素分析和核磁共振确定了其组成,并测量了该离子液体的粘度和电导性能,然后使用多孔的聚偏氟乙烯作为支撑制备了离子液体电解质复合膜,120 ℃时通过交流阻抗测得其电导率为2.7×10^-2 S·cm^-1。最后将该复合膜组装在单电池中测试了不同温度下的性能,常压下120 ℃时可获得0.85 mW·cm^-2的功率密度,结果表明该复合膜的质子传导可以完全不依赖水,从而能够实现高温操作。     

Porous Poly(Ionic Liquid) Membranes as Efficient and Recyclable Absorbents for Heavy Metal Ions

Heavy metal ion pollution has become a serious environmental problem. Herein, this study reports the synthesis of poly(ionic liquid) (PIL) membranes via in situ photo‐crosslinking of vinyl imidazole with both hydrophilic and hydrophobic ionic liquid monomers. The resultant amphiphilic polymer membranes are porous and exhibit high absorption capacity of metal ions (including Hg²⁺, Pb²⁺, Cu²⁺, Cd²⁺, and Zn²⁺) in both high (1000 mg L⁻¹) and low (10 mg L⁻¹) concentration metal ion solutions. These metal ionic absorption membranes are easily regenerated in acid solution and can be reused without significant decreases of absorption capacity after many cycles. These PIL membranes may have potential applications as eco‐friendly and safe heavy metal ion removal materials.

     

添加剂对离子液体中电沉积金属钴的影响

在含有氯化钴的室温离子液体氯化1-甲基-3-乙基咪唑(EMIC)和乙二醇(EG)体系中,采用扫描电子显微镜(FE-SEM）、阴极极化曲线、循环伏安及X射线衍射等方法研究了添加剂对电沉积金属钴的影响。结果表明,在EMIC-EG-CoCl₂熔盐中加入丁炔二醇能够有效地改善钴镀层的外观质量,丁炔二醇的加入量在0.3～0.7 g·L^-1范围内,能够得到银灰色、具有金属光泽的良好镀层。从FE-SEM照片可以看出,在EMIC-EG-CoCl₂熔盐中加入丁炔二醇后,使金属钴的结晶变得更加细致;阴极极化曲线表明,丁炔二醇的加入不仅增大了阴极极化,而且还消除了钴的欠电势沉积;循环伏安测试证明,添加剂的加入对阴极沉积过程有阻化作用;XRD分析证实,丁炔二醇的加入使金属钴的衍射峰变宽,晶粒尺寸为纳米级。     

离子液体作流动相添加剂高效液相色谱法分离莨菪类生物碱

建立了以离子液体1-辛基-甲基咪唑六氟磷酸盐(Omin PF6)为高效液相色谱流动相添加剂分离莨菪类生物碱的方法,探讨了离子液体的保留模型及机理。采用高效液相色谱法,考察了检测波长、有机相种类和比例、离子液体的种类、p H值和浓度、缓冲盐体系等因素对莨菪类生物碱色谱行为的影响。结果显示,当离子液体作为流动相添加剂时,可明显改善此类生物碱的分离效果,减少色谱峰的拖尾,提高分离效率。研究显示,Omin PF6浓度与容量因子的变化符合溶质计量置换保留模型(SDM-R),且保留过程以竞争吸附为主。     

离子液体型表面活性剂研究

以1-甲基咪唑为原料, 制备了6个常规离子液体: 1-正丁基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[bmim][BF₄]及[bmim][PF₆])、1-正己基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[hmim][BF₄]及[hmim][PF₆])、1-正十六烷基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[C₁₆mim][BF₄]及[C₁₆mim][PF₆])和4个功能化离子液体: 1-(2-羟乙基)-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[2-hemim][BF₄]及[2-hemim][PF₆])、1-乙氧羰基甲基-3-甲基咪唑四氟硼酸盐及六氟磷酸盐(简称[eocmmim][BF₄]及[eocmmim][PF₆]). 研究了这两类离子液体的一些物理性能, 旨在挖掘离子液体在香料香精化妆品工业中的应用价值. 分别检测了它们与一般溶剂的互溶性, 并测定了它们的表面张力和发泡性能, 实验结果表明, 仅[C₁₆mim][BF₄]和[C₁₆mim][PF₆]具有发泡性能, 发泡力分别为68和120 mm.     

离子液体及离子液体膜在天然气净化方面的应用

天然气净化对天然气这一清洁、高效的一次能源及我国快速增长的消费需求具有重要的战略意义。离子液体因挥发性低、溶解能力强、结构和性质可调控性强等优点,在离子液体膜净化气体方面获得高度关注。本文系统地总结了离子液体膜富集分离CO₂及其他气体的性能,包括常规离子液体、功能化离子液体、聚合物离子液体、离子液体混合物;讨论了离子液体结构(如阳离子取代基链长、取代基对称性、阴离子结构大小、阴离子氟化)、膜支撑材料性能(如水溶性、孔径大小)及水含量等因素对膜性能的影响;对各种方法的优缺点及使用条件进行详细的阐述;并提出今后离子液体膜在气体净化方面的发展方向。     

PEG接枝PAN/PS高分子颗粒的形态控制研究

采用甲基丙烯酸单封端聚乙二醇大分子单体(MAA—PEG)为反应性稳定剂,使之与苯乙烯／丙烯腈在乙醇／水混合介质中三元分散共聚,利用单体间反应性差异及聚合物溶解性的不同,制备具有特殊形态的高分子颗粒．电子显微镜观察发现,颗粒形态与反应时间、单体配比、MAA—PEG浓度及分子量有关．X射线光电子能谱研究表明,增加反应时间,颗粒表面聚集的亲水性PEG成分增加,中心是聚苯乙烯,外部凸起部主要为聚丙烯腈,高分子颗粒具有核-壳结构．调节苯乙烯浓度、MAA—PEG浓度及介质组成可以控制颗粒大小,影响颗粒形态的主要因素是单体反应性差异和MAA—PEG的分子量及浓度．     

离子液体中ZnO纳米棒的制备与表征

离子液体中ZnO纳米棒的制备与表征;离子液体;ZnO纳米棒;热分解     

Study on the Morphology Feature of 1-Butyl-3-methylimidazolium Tetrafluoroborate Based Ionic Liquid Reverse Microemulsions

The micromorphology of 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF₄)-in-cyclohexane and bmimBF₄-in-triethylamine ionic liquid microemulsions was investigated by two-dimensional NMR and freeze-fracture transmission electron microscopy. The reverse micelles of Triton X-100/cyclohexane were destroyed by adding bmimBF₄ and reverse microemulsions were induced to form by successively adding bmimBF₄. However, no micelles appeared in triethylamine. But if adding bmimBF₄ to a certain extent, a reverse microemulsion was also formed. The driving force of such aggregations could be attributed to the presence of different types of interactions between Triton X-100 and bmimBF₄. A staggered arrangement of surfactant led to the irregular droplet structure and large aggregate size.     

功能性离子液体支载液相有机合成研究进展

阐述了功能性离子液体支载液相有机合成的概念、特点及其在小分子杂环化合物、多肽、寡糖合成等有机反应中的应用, 以及功能性离子液体支载的催化剂和试剂在液相有机合成中的应用. 研究表明功能性离子液体作为一种新型的高负载量的可溶性载体可以广泛应用于液相有机合成中, 有效地促进了反应的进行, 简化了分离手段, 显著地提高了反应的选择性和收率.     

Preparation of Polystyrene Particles by Dispersion Polymerization in an Ionic Liquid

Submicron‐sized monodisperse polystyrene (PS) particles were successfully prepared by dispersion polymerization of styrene in an ionic liquid, N,N‐diethyl‐N‐methyl‐N‐(2‐methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide ([DEME][TFSI]) at 70 °C with poly(vinyl pyrrolidone) (PVP) as a stabilizer. At the optimum PVP and styrene concentrations with regard to preparation of stable polymer particles, the number‐average diameter and coefficient of variation were 350 nm and 5.7%, respectively. The particle size increased with a decrease in the PVP concentration and an increase in the styrene concentration. Moreover, we succeeded in producing PS particles by thermal polymerization in the absence of a radical initiator at 130 °C in [DEME][TFSI] using a conventional reactor (not autoclave) utilizing the advantages of non‐volatility and thermal stability of the ionic liquid.

     

Kinetic Study of Curing Bisphenol A Dicyanate Ester with Ionic Liquid Additive

A kinetic study of the trimerization reaction of bisphenol A dicyanate ester with an aromatic imidazolium‐based ionic liquid (IL) as additive is performed using dynamic and isothermal differential scanning calorimetry. The reaction follows second‐order autocatalytic kinetics, and a slight acceleration effect is observed in the presence of the aromatic IL relative to the neat resin. The activation energy also increases with the IL additive, whereas the glass transition temperature (T_g) is depressed, consistent with the Fox equation and a homogeneous one‐phase material. A model incorporating diffusion effects is able to describe the dynamic and isothermal curing data for both the neat resin system and that containing aromatic IL. A comparison with aliphatic‐based IL additive indicates that the reaction is more accelerated with aliphatic IL than with the aromatic IL in spite of the fact that the aliphatic additive phase separates during cure. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1315–1324     

多面体烷氯乙基脲的合成新方法研究

运用酰氟为中间体,在离子液体中,以多面体烷二羧酸为原料,研究了多面体烷氯乙基脲的合成新方法.在[bmim][BF4]离子液体中,合成了12个未见文献报道的多面体烷氯乙基脲,结构经核磁共振氢谱、碳谱和质谱确证.该方法与以酰氯为中间体的溶剂反应相比,具有产率高、分离简单和环境友好的特点.     

Facile Synthesis of Benzotriazole Derivatives Using Nanoparticles of Organosilane-Based Nitrite Ionic Liquid Immobilized on Silica and Two Room-Temperature Nitrite Ionic Liquids

Nanoparticles of organosilane-based nitrite ionic liquid immobilized on silica, 1-butyl-3-methylimidazolium nitrite, and 1-(3-trimethoxysilylpropyl)-3-methylimidazolium nitrite were used as effective reagents for the preparation of benzotriazole derivatives from 1,2-diaminobenzenes at room temperature under mild solvent-free conditions. These ionic liquids play as nitrosonium sources in this procedure.1,2-Diaminobenzene derivatives have been treated with ionic liquids to give the related diaminobenzenes in very good to excellent yields in short reaction times.

Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the full experimental and spectral details.     

氨基甲酸酯功能化离子液体高效液相色谱固定相的制备与初步评价

合成一种了氨基酸衍生物：4,4′-二苯亚甲基桥联-二[2-(1-咪唑基)-3-苯基丙醇氨基甲酸酯](ImPh-Carb),并将其键合到硅胶上制备了一种新的氨基甲酸酯功能化的离子液体HPLC固定相（ImPh-Carb-Silica）。 利用1H NMR、13C NMR、MS和FTIR对ImPh-Carb进行了表征;通过FTIR和元素分析对ImPh-Carb-Silica固定相进行了表征,根据N含量计算得到ImPh-Carb-Silica的键合量为0.19 mmol/g。 以5种芳烃、5种酚类化合物和4种有机磷农药为分析物,分别在正相和反相色谱模式下对固定相的色谱分离性能进行了评价,同时考察了流动相的变化与溶质保留因子lg k之间的关系。 结果表明,该固定相与溶质分子间存在多重作用力,如疏水、氢键、π-π和偶极-诱导偶极作用等,使其能同时在正相和反相色谱模式下使用;在正相色谱条件下固定相对酚类化合物和有机磷农药表现出较好的分离选择性。     

Direct Electrochemistry and Electrocatalysis of Hemoglobin Immobilized in a Polymeric Ionic Liquid Film

A polymer film based on polymeric ionic liquid, which was poly(1‐vinyl‐3‐butylimidazolium chloride) (poly(ViBuIm⁺Cl^?)for short), was firstly used as matrix to immobilize hemoglobin (Hb). FTIR and UV‐vis spectra demonstrated that the native structure of Hb was well preserved after entrapped into the polymer film. The Hb immobilized in the poly(ViBuIm⁺Cl^?) film showed a fast direct electron transfer for the Hb‐Fe^III/Fe^II redox couple. Based on the direct electron transfer of the immobilized Hb, polyvinyl alcohol (PVA)/Hb/poly(ViBuIm⁺Cl^?)/GC electrode displayed good sensitivity and wide linear range for the detection of H₂O₂. The linear range of the PVA/Hb/poly(ViBuIm⁺Cl^?)/GC electrode to H₂O₂ is from 3.5 to 224 μM with a limit of detection of 1.17 μM. Such an avenue, which integrated polymeric ionic liquid and redox protein via a simple method, may provide a novel and efficient platform for the fabrication of biosensors, biofuel cells and other bioelectrochemical devices.