Efficient and green synthesis of tetrasubstituted pyrroles promoted by task-specific basic ionic liquids as catalyst in aqueous media

Synthesis of tetrasubstituted pyrroles by the three-component condensation reaction of acid chlorides, dialkyl acetylenedicarboxylates, and amino acids in the presence of various room-temperature ionic liquids (RTILs) as catalysts in water is reported. Among the ionic liquids used, the basic functionalized ionic liquid, butyl methyl imidazolium hydroxide [bmim]OH, was the most effective catalyst. The influence of reaction temperature, reaction time, and amount of ionic liquid on the reaction was investigated. The [bmim]OH/H₂O catalyst system could be reused for at least five recycles without appreciable loss of efficiency.     

Hydrodynamic sono-voltammetry of ferrocene in [Tf2N] based ionic liquid media

The present work deals with the hydrodynamic behavior of several room-temperature ionic liquids presenting the same bis(trifluoromethanesulfonyles)imide anion, associated with four different cations: 1-butyl-3-methylimidazolium, 1-octyl-3-methylimidazolium, N-trimethyl-N-propylammonium and 1-butyl-1-methylpyrrolidinium cations. Steady state voltammetry was used as an electrochemical technique to characterize mass transfer in both silent and sonicated conditions, using a rotating disk electrode. Results obtained in RTILs media are compared to those acquired in synthetic solutions of controlled viscosity, in order to develop a better understanding of the phenomena involved in such media.     

离子液体存在下铜的电沉积及其表面增强拉曼散射效应研究

离子液体作为一种绿色介质,在电化学领域中的研究正在兴起,引起了研究者的浓厚兴趣。文章运用循环伏安法研究了离子液体(1-丁基-3-甲基咪唑四氟硼酸盐,[bmim]BF4)存在时,酸性硫酸铜溶液中铜在铜电极上的电化学沉积行为。研究表明,[bmim]BF4的加入使铜的沉积峰电位负移,沉积电流增加。采用扫描电镜(SEM)和X射线衍射(XRD)对铜镀层的形貌及结构进行表征,结果显示离子液体的存在可使铜镀层的层状晶粒尺寸减小,镀层出现(220)高择优取向。以甲基橙(MO)为探针分子,研究了所得铜镀层的表面增强拉曼散射(SERS)效应,发现离子液体存在下得到的铜镀层是较好的SERS基底,具有良好的增强效果及稳定性。对MO分子的增强因子可达4.7×105,而且保存了60天后,其检测灵敏度没有显著的降低。     

Solvation and Rotational Diffusion of Solutes in Room Temperature Ionic Liquids as Studied by EPR Spectroscopy with Nitroxide Spin Probing Method

In this article, we briefly introduced our studies on solvation and rotational diffusion of solutes in room temperature ionic liquids (RTILs) by electron paramagnetic resonance with nitroxide spin probing method. Most of the rotational correlation times for the nitroxide radicals are within the range calculated on the basis of Stokes–Einstein–Debye hydrodynamic theory with stick and slip boundary conditions or Gierer–Wirtz theory except for smaller solutes in some RTILs with smaller BF₄ and PF₆ anions. In RTILs with 1-butyl-3-methylimidazolium as cation and BF₄ or PF₆ as anion, nitroxide radicals undergo rotational diffusion like supercooled liquids and nitroxide radical with smaller volume rotationally slips.     

Unusual aspects of ion‐pairing effects in room temperature ionic liquids

Herein, we report our observations on voltammetric investigations about the redox behaviour of para‐nitrotoluene, 1,4‐benzoquinone and ferrocene, aimed at exploring the unusual aspects of ion‐pairing phenomena in imidazolium‐based room temperature ionic liquids (RTILs). Our observations indicate that the stabilization of electrogenerated ion/radical ion intermediates depends upon the potential of the working electrode and the overall composition of RTILs. In light of observed relative trends and quantum mechanical calculations, we propose that the ion‐pair stabilization of electrogenerated charged species in RTILs is closely related to the structural organization and composition of electrode/RTIL interface. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of silver nanoparticle in imidazolium and pyrolidium based ionic liquid reverse micelles: A step forward in nanostructure inorganic material in room temperature ionic liquid field

Two silver salts, silver tetrafluoroborate and silver trifluoromethanesulfonate were dissolved in two different room temperature ionic liquids (RTILs), 1-Butyl-3 methyl imidazolium tetrafluoroborate ([Bmim][BF₄]) and 1-Butyl-1 methyl pyrrolidinium trifluoromethanesulfonate ([Bmpy][Tfms]). Triton x-100 (TX-100) surfactant and cyclohexane as nonpolar medium are used to dissolve these RTILs to create reverse micellar system. Pure reverse micellar system is characterized by dynamic light scattering (DLS) measurement. These pure RTIL reverse micellar systems are used to prepare stable silver nanoparticle solution without using any other auxiliary solvent in the whole process.     

Effect of cavitation intensity control on self-assembling of alkanethiols on gold in room temperature ionic liquids

This study investigates the effect of cavitation intensity on self-assembling of alkanethiol molecules on gold in room temperature ionic liquids (RTILs) under low frequency ultrasound irradiation (20 kHz). The use of RTILs, with low vapor pressure, enabled cavitation activity to be controlled up to quenching through pressure decrease within an argon-saturated atmosphere. This control possibility was used to acquire deeper insights into the role of cavitation on self-assembling processes. It was shown by electrochemical, contact angles and Polarization Modulation - Infrared Reflection Absorption Spectroscopy (PM-IRRAS) measurements that cavitation activates orientation and organization of self-assembled monolayers (SAM). X-ray Photoelectron Spectroscopy (XPS) revealed that, even if chemical adsorption of molecules is highly activated under ultrasound irradiation, it is not dependent on acoustic cavitation intensity.     

Double layer in ionic liquids: overscreening versus crowding

We develop a simple Landau-Ginzburg-type continuum theory of solvent-free ionic liquids and use it to predict the structure of the electrical double layer. The model captures overscreening from short-range correlations, dominant at small voltages, and steric constraints of finite ion sizes, which prevail at large voltages. Increasing the voltage gradually suppresses overscreening in favor of the crowding of counterions in a condensed inner layer near the electrode. This prediction, the ion profiles, and the capacitance-voltage dependence are consistent with recent computer simulations and experiments on room-temperature ionic liquids, using a correlation length of order the ion size.     

Fluorescence Characteristics of Bisphenol A in Room Temperature Ionic Liquids

Room temperature ionic liquids (RTILs) are emerging as a new class of ‘green’ solvents for use in a wide range of chemical processes. RTILs can sensitize or quench fluorescence of organic chemicals and their interactions still remain unclear, especially for weakly fluorescent chemicals. Herein, we report the effects of six RTILs on the fluorescence behavior of bisphenol A (BPA). The fluorescence intensities (FIs) of BPA in a RTIL-acetonitrile system were significantly quenched compared to acetonitrile. The quenching effect was stronger for [C_nMIM]BF₄ than [C_nMIM]PF₆. A decreasing trend of fluorescence lifetime (FL) of BPA was observed for [C₆MIM]PF₆ (4.26 to 3.86 ns) and [C₁₄MIM]PF₆ (4.15 to 3.78 ns) with increasing RTIL concentrations in the range of 1–10 mM. The quenching mode was consistent with a static quenching mechanism based on the consistency of FL and FI results. The emission bands of BPA and RTILs did not interfere with each other when RTILs were used as the solvent. The investigated RTILs enhanced the FIs of strongly fluorescing chemicals (12.0?~?19.0-fold for norfloxacin and 6.1?~?8.5-fold for dansyl chloride), but quenched those of weakly fluorescing chemicals (BPA). These results demonstrate that RTILs have different fluorescent effects on organic chemicals with different fluorophores. The interactions between RTILs and BPA result from many factors in addition to viscosity, such as solvent electrostatic dielectric constant, refractive index, density, polarization and molecular interaction. These results provide a theoretical foundation for application of RTILs in the analysis of weakly fluorescing chemical.     

Thermal behaviour of two room-temperature ionic liquids containing the methylimidazolium cation

We have investigated the glass transition relaxation of two room-temperature ionic liquids using Modulated Temperature Differential Scanning Calorimetry (MTDSC). Furthermore, conventional DSC was used to clarify their crystallisation behaviour. One of the liquids avoids crystallisation, while the other shows cold crystallisation. A step-by-step temperature scanning experimental procedure was used to analyse in detail the thermal behaviour of the latter in the crystallisation and melting temperature regions. The existence of polymorphism is discussed.     

质子酸功能化离子液体中银纳米颗粒的制备及其光学性能研究

以质子酸功能化离子液体1-丁基-3-甲基咪唑磷酸二氢盐([Bmim]H₂PO₄)为反应介质和表面活性剂,采用简单的化学还原法制备了具有形状各向异性的块状银纳米颗粒。通过X射线衍射(XRD)、扫描电镜(SEM)、紫外-可见(UV-Vis)吸收光谱等一系列手段对其结构、形貌及光吸收特性进行了表征。结果表明,所制备的银纳米块具有立方结构,其平均横向尺寸约为30 nm,在硅片上自组装形成密堆积结构的多层膜。以1,2-二(4-吡啶基)乙烯(BPE)作为探针分子,研究所制备银纳米颗粒的表面增强拉曼散射(SERS)活性。结果表明所制的银纳米颗粒是较好的SERS基底,具有良好的增强效果,痕检能力及稳定性。对BPE分子的最低检测浓度可低至10-9mol·L-1,而且保存了90天后,其检测灵敏度没有显著的降低。     

Effects of Ionic Liquids on Fluorescence Characteristics of 17α- and 17β-estradiol

Herein, we report the effects of six different room temperature ionic liquids (RTILs) on fluorescence spectra of 17α-estradiol (EE1) and 17β-estradiol (E2). The selected RTILs belonged to the compound classes of 1-alkyl-3-methylimidazolium tetrafluoroborate ([C_nMIM]BF₄) and 1-alkyl-3-methyl imidazolium hexafluorophosphate ([C_nMIM]PF₆). RTILs had a gradual quenching effect on fluorescence intensity (FI) of EE1 and E2, and the quenching process followed the well-known Stern-Volmer theory. The quenching mechanism of EE1 and E2 by RTILs was demonstrated to be dynamic quenching. Additionally, the overall quenching efficiency by [C_nMIM]BF₄ was higher than [C_nMIM]PF₆. The increased carbon chain length of RTILs did not lead to obvious differences in FI for EE1 and E2. The quenching efficiency showed irregular trend at three different temperatures (25, 35 and 45 °C). RTILs such as [C₄MIM]PF₆ had the different fluorescent effects on organic chemicals with different fluorophores. The enhancing effects of [C₄MIM]PF₆ were observed on strong fluorescence chemicals (dansyl chloride, rhrodamine B, 1,10-phenanthroline, norfloxacin), while quenching effect on weak fluorescence chemicals (EE1 and E2). In theory, these results provide a theoretical foundation for deep insight into their interaction mechanism between RTILs and estradiol.     

RETRACTED ARTICLE: Polymer electrolytes: characteristics and peculiarities

Polymer electrolytes are an important component of many electrochemical devices. This paper reviews state-of-the-art of the electrochemical and physical properties of polymer electrolytes. This review mainly encompasses the properties of different salts, solvents, and polymer hosts, which are encaged in liquid electrolytes. The additions of filler in polymer electrolytes result in composite polymer electrolytes, having high mechanical integrity and ionic conductivity, that are ideal electrolyte for these applications. The next generation state-of-the-art room-temperature ionic liquids based electrolytes, which are far superior to corresponding nonionic solvent-based electrolytes, are also discussed. An erratum to this article can be found at     

Effects of Room Temperature Ionic Liquids on Fluorescence Characteristics of 17β-estradiol and its Derivative

Previous reports have seldom concerned about the RTILs (Room temperature ionic liquids), and their effects on derivatization reaction or derivatives. In this study, we reported that the effects of four different RTILs, i.e., [EMIM]PF₆, [BMIM]PF₆, [HMIM]PF₆ and [OMIM]PF₆, on fluorescence spectra of 17 β-estradiol (E2), and its derivatization solvent dansyl chloride (DNSCl) and the derivative. [BMIM]PF₆ had a significant quenching effect on the fluorescence intensity of E2, suggesting the formation of [BMIM]PF₆/E2 complexes and possible buried E2 molecular in a more hydrophobic microenvironment. The estimated Stern-Volmer quenching constant (Ksv = 0.3519) proved that E2 quenching caused by [BMIM]PF₆ was a dynamic quenching process. Four RTILs, with different alkyl chain-length in imidazolium cation, resulted in different quenching intensities to E2 as follows: [EMIM]PF₆ > [BMIM]PF₆ > [HMIM]PF₆ > [OMIM]PF₆. At 5 mg L⁻¹ of DNSCl, [BMIM]PF₆, [HMIM]PF₆ and [OMIM]PF₆ increased the fluorescence intensities of E2 in water by 8.5, 7.6 and 6.1 times, respectively, and a 37-nm hypsochromic shift occurred. The fluorescence intensity for [BMIM]PF₆-extracted derivative of E2 increased more than two times compared with that for the control. In conclusion, this study demonstrated that above four hexafluorophosphate salt ionic liquids could be used in derivatization reaction to enhance fluorescent sensitivity in E2 trace residual analysis.     

Acoustic cavitation in 1-butyl-3-methylimidazolium bis(triflluoromethyl-sulfonyl)imide based ionic liquid

In this work, a comparison between the temperatures/pressures within acoustic cavitation bubble in an imidazolium-based room-temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium bis(triflluoromethyl-sulfonyl)imide ([BMIM][NTf₂]), and in water has been made for a wide range of cavitation parameters including frequency (140–1000 kHz), acoustic intensity (0.5–1 W cm⁻²), liquid temperature (20–50 °C) and external static pressure (0.7–1.5 atm). The used cavitation model takes into account the liquid compressibility as well as the surface tension and the viscosity of the medium. It was found that the bubble temperatures and pressures were always much higher in the ionic liquid compared to those predicted in water. The valuable effect of [BMIM][NTf₂] on the bubble temperature was more pronounced at higher acoustic intensity and liquid temperature and lower frequency and external static pressure. However, confrontation between the predicted and the experimental estimated temperatures in ionic liquids showed an opposite trend as the temperatures measured in some pure ionic liquids are of the same order as those observed in water. The injection of liquid droplets into cavitation bubbles, the pyrolysis of ionic liquids at the bubble-solution interface as well as the lower number of collapsing bubbles in the ionic liquid may be the responsible for the lower measured bubble temperatures in ionic liquids, as compared with water.     

Fluorescence Quenching of 4-tert-Octylphenol by Room Temperature Ionic Liquids and its Application

The interactions between room temperature ionic liquids (RTILs) and weak fluorescent chemicals still remain unclear, which hinders the complete and efficient utilization of these “green” solvents in fluorescent analyses of organic chemicals. Herein, we reported the effects of four RTILs, [C₈MIM]BF_4, [C₁₄MIM]BF_4, [C₈MIM]PF₆ and [C₁₄MIM]PF₆, on fluorescence behavior of 4-tert-octylphenol (4-t-OP). In the fortified concentration range of 0.2–1.0 mM, the quenching effects were increased with increasing concentrations of RTILs. However, no obvious variation of peak shape of 4-t-OP was observed in the quenching process, suggesting no formation of ground-state complex between fluorophores in 4-t-OP and quencher (ionic liquids). As for anion effect, the fluorescence quenching efficiency of 4-t-OP by BF₄ ^- was greater than PF₆ ^-, but the carbon chain length on the imidazolium ring had no significant relationship with fluorescence intensity of 4-t-OP. Both Ksv values (>1.0?×?10³?L/mol.s) and the different temperature effects demonstrated that the quenching of 4-t-OP by four RTILs was the presence of dynamic and static quenching mechanism. The FI of dansyl chloride within [C₈MIM]BF₄ increased nearly 5-fold as compared to the control, showing a sensitizing effect on the strong fluorescent chemicals, while a quenching effect on 4-t-OP belonging to weak fluorescent chemicals. The fluorescence-enhanced amplitude of dansyl chloride in [C₈MIM]PF₆ was greater than [C₈MIM]BF_4. The fluorescence quenching of 4-t-OP by [C₈MIM]PF₆ did not belong to FRET phenomenon because of no overlap of emission spectrum of 4-t-OP and absorption spectrum of [C₈MIM]PF₆. When 0.6 mM [C₈MIM]PF₆ in acetonitrile was used as the solvent, the detection limit of 4-t-OP was 3.7 μg/L, and the linearity range was 0.01–0.8 mg/L (R²?=?0.9990). In summary, these results provide a theoretical foundation for the application of RTILs in weak fluorescent chemicals.     

Polarization effects in ionic solids and melts

Ionic solids and melts are compounds in which the interactions are dominated by electrostatic effects. However, the polarization of the ions also plays an important role in many respects as has been clarified in recent years thanks to the development of realistic polarizable interaction potentials. After detailing these models, we illustrate the importance of polarization effects on a series of examples concerning the structural properties, such as the stabilization of particular crystal structures or the formation of highly-coordinated multivalent ions in the melts, as well as the dynamic properties such as the diffusion of ionic species. The effects on the structure of molten salt interfaces (with vacuum and electrified metal) is also described. Although most of the results described here concern inorganic compounds (molten fluorides and chlorides, ionic oxides...), the particular case of the room-temperature ionic liquids, a special class of molten salts in which at least one species is organic, will also be briefly discussed to indicate how the ideas gained from the study of ‘simple’ molten salts are being transferred to these more complex systems.     

Behavior of Short Nitroxide Biradical in Room Temperature Ionic Liquids

The intramolecular electron spin exchange in short nitroxide biradical O=S(OR₆)₂ (I), where OR₆ is 1-oxyl-2,2,6,6-tetramethyl-4-oxypiperidine, dissolved in the room temperature ionic liquids (RTILs) 1-octyl-3-methylimidazolium hexafluorophosphate (omimPF₆), 1-octyl-3-methylimidazolium tetrafluoroborate (omimBF₄), 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF₄), and 1-ethyl-3-methylimidazolium tetrafluoroborate (emimBF₄) has been studied by electron paramagnetic resonance (EPR) spectroscopy as a function of temperature. Temperature variations of the isotropic nitrogen hyperfine splitting constant a were measured from EPR spectra. Thermodynamic parameters of the conformational rearrangements were calculated and compared with literature data. These intramolecular movements in rather rigid short-chain biradical I dissolved in four different RTILs are described well by the Debye–Stokes–Einstein law. Unrestricted density-functional-theory calculations of the geometry and electronic structure of the biradical were carried out using the ORCA program package, and showed that the O=S< group is available for the interaction with anions and cations of RTIL. The possible mechanism of such conformational transitions in biradical I in RTIL is discussed.     

Light absorption coefficients of ionic liquids under electric field

Ionic liquids have attracted a lot of research attention for their applications in novel optoelectronic structures and devices as an optical means of regulating electricity. Although the electro-optic effect of ionic liquids is mentioned in some literature, quantitative testing and analysis are hardly found in light absorption coefficients of ionic liquids under an electric field. In the present study, an experimental apparatus is designed to measure the absorption coefficients of ionic liquids under different electric fields. Five groups of imidazole ionic liquids are experimentally investigated and an inversion is performed to determine the spectral absorption coefficients of the imidazole ionic liquids under the electric fields. Different intensities with multiple interface refractions and reflections are also considered, and the various measurement errors are analyzed through uncertainties propagation analysis. Spectral absorptions of ionic liquids from 300 nm to 2500 nm are obtained and the absorption coefficients are retrieved. It is found that the absorption behavior of ionic liquids changes in some frequency bands under an applied electric field. The experimental results show that the absorption coefficient of the ionic liquid increases with the voltage increasing at 1520 nm and 1920 nm. The change rate is affected by the types of anions and cations in the ionic liquid and the diffusion rate of the ions therein. This study provides illustrations for the ionic liquid-based electro-optical regulation in terms of physical property parameters and the testing technique.     

Measuring the solubility of benzoic acid in room temperature ionic liquids using chronoamperometric techniques

The electrochemical reduction of benzoic acid (BZA) has been studied at platinum micro‐electrodes (10 and 2 µm diameters) in acetonitrile (MeCN) and six room temperature ionic liquids (RTILs): [C₂mim][NTf₂], [C₄mim][NTf₂], [C₄mpyrr][NTf₂], [C₄mim][BF₄], [C₄mim][NO₃] and [C₄mim][PF₆] (where [C_nmim]⁺ = 1‐alkyl‐3‐methylimidazolium, [NTf₂]^? = bis(trifluoromethylsulphonyl)imide, [C₄mpyrr]⁺ = N‐butyl‐N‐methylpyrrolidinium, [BF₄]^? = tetrafluoroborate, [NO₃]^? = nitrate and [PF₆]^? = hexafluorophosphate). Based on the theoretical fitting to experimental chronoamperometric transients in [C₄mpyrr][NTf₂] and MeCN at several concentrations and on different size electrodes, it is suggested that a fast chemical step preceeds the electron transfer step in a CE mechanism (given below) in both RTILs and MeCN, leading to the appearance of a simple one‐electron transfer mechanism. The six RTIL solvents and MeCN were saturated with BZA, and potential‐step chronoamperometry revealed diffusion coefficients of 170, 4.6, 3.2, 2.7, 1.8, 0.26 and 0.96 × 10^?11 m² s^?1 and solubilities of 850, 75, 78, 74, 220, 2850 and 48 mM in MeCN and the six ionic liquids, respectively, at 298 K. The high solubility of BZA in [C₄mim][NO₃] may suggest a strong interaction of the dissolved proton with the nitrate anion. Although there are relatively few literature reports of solubilities of organic solutes in RTILs at present, these results suggest the need for further studies on the solubilities of organic species (particularly acids) in RTILs, because of the contrasting interaction of dissolved species with the RTIL ions. Chronoamperometry is suggested as a convenient methodology for this purpose. Copyright © 2008 John Wiley & Sons, Ltd.