Room temperature ionic liquid as a novel medium for liquid/liquid extraction of metal ions

Room temperature ionic liquids (RTILs) have been used as novel solvents to replace traditional volatile organic solvents in organic synthesis, solvent extraction, and electrochemistry. The hydrophobic character and water immiscibility of certain ionic liquids allow their use in solvent extraction of hydrophobic compounds. In this work, a typical room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆], was used as an alternative solvent to study liquid/liquid extraction of heavy metal ions. Dithizone was employed as a metal chelator to form neutral metal-dithizone complexes with heavy metal ions to extract metal ions from aqueous solution into [C₄mim][PF₆]. This extraction is possible due to the high distribution ratios of the metal complexes between [C₄mim][PF₆] and aqueous phase. Since the distribution ratios of metal dithiozonates between [C₄mim][PF₆] and aqueous phase are strongly pH dependent, the extraction efficiencies of metal complexes can be manipulated by tailoring the pH value of the extraction system. Hence, the extraction, separation, and preconcentraction of heavy metal ions with the biphasic system of [C₄mim][PF₆] and aqueous phase can be achieved by controlling the pH value of the extraction system. Preliminary results indicate that the use of [C₄mim][PF₆] as an alternate solvent to replace traditional organic solvents in liquid/liquid extraction of heavy metal ions is very promising.     

Extraction and high performance liquid chromatographic determination of 3-indole butyric acid in pea plants by using imidazolium-based ionic liquids as extractant

In this paper, imidazolium-based ionic liquids [C₄mim][PF₆], [C₆mim][PF₆], [C₈mim][PF₆], [C₆mim][BF₄] and [C₈mim][BF₄] were tested as extracting solvents for removal of 3-indole butyric acid (IBA) from aqueous media with subsequent determination using HPLC. Percent extraction of IBA was strongly affected by pH of aqueous phases and the chemical structures of ionic liquids (ILs). Extraction of IBA was quantitative in the pH values lower than pK_a of IBA. Considering both extraction and stripping efficiencies of IBA, [C₄mim][PF₆] was found to act more efficient than other studied ILs. Capacity of [C₄mim][PF₆] was 17.6 × 10⁻⁴ mmol IBA per 1.0 mL of IL. Ionic strength of aqueous phase and temperature had shown no serious effects on extraction efficiency of IBA. A preconcentration factor of 100 and a relative standard deviation of 1.16% were obtained. It was found that ionic liquid phase was reusable almost five times for extraction/stripping purposes. 3-Indole acetic acid showed interferential effect in the extraction step. In order to assess the applicability of the method, extraction and stripping of IBA from pea plants and some other samples were studied.     

Determination of Triazines by Ultrasonic-Assisted Ionic Liquid Microextraction Coupled with High Performance Liquid Chromatography

The determination of triazine herbicides by ultrasonic‐assisted ionic liquid microextraction coupled with high‐performance liquid chromatography was described. 1‐Hexyl‐3‐methylimidazolium hexafluorophosphate ([C₆MIm][PF₆]) was used as the extraction solvent and some extraction parameters, including volume of [C₆MIm][PF₆], extraction temperature and time, salt concentration and pH values of sample solution, were examined and optimized. The isolation of the target compounds from the matrix was found to be efficient when triazines in 10 mL of sample solution was extracted with 100 µL of [C₆MIm][PF₆] for 40 min at 50°C. The detection limits for the triazine range from 0.36 to 1.41 µg·L^?1. The satisfactory recoveries (82.3% –120.3%) with relative standard deviations ≦10.1% were obtained for the four triazine herbicides from six kinds of practical water samples.     

A Novel Room Temperature Ionic Liquid Extraction Spectrophotometric Determination of Trace Germanium in Natural Water with Methybenzeneazosalicylfluorone

Abstract

This paper describes a highly sensitive and selective extraction spectrophotometric method for determination of trace germanium in natural water with new a chromogenic reagent methybenzeneazosalicylfluorone abbreviated as MBASF, in which a typical room temperature ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate abbreviated as [C₄mim][PF₆] was used as novel medium for liquid/liquid extraction of germanium(IV). In the presence of TritonX‐100, MBASF reacted with germanium(IV) to form a red complex rapidly, the complex was then extracted into the [C₄mim][PF₆] phase, the absorbance of the complex in ionic liquid at 496 nm was recorded and used to determine trace germanium(IV). The apparent molar absorptivity of the complex and the detection limit for the real sample were found to be 3.12×10⁶ L mol^?1 cm^?1 and 0.2 ng mL^?1, respectively. The absorbance of the complex at 496 nm increases linearly with the concentration up to 4 µg of germanium (IV) in 250 mL of aqueous solution. The interference study show the determination of germanium is free from the interference of almost all positive and negative ions found in the natural water samples. The determination of germanium in natural water was carried out by the present method and electrothermal atomic absorption spectrometry (AAS). The results were satisfactorily comparable so that the applicability of the proposed method was confirmed using the real samples. Moreover, the extraction mechanism with the ionic liquid system was also investigated. We think the extraction performance of the ionic liquid system is a combination of ion‐pairing effect between imidazolium cation and basic solute in the aqueous phase with the dissolution of polar molecule in ionic liquid phase. A wise choice of the appropriate combination of anion with imidazolium cation hydrophobicity allows playing with solute selectivity.     

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.     

Separation of no-carrier-added 109Cd from natural silver target using RTIL 1-butyl-3-methylimidazolium hexafluorophosphate

The room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆] has various applications in the separation of a range of metal ions replacing volatile and toxic traditional organic solvents in liquid–liquid extraction systems. In this study, the RTIL [C₄mim][PF₆] was used to separate no-carrier-added (NCA) ¹⁰⁹Cd from α-particle irradiated Ag target. A natural Ag foil was bombarded by 30 MeV α-particles to produce ¹⁰⁹Cd. After the decay of all co-produced short-lived products, NCA ¹⁰⁹Cd was separated from the bulk Ag using [C₄mim][PF₆] as extractant from HNO₃ medium. Ammoniumpyrrolidine dithiocarbamate (APDC) was used as a complexing agent. At the optimum condition, 3 M HNO₃, 0.01 M APDC in presence of [C₄mim][PF₆], ~99 % bulk Ag was extracted to the IL phase, leaving NCA ¹⁰⁹Cd in the aqueous phase. The amount of Ag became negligibly small after re-extraction in the same condition. The ionic liquid was recovered by washing it with 1 M HCl.     

Ionic liquids enhanced oil recovery from oily sludge-experiment and mechanism

The oily sludge would cause environment pollution, and would cause the heavy oil waste. Therefore, it was vital for us to find novel methods to obtain heavy oil from the oily sludges. In this study, the [C₁₂mim][PF₆] and [C₁₂mim][Br] ionic liquids(ILs) were used to enhance the oil recovery. The toluene could obtain the highest oil recovery, and both the two ILs could increase the oil recovery. Toluene could obtain the highest oil recovery (89.4 wt%), and n-octane could obtain the lowest oil recovery (76.8 wt%). [C₁₂mim] [PF₆] could efficiently increase the heavy oil recovery to 91.2 wt%(by toluene). The [C₁₂mim][Br] could increase the heavy oil recovery further. Both the [C₁₂mim] [PF₆] and the [C₁₂mim][Br] ionic liquids could increase the heavy ois C/H ratio, decrease heavy oil viscosity and increase the sands hydrophilicity. The [C₁₂mim][Br] ionic liquids showed better effect. In addition, the ionic liquids could increase the solvents recovery, and the ionic liquids recovery were high. Therefore, the ionic liquids enhanced oil recovery could be recycled to ten times. The two ionic liquids could effectively decrease the heavy oil interaction force, and when the ionic liquids increased to 200 ppm, the force remained stable. In the end, the ionic liquids enhancing solvent extraction mechanism was put forward.     

Ionic liquid-based single-drop liquid-phase microextraction combined with high-performance liquid chromatography for the determination of sulfonamides in environmental water

A simple, rapid and environment‐friendly technique of single‐drop liquid‐phase microextraction has been developed for the determination of sulfonamides in environmental water. Several important parameters including stirring rate, extraction solvent, extraction pH, salinity and extraction time were optimized to maximize the extract efficiency. Extraction solvent 1‐octyl‐3‐methylimidazolium hexafluorophosphate [C₈MIM][PF₆] ionic liquid showed better extraction efficiency than 1‐butyl‐3‐methylimidazolium hexafluorophosphate [C₄MIM][PF₆] and 1‐octanol. The optimum experimental conditions were: pH, 4.5; sodium chloride content, 36% w/v; extraction time, 20 min. This method provided low detection limits (0.5–1 ng/mL), good repeatability (the RSD ranging from 4.2 to 9.9%, n=5) and wide linear range (1–1500 ng/mL), with determination coefficients (r²) higher than 0.9989 for all the target compounds. Real sample analysis showed relative recoveries between 63.5 and 115.8% for all the target compounds.     

Effect of Ionic Liquid Anion Type in the Performance of Solid Polymer Electrolytes Based on Poly(Vinylidene fluoride‐trifluoroethylene)

The effect of different anions within the ionic liquid in the characteristics of solid polymer electrolytes (SPEs) based on P(VDF‐TrFE) has been investigated. 1‐ethyl‐3‐methylimidazolium acetate, [C₂mim][OAc], 1‐ethyl‐3‐methylimidazolium triflate, [C₂mim][(CF₃SO₃)], 1‐ethyl‐3‐methylimidazolium lactate, [C₂mim][Lactate], 1‐ethyl‐3‐methylimidazolium thiocyanate, [C₂mim][SNC] and 1‐ethyl‐3‐methylimidazolium hydrogen sulfate [C₂mim][HSO₄] have been used in SPE prepared by solvent casting. The polymer phase, thermal and electrochemical properties of the SPE have been determined. The thermal and electrical properties of the SPEs strongly depend on the selected IL, as determined by their different interactions with the polymer matrix. The room temperature ionic conductivity increases in the following way for the different anions: [SNC]>[CF₃SO₃)]>[HSO₄]>[Lactate]>[OAc], which is mainly dependent on the viscosity of the ionic liquid.     

Insights into the Mechanism of Extraction of Uranium (VI) from Nitric Acid Solution into an Ionic Liquid by using Tri‐n‐butyl phosphate

We present new results on the liquid–liquid extraction of uranium (VI) from a nitric acid aqueous phase into a tri‐n‐butyl phosphate/1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (TBP/[C₄mim][Tf₂N]) phase. The individual solubilities of the ionic‐liquid ions in the upper part of the biphasic system are measured over the whole acidic range and as a function of the TBP concentration. New insights into the extraction mechanism are obtained through the in situ characterization of the extracted uranyl complexes by coupling UV/Vis and extended X‐ray absorption fine structure (EXAFS) spectroscopy. We propose a chemical model to explain uranium (VI) extraction that describes the data through a fit of the uranyl distribution ratio D_U. In this model, at low acid concentrations uranium (VI) is extracted as the cationic complex [UO₂(TBP)₂]²⁺, by an exchange with one proton and one C₄mim⁺. At high acid concentrations, the extraction proceeds through a cationic exchange between [UO₂(NO₃)(HNO₃)(TBP)₂]⁺ and one C₄mim⁺. As a consequence of this mechanism, the variation of D_U as a function of TBP concentration depends on the C₄mim⁺ concentration in the aqueous phase. This explains why noninteger values are often derived by analysis of D_U versus [TBP] plots to determine the number of TBP molecules involved in the extraction of uranyl in an ionic‐liquid phase.     

Ultrasound assisted ionic liquid dispersive liquid phase extraction of lovastatin and simvastatin: A new pretreatment procedure

A fast and novel sample preparation procedure: ultrasound assisted ionic liquid (IL) dispersive liquid extraction for the concentration of lovastatin and simvastatin in aqueous samples was developed. An IL ([C₆MIM][PF₆]) was used as the extraction solvent, and the factors affecting the extraction efficiency such as initial temperature, the volume of IL, pH of water samples, cooling time, and salt concentration were optimized. In combination with HPLC‐UV, both lovastatin and simvastatin exhibited a good linear range of 1–100 ng/mL. The limits of detection (LODs) of lovastatin and simvastatin were 0.17 and 0.29 ng/mL, respectively. Precisions of the proposed method (RSDs, n = 9) were 4.12 and 4.52%, respectively. This method has been successfully applied for the analysis of target compounds in three real water samples and good spiking recoveries were obtained in the range of 90.0–102.2% for lovastatin and 80.5–112.0% for simvastatin. These results indicated that ultrasound assisted IL dispersive liquid phase extraction would have good application prospect in the pretreatment of environmental samples.     

Comparison of two ultrasound‐enhanced microextractions combined with HPLC for determining acaricides in water

An ultrasound‐enhanced in situ solvent formation microextraction has been developed first time and compared with ultrasound‐enhanced ionic‐liquid‐assisted dispersive liquid–liquid microextraction for the HPLC analysis of acaricides in environmental water samples. A ionic liquid ([C₈MIM][PF₆]) was used as the green extraction solvent through two pathways. The experimental parameters, such as the type and volume of both of the extraction solvent disperser solvent, ultrasonication time, and salt addition, were investigated and optimized. The analytical performance using the optimized conditions proved the feasibility of the developed methods for the quantitation of trace levels of acaricides by obtaining limits of detection that range from 0.54 to 3.68 μg/L. The in situ solvent formation microextraction method possesses more positive characteristics than the ionic‐liquid‐assisted dispersive liquid–liquid microextraction method (except for spirodiclofen determination) when comparing the validation parameters. Both methods were successfully applied to determining acaricides in real water samples.     

Ionic liquid for single‐drop microextraction followed by high‐performance liquid chromatography‐ultraviolet detection to determine carbonyl compounds in environmental waters

A sensitive method based on ionic liquid for single‐drop liquid microextraction coupled with HPLC‐UV was developed for the determination of carbonyl compounds in environmental waters using 1‐octyl‐3‐methylimidazolium hexafluorophosphate [C₈min][PF₆] as extraction solvent and 2,4‐dinitrophenylhydrazine as derivatizing agent. The extraction parameters affecting the enrichment factors such as solvent volume, pH, extraction time and salt concentration were investigated. A homemade funnel form polytetrafluoroethylene sleeve was fixed at the tip of the syringe needle and this allowed the use of 10 μL drop of ionic liquid for direct immersion extraction. Under the optimal conditions, the remarkable enrichment factors up to 150‐fold were obtained depending on the target analytes. The method has been validated when rectilinear relationship was obtained between the concentrations of analytes and peak area in the range of 5–100 ng/mL, the correlation coefficients were from 0.995 to 0.998, and the limit of detection was in the range of 0.04–2.03 ng/mL. The method was applied to monitor the concentration of carbonyl compounds in environmental waters with spiked recovery in the range of 84.2–106.9%.     

Isolation and purification of alkaloids from the fruits of Macleaya cordata by ionic‐liquid‐modified high‐speed counter‐current chromatography

Macleaya cordata (Willd) R. Br. is a medicinal plant. The most important bioactive compounds of M. cordata are alkaloids that have many biological activities including antifungal, anti‐inflammatory, and antitumor. In this study, an ionic‐liquid‐modified high‐speed counter‐current chromatography method was established to obtain alkaloids from the fruits of M. cordata. The conditions of ionic‐liquid‐modified high‐speed counter‐current chromatography, including solvent systems, the content of ionic liquid (1‐butyl‐3‐methylimidazolium tetrafluoroborate [C₄mim][BF₄]), and the posttreatment of the ionic liquid, were investigated. Five alkaloids protopine, allocryptopine, sanguinarine, 8‐O‐demethylchelerythrine, and chelerythrine were separated from the extract of the fruits using a high speed counter‐current chromatography with two‐phase solvent system composed of dichloromethane/methanol/0.3 mol/L hydrochloric acid aqueous solution/[C₄mim][BF₄] (4:2:2:0.015, v/v). Their purities were 96.33, 95.56, 97.94, 96.22, and 97.90%, respectively. The results indicated that a small amount of ionic liquids as modifier of the two‐phase solvent system could shorten the separation time and improve the separation efficiency of the alkaloids from the fruits. The ionic‐liquid‐modified high‐speed counter‐current chromatography would provide a feasible way for highly effective separation of alkaloids from natural products.     

Temperature‐controlled ionic liquid dispersive liquid‐phase microextraction combined with HPLC with ultraviolet detector for the determination of fungicides

Present study described a simple, environmental benign, easy to operate, and determination method for fungicides including thiram, metalaxyl, diethofencarb, myclobutanil, and tebuconazole. The method is based on temperature‐controlled ionic liquid dispersive liquid phase microextraction coupled to HPLC with ultraviolet detector. In the enrichment procedure, ionic liquid 1‐octyl‐3‐methylimidazolium hexafluorophosphate [C₈MIM][PF₆] was used as the extraction solvent. Variable affecting parameters such as the volume of [C₈MIM][PF₆], temperature, extraction time, centrifuging time, and salting‐out effect have been optimized in detail. Under the optimal conditions, this method has been found to have good linear relationship in the concentration range of 1.0–100 μg/L and excellent detection sensitivity with LODs (S/N = 3) in the range of 0.32–0.79 μg/L. Precisions of proposed method were in the range of 3.7–5.9% for intraday and 7.8–11.0% for interday (RSDs, n = 6). The proposed method was used for the analysis of real water samples and good spiked recoveries at two different spiked levels were achieved in the range of 84.6–102%.     

Ionic liquids extraction of Para Red and Sudan dyes from chilli powder, chilli oil and food additive combined with high performance liquid chromatography

A simple analytical method, based on the coupling of ionic liquid-based extraction with high performance liquid chromatography (HPLC), is developed for the determination of Sudan dyes (I, II, III and IV) and Para Red in chilli powder, chilli oil and food additive samples. Two ionic liquids (ILs), 1-butyl-3-methylimidazolium hexafluorophosphate ([C₄mim][PF₆]) and 1-octyl-3-methylimidazolium hexafluorophosphate ([C₈mim][PF₆]), were compared as extraction solvents; experiments indicated that the latter possesses higher recoveries for each analyte. Parameters related to extraction of Sudan dyes and Para Red were also optimized. Under the optimal conditions, good reproducibility of extraction performance was obtained, with the relative standard deviation (RSD) values ranging from 2.0% to 3.5%. The detection limits of Sudan dyes and Para Red (LOD, S/N = 3) were in the range of 7.0-8.2 μg kg⁻¹ for chilli powder and 11.2-13.2 μg L⁻¹ for chilli oil and food additive. The recoveries were in the range of 76.8-109.5% for chilli powder samples and 70.7-107.8% for chilli oil and food additive samples.     

[C12mim]Br: A Temperature‐dependent Phase Transfer Catalyst and Its Application for Aerobic Oxidative Synthesis of 2‐Aryl Benzimidazoles,Benzoxazoles or Benzothiozoles Catalyzed by TEMPO Based Ionic Liquid

The application of [C₁₂mim]Br ionic liquid/o‐xylene temperature‐dependent biphasic system into the [Imim‐TEMPO][Cl]/O₂‐promoted condensation between o‐phenylenediamines, o‐aminophenol or o‐aminothiophenol with aldehydes for preparing benzimidazoles, benzoxazoles or benzothiozoles is described. Several aldehydes and o‐phenylenediamines, o‐aminophenol or o‐aminothiophenol were reacted efficiently to form corresponding products in excellent yields. Both the [Imim‐TEMPO][Cl] and [C₁₂mim]Br could be reused at least eight times without significantly decreasing the catalytic activity.     

A practical synthesis of 2‐aminobenzothiazoles via copper(I)‐catalyzed tandem reaction of 2‐iodoanilines with isothiocyanates in ionic liquids

A copper(I)‐catalyzed tandem reaction of 2‐iodoanilines with isothiocyanates was achieved in hydrophobic [bmim][PF₆] ionic liquid under mild conditions, generating a variety of 2‐aminobenzothiazoles in good to excellent yields. The tandem reaction that was carried out in [bmim][PF₆] has some obvious advantages such as accelerated reaction rate and increased yield as compared with the reaction run in volatile solvents such as toluene. Furthermore, the CuI/1,10‐phenanthroline catalytic system can be reused up to eight times without loss of activity and efficiency. Copyright © 2016 John Wiley & Sons, Ltd.     

Reverse ATRP Process of Methacrylonitrile in [C4mim][PF6]

In this original experiment, an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C₄mim][PF₆]), was used as the reaction media for reverse atom transfer radical polymerization of methacrylonitrile (MAN) initiated by azobisisobutyronitrile (AIBN) with FeCl₃ and isophthalic acid (IA) as catalyst and ligand. The polymerization in [C₄mim][PF₆] proceeded in a well-controlled manner as evidenced by kinetic studies. Compared with the polymerization in N, N-dimethylformamide (DMF), the polymerization in [C₄mim][PF₆] not only showed better control of molecular weight and narrower molecular weight distribution but also provided more rapid reaction rate with the ratio of [MAN]:[AIBN]:[FeCl₃]:[IA] at 300:1:2:4. The block copolymer PMAN-b-PSt was obtained via a conventional ATRP process in [C₄mim][PF₆] by using the resulting PMAN as macroinitiator. [C₄mim][PF₆] and FeCl₃/IA could be easily recycled and reused and had no effect on the living nature of reverse atom transfer radical polymerization of MAN.     

Liquid–liquid equilibrium and interfacial tension of the ternary system heptane + thiophene + 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide

The liquid–liquid equilibrium (LLE) of the ternary system comprising heptane, thiophene and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C₂mim][NTf₂]) was determined at 25 °C and atmospheric pressure, for preliminary evaluation of the potential of this ionic liquid as solvent for the desulfurisation of transportation fuels. Classical parameters such as solute distribution ratio and selectivity were calculated from the LLE data and subsequently analysed. The LLE data were also correlated by means of the ‘Non-Random Two-Liquid’ (NRTL) equation. Besides the LLE, another critical property for the design of extraction processes, namely the interfacial tension, was determined in parallel, throughout the immiscibility domain of the ternary system. For the first time, the LLE and the interfacial tension of a ternary system involving an ionic liquid are jointly reported.