Ionic liquid‐based dispersive liquid–liquid microextraction followed by RP‐HPLC determination of saquinavir in rat serum: application to pharmacokinetics

An ionic liquid‐based dispersive liquid–liquid microextraction followed by RP‐HPLC determination of the most commonly prescribed protease inhibitor, saquinavir, in rat plasma was developed and validated. The effects of different ionic liquids, dispersive solvents, extractant/disperser ratio and salt concentration on sample recovery and enrichment were studied. Among the ionic liquids investigated, 1‐butyl‐3‐methylimidazolium hexafluorophosphate was found to be most effective for extraction of saquinavir from rat serum. The recovery was found to be 95% at an extractant/disperser ratio of 0.43 using 1‐butyl‐3‐methylimidazolium hexafluorophosphate and methanol as extraction and dispersive solvents. The recovery was further enhanced to 99.5% by addition of 5.0% NaCl. A threefold enhancement in detection and quantification limits was achieved, at 0.01 and 0.03 µg/mL, compared with the conventional protein precipitation method. A linear relationship was observed in the range of 0.035–10.0 µg/mL with a correlation coefficient (r²) of 0.9996. The method was validated and applied to study pharmacokinetics of saquinavir in rat serum. Copyright © 2014 John Wiley & Sons, Ltd.     

Highly Sensitive Electrochemiluminescent Insecticide Sensor Based on ZnO Nanocrystals Anchored Nickel Foam for Determination of Imidacloprid in Real Samples

In this work, a novel electrochemiluminescent (ECL) pesticide sensor based on zinc oxide nanocrystals decorated nickel foam is proposed for determination of imidacloprid for the first time. The silica film was used as a morphology‐controlling factor for modification of the electrode with zinc oxide nanocrystals. Zinc oxide was selected as luminescent material due to its cheapness, non‐toxicity, high thermal stability and excellent luminescence properties which truly adhered on the surface of nickel foam. The K₂S₂O₈ was used as strong co‐reactant for this purpose. The silica template plays an important role in controlling the size of ZnO nanocrystals. The Physical morphology of the ZnO/Ni‐foam electrode was performed by electrochemical impedance spectroscopy, Brunauer‐Emmett‐Teller (BET), X‐Ray diffraction analysis, field emission scanning electron microscopy, and energy‐dispersive X‐ray analysis. The ultra‐sensitive electrochemiluminescence method was successfully used for ultra‐trace determination of imidacloprid. The linear dynamic range and low detection limit were obtained 3×10^?14 ?8×10^?8 M and 4.4×10^?15 M, respectively. Also, the relative standard deviation for 15 repetitive optical signals was calculated 1.09 %.The present ECL sensor exhibited superior performance toward the accurate determination of imidacloprid with good reproducibility and stability.     

Solid-Phase Extraction of Caffeine and Theophylline from Green Tea by a New Ionic Liquid-Modified Functional Polymer Sorbent

The new ionic liquid-modified polymer sorbent was developed by surface chemical modification of the synthesized polymer particles using ionic liquids. The obtained ionic liquid-modified polymer was successfully used as a special sorbent in a solid-phase extraction (SPE) process to isolate caffeine and theophylline from green tea. A comparison of different SPE cartridges using the blank polymer, C₁₈, and ionic liquid-modified polymer revealed that the highest recovery was obtained using ionic liquid-modified polymer sorbent. Quantitative analysis was carried out by using a C₁₈ column (5 µm, 150 × 4.6 mm) as an analytical column. Good linearity was obtained from 5 × 10^?4 to 0.5 mg/mL (r²>0.999) for the two analytes with relative standard deviations <4.5%.     

Polymerization of the new double‐charged monomer bis‐1,3(N,N,N‐trimethylammonium dicyanamide)‐2‐propylmethacrylate and ionic conductivity of the novel polyelectrolytes

The achievement of high ionic conductivity in single‐ion conducting polymer electrolytes is one of the important aims for various electrochemical devices including modern lithium batteries. One way to enhance the ionic conductivity in polyelectrolyte systems is to increase the quantity of charge carriers in each monomer unit. Highly charged poly(bis‐1,3(N,N,N‐trimethylammonium)‐2‐propylmethacrylate) with one of the most conducting anions, namely dicyanamide, was prepared via free radical bulk polymerization or using ionic liquids as reaction medium. The cationic polymers of the double‐charged monomer have molar masses up to = 1,830,000 g/mol and the ionic conductivity equal to 5.51 × 10^?5 S / cm at 25°C. The film forming ability, crystallinity, thermal stability, and glass transition temperatures of the new polymeric ionic liquids obtained from detailed studies are presented. Copyright © 2009 John Wiley & Sons, Ltd.     

Application of anion‐exchange imidazolium silica for the multiphase dispersive extraction of phenolic acids

This paper reports the application of a multiphase dispersive extraction method to the extraction, separation, and determination of the phenolic acids from Salicornia herbacea L. using silica‐confined ionic liquids as sorbents. A suitable sorbent for phenolic acid extraction and separation was first identified based on the adsorption behavior of the phenolic acids on different silica‐confined ionic liquids. The sample was then mixed with the optimized sorbent and solvent to achieve multiphase dispersive extraction. The sample/sorbent ratio was optimized using theoretical calculations from the adsorption isotherm and experiments. After transferring the supernatant to an empty cartridge, an SPE process was used to separate the three phenolic acids from the other interference. Through systematic optimization, the optimal conditions produced high recovery rates of protocatechuic acid (91.20%), caffeic acid (94.03%), and ferulic acid (91.33%). Overall, the proposed method is expected to have wide applicability.     

Preparation of ionic liquid/silica nanocomposites possessing no weight loss characteristic after calcination at 800 °C

Tetraethoxysilane reacted with silica nanoparticles in the presence of a variety of ionic liquids such as phosphonium-, ammonium-, and imidazolium-type ionic liquids under alkaline conditions to afford the corresponding ionic liquid/silica nanocomposites with a good dispersibility and stability in numerous solvents. It was demonstrated that these ionic liquid nanocomposites can be classified into the nanocomposites possessing no weight loss and weight loss characteristics after calcination at 800 °C, respectively, according to the ionic liquid structures in the composites. The ionic liquids except for 1-ethyl-3-methylimidazolium hydrogen sulfate were found to afford the corresponding ionic liquid/silica nanocomposites possessing no weight loss characteristic even after calcination at 800 °C.

A novel polymer gel electrolyte: Direct polymerization of ionic liquid from surface of silica nanoparticles

A novel polymer electrolyte is synthesized by directly grafting poly ionic liquids onto silica nanoparticles. The kinetic study of this surface‐initiated polymerization has also been included. A gel‐state electrolyte is formed by mixing this type of polymer/silica nanocomposite with ionic liquids under 60 °C, which exhibits an excellent conductivity of 0.8 mS/cm at room temperature and 14.7 mS/cm at 90 °C. In addition, the mechanism of gel formation has also been discussed in this article. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 121–127     

Fabrication of Superoxide Dismutase (SOD) Imprinted Poly(ionic liquid)s via eATRP and its Application in Electrochemical Sensor

Superoxide dismutase (SOD) plays an important role in nearly all living cells. In this study, SOD imprinted poly(ionic liquid)s (SIPILs) were prepared on the surface of the bare Au electrode modified with nano‐palladium and nano‐gold (Au/nPd/nAu/SIPILs). SIPILs was synthesized with 1‐vinyl‐3‐propyl imidazole sulfonate ionic liquids as functional monomers via electrochemically mediated atom transfer radical polymerization (eATRP) catalyzed by SOD. The Au/nPd/nAu/SIPILs was examined by cyclic voltammetry (CV), scanning electron microscope (SEM), energy‐dispersive spectrometer (EDS) and X‐ray photoelectron spectroscopy (XPS). The Au/nPd/nAu/SIPILs was also used as an electrochemical sensor to determine SOD by differential pulse voltammetry (DPV). Under the optimal conditions, the detection range of SOD was from 1.0×10^?8 to 1.0×10² mg L^?1 with a limit of detection of 8.90×10^?9 mg L^?1 (S/N=3). Compared with other methods, the sensor based on SIPILs had the broader linear range and lower detection limit.     

以N为中心的阴离子离子液体的合成、表征及应用

首次通过不同阴离子的钾盐和不同的季铵化的咪唑,吡咯溴盐/氯盐进行离子交换,合成了一系列含氰基官能团的阴离子功能化离子液体。通过红外、核磁共振、质谱对离子液体的结构进行表征;通过TGA对离子液体的热稳定性进行测定,结果发现功能化离子液体具有良好的热稳定性,其分解温度在224-289℃范围内。将功能化离子液体[EMIm][N(CN)COC2H5]作为配体应用于无膦配体的Suzuki偶联反应,发现在反应中加入功能化离子液体[EMIm][N(CN)COC2H5]可以使反应收率提高10-20%。     

Porous texture of silica aerogels made with ionic liquids as gelation catalysts

The effect of four ionic liquids on the porous texture of silica aerogels synthesized from mixed tetramethoxysilane and methyltrimethoxysilane and dried by the CO₂ supercritical method, was studied. Two of these ionic liquids were composed of BF₄ ⁻ anions while the other two included Cl⁻ anions. The synthesis of gels from ionic liquids did not require another acidic catalyst for silica hydrolysis, nor a basic catalyst for silica condensation. These aerogels were compared with traditional aerogels made according to a double step catalysis, which first involved hydrolysis with HCl followed by condensation with pH 9 Tris HCl buffer. Gel mass analysis and thermogravimetric data showed that, when the initial molar of ionic liquid to Si was 1.58, only ~2% (by mass) of the initial ionic liquids consisting of BF₄ ⁻ anions and ~10% (by mass) of ionic liquids containing Cl⁻ anions, remained in the aerogels after supercritical drying. Moreover, X-ray diffraction confirmed that in ionic liquids based on BF₄ ⁻ anions, evaporation of the volatile components before supercritical CO₂ drying led to the formation of regularly ordered mesopores.     

Design of guanidinium ionic liquid based microwave‐assisted extraction for the efficient extraction of Praeruptorin A from Radix peucedani

A series of novel tetramethylguanidinium ionic liquids and hexaalkylguanidinium ionic liquids have been synthesized based on 1,1,3,3‐tetramethylguanidine. The structures of the ionic liquids were confirmed by ¹H NMR spectroscopy and mass spectrometry. A green guanidinium ionic liquid based microwave‐assisted extraction method has been developed with these guanidinium ionic liquids for the effective extraction of Praeruptorin A from Radix peucedani. After extraction, reversed‐phase high‐performance liquid chromatography with UV detection was employed for the analysis of Praeruptorin A. Several significant operating parameters were systematically optimized by single‐factor and L₉ (3⁴) orthogonal array experiments. The amount of Praeruptorin A extracted by [1,1,3,3‐tetramethylguanidine]CH₂CH(OH)COOH is the highest, reaching 11.05 ± 0.13 mg/g. Guanidinium ionic liquid based microwave‐assisted extraction presents unique advantages in Praeruptorin A extraction compared with guanidinium ionic liquid based maceration extraction, guanidinium ionic liquid based heat reflux extraction and guanidinium ionic liquid based ultrasound‐assisted extraction. The precision, stability, and repeatability of the process were investigated. The mechanisms of guanidinium ionic liquid based microwave‐assisted extraction were researched by scanning electron microscopy and IR spectroscopy. All the results show that guanidinium ionic liquid based microwave‐assisted extraction has a huge potential in the extraction of bioactive compounds from complex samples.     

Ionic IPNs as novel candidates for highly conductive solid polymer electrolytes

Five ionic imidazolium based monomers, namely 1‐vinyl‐3‐ethylimidazolium bis(trifluoromethylsulfonyl)imide (ILM1), 1‐vinyl‐3‐(diethoxyphosphinyl)‐propylimidazolium bis(trifluoromethylsulfonyl)imide (ILM2), 1‐[2‐(2‐methyl‐acryloyloxy)‐propyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM3), 1‐[2‐(2‐methyl‐acryloyloxy)‐undecyl]‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (ILM4), 1‐vinyl‐3‐ethylimidazolium dicyanamide (ILM5) were prepared and used for the synthesis of linear polymeric ionic liquids (PILs), crosslinked networks with polyethyleneglycol dimethacrylate (PEGDM) and interpenetrating polymer networks (IPNs) based on polybutadiene (PB). The ionic conductivities of IPNs prepared using an in situ strategy were found to depend on the ILM nature, T_g and the ratio of the other components. Novel ionic IPNs are characterized by increased flexibility, small swelling ability in ionic liquids (ILs) along with high conductivity and preservation of mechanical stability even in a swollen state. The maximum conductivity for a pure IPN was equal to 3.6 × 10^?5 S/cm at 20 °C while for IPN swollen in [1‐Me‐3‐Etim] (CN)₂N σ reached 8.5 × 10^?3 S/cm at 20 °C or 1.4 × 10^?2 S/cm at 50 °C. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4245–4266, 2009     

Chemical and thermal stability of N‐heterocyclic ionic liquids in catalytic C–H activation reactions

¹H‐NMR spectrum analyses are applied to study the chemical and thermal stability of selected N‐heterocyclic ionic liquids within the reaction system that can highly efficiently activate a C–H bond of methane and convert it into the C–O bond in methanol. Our results indicate that under such reaction conditions involving using a powerful Pt‐based catalyst and strong acidic solvent, the aromatic ring of an imidazolium cation becomes unstable generating an ammonium ion (NH₄⁺). Our results also suggest that the instability of the imidazolium ring is more chemically (participation in reactions) than thermally based. Modifications of the aromatic ring structure such as pyrazolium and triazolium cations can increase the chemical/thermal stability of ionic liquids under these reaction conditions. Copyright © 2014 John Wiley & Sons, Ltd.     

Solubilization of fullerene into ionic liquids by the use of fluoroalkyl end‐capped oligomers

Fluoroalkyl end‐capped oligomers were solubilized into a variety of ionic liquids such as N‐methylpyrazolium tetrafluoroborate, 3‐methylpyrazolium tetrafluoroborate and 1‐butyl‐3‐methylimidazolium hexafluorophosphate, and these fluorinated oligomers were able to reduce the surface tension of these ionic liquids. Interestingly, these fluorinated oligomers were able to solubilize fullerene into ionic liquids effectively. Fluoroalkyl end‐capped fullerene co‐oligomers, which were prepared by the oligomerizations of fluoroalkanoyl peroxides with radical polymerizable monomers such as acryloylmorpholine in the presence of fullerene, were more effective in solubilizing fullerene into ionic liquids compared to the corresponding fluoroalkyl end‐capped homo‐oligomers possessing no fullerene units. Fluoroalkyl end‐capped fullerene co‐oligomers/fullerene/ionic liquid complexes thus obtained were applied to the arrangements of fullerenes above the poly(methyl methacrylate) (PMMA) surface, and the higher fluorescent intensity of fullerene was obtained in the modified PMMA surface, although the reverse side of this modified film surface afforded an extremely weak fluorescent intensity. Copyright © 2005 John Wiley & Sons, Ltd.     

Preparation,characterisation and modification of carbon‐based monolithic rods for chromatographic applications

A range of porous carbon‐based monolithic (PCM) rods with flow‐through pore sizes of 1, 2, 5 and 10 μm, were produced using a silica particle template method. The rods were characterised using SEM and energy‐dispersive X‐ray spectroscopy, BET surface area and porous structure analysis, dilatometry and thermal gravimetry. SEM evaluation of the carbon monolithic structures revealed an interconnected rigid bimodal porous structure and energy‐dispersive X‐ray spectroscopy analysis verified the quantitative removal of the embedded silica beads. The specific surface areas of the 1, 2, 5 and 10 μm rods were 178, 154, 84 and 125 m²/g after pyrolysis and silica removal, respectively. Shrinkage of the monolithic rods during pyrolysis is proportional to the particle size of the silica used and ranged from 9 to 12%. Mercury porosimetry showed a narrow distribution of pore sizes, with an average of ～700 nm for the 1 μm carbon monolith. The suitability of bare and surface oxidised PCM rods for the use as a stationary phase for reversed and normal phase LC was explored. The additional modification of PCM rods with gold micro‐particles followed by 6‐mercaptohexanoic acid was performed and ion‐exchange properties were evaluated.     

Preparation and applications of novel fluoroalkyl end‐capped oligomers/polyimide/silica nanocomposites

Fluoroalkyl end‐capped acrylic acid, N,N‐dimethylacrylamide, N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide and vinyltrimethoxysilane oligomers reacted with polyamic acid possessing trimethoxysilyl groups under alkaline conditions to yield the corresponding fluoroalkyl end‐capped oligomers/polyamic acid/silica nanocomposites. These isolated fluorinated composite powders were found to afford nanometer size‐controlled fine particles with a good dispersibility and stability in water and traditional organic solvents. We succeeded in preparing new fluoroalkyl end‐capped oligomers/polyimide/silica nanocomposites by the imidization of fluorinated polyamic acid silica nanocomposites through the stepwise heating at 110 and 270°C under air atmosphere conditions. These fluorinated polyimide/silica nanocomposites thus obtained were applied to the surface modification of glass and poly(methyl methacrylate) (PMMA) to exhibit good hydro‐ and oleo‐phobic characteristics imparted by fluoroalkyl groups in the composites on their surface. In addition, the surface morphology of the modified glass treated with these fluorinated nanocomposites were analyzed by using FE‐SEM and DFM. Copyright © 2011 John Wiley & Sons, Ltd.     

Mass Distribution and Diffusion of [1‐Butyl‐3‐methylimidazolium][Y] Ionic Liquids Adsorbed on the Graphite Surface at 300–800 K

The structure and diffusion behavior of 1‐butyl‐3‐methylimidazolium ([bmim]⁺) ionic liquids with [Cl]^?, [PF₆]^?, and [Tf₂N]^? counterions near a hydrophobic graphite surface are investigated by molecular dynamics simulation over the temperature range of 300–800 K. Near the graphite surface the structure of the ionic liquid differs from that in the bulk and it forms a well‐ordered region extending over 30 Å from the surface. The bottom layer of the ionic liquid is stable over the investigated temperature range due to the inherent slow dynamics of the ionic liquid and the strong Coulombic interactions between cation and anion. In the bottom layer, diffusion is strongly anisotropic and predominantly occurs along the graphite surface. Diffusion perpendicular to the interface (interfacial mass transfer rate k_t) is very slow due to strong ion–substrate interaction. The diffusion behaviors of the three ionic liquids in the two directions all follow an Arrhenius relation, and the activation barrier increases with decreasing anion size. Such an Arrhenius relation is applied to surface‐adsorbed ionic liquids for the first time. The ion size and the surface electrical charge density of the anions are the major factors determining the diffusion behavior of the ionic liquid adjacent to the graphite surface.     

Adding magnetic ionic liquid monomers to the emulsion polymerization tool‐box: Towards polymer latexes and coatings with new properties

Magnetic ionic liquid monomers were synthesized and then polymerized to get magnetic polymer latexes and films. First, a series of 1‐vinyl‐3‐dodecyl‐imidazolium monomers having metal halides counter‐anions such as FeCl₃Br^?, CoCl₂Br^?, and MnCl₂Br^? were synthesized. These ionic liquid monomers were first homopolymerized to lead to magnetic poly(ionic liquids) and characterized. Secondly, magnetic latexes were synthesized by using the magnetic ionic liquids as surfmers (surfactant + monomer) in the emulsion polymerization of methyl methacrylate/n‐butyl acrylate. It was found that the powders obtained by freeze‐drying the latexes presented a paramagnetic behavior with weak antiferromagnetic interactions between the adjacent metal ions. Although the ratio of magnetic ionic liquid/monomer was only 2% these poly(methyl methacrylate‐co‐butyl acrylate) powders and latexes responded to a magnetic field due to the surfmer paramagnetic nature. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1145–1152     

Microwave‐assisted preparation of poly(ionic liquids)‐modified magnetic nanoparticles for pesticide extraction

Novel poly(ionic liquids) were synthesized and immobilized on prepared magnetic nanoparticles, which were used to extract pesticides from fruit and vegetable samples by dispersive solid‐phase extraction prior to high‐performance liquid chromatography analysis. Compared with monomeric ionic liquids, poly(ionic liquids) have a larger effective contact area and higher viscosity, so they can achieve higher extraction efficiency and be used repeatedly without a decrease in analyte recovery. The immobilized poly(ionic liquids) were rapidly separated from the sample matrix, providing a simple approach for sample pretreatment. The nature and volume of the desorption solvent and amount of poly(ionic liquid)‐modified magnetic material were optimized for the extraction process. Under optimum conditions, calibration curves were linear (R² > 0.9988) for pesticide concentrations in the range of 0.100–10.000 μg/L. The relative standard deviations for repeated determinations of the four analytes were 2.29–3.31%. The limits of detection and quantification were 0.29–0.88 and 0.97–2.93 μg/L, respectively. Our results demonstrate that the developed poly(ionic liquid)‐modified material is an effective absorbent to extract pesticides from fruit and vegetable samples.     

含氰基基团的以C为中心的不对称阴离子离子液体的合成、表征及应用

首次通过不对称阴离子的钠盐/钾盐和不同的季胺化的咪唑,吡咯溴盐/氯盐进行离子交换,合成了一系列含氰基官能团的不对称阴离子功能化离子液体。通过红外、核磁共振、质谱和元素分析对离子液体的结构进行表征;通过TGA对离子液体的热稳定性进行测定,结果发现不对称功能化离子液体具有良好的热稳定性,其分解温度在219-319℃范围内。将功能化离子液体[Bmim][C(CN)2COCH3]作为弱配体应用于模型的Suzuki偶联反应,发现在反应中加入功能化离子液体[Bmim][C(CN)2COCH3]可以使反应收率提高10-15%。