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Sample records for based ionic liquid

  1. Phosphonium-based ionic liquids and uses

    SciTech Connect

    Del Sesto, Rico E; Koppisch, Andrew T; Lovejoy, Katherine S; Purdy, Geraldine M

    2014-12-30

    Phosphonium-based room temperature ionic liquids ("RTILs") were prepared. They were used as matrices for Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry and also for preparing samples of dyes for analysis.

  2. Ionic Vapor Composition in Pyridinium-Based Ionic Liquids.

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-05-26

    Strong electrostatic interactions in ionic compounds make vaporization a complex process. The gas phase can contain a broad range of ionic clusters, and the cluster composition can differ greatly from that in the liquid phase. Room-temperature ionic liquids (RTILs) constitute a complicated case due to their ionic nature, asymmetric structure, and a huge versatility of ions and ionic clusters. This work reports vapor-liquid equilibria and vapor compositions of butylpyridinium (BPY) RTILs formed with hexafluorophosphate (PF6), trifluoromethanesulfonate (TF), and bis(trifluoromethanesulfonyl)imide (TFSI) anions. Unlike inorganic crystals, the pyridinium-based RTILs contain significant percentages of charged clusters in the vapor phase. Ion triplets and ion quadruplets each constitute up to 10% of the vapor phase composition. Triples prevail over quadruples in [BPY][PF6] due to the size difference of the cation and the anion. The percentage of charged ionic clusters in the gas phase is in inverse proportion to the mass of the anion. The largest identified vaporized ionic cluster comprises eight ions, with a formation probability below 1%. Higher temperature fosters formation of larger clusters due to an increase of the saturated vapor density. PMID:27165866

  3. New triazolium based ionic liquid crystals

    SciTech Connect

    Stappert, Kathrin; Unal, Derya; Mallick, Bert; Mudring, Anja-Verena

    2014-01-01

    A set of novel 1,2,3-triazolium based ionic liquid crystals was synthesized and their mesomorphic behaviour studied by DSC (differential scanning calorimetry), POM (polarizing optical microscopy) and SAXS (small angle X-ray scattering). Beside the variation of the chain length (C10, C12 and C14) at the 1,2,3-triazolium cation also the anion has been varied (Br-, I-, I3-, BF4-, SbF6-, N(CN)2-, Tf2N-) to study the influence of ion size, symmetry and H-bonding capability on the mesophase formation. Interestingly, for the 1,3-didodecyl-1,2,3-triazolium cation two totally different conformations were found in the crystal structure of the bromide (U-shaped) and the triiodide (rod shaped).

  4. Ionic conductivity studies of gel polyelectrolyte based on ionic liquid

    NASA Astrophysics Data System (ADS)

    Cha, E. H.; Lim, S. A.; Park, J. H.; Kim, D. W.; Macfarlane, D. R.

    Novel lithium polyelectrolyte-ionic liquids have been prepared and characterized of their properties. Poly(lithium 2-acrylamido-2-methyl propanesulfonate) (PAMPSLi) and its copolymer with N-vinyl formamide (VF) also has been prepared as a copolymer. 1-Ethyl-3-methylimidazolium tricyanomethanide (emImTCM) and N, N-dimethyl- N-propyl- N-butyl ammonium tricyanomethanide (N 1134TCM) which are chosen because of the same with the anion of ionic liquid were prepared. The ionic conductivity of copolymer system (PAMPSLi/PVF/emImTCM: 5.43 × 10 -3 S cm -1 at 25 °C) exhibits about over four times higher than that of homopolymer system (PAMPSLi/emImTCM: 1.28 × 10 -3 S cm -1 at 25 °C). Introduction of vinyl formamide into the copolymer type can increase the dissociation of the lithium cations from the polymer backbone. The ionic conductivity of copolymer with emImTCM (PAMPSLi/PVF/emImTCM) exhibits the higher conductivity than that of PAMPSLi/PVF/N 1134TCM (2.48 × 10 -3 S cm -1). Because of using the polymerizable anion it is seen to maintain high flexibility of imidazolium cation effectively to exhibit the higher conductivity. And also the viscosity of emImTCM (19.56 cP) is lower than that of N 1134TCM (28.61 cP). Low viscosity leads to a fast rate of diffusion of redox species.

  5. Ionic liquid based multifunctional double network gel

    NASA Astrophysics Data System (ADS)

    Ahmed, Kumkum; Higashihara, Tomoya; Arafune, Hiroyuki; Kamijo, Toshio; Morinaga, Takashi; Sato, Takaya; Furukawa, Hidemitsu

    2015-04-01

    Gels are a promising class of soft and wet materials with diverse application in tissue engineering and bio-medical purpose. In order to accelerate the development of gels, it is required to synthesize multi-functional gels of high mechanical strength, ultra low surface friction and suitable elastic modulus with a variety of methods and new materials. Among many types of gel ionic gel made from ionic liquids (ILs) could be used for diverse applications in electrochemical devices and in the field of tribology. IL, a promising materials for lubrication, is a salt with a melting point lower than 100 °C. As a lubricant, ILs are characterized by an extremely low vapor pressure, high thermal stability and high ion conductivity. In this work a novel approach of making double network DN ionic gel using IL has been made utilizing photo polymerization process. A hydrophobic monomer Methyl methacrylate (MMA) has been used as a first network and a hydrophobic IL monomer, N,N-diethyl-N-(2-mthacryloylethyl)-N-methylammonium bistrifluoromethylsulfonyl)imide (DEMM-TFSI) has been used as a second network using photo initiator benzophenon and crosslinker triethylene glycol dimethacrylate (TEGDMA). The resulting DN ionic gel shows transparency, flexibility, high thermal stability, good mechanical toughness and low friction coefficient value which can be a potential candidate as a gel slider in different mechanical devices and can open a new area in the field of gel tribology.

  6. Magnetic microemulsions based on magnetic ionic liquids.

    PubMed

    Klee, Andreas; Prevost, Sylvain; Kunz, Werner; Schweins, Ralf; Kiefer, Klaus; Gradzielski, Michael

    2012-11-28

    Microemulsions with magnetic properties were formed by employing a magnetic room temperature ionic liquid (MRTIL) as polar phase, cyclohexane as oil, and an appropriate mixture of ionic surfactant and decanol as a cosurfactant. By means of small-angle neutron scattering (SANS) and electric conductivity the microemulsion structure could be confirmed, where the classical structural sequence of oil-continuous-bicontinuous-polar phase continuous is observed with increasing ratio [polar phase]/[oil]. Accordingly a maximum of the structural size is observed at about equal volumes of oil and MRTIL contained. Therefore this system is structurally the same as normal microemulsions but with the magnetic properties added to it by the incorporation into the systems formulation. PMID:23060241

  7. Extraction of proteins with ionic liquid aqueous two-phase system based on guanidine ionic liquid.

    PubMed

    Zeng, Qun; Wang, Yuzhi; Li, Na; Huang, Xiu; Ding, Xueqin; Lin, Xiao; Huang, Songyun; Liu, Xiaojie

    2013-11-15

    Eight kinds of green ionic liquids were synthesized, and an ionic liquid aqueous two-phase system (ILATPS) based on 1,1,3,3-tetramethylguandine acrylate (TMGA) guanidine ionic liquid was first time studied for the extraction of proteins. Single factor experiments proved that the extraction efficiency of bovine serum albumin (BSA) was influenced by the mass of IL, K2HPO4 and BSA, also related to the separation time and temperature. The optimum conditions were determined through orthogonal experiment by the five factors described above. The results showed that under the optimum conditions, the extraction efficiency could reach up to 99.6243%. The relative standard deviations (RSD) of extraction efficiencies in precision experiment, repeatability experiment and stability experiment were 0.8156% (n=5), 1.6173% (n=5) and 1.6292% (n=5), respectively. UV-vis and FT-IR spectra confirmed that there were no chemical interactions between BSA and ionic liquid in the extraction process, and the conformation of the protein was not changed after extraction. The conductivity, DLS and TEM were combined to investigate the microstructure of the top phase and the possible mechanism for the extraction. The results showed that hydrophobic interaction, hydrogen bonding interaction and the salt out effect played important roles in the transferring process, and the aggregation and embrace phenomenon was the main driving force for the separation. All these results proved that guanidine ionic liquid-based ATPSs have the potential to offer new possibility in the extraction of proteins. PMID:24148423

  8. Morphology and charge transport in ammonium based polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Heres, Maximilian; Minutolo, Joseph; Shamblin, Jacob; Long, Maik; Berdzinski, Stefan; Stremel, Veronika; Sangoro, Joshua

    2015-03-01

    Ionic conduction, structural dynamics and morphology in a series of ammonium based polymerized ionic liquids are investigated using broadband dielectric spectroscopy, temperature-modulated differential scanning calorimetry, and neutron as well as x-ray scattering techniques. The dielectric spectra are dominated on the low frequency regime by electrode polarization while hopping conduction is the underlying mechanism at higher frequencies. At their respective calorimetric glass transition temperatures, a strong correlation between the morphology and ionic conductivity is found. These results are discussed within the recent approaches proposed to explain the decoupling of charge transport from structural dynamics. UT/ORNL Science Alliance.

  9. Thermophysical properties of phosphonium-based ionic liquids

    PubMed Central

    Bhattacharjee, Arijit; Lopes-da-Silva, José A.; Freire, Mara G.; Coutinho, João A. P.; Carvalho, Pedro J.

    2015-01-01

    Experimental data for density, viscosity, refractive index and surface tension of four phosphonium-based ionic liquids were measured in the temperature range between (288.15 and 353.15) K and at atmospheric pressure. The ionic liquids considered include tri(isobutyl) methylphosphonium tosylate, [Pi(444)1][Tos], tri(butyl)methylphosphonium methylsulfate, [P4441][CH3SO4], tri(butyl)ethylphosphonium diethylphosphate, [P4442][(C2H5O)2PO2], and tetraoctylphosphonium bromide, [P8888][Br]. Additionally, derivative properties, such as the isobaric thermal expansion coefficient, the surface thermodynamic properties and the critical temperatures for the investigated ionic liquids were also estimated and are presented and discussed. Group contribution methods were evaluated and fitted to the density, viscosity and refractive index experimental data. PMID:26435574

  10. Sulfonium-based Ionic Liquids Incorporating the Allyl Functionality

    PubMed Central

    Zhao, Dongbin; Fei, Zhaofu; Ang, Wee Han; Dyson, Paul J.

    2007-01-01

    A series of sulfonium halides bearing allyl groups have been prepared and characterized. Anion metathesis with Li[Tf2N] and Ag[N(CN)2] resulted in sulfonium-based ionic liquids which exhibit low viscosities at room temperature. The solid state structure of one of the halide salts was determined by single crystal X-ray diffraction.

  11. A New Volume-Based Approach for Predicting Thermophysical Behavior of Ionic Liquids and Ionic Liquid Crystals.

    PubMed

    Nelyubina, Yulia V; Shaplov, Alexander S; Lozinskaya, Elena I; Buzin, Mikhail I; Vygodskii, Yakov S

    2016-08-17

    Volume-based prediction of melting points and other properties of ionic liquids (ILs) relies on empirical relations with volumes of ions in these low-melting organic salts. Here we report an accurate way to ionic volumes by Bader's partitioning of electron densities from X-ray diffraction obtained via a simple database approach. For a series of 1-tetradecyl-3-methylimidazolium salts, the volumes of different anions are found to correlate linearly with melting points; larger anions giving lower-melting ILs. The volume-based concept is transferred to ionic liquid crystals (ILs that adopt liquid crystalline mesophases, ILCs) for predicting the domain of their existence from the knowledge of their constituents. For 1-alkyl-3-methylimidazolium ILCs, linear correlations of ionic volumes with the occurrence of LC mesophase and its stability are revealed, thus paving the way to rational design of ILCs by combining suitably sized ions. PMID:27479022

  12. Thermoreversible (Ionic-Liquid-Based) Aqueous Biphasic Systems

    PubMed Central

    Passos, Helena; Luís, Andreia; Coutinho, João A. P.; Freire, Mara G.

    2016-01-01

    The ability to induce reversible phase transitions between homogeneous solutions and biphasic liquid-liquid systems, at pre-defined and suitable operating temperatures, is of crucial relevance in the design of separation processes. Ionic-liquid-based aqueous biphasic systems (IL-based ABS) have demonstrated superior performance as alternative extraction platforms, and their thermoreversible behaviour is here disclosed by the use of protic ILs. The applicability of the temperature-induced phase switching is further demonstrated with the complete extraction of two value-added proteins, achieved in a single-step. It is shown that these temperature-induced mono(bi)phasic systems are significantly more versatile than classical liquid-liquid systems which are constrained by their critical temperatures. IL-based ABS allow to work in a wide range of temperatures and compositions which can be tailored to fit the requirements of a given separation process. PMID:26843320

  13. Thermoreversible (Ionic-Liquid-Based) Aqueous Biphasic Systems

    NASA Astrophysics Data System (ADS)

    Passos, Helena; Luís, Andreia; Coutinho, João A. P.; Freire, Mara G.

    2016-02-01

    The ability to induce reversible phase transitions between homogeneous solutions and biphasic liquid-liquid systems, at pre-defined and suitable operating temperatures, is of crucial relevance in the design of separation processes. Ionic-liquid-based aqueous biphasic systems (IL-based ABS) have demonstrated superior performance as alternative extraction platforms, and their thermoreversible behaviour is here disclosed by the use of protic ILs. The applicability of the temperature-induced phase switching is further demonstrated with the complete extraction of two value-added proteins, achieved in a single-step. It is shown that these temperature-induced mono(bi)phasic systems are significantly more versatile than classical liquid-liquid systems which are constrained by their critical temperatures. IL-based ABS allow to work in a wide range of temperatures and compositions which can be tailored to fit the requirements of a given separation process.

  14. Fixed Junction Photovoltaic Devices Based On Polymerizable Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Limanek, Austin; Leger, Janelle, , Dr.

    Recently, polymer-based photovoltaic devices (PPVs) have received significant attention as a possible affordable, large area and flexible solar energy technology. In particular, research on chemically fixed p-i-n junctions in polymer photovoltaic devices has shown promising results. These devices are composed of ionic monomers in a polymer matrix sandwiched between two electrodes. When a potential is applied, the ionic monomers migrate towards their corresponding electrodes, enabling electrochemical doping of the polymer. This leads to the formation of bonds between the polymer and ionic monomers, resulting in the formation of a chemically fixed p-i-n junction. However, early devices suffered from long charging times and low overall response. This has been attributed to the low phase compatibility between the ionic monomers and the polymer. It has been shown for light-emitting electrochemical cells, replacing the ionic monomers with polymerizable ionic liquids (PILs) mitigates these challenges. We will present the use of PILs as the dopant in fixed junction PPV devices. Preliminary devices demonstrate significantly improved performance, decreased charging times, and high open circuit voltages. This research supported by the National Science Foundation DMR-1057209.

  15. Solvent extraction of rare-earth ions based on functionalized ionic liquids

    SciTech Connect

    Sun, Xiaoqi; Dai, Sheng; Luo, Huimin

    2012-01-01

    We herein report the achievement of enhanced extractabilities and selectivities for separation of rare earth elements based on functionalized ionic liquids. This work highlights the potential of developing a comprehensive ionic liquid-based extraction strategy for rare earth elements using ionic liquids as both extractant and diluent.

  16. Synthesis and Characterization of Tetramethylethylenediamine-Based Hypergolic Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Fei, Teng; Cai, Huiwu; Zhang, Yanqiang; Liu, Long; Zhang, Suojiang

    2016-04-01

    Four energetic salts (including two ionic liquids) based on 2-(dimethylamino)-N,N,N-trimethylethanaminium and N,N‧-dialkyl-N,N,N‧,N‧-tetramethylethane-1,2-diaminium was prepared and characterized by 1H- and 13C-NMR, infrared and Raman spectroscopies, and elemental analysis. Their physicochemical properties such as melting and decomposition temperatures, density, viscosity, heat of formation, detonation performance, and specific impulse were measured or calculated. With thermal stability up to 200°C, the resulting ionic liquids show densities from 1.02 to 1.19 g cm-3 and heats of formation from 85.1 to 154.4 kJ mol-1. Moreover, 2-(dimethylamino)-N,N,N-trimethylethanaminium dicyanamide is hypergolic with the oxidizer (100% HNO3) and exhibits potential as a green fuel for bipropellants.

  17. Carbon Dioxide and Ionic Liquid Refrigerants: Compact, Efficient Air Conditioning with Ionic Liquid-Based Refrigerants

    SciTech Connect

    2010-10-01

    BEETIT Project: Notre Dame is developing an air-conditioning system with a new ionic liquid and CO2 as the working fluid. Synthetic refrigerants used in air conditioning and refrigeration systems are potent GHGs and can trap 1,000 times more heat in the atmosphere than CO2 alone—making CO2 an attractive alternative for synthetic refrigerants in cooling systems. However, operating cooling systems with pure CO2 requires prohibitively high pressures and expensive hardware. Notre Dame is creating a new fluid made of CO2 and ionic liquid that enables the use of CO2 at low pressures and requires minimal changes to existing hardware and production lines. This new fluid also produces no harmful emissions and can improve the efficiency of air conditioning systems— enabling new use of CO2 as a refrigerant in cooling systems.

  18. Rheology of Imidazolium-Based Ionic Liquids with Aromatic Functionality.

    PubMed

    Tao, Ran; Simon, Sindee L

    2015-09-01

    A series of imidazolium-based ionic liquids with cyclic and aromatic groups and a bis[(trifluoromethane)sulfonyl]amide anion were characterized using dynamic and steady shear rheology in a wide temperature range. The cations investigated include 1-(cyclohexylmethyl)-3-methylimidazolium ([CyhmC1im](+)), 1-benzyl-3-methylimidazolium ([BnzC1im](+)), 1,3-dibenzylimidazolium ([(Bnz)2im](+)), and 1-(2-naphthylmethyl)-3-methylimidazolium ([NapmC1im](+)). Rheological properties are reported from terminal flow to the glassy state. All ionic liquids show very similar flow behavior with a glassy modulus approaching 1 GPa. The temperature dependences of the shift factors used for time-temperature superposition and the viscosity both follow the same VFT or WLF relationship, and the dynamic fragility at Tg ranges from 117 to 130 for the aromatic ionic liquids investigated, considerably more fragile, in the Angell sense, than the aliphatic analogs. Additionally, an anomalous aging effect in the dynamic viscosity response (i.e., a maximum observed at intermediate frequencies) was found using a strain-controlled rheometer but not using a stress-controlled rheometer. PMID:26230926

  19. Novel polymer electrolytes based on gelatin and ionic liquids

    NASA Astrophysics Data System (ADS)

    Leones, Rita; Sentanin, F.; Rodrigues, Luísa C.; Ferreira, Rute A. S.; Marrucho, Isabel M.; Esperança, José M. S. S.; Pawlicka, Agnieszka; Carlos, Luís D.; Manuela Silva, M.

    2012-12-01

    This study describes the results of the characterization of polymer electrolytes using gelatin matrix doped with europium triflate and/or different ionic liquids. Samples of solvent-free electrolytes were prepared and characterized by ionic conductivity measurements, thermal analysis, electrochemical stability, X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence spectroscopy. Electrolyte samples are thermally stable up to approximately 220 °C. All the materials synthesized are totally amorphous. The room temperature conductivity maximum of this electrolyte system is based on ionic liquid 1-ethyl-3-methylimidazolium acetate, (C2mim)(OAc) (1.18 × 10-4 S cm-1 at 30 °C). The electrochemical stability domain of all samples is about 2.0 V versus Li/Li+. This new series of materials represents a promising alternative in polymer electrolytes research field. The preliminary studies carried out with electrochromic devices (ECDs) incorporating optimized compositions have confirmed that these materials may perform as satisfactory multifunctional component layers in the field of "smart windows". This new materials, will open a land of promising applications in many areas: optics, energy, medicine for example as membranes and separation devices, ECD-based devices, sensors, etc.

  20. Rapid Preparation of Silsesquioxane-Based Ionic Liquids.

    PubMed

    Li, Liguo; Liu, Hongzhi

    2016-03-24

    Three new hybrid ionic liquids (ILs) based on cage silsesquioxane (SQ) were rapidly prepared in high yields from octa(mercaptopropyl)silsesquioxane and 1-allyl-3-methylimidazolium salts (Br(-) , BF4 (-) , PF6 (-) ) through the photochemical thiol-ene reaction. These SQ-based ILs exhibited low glass transition temperatures and good thermal stability. The unique amphiphilic nature of these hybrid ILs cause them to self-assemble into perfect vesicles with "yolk-shell" structures, in which cages formed the "yolk" due to their aggregation and outer anions formed the "shell". PMID:26864313

  1. Novel thiosalicylate-based ionic liquids for heavy metal extractions.

    PubMed

    Leyma, Raphlin; Platzer, Sonja; Jirsa, Franz; Kandioller, Wolfgang; Krachler, Regina; Keppler, Bernhard K

    2016-08-15

    This study aims to develop novel ammonium and phosphonium ionic liquids (ILs) with thiosalicylate (TS) derivatives as anions and evaluate their extracting efficiencies towards heavy metals in aqueous solutions. Six ILs were synthesized, characterized, and investigated for their extracting efficacies for cadmium, copper, and zinc. Liquid-liquid extractions of Cu, Zn, or Cd with ILs after 1-24h using model solutions (pH 7; 0.1M CaCl2) were assessed using flame atomic absorption spectroscopy (F-AAS). Phosphonium-based ILs trihexyltetradecylphosphonium 2-(propylthio)benzoate [P66614][PTB] and 2-(benzylthio)benzoate [P66614][BTB] showed best extraction efficiency for copper and cadmium, respectively and zinc was extracted to a high degree by [P66614][BTB] exclusively. PMID:27131456

  2. Ionic Liquids Database- (ILThermo)

    National Institute of Standards and Technology Data Gateway

    SRD 147 Ionic Liquids Database- (ILThermo) (Web, free access)   IUPAC Ionic Liquids Database, ILThermo, is a free web research tool that allows users worldwide to access an up-to-date data collection from the publications on experimental investigations of thermodynamic, and transport properties of ionic liquids as well as binary and ternary mixtures containing ionic liquids.

  3. Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors

    PubMed Central

    Behera, Kamalakanta; Pandey, Shubha; Kadyan, Anu; Pandey, Siddharth

    2015-01-01

    Due to their unusual physicochemical properties (e.g., high thermal stability, low volatility, high intrinsic conductivity, wide electrochemical windows and good solvating ability), ionic liquids have shown immense application potential in many research areas. Applications of ionic liquid in developing various sensors, especially for the sensing of biomolecules, such as nucleic acids, proteins and enzymes, gas sensing and sensing of various important ions, among other chemosensing platforms, are currently being explored by researchers worldwide. The use of ionic liquids for the detection of carbon dioxide (CO2) gas is currently a major topic of research due to the associated importance of this gas with daily human life. This review focuses on the application of ionic liquids in optical and electrochemical CO2 sensors. The design, mechanism, sensitivity and detection limit of each type of sensor are highlighted in this review. PMID:26690155

  4. Low-melting mixtures based on choline ionic liquids.

    PubMed

    Rengstl, Doris; Fischer, Veronika; Kunz, Werner

    2014-11-01

    In this article a strategy is proposed for the design of low toxic, room temperature liquid low-melting mixtures (LMMs) which are entirely composed of natural materials. From literature it is well known that, in general, deep eutectic solvents based on choline chloride and dicarboxylic acids are LMMs, but not liquids at room temperature, with one exception: a 1 : 1 molar mixture of malonic acid and choline chloride. Therefore, the starting point of this study was the decrease of the melting point of one of the components, namely the dicarboxylic acid, which is succinic, glutaric or adipic acid. For this purpose, one of the two protons of the acidic group was exchanged by a bulky unsymmetrical choline cation. The resulting ionic liquids (ILs) were still solid at room temperature, but have a reduced melting temperature compared to the corresponding acids. In the second step, mixtures of these ILs with choline chloride were prepared. It turned out that choline glutarate-choline chloride mixtures are liquids at room temperature at compositions containing 95-98 wt% of choline glutarate. Finally, urea was added as another hydrogen bond donor. Density, conductivity and viscosity measurements were performed for all obtained mixtures. Moreover, a Walden plot was drawn which indicates that all mixtures are liquids with fully dissociated ions moving independently. Therefore, they are considered as "good" ionic liquids and, thus, for example they can be used to exchange more toxic or less biodegradable ILs in application processes. A brief outlook containing application possibilities is given. It is demonstrated that choline dodecylsulfate is readily soluble in these mixtures, forming aggregates in the LMM at temperatures exceeding 55 °C. PMID:25242504

  5. Gelatin-ionic liquid based platform for glucose detection.

    PubMed

    Sharma, Anshu; Rawat, Kamla; Solanki, Pratima R; Bohidar, H B

    2015-01-01

    Herein, we have fabricated a novel platform consisting of gelatin B in ionic liquid [1-ethyl- 3-methylimidazolium chloride [C2mim][Cl] (ionic liquid, IL)] formed ionogels (Ig) by dissolution method and used it for glucose detection. The ionogels were deposited onto indium tin oxide (ITO) coated glass plate using drop casting technique. Glucose oxidase (GOx) was selected as a model enzyme to investigate its interaction with Ig/ITO electrode using electrochemical and optical methods. Structural and morphological studies of the Ig/ITO electrode were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy and cyclic voltmmetry before and after GOx immobilization. It was found that [C2mim][Cl] enhanced electrocatalytic behaviour of the fabricated electrode which provided electron transfer rate constant as Ks ≈ 0.113 s(-1). Response study of GOx/Ig/ITO bioelectrode as a function of glucose concentration was monitored. These gelatin-ionic liquid based bioelectrodes showed following results obtained from electrochemical technique linearity ≈ 1-20 mM, and low value of Michaelis-Menten constant, Km ≈ 0.174 mM with sensitivity ≈ 4.6µA mM(-1) cm(-2). In contrast, the optical detection of glucose exhibited linearity in the range of 6-20 mM, value of Km ≈ 3.8 mM with sensitivity 6.76 x 10(-3) Abs/mM cm(2). This clearly indicated that the prepared ionogel based electrodes will provide a promising platform for glucose detection. PMID:25858131

  6. Imidazolium-based ionic liquids grafted on solid surfaces.

    PubMed

    Xin, Bingwei; Hao, Jingcheng

    2014-01-01

    Supported ionic liquids (SILs), which refer to ionic liquids (ILs) immobilized on supports, are among the most important derivatives of ILs. The immobilization process of ILs can transfer their desired properties to substrates. Combination of the advantages of ILs with those of support materials will derive novel performances while retaining properties of both moieties. SILs have been widely applied in almost all of fields involving ILs, and have brought about drastic expansion of the ionic liquid area. As green media in organic catalytic reactions, based on utilizing the ability of ILs to stabilize the catalysts, they have many advantages over free ILs, including avoiding the leaching of ILs, reducing their amount, and improving the recoverability and reusability of both themselves and catalysts. This has critical significance from both environmental and economical points of view. As novel functional materials in surface science and material chemistry, SILs are ideal surface modifying agents. They can modify and improve the properties of solids, such as wettability, lubricating property, separation efficiency and electrochemical response. With the achievements in the field of ILs, using magnetic nanoparticles (MNPs) to SILs has drawn increasing attention in catalytic reactions and separation technologies, and achieved substantial progress. The combination of MNPs and ILs renders magnetic SILs, which exhibit the unique properties of ILs as well as facile separation by an external magnetic field. In this article, we focus on imidazolium-based ILs covalently grafted to non-porous and porous inorganic materials. The excellent stability and durability of this kind of SILs offer a great advantage compared with free ILs and IL films physically adsorbed on substrates without covalent bonds. Including examples from our own research, we overview mainly the applications and achievements of covalent-linked SILs in catalytic reactions, surface modification, separation

  7. Picosecond time-resolved fluorescence study on solute-solvent interaction of 2-aminoquinoline in room-temperature ionic liquids: aromaticity of imidazolium-based ionic liquids.

    PubMed

    Iwata, Koichi; Kakita, Minoru; Hamaguchi, Hiro-o

    2007-05-10

    Time-resolved fluorescence spectra and fluorescence anisotropy decay of 2-aminoquinoline (2AQ) have been measured in eight room-temperature ionic liquids, including five imidazolium-based aromatic ionic liquids and three nonaromatic ionic liquids. The same experiments have also been carried out in several ordinary molecular liquids for comparison. The observed time-resolved fluorescence spectra indicate the formation of pi-pi aromatic complexes of 2AQ in some of the aromatic ionic liquids but not in the nonaromatic ionic liquids. The fluorescence anisotropy decay data show unusually slow rotational diffusion of 2AQ in the aromatic ionic liquids, suggesting the formation of solute-solvent complexes. The probe 2AQ molecule is likely to be incorporated in the possible local structure of ionic liquids, and hence the anisotropy decays only through the rotation of the whole local structure, making the apparent rotational diffusion of 2AQ slow. The rotational diffusion time decreases rapidly by adding a small amount of acetonitrile to the solution. This observation is interpreted in terms of the local structure formation in the aromatic ionic liquids and its destruction by acetonitrile. No unusual behavior upon addition of acetonitrile has been found for the nonaromatic ionic liquids. It is argued that the aromaticity of the imidazolium cation plays a key role in the local structure formation in imidazolium-based ionic liquids. PMID:17428083

  8. The Interactions between Imidazolium-Based Ionic Liquids and Stable Nitroxide Radical Species: A Theoretical Study.

    PubMed

    Zhang, Shaoze; Wang, Guimin; Lu, Yunxiang; Zhu, Weiliang; Peng, Changjun; Liu, Honglai

    2016-08-01

    In this work, the interactions between imidazolium-based ionic liquids and some stable radicals based on 2,2,6,6-tetramethylpiperidine-1-yloxyl (TEMPO) have been systematically investigated using density functional theory calculations at the level of M06-2x. Several different substitutions, such as hydrogen bonding formation substituent (OH) and ionic substituents (N(CH3)3(+) and OSO3(-)), are presented at the 4-position of the spin probe, which leads to additional hydrogen bonds or ionic interactions between these substitutions and ionic liquids. The interactions in the systems of the radicals containing ionic substitutions with ionic liquids are predicted much stronger than those in the systems of neutral radicals, resulting in a significant reduction of the mobility of ionic radicals in ionic liquids. To further understand the nature of these interactions, the natural bond order, atoms in molecules, noncovalent interaction index, electron density difference, energy decomposition analysis, and charge decomposition analysis schemes were employed. The additional ionic interactions between ionic radicals and counterions in ionic liquids are dominantly contributed from the electrostatic term, while the orbital interaction plays a major role in other interactions. The results reported herein are important to understand radical processes in ionic liquids and will be very useful in the design of task-specific ionic liquids to make the processes more efficient. PMID:27428048

  9. Separation of Fission Products Based on Ionic Liquids: Anion Effect

    SciTech Connect

    Luo, Huimin; Dai, Sheng; Bonnesen, Peter V.

    2004-03-28

    The applications of ionic liquids (ILs) as new separation media have been actively investigated recently. The most commonly studied class of ILs for such applications is based on dialkyl imidazolium cations. In comparison with conventional molecular solvents, ILs exhibit enhanced distribution coefficients for a number of complexing neutral ligands in extraction of metal ions from aqueous solutions. The effect of the alkyl chain length of imidazolium cations on the distribution coefficients of solvent extraction using crown ethers was the subject of a number of the previous investigations. The distribution coefficients have been found to decrease with the alkyl chain length of the IL cations. This observation implies that the extraction process also involves the exchange of the IL cations with metal ions. The longer the alkyl chain lengths of the IL cations are, the more hydrophobic the IL cations are and the more difficult to be transported into aqueous phases via ion exchange. Accordingly, the ion-exchange process is another unique property of IL-based extractions involving charged species. Here, we report the investigation about the effect of the variation of IL anions on the solvent extraction of metal ions using crown ethers as extractants. The elucidation of different solvation effects involved in ionic liquids could lead to optimized separation media for these novel solvents.

  10. Mixed ionic liquids: the case of pyridinium-based fluids.

    PubMed

    Aparicio, Santiago; Atilhan, Mert

    2012-03-01

    We report in this work a combined experimental and computational study on the molecular level structuring of binary ionic liquid mixtures comprising pyridium cations. The effect of anions on liquid structure was analyzed from the mixing (mixture 1) of [b3mpy][BF(4)] and [b3mpy][N(CN)(2)] ionic liquids, in the full composition range, leading to [b3mpy][BF(4)](x)[N(CN)(2)](1-x) mixed ionic liquids. The effect of the length of alkylic chains in cations was studied with mixtures (mixture 2) of [b3mpy][BF(4)] and [o3mpy][BF(4)] ionic liquids, also studied in the full composition range, leading to [b3mpy](x)[o3mpy](1-x)[BF(4)] ionic liquids. Fourier transform infrared-attenuated total reflection spectra were recorded and analyzed as a function of anionic and cationic composition for the two studied mixture types. Classical molecular dynamics simulations were also performed for mixtures 1 and 2 as a function of anionic and cationic composition. The reported experimental and computational results show that the properties of the studied mixed systems change in an almost linear way, leading to almost ideal mixtures from the thermodynamic viewpoint, and thus pointing to simple dilution effects of the involved ions controlling the mixture properties. PMID:22309042

  11. Amphiphilic behavior of two phosphonium based ionic liquids.

    PubMed

    Mukherjee, Indrajyoti; Mukherjee, Suvasree; Naskar, Bappaditya; Ghosh, Soumen; Moulik, Satya P

    2013-04-01

    Solution and surface chemical behavior of two phosphonium based ionic liquids triisobutyl (methyl) phosphonium tosylate (IL-1) and trihexyl (tetradecyl) phosphonium bis 2,4,4-(trimethylpentyl)phosphinate (IL-2) have been studied. The polar IL-1 is surface active and water soluble, whereas the weakly polar IL-2 is more surface active with very low aqueous solubility. IL-1 does not form micelles but affects the micellization properties of ionic, nonionic, and zwitterionic surfactants more strongly than conventional electrolytes. IL-2 itself forms micelles and mixed micelles with Triton X-100 (TX-100) in aqueous solution. It also forms Langmuir monolayers of liquid expanded type, at the air/water interface. IL-1 can replace water in forming microemulsions with the oil isopropylmyristate (IPM), stabilized by IL-2 (surfactant)+isopropanol (IP as a co-surfactant) like the IL-1/IPM/(IL-2+IP) system. It produces a large monophasic zone in the pseudoternary phase diagram. The thermodynamics of formation of the microemulsions of IL-1 in oil (IPM) have been examined. The dimensions and the polydispersity of the dispersed nano-droplets in the microemulsions have been determined by DLS. The thermal stability of the microemulsion forming systems has also been studied. ILs studied against Sarcoma-180 cell lines have evidenced proficient anti-cancer activity of IL-1 and moderate activity of IL-2. PMID:23317771

  12. Synthesis and Characterization of Thiazolium-Based Room Temperature Ionic Liquids for Gas Separations

    SciTech Connect

    Hillesheim, PC; Mahurin, SM; Fulvio, PF; Yeary, JS; Oyola, Y; Jiang, DE; Dai, S

    2012-09-05

    A series of novel thiazolium-bis(triflamide) based ionic liquids has been synthesized and characterized. Physicochemical properties of the ionic liquids such as thermal stability, phase transitions, and infrared spectra were analyzed and compared to the imidazolium-based congeners. Several unique classes of ancillary substitutions are examined with respect to impacts on overall structure, in addition to their carbon dioxide absorption properties in supported ionic-liquid membranes for gas separation.

  13. Cyanoborohydride-based ionic liquids as green aerospace bipropellant fuels.

    PubMed

    Zhang, Qinghua; Yin, Ping; Zhang, Jiaheng; Shreeve, Jean'ne M

    2014-06-01

    In propellant systems, the most common bipropellants are composed of two chemicals, a fuel (or reducer) and an oxidizer. Currently, the choices for propellant fuels rely mainly on hydrazine and its methylated derivatives, even though they are extremely toxic, highly volatile, sensitive to adiabatic compression (risk of detonation), and, therefore, difficult to handle. With this background, the search for alternative green propellant fuels has been an urgent goal of space science. In this study, a new family of cyanoborohydride-based ionic liquids (ILs) with properties and performances comparable to hydrazine derivatives were designed and synthesized. These new ILs as bipropellant fuels, have some unique advantages including negligible vapor pressure, ultra-short ignition delay (ID) time, and reduced synthetic and storage costs, thereby showing great application potential as environmentally friendly fuels in bipropellant formulations. PMID:24737218

  14. Ionic liquid-based green processes for energy production.

    PubMed

    Zhang, Suojiang; Sun, Jian; Zhang, Xiaochun; Xin, Jiayu; Miao, Qingqing; Wang, Jianji

    2014-11-21

    To mitigate the growing pressure on resource depletion and environment degradation, the development of green processes for the production of renewable energy is highly required. As a class of novel and promising media, ionic liquids (ILs) have shown infusive potential applications in energy production. Aiming to offer a critical overview regarding the new challenges and opportunities of ILs for developing green processes of renewable energy, this article emphasises the role of ILs as catalysts, solvents, or electrolytes in three broadly interesting energy production processes from renewable resources, such as CO2 conversion to fuels and fuel additives, biomass pretreatment and conversion to biofuels, as well as solar energy and energy storage. It is expected that this article will stimulate a generation of new ideas and new technologies in IL-based renewable energy production. PMID:24553494

  15. NMR Characterization of Ionicity and Transport Properties for a Series of Diethylmethylamine Based Protic Ionic Liquids.

    PubMed

    Davidowski, Stephen K; Thompson, Forrest; Huang, Wei; Hasani, Mohammad; Amin, Samrat A; Angell, C Austen; Yarger, Jeffery L

    2016-05-12

    The ionicity and transport properties of a series of diethylmethylamine (DEMA) based protic ionic liquids (PILs) were characterized, principally utilizing nuclear magnetic resonance (NMR) spectroscopy. PILs were formed via the protonation of DEMA by an array of acids spanning a large range of acidities. A correlation between the (1)H chemical shift of the exchangeable proton and the acidity of the acid used for the synthesis of the PIL was observed. The gas phase proton affinity of the acid was found to be a better predictor of the extent of proton transfer than the commonly used aqueous ΔpKa. Pulsed field gradient (PFG) NMR was used to determine the diffusivity of the exchangeable proton in a subset of the PILs. The exchangeable proton diffuses with the acid if the PIL is synthesized with a weak acid, and with the base if a strong acid is used. The ionicity of the PILs was characterized using the Walden analysis and by comparing to the ideal Nernst-Einstein conductivity predicted from the (1)H PFG-NMR results. PMID:27088704

  16. Development of ionic gels using thiol-based monomers in ionic liquid

    NASA Astrophysics Data System (ADS)

    Ahmed, Kumkum; Naga, Naofumi; Kawakami, Masaru; Furukawa, Hidemitsu

    2016-04-01

    Ionic gels (IGs) using ionic liquids (ILs) can propose diverse applications in the field of optics, sensors and separation have opened wide prospects in materials science. ILs have attracted remarkable interest for gel polymer electrolytes and batteries based on their useful properties such as non-volatility, non-flammability, a wide electrochemical window, high thermal stability and a high ionic conductivity. The formation of gel in IL media makes it possible to immobilize ILs within organic or inorganic matrices and to take advantage of their unique properties in the solid state, thus eliminating some shortcomings related to shaping and risk of leakage. In this work for the first time we used multifunctional thiol monomers having uniform structure and good compatibility with the IL of our interest. Therefore we focused on developing thiol monomer-based IGs using multifunctional thiol monomers and acrylate crosslinkers utilizing thiol-ene reaction between monomer and crosslinking molecules in an IL medium and characterize their physico-chemical properties like thermal, conductive, mechanical properties etc.. This work has been focused mainly to improve the mechanical strength of IGs and make prospects of IGs in tribology and lubricants.

  17. Acidic Ionic Liquids.

    PubMed

    Amarasekara, Ananda S

    2016-05-25

    Ionic liquid with acidic properties is an important branch in the wide ionic liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids, especially focusing on the developments in the last four years. The structural diversity and synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In addition, an unambiguous classification system for various types of acidic ionic liquids is presented in the introduction. The physical properties including acidity, thermo-physical properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids are covered in the next sections. The final section provides a comprehensive review on applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation, ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfurization of gasoline/diesel, metal processing, and metal electrodeposition. PMID:27175515

  18. Electrolytic Conductivity of Four Imidazolium-Based Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Calado, Marta S.; Diogo, João C. F.; Correia da Mata, José L.; Caetano, Fernando J. P.; Visak, Zoran P.; Fareleira, João M. N. A.

    2013-07-01

    In this article, electrolytic (ionic) conductivity measurements of four ionic liquids (ILs), namely, 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] imide ([Cmim][NTf]), 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([Cmim][OTf]), 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([Cmim][NTf]), and 1-ethyl-3-methylimidazolium ethyl sulfate ([Cmim][EtSO]) (ECOENG212), were performed in a temperature range of (288.15 to 333.15) K. [Cmim][NTf] was chosen to be a reference ionic liquid for several properties, including the electrolytic conductivity by the IUPAC Project 2002-005-1-100. For that reason, the measurements performed with that ionic liquid primarily serve the purpose to validate the instrumentation and the experimental procedure used in this work. The measurements were carried out using a complex impedance method, applying a novel electronic device designed and constructed for this purpose. The complete setup includes a Schott Instruments LF 913 T, used as a four-electrode conductivity cell, and a lock-in amplifier. The cell was calibrated using standard reference KCl aqueous solutions. The measurements of the impedance of the conductivity cell were carried out along a range of frequencies from (0.2 to 30) kHz, and the results were extrapolated to infinite frequency, in order to determine the electrolytic conductivity of the liquid samples. The results obtained for the ionic liquid [Cmim][NTf] were compared to reference data, and it was estimated that the overall uncertainty of the present results is better than 2 %. All the data obtained were compared with available literature data, and were analyzed and discussed in respect to the effect of temperature, cation alkyl chain length, and anion.

  19. Carbenes from ionic liquids.

    PubMed

    Hollóczki, Oldamur; Nyulászi, László

    2014-01-01

    In the last decade an explosive development has been observed in the fields of both ionic liquids (ILs) as potential chemically inert solvents with many possible technical applications, and N-heterocyclic carbenes (NHCs) as catalysts with superb performance. Since the cations of many ILs can be deprotonated by strong bases yielding NHCs, this two fields are inherently connected. It has only recently been recognized that some of the commonly used basic anions of the ILs (such as acetate) are able to deprotonate azolium cations. While the resulting NHC could clearly be observed in the vapor phase, in the liquid - where the mutual electrostatic interactions within the ion network stabilize the ion pairs - the neutral NHC cannot be detected by commonly used analytical techniques; however, from these ionic liquids NHCs can be trapped, e.g., by complex formation, or more importantly these ILs can be directly used as catalysts, since the NHC content is sufficiently large for these applications. Apart from imidazole-2-ylidenes, the formation of other highly reactive neutral species ("abnormal carbenes," 2-alkylideneimidazoles, pyridine-ylidenes or pyridinium-ylides) is feasible in highly basic ionic liquids. The cross-fertilizing overlap between the two fields may provide access to a great advance in both areas, and we give an overview here on the results published so far, and also on the remaining possibilities and challenges in the concept of "carbenes from ionic liquids." PMID:23539381

  20. Superfluorinated Ionic Liquid Crystals Based on Supramolecular, Halogen-Bonded Anions.

    PubMed

    Cavallo, Gabriella; Terraneo, Giancarlo; Monfredini, Alessandro; Saccone, Marco; Priimagi, Arri; Pilati, Tullio; Resnati, Giuseppe; Metrangolo, Pierangelo; Bruce, Duncan W

    2016-05-17

    Unconventional ionic liquid crystals in which the liquid crystallinity is enabled by halogen-bonded supramolecular anions [Cn F2 n+1 -I⋅⋅⋅I⋅⋅⋅I-Cn F2 n+1 ](-) are reported. The material system is unique in many ways, demonstrating for the first time 1) ionic, halogen-bonded liquid crystals, and 2) imidazolium-based ionic liquid crystals in which the occurrence of liquid crystallinity is not driven by the alkyl chains of the cation. PMID:27073033

  1. Tailored ionic liquid-based surfactants for the formation of microemulsions with water and a hydrophobic ionic liquid.

    PubMed

    Porada, Jan H; Zauser, Diana; Feucht, Birgit; Stubenrauch, Cosima

    2016-08-14

    Microemulsions (μe) with water and a hydrophobic ionic liquid (IL) usually require 45-60 wt% surfactant to solubilize equal amounts of water and IL. To increase the efficiency we designed a new class of surfactants by combining a hydrophilic but IL-ophobic carbohydrate-based part with a hydrophobic but IL-ophilic IL-based part. These surfactants allow formulating microemulsions with 20 wt% surfactant only which opens up a new arena for efficient water-IL μes. PMID:27405741

  2. Thermophysical properties of sulfonium- and ammonium-based ionic liquids

    PubMed Central

    Bhattacharjee, Arijit; Luís, Andreia; Lopes-da-Silva, José A.; Freire, Mara G.; Carvalho, Pedro J.; Coutinho, João A. P.

    2014-01-01

    Experimental data for the density, viscosity, refractive index and surface tension of four sulfonium- and ammonium-based Ionic Liquids (ILs) with the common bis(trifluoromethylsulfonyl)imide anion were measured in the temperature range between 288.15 and 353.15 K and at atmospheric pressure. The ILs considered include butyltrimethylammonium bis(trifluoromethylsulfonyl)imide, [N4111][NTf2], tributylmethylammonium bis(trifluoromethylsulfonyl)imide, [N4441][NTf2], diethylmethylsulfonium bis(trifluoromethylsulfonyl)imide, [S221][NTf2], and triethylsulfonium bis(trifluoromethylsulfonyl)imide, [S222][NTf2]. Based on the gathered results and on data taken from literature, the impact of the cation isomerism and of the size of the aliphatic tails, as well as the effect resulting from the substitution of a nitrogen by a sulfur atom as the cation central atom, on the thermophysical properties of sulfonium- and ammonium-based ILs is here discussed. Remarkably, more symmetric cations present a lower viscosity for the same, and sometimes even for higher, alkyl chain lengths at the cation. Additional derivative properties, such as the isobaric thermal expansion coefficient, the surface thermodynamic properties and the critical temperature for the investigated ILs were also estimated and are presented and discussed. PMID:25516634

  3. Revisiting ether-derivatized imidazolium-based ionic liquids.

    PubMed

    Fei, Zhaofu; Ang, Wee Han; Zhao, Dongbin; Scopelliti, Rosario; Zvereva, Elena E; Katsyuba, Sergey A; Dyson, Paul J

    2007-08-30

    A series of ether-derivatized imidazolium halides have been prepared and characterized. Contrary to literature reports, they are all crystalline solids and have melting points well above room temperature (50-100 degrees C). Single crystals of the imidazolium salts, obtained in situ by slow cooling from their molten state to room temperature, were analyzed by X-ray crystallography, revealing various anion-cation interactions in the solid state. Exchange of the halides with [Tf(2)N]- yielded room temperature ionic liquids with viscosities that are comparable to related 1-alkyl-3-methylimidazolium ionic liquids. Density functional theory combined with IR spectroscopy has been used to analyze the role of functionalization of the imidazolium side chain on the formation of the molecular and supramolecular structure of the compounds and its possible impact on their physical properties. PMID:17676796

  4. Oxidative desulfurization of fuel oil by pyridinium-based ionic liquids.

    PubMed

    Zhao, Dishun; Wang, Yanan; Duan, Erhong

    2009-01-01

    In this work, an N-butyl-pyridinium-based ionic liquid [BPy]BF(4) was prepared. The effect of extraction desulfurization on model oil with thiophene and dibenzothiophene (DBT) was investigated. Ionic liquids and hydrogen peroxide (30%) were tested in extraction-oxidation desulfurization of model oil. The results show that the ionic liquid [BPy]BF(4) has a better desulfurization effect. The best technological conditions are: V(IL)/V(Oil) /V(H(2)O(2)) = 1:1:0.4, temperature 55 degrees C, the time 30 min. The ratio of desulfurization to thiophene and DBT reached 78.5% and 84.3% respectively, which is much higher than extraction desulfurization with simple ionic liquids. Under these conditions, the effect of desulfurization on gasoline was also investigated. The used ionic liquids can be recycled up to four times after regeneration. PMID:19924069

  5. Influence of oxygen functionalities on the environmental impact of imidazolium based ionic liquids.

    PubMed

    Deng, Yun; Besse-Hoggan, Pascale; Sancelme, Martine; Delort, Anne-Marie; Husson, Pascale; Gomes, Margarida F Costa

    2011-12-30

    Several physico-chemical properties relevant to determine the environmental impact of ionic liquids - aqueous solubility, octanol-water partition coefficient and diffusion coefficients in water at infinite dilution - together with toxicity and biodegradability of ionic liquids based on 1-alkyl-3-methylimidazolium cations with or without different oxygenated functional groups (hydroxyl, ester and ether) are studied in this work. The presence of oxygen groups on the imidazolium cation reduces the toxicity of ionic liquids 1-alkyl-3-methylimidazolium with bis(trifluoromethylsulfonyl)imide or octylsulfate anions and simultaneously decreases the value of their octanol-water partition coefficient. The presence of ester functions renders the ionic liquids more easily biodegradable, especially for long alkyl side-chains in the cation but leads to hydrolysis with the formation of reaction products that accumulate. The imidazolium ring is resistant to biodegradability and to abiotic degradation. The oxygen functionalised ionic liquids are more soluble in water and, diffuse more slowly in this medium. PMID:22071261

  6. Determination of rifaximin in rat serum by ionic liquid based dispersive liquid-liquid microextraction combined with RP-HPLC.

    PubMed

    Rao, Ramisetti Nageswara; Vali, Rajavarapu Mastan; Rao, Alamanda Vara Prasada

    2012-08-01

    An efficient and environmental friendly ionic liquid based dispersive liquid-liquid microextraction procedure was optimized for determination of rifaximin in rat serum by reverse phase high-performance liquid chromatography. The effect of ionic liquids, dispersive solvents, extractant/disperser ratio, and salt concentrations on sample recovery and enrichment factors were studied. Among the five ionic liquids studied in the present investigation, 1-butyl-3-methylimidazolium hexafluorophosphate was found to be most effective for extraction of rifaximin. The recovery was found to be more than 98% using 1-butyl-3-methylimidazolium hexafluorophosphate and methanol as extraction and dispersive solvents, at an extractant/disperser ratio of 0.43. The recovery was further enhanced to 99.5% by the addition of 5.0% NaCl solution. A threefold enhancement in detection limit was achieved when compared to protein precipitation. The ionic liquid containing the extracted rifaximin was directly injected into HPLC system. The linear relationship was observed in the range of 0.03-10.0 μg/mL with the correlation coefficient (r(2)) 0.9998. Limits of detection and quantification were found to be 0.01 and 0.03 μg/mL, respectively. The relative standard deviation was 2.5%. The method was validated and applied to study pharmacokinetics of rifaxmin in rat serum. PMID:22753340

  7. Spectroscopic Studies of Imidizolium and Pyridinium Based Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Booth, Ryan; Stearns, Jaime

    2015-03-01

    Ionic liquids (ILs) have been shown to be extremely useful in areas ranging from chemical synthesis to energetic materials. Furthermore, ILs are thought to be a potential replacement for hydrazine as satellite propellants because a subset are hypergolic with nitric acid. While ILs are useful, however, there is a lack of understanding of the microscopic origins for their macroscopic properties (e.g. viscosity). An example of this is that [emim+][tf2N-] is three times less viscous than its methylated counterpart [emmim+][tf2N-] and there is some discord regarding the reason. We have investigated the molecular properties of such IL pairs using UV and IR spectroscopy in the gas phase on both imidozolium and pyridinium-based ([pyr+]) ILs. UV data show that the photophysics of [emmim+][tf2N-] is different than [emim+][tf2N-] in that there is a lack of evidence for the existence of a charge transfer (CT) state (as was seen in [emim+][tf2N-]). Preliminary UV spectra for the [pyr+] ILs show at least two distinct peaks in the region from 208-270 nm, which are tentatively established as CT states between the anion and cation. IR spectra deliver structural information for both sets of ILs and should provide insight into the correlation between microscopic and macroscopic properties.

  8. Distributed polarizability models for imidazolium-based ionic liquids.

    PubMed

    Millot, Claude; Chaumont, Alain; Engler, Etienne; Wipff, Georges

    2014-09-25

    Quantum chemical calculations are used to derive distributed polarizability models sufficiently accurate and compact to be used in classical molecular dynamics simulations of imidazolium-based room temperature ionic liquids. Two distributed polarizability models are fitted to reproduce the induction energy of three imidazolium cations (1,3-dimethyl-, 1-ethyl-3-methyl-, and 1-butyl-3-methylimidazolium) and four anions (tetrafluoroborate, hexafluorophosphate, nitrate, and thiocyanate) polarized by a point charge located successively on a grid of surrounding points. The first model includes charge-flow polarizabilities between first-neighbor atoms and isotropic dipolar polarizability on all atoms (except H), while the second model includes anisotropic dipolar polarizabilities on all atoms (except H). For the imidazolium cations, particular attention is given to the transferability of the distributed polarizability sets. The molecular polarizability and its anisotropy rebuilt by the distributed models are found to be in good agreement with the exact ab initio values for the three cations and 23 additional conformers of 1-ethyl-3-methyl-, 1-butyl-3-methyl-, 1-pentyl-3-methyl-, and 1-hexyl-3-methylimidazolium cations. PMID:25133873

  9. Ionic liquids as novel solvents for ionic polymer transducers

    NASA Astrophysics Data System (ADS)

    Bennett, Matthew D.; Leo, Donald J.

    2004-07-01

    The use of ionic liquids as solvents for ionic polymer (specifically, Nafion) transducers is demonstrated. Ionic liquids are attractive for this application because of their high inherent stability. Ionic liquids are salts that exist as liquids at room temperature and have no measureable vapor pressure. Therefore, the use of ionic liquids as solvents for ionic polymer transducers can eliminate the traditional problem of water evaporation in these devices. Another benefit of the use of ionic liquids in this way is the reduction or elimination of the characteristic back-relaxation common in water-solvated ionic polymer actuators. The results demonstrate that the viscosity of the ionic liquid and the degree to which the ionic liquid swells the membrane are the important physical parameters to consider. Five ionic liquids were studied, based on substituted pyrrolidinium, phosphonium, or imidazolium cations and fluoroanions. Of these five ionic liquids, transduction is demonstrated in three of them and the best results are obtained with 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ionic liquid. This substance has an electrochemical stability window of 4.1 V, a melting point of -10 °C, and a viscosity of 35-45 cP [19]. Results demonstrate that platinum-plated Nafion transducers solvated with this ionic liquid exhibit sensing and actuation responses and that these transducers are stable in air. Endurance testing of this sample reveals a decrease in the free strain of only 25 % after 250,000 actuation cycles in air.

  10. Charge Transport and Dynamics in Confined Phosphonium-based Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Cosby, Tyler; Tsunashima, Katsuhiko; Sangoro, Joshua

    Charge transport and structural dynamics in a homologous series of phosphonium-based ionic liquids confined in silica nanopores are investigated by broadband dielectric spectroscopy and Fourier transform infrared spectroscopy. The impact of alkyl chain length and hydrophobic aggregation on the physicochemical properties as well as the interplay between confinement effects and pore-wall interactions through silica surface silanization are investigated. The results are discussed within the framework of current understanding of confinement effects in ionic liquid systems, especially in comparison to imidazolium-based ionic liquids. NSF DMR Polymers Program.

  11. Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid

    NASA Astrophysics Data System (ADS)

    Berger, Claudia A.; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

    2016-07-01

    The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer.The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important

  12. Dysprosium electrodeposition from a hexaalkylguanidinium-based ionic liquid.

    PubMed

    Berger, Claudia A; Arkhipova, Maria; Maas, Gerhard; Jacob, Timo

    2016-08-01

    The rare-earth element dysprosium (Dy) is an important additive that increases the magnetocrystalline anisotropy of neodymium magnets and additionally prevents from demagnetizing at high temperatures. Therefore, it is one of the most important elements for high-tech industries and is mainly used in permanent magnetic applications, for example in electric vehicles, industrial motors and direct-drive wind turbines. In an effort to develop a more efficient electrochemical technique for depositing Dy on Nd-magnets in contrast to commonly used costly physical vapor deposition, we investigated the electrochemical behavior of dysprosium(iii) trifluoromethanesulfonate in a custom-made guanidinium-based room-temperature ionic liquid (RTIL). We first examined the electrodeposition of Dy on an Au(111) model electrode. The investigation was carried out by means of cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS). The initial stages of metal deposition were followed by in situ scanning tunneling microscopy (STM). CV measurements revealed a large cathodic reduction peak, which corresponds to the growth of monoatomic high islands, based on STM images taken during the initial stages of deposition. XPS identified these deposited islands as dysprosium. A similar reduction peak was also observed on an Nd-Fe-B substrate, and positively identified as deposited Dy using XPS. Finally, we varied the concentration of the Dy precursor, electrolyte flow and temperature during Dy deposition and demonstrated that each of these parameters could be used to increase the thickness of the Dy deposit, suggesting that these parameters could be tuned simultaneously in a temperature-controlled flow cell to enhance the thickness of the Dy layer. PMID:27121463

  13. Water-in-ionic liquid microemulsion formation in solvent mixture of aprotic and protic imidazolium-based ionic liquids.

    PubMed

    Kusano, Takumi; Fujii, Kenta; Hashimoto, Kei; Shibayama, Mitsuhiro

    2014-10-14

    We report that water-in-ionic liquid microemulsions (MEs) are stably formed in an organic solvent-free system, i.e., a mixture of aprotic (aIL) and protic (pIL) imidazolium-based ionic liquids (ILs) containing the anionic surfactant dioctyl sulfosuccinate sodium salt (AOT). Structural investigations using dynamic light, small-angle X-ray, and small-angle neutron scatterings were performed for MEs formed in mixtures of aprotic 1-octyl-3-methylimidazolium ([C8mIm(+)]) and protic 1-alkylimidazolium ([CnImH(+)], n = 4 or 8) IL with a common anion, bis(trifluoromethanesulfonyl)amide ([TFSA(-)]). It was found that the ME structure strongly depends on the mixing composition of the aIL/pIL in the medium. The ME size appreciably increases with increasing pIL content in both [C8mIm(+)][TFSA(-)]/[C8ImH(+)][TFSA(-)] and [C8mIm(+)][TFSA(-)]/[C4ImH(+)][TFSA(-)] mixtures. The size is larger for the n = 8 system than that for the n = 4 system. These results indicate that the shell part of MEs is composed of both AOT and pIL cation, and the ME size can be tuned by pIL content in the aIL/pIL mixtures. PMID:25226398

  14. Charge Transport and Dynamics in Confined Ammonium and Phosphonium-based Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Harris, Matthew; Cosby, Tyler; Tsunashima, Katsuhiko; Sangoro, Joshua

    Charge transport and structural dynamics in a homologous series of ammonium and phosphonium ionic liquids confined in silica nanopores are investigated by broadband dielectric spectroscopy and Fourier transform infrared spectroscopy. The impact of the central atom of the cation on the physicochemical properties as well as the interplay between confinement effects and pore-wall interactions through silica surface silanization are investigated. The results are discussed within the framework of current understanding of confinement effects in ionic liquid systems, especially in comparison to imidazolium-based ionic liquids.

  15. 3-Methylpiperidinium ionic liquids.

    PubMed

    Belhocine, Tayeb; Forsyth, Stewart A; Gunaratne, H Q Nimal; Nieuwenhuyzen, Mark; Nockemann, Peter; Puga, Alberto V; Seddon, Kenneth R; Srinivasan, Geetha; Whiston, Keith

    2015-04-28

    A wide range of room temperature ionic liquids based on the 3-methylpiperdinium cation core were produced from 3-methylpiperidine, which is a derivative of DYTEK® A amine. First, reaction with 1-bromoalkanes or 1-bromoalkoxyalkanes generated the corresponding tertiary amines (Rmβpip, R = alkyl or alkoxyalkyl); further quaternisation reactions with the appropriate methylating agents yielded the quaternary [Rmmβpip]X salts (X(-) = I(-), [CF3CO2](-) or [OTf](-); Tf = -SO2CF3), and [Rmmβpip][NTf2] were prepared by anion metathesis from the corresponding iodides. All [NTf2](-) salts are liquids at room temperature. [Rmmβpip]X (X(-) = I(-), [CF3CO2](-) or [OTf](-)) are low-melting solids when R = alkyl, but room temperature liquids upon introduction of ether functionalities on R. Neither of the 3-methylpiperdinium ionic liquids showed any signs of crystallisation, even well below 0 °C. Some related non-C-substituted piperidinium and pyrrolidinium analogues were prepared and studied for comparison. Crystal structures of 1-hexyl-1,3-dimethylpiperidinium tetraphenylborate, 1-butyl-3-methylpiperidinium bromide, 1-(2-methoxyethyl)-1-methylpiperidinium chloride and 1-(2-methoxyethyl)-1-methylpyrrolidinium bromide are reported. Extensive structural and physical data are collected and compared to literature data, with special emphasis on the systematic study of the cation ring size and/or asymmetry effects on density, viscosity and ionic conductivity, allowing general trends to be outlined. Cyclic voltammetry shows that 3-methylpiperidinium ionic liquids, similarly to azepanium, piperidinium or pyrrolidinium counterparts, are extremely electrochemically stable; the portfolio of useful alternatives for safe and high-performing electrolytes is thus greatly extended. PMID:25669485

  16. Antitumor Activity of Ionic Liquids Based on Ampicillin.

    PubMed

    Ferraz, Ricardo; Costa-Rodrigues, João; Fernandes, Maria H; Santos, Miguel M; Marrucho, Isabel M; Rebelo, Luís Paulo N; Prudêncio, Cristina; Noronha, João Paulo; Petrovski, Željko; Branco, Luís C

    2015-09-01

    Significant antiproliferative effects against various tumor cell lines were observed with novel ampicillin salts as ionic liquids. The combination of anionic ampicillin with appropriate ammonium, imidazolium, phosphonium, and pyridinium cations yielded active pharmaceutical ingredient ionic liquids (API-ILs) that show potent antiproliferative activities against five different human cancer cell lines: T47D (breast), PC3 (prostate), HepG2 (liver), MG63 (osteosarcoma), and RKO (colon). Some API-ILs showed IC50 values between 5 and 42 nM, activities that stand in dramatic contrast to the negligible cytotoxic activity level shown by the ampicillin sodium salt. Moreover, very low cytotoxicity against two primary cell lines-skin (SF) and gingival fibroblasts (GF)-indicates that the majority of these API-ILs are nontoxic to normal human cell lines. The most promising combination of antitumor activity and low toxicity toward healthy cells was observed for the 1-hydroxyethyl-3-methylimidazolium-ampicillin pair ([C2 OHMIM][Amp]), making this the most suitable lead API-IL for future studies. PMID:26190053

  17. 81929 - Fission-Product Separation Based on Room - Temperature Ionic Liquids

    SciTech Connect

    Robin D. Rogers

    2004-12-09

    This project has demonstrated that Sr2+ and Cs+ can be selectively extracted from aqueous solutions into ionic liquids using crown ethers and that unprecedented large distribution coefficients can be achieved for these fission products. The volume of secondary wastes can be significantly minimized with this new separation technology. Through the current EMSP funding, the solvent extraction technology based on ionic liquids has been shown to be viable and can potentially provide the most efficient separation of problematic fission products from high level wastes. The key results from the current funding period are the development of highly selective extraction process for cesium ions based on crown ethers and calixarenes, optimization of selectivities of extractants via systematic change of ionic liquids, and investigation of task-specific ionic liquids incorporating both complexant and solvent characteristics.

  18. Ionic liquid based dispersive liquid-liquid microextraction for the extraction of pesticides from bananas.

    PubMed

    Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Asensio-Ramos, María; Rodríguez-Delgado, Miguel Angel

    2009-10-23

    This paper describes a dispersive liquid-liquid microextraction (DLLME) procedure using room temperature ionic liquids (RTILs) coupled to high-performance liquid chromatography with diode array detection capable of quantifying trace amounts of eight pesticides (i.e. thiophanate-methyl, carbofuran, carbaryl, tebuconazole, iprodione, oxyfluorfen, hexythiazox and fenazaquin) in bananas. Fruit samples were first homogenized and extracted (1g) with acetonitrile and after suitable evaporation and reconstitution of the extract in 10 mL of water, a DLLME procedure using 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]) as extraction solvent was used. Experimental conditions affecting the DLLME procedure (sample pH, sodium chloride percentage, ionic liquid amount and volume of disperser solvent) were optimized by means of an experimental design. In order to determine the presence of a matrix effect, calibration curves for standards and fortified banana extracts (matrix matched calibration) were studied. Mean recovery values of the extraction of the pesticides from banana samples were in the range of 69-97% (except for thiophanate-methyl and carbofuran, which were 53-63%) with a relative standard deviation lower than 8.7% in all cases. Limits of detection achieved (0.320-4.66 microg/kg) were below the harmonized maximum residue limits established by the European Union (EU). The proposed method, was also applied to the analysis of this group of pesticides in nine banana samples taken from the local markets of the Canary Islands (Spain). To the best of our knowledge, this is the first application of RTILs as extraction solvents for DLLME of pesticides from samples different than water. PMID:19700165

  19. Pesticide extraction from table grapes and plums using ionic liquid based dispersive liquid-liquid microextraction.

    PubMed

    Ravelo-Pérez, Lidia M; Hernández-Borges, Javier; Herrera-Herrera, Antonio V; Rodríguez-Delgado, Miguel Angel

    2009-12-01

    Room temperature ionic liquids (RTILs) have been used as extraction solvents in dispersive liquid-liquid microextraction (DLLME) for the determination of eight multi-class pesticides (i.e. thiophanate-methyl, carbofuran, carbaryl, tebuconazole, iprodione, oxyfluorfen, hexythiazox, and fenazaquin) in table grapes and plums. The developed method involves the combination of DLLME and high-performance liquid chromatography with diode array detection. Samples were first homogenized and extracted with acetonitrile. After evaporation and reconstitution of the extract in water containing sodium chloride, a quick DLLME procedure that used the ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate ([C(6)MIM][PF(6)]) and methanol was developed. The RTIL dissolved in a very small volume of acetonitrile was directed injected in the chromatographic system. The comparison between the calibration curves obtained from standards and from spiked sample extracts (matrix-matched calibration) showed the existence of a strong matrix effect for most of the analyzed pesticides. A recovery study was also developed with five consecutive extractions of the two types of fruits spiked at three concentration levels. Mean recovery values were in the range of 72-100% for table grapes and 66-105% for plum samples (except for thiophanate-methyl and carbofuran, which were 64-75% and 58-66%, respectively). Limits of detection (LODs) were in the range 0.651-5.44 microg/kg for table grapes and 0.902-6.33 microg/kg for plums, representing LODs below the maximum residue limits (MRLs) established by the European Union in these fruits. The potential of the method was demonstrated by analyzing 12 commercial fruit samples (six of each type). PMID:19779926

  20. A New Class of Ionic Liquids: Anion Amphiprotic Ionic Liquids.

    PubMed

    Treskow, Marcel; Pitawala, Jagath; Arenz, Sven; Matic, Aleksandar; Johansson, Patrik

    2012-08-16

    We here present a new class of protic ionic liquids, anion amphiprotic ionic liquids (AAILs). These materials are protonation equilibrium free protic ionic liquids and interesting in their own right by not following the classical Brønsted acid-base neutralization concept. Due to the very simple synthesis route applied and their stable basic chemistry, we believe in a potential use for manifold applications. This is supported by the combination of practical material properties, foremost, a general intrinsic stability versus reversal of the formation reaction toward neutral species, broad liquidus ranges, long-term thermal stabilities, high conductivities, protic characteristics, and a general stability versus water. PMID:26295756

  1. Versatile cation transport in imidazolium based polymerized ionic liquids

    NASA Astrophysics Data System (ADS)

    Evans, Christopher; Segalman, Rachel

    Polymerized ionic liquids (PIL) with tethered imidazolium groups are able to conduct a diverse array of cations relevant for energy applications. The well-known complexation of imidazolium with transition metals is exploited to bind ions such as H +, Li+, Cu2+, and Ni2+ by doping the neutral PIL with the appropriate Cation-TFSI- salt. Conductivities were first determined via AC impedance indicating that H+ salts lead to the highest conductivity (due to low ion mass and potential Grotthus mechanism) followed by Cu2+, Li+, Ag+, and Ni2+. The equilibrium constant for imidazolium complexation is larger for Cu2+ relative to Li-, Ag-, and Ni-imidazolium complexes leading to greater salt dissociation and higher conductivities. For LiTFSI and CuTFSI2 salts, metallic lithium or copper electrodes were employed in battery cells to pass a steady DC current and confirm that the cations are in fact carrying current. Interestingly, the divalent Cu2+ also ionically crosslinks the polymer leading to a plateau in the viscosity. Thus, divalent ions provide an unique route to high conductivity, high modulus polymeric electrolytes. Future studies involving ZnTFSI2 and MgTFSI2 for battery applications are proposed to examine how versatile the PIL platform is for cation transport.

  2. Electrochemical Stability Window of Imidazolium-Based Ionic Liquids as Electrolytes for Lithium Batteries.

    PubMed

    Kazemiabnavi, Saeed; Zhang, Zhengcheng; Thornton, Katsuyo; Banerjee, Soumik

    2016-06-30

    This paper presents the computational assessment of the electrochemical stability of a series of alkyl methylimidazolium-based ionic liquids for their use as lithium battery electrolytes. The oxidation and reduction potentials of the constituent cation and anion of each ionic liquid with respect to a Li(+)/Li reference electrode were calculated using density functional theory following the method of thermodynamic cycles, and the electrochemical stability windows (ESW)s of these ionic liquids were obtained. The effect of varying the length of alkyl side chains of the methylimidazolium-based cations on the redox potentials and ESWs was investigated. The results show that the limits of the ESWs of these methylimidazolium-based ionic liquids are defined by the oxidation potential of the anions and the reduction potential of alkyl-methylimidazolium cations. Moreover, ionic liquids with [PF6](-) anion have a wider ESW. In addition to characterizing structure-function relationships, the accuracy of the computational approach was assessed through comparisons of the data against experimental measurements of ESWs. The potentials calculated by the thermodynamic cycle method are in good agreement with the experimental data while the HOMO/LUMO method overestimates the redox potentials. This work demonstrates that these approaches can provide guidance in selecting ionic liquid electrolytes when designing high-voltage rechargeable batteries. PMID:27266487

  3. Saturation properties of 1-alkyl-3-methylimidazolium based ionic liquids.

    PubMed

    Rane, Kaustubh S; Errington, Jeffrey R

    2014-07-24

    We study the liquid-vapor saturation properties of room temperature ionic liquids (RTILs) belonging to the homologous series 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Cnmim][NTf2]) using Monte Carlo simulation. We examine the effect of temperature and cation alkyl chain length n on the saturated densities, vapor pressures, and enthalpies of vaporization. These properties are explicitly calculated for temperatures spanning from 280 to 1000 K for RTILs with n = 2, 4, 6, 8, 10, and 12. We also explore how the identity of the anion influences saturation properties. Specifically, we compare results for [C(4)mim][NTf2] with those for 1-butyl-3-methylimidazolium tetrafluoroborate ([C(4)mim][BF4]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([C(4)mim][PF6]). Simulations are completed with a recently developed realistic united-atom force field. A combination of direct grand canonical and isothermal-isobaric temperature expanded ensemble simulations are used to construct phase diagrams. Our results are compared with experimental data and Gibbs ensemble simulation data. Overall, we find good agreement between our results and those measured experimentally. We find that the vapor pressures and enthalpies of vaporization show a strong dependence on the size of the alkyl chain at low temperatures, whereas no particular trend is observed at high temperatures. Finally, we also discuss the effect of temperature on liquid phase nanodomains observed in RTILs with large hydrophobic groups. We do not observe a drastic change in liquid phase structure upon variation of the temperature, which suggests there is not a sharp phase transition between a nanostructured and homogeneous liquid, as has been suggested in earlier studies. PMID:24986360

  4. Properties of the Nafion membrane impregnated with hydroxyl ammonium based ionic liquids

    NASA Astrophysics Data System (ADS)

    Garaev, Valeriy; Kleperis, Janis; Pavlovica, Sanita; Vaivars, Guntars

    2012-08-01

    In this work, the Nafion 112 membrane impregnated with nine various hydroxyl ammonium based ionic liquids have been investigated. The used ionic liquids were combined from hydroxyl ammonium cations (2-hydroxyethylammonium/HEA, bis(2- hydroxyethyl)ammonium/BHEA, tris(2-hydroxyethyl)ammonium/THEA) and carboxylate anions (formate, acetate, lactate). The membranes are characterized by conductivity and thermal stability measurements. It was found, that almost all composites have 10 times higher ion conductivity than a pure Nafion 112 at 90 °C in ambient environment due to the higher thermal stability. The thermal stability of Nafion membrane was increased by all studied nine ionic liquids. In this work, only biodegradable ionic liquids were used for composite preparation.

  5. Thermophysical properties of two ammonium-based protic ionic liquids

    PubMed Central

    Bhattacharjee, Arijit; Coutinho, João A. P.; Freire, Mara G.; Carvalho, Pedro J.

    2015-01-01

    Experimental data for density, viscosity, refractive index and surface tension are reported, for the first time, in the temperature range between 288.15 K and 353.15 K and at atmospheric pressure for two protic ionic liquids, namely 2-(dimethylamino)-N,N-dimethylethan-1-ammonium acetate, [N11{2(N11)}H][CH3CO2], and N-ethyl-N,N-dimethylammonium phenylacetate, [N112H][C7H7CO2]. The effect of the anion aromaticity and the cation’s aliphatic tails on the studied properties is discussed. From the measured properties temperature dependency the derived properties, such as the isobaric thermal expansion coefficient, the surface entropy and enthalpy, and the critical temperature, were estimated. PMID:26435554

  6. New ionic liquids based on complexation of dipropylsulfide and AlCl3 for electrochodeposition of aluminum

    DOE PAGESBeta

    Fang, Youxing; Jiang, Xueguang; Dai, Sheng; Sun, Xiao-Guang

    2015-01-01

    A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 x 10-4 S cm-1. This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

  7. Mutual solubility of water and structural/positional isomers of N-alkylpyridinium-based ionic liquids.

    PubMed

    Freire, Mara G; Neves, Catarina M S S; Shimizu, Karina; Bernardes, Carlos E S; Marrucho, Isabel M; Coutinho, João A P; Canongia Lopes, José N; Rebelo, Luís Paulo N

    2010-12-01

    Despite many previous important contributions to the characterization of the liquid-liquid phase behavior of ionic liquids (ILs) plus water systems, a gap still exists as far as the effect of isomers (of ILs) is concerned. Therefore, in this work, a comprehensive study of the liquid-liquid equilibria between water and isomeric pyridinium-based ionic liquids has been performed. Atmospheric pressure mutual solubilities between water and pyridinium-based ionic liquids combined with the common anion bis[(trifluoromethyl)sulfonyl]imide were experimentally determined between (288.15 and 318.15) K. The main goal of this work is to study the isomeric effects on the pyridinium-based cation, namely, the structural and positional isomerism, as well as the alkyl side chain length. To the best of our knowledge, the influence of both structural and positional isomerism on the liquid-liquid behavior in ionic-liquid-water-containing systems is an unexplored field and is here assessed for the first time. Moreover, from the experimental solubility data, several infinite dilution molar thermodynamic functions of solution, namely, the Gibbs energy, the enthalpy, and the entropy, were estimated and discussed. In addition, aiming at gathering a broader picture of the underlying thermodynamic solvation phenomenon, molecular dynamics simulations were also carried out for the same experimental systems. PMID:21077599

  8. On the viscosity of pyridinium based ionic liquids: an experimental and computational study.

    PubMed

    Bandrés, Isabel; Alcalde, Rafael; Lafuente, Carlos; Atilhan, Mert; Aparicio, Santiago

    2011-11-01

    A study on the viscosity of eight pyridinium based ionic liquids is reported for wide pressure and temperature ranges. Measurements were performed using an electromagnetic moving piston viscometer. Experimental data were fitted to a Tait-like equation demonstrating good correlations, which was used to calculate pressure/viscosity and temperature/viscosity coefficients. The effect of the involved anions and cation on the ionic liquid viscosity was analyzed from a molecular viewpoint using hole theory, quantum chemistry calculations using density functional theory, and classical molecular dynamics simulations. The analysis of the experimental and computational results shows the complex effects controlling viscosity of studied fluids, including strength of ionic pairs, molecular sizes, and mobility and effects rising from the availability and cavity sizes distributions in pyridinium-based ionic liquids. PMID:21942824

  9. Why are ionic liquids liquid? A simple explanation based on lattice and solvation energies.

    PubMed

    Krossing, Ingo; Slattery, John M; Daguenet, Corinne; Dyson, Paul J; Oleinikova, Alla; Weingärtner, Hermann

    2006-10-18

    We have developed a simple and quantitative explanation for the relatively low melting temperatures of ionic liquids (ILs). The basic concept was to assess the Gibbs free energy of fusion (Delta(fus)G) for the process IL(s) --> IL(l), which relates to the melting point of the IL. This was done using a suitable Born-Fajans-Haber cycle that was closed by the lattice (i.e., IL(s) --> IL(g)) Gibbs energy and the solvation (i.e., IL(g) --> IL(l)) Gibbs energies of the constituent ions in the molten salt. As part of this project we synthesized and determined accurate melting points (by DSC) and dielectric constants (by dielectric spectroscopy) for 14 ionic liquids based on four common anions and nine common cations. Lattice free energies (Delta(latt)G) were estimated using a combination of Volume Based Thermodynamics (VBT) and quantum chemical calculations. Free energies of solvation (Delta(solv)G) of each ion in the bulk molten salt were calculated using the COSMO solvation model and the experimental dielectric constants. Under standard ambient conditions (298.15 K and 10(5) Pa) Delta(fus)G degrees was found to be negative for all the ILs studied, as expected for liquid samples. Thus, these ILs are liquid under standard ambient conditions because the liquid state is thermodynamically favorable, due to the large size and conformational flexibility of the ions involved, which leads to small lattice enthalpies and large entropy changes that favor melting. This model can be used to predict the melting temperatures and dielectric constants of ILs with good accuracy. A comparison of the predicted vs experimental melting points for nine of the ILs (excluding those where no melting transition was observed and two outliers that were not well described by the model) gave a standard error of the estimate (s(est)) of 8 degrees C. A similar comparison for dielectric constant predictions gave s(est) as 2.5 units. Thus, from very little experimental and computational data it is

  10. Communication: Nanoscale structure of tetradecyltrihexylphosphonium based ionic liquids

    NASA Astrophysics Data System (ADS)

    Hettige, Jeevapani J.; Araque, Juan C.; Kashyap, Hemant K.; Margulis, Claudio J.

    2016-03-01

    In a recent communication [J. J. Hettige et al., J. Chem. Phys. 140, 111102 (2014)], we investigated the anomalous temperature dependence of the X-ray first sharp diffraction peak (or prepeak) in the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)-amide ionic liquid. Contrary to what was expected and often observed, the first sharp diffraction peak in this system was shown to increase in intensity with increasing temperature. This implies higher intermediate-range periodicity at a higher temperature. Is this counter-intuitive behavior specific to the combination of cation and anion? The current work analyzes the structural behavior of the same cation coupled with six different anions ranging from the small and spherically symmetric Cl- to the more structurally complex and charge-diffuse NTf2-. In all cases, the same temperature behavior trend for the prepeak is observed independent of anionic nature. We will show that the intensity increase in the prepeak region is associated with the structural behavior of charged liquid subcomponents. Instead, upon a temperature increase, the apolar subcomponents contribute to what would be an expected decrease of prepeak intensity.

  11. A spin-crossover ionic liquid from the cationic iron(III) Schiff base complex.

    PubMed

    Okuhata, Megumi; Funasako, Yusuke; Takahashi, Kazuyuki; Mochida, Tomoyuki

    2013-09-01

    A thermochromic magnetic ionic liquid containing a cationic iron(III) Schiff-base complex has been developed, whose color and magnetic moment change with temperature because of spin crossover in the liquid state. This spin-crossover behavior closely resembles that of a solid having the same cation. PMID:23872624

  12. Ionic Liquid Epoxy Resin Monomers

    NASA Technical Reports Server (NTRS)

    Paley, Mark S. (Inventor)

    2013-01-01

    Ionic liquid epoxide monomers capable of reacting with cross-linking agents to form polymers with high tensile and adhesive strengths. Ionic liquid epoxide monomers comprising at least one bis(glycidyl) N-substituted nitrogen heterocyclic cation are made from nitrogen heterocycles corresponding to the bis(glycidyl) N-substituted nitrogen heterocyclic cations by a method involving a non-nucleophilic anion, an alkali metal cation, epichlorohydrin, and a strong base.

  13. Fast Ignition and Sustained Combustion of Ionic Liquids

    NASA Technical Reports Server (NTRS)

    Joshi, Prakash B. (Inventor); Piper, Lawrence G. (Inventor); Oakes, David B. (Inventor); Sabourin, Justin L. (Inventor); Hicks, Adam J. (Inventor); Green, B. David (Inventor); Tsinberg, Anait (Inventor); Dokhan, Allan (Inventor)

    2016-01-01

    A catalyst free method of igniting an ionic liquid is provided. The method can include mixing a liquid hypergol with a HAN (Hydroxylammonium nitrate)-based ionic liquid to ignite the HAN-based ionic liquid in the absence of a catalyst. The HAN-based ionic liquid and the liquid hypergol can be injected into a combustion chamber. The HAN-based ionic liquid and the liquid hypergol can impinge upon a stagnation plate positioned at top portion of the combustion chamber.

  14. Applications of ionic liquids.

    PubMed

    Patel, Divia Dinesh; Lee, Jong-Min

    2012-06-01

    Ionic liquids have recently gained popularity in the scientific community owing to their special properties and characteristics. One of the reasons why ionic liquids have been termed "green solvents" is due to their negligible vapour pressure. Their use in electrochemical, biological and metal extraction applications is discussed. Wide research has been carried out for their use in batteries, solar panels, fuel cells, drug deliveries and biomass pretreatments. This work aims to consolidate the various findings from previous works in these areas. PMID:22711528

  15. Atomistic insight into orthoborate-based ionic liquids: force field development and evaluation.

    PubMed

    Wang, Yong-Lei; Shah, Faiz Ullah; Glavatskih, Sergei; Antzutkin, Oleg N; Laaksonen, Aatto

    2014-07-24

    We have developed an all-atomistic force field for a new class of halogen-free chelated orthoborate-phosphonium ionic liquids. The force field is based on an AMBER framework with determination of force field parameters for phosphorus and boron atoms, as well as refinement of several available parameters. The bond and angle force constants were adjusted to fit vibration frequency data derived from both experimental measurements and ab initio calculations. The force field parameters for several dihedral angles were obtained by fitting torsion energy profiles deduced from ab initio calculations. To validate the proposed force field parameters, atomistic simulations were performed for 12 ionic liquids consisting of tetraalkylphosphonium cations and chelated orthoborate anions. The predicted densities for neat ionic liquids and the [P6,6,6,14][BOB] sample, with a water content of approximately 2.3-2.5 wt %, are in excellent agreement with available experimental data. The potential energy components of 12 ionic liquids were discussed in detail. The radial distribution functions and spatial distribution functions were analyzed and visualized to probe the microscopic ionic structures of these ionic liquids. There are mainly four high-probability regions of chelated orthoborate anions distributed around tetraalkylphosphonium cations in the first solvation shell, and such probability distribution functions are strongly influenced by the size of anions. PMID:25020237

  16. Complex Structural and Dynamical Interplay of Cyano-Based Ionic Liquids.

    PubMed

    Weber, Henry; Kirchner, Barbara

    2016-03-10

    We carried out ab initio molecular dynamics simulations for the three cyano-based ionic liquids, 1-ethyl-3-methylimidazolium tetracyanoborate ([C2C1Im][B(CN)4]), 1-ethyl-3-methyl-imidazolium dicyanamide ([C2C1Im][N(CN)2]), and 1-ethyl-3-methylimidazolium thiocyanate ([C2C1Im][SCN]). We found that the [SCN]-based ionic liquid is much more prone to π-π stacking interactions as opposed to the other two ionic liquids, contrary to the fact that all liquids bear the same cation. Hydrogen bonding is strong in the dicyanamide- and the thiocyanate-based ionic liquids and it is almost absent in the tetracyanoborate liquid. The anion prefers to stay on-top of the imidazolium ring with the highest priority for the [N(CN)2](-) anion followed by the [B(CN)4](-) anion. We find that experimental viscosity trends cannot be correlated to the hydrogen bond dynamics which is fastest for [B(CN)4](-) followed by [SCN](-) and [N(CN)2](-). For the dynamics of the cation on-top of itself, we find the order of [B(CN)4](-) followed by [N(CN)2](-) and finally by [SCN](-). Interestingly, this trend correlates well with the viscosity, suggesting a relation between the cation-cation dynamics and the viscosity at least for these cyano-based ionic liquids. These findings, especially the apparent correlation between cation-cation dynamics and the viscosity, might be useful for the suggestion of better ionic liquids in electrolyte applications. PMID:26882454

  17. Structures and Electronic Properties of Lithium Chelate-Based Ionic Liquids.

    PubMed

    Si, Dawei; Chen, Kexian; Yao, Jia; Li, Haoran

    2016-04-28

    The conformations, electronic properties, and interaction energies of four chelate-based ionic liquids [Li(EA)][Tf2N], [Li(HDA)][Tf2N], [Li(DEA)][Tf2N], and [Li(DOBA)][Tf2N] have been theoretically explored. The reliability of the located conformers has been confirmed via the comparison between the simulated and experimental infrared spectra. Our results show that the N-Li and O-Li coordinate bonds in cation are elongated as the numbers of coordinate heteroatoms of alkanolamine ligands to Li(+) increased. Also the binding energies between Li(+) and ligands are increased and the interaction energies between cations and Tf2N anion are decreased. The cation-anion interaction energies follow the order of [Li(DOBA)][Tf2N] < [Li(HDA)][Tf2N] < [Li(DEA)][Tf2N] < [Li(EA)][Tf2N], which fall within the energetic ranges of conventional ionic liquids. Interestingly, the strongest stabilization orbital interactions in these ionic liquids and their cations revealed by the natural bond orbital analysis lie in the interaction between the lone pair (LP) of the coordinate heteroatoms in ligands or anion as donors and the vacant valence shell nonbonding orbital (LP*) of Li(+) as acceptors, which are very different from that of conventional ionic liquids. Moreover, the charges transferred from cations to anion are quite similar, and the charge of Li(+) is proposed for possibly predicting the order of the interaction energies of ionic liquids in series. The present study allows for the deeper understanding the differences between chelate-based ionic liquids and conventional ionic liquids. PMID:27070194

  18. The use of ionic liquids based on choline chloride for metal deposition: A green alternative?

    PubMed

    Haerens, Kurt; Matthijs, Edward; Chmielarz, Andrzej; Van der Bruggen, Bart

    2009-08-01

    Ionic liquids are studied intensively for different applications. They tend to be denoted as "green solvents", largely because of their low vapour pressure. In recent years toxicity and biotoxicity of ionic liquids have also been investigated, which proved that not all of these are "green". In this paper the use of ionic liquids based on choline chloride and ethylene glycol in electrochemistry is discussed in the context of their use as green solvents. Due to their low toxicity and ready biodegradability, these deep eutectic solvents are promising for the electrodeposition of metals. The influence of the use of these liquids as metal deposition baths on the waste water is investigated. Drag-out was found to be the most influencing parameter on the environmental impact of the process, as it is three times higher compared to classical solutions due to the higher viscosity of the ionic liquid. There are no major changes needed in the rinsing configuration of classic electroplating plants, and ion exchange to remove the metal out of the waste water was not hindered by the presence of the ionic liquid. The formation of by-products during the deposition of metals has to be further investigated and evaluated in consideration of the environmental impact. PMID:19523749

  19. Different antibacterial activity of novel theophylline-based ionic liquids - Growth kinetic and cytotoxicity studies.

    PubMed

    Borkowski, Andrzej; Ławniczak, Łukasz; Cłapa, Tomasz; Narożna, Dorota; Selwet, Marek; Pęziak, Daria; Markiewicz, Bartosz; Chrzanowski, Łukasz

    2016-08-01

    The aim of this study was to investigate novel theophylline-based ionic liquids and their cytotoxic effects towards model Gram-positive and Gram-negative bacteria (Bacillus cereus and Escherichia coli, respectively). Growth kinetics, respiratory rates and dehydrogenase activities were studied in the presence of ionic liquids at concentrations ranging from 10 to 1000mg/L. Additionally, the influence of ionic liquids on bacterial cells associated with specific interactions based on the structure of cell wall was evaluated. This effect was assessed by viability tests and scanning electron microscope observations. The obtained results confirmed that ionic liquids exhibit different levels of toxicity in relation to Gram-positive and Gram-negative bacteria. Those effects are associated with the chemical structure of the cationic species of the ionic liquids and their critical micelle concentration value. It was established that the presence of an alkyl or allyl group increased the toxicity, whereas the presence of an aryl group in the cation decreased the toxic effect of ILs. Results presented in this study also revealed unexpected effects of self-aggregation of E. coli cells. Overall, it was established that the studied ILs exhibited higher toxicity towards Gram-positive bacteria due to different interactions between the ILs and the cell membranes. These findings may be of importance for the design of ILs with targeted antimicrobial properties. PMID:27082812

  20. CuO nanostructures: optical properties and morphology control by pyridinium-based ionic liquids.

    PubMed

    Sabbaghan, Maryam; Shahvelayati, Ashraf Sadat; Madankar, Kamelia

    2015-01-25

    Copper oxide nanostructures have been synthesized by a simple reflux method in aqueous medium of pyridinium based ionic liquids. The structural and optical properties of CuO nanostructures were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), photoluminescence spectroscopy (PL) and UV-visible. The morphologies of the nanostructures can be controlled by changing the amount of NaOH and ionic liquids. The results show that the use identical pyridinium based ionic liquids in ratio of 4:1 NaOH/Cu(OAc)2⋅H2O yield minor differences in morphology of CuO nanostructures. Different morphologies of CuO nanostructures were obtained by changing the ratio NaOH/Cu(OAc)2⋅H2O to 2:1. Ionic liquids play an important role on optical properties of CuO nanostructures. The results of optical measurements of the CuO nanostructures illustrate that band gaps are estimated to be 1.67-1.85 eV. PL patterns studies show that the ionic liquids can be effect on PL patterns of the samples. The reasons of these phenomena are discussed. PMID:25128679

  1. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng; Luo, Huimin

    2011-11-01

    Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic ligand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

  2. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng [Knoxville, TN; Luo, Huimin [Knoxville, TN

    2008-09-09

    Ionic compounds which are liquids at room temperature are formed by the method of mixing a neutral organic liqand with the salt of a metal cation and its conjugate anion. The liquids are hydrophobic, conductive and stable and have uses as solvents and in electrochemical devices.

  3. Ionic liquid-based dispersive liquid-liquid microextraction for the determination of formaldehyde in wastewaters and detergents.

    PubMed

    Arvand, Majid; Bozorgzadeh, Elahe; Shariati, Shahab; Zanjanchi, Mohammad Ali

    2012-12-01

    Spectrophotometry in combination with ionic liquid-based dispersive liquid-liquid microextraction (DLLME) was applied for the extraction and determination of formaldehyde in real samples. The method is based on the reaction of formaldehyde with methyl acetoacetate in the presence of ammonia. The variation in the absorbance of the reaction product was measured at 375 nm. An appropriate mixture of ethanol (disperser solvent) and ionic liquid, 1-hexyl-3-methylimidazoliumhexafluoro-phosphate [C(6)MIM][PF(6)] (extraction solvent) was rapidly injected into a water sample containing formaldehyde. After extraction, sedimented phase was analyzed by spectrophotometry. Under the optimum conditions, the calibration graph was linear in the range of 0.1-20 ng mL(-1) with the detection limit of 0.02 ng mL(-1) and limit of quantification of 0.08 ng mL(-1) for formaldehyde. The relative standard deviation (RSD%, n = 5) for the extraction and determination of 0.8 ng mL(-1) of formaldehyde in the aqueous samples was 2.5%. The results showed that DLLME is a very simple, rapid, sensitive, and efficient analytical method for the determination of trace amounts of formaldehyde in wastewaters and detergents, and suitable results were obtained. PMID:22258742

  4. Ion segregation in an ionic liquid confined within chitosan based chemical ionogels.

    PubMed

    Guyomard-Lack, A; Buchtová, N; Humbert, B; Le Bideau, J

    2015-10-01

    Ionogels based on in situ crosslinking of chitosan in the ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIm Ac) are synthesized, and studied from macroscopic properties to preferred interactions at the host matrix/EMIm Ac interface. It is highlighted that the imidazolium cations of the ionic liquid (IL) show preferred interactions with the chitosan host matrix. This exemplifies how the confinement of ILs, through an interface effect, can induce the breakdown of aggregated regions found systematically in bulk ILs and can increase the fragility of ILs. These biopolymer based ionogels could find application as biosensors and in the field of energy. PMID:26313702

  5. Mutual Lewis acid-base interactions of cations and anions in ionic liquids.

    PubMed

    Holzweber, Markus; Lungwitz, Ralf; Doerfler, Denise; Spange, Stefan; Koel, Mihkel; Hutter, Herbert; Linert, Wolfgang

    2013-01-01

    Solute properties are known to be strongly influenced by solvent molecules due to solvation. This is due to mutual interaction as both the properties of the solute and of the solvent strongly depend on each other. The present paper is based on the idea that ionic liquids are cations solvated by anions and anions solvated by cations. To show this (in this system strongly pronounced) interaction the long time established donor-acceptor concept for solvents and ions in solution by Viktor Gutmann is extended to ionic liquids. A number of solvent parameters, such as the Kamlet-Abboud-Taft and the Dimroth-Reichardt E(T) scale for ionic liquids neglect this mutual influence, which, however, seems to be in fact necessary to get a proper description of ionic liquid properties. It is shown how strong such parameters vary when the influence of the counter ion is taken into account. Furthermore, acceptor and donor numbers for ionic liquids are presented. PMID:23180598

  6. Electrolytes based on alkoxysilyl-functionalized ionic liquids: viscoelastic properties and conductivity.

    PubMed

    Slemenik Perše, L; Colović, M; Hajzeri, M; Orel, B; Surca Vuk, A

    2014-08-14

    Ionic liquids can be successfully used as electrolytes in electrochemical devices when they are in their quasi-solid state. Among several methods of solidification, a sol-gel process was chosen and a set of alkoxysilyl-functionalized iodide imidazolium-based ionic liquids were synthesized. The electrolytes were prepared by mixing these ionic liquids with a non-polymerisable ionic liquid (1-methyl-3-propylimidazolium iodide (MPIm(+)I(-))). Iodine was dissolved in an electrolyte matrix in order to form an I3(-)/I(-) redox couple. The change of the structure from sol to gel was followed by rheological tests in order to show the effect of different rheological parameters on the gelation process. The solvolysis with glacial acetic acid and condensation were followed by rheological experiments on the samples taken from a batch, and in situ on the rheometer. The formed three-dimensional sol-gel networks of various alkoxysilyl-functionalized ionic liquids differed in their microstructures and viscoelastic properties that were correlated with conductivity. The results show that the conductivity of approximately 10(-3) S cm(-1) at room temperature was achieved for the gels with relatively high values of elastic modulus and noticeable viscous contribution. It is shown that not only the viscosity but also the viscoelastic behavior and especially the relationship between viscous and elastic moduli (phase shift) together with the time of gelation are essential for the high conductivity of electrolytes. PMID:24955729

  7. Recombination of Photogenerated Lophyl Radicals in Imidazolium-Based Ionic Liquids

    SciTech Connect

    Strehmel, V.; Wishart, J.; Polyansky, D.E.; Strehmel, B.

    2009-10-20

    Laser flash photolysis is applied to study the recombination reaction of lophyl radicals in ionic liquids in comparison with dimethylsulfoxide as an example of a traditional organic solvent. The latter exhibits a similar micropolarity as the ionic liquids. The ionic liquids investigated are 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (1), 1-hexyl-3-methylimidazolium hexafluorophosphate (2), and 1-butyl-3-methylimidazolium tetafluoroborate (3). The recombination of the photolytic generated lophyl radicals occur significantly faster in the ionic liquids than expected from their macroscopic viscosities and is a specific effect of these ionic liquids. On the other hand, this reaction can be compared with the macroscopic viscosity in the case of dimethylsulfoxide. Activation parameters obtained for lophyl radical recombination suggest different, anion-dependent mechanistic effects. Quantum chemical calculations based on density functional theory provide a deeper insight of the molecular properties of the lophyl radical and its precursor. Thus, excitation energies, spin densities, molar volumes, and partial charges are calculated. Calculations show a spread of spin density over the three carbon atoms of the imidazolyl moiety, while only low spin density is calculated for the nitrogens.

  8. X-ray Photoelectron Spectroscopy of Pyridinium-Based Ionic Liquids: Comparison to Imidazolium- and Pyrrolidinium-Based Analogues.

    PubMed

    Men, Shuang; Mitchell, Daniel S; Lovelock, Kevin R J; Licence, Peter

    2015-07-20

    We investigate eight 1-alkylpyridinium-based ionic liquids of the form [Cn Py][A] by using X-ray photoelectron spectroscopy (XPS). The electronic environment of each element of the ionic liquids is analyzed. In particular, a reliable fitting model is developed for the C 1s region that applies to each of the ionic liquids. This model allows the accurate charge correction of binding energies and the determination of reliable and reproducible binding energies for each ionic liquid. Shake-up/off phenomena are determinedfor both C 1s and N 1s spectra. The electronic interaction between cations and anions is investigated for both simple ionic liquids and an example of an ionic-liquid mixture; the effect of the anion on the electronic environment of the cation is also explored. Throughout the study, a detailed comparison is made between [C8 Py][A] and analogues including 1-octyl-1-methylpyrrolidinium- ([C8 C1 Pyrr][A]), and 1-octyl-3-methylimidazolium- ([C8 C1 Im][A]) based samples, where X is common to all ionic liquids. PMID:25952131

  9. Ionic liquid based lithium battery electrolytes: charge carriers and interactions derived by density functional theory calculations.

    PubMed

    Angenendt, Knut; Johansson, Patrik

    2011-06-23

    The solvation of lithium salts in ionic liquids (ILs) leads to the creation of a lithium ion carrying species quite different from those found in traditional nonaqueous lithium battery electrolytes. The most striking differences are that these species are composed only of ions and in general negatively charged. In many IL-based electrolytes, the dominant species are triplets, and the charge, stability, and size of the triplets have a large impact on the total ion conductivity, the lithium ion mobility, and also the lithium ion delivery at the electrode. As an inherent advantage, the triplets can be altered by selecting lithium salts and ionic liquids with different anions. Thus, within certain limits, the lithium ion carrying species can even be tailored toward distinct important properties for battery application. Here, we show by DFT calculations that the resulting charge carrying species from combinations of ionic liquids and lithium salts and also some resulting electrolyte properties can be predicted. PMID:21591707

  10. Ionic-liquid-based dispersive liquid-liquid microextraction for high-throughput multiple food contaminant screening.

    PubMed

    Ho, Yee-Man; Tsoi, Yeuk-Ki; Leung, Kelvin Sze-Yin

    2013-12-01

    This paper describes an innovation of dispersive liquid-liquid microextraction enabling multiple-component analysis of eight high-priority food contaminants in two chemically distinctive families: Sudan dyes and phthalate plasticizers. To provide convenient sample handling for solid and solid-containing matrices, a modified dispersive liquid-liquid microextraction procedure used an extractant precoated frit to perform simultaneous filtration, solvent mixing, and phase dispersion in one simple step. A binary ionic liquid extractant system was carefully tuned to deliver high quality analysis based only on affordable LC with diode array detector instrumentation. The method is comprehensively validated for robust quantification with good precision (6.9-9.8% RSD) in a linear 2-1000 μg/L range. Having accomplished enrichment factors up to 451, the treatment enables sensitive detection at 0.09-1.01 μg/L levels. Analysis of six high-risk solid condiments and sauces further verified its practical applicability within a 70-120% recovery range. Compared to other approaches, the current dispersive liquid-liquid microextraction treatment offers major advantages in terms of minimal solvent (1.5 mL) and sample (0.1 g) consumption, ultra-high analytical throughput (6 min), and the ability to handle complex solid matrices. The idea of performing simultaneous analysis for multiple contaminants presented here fosters a more effective mode of operation in food control routines. PMID:24039178

  11. Partition coefficients of organic compounds between water and imidazolium-, pyridinium-, and phosphonium-based ionic liquids.

    PubMed

    Padró, Juan M; Pellegrino Vidal, Rocío B; Reta, Mario

    2014-12-01

    The partition coefficients, P IL/w, of several compounds, some of them of biological and pharmacological interest, between water and room-temperature ionic liquids based on the imidazolium, pyridinium, and phosphonium cations, namely 1-octyl-3-methylimidazolium hexafluorophosphate, N-octylpyridinium tetrafluorophosphate, trihexyl(tetradecyl)phosphonium chloride, trihexyl(tetradecyl)phosphonium bromide, trihexyl(tetradecyl)phosphonium bis(trifluoromethylsulfonyl)imide, and trihexyl(tetradecyl)phosphonium dicyanamide, were accurately measured. In this way, we extended our database of partition coefficients in room-temperature ionic liquids previously reported. We employed the solvation parameter model with different probe molecules (the training set) to elucidate the chemical interactions involved in the partition process and discussed the most relevant differences among the three types of ionic liquids. The multiparametric equations obtained with the aforementioned model were used to predict the partition coefficients for compounds (the test set) not present in the training set, most being of biological and pharmacological interest. An excellent agreement between calculated and experimental log P IL/w values was obtained. Thus, the obtained equations can be used to predict, a priori, the extraction efficiency for any compound using these ionic liquids as extraction solvents in liquid-liquid extractions. PMID:25326892

  12. Electroplating Using Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Abbott, Andrew P.; Frisch, Gero; Ryder, Karl S.

    2013-07-01

    Electroplating is a key technology in many large-scale industrial applications such as corrosion-resistant and decorative coatings. Issues with current aqueous processes, such as toxicity of reagents and low current efficiencies, can often be overcome by using ionic liquids, and this approach has turned ionometallurgy into a fast-growing area of research. This review outlines the interactions in ionic liquids that are responsible for the advantageous properties of these solvents in electroplating. It summarizes recent research in which these properties have been analyzed or exploited and highlights fundamental issues in research and technology that need to be addressed.

  13. NOvel Fission Product Separation Based on Room-Temperature Ionic liquids

    SciTech Connect

    Hussey, Charles L.

    2005-11-13

    The effective extraction of Cs+ and Sr2+ into a relatively new and heretofore untested hydrophobic ionic liquid, tri-n-butylmethylammonium bis[(trifluoromethyl)sulfonyl]imide was demonstrated with calix[4]arene-bis(tert-octylbenzo-crown-6) and dicyclohexano-18-crown-6, respectively. The coordinated Cs+ and Sr2+ were subsequently removed from the ionic liquid extraction solvent by an electrochemical reduction process carried out at mercury electrodes. This process is non-destructive, permitting the ionic liquid and ionophores to be recycled. Although the process is based on mercury electrodes, this is a benefit rather than a detriment because the liquid mercury containing the Cs and Sr can be easily transported to another electrochemical cell where the Cs and Sr could be electrochemically recovered from the mercury amalgam and concentrated into a minimum volume of water or some other inexpensive solvent. This should facilitate the development of a suitable waste form for the extracted Cs+ and Sr2+. Thus, the feasibility of the proposed ionic liquid-based extraction cycle for the removal of 137Cs+ and 90Sr2+ from simulated aqueous tank waste was demonstrated.

  14. Electrochemical Polishing Applications and EIS of a Novel Choline Chloride-Based Ionic Liquid

    SciTech Connect

    Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.; Abdel-Fattah, Tarek M.

    2013-06-01

    Minimal surface roughness is a critical feature for high-field superconducting radio frequency (SRF) cavities used to engineer particle accelerators. Current methods for polishing Niobium cavities typically utilize solutions containing a mixture of concentrated sulfuric and hydrofluoric acid. Polishing processes such as these are effective, yet there are many hazards and costs associated with the use (and safe disposal) of the concentrated acid solutions. An alternative method for electrochemical polishing of the cavities was explored using a novel ionic liquid solution containing choline chloride. Potentiostatic electrochemical impedance spectroscopy (EIS) was used to analyze the ionic polishing solution. Final surface roughness of the Nb was found to be comparable to that of the acid-polishing method, as assessed by atomic force microscopy (AFM). This indicates that ionic liquid-based electrochemical polishing of Nb is a viable replacement for acid-based methods for preparation of SRF cavities.

  15. Water-free rare-earth-metal ionic liquids/ionic liquid crystals based on hexanitratolanthanate(III) anion.

    PubMed

    Ji, Shun-Ping; Tang, Meng; He, Ling; Tao, Guo-Hong

    2013-04-01

    The hexanitratolanthanate anion (La(NO(3))(6)(3-)) is an interesting symmetric anion suitable to construct the component of water-free rare-earth-metal ionic liquids. The syntheses and structural characterization of eleven lanthanum nitrate complexes, [C(n)mim](3)[La(NO(3))(6)] (n=1, 2, 4, 6, 8, 12, 14, 16, 18), including 1,3-dimethylimidazolium hexanitratolanthanate ([C(1)mim](3)[La(NO(3))(6)], 1), 1-ethyl-3-methylimidazolium hexanitratolanthanate ([C(2)mim](3)[La(NO(3))(6)], 2), 1-butyl-3-methylimidazolium hexanitratolanthanate ([C(4)mim](3)[La(NO(3))(6)], 3), 1-isobutyl-3-methylimidazolium hexanetratolanthanate ([isoC(4)mim](3)[La(NO(3))(6)], 4), 1-methyl-3-(3'-methylbutyl)imidazolium hexanitratolanthanate ([MC(4)mim](3)[La(NO(3))(6)], 5), 1-hexyl-3-methylimidazolium hexanitratolanthanate ([C(6)mim](3)[La(NO(3))(6)], 6), 1-methyl-3-octylimidazolium hexanitratolanthanate ([C(8)mim](3)[La(NO(3))(6)], 7), 1-dodecyl-3-methylimidazolium hexanitratolanthanate ([C(12)mim](3)[La(NO(3))(6)], 8), 1-methyl-3-tetradecylimidazolium hexanitratolanthanate ([C(14)mim](3)[La-(NO(3))(6)], 9), 1-hexadecyl-3-methylimid-azolium hexanitratolanthanum ([C(16)dmim](3)[La(NO(3))(6)], 10), and 1-methyl-3-octadecylimidazolium hexanitratolanthanate ([C(18)mim](3)[La(NO(3))(6)], 11) are reported. All new compounds were characterized by (1)H and (13)C NMR, and IR spectroscopy as well as elemental analysis. The crystal structure of compound 1 was determined by using single-crystal X-ray diffraction, giving the following crystallographic information: monoclinic; P2(1)/c; a=15.3170 (3), b=14.2340 (2), c=13.8954(2) Å; β=94.3453(15)°, V=3020.80(9) Å(3), Z=4, ρ=1.764 g cm(-3). The coordination polyhedron around the lanthanum ion is rationalized by six nitrate anions with twelve oxygen atoms. No hydrogen-bonding network or water molecule was found in 1. The thermodynamic stability of the new complexes was investigated by using thermogravimetric analysis (TGA). The water

  16. X‐ray Photoelectron Spectroscopy of Pyridinium‐Based Ionic Liquids: Comparison to Imidazolium‐ and Pyrrolidinium‐Based Analogues

    PubMed Central

    Mitchell, Daniel S.; Lovelock, Kevin R. J.

    2015-01-01

    Abstract We investigate eight 1‐alkylpyridinium‐based ionic liquids of the form [CnPy][A] by using X‐ray photoelectron spectroscopy (XPS). The electronic environment of each element of the ionic liquids is analyzed. In particular, a reliable fitting model is developed for the C 1s region that applies to each of the ionic liquids. This model allows the accurate charge correction of binding energies and the determination of reliable and reproducible binding energies for each ionic liquid. Shake‐up/off phenomena are determinedfor both C 1s and N 1s spectra. The electronic interaction between cations and anions is investigated for both simple ionic liquids and an example of an ionic‐liquid mixture; the effect of the anion on the electronic environment of the cation is also explored. Throughout the study, a detailed comparison is made between [C8Py][A] and analogues including 1‐octyl‐1‐methylpyrrolidinium‐ ([C8C1Pyrr][A]), and 1‐octyl‐3‐methylimidazolium‐ ([C8C1Im][A]) based samples, where X is common to all ionic liquids. PMID:25952131

  17. Modeling the structure and thermodynamics of ferrocenium-based ionic liquids.

    PubMed

    Bernardes, Carlos E S; Mochida, Tomoyuki; Canongia Lopes, José N

    2015-04-21

    A new force-field for the description of ferrocenium-based ionic liquids is reported. The proposed model was validated by confronting Molecular Dynamics simulations results with available experimental data-enthalpy of fusion, crystalline structure and liquid density-for a series of 1-alkyl-2,3,4,5,6,7,8,9-octamethylferrocenium bis(trifluoromethylsulfonyl)imide ionic liquids, [CnFc][NTf2] (3 ≤ n ≤ 10). The model is able to reproduce the densities and enthalpies of fusion with deviations smaller than 2.6% and 4.8 kJ mol(-1), respectively. The MD simulation trajectories were also used to compute relevant structural information for the different [CnFc][NTf2] ionic liquids. The results show that, unlike other ILs, the alkyl side chains present in the cations are able to interact directly with the ferrocenium core of other ions. Even the ferrocenium charged cores (with relatively mild charge densities) are able to form small contact aggregates. This causes the partial rupture of the polar network and precludes the formation of extended nano-segregated polar-nonpolar domains normally observed in other ionic liquids. PMID:25797914

  18. Azobenzene-based organic salts with ionic liquid and liquid crystalline properties

    DOE PAGESBeta

    Stappert, Kathrin; Muthmann, Johanna; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    Two sets of new azobenzene-based bromide salts are synthesized, and their thermal photochromic properties are studied. Both sets are based on the imidazolium cation. The first set (1) features a symmetric biscation where two imidazolium head groups (Im) with different alkyl chains (Cn) are connected to a central azobenzene unit (Azo): [Azo(C1-Im-Cn)2]; n = 6, 8, 10, 12, 14. The other one contains an n-alkyl-imidazolium cation (Cn-Im) bearing a terminal azobenzene unit (C1-Azo) substituted with an alkoxy chain (O-Cm) of either two (2) or six (3) carbon atoms: [C1-Azo-O-Cm-Im-Cn]; m = 2, n = 8, 10, 12 and m =more » 6, n = 8, 10, 12, 14, 16. For both cation classes, the influence of alkyl chains of varying length on the thermal phase behavior was investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). For five compounds (Azo(-C1-Im-C12)2 (1d), Azo(-C1-Im-C12)2 (1e), C1-Azo-O-C2-Im-C10 (2b), C1-Azo-O-C2-Im-C12 (2c), and C1-Azo-O-C6-Im-C16 (3e)), the formation of a liquid crystalline phase was observed. The biscationic salts (1) are all comparatively high melting organic salts (180–240 °C), and only the two representatives with long alkylchains (C12 and C14) exhibit liquid crystallinity. The monocationic salts with an O–C2 bridge (2) melt between 140 and 170 °C depending on the alkyl chain length, but from an alkyl chain of 10 and more carbon atoms on they form a smectic A liquid crystalline phase. The representatives of the third set with a O–C6 bridge qualify as ionic liquids with melting points less than 100 °C. However, only the representative with a hexadecyl chain forms a liquid crystalline phase. Representative single crystals for all sets of cations could be grown that allowed for single crystal structure analysis. Together with small-angle X-ray scattering experiments they allow for a more detailed understanding of the thermal properties. As a result, through irradiation with UV-light (320–366 nm) all

  19. Azobenzene-based organic salts with ionic liquid and liquid crystalline properties

    SciTech Connect

    Stappert, Kathrin; Muthmann, Johanna; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    Two sets of new azobenzene-based bromide salts are synthesized, and their thermal photochromic properties are studied. Both sets are based on the imidazolium cation. The first set (1) features a symmetric biscation where two imidazolium head groups (Im) with different alkyl chains (Cn) are connected to a central azobenzene unit (Azo): [Azo(C1-Im-Cn)2]; n = 6, 8, 10, 12, 14. The other one contains an n-alkyl-imidazolium cation (Cn-Im) bearing a terminal azobenzene unit (C1-Azo) substituted with an alkoxy chain (O-Cm) of either two (2) or six (3) carbon atoms: [C1-Azo-O-Cm-Im-Cn]; m = 2, n = 8, 10, 12 and m = 6, n = 8, 10, 12, 14, 16. For both cation classes, the influence of alkyl chains of varying length on the thermal phase behavior was investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). For five compounds (Azo(-C1-Im-C12)2 (1d), Azo(-C1-Im-C12)2 (1e), C1-Azo-O-C2-Im-C10 (2b), C1-Azo-O-C2-Im-C12 (2c), and C1-Azo-O-C6-Im-C16 (3e)), the formation of a liquid crystalline phase was observed. The biscationic salts (1) are all comparatively high melting organic salts (180–240 °C), and only the two representatives with long alkylchains (C12 and C14) exhibit liquid crystallinity. The monocationic salts with an O–C2 bridge (2) melt between 140 and 170 °C depending on the alkyl chain length, but from an alkyl chain of 10 and more carbon atoms on they form a smectic A liquid crystalline phase. The representatives of the third set with a O–C6 bridge qualify as ionic liquids with melting points less than 100 °C. However, only the representative with a hexadecyl chain forms a liquid crystalline phase. Representative single crystals for all sets of cations could be grown that allowed for single crystal structure analysis. Together with small-angle X-ray scattering experiments they allow for a more detailed understanding of the thermal properties. As a result, through irradiation with UV

  20. Refolding effects of partially immiscible ammonium-based ionic liquids on the urea-induced unfolded lysozyme structure.

    PubMed

    Bisht, Meena; Kumar, Awanish; Venkatesu, Pannuru

    2016-05-14

    The activity of lysozyme over a Micrococcus lysodeikticus cell suspension increased to 13% of the initial value in the presence of 1% v/v ammonium-based ionic liquids after deactivation with 4.0 M urea. This increase in activity reflects the refolding ability of the ionic liquids against the denaturation effects of urea on lysozyme. PMID:27094019

  1. New ionic liquids based on complexation of dipropylsulfide and AlCl3 for electrochodeposition of aluminum

    SciTech Connect

    Fang, Youxing; Jiang, Xueguang; Dai, Sheng; Sun, Xiao-Guang

    2015-01-01

    A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl3 has been prepared. The equivalent concentration of AlCl3 in the ionic liquid is as high as 2.3 M. More importantly, it is highly fluidic and exhibits an ambient ionic conductivity of 1.25 x 10-4 S cm-1. This new ionic liquid can be successfully used as an electrolyte for electrodeposition of aluminum.

  2. Micro magnetofluidics: droplet manipulation of double emulsions based on paramagnetic ionic liquids.

    PubMed

    Misuk, Viktor; Mai, Andreas; Giannopoulos, Konstantinos; Alobaid, Falah; Epple, Bernd; Loewe, Holger

    2013-12-01

    The ability to control and manipulate discrete fluid droplets by magnetic fields offers new opportunities in microfluidics. A surfactant-free and easy to realize technique for the continuous generation of double emulsion droplets, composed of an organic solvent and a paramagnetic ionic liquid, is applied. The inner phase of the emulsion droplet consists of imidazolium-based ionic liquids with either iron, manganese, nickel or dysprosium containing anions which provide paramagnetic behaviour. The double emulsion droplets are dispersed in a continuous phase of FC-40. All substances - the organic phase, the paramagnetic ionic liquid and the continuous phase -are immiscible. The magnetic properties of ionic liquids allow, through the influence of external magnetic fields, the manipulation of individual emulsion droplets such as capture and release, rotation and distortion. Arrays of magnets allow a coalescence of emulsion droplets and their subsequent mixing by flowing through an alternating permanent magnetic field. In addition, the double emulsion droplets can be split and reunified, or continuously separated into their original phases. PMID:24108233

  3. Phase Transitions of Triflate-Based Ionic Liquids under High Pressure.

    PubMed

    Faria, Luiz F O; Ribeiro, Mauro C C

    2015-11-01

    Raman spectroscopy has been used to study phase transitions of ionic liquids based on the triflate anion, [TfO](-), as a function of pressure or temperature. Raman spectra of ionic liquids containing the cations 1-butyl-3-methylimidazolium, [C4C1Im](+), 1-octyl-3-methylimidazolium, [C8C1Im](+), 1-butyl-2,3-dimethylimidazolium, [C4C1C1Im](+), and 1-butyl-1-methylpyrrolidinium, [C4C1Pyr](+), were compared. Vibrational frequencies and binding energy of ionic pairs were calculated by quantum chemistry methods. The ionic liquids [C4C1Im][TfO] and [C4C1Pyr][TfO] crystallize at 1.0 GPa when the pressure is increased in steps of ∼ 0.2 GPa from the atmospheric pressure, whereas [C8C1Im][TfO] and [C4C1C1Im][TfO] do not crystallize up to 2.3 GPa of applied pressure. The low-frequency range of the Raman spectrum of [C4C1Im][TfO] indicates that the system undergoes glass transition, rather than crystallization, when the pressure applied on the liquid has been increased above 2.0 GPa in a single step. Strong hysteresis of spectral features (frequency shift and bandwidth) of the high-pressure crystalline phase when the pressure was released stepwise back to the atmospheric pressure has been found . PMID:26457868

  4. Thermodynamical and structural properties of imidazolium based ionic liquids from molecular simulation

    NASA Astrophysics Data System (ADS)

    Raabe, Gabriele; Köhler, Jürgen

    2008-04-01

    We have performed molecular dynamics simulations to determine the densities and heat of vaporization as well as structural information for the 1-alkyl-3-methyl-imidazolium based ionic liquids [amim][Cl] and [amim][BF4] in the temperature range from 298to363K. In this simulation study, we used an united atom model of Liu et al. [Phys. Chem. Chem. Phys. 8, 1096 (2006)] for the [emim+] and [bmim+] cations, which we have extended for simulation in [hmim]-ILs and combined with parameters of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] for the [Cl-] anion. Our simulation results prove that both the original united atoms approach by Liu et al. and our extension yield reasonable predictions for the ionic liquid with a considerably reduced computational expense than that required for all atoms models. Radial distribution functions and spatial distribution functions where employed to analyze the local structure of this ionic liquid, and in which way it is influenced by the type of the anion, the size of the cation, and the temperature. Our simulations give evidence for the occurrence of tail aggregations in these ionic liquids with increasing length of the side chain and also increasing temperature.

  5. Acetylcholinesterase biosensor for carbamate drugs based on tetrathiafulvalene-tetracyanoquinodimethane/ionic liquid conductive gels.

    PubMed

    Zamfir, Lucian-Gabriel; Rotariu, Lucian; Bala, Camelia

    2013-08-15

    A highly sensitive acetylcholinesterase biosensor was developed for detection of carbamate drugs based on TTF-TCNQ-ionic liquid gel thiocholine sensor. The TTF-TCNQ-ionic/ionic liquid gel was characterized by FT-IR and scanning electron microscopy. The electrocatalytic behavior of TTF-TCNQ-ionic liquid gels toward oxidation of thiocholine was thoroughly investigated. 1-Ethyl-3-methylimidazolium tetracyanoborate gel based sensor allowed amperometric detection of thiocholine at +400 mV vs. Ag/AgCl with a high sensitivity of 55.9±1.2 μA mM(-1)cm(-2) and a low detection limit equal to 7.6 μM. The catalytic rate constant and diffusion constant of thiocholine were estimated from chronoamperometric data. The proposed biosensor based on AChE immobilized in sol-gel matrix was used for the detection of two carbamate therapeutic drugs. Very low detection limits of 26 pM eserine and 0.3 nM neostigmine were achieved. The analysis of spiked tap water proved the biosensor capability to be used as a screening method for detection of carbamate drugs in wastewaters. PMID:23500478

  6. Solvent systems for countercurrent chromatography: an aqueous two phase liquid system based on a room temperature ionic liquid.

    PubMed

    Ruiz-Angel, Maria Jose; Pino, Veronica; Carda-Broch, Samuel; Berthod, Alain

    2007-06-01

    A new aqueous two phase liquid system (ATPS) based on the ionic liquid 1-butyl-3-methyl imidazolium chloride (BMIM Cl), potassium dibasic phosphate (K(2)HPO(4)) and water was recently proposed in the literature. The full phase diagram of this ATPS was prepared and some tie lines were fully determined. It was compared to classical ATPSs based on polyethylene glycol with an average molecular mass of 1000 (PEG 1000) and 10,000 (PEG 10000) and K(2)HPO(4). Two countercurrent chromatography (CCC) columns, a hydrostatic Sanki and a J type hydrodynamic CCC columns were used to test the liquid phase retention of these ATPSs in all possible configurations. It was found that the BMIM Cl ATPS liquid phases were much easier to retain in the two CCC columns than the PEG 1000 ATPS phases. Using protein and alcohol solutes, it was established that the BMIM Cl ATPS has a polarity completely different from that of the PEG 1000 ATPS. For example, ovalbumin partitions equally between the two phases of the PEG 1000 ATPS (K(D)=1.4) when it is completely located in the BMIM Cl upper phase of the ionic liquid ATPS (K(D)=180). The discrimination factor of the ionic liquid system and its intrinsic hydrophobicity were respectively found three times higher and ten times lower than the respective values of the PEG 1000 ATPS. PMID:17166506

  7. Partition coefficients of organic compounds in new imidazolium based ionic liquids using inverse gas chromatography.

    PubMed

    Revelli, Anne-Laure; Mutelet, Fabrice; Jaubert, Jean-Noël

    2009-06-01

    Partition coefficients of organic compounds in four ionic liquids: 1-ethanol-3-methylimidazolium tetrafluoroborate, 1-ethanol-3-methylimidazolium hexafluorophosphate, 1,3-dimethylimidazolium dimethylphosphate and 1-ethyl-3-methylimidazolium diethylphosphate were measured using inverse gas chromatography from 303.3 to 332.55K. The influence of gas-liquid and gas-solid interfacial adsorption of different solutes on ionic liquids was also studied. Most of the polar solutes were retained largely by partition while light hydrocarbons were retained predominantly by interfacial adsorption on the ionic liquids studied in this work. The solvation characteristics of the ionic liquids were evaluated using the Abraham solvation parameter model. PMID:19414174

  8. Ionic nanoparticle networks: development and perspectives in the landscape of ionic liquid based materials.

    PubMed

    Neouze, Marie-Alexandra; Kronstein, Martin; Tielens, Frederik

    2014-09-28

    This feature article gives an overview of the research performed on ionic nanoparticle networks (INNs). These INNs are hybrid materials consisting of inorganic nanoparticles and ionic linkers, such as imidazolium, bisimidazolium or pyridinium. The synthesis and properties of INNs, for catalysis or sensorics, are presented. At each step INN materials are compared to other hybrid materials of similar composition such as ionogels or suspensions of imidazolium modified nanoparticles. PMID:24968952

  9. Role of the Hofmeister series in the formation of ionic-liquid-based aqueous biphasic systems.

    PubMed

    Shahriari, Shahla; Neves, Catarina M S S; Freire, Mara G; Coutinho, João A P

    2012-06-21

    Among the numerous and interesting features of ionic liquids is their ability to form aqueous biphasic systems (ABSs) when combined with inorganic or organic salts in aqueous media. In this work, a wide range of salts was studied, aiming at gathering a detailed picture on the molecular mechanisms that govern the ability of the salt ions to induce the formation of ionic-liquid-based ABSs. For that purpose, 1-butyl-3-methylimidazolium trifluoromethanesulfonate was chosen due to its facility to undergo liquid-liquid demixing in aqueous media containing conventional salts. The corresponding ternary phase diagrams, tie-lines, and tie-line lengths were determined at 298 K and atmospheric pressure. With the large body of data measured in this work, it was possible to establish a scale on the salt cation and anion abilities to induce the formation of ionic-liquid-based ABSs, which follows the Hofmeister series, and to show that the molar entropy of hydration of the salt ions is the driving force for aqueous two-phase system formation. PMID:22594382

  10. Biocatalytic transformations in ionic liquids.

    PubMed

    van Rantwijk, Fred; Madeira Lau, Rute; Sheldon, Roger A

    2003-03-01

    Room temperature ionic liquids are non-volatile, thermally stable and highly polar; they are also moderately hydrophilic solvents. Here, we discuss their use as reaction media for biocatalysis. Enzymes of widely diverging types are catalytically active in ionic liquids or aqueous biphasic ionic liquid systems. Lipases, in particular, maintain their activity in anhydrous ionic liquid media; the (enantio)selectivity and operational stability are often better than in traditional media. The unconventional solvent properties of ionic liquids have been exploited in biocatalyst recycling and product recovery schemes that are not feasible with traditional solvent systems. PMID:12628370

  11. Conductivity Scaling Relationships in Nanostructured Membranes based on Protic Polymerized Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Sanoja, Gabriel; Lynd, Nathaniel; Segalman, Rachel

    2015-03-01

    Nanostructured membranes based on protic polymerized ionic liquids are of great interest for a variety of electrochemical applications. Understanding the relationship between composition, structure, and ionic conductivity for these materials is essential for designing novel membranes with improved properties. In this work, we explore the effect of volume fraction of ionic liquid on conductivity, σ using a model system composed of poly[isoprene-block-(ethylene oxide-stat-histamine glycidyl ether) diblock copolymers [PI- b - P(EO-stat-HGE)] and the resulting [PI- b - P(EO-stat-IL)] obtained after treatment with trifluoroacetic acid. These materials self-assemble into lamellar structures with volume fractions of ionic liquid ranging from 0.50 to 0.90 as demonstrated by SAXS. PI- b - P(EO-stat-IL) membranes exhibit conductivities up to 4 x 10-3 S/cm at room temperature. In addition, PI- b - P(EO-stat-IL) based membranes have lower water uptake (λ = 8-10) in comparison with most proton conducting membranes reported elsewhere. The low λ in these membranes might translate into a stronger effect of morphology on transport properties. Joint Center for Artificial Photosynthesis.

  12. Bio-based ionic liquid crystalline quaternary ammonium salts: properties and applications.

    PubMed

    Sasi, Renjith; Rao, Talasila P; Devaki, Sudha J

    2014-03-26

    In the present work, we describe the preparation, properties, and applications of novel ionic liquid crystalline quaternary ammonium salts (QSs) of 3-pentadecylphenol, a bio-based low-cost material derived from cashew nut shell liquid. Amphotropic liquid crystalline phase formation in QSs was characterized using a combination of techniques, such as DSC, PLM, XRD, SEM, and rheology, which revealed the formation of one, two, and three dimensionally ordered mesophases in different length scales. On the basis of these results, a plausible mechanism for the formation of specific modes of packing in various mesophases was proposed. Observation of anisotropic ionic conductivity and electrochemical stability suggests their application as a solid electrolyte. PMID:24571658

  13. Dissolving Polymers in Ionic Liquids.

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John

    2009-03-01

    Dissolution and phase behavior of polymers in ionic liquids have been assessed by solution characterization techniques such as intrinsic viscosity and light scattering (static and dynamic). Elevated viscosity proved the greatest obstacle. As yet, whether principles standard to conventional polymer solutions apply to ionic liquid solutions is uncertain, especially for polymers such as polyelectrolytes and hydrophilic block copolymers that may specifically interact with ionic liquid anions or cations. For flexible polyelectrolytes (polymers releasing counterions into high dielectric solvents), characterization in ionic liquids suggests behaviors more typical of neutral polymer. Coil sizes and conformations are approximately the same as in aqueous buffer. Further, several globular proteins dissolve in a hydrophilic ionic liquid with conformations analogous to those in buffer. General principles of solubility, however, remain unclear, making predictions of which polymer dissolves in which ionic liquid difficult; several otherwise intractable polymers (e.g., cellulose, polyvinyl alcohol) dissolve and can be efficiently functionalized in ionic liquids.

  14. Thermodynamic studies of partitioning behavior of cytochrome c in ionic liquid-based aqueous two-phase system.

    PubMed

    Lu, Yanmin; Lu, Wenjuan; Wang, Wei; Guo, Qingwei; Yang, Yanzhao

    2011-09-15

    The ionic liquid/aqueous two-phase extraction systems (ATPSs) based on imidazolium ionic liquids were used to extract cytochrome c. Effects of the alkyl chain length of the ionic liquid cations, concentration of potassium citrate, temperature and pH on the extraction efficiency have been investigated. The thermodynamic parameters (ΔG(T)°, ΔH(T)° and ΔS(T)°) associated with Cyt-c partitioning in aqueous two phase systems were determined. Thermodynamic studies indicated that the partitioning of Cyt-c was driven by both hydrophobic and electrostatic interactions in the extraction process. Under the optimum conditions, experiment results showed that 94% of the cytochrome c could be extracted into the ionic liquid-rich phase in a one-step extraction. The structural characterization of Cyt-c in the IL ATPS was investigated by UV-vis and circular dichroism (CD) spectra. The results demonstrated that no direct bonding interaction observed between ionic liquid and cytochrome c, while the native properties of the cytochrome c were not altered. Compared with traditional liquid-liquid extractions based on toxic organic solvents, ionic liquid/aqueous two phase extraction offers clear advantages due to no use of volatile organic solvent and low consumption of imidazolium ionic liquids. PMID:21807231

  15. Performance of solid state supercapacitors based on polymer electrolytes containing different ionic liquids

    NASA Astrophysics Data System (ADS)

    Tiruye, Girum Ayalneh; Muñoz-Torrero, David; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

    2016-09-01

    Four Ionic Liquid based Polymer Electrolytes (IL-b-PE) were prepared by blending a Polymeric Ionic Liquid, Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PILTFSI), with four different ionic liquids: 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR14TFSI) (IL-b-PE1), 1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide (PYR14FSI) (IL-b-PE2), 1-(2-hydroxy ethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (HEMimTFSI) (IL-b-PE3), and 1-Butyl-1-methylpyrrolidinium dicyanamide, (PYR14DCA) (IL-b-PE4). Physicochemical properties of IL-b-PE such as ionic conductivity, thermal and electrochemical stability were found to be dependent on the IL properties. For instance, ionic conductivity was significantly higher for IL-b-PE2 and IL-b-PE4 containing IL with small size anions (FSI and DCA) than IL-b-PE1 and IL-b-PE3 bearing IL with bigger anion (TFSI). On the other hand, wider electrochemical stability window (ESW) was found for IL-b-PE1 and IL-b-PE2 having ILs with electrochemically stable pyrrolidinium cation and FSI and TFSI anions. Solid state Supercapacitors (SCs) were assembled with activated carbon electrodes and their electrochemical performance was correlated with the polymer electrolyte properties. Best performance was obtained with SC having IL-b-PE2 that exhibited a good compromise between ionic conductivity and electrochemical window. Specific capacitance (Cam), real energy (Ereal) & real power densities (Preal) as high as 150 F g-1, 36 Wh kg-1 & 1170 W kg-1 were found at operating voltage of 3.5 V.

  16. Peculiar surface behavior of some ionic liquids based on active pharmaceutical ingredients

    NASA Astrophysics Data System (ADS)

    Restolho, José; Mata, José Luis; Saramago, Benilde

    2011-02-01

    The ionic liquids based on biologically active cations and anions, commonly designated by ionic liquids based on active pharmaceutical ingredients (ILs-APIs), are interesting compounds for use in pharmaceutical applications. Lidocaine docusate, ranitidine docusate, and didecyldimethylammonium ibuprofen are examples of promising ILs-APIs that were recently synthesized. They were submitted to biological testing and calorimetric measurements, but nothing is known about their surface properties. In this work, we measured the surface tension and the contact angles on both hydrophilic and hydrophobic surfaces in a temperature range as wide as possible. Based on the wettability data, the polarity fractions were estimated using the Fowkes theory. The peculiar surface behavior observed was tentatively attributed to the presence of mesophases.

  17. Peculiar surface behavior of some ionic liquids based on active pharmaceutical ingredients.

    PubMed

    Restolho, José; Mata, José Luis; Saramago, Benilde

    2011-02-21

    The ionic liquids based on biologically active cations and anions, commonly designated by ionic liquids based on active pharmaceutical ingredients (ILs-APIs), are interesting compounds for use in pharmaceutical applications. Lidocaine docusate, ranitidine docusate, and didecyldimethylammonium ibuprofen are examples of promising ILs-APIs that were recently synthesized. They were submitted to biological testing and calorimetric measurements, but nothing is known about their surface properties. In this work, we measured the surface tension and the contact angles on both hydrophilic and hydrophobic surfaces in a temperature range as wide as possible. Based on the wettability data, the polarity fractions were estimated using the Fowkes theory. The peculiar surface behavior observed was tentatively attributed to the presence of mesophases. PMID:21341864

  18. Cyclic phosphonium ionic liquids

    PubMed Central

    Mukhlall, Joshua A; Romeo, Alicia R; Gohdo, Masao; Ramati, Sharon; Berman, Marc; Suarez, Sophia N

    2014-01-01

    Summary Ionic liquids (ILs) incorporating cyclic phosphonium cations are a novel category of materials. We report here on the synthesis and characterization of four new cyclic phosphonium bis(trifluoromethylsulfonyl)amide ILs with aliphatic and aromatic pendant groups. In addition to the syntheses of these novel materials, we report on a comparison of their properties with their ammonium congeners. These exemplars are slightly less conductive and have slightly smaller self-diffusion coefficients than their cyclic ammonium congeners. PMID:24605146

  19. Externally Wetted Ionic Liquid Thruster

    NASA Astrophysics Data System (ADS)

    Lozano, P.; Martinez-Sanchez, M.; Lopez-Urdiales, J. M.

    2004-10-01

    This paper presents initial developments of an electric propulsion system based on ionic liquid ion sources (ILIS). Propellants are ionic liquids, which are organic salts with two important characteristics; they remain in the liquid state at room temperature and have negligible vapor pressure, thus allowing their use in vacuum. The working principles of ILIS are similar to those of liquid metal ion sources (LMIS), in which a Taylor cone is electrostatically formed at the tip of an externally wetted needle while ions are emitted directly from its apex. ILIS have the advantage of being able to produce negative ions that have similar masses than their positive counterparts with similar current levels. This opens up the possibility of achieving plume electrical neutrality without electron emitters. The possible multiplexing of these emitters is discussed in terms of achievable thrust density for applications other than micro-propulsion.

  20. Ultrasound-assisted ionic liquid-based homogeneous liquid-liquid microextraction high-performance liquid chromatography for determination of tanshinones in Salvia miltiorrhiza Bge. root.

    PubMed

    Wang, Zhibing; Cao, Bocheng; Yu, Aimin; Zhang, Hanqi; Qiu, Fangping

    2015-02-01

    The ultrasound-assisted ionic liquid-based homogeneous liquid-liquid microextraction has been developed and applied to the extraction of four tanshinones, including dihydrotanshinone, tanshinone I, cryptotanshinone and tanshinone IIA in Salvia miltiorrhiza Bge. root. High performance liquid chromatography was applied to the separation and determination of the analytes. The ionic liquid was used as extraction solvent and target analytes were extracted with help of ultrasound. Then, ion-pairing agent was added into the sample solution, which resulted in the formation of water-insoluble ionic liquid in the solution. The phase separation was performed by centrifugation. The extraction, concentration and purification of target analytes were performed simultaneously. The experimental parameters, including type and volume of ionic liquid, sample amount, the size of sample particle, pH value of extraction medium, extraction temperature, extraction time, amount of ion-pairing agent and centrifuging time, were investigated and optimized. The calibration curves showed good linear relationship (r>0.9997). The limits of detection and quantification were in the range of 0.052-0.093 and 0.17-0.31 μg mL(-1), respectively. The recoveries were between 70.45% and 94.23% with relative standard deviations lower than 5.31%. The present method is free of volatile organic solvents, and represents lower expenditures of sample, extraction time and solvent, compared with UAE and HRE. There was no obvious difference in the extraction yields of active constitutions obtained by the three extraction methods. PMID:25497891

  1. Wettability by Ionic Liquids.

    PubMed

    Liu, Hongliang; Jiang, Lei

    2016-01-01

    Ionic liquids (ILs) have become particularly attractive recently because they have demonstrated themselves to be important construction units in the broad fields of chemistry and materials science, from catalysis and synthesis to analysis and electrochemistry, from functional fluids to clean energy, from nanotechnology to functional materials. One of the greatest issues that determines the performance of ILs is the wettability of correlated surfaces. In this concept article, the key developments and issues in IL wettability are surveyed, including the electrowetting of ILs in gas-liquid-solid systems and liquid-liquid-solid systems, ILs as useful probe fluids, the superwettability of Ils, and future directions in IL wettability. This should generate extensive interest in the field and encourage more scientists to engage in this area to tackle its scientific challenges. PMID:26619157

  2. Comparative in vitro study of cholinium-based ionic liquids and deep eutectic solvents toward fish cell line.

    PubMed

    Radošević, Kristina; Železnjak, Jelena; Cvjetko Bubalo, Marina; Radojčić Redovniković, Ivana; Slivac, Igor; Gaurina Srček, Višnja

    2016-09-01

    With the advent of ionic liquids, much was expected concerning their applicability as an alternative to organic solvents in the chemical technology and biotechnology fields. However, the most studied and commonly used ionic liquids based on imidazolium and pyridinium were found not to be as environmentally friendly as it was first expected. Therefore, a new generation of alternative solvents named natural ionic liquids and deep eutectic solvents, composed of natural and/or renewable compounds, have come into focus in recent years. Since the number of newly synthesized chemicals increases yearly, simple and reliable methods for their ecotoxicological assessment are necessary. Permanent fish cell lines can serve as a test system for the evaluation of a chemical's cytotoxicity. This paper presents research results on the cytotoxic effects on Channel Catfish Ovary (CCO) cell line induced by fifteen cholinium-based ionic liquids and deep eutectic solvents. Based on the decrease in cell viability, the most obvious toxic effect on CCO cells was caused by ionic liquid choline oxalate, while other solvents tested exhibited low cytotoxicity. Therefore, we can conclude that cholinium-based ionic liquids and deep eutectic solvents are comparatively less toxic to CCO cells than conventional ionic liquids. PMID:27179607

  3. Influence of Ionic Liquids on the Selectivity of Ion Exchange-Based Polymer Membrane Sensing Layers.

    PubMed

    Mendecki, Lukasz; Callan, Nicole; Ahern, Meghan; Schazmann, Benjamin; Radu, Aleksandar

    2016-01-01

    The applicability of ion exchange membranes is mainly defined by their permselectivity towards specific ions. For instance, the needed selectivity can be sought by modifying some of the components required for the preparation of such membranes. In this study, a new class of materials -trihexyl(tetradecyl)phosphonium based ionic liquids (ILs) were used to modify the properties of ion exchange membranes. We determined selectivity coefficients for iodide as model ion utilizing six phosphonium-based ILs and compared the selectivity with two classical plasticizers. The dielectric properties of membranes plasticized with ionic liquids and their response characteristics towards ten different anions were investigated using potentiometric and impedance measurements. In this large set of data, deviations of obtained selectivity coefficients from the well-established Hofmeister series were observed on many occasions thus indicating a multitude of applications for these ion-exchanging systems. PMID:27438837

  4. Influence of Ionic Liquids on the Selectivity of Ion Exchange-Based Polymer Membrane Sensing Layers

    PubMed Central

    Mendecki, Lukasz; Callan, Nicole; Ahern, Meghan; Schazmann, Benjamin; Radu, Aleksandar

    2016-01-01

    The applicability of ion exchange membranes is mainly defined by their permselectivity towards specific ions. For instance, the needed selectivity can be sought by modifying some of the components required for the preparation of such membranes. In this study, a new class of materials –trihexyl(tetradecyl)phosphonium based ionic liquids (ILs) were used to modify the properties of ion exchange membranes. We determined selectivity coefficients for iodide as model ion utilizing six phosphonium-based ILs and compared the selectivity with two classical plasticizers. The dielectric properties of membranes plasticized with ionic liquids and their response characteristics towards ten different anions were investigated using potentiometric and impedance measurements. In this large set of data, deviations of obtained selectivity coefficients from the well-established Hofmeister series were observed on many occasions thus indicating a multitude of applications for these ion-exchanging systems. PMID:27438837

  5. Optimizing the electrochemical performance of imidazolium-based polymeric ionic liquids by varying tethering groups

    NASA Astrophysics Data System (ADS)

    Jia, Zhe

    Increasing efforts have been made in the area of sustainable alternative energy devices in the past few decades in order to develop high efficiency, low-cost electrochemical devices with sufficient long-term stability. Due to the drawbacks of conventional organic liquid electrolytes, such as leakage, volatility, flammability, and toxicity, the synthesis of solvent-free electrolyte materials has been studied world-wide. Among all the alternatives, polymer electrolytes are of great interest and have attracted many research groups. Solid-state polymer electrolytes and in particular, polymer ionic liquids (PILs), considered to be promising candidates, have been under studied widely. Ionic Liquids (ILs), defined as organic/inorganic salts with m.p. lower than 100 °C, offer good chemical stability, low flammability, negligible vapor pressure and high ionic conductivity. PILs, as the polymerized state of ILs, not only present some of the unique properties of ILs, but also benefit from the intrinsic properties of polymers, such as better thermal and chemical stability, enhanced mechanical properties, and tunable solution properties. The constrained structure of PILs may help to overcome fabrication and leakage problems associated with simple liquid electrolytes, but typically also leads to lower ionic conductivity. Once polymerized, the ionic conductivity of PILs drops substantially, usually by several orders of magnitude compared to the corresponding monomers. Therefore, to improve PILs chain mobilitiy is crucial. Previous studies suggest that a flexible tethering group should make the polymer backbone less rigid and increase electrolyte ion mobility. To investigate how tethering groups affect both electrochemical performance and physical properties of free ILs and PILs, we first report the synthesis and characterization of a novel class of imidazolium (Im) based IL model compounds and their corresponding PILs. Poly(ethylene oxide)s (PEOs), considered to be promising

  6. Tandem dissolution of UO3 in amide-based acidic ionic liquid and in situ electrodeposition of UO2 with regeneration of the ionic liquid: a closed cycle.

    PubMed

    Wanigasekara, Eranda; Freiderich, John W; Sun, Xiao-Guang; Meisner, Roberta A; Luo, Huimin; Delmau, Lætitia H; Dai, Sheng; Moyer, Bruce A

    2016-06-21

    A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO3 to UO2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid [DMAH][NTf2] in [EMIM][NTf2] serving as the diluent. A sequential dissolution, electroreduction, and regeneration cycle is presented. PMID:27255672

  7. Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte

    NASA Astrophysics Data System (ADS)

    Li, Qin; Ardebili, Haleh

    2016-01-01

    The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.

  8. Perfluoro anion based binary and ternary ionic liquids as electrolytes for dye-sensitized solar cells

    NASA Astrophysics Data System (ADS)

    Lin, Hsi-Hsin; Peng, Jia-De; Suryanarayanan, V.; Velayutham, D.; Ho, Kuo-Chuan

    2016-04-01

    In this work, eight new ionic liquids (ILs) based on triethylammonium (TEA) or n-methylpiperidinium (NMP) cations and perfluoro carboxylate (PFC) anions having different carbon chain lengths are synthesized and their physico-chemical properties such as density, decomposition temperature, viscosity and conductivity are determined. Photovoltaic characteristics of dye-sensitized solar cells (DSSCs) with binary ionic liquids electrolytes, containing the mixture of the synthesized ILs and 1-methyl-3-propyl imidazolium iodide (PMII) (v/v = 35/65), are evaluated. Among the different ILs, solar cells containing NMP based ILs show higher VOC than that of TEA, whereas, higher JSC is noted for the DSSCs incorporated with the latter when compared to the former. Further, the photo-current of the DSSCs decreases with the increase of the carbon chain length of perfluoro carboxylate anionic group of ILs. The cell performance of the DSSC containing ternary ionic liquids-based electrolytes compose of NMP-2C/TEA-2C/PMII (v/v/v = 28/7/65) exhibits a JSC of 12.99 mA cm-2, a VOC of 639.0 mV, a FF of 0.72, and a cell efficiency of 6.01%. The extraordinary durability of the DSSC containing the above combination of electrolytes stored in dark at 50 °C is proved to be unfailing up to 1200 h.

  9. Antibacterial Activity of Imidazolium-Based Ionic Liquids Investigated by QSAR Modeling and Experimental Studies.

    PubMed

    Hodyna, Diana; Kovalishyn, Vasyl; Rogalsky, Sergiy; Blagodatnyi, Volodymyr; Petko, Kirill; Metelytsia, Larisa

    2016-09-01

    Predictive QSAR models for the inhibitors of B. subtilis and Ps. aeruginosa among imidazolium-based ionic liquids were developed using literary data. The regression QSAR models were created through Artificial Neural Network and k-nearest neighbor procedures. The classification QSAR models were constructed using WEKA-RF (random forest) method. The predictive ability of the models was tested by fivefold cross-validation; giving q(2) = 0.77-0.92 for regression models and accuracy 83-88% for classification models. Twenty synthesized samples of 1,3-dialkylimidazolium ionic liquids with predictive value of activity level of antimicrobial potential were evaluated. For all asymmetric 1,3-dialkylimidazolium ionic liquids, only compounds containing at least one radical with alkyl chain length of 12 carbon atoms showed high antibacterial activity. However, the activity of symmetric 1,3-dialkylimidazolium salts was found to have opposite relationship with the length of aliphatic radical being maximum for compounds based on 1,3-dioctylimidazolium cation. The obtained experimental results suggested that the application of classification QSAR models is more accurate for the prediction of activity of new imidazolium-based ILs as potential antibacterials. PMID:27086199

  10. Triazolium based ionic liquid crystals: Effect of asymmetric substitution

    SciTech Connect

    Stappert, K.; Mudring, A. -V.

    2015-01-27

    A new series of ten different asymmetrical 1-dodecyl-3-alkyl-triazolium bromides, [C12CnTr][Br], has been synthesized and their mesomorphic behavior studied by DSC (differential scanning calorimetry), POM (polarizing optical microscopy) and SAXS (small angle X-ray scattering). The influence of the chain length of the triazolium salts is investigated to explore the effect of asymmetric substitution on the phase behaviour of these compounds. For that reason, the length of one alkyl chain was varied from 14 to 1 carbon atoms (n = 14, 12, 10, 8–4, 2, 1) while the other alkyl chain was kept at 12 carbon. Single crystal X-ray structure analysis of compounds [C12C12Tr][Br] and [C12C5Tr][Br] reveal that the cations adopt a U-shaped conformation with head-to-head arranged triazolium cores. In contrast, for [C12C1Tr][Br], a rod like shape of the cation with interdigitated alkyl chains is found. All investigated compounds are thermotropic liquid crystals. Higher ordered smectic phases, smectic C as well as smectic A phases were found depending on the chain length of the cation. Moreover, the clearing point temperature decreases with decreasing chain length with exception for the n-dodecyl-3-alkyltrizoliumbromides with the two shortest alkyl chains, [C12C2Tr][Br] and [C12C1Tr][Br], which present higher clearing temperatures (86 and 156 °C) and are structurally distinctly different.

  11. Triazolium based ionic liquid crystals: Effect of asymmetric substitution

    DOE PAGESBeta

    Stappert, K.; Mudring, A. -V.

    2015-01-27

    A new series of ten different asymmetrical 1-dodecyl-3-alkyl-triazolium bromides, [C12CnTr][Br], has been synthesized and their mesomorphic behavior studied by DSC (differential scanning calorimetry), POM (polarizing optical microscopy) and SAXS (small angle X-ray scattering). The influence of the chain length of the triazolium salts is investigated to explore the effect of asymmetric substitution on the phase behaviour of these compounds. For that reason, the length of one alkyl chain was varied from 14 to 1 carbon atoms (n = 14, 12, 10, 8–4, 2, 1) while the other alkyl chain was kept at 12 carbon. Single crystal X-ray structure analysis ofmore » compounds [C12C12Tr][Br] and [C12C5Tr][Br] reveal that the cations adopt a U-shaped conformation with head-to-head arranged triazolium cores. In contrast, for [C12C1Tr][Br], a rod like shape of the cation with interdigitated alkyl chains is found. All investigated compounds are thermotropic liquid crystals. Higher ordered smectic phases, smectic C as well as smectic A phases were found depending on the chain length of the cation. Moreover, the clearing point temperature decreases with decreasing chain length with exception for the n-dodecyl-3-alkyltrizoliumbromides with the two shortest alkyl chains, [C12C2Tr][Br] and [C12C1Tr][Br], which present higher clearing temperatures (86 and 156 °C) and are structurally distinctly different.« less

  12. Membrane-based recovery of glucose from enzymatic hydrolysis of ionic liquid pretreated cellulose.

    PubMed

    Abels, Christian; Thimm, Kristof; Wulfhorst, Helene; Spiess, Antje Christine; Wessling, Matthias

    2013-12-01

    In this work, a membrane-based downstream process for the recovery of glucose from cellulose hydrolysis is described and evaluated. The cellulose is pretreated with the ionic liquid 1,3-dimethyl-imidazolium dimethylphosphate to reduce its crystallinity. After enzymatic conversion of cellulose to glucose the hydrolysate is filtered with an ultrafiltration membrane to remove residual particulates and enzymes. Nanofiltration is applied to purify the glucose from molecular intermediates, such as cellobiose originating from the hydrolysis reaction. Finally, the ionic liquid is removed from the hydrolysate via electrodialysis. Technically, these process steps are feasible. An economic analysis of the process reveals that the selling price of glucose from this production process is about 2.75 €/kg which is too high as compared to the current market price. PMID:24084205

  13. Microwave-Assisted Syntheses in Recyclable Ionic Liquids: Photoresists Based on Renewable Resources

    PubMed Central

    Petit, Charlotte; Luef, Klaus P; Edler, Matthias; Griesser, Thomas; Kremsner, Jennifer M; Stadler, Alexander; Grassl, Bruno; Reynaud, Stéphanie; Wiesbrock, Frank

    2015-01-01

    The copoly(2-oxazoline) pNonOx80-stat-pDc=Ox20 can be synthesized from the cationic ring-opening copolymerization of 2-nonyl-2-oxazoline NonOx and 2-dec-9′-enyl-2-oxazoline Dc=Ox in the ionic liquid n-hexyl methylimidazolium tetrafluoroborate under microwave irradiation in 250 g/batch quantities. The polymer precipitates upon cooling, enabling easy recovery of the polymer and the ionic liquid. Both monomers can be obtained from fatty acids from renewable resources. pNonOx80-stat-pDc=Ox20 can be used as polymer in a photoresist (resolution of 1 μm) based on UV-induced thiol–ene reactions. PMID:26354027

  14. Interaction and dynamics of ionic liquids based on choline and amino acid anions

    SciTech Connect

    Campetella, M.; Bodo, E. Caminiti, R. Martino, A.; Gontrani, L.; D’Apuzzo, F.; Lupi, S.

    2015-06-21

    The combination of amino acid anions with the choline cation gives origin to a new and potentially important class of organic ionic liquids that might represent a viable and bio-compatible alternative with respect to the traditional ones. We present here a detailed study of the bulk phase of the prototype system composed of the simplest amino acid (alanine) anion and the choline cation, based on ab initio and classical molecular dynamics. Theoretical findings have been validated by comparing with accurate experimental X-ray diffraction data and infrared spectra. We find that hydrogen bonding (HB) features in these systems are crucial in establishing their local geometric structure. We have also found that these HBs once formed are persistent and that the proton resides exclusively on the choline cation. In addition, we show that a classical force field description for this particular ionic liquid can be accurately performed by using a slightly modified version of the generalized AMBER force field.

  15. Polymer electrolytes containing guanidinium-based polymeric ionic liquids for rechargeable lithium batteries

    NASA Astrophysics Data System (ADS)

    Li, Mingtao; Yang, Li; Fang, Shaohua; Dong, Siming; Hirano, Shin-ichi; Tachibana, Kazuhiro

    2011-10-01

    The electrochemical properties of solvent-free, quaternary polymer electrolytes based on a novel polymeric ionic liquid (PIL) as polymer host and incorporating 1g13TFSI ionic liquid, LiTFSI salt and nano-scale silica are reported. The PIL-LiTFSI-1g13TFSI-SiO2 electrolyte membranes are found to be chemically stable even at 80 °C in contact with lithium anode and thermally stable up to 320 °C. Particularly, the quaternary polymer electrolytes exhibit high lithium ion conductivity at high temperature, wide electrochemical stability window, time-stable interfacial resistance values and good lithium stripping/plating performance. Batteries assembled with the quaternary polymer electrolyte at 80 °C are capable to deliver 140 mAh g-1 at 0.1C rates with very good capacity retention.

  16. Interaction and dynamics of ionic liquids based on choline and amino acid anions

    NASA Astrophysics Data System (ADS)

    Campetella, M.; Bodo, E.; Caminiti, R.; Martino, A.; D'Apuzzo, F.; Lupi, S.; Gontrani, L.

    2015-06-01

    The combination of amino acid anions with the choline cation gives origin to a new and potentially important class of organic ionic liquids that might represent a viable and bio-compatible alternative with respect to the traditional ones. We present here a detailed study of the bulk phase of the prototype system composed of the simplest amino acid (alanine) anion and the choline cation, based on ab initio and classical molecular dynamics. Theoretical findings have been validated by comparing with accurate experimental X-ray diffraction data and infrared spectra. We find that hydrogen bonding (HB) features in these systems are crucial in establishing their local geometric structure. We have also found that these HBs once formed are persistent and that the proton resides exclusively on the choline cation. In addition, we show that a classical force field description for this particular ionic liquid can be accurately performed by using a slightly modified version of the generalized AMBER force field.

  17. Development of an ionic liquid based dispersive liquid-liquid microextraction method for the analysis of polycyclic aromatic hydrocarbons in water samples.

    PubMed

    Pena, M Teresa; Casais, M Carmen; Mejuto, M Carmen; Cela, Rafael

    2009-09-01

    A simple, rapid and efficient method, ionic liquid based dispersive liquid-liquid microextraction (IL-DLLME), has been developed for the first time for the determination of 18 polycyclic aromatic hydrocarbons (PAHs) in water samples. The chemical affinity between the ionic liquid (1-octyl-3-methylimidazolium hexafluorophosphate) and the analytes permits the extraction of the PAHs from the sample matrix also allowing their preconcentration. Thus, this technique combines extraction and concentration of the analytes into one step and avoids using toxic chlorinated solvents. The factors affecting the extraction efficiency, such as the type and volume of ionic liquid, type and volume of disperser solvent, extraction time, dispersion stage, centrifuging time and ionic strength, were optimised. Analysis of extracts was performed by high performance liquid chromatography (HPLC) coupled with fluorescence detection (Flu). The optimised method exhibited a good precision level with relative standard deviation values between 1.2% and 5.7%. Quantification limits obtained for all of these considered compounds (between 0.1 and 7 ng L(-1)) were well below the limits recommended in the EU. The extraction yields for the different compounds obtained by IL-DLLME, ranged from 90.3% to 103.8%. Furthermore, high enrichment factors (301-346) were also achieved. The extraction efficiency of the optimised method is compared with that achieved by liquid-liquid extraction. Finally, the proposed method was successfully applied to the analysis of PAHs in real water samples (tap, bottled, fountain, well, river, rainwater, treated and raw wastewater). PMID:19646707

  18. Properties of some ionic liquids based on1-methyl-3-octylimidazolium and 4-methyl-N-butylpyridinium cations.

    SciTech Connect

    Papaiconomou, Nicolas; Yakelis, Neal; Salminen, Justin; Bergman,Robert; Prausnitz, John M.

    2005-09-29

    Syntheses are reported for ionic liquids containing 1-methyl-3octylimidazolium and 4-methyl-N-butylpyridinium cations, and trifluoromethansulfonate, dicyanamide, bis(trifluoromethylsulfonyl)imide, and nonafluorobutanesulfonate anions. Densities, melting points and glass transition points, solubility in water as well as polarities have been measured. Ionic liquids based on pyridinium cations exhibit higher melting points, lower solubility in water, and higher polarity than those based on imidazolium cations.

  19. Ionic-Liquid-Based Polymer Electrolytes for Battery Applications.

    PubMed

    Osada, Irene; de Vries, Henrik; Scrosati, Bruno; Passerini, Stefano

    2016-01-11

    The advent of solid-state polymer electrolytes for application in lithium batteries took place more than four decades ago when the ability of polyethylene oxide (PEO) to dissolve suitable lithium salts was demonstrated. Since then, many modifications of this basic system have been proposed and tested, involving the addition of conventional, carbonate-based electrolytes, low molecular weight polymers, ceramic fillers, and others. This Review focuses on ternary polymer electrolytes, that is, ion-conducting systems consisting of a polymer incorporating two salts, one bearing the lithium cation and the other introducing additional anions capable of plasticizing the polymer chains. Assessing the state of the research field of solid-state, ternary polymer electrolytes, while giving background on the whole field of polymer electrolytes, this Review is expected to stimulate new thoughts and ideas on the challenges and opportunities of lithium-metal batteries. PMID:26783056

  20. Osmotic pressure of ionic liquids in an electric double layer: Prediction based on a continuum model

    NASA Astrophysics Data System (ADS)

    Moon, Gi Jong; Ahn, Myung Mo; Kang, In Seok

    2015-12-01

    An analysis has been performed for the osmotic pressure of ionic liquids in the electric double layer (EDL). By using the electromechanical approach, we first derive a differential equation that is valid for computing the osmotic pressure in the continuum limit of any incompressible fluid in EDL. Then a specific model for ionic liquids proposed by Bazant et al. [M. Z. Bazant, B. D. Storey, and A. A. Kornyshev, Phys. Rev. Lett. 106, 046102 (2011), 10.1103/PhysRevLett.106.046102] is adopted for more detailed computation of the osmotic pressure. Ionic liquids are characterized by the correlation and the steric effects of ions and their effects are analyzed. In the low voltage cases, the correlation effect is dominant and the problem becomes linear. For this low voltage limit, a closed form formula is derived for predicting the osmotic pressure in EDL with no overlapping. It is found that the osmotic pressure decreases as the correlation effect increases. The osmotic pressures at the nanoslit surface and nanoslit centerline are also obtained for the low voltage limit. For the cases of moderately high voltage with high correlation factor, approximate formulas are derived for estimating osmotic pressure values based on the concept of a condensed layer near the electrode. In order to corroborate the results predicted by analytical studies, the full nonlinear model has been solved numerically.

  1. A Combined Experimental and Molecular Dynamics Study of Iodide-Based Ionic Liquid and Water Mixtures.

    PubMed

    Nickerson, Stella D; Nofen, Elizabeth M; Chen, Haobo; Ngan, Miranda; Shindel, Benjamin; Yu, Hongyu; Dai, Lenore L

    2015-07-16

    Iodide-based ionic liquids have been widely employed as iodide sources in electrolytes for applications utilizing the triiodide/iodide redox couple. While adding a low-viscosity solvent such as water to ionic liquids can greatly enhance their usefulness, mixtures of highly viscous iodide-containing ILs with water have never been studied. This paper investigates, for the first time, mixtures of water and the ionic liquid 1-butyl-3-methylimidazolium iodide ([BMIM][I]) through a combined experimental and molecular dynamics study. The density, melting point, viscosity, and conductivity of these mixtures were measured by experiment. The composition region below 50% water by mole was found to differ dramatically from the region above 50% water, with trends in density and melting point differing before and after that point. Water was found to have a profound effect on viscosity and conductivity of the IL, and the effect of hydrogen bonding was discussed. Molecular dynamics simulations representing the same mixture compositions were performed. Molecular ordering was observed, as were changes in this ordering corresponding to water content. Molecular ordering was related to the experimentally measured mixture properties, providing a possible explanation for the two distinct composition regions identified by experiment. PMID:26090562

  2. Influence of Cation Size on the Ionicity, Fluidity, and Physiochemical Properties of 1,2,4-Triazolium Based Ionic Liquids.

    PubMed

    Singh, Dharmendra; Gardas, Ramesh L

    2016-06-01

    Interpreting the physiochemical properties and structure-property correlations of ionic liquids (ILs) is a key to the enlargement of their optimized structures for specific applications. In this work, a series of ILs based on 1-alkyl-1,2,4-triazolium cation with trifluoromethanesulfonate anion were synthesized and the effect of cation and temperature on physiochemical properties such as density, viscosity, speed of sound, conductivity, and rheology was studied. Temperature dependence densities were correlated with the densities estimated by the Gardas and Coutinho model, whereas viscosity and molar conductivity have been found to satisfy the Vogel-Tammann-Fulcher (VTF) equation over the studied temperature range 293.15-343.15 K. Further, to explore the wide range of applications, ionicity has been tested by correlating the fluidity with molar conductivity and it was found that synthesized ILs can be referred to as "good ILs". Furthermore, the fluidity behavior describing the interactions between the cation and anion of ILs was investigated through their rheological properties, and the Newtonian behavior of ILs has been examined by varying the effect of shear rate on viscosity. Finally, the impact of structure variants in terms of the N-1 functionalized 1,2,4-triazole ring has been analyzed over the studied properties. PMID:27158831

  3. Tandem dissolution of UO 3 in amide-based acidic ionic liquid and in situ electrodeposition of UO 2 with regeneration of the ionic liquid: a closed cycle

    DOE PAGESBeta

    Wanigasekara, Eranda; Freiderich, John W.; Sun, Xiao-Guang; Meisner, Roberta A.; Luo, Huimin; Delmau, Lætitia H.; Dai, Sheng; Moyer, Bruce A.

    2016-05-19

    A closed cycle is demonstrated for the tandem dissolution and electroreduction of UO3 to UO2 with regeneration of the acidic ionic liquid. The dissolution is achieved by use of the acidic ionic liquid N,N-dimethylacetimidium bis(trifluoromethanesulfonimide) in 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonimide) serving as the diluent. Bulk electrolysis performed at 1.0 V vs. Ag reference yields a dark brown-black uranium deposit (UO2) on the cathode. Anodic oxidation of water in the presence of dimethylacetamide regenerates the acidic ionic liquid. We have demonstrated the individual steps in the cycle together with a sequential dissolution, electroreduction, and regeneration cycle.

  4. Ionic liquid based hollow fiber supported liquid phase microextraction of ultraviolet filters.

    PubMed

    Ge, Dandan; Lee, Hian Kee

    2012-03-16

    Hollow fiber protected liquid phase microextraction using an ionic liquid as supported phase and acceptor phase (IL-HF-LPME) is proposed for the determination of four ultraviolet (UV) filters (benzophenone, 3-(4-methylbenzylidene)-camphor, 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone) in water samples for the first time. In the present study, four different ILs 1-hexyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate) [HMIM][FAP], 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate [BMPL][FAP], 1-butyl-3-methylimidazolium phosphate ([BMIM][PO(4)]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]) were evaluated as extraction solvent. Only [HMIM][FAP] showed high chemical affinity to the analytes which permits a selective isolation of the UV filters from the sample matrix, allowing also their preconcentration. IL-HF-LPME and high performance liquid chromatography provides repeatability from 1.1% to 8.2% and limits of detection between 0.3 and 0.5 ng/ml. Real water samples spiked with the analytes extracted were analyzed, and yielded relative recoveries ranging from 82.6% to 105.9%. PMID:22307149

  5. Neural networks applied to determine the thermophysical properties of amino acid based ionic liquids.

    PubMed

    Cancilla, John C; Perez, Ana; Wierzchoś, Kacper; Torrecilla, José S

    2016-03-01

    A series of models based on artificial neural networks (ANNs) have been designed to estimate the thermophysical properties of different amino acid-based ionic liquids (AAILs). Three different databases of AAILs were modeled using these algorithms with the goal set to estimate the density, viscosity, refractive index, ionic conductivity, and thermal expansion coefficient, and requiring only data regarding temperature and electronic polarizability of the chemicals. Additionally, a global model was designed combining all of the databases to determine the robustness of the method. In general, the results were successful, reaching mean prediction errors below 1% in many cases, as well as a statistically reliable and accurate global model. Attaining these successful models is a relevant fact as AAILs are novel biodegradable and biocompatible compounds which may soon make their way into the health sector forming a part of useful biomedical applications. Therefore, understanding the behavior and being able to estimate their thermophysical properties becomes crucial. PMID:26899458

  6. Ionic liquids and their bases: Striking differences in the dynamic heterogeneity near the glass transition

    PubMed Central

    Grzybowska, K.; Grzybowski, A.; Wojnarowska, Z.; Knapik, J.; Paluch, M.

    2015-01-01

    Ionic liquids (ILs) constitute an active field of research due to their important applications. A challenge for these investigations is to explore properties of ILs near the glass transition temperature Tg, which still require our better understanding. To shed a new light on the issues, we measured ILs and their base counterparts using the temperature modulated calorimetry. We performed a comparative analysis of the dynamic heterogeneity at Tg for bases and their salts with a simple monoatomic anion (Cl–). Each pair of ionic and non-ionic liquids is characterized by nearly the same chemical structure but their intermolecular interactions are completely different. We found that the size of the dynamic heterogeneity of ILs near Tg is considerably smaller than that established for their dipolar counterparts. Further results obtained for several other ILs near Tg additionally strengthen the conclusion about the relatively small size of the dynamic heterogeneity of molecular systems dominated by electrostatic interactions. Our finding opens up new perspectives on designing different material properties depending on intermolecular interaction types. PMID:26582136

  7. Ionic liquids and their bases: Striking differences in the dynamic heterogeneity near the glass transition

    NASA Astrophysics Data System (ADS)

    Grzybowska, K.; Grzybowski, A.; Wojnarowska, Z.; Knapik, J.; Paluch, M.

    2015-11-01

    Ionic liquids (ILs) constitute an active field of research due to their important applications. A challenge for these investigations is to explore properties of ILs near the glass transition temperature Tg, which still require our better understanding. To shed a new light on the issues, we measured ILs and their base counterparts using the temperature modulated calorimetry. We performed a comparative analysis of the dynamic heterogeneity at Tg for bases and their salts with a simple monoatomic anion (Cl-). Each pair of ionic and non-ionic liquids is characterized by nearly the same chemical structure but their intermolecular interactions are completely different. We found that the size of the dynamic heterogeneity of ILs near Tg is considerably smaller than that established for their dipolar counterparts. Further results obtained for several other ILs near Tg additionally strengthen the conclusion about the relatively small size of the dynamic heterogeneity of molecular systems dominated by electrostatic interactions. Our finding opens up new perspectives on designing different material properties depending on intermolecular interaction types.

  8. Ionic liquids, electrolyte solutions including the ionic liquids, and energy storage devices including the ionic liquids

    SciTech Connect

    Gering, Kevin L.; Harrup, Mason K.; Rollins, Harry W.

    2015-12-08

    An ionic liquid including a phosphazene compound that has a plurality of phosphorus-nitrogen units and at least one pendant group bonded to each phosphorus atom of the plurality of phosphorus-nitrogen units. One pendant group of the at least one pendant group comprises a positively charged pendant group. Additional embodiments of ionic liquids are disclosed, as are electrolyte solutions and energy storage devices including the embodiments of the ionic liquid.

  9. Protic ionic liquids based on the dimeric and oligomeric anions: [(AcO)xH(x-1)]-.

    PubMed

    Johansson, K M; Izgorodina, E I; Forsyth, M; MacFarlane, D R; Seddon, K R

    2008-05-28

    We describe a fluidity and conductivity study as a function of composition in N-methylpyrrolidine-acetic acid mixtures. The simple 1 : 1 acid-base mixture appears to form an ionic liquid, but its degree of ionicity is quite low and such liquids are better thought of as poorly dissociated mixtures of acid and base. The composition consisting of 3 moles acetic acid and 1 mole N-methylpyrrolidine is shown to form the highest ionicity mixture in this binary due to the presence of oligomeric anionic species [(AcO)(x)H(x-1)](-) stabilised by hydrogen bonds. These oligomeric species, being weaker bases than the acetate anion, shift the proton transfer equilibrium towards formation of ionic species, thus generating a higher degree of ionicity than is present at the 1 : 1 composition. A Walden plot analysis, thermogravimetric behaviour and proton NMR data, as well as ab initio calculations of the oligomeric species, all support this conclusion. PMID:18473045

  10. Ionic-liquid-based dispersive liquid-liquid microextraction combined with high-performance liquid chromatography for the determination of multiclass pesticide residues in water samples.

    PubMed

    Tadesse, Bezuayehu; Teju, Endale; Gure, Abera; Megersa, Negussie

    2015-03-01

    Ionic-liquid-based dispersive liquid-liquid microextraction in combination with high-performance liquid chromatography and diode array detection has been proposed for the simultaneous analysis of four multiclass pesticide residues including carbaryl, methidathion, chlorothalonil, and ametryn from water samples. The major experimental parameters including the type and volume of ionic liquid, sample pH, type, and volume of disperser solvent and cooling time were investigated and optimum conditions were established. Under the optimum experimental conditions, limits of detection and quantification of the method were in the range of 0.1-1.8 and 0.4-5.9 μg/L, respectively, with satisfactory enrichment factors ranging from 10-20. The matrix-matched calibration curves, which were constructed for lake water, as a representative matrix were linear over wide range with coefficients of determination of 0.996 or better. Intra- and interday precisions, expressed as relative standard deviations, were in the range of 1.1-9.7 and 3.1-7.8%, respectively. The relative recoveries of the spiked environmental water samples at one concentration level were in the range of 77-102%. The results of the present study revealed that the proposed method is simple, fast, and uses environmentally friendly extraction solvent for the analysis of the target pesticide residues in environmental water samples. PMID:25641819

  11. Development of an ionic-liquid-based dispersive liquid-liquid microextraction method for the determination of antichagasic drugs in human breast milk: Optimization by central composite design.

    PubMed

    Padró, Juan M; Pellegrino Vidal, Rocío B; Echevarria, Romina N; Califano, Alicia N; Reta, Mario R

    2015-05-01

    Chagas disease constitutes a major public health problem in Latin America. Human breast milk is a biological sample of great importance for the analysis of therapeutic drugs, as unwanted exposure through breast milk could result in pharmacological effects in the nursing infant. Thus, the goal of breast milk drug analysis is to inquire to which extent a neonate may be exposed to a drug during lactation. In this work, we developed an analytical technique to quantify benznidazole and nifurtimox (the two antichagasic drugs currently available for medical treatment) in human breast milk, with a simple sample pretreatment followed by an ionic-liquid-based dispersive liquid-liquid microextraction combined with high-performance liquid chromatography and UV detection. For this technique, the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate has been used as the "extraction solvent." A central composite design was used to find the optimum values for the significant variables affecting the extraction process: volume of ionic liquid, volume of dispersant solvent, ionic strength, and pH. At the optimum working conditions, the average recoveries were 77.5 and 89.7%, the limits of detection were 0.06 and 0.09 μg/mL and the interday reproducibilities were 6.25 and 5.77% for benznidazole and nifurtimox, respectively. The proposed methodology can be considered sensitive, simple, robust, accurate, and green. PMID:25711461

  12. Effect of ionic size on solvate stability of glyme-based solvate ionic liquids.

    PubMed

    Mandai, Toshihiko; Yoshida, Kazuki; Tsuzuki, Seiji; Nozawa, Risa; Masu, Hyuma; Ueno, Kazuhide; Dokko, Kaoru; Watanabe, Masayoshi

    2015-01-29

    A series of binary mixtures composed of glymes (triglyme, G3; tetraglyme, G4; pentaglyme, G5) and alkali-metal bis(trifluoromethanesulfonyl)amide salts (M[TFSA]; M = Li, Na, and K) were prepared, and the correlation between the composition and solvate stability was systematically investigated. Their phase diagrams and Raman spectra suggested complexation of the glymes with M[TFSA] in 1:1 and/or 2:1 molar ratio(s). From isothermal stability measurements, it was found that the formation of structurally stable complexes in the solid state did not necessarily ensure their thermal stability in the liquid state, especially in the case of 2:1 complexes, where uncoordinating or highly exchangeable glyme ligands existed in the molten complexes. The phase-state-dependent Raman spectra also supported the presence of free glymes in certain liquid complexes. The effect of the electric field induced by the alkali-metal cations on the oxidative stability of certain glyme complexes was examined by linear sweep voltammetry and quantum chemical calculations. Although the actual oxidative stability of complexes did not necessarily reflect the calculated HOMO energy levels of the glymes, the strong electric field induced by the smaller M(+) cations and proper coordination structures impart high stability to the glyme complexes. The results of thermogravimetry of complexes with different M(+) cations revealed that a balance of competitive interactions of the M(+) ions with the glymes and [TFSA](-) anions predominates the thermal stability. PMID:25530321

  13. Li Ion Conducting Polymer Gel Electrolytes Based on Ionic Liquid/PVDF-HFP Blends

    PubMed Central

    Ye, Hui; Huang, Jian; Xu, Jun John; Khalfan, Amish; Greenbaum, Steve G.

    2009-01-01

    Ionic liquids thermodynamically compatible with Li metal are very promising for applications to rechargeable lithium batteries. 1-methyl-3-propylpyrrolidinium bis(trifluoromethanesulfonyl)imide (P13TFSI) is screened out as a particularly promising ionic liquid in this study. Dimensionally stable, elastic, flexible, nonvolatile polymer gel electrolytes (PGEs) with high electrochemical stabilities, high ionic conductivities and other desirable properties have been synthesized by dissolving Li imide salt (LiTFSI) in P13TFSI ionic liquid and then mixing the electrolyte solution with poly(vinylidene-co-hexafluoropropylene) (PVDF-HFP) copolymer. Adding small amounts of ethylene carbonate to the polymer gel electrolytes dramatically improves the ionic conductivity, net Li ion transport concentration, and Li ion transport kinetics of these electrolytes. They are thus favorable and offer good prospects in the application to rechargeable Li batteries including open systems like Li/air batteries, as well as more “conventional” rechargeable lithium and lithium ion batteries. PMID:20354587

  14. Enzyme catalysis in ionic liquids.

    PubMed

    Kragl, Udo; Eckstein, Marrit; Kaftzik, Nicole

    2002-12-01

    Ionic liquids offer new possibilities for the application of solvent engineering to biocatalytic reactions. Although in many cases ionic liquids have simply been used to replace organic solvents, they have often led to improved process performance. Unlike conventional organic solvents, ionic liquids possess no vapor pressure, are able to dissolve many compounds, and can be used to form two-phase systems with many solvents. To date, reactions involving lipases have benefited most from the use of ionic liquids, but the use of ionic liquids with other enzymes and in whole-cell processes has also been described. In some cases, remarkable results with respect to yield, (enantio)selectivity or enzyme stability were observed. PMID:12482515

  15. Electrodeposition in Ionic Liquids.

    PubMed

    Zhang, Qinqin; Wang, Qian; Zhang, Suojiang; Lu, Xingmei; Zhang, Xiangping

    2016-02-01

    Due to their attractive physico-chemical properties, ionic liquids (ILs) are increasingly used as deposition electrolytes. This review summarizes recent advances in electrodeposition in ILs and focuses on its similarities and differences with that in aqueous solutions. The electrodeposition in ILs is divided into direct and template-assisted deposition. We detail the direct deposition of metals, alloys and semiconductors in five types of ILs, including halometallate ILs, air- and water-stable ILs, deep eutectic solvents (DESs), ILs with metal-containing cations, and protic ILs. Template-assisted deposition of nanostructures and macroporous structures in ILs is also presented. The effects of modulating factors such as deposition conditions (current density, current density mode, deposition time, temperature) and electrolyte components (cation, anion, metal salts, additives, water content) on the morphology, compositions, microstructures and properties of the prepared materials are highlighted. PMID:26530378

  16. Safe lithium-ion battery with ionic liquid-based electrolyte for hybrid electric vehicles

    NASA Astrophysics Data System (ADS)

    Damen, Libero; Lazzari, Mariachiara; Mastragostino, Marina

    2011-10-01

    A lithium-ion battery featuring graphite anode, LiFePO4-C cathode and an innovative, safe, ionic liquid-based electrolyte, was assembled and characterized in terms of specific energy and power after the USABC-DOE protocol for power-assist hybrid electric vehicle (HEV) application. The test results show that the battery surpasses the energy and power goals stated by USABC-DOE and, hence, this safe lithium-ion battery should be suitable for application in the evolving HEV market.

  17. Towards safer sodium-ion batteries via organic solvent/ionic liquid based hybrid electrolytes

    NASA Astrophysics Data System (ADS)

    Monti, Damien; Ponrouch, Alexandre; Palacín, M. Rosa; Johansson, Patrik

    2016-08-01

    Hybrid electrolytes aimed at application in sodium-ion batteries (SIB) consisting of an organic solvent mixture (EC:PC) and different ionic liquids (ILs); EMImTFSI, BMImTFSI, and Pyr13TFSI, and with the NaTFSI salt providing the Na+ charge carriers have here been extensively studied. The physico-chemical and electrochemical characterisation includes ionic conductivity, viscosity, density, cation coordination and solvation, various safety measures, and electrochemical stability window (ESW). Hybrid electrolytes with 10-50% of IL content were found to have ionic conductivities on par with comparable organic solvent based electrolytes, but with highly enhanced safety properties. A systematic Raman spectroscopy study of the cation coordination and solvation before and after electrolyte safety tests by ignition suggest that IL cations and TFSI remain stable when ignited while organic solvents are consumed. Finally, the solid electrolyte interphase (SEI) formed when using hybrid electrolytes has both better mechanical and electrochemical stability than the SEI derived from pure IL based electrolytes. For a half-cell with a hard carbon (HC) electrode and a hybrid electrolyte with a composition of 0.8 m NaTFSI in EC0.45:PC0.45:Pyr13TFSI0.10 encouraging results were obtained for IL based electrolytes - ca. 182 mAhg-1 at C/10 over 40 cycles.

  18. Ultrafast Torsional Relaxation of Thioflavin-T in Tris(pentafluoroethyl)trifluorophosphate (FAP) Anion-Based Ionic Liquids.

    PubMed

    Singh, Prabhat K; Mora, Aruna K; Nath, Sukhendu

    2015-11-01

    Ultrafast spectroscopy on solutes, whose dynamics is very sensitive to the friction in its local environment, has strong potential to report on the microenvironment existing in complex fluids such as ionic liquids. In this work, the torsional relaxation dynamics of Thioflavin-T (ThT), an ultrafast molecular rotor, is investigated in two fluoroalkylphosphate ([FAP])-based ionic liquids, namely, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([EMIM][FAP]) and 1-(2-hydroxyethyl)-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([OHEMIM][FAP]), using ultrafast fluorescence up-conversion spectroscopy. The emission quantum yield and the excited-state fluorescence lifetime measurement suggest that the torsional relaxation of Thioflavin-T, in this class of ionic liquids, is guided by the viscosity of the medium. The temporal profile of the dynamic Stokes' shift of ThT, measured from time-resolved emission spectrum (TRES), displays a multiexponential behavior in both ionic liquids. The long time dynamics of the Stokes' shift is reasonably slower for the hydroxyethyl derivative as compared to the ethyl derivative, which is in accordance with their measured shear viscosity. However, the short time dynamics of Stokes' shift is very similar in both the ionic liquids, and seems to be independent of the measured shear viscosity of the ionic liquid. We rationalize these observations in terms of different locations of ThT in these ionic liquids. These results suggest that despite having a higher bulk viscosity in the ionic liquid, they can provide unique microenvironment in their complex structure, where the reaction can be faster than expected from their measured shear viscosity. PMID:26457972

  19. Development of AMOEBA force field for 1,3-dimethylimidazolium based ionic liquids.

    PubMed

    Starovoytov, Oleg N; Torabifard, Hedieh; Cisneros, G Andrés

    2014-06-26

    The development of AMOEBA (a multipolar polarizable force field) for imidazolium based ionic liquids is presented. Our parametrization method follows the AMOEBA procedure and introduces the use of QM intermolecular total interactions as well as QM energy decomposition analysis (EDA) to fit individual interaction energy components. The distributed multipoles for the cation and anions have been derived using both the Gaussian distributed multipole analysis (GDMA) and Gaussian electrostatic model-distributed multipole (GEM-DM) methods.1 The intermolecular interactions of a 1,3-dimethylimidazolium [dmim(+)] cation with various anions, including fluoride [F(-)], chloride [Cl(-)], nitrate [NO(3)(-)], and tetraflorouborate [BF(4)(-)], were studied using quantum chemistry calculations at the MP2/6-311G(d,p) level of theory. Energy decomposition analysis was performed for each pair using the restricted variational space decomposition approach (RVS) at the HF/6-311G(d,p) level. The new force field was validated by running a series of molecular dynamic (MD) simulations and by analyzing thermodynamic and structural properties of these systems. A number of thermodynamic properties obtained from MD simulations were compared with available experimental data. The ionic liquid structure reproduced using the AMOEBA force field is also compared with the data from neutron diffraction experiment and other MD simulations. Employing GEM-DM force fields resulted in a good agreement on liquid densities ρ, enthalpies of vaporization ΔH(vap), and diffusion coefficients D(±) in comparison with conventional force fields. PMID:24901255

  20. Ion transport and structural dynamics in homologous ammonium and phosphonium-based room temperature ionic liquids

    SciTech Connect

    Griffin, Philip J.; Holt, Adam P.; Tsunashima, Katsuhiko; Sangoro, Joshua R.; Kremer, Friedrich; Sokolov, Alexei P.

    2015-02-28

    Charge transport and structural dynamics in a homologous pair of ammonium and phosphonium based room temperature ionic liquids (ILs) have been characterized over a wide temperature range using broadband dielectric spectroscopy and quasi-elastic light scattering spectroscopy. We have found that the ionic conductivity of the phosphonium based IL is significantly enhanced relative to the ammonium homolog, and this increase is primarily a result of a lower glass transition temperature and higher ion mobility. Additionally, these ILs exhibit pronounced secondary relaxations which are strongly influenced by the atomic identity of the cation charge center. While the secondary relaxation in the phosphonium IL has the expected Arrhenius temperature dependence characteristic of local beta relaxations, the corresponding relaxation process in the ammonium IL was found to exhibit a mildly non-Arrhenius temperature dependence in the measured temperature range—indicative of molecular cooperativity. These differences in both local and long-range molecular dynamics are a direct reflection of the subtly different inter-ionic interactions and mesoscale structures found in these homologous ILs.

  1. Phase equilibria and modeling of pyridinium-based ionic liquid solutions.

    PubMed

    Domańska, Urszula; Królikowski, Marek; Ramjugernath, Deresh; Letcher, Trevor M; Tumba, Kaniki

    2010-11-25

    The phase diagrams of the ionic liquid (IL) N-butyl-4-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide ([BM(4)Py][NTf(2)]) with water, an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol), an aromatic hydrocarbon (benzene, toluene, ethylbenzene, n-propylbenzene), an alkane (n-hexane, n-heptane, n-octane), or cyclohexane have been measured at atmospheric pressure using a dynamic method. This work includes the characterization of the synthesized compound by water content and also by differential scanning calorimetry. Phase diagrams for the binary systems of [BM(4)Py][NTf(2)] with all solvents reveal eutectic systems with regards to (solid-liquid) phase equilibria and show immiscibility in the liquid phase region with an upper critical solution temperature (UCST) in most of the mixtures. The phase equilibria (solid, or liquid-liquid) for the binary systems containing aliphatic hydrocarbons reported here exhibit the lowest solubility and the highest immiscibility gap, a trend which has been observed for all ILs. The reduction of experimental data has been carried out using the nonrandom two-liquid (NRTL) correlation equation. The phase diagrams reported here have been compared with analogous phase diagrams reported previously for systems containing the IL N-butyl-4-methylpyridinium tosylate and other pyridinium-based ILs. The influence of the anion of the IL on the phase behavior has been discussed. PMID:20964426

  2. Gelled Ionic Liquid-Based Membranes: Achieving a 10,000 GPU Permeance for Post-Combustion Carbon Capture with Gelled Ionic Liquid-Based Membranes

    SciTech Connect

    2011-02-02

    IMPACCT Project: Alongside Los Alamos National Laboratory and the Electric Power Research Institute, CU-Boulder is developing a membrane made of a gelled ionic liquid to capture CO2 from the exhaust of coal-fired power plants. The membranes are created by spraying the gelled ionic liquids in thin layers onto porous support structures using a specialized coating technique. The new membrane is highly efficient at pulling CO2 out of coal-derived flue gas exhaust while restricting the flow of other materials through it. The design involves few chemicals or moving parts and is more mechanically stable than current technologies. The team is now working to further optimize the gelled materials for CO2 separation and create a membrane layer that is less than 1 micrometer thick.

  3. Predicting cellulose solvating capabilities of acid-base conjugate ionic liquids.

    PubMed

    Parviainen, Arno; King, Alistair W T; Mutikainen, Ilpo; Hummel, Michael; Selg, Christoph; Hauru, Lauri K J; Sixta, Herbert; Kilpeläinen, Ilkka

    2013-11-01

    Different acid-base conjugates were made by combining a range of bases and superbases with acetic and propionic acid. Only the combinations that contained superbases were capable of dissolving cellulose. Proton affinities were calculated for the bases. A range, within which cellulose dissolution occurred, when combined with acetic or propionic acid, was defined for further use. This was above a proton affinity value of about 240 kcal mol(-1) at the MP2/6-311+G(d,p)//MP2/ 6-311+G(d,p) ab initio level. Understanding dissolution allowed us to determine that cation acidity contributed considerably to the ability of ionic liquids to dissolve cellulose and not just the basicity of the anion. By XRD analyses of suitable crystals, hydrogen bonding interactions between anion and cation were found to be the dominant interactions in the crystalline state. From determination of viscosities of these conjugates over a temperature range, certain structures were found to have as low a viscosity as 1-ethyl-3-methylimidazolium acetate, which was reflected in their high rate of cellulose dissolution but not necessarily the quantitative solubility of cellulose in those ionic liquids. 1,5-Diazabicyclo[4.3.0]non-5-enium propionate, which is one of the best structures for cellulose dissolution, was then distilled using laboratory equipment to demonstrate its recyclability. PMID:24106149

  4. How does lithium oxalyldifluoroborate enable the compatibility of ionic liquids and carbon-based capacitors?

    NASA Astrophysics Data System (ADS)

    Chen, Renjie; Chen, Yan; Xu, Bin; Zhang, Rong; He, Zhouying; Wu, Feng; Li, Li

    2015-02-01

    Lithium oxalyldifluoroborate (LiODFB) has several unique characteristics, such as high ionic conductivity over a wide temperature range and the ability to form and stabilize solid electrolyte interface films on graphite surfaces. A series of binary, room-temperature, molten electrolytes composed of LiODFB and organic compounds with acylamino groups (acetamide, oxazolidinone or OZO) have been synthesized. Fourier-transform infrared (FT-IR) spectroscopy indicates that Cdbnd O and N-H functional groups undergo blue or red shifts upon addition of LiODFB. The electrolytes have excellent thermal stabilities and electrochemical characteristics that allow them to be promising electrolytes for electrochemical double layer capacitors (EDLCs). Here, we examine 1:5 molar ratio LiODFB and acetamide/OZO ionic liquid (IL) electrolytes in EDLCs. IL compatibility with two types of carbon-based electrodes is investigated theoretically and experimentally. We simulate possible structures and ion diameters for the ILs, which must be compatible with pore sizes of the carbon electrodes. Mesoporous activated carbon AC2, with a pore size similar to the ionic diameter of LiODFB-acetamide, has a specific capacitance of 154.2 Fg-1 at 20 m Ag-1. Additionally, typical capacitive and reversibility behaviors can be seen in the charge-discharge curves over 0-2 V. Finally, the EDLCs exhibit good charging/discharging performances.

  5. Evaluation of solubility and partition properties of ampicillin-based ionic liquids.

    PubMed

    Florindo, Catarina; Araújo, João M M; Alves, Filipa; Matos, Carla; Ferraz, Ricardo; Prudêncio, Cristina; Noronha, João Paulo; Petrovski, Željko; Branco, Luís; Rebelo, Luís Paulo N; Marrucho, Isabel M

    2013-11-18

    In order to overcome the problems associated with low water solubility, and consequently low bioavailability of active pharmaceutical ingredients (APIs), herein we explore a modular ionic liquid synthetic strategy for improved APIs. Ionic liquids containing L-ampicillin as active pharmaceutical ingredient anion were prepared using the methodology developed in our previous work, using organic cations selected from substituted ammonium, phosphonium, pyridinium and methylimidazolium salts, with the intent of enhancing the solubility and bioavailability of L-ampicillin forms. In order to evaluate important properties of the synthesized API-ILs, the water solubility at 25 °C and 37 °C (body temperature) as well as octanol-water partition coefficients (Kow's) and HDPC micelles partition at 25 °C were measured. Critical micelle concentrations (CMC's) in water at 25 °C and 37 °C of the pharmaceutical ionic liquids bearing cations with surfactant properties were also determined from ionic conductivity measurements. PMID:23978632

  6. Ionic liquids for rechargeable lithium batteries

    SciTech Connect

    Salminen, Justin; Papaiconomou, Nicolas; Kerr, John; Prausnitz,John; Newman, John

    2005-09-29

    We have investigated possible anticipated advantages of ionic-liquid electrolytes for use in lithium-ion batteries. Thermal stabilities and phase behavior were studied by thermal gravimetric analysis and differential scanning calorimetry. The ionic liquids studied include various imidazoliumTFSI systems, pyrrolidiniumTFSI, BMIMPF{sub 6}, BMIMBF{sub 4}, and BMIMTf. Thermal stabilities were measured for neat ionic liquids and for BMIMBF{sub 4}-LiBF{sub 4}, BMIMTf-LiTf, BMIMTFSI-LiTFSI mixtures. Conductivities have been measured for various ionic-liquid lithium-salt systems. We show the development of interfacial impedance in a Li|BMIMBF{sub 4} + LiBF{sub 4}|Li cell and we report results from cycling experiments for a Li|BMIMBF{sub 4} + 1 mol/kg LIBF{sub 4}|C cell. The interfacial resistance increases with time and the ionic liquid reacts with the lithium electrode. As expected, imidazolium-based ionic liquids react with lithium electrodes. We seek new ionic liquids that have better chemical stabilities.

  7. Thermodynamics of Imidazolium-Based Ionic Liquids Containing PF6 Anions.

    PubMed

    Zaitsau, Dzmitry H; Yermalayeu, Andrei V; Emel'yanenko, Vladimir N; Butler, Simon; Schubert, Thomas; Verevkin, Sergey P

    2016-08-18

    Imidazolium-based ionic liquids (ILs) with PF6(-) anions are considered as low-cost solvents for separation processes, but they exhibit restricted thermal stabilities. Reliable measurements of vaporization thermodynamics by conventional methods have failed. In this work, we applied a quartz-crystal microbalance method to determine for the first time the absolute vapor pressures for the [Cnmim][PF6] family, with n = 2, 4, 6, 8, and 10, in the temperature range 403-461 K. An absence of decomposition of ILs in experimental conditions was determined by the attenuated total reflection-infrared spectroscopy. The consistency of the experimental results within the homologous series was established through enthalpy and entropy analyses of the liquid and gas phases as well as by molecular dynamics simulations. PMID:27462931

  8. Development of novel ionic liquid-based microemulsion formulation for dermal delivery of 5-Fluorouracil.

    PubMed

    Goindi, Shishu; Arora, Prabhleen; Kumar, Neeraj; Puri, Ashana

    2014-08-01

    The present study was aimed at synthesizing an imidazole-based ionic liquid 1-butyl-3-methylimidazolium bromide (BMIMBr) and subsequent development of a novel ionic liquid-in-oil (IL/o) microemulsion (ME) system for dermal delivery of a poorly permeating drug 5-fluorouracil (5-FU). A significant enhancement in the solubility of 5-FU was observed in BMIMBr. IL/o MEs of 5-FU were prepared using isopropyl myristate, Tween 80/Span 20, and BMIMBr. Results of ex vivo skin permeation studies through mice skin indicated that the selected IL/o ME exhibited 4-fold enhancement in percent drug permeation as compared to aqueous solution, 2.3-fold as compared to hydrophilic ointment, and 1.6-fold greater permeation than water in oil (w/o) ME. The results of in vivo studies against dimethylbenz(a)anthracene (DMBA)/12-O-tetradecanoylphorbol-13-acetate (TPA)-induced mice skin carcinogenesis demonstrated that the IL/o ME could effectively treat skin cancer in 4 weeks. In addition, the side effects such as erythema and irritation associated with the conventional formulations were not observed. Histopathological studies showed that the use of IL/o ME caused no anatomic and pathological changes in the skin structure of mice. These studies suggest that the use of IL-based ME system can efficiently enhance the solubility and permeability of 5-FU and hence its therapeutic efficacy. PMID:24668136

  9. Ionic Liquids to Replace Hydrazine

    NASA Technical Reports Server (NTRS)

    Koelfgen, Syri; Sims, Joe; Forton, Melissa; Allan, Barry; Rogers, Robin; Shamshina, Julia

    2011-01-01

    A method for developing safe, easy-to-handle propellants has been developed based upon ionic liquids (ILs) or their eutectic mixtures. An IL is a binary combination of a typically organic cation and anion, which generally produces an ionic salt with a melting point below 100 deg C. Many ILs have melting points near, or even below, room temperature (room temperature ionic liquids, RTILs). More importantly, a number of ILs have a positive enthalpy of formation. This means the thermal energy released during decomposition reactions makes energetic ILs ideal for use as propellants. In this specific work, to date, a baseline set of energetic ILs has been identified, synthesized, and characterized. Many of the ILs in this set have excellent performance potential in their own right. In all, ten ILs were characterized for their enthalpy of formation, density, melting point, glass transition point (if applicable), and decomposition temperature. Enthalpy of formation was measured using a microcalorimeter designed specifically to test milligram amounts of energetic materials. Of the ten ILs characterized, five offer higher Isp performance than hydrazine, ranging between 10 and 113 seconds higher than the state-of-the-art propellant. To achieve this level of performance, the energetic cations 4- amino-l,2,4-triazolium and 3-amino-1,2,4-triazolium were paired with various anions in the nitrate, dicyanamide, chloride, and 3-nitro-l,2,4-triazole families. Protonation, alkylation, and butylation synthesis routes were used for creation of the different salts.

  10. Atomic Resolution Insights into the Structural Aggregations and Optical Properties of Neat Imidazolium-Based Ionic Liquids.

    PubMed

    Du, Likai; Geng, Cuihuan; Zhang, Dongju; Lan, Zhenggang; Liu, Chengbu

    2016-07-14

    A fundamental understanding of the structural heterogeneity and optical properties of ionic liquids is crucial for their potential applications in catalysis, optical measurement, and solar cells. Herein, a synergistic approach combining molecular dynamics simulations, excited-state calculations, and statistical analysis was used to explore the explicit correlation between the structural and optical properties of one imidazolium amino acid-based ionic liquid, 1-butyl-3-methylimidazolium glycine. The estimated absorption spectrum successfully rationalizes the unusual and non-negligible absorption band beyond 300 nm for the neat imidazolium-based ionic liquid. The absorption behavior of imidazolium-based ionic liquids is shown to be sensitive to the details of their locally heterogeneous environments. We quantitatively highlight the imidazolium moiety and its various molecular aggregations, rather than the monomeric imidazolium moiety, that are responsible for the absorption characteristics. These results would improve our understanding of the preliminary interplay between structural heterogeneity and optical properties for neat imidazolium-based ionic liquids. PMID:27276660

  11. Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. II. Dynamical properties

    NASA Astrophysics Data System (ADS)

    Costa, Luciano T.; Ribeiro, Mauro C. C.

    2007-10-01

    Dynamical properties of polymer electrolytes based on poly(ethylene oxide) (PEO) and ionic liquids of 1-alkyl-3-methylimidazolium cations were calculated by molecular dynamics simulations with previously proposed models [L. T. Costa and M. C. Ribeiro, J. Chem. Phys. 124, 184902 (2006)]. The effect of changing the ionic liquid concentration, temperature, and the 1-alkyl-chain lengths, [1,3-dimethylimidazolium]PF6 and [1-butyl-3-methylimidazolium]PF6 ([dmim]PF6 and [bmim]PF6), was investigated. Cation diffusion coefficient is higher than those of anion and oxygen atoms of PEO chains. Ionic mobility in PEO /[bmim]PF6 is higher than in PEO /[dmim]PF6, so that the ionic conductivity κ of the former is approximately ten times larger than the latter. The ratio between κ and its estimate from the Nernst-Einstein equation κ /κNE, which is inversely proportional to the strength of ion pairs, is higher in ionic liquid polymer electrolytes than in polymer electrolytes based on inorganic salts with Li+ cations. Calculated time correlation functions corroborate previous evidence from the analysis of equilibrium structure that the ion pairs in ionic liquid polymer electrolytes are relatively weak. Structural relaxation at distinct spatial scales is revealed by the calculation of the intermediate scattering function at different wavevectors. These data are reproduced with stretched exponential functions, so that temperature and wavevector dependences of best fit parameters can be compared with corresponding results for polymer electrolytes containing simpler ions.

  12. Advances in the electrodeposition of aluminum from ionic liquid based electrolytes

    NASA Astrophysics Data System (ADS)

    Leadbetter, Kirt C.

    Aluminum plating is of considerable technical and economic interest because it provides an eco-friendly substitute for cadmium coatings used on many military systems. However, cadmium has been determined to be a significant environmental safety and occupational health (ESOH) hazard because of its toxicity and carcinogenic nature. Furthermore, the cost of treating and disposing of generated wastes, which often contain cyanide, is costly and is becoming prohibitive in the face of increasingly stringent regulatory standards. The non-toxic alternative aluminum is equivalent or superior in performance to cadmium. In addition, it could serve to provide an alternative to hexavalent chromium coatings used on military systems for similar reasons to that of cadmium. Aluminum is a beneficial alternative in that it demonstrates self-healing corrosion resistance in the form of a tightly-bound, impervious oxide layer. A successfully plated layer would be serviceable over a wider temperature range, 925 °F for aluminum compared to 450 oF for cadmium. In addition, an aluminum layer can be anodized to make it non-conducting and colorable. In consideration of the plating process, aluminum cannot be deposited from aqueous solutions because of its reduction potential. Therefore, nonaqueous electrolytes are required for deposition. Currently, aluminum can be electrodeposited in nonaqueous processes that use hazardous chemicals such as toluene and pyrophoric aluminum alkyls. Electrodeposition from ionic liquids provides the potential for a safer method that could be easily scaled up for industrial application. The plating process could be performed at a lower temperature and higher current density than other commercially available aluminum electrodeposition processes; thus a reduced process cost could be possible. The current ionic liquid based electrolytes are more expensive; however production on a larger scale and a long electrolyte lifetime are associated with a reduction in price

  13. Ionic liquid based polymeric liposomes: A stable and biocompatible soft platform for bioelectrochemistry.

    PubMed

    Tian, Yanping; Xia, Jiarui; Zhang, Ling; Zhang, Junhui; Jiang, Yi; Zhang, Yao; Yang, Lini; Zhang, Qian; Xia, Lixin

    2016-10-01

    Polymeric liposomes (denoted as ILs-polysomes) are a biocompatible and conductive nanomaterial, which was first utilised as the electrode material for immobilising and biosensing redox enzyme horseradish peroxide (HRP). The morphology and surface property of IL-polysomes was characterised and systematically compared with unpolymerised ionic liquid based liposomes (denoted as ILs-liposomes). Differing from IL-liposomes, IL-polysomes preserves their original morphology and bilayer membrane structure on glassy carbon (GC) electrodes due to the cross-linking of polymerised lipids, thus exhibiting excellent stability and specific biocompability. Because of the existence of imidazolium ionic liquid moieties on the outer surface, IL-polysomes displays a positive charge in aqueous solution, leading to oppositely charged HRP self-assembling onto the vesicles to form HRP/IL-polysomes/PVA/GC electrodes. Owing to the combined merits of ILs and liposomes, electron transfer between HRP-Fe(III)/Fe(II) redox couples of immobilised enzymes and GC electrodes can be achieved. Therefore, HRP/IL-polysomes/PVA/GC electrodes exhibited good electrocatalytic performance toward the electrocatalysis of H2O2. Accordingly, IL-polysomes could act as an efficient charged platform for the self-assembled redox enzymes to realise direct electrochemistry. IL-polysomes have a promising application in the fabrication of third-generation electrochemical biosensors. PMID:27196632

  14. Ionic liquids-based crosslinked copolymer sorbents for headspace solid-phase microextraction of polar alcohols.

    PubMed

    Feng, Juanjuan; Sun, Min; Wang, Xusheng; Liu, Xia; Jiang, Shengxiang

    2012-07-01

    Halogen-based polymeric ionic liquid (PIL) fibers, which have proved efficient for solid-phase microextraction (SPME) of polar compounds, were with very limited fiber lifetimes. In this work, a novel crosslinked PIL sorbent with satisfactory stability and durability was prepared in situ via crosslinking polymerization processes on microstructured-silver coated stainless steel wire. 1,1'-(1,6-Hexanediyl)bis(1-vinylimidazolium) bibromide ionic liquid was synthesized and used as the crosslinking agent, with 1-vinyl-3-octylimidazolium bromide as monomer. Extraction properties of the fiber for polar alcohols in polar aqueous matrix were examined using headspace SPME (HS-SPME) coupled to gas chromatography-flame ionization detection (GC-FID). Under the optimized extraction and desorption conditions, the established method exhibited high extraction capacity. Wide linear ranges were obtained with correlation coefficients (R) ranging from 0.9947 to 0.9999. Limits of detection were in the range of 0.5-20 μg L⁻¹. Compared with the non-crosslinked PIL fiber, the proposed crosslinked PIL fiber was with higher thermal stability and durability and longer lifetime. Four different liquor beverages were analyzed as real samples and good results were obtained. PMID:22673810

  15. A theoretical and experimental evaluation of imidazolium-based ionic liquids for atmospheric mercury capture.

    PubMed

    Iuga, Cristina; Solís, Corina; Alvarez-Idaboy, J Raúl; Martínez, Miguel Angel; Mondragón, Ma Antonieta; Vivier-Bunge, Annik

    2014-05-01

    In this work, the capacity of three different imidazolium-based ionic liquids (ILs) for atmospheric mercury capture has been evaluated. Theoretical calculations using monomer and dimer models of ILs showed that [BMIM]⁺[SCN]⁻ and [BMIM]⁺[Cl]⁻ ionic liquids capture gaseous Hg⁰, while [BMIM]⁺[PF₆]⁻ shows no ability for this purpose. These findings are supported by experimental data obtained using particle induced X-ray emission (PIXE) trace element analysis. Experimental and theoretical infrared data of the ILs were obtained before and after exposure to Hg. In all cases, no displacement of the bands was observed, indicating that the interaction does not significantly affect the force constants of substrate bonds. This suggests that van der Waals forces are the main forces responsible for mercury capture. Since the anion-absorbate is the driving force of the interaction, the largest charge-volume ratio of [Cl]⁻ could explain the higher affinity for mercury sequestration of the [BMIM]⁺[Cl]⁻ salt. PMID:24781855

  16. Why are some cyano-based ionic liquids better glucose solvents than water?

    PubMed

    Batista, Marta L S; Passos, Helena; Henriques, Bruno J M; Maginn, Edward J; Pinho, Simão P; Freire, Mara G; Gomes, José R B; Coutinho, João A P

    2016-07-28

    Among different classes of ionic liquids (ILs), those with cyano-based anions have been of special interest due to their low viscosity and enhanced solvation ability for a large variety of compounds. Experimental results from this work reveal that the solubility of glucose in some of these ionic liquids may be higher than in water - a well-known solvent with enhanced capacity to dissolve mono- and disaccharides. This raises questions on the ability of cyano groups to establish strong hydrogen bonds with carbohydrates and on the optimal number of cyano groups at the IL anion that maximizes the solubility of glucose. In addition to experimental solubility data, these questions are addressed in this study using a combination of density functional theory (DFT) and molecular dynamics (MD) simulations. Through the calculation of the number of hydrogen bonds, coordination numbers, energies of interaction and radial and spatial distribution functions, it was possible to explain the experimental results and to show that the ability to favorably interact with glucose is driven by the polarity of each IL anion, with the optimal anion being dicyanamide. PMID:27353302

  17. Ionic Liquid-Based Polymer Electrolytes via Surfactant-Assisted Polymerization at the Plasma-Liquid Interface.

    PubMed

    Tran, Quoc Chinh; Bui, Van-Tien; Dao, Van-Duong; Lee, Joong-Kee; Choi, Ho-Suk

    2016-06-29

    We first report an innovative method, which we refer to as interfacial liquid plasma polymerization, to chemically cross-link ionic liquids (ILs). By this method, a series of all-solid state, free-standing polymer electrolytes is successfully fabricated where ILs are used as building blocks and ethylene oxide-based surfactants are employed as an assisted-cross-linking agent. The thickness of the films is controlled by the plasma exposure time or the ratio of surfactant to ILs. The chemical structure and properties of the polymer electrolyte are characterized by scanning electron microscopy (SEM), Fourier transformation infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR) spectroscopy, X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC), and electrochemical impedance spectroscopy (EIS). Importantly, the underlying polymerization mechanism of the cross-linked IL-based polymer electrolyte is studied to show that fluoroborate or halide anions of ILs together with the aid of a small amount of surfactants having ethylene oxide groups are necessary to form cross-linked network structures of the polymer electrolyte. The ionic conductivity of the obtained polymer electrolyte is 2.28 × 10(-3) S·cm(-1), which is a relatively high value for solid polymer electrolytes synthesized at room temperature. This study can serve as a cornerstone for developing all-solid state polymer electrolytes with promising properties for next-generation electrochemical devices. PMID:27281115

  18. Hydrophobic ionic liquids

    DOEpatents

    Koch, V.R.; Nanjundiah, C.; Carlin, R.T.

    1998-10-27

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas shown in a diagram wherein R{sub 1}, R{sub 2}, R{sub 3}, R{sub 4}, R{sub 5}, and R{sub 6} are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F-, Cl-, CF{sub 3}-, SF{sub 5}-, CF{sub 3}S-, (CF{sub 3}){sub 2}CHS- or (CF{sub 3}){sub 3}CS-; and X{sup {minus}} is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 {angstrom}{sup 3}. 4 figs.

  19. Hydrophobic ionic liquids

    DOEpatents

    Koch, Victor R.; Nanjundiah, Chenniah; Carlin, Richard T.

    1998-01-01

    Ionic liquids having improved properties for application in non-aqueous batteries, electrochemical capacitors, electroplating, catalysis and chemical separations are disclosed. Exemplary compounds have one of the following formulas: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, and R.sub.6 are either H; F; separate alkyl groups of from 1 to 4 carbon atoms, respectively, or joined together to constitute a unitary alkylene radical of from 2 to 4 carbon atoms forming a ring structure converging on N; or separate phenyl groups; and wherein the alkyl groups, alkylene radicals or phenyl groups may be substituted with electron withdrawing groups, preferably F--, Cl--, CF.sub.3 --, SF.sub.5 --, CF.sub.3 S--, (CF.sub.3).sub.2 CHS-- or (CF.sub.3).sub.3 CS--; and X.sup.- is a non-Lewis acid-containing polyatomic anion having a van der Waals volume exceeding 100 .ANG..sup.3.

  20. Superbase-derived protic ionic liquids

    DOEpatents

    Dai, Sheng; Luo, Huimin; Baker, Gary A.

    2013-09-03

    Protic ionic liquids having a composition of formula (A.sup.-)(BH.sup.+) wherein A.sup.- is a conjugate base of an acid HA, and BH.sup.+ is a conjugate acid of a superbase B. In particular embodiments, BH.sup.+ is selected from phosphazenium species and guanidinium species encompassed, respectively, by the general formulas: ##STR00001## The invention is also directed to films and membranes containing these protic ionic liquids, with particular application as proton exchange membranes for fuel cells.

  1. Electrochemical co-deposition of magnesium with lithium from quaternary ammonium-based ionic liquid

    NASA Astrophysics Data System (ADS)

    Shimamura, Osamu; Yoshimoto, Nobuko; Matsumoto, Mami; Egashia, Minato; Morita, Masayuki

    Electrochemical deposition of magnesium (Mg) has been successfully achieved from an ionic liquid (IL) solution based on quaternary ammonium salt containing lithium (Li) salt. Irreversible electrochemical behavior was generally observed in the IL-based electrolytes containing simple Mg salt. In the IL-based electrolyte dissolving both Mg and Li salts, electrochemical reduction and oxidation of magnesium cation (Mg 2+) have become detectable. Such reversible processes correspond respectively to cathodic deposition and anodic dissolution of metallic Mg, which are accompanied by the co-deposition/co-dissolution of Li. Potentiostatic electrolysis of IL dissolving binary Mg and Li salts gave metallic deposit consisting of both elements with total current efficiency of ca. 52%.

  2. Ionic Liquid Crystals: Versatile Materials.

    PubMed

    Goossens, Karel; Lava, Kathleen; Bielawski, Christopher W; Binnemans, Koen

    2016-04-27

    This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions. PMID:27088310

  3. Ionic liquid-based matrix solid-phase dispersion coupled with homogeneous liquid-liquid microextraction of synthetic dyes in condiments.

    PubMed

    Wang, Zhibing; Zhang, Liyuan; Li, Na; Lei, Lei; Shao, Mingyuan; Yang, Xiao; Song, Ying; Yu, Aimin; Zhang, Hanqi; Qiu, Fangping

    2014-06-27

    The ionic liquid-based matrix solid-phase dispersion homogeneous liquid-liquid microextraction (IL-based MSPD-HLLME) was developed and applied to the extraction of four banned dyes, including chrysoidin, safranine O, auramine O and rhodamine B, in condiment samples. High performance liquid chromatography was applied to the separation and determination of the analytes. The solid sample was directly treated by MSPD using ionic liquid as dispersant and the eluate obtained in MSPD was treated by HLLME. Some experimental parameters, including type of dispersant, ratio of sample to dispersant, type and volume of ionic liquid, type and volume of elution solvent, pH value and ionic strength of the elution solvent, amount of ion-pairing agent (NH4PF6) and extraction time, were investigated and optimized. The linearities for determining the analytes were in the range of 60-2000μgkg(-1) for chrysoidin, 40-2000μgkg(-1) for safranine O and 20-1000μgkg(-1) for auramine O and rhodamine B, with the correlation coefficients ranging from 0.9964 to 0.9991. The limits of detection for the analytes were between 6.7 and 26.8μgkg(-1) and the limits of quantification were between 15.99 and 58.48μgkg(-1). When the present method was applied to the analysis of spiked condiment samples, the recoveries of the analytes ranged from 90.69 to 113.52% and relative standard deviations were lower than 8.2%. The present method combined the advantages of MSPD and HLLME, and could be applied for the determination of synthetic dyes in condiment samples. PMID:24857032

  4. Determination of metal ions in tea samples using task-specific ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction coupled to liquid chromatography with ultraviolet detection.

    PubMed

    Werner, Justyna

    2016-04-01

    Task-specific ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction was used for the preconcentration of cadmium(II), cobalt(II), and lead(II) ions in tea samples, which were subsequently analyzed by liquid chromatography with UV detection. The proposed method of preconcentration is free of volatile organic compounds, which are often used as extractants and dispersing solvents in classic techniques of microextraction. A task-specific ionic liquid trioctylmethylammonium thiosalicylate was used as an extractant and a chelating agent. Ultrasound was used to disperse the ionic liquid. After microextraction, the phases were separated by centrifugation, and the ionic liquid phase was solubilized in methanol and directly injected into the liquid chromatograph. Selected microextraction parameters, such as the volume of ionic liquid, the pH of the sample, the duration of ultrasound treatment, the speed and time of centrifugation, and the effect of ionic strength, were optimized. Under optimal conditions an enrichment factor of 200 was obtained for each analyte. The limits of detection were 0.002 mg/kg for Cd(II), 0.009 mg/kg for Co(II), and 0.013 mg/kg for Pb(II). The accuracy of the proposed method was evaluated by an analysis of the Certified Reference Materials (INCT-TL-1, INCT-MPH-2) with the recovery values in the range of 90-104%. PMID:26891114

  5. Ionic liquid-based dispersive liquid-liquid microextraction followed by RP-HPLC determination of saquinavir in rat serum: application to pharmacokinetics.

    PubMed

    Ramisetti, Nageswara Rao; Nimmu, Narendra Varma; Challa, Gangu Naidu

    2014-12-01

    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 (r(2) ) of 0.9996. The method was validated and applied to study pharmacokinetics of saquinavir in rat serum. PMID:24944096

  6. Ionic liquid-based homogeneous liquid-liquid microextraction for the determination of antibiotics in milk by high-performance liquid chromatography.

    PubMed

    Gao, Shiqian; Jin, Haiyan; You, Jingyan; Ding, Yi; Zhang, Nan; Wang, Ying; Ren, Ruibing; Zhang, Rui; Zhang, Hanqi

    2011-10-14

    Ionic liquid-based homogeneous liquid-liquid microextraction (IL-based HLLME) high-performance liquid chromatography was developed and applied to the extraction, separation and determination of some antibiotics in milk. The proteins and lipids were removed by adding salt and adjusting the pH value. The homogeneous extraction was applied to the improvement of recoveries for IL phase and analytes. The experimental parameters of the IL-based HLLME, including salt concentration in sample solution, pH value of sample solution, volume of [C(6)MIM][BF(4)], amount of ion-pairing agent (NH(4)PF(6)), and extraction time, were evaluated. The limits of detection for enoxacin, pefloxacin, norfloxacin, enrofloxacin, sulfamethoxazole and sulfadimethoxine were 15.8, 7.07, 5.13, 4.00, 7.79 and 8.33 μg L(-1), respectively. When the proposed method was applied to the analysis of milk samples the recoveries of the analytes ranged from 92.5 to 118.6% and relative standard deviations were lower than 7.00%. PMID:21907341

  7. Dielectric Properties of Polypropylene-Based Nanocomposites with Ionic Liquid-Functionalized Multiwalled Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Xu, Pei; Gui, Haoguan; Hu, Yadong; Bahader, Ali; Ding, Yunsheng

    2014-07-01

    Nanocomposites were prepared from polypropylene (PP) and untreated multiwalled carbon nanotubes (MWCNTs) or MWCNTs surface-functionalized with ionic liquids (MIL), as fillers, and their dielectric properties were compared. The physical (cation-π/π-π) interaction between the ionic liquids and the MWCNTs was apparent from Raman spectroscopy and from thermogravimetric analysis. Morphology characterization revealed that ionic liquids improve the dispersibility of MWCNTs in the PP matrix. It is suggested that the substantial increase in the dielectric permittivity of the nanocomposites compared with that of the PP originates from a remarkable Maxwell-Wagner-Sillars (MWS) effect at percolation threshold where mobile charge carriers are blocked at internal interfaces between the MIL and the PP matrix. The high polarity of ionic liquids may reinforce the MWS effect, and the nonconducting organic groups of the ionic liquids promote the low loss tangent and low conductivity of the MIL/PP nanocomposites. Compared with MWCNTs/PP nanocomposites, lower loss tangent and higher dielectric permittivity were observed for MIL/PP nanocomposites, making the material more attractive for application in electronics.

  8. Structural and Spectroscopic Characterizations of Amide-AlCl3-Based Ionic Liquid Analogues.

    PubMed

    Hu, Pengcheng; Zhang, Rui; Meng, Xianghai; Liu, Haiyan; Xu, Chunming; Liu, Zhichang

    2016-03-01

    Several amide-AlCl3-based ionic liquid (IL) analogues were synthesized through a one-step method using three different structure amides as donor molecules. The effects of the steric and inductive effects of the methyl group substituted on the N atom on the asymmetric splitting of AlCl3 and the coordination site of the amide were investigated by (27)Al NMR, Raman, in situ IR, and UV-vis spectra for these IL analogues. Bidentate coordination through both the O and N atoms was dominant in the N-methylacetamide-AlCl3- and N,N-dimethylacetamide-AlCl3-based IL analogues because of the inductive effect of the methyl group. By contrast, the acetamide-AlCl3-based IL analogue presented mainly in the form of monodentate coordination via the O atom. Compared with monodentate coordination, bidentate coordination was favorable to the asymmetric splitting of AlCl3 with the same amide-AlCl3 molar ratio. Under the influence of the steric and inductive effects of the methyl group, the ionic species percentages in these IL analogues ranked in the following order: N-methylacetamide > N,N-dimethylacetamide > acetamide. PMID:26848508

  9. Water-in-ionic liquid microemulsion-based organogels as novel matrices for enzyme immobilization.

    PubMed

    Pavlidis, Ioannis V; Tzafestas, Kyriakos; Stamatis, Haralambos

    2010-08-01

    The use of water-in-ionic liquid microemulsion-based organogels (w/IL MBGs) as novel supports for the immobilization of lipase B from Candida antarctica and lipase from Chromobacterium viscosum was investigated. These novel lipase-containing w/IL MBGs can be effectively used as solid phase biocatalysts in various polar and non-polar organic solvents or ILs, exhibiting up to 4.4-fold higher esterification activity compared to water-in-oil microemulsion-based organogels. The immobilized lipases retain their activity for several hours at 70 degrees C, while their half life time is up to 25-fold higher compared to that observed in w/IL microemulsions. Fourier-transform infrared spectroscopy data indicate that immobilized lipases adopt a more rigid structure, referring to the structure in aqueous solution, which is in correlation with their enhanced catalytic behavior observed. PMID:20449844

  10. A detailed assignment of NEXAFS resonances of imidazolium based ionic liquids.

    PubMed

    Ehlert, Christopher; Holzweber, Markus; Lippitz, Andreas; Unger, Wolfgang E S; Saalfrank, Peter

    2016-03-16

    In Near Edge X-Ray Absorption Fine Structure (NEXAFS) spectroscopy X-Ray photons are used to excite tightly bound core electrons to low-lying unoccupied orbitals of the system. This technique offers insight into the electronic structure of the system as well as useful structural information. In this work, we apply NEXAFS to two kinds of imidazolium based ionic liquids ([CnC1im](+)[NTf2](-) and [C4C1im](+)[I](-)). A combination of measurements and quantum chemical calculations of C K and N K NEXAFS resonances is presented. The simulations, based on the transition potential density functional theory method (TP-DFT), reproduce all characteristic features observed by the experiment. Furthermore, a detailed assignment of resonance features to excitation centers (carbon or nitrogen atoms) leads to a consistent interpretation of the spectra. PMID:26948544

  11. Ionic liquid-based ultrasound-assisted extraction of fangchinoline and tetrandrine from Stephaniae tetrandrae.

    PubMed

    Zhang, Lijin; Geng, Yanling; Duan, Wenjuan; Wang, Daijie; Fu, Maorun; Wang, Xiao

    2009-10-01

    An ionic liquid-based ultrasound-assisted extraction method has been developed for the effective extraction of fangchinoline and tetrandrine from Stephaniae tetrandrae. The effects of some ultrasound-assisted extraction parameters including the concentration of [BMIM][BF(4)], pH, ultrasonic power and time were investigated to optimize the ultrasound-assisted extraction conditions. Compared to the regular ultrasound-assisted extraction and traditional refluent extraction, the proposed [BMIM][BF(4)]-based ultrasound-assisted extraction offered shorter extraction times (from 6 h to 40 min) and remarkable higher efficiencies (approximately 30% improved), which supported the suitability of the proposed approach. In addition, the proposed approach was confirmed by the good correlation coefficient (R(2)), recovery and reproducibility (RSD, n = 5), which were in the range of 0.9992-0.9995, 85.5-101.1%, and 1.87-4.33%, respectively. PMID:19764054

  12. Guide to CO{sub 2} separations in imidazolium-based room-temperature ionic liquids

    SciTech Connect

    Bara, J.E.; Carlisle, T.K.; Gabriel, C.J.; Camper, D.; Finotello, A.; Gin, D.L.; Noble, R.D.

    2009-03-18

    Room-temperature ionic liquids (RTILs) are nonvolatile, tunable solvents. The solubilities of gases, particularly CO{sub 2}, N{sub 2}, and CH{sub 4}, have been studied in a number of RTILs. Process temperature and the chemical structures of the cation and anion have significant impacts on gas solubility and gas pair selectivity. Models based on regular solution theory and group contributions are useful to predict and explain CO{sub 2} solubility and selectivity in imidazolium-based RTILs. In addition to their role as a physical solvent, RTILs might also be used in supported ionic liquid membranes (SILMs) as a highly permeable and selective transport medium. Performance data for SILMs indicates that they exhibit large permeabilities as well as CO{sub 2}/N{sub 2} selectivities that outperform many polymer membranes. Furthermore, the greatest potential of RTILs for CO{sub 2} separations might lie in their ability to chemically capture CO{sub 2} when used in combination with amines. Amines can be tethered to the cation or the anion, or dissolved in RTILs, providing a wide range of chemical solvents for CO{sub 2} capture. However, despite all of their promising features, RTILs do have drawbacks to use in CO{sub 2} separations, which have been overlooked as appropriate comparisons of RTILs to common organic solvents and polymers have not been reported. A thorough summary of the capabilities-and limitations-of imidazolium-based RTILs in CO{sub 2}-based separations with respect to a variety of materials is thus provided.

  13. NOVEL FISSION PRODUCT SEPARATION BASED ON ROOM-TEMPERATURE IONIC LIQUIDS

    SciTech Connect

    Hussey, Charles L.

    2004-06-01

    The DoE/NE underground storage tanks at Hanford, SRS, and INEEL contain liquid wastes with high concentrations of radioactive species, mainly 137Cs and 90Sr. Because the other components of the liquid waste are mainly sodium nitrate and sodium hydroxide, most of this tank waste can be treated inexpensively as low-level waste if 137Cs and 90Sr can be selectively removed. Many ionophores (crown ether and calixarene compounds) have been synthesized for the purpose of selectively extracting Cs+ and Sr2+ from an aqueous phase into an immiscible organic phase. Recent studies conducted at ORNL1,2 reveal that hydrophobic ionic liquids might be better solvents for extracting metal ions from aqueous solutions with these ionophores than conventional immiscible organic solvents, such as benzene, toluene, and dichloromethane, because both Cs+ and Sr2+ exhibit larger distribution coefficients in the ionic liquids. In addition, the vapor pressures of these ionic liquids are insignificant. Thus, there is little or no vaporization loss of these solvents. Most of the ionic liquids under investigation are relatively nontoxic compared to the hydrocarbon solvents that they replace, classifying them as ''green'' solvents.

  14. Theoretical studies on CO2 capture behavior of quaternary ammonium-based polymeric ionic liquids.

    PubMed

    Wang, Tao; Ge, Kun; Chen, Kexian; Hou, Chenglong; Fang, Mengxiang

    2016-05-14

    Quaternary ammonium-based polymeric ionic liquids (PILs) are novel CO2 sorbents as they have high capacity, high stability and high binding energy. Moreover, the binding energy of ionic pairs to CO2 is tunable by changing the hydration state so that the sorbent can be regenerated through humidity adjustment. In this study, theoretical calculations were conducted to reveal the mechanism of the humidity swing CO2 adsorption, based on model compounds of quaternary ammonium cation and carbonate anions. The electrostatic potential map demonstrates the anion, rather than the cation, is chemically preferential for CO2 adsorption. Further, the proton transfer process from water to carbonate at the sorbent interface is successfully depicted with an intermediate which has a higher energy state. By determining the CO2 adsorption energy and activation energy at different hydration states, it is discovered that water could promote CO2 adsorption by reducing the energy barrier of proton transfer. The adsorption/desorption equilibrium would shift to desorption by adding water, which constitutes the theoretical basis for humidity swing. By analyzing the hydrogen bonding and structure of the water molecules, it is interesting to find that the CO2 adsorption weakens the hydrophilicity of the sorbent and results in release of water. The requirement of latent heat for the phase change of water could significantly reduce the heat of adsorption. The special "self-cooling" effect during gas adsorption can lower the temperature of the sorbent and benefit the adsorption isotherms. PMID:27115032

  15. Molecular dynamics simulation of imidazolium-based ionic liquids. II. Transport coefficients.

    PubMed

    Kowsari, M H; Alavi, Saman; Ashrafizaadeh, Mahmud; Najafi, Bijan

    2009-01-01

    A systematic molecular dynamics study is performed to determine the dynamics and transport properties of 12 room-temperature ionic liquids family with 1-alkyl-3-methylimidazolium cation, [amim](+) (alkyl = methyl, ethyl, propyl, and butyl), with counterions, PF(6)(-), NO(3)(-), and Cl(-). The goal of the work is to provide molecular level understanding of the transport coefficients of these liquids as guidance to experimentalists on choosing anion and cation pairs to match required properties of ionic liquid solvents. In the earlier paper (Part I), we characterized the dynamics of ionic liquids and provided a detailed comparison of the diffusion coefficients for each ion using the Einstein and Green-Kubo formulas. In this second part, other transport properties of imidazolium salts are calculated, in particular, the electrical conductivity is calculated from the Nernst-Einstein and Green-Kubo formulas. The viscosity is also determined from the Stokes-Einstein relation. The results of the calculated transport coefficients are consistent with the previous computational and experimental studies of imidazolium salts. Generally, the simulations give electrical conductivity lower than experiment while the viscosity estimate is higher than experiment. Within the same cation family, the ionic liquids with the NO(3)(-) counterion have the highest electrical conductivities: sigma[NO(3)](-)>sigma[PF(6)](-)>sigma[Cl](-). The [dmim][X] series, due to their symmetric cationic structure and good packing and the [bmim][X] series due to higher inductive van der Waals interactions of [bmim](+), have the highest viscosities in these ionic liquid series. Our simulations show that the major factors determining the magnitude of the self-diffusion, electrical conductivity, and viscosity are the geometric shape, ion size, and the delocalization of the ionic charge in the anion. PMID:19140627

  16. Ionic liquid matrix-based dispersive liquid-liquid microextraction for enhanced MALDI-MS analysis of phospholipids in soybean.

    PubMed

    Shrivas, Kamlesh; Tapadia, Kavita

    2015-09-15

    Ionic liquid matrix (ILM) is found to be a very versatile substance for analysis of broad range of organic molecules in matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) due to good solubility for a variety of analytes, formation of homogenous crystals and high vacuum stability of the matrix. In the present work, an ILM, cyno-4-hydroxycinnamic acid-butylamine (CHCAB) was employed in dispersive liquid-liquid microextraction (DLLME) as sample probe and matrix for extraction and ionization of phospholipids from food samples (soybean) prior to MALDI-MS analysis. With the employed technique, 8-125 fold improvement in signal intensity and limit of detection were achieved for the analysis of phospholipids. The best extraction efficiency of phospholipids in ILM-DLLME was obtained with 5min extraction time in presence 30mg/mL CHCAB and 1.2% NaCl using chloroform as an extracting solvent and methanol as a dispersing solvent. Further, the developed ILM-DLLME procedure has been successfully applied for the analysis of phospholipids in soybean samples in MALDI-MS. PMID:26276066

  17. Electrochemical reduction of aromatic ketones in 1-butyl-3-methylimidazolium-based ionic liquids in the presence of carbon dioxide: the influence of the ketone substituent and the ionic liquid anion on bulk electrolysis product distribution.

    PubMed

    Zhao, Shu-Feng; Horne, Mike; Bond, Alan M; Zhang, Jie

    2015-07-15

    Electrochemical reduction of aromatic ketones, including acetophenone, benzophenone and 4-phenylbenzophenone, has been undertaken in 1-butyl-3-methylimidazolium-based ionic liquids containing tetrafluoroborate ([BF4](-)), trifluoromethanesulfonate ([TfO](-)) and tris(pentafluoroethyl)trifluorophosphate ([FAP](-)) anions in the presence of carbon dioxide in order to investigate the ketone substituent effect and the influence of the acidic proton on the imidazolium cation (C2-H) on bulk electrolysis product distribution. For acetophenone, the minor products were dimers (<10%) in all ionic liquids, which are the result of acetophenone radical anion coupling. For benzophenone and 4-phenylbenzophenone, no dimers were formed due to steric hindrance. In these cases, even though carboxylic acids were obtained, the main products generated were alcohols (>50%) derived from proton coupled electron transfer reactions involving the electrogenerated radical anions and C2-H. In the cases of both acetophenone and benzophenone, the product distribution is essentially independent of the ionic liquid anion. By contrast, 4-phenylbenzophenone shows a product distribution that is dependent on the ionic liquid anion. Higher yields of carboxylic acids (∼40%) are obtained with [TfO](-) and [FAP](-) anions because in these ionic liquids the C2-H is less acidic, making the formation of alcohol less favourable. In comparison with benzophenone, a higher yield of carboxylic acid (>30% versus ∼15%) was obtained with 4-phenylbenzophenone in all ionic liquids due to the weaker basicity of 4-phenylbenzophenone radical anion. PMID:26136079

  18. The force field for imidazolium-based ionic liquids: Novel anions with polar residues

    NASA Astrophysics Data System (ADS)

    Fileti, Eudes Eterno; Chaban, Vitaly V.

    2015-07-01

    Many molecules can be converted into ions via relatively simple procedures. These ions can be combined into ionic liquids (ILs). We develop a new force field (FF) for the seven selected AAILs comprising 1-ethyl-3-methylimidazolium cation and amino acid anions with polar residues. All anions were obtained via deprotonation of carboxyl group in analogy with acetate anion. We account for peculiar interactions between the anion and the cation by fitting electrostatic potential for an ion pair, in contrast to isolated ions. Furthermore, we account for hydrogen bonds obtained via electronic structure consideration. The developed model fosters computational investigation of ionic liquids.

  19. Exploring Sustainable Rocket Fuels: [Imidazolyl-Amine-BH2](+)-Cation-Based Ionic Liquids as Replacements for Toxic Hydrazine Derivatives.

    PubMed

    Huang, Shi; Qi, Xiujuan; Zhang, Wenquan; Liu, Tianlin; Zhang, Qinghua

    2015-12-01

    The application of hypergolic ionic liquids as propellant fuels is a newly emerging area in the fields of chemistry and propulsion science. Herein, a new class of [imidazolyl-amine-BH2](+)-cation-based ionic liquids, which included fuel-rich anions, such as dicyanamide (N(CN)2(-)) and cyanoborohydride (BH3CN(-)) anions, were synthesized and characterized. As expected, all of the ionic liquids exhibited spontaneous combustion upon contact with the oxidizer 100 % HNO3. The densities of these ionic liquids varied from 0.99-1.12 g cm(-3), and the heats of formation, predicted based on Gaussian 09 calculations, were between -707.7 and 241.8 kJ mol(-1). Among them, the salt of compound 5, that is, (1-allyl-1H-imidazole-3-yl)-(trimethylamine)-dihydroboronium dicyanamide, exhibited the lowest viscosity (168 MPa s), good thermal properties (Tg <-70 °C, Td >130 °C), and the shortest ignition-delay time (18 ms) with 100 % HNO3. These ionic fuels, as "green" replacements for toxic hydrazine-derivatives, may have potential applications as bipropellant formulations. PMID:26247801

  20. Extraction of Biomolecules Using Phosphonium-Based Ionic Liquids + K3PO4 Aqueous Biphasic Systems

    PubMed Central

    Louros, Cláudia L. S.; Cláudio, Ana Filipa M.; Neves, Catarina M. S. S.; Freire, Mara G.; Marrucho, Isabel M.; Pauly, Jérôme; Coutinho, João A. P.

    2010-01-01

    Aqueous biphasic systems (ABS) provide an alternative and efficient approach for the extraction, recovery and purification of biomolecules through their partitioning between two liquid aqueous phases. In this work, the ability of hydrophilic phosphonium-based ionic liquids (ILs) to form ABS with aqueous K3PO4 solutions was evaluated for the first time. Ternary phase diagrams, and respective tie-lines and tie-lines length, formed by distinct phosphonium-based ILs, water, and K3PO4 at 298 K, were measured and are reported. The studied phosphonium-based ILs have shown to be more effective in promoting ABS compared to the imidazolium-based counterparts with similar anions. Moreover, the extractive capability of such systems was assessed for distinct biomolecules (including amino acids, food colourants and alkaloids). Densities and viscosities of both aqueous phases, at the mass fraction compositions used for the biomolecules extraction, were also determined. The evaluated IL-based ABS have been shown to be prospective extraction media, particularly for hydrophobic biomolecules, with several advantages over conventional polymer-inorganic salt ABS. PMID:20480041

  1. Ionic-liquid-based dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography for the forensic determination of methamphetamine in human urine.

    PubMed

    Wang, Ruifeng; Qi, Xiujuan; Zhao, Lei; Liu, Shimin; Gao, Shuang; Ma, Xiangyuan; Deng, Youquan

    2016-07-01

    Determination of methamphetamine in forensic laboratories is a major issue due to its health and social harm. In this work, a simple, sensitive, and environmentally friendly method based on ionic liquid dispersive liquid-liquid microextraction combined with high-performance liquid chromatography was established for the analysis of methamphetamine in human urine. 1-Octyl-3-methylimidazolium hexafluorophosphate with the help of disperser solvent methanol was selected as the microextraction solvent in this process. Various parameters affecting the extraction efficiency of methamphetamine were investigated systemically, including extraction solvent and its volume, disperser solvent and its volume, sample pH, extraction temperature, and centrifugal time. Under the optimized conditions, a good linearity was obtained in the concentration range of 10-1000 ng/mL with determination coefficient >0.99. The limit of detection calculated at a signal-to-noise ratio of 3 was 1.7 ng/mL and the relative standard deviations for six replicate experiments at three different concentration levels of 100, 500, and 1000 ng/mL were 6.4, 4.5, and 4.7%, respectively. Meanwhile, up to 220-fold enrichment factor of methamphetamine and acceptable extraction recovery (>80.0%) could be achieved. Furthermore, this method has been successfully employed for the sensitive detection of a urine sample from a suspected drug abuser. PMID:27135774

  2. Robust High-performance Dye-sensitized Solar Cells Based on Ionic Liquid-sulfolane Composite Electrolytes.

    PubMed

    Lau, Genevieve P S; Décoppet, Jean-David; Moehl, Thomas; Zakeeruddin, Shaik M; Grätzel, Michael; Dyson, Paul J

    2015-01-01

    Novel ionic liquid-sulfolane composite electrolytes based on the 1,2,3-triazolium family of ionic liquids were developed for dye-sensitized solar cells. The best performing device exhibited a short-circuit current density of 13.4 mA cm(-2), an open-circuit voltage of 713 mV and a fill factor of 0.65, corresponding to an overall power conversion efficiency (PCE) of 6.3%. In addition, these devices are highly stable, retaining more than 95% of the initial device PCE after 1000 hours of light- and heat-stress. These composite electrolytes show great promise for industrial application as they allow for a 14.5% improvement in PCE, compared to the solvent-free eutectic ionic liquid electrolyte system, without compromising device stability. PMID:26670595

  3. Understanding the large solubility of lidocaine in 1-n-butyl-3-methylimidazolium based ionic liquids using molecular simulation

    NASA Astrophysics Data System (ADS)

    Ley, Ryan T.; Paluch, Andrew S.

    2016-02-01

    Room temperature ionic liquids have been proposed as replacement solvents in a wide range of industrial separation processes. Here, we focus on the use of ionic liquids as solvents for the pharmaceutical compound lidocaine. We show that the solubility of lidocaine in seven common 1-n-butyl-3-methylimidazolium based ionic liquids is greatly enhanced relative to water. The predicted solubility is greatest in [BMIM]+[CH3CO2]-, which we find results from favorable hydrogen bonding between the lidocaine amine hydrogen and the [CH3CO2]- oxygen, favorable electrostatic interactions between the lidocaine amide oxygen with the [BMIM]+ aromatic ring hydrogens, while lidocaine does not interfere with the association of [BMIM]+ with [CH3CO2]-. Additionally, by removing functional groups from the lidocaine scaffold while maintaining the important amide group, we found that as the van der Waals volume increases, solubility in [BMIM]+[CH3CO2]- relative to water increases.

  4. Robust High-performance Dye-sensitized Solar Cells Based on Ionic Liquid-sulfolane Composite Electrolytes

    PubMed Central

    Lau, Genevieve P. S.; Décoppet, Jean-David; Moehl, Thomas; Zakeeruddin, Shaik M.; Grätzel, Michael; Dyson, Paul J.

    2015-01-01

    Novel ionic liquid-sulfolane composite electrolytes based on the 1,2,3-triazolium family of ionic liquids were developed for dye-sensitized solar cells. The best performing device exhibited a short-circuit current density of 13.4 mA cm−2, an open-circuit voltage of 713 mV and a fill factor of 0.65, corresponding to an overall power conversion efficiency (PCE) of 6.3%. In addition, these devices are highly stable, retaining more than 95% of the initial device PCE after 1000 hours of light- and heat-stress. These composite electrolytes show great promise for industrial application as they allow for a 14.5% improvement in PCE, compared to the solvent-free eutectic ionic liquid electrolyte system, without compromising device stability. PMID:26670595

  5. Active chemisorption sites in functionalized ionic liquids for carbon capture.

    PubMed

    Cui, Guokai; Wang, Jianji; Zhang, Suojiang

    2016-07-25

    Development of novel technologies for the efficient and reversible capture of CO2 is highly desired. In the last decade, CO2 capture using ionic liquids has attracted intensive attention from both academia and industry, and has been recognized as a very promising technology. Recently, a new approach has been developed for highly efficient capture of CO2 by site-containing ionic liquids through chemical interaction. This perspective review focuses on the recent advances in the chemical absorption of CO2 using site-containing ionic liquids, such as amino-based ionic liquids, azolate ionic liquids, phenolate ionic liquids, dual-functionalized ionic liquids, pyridine-containing ionic liquids and so on. Other site-containing liquid absorbents such as amine-based solutions, switchable solvents, and functionalized ionic liquid-amine blends are also investigated. Strategies have been discussed for how to activate the existent reactive sites and develop novel reactive sites by physical and chemical methods to enhance CO2 absorption capacity and reduce absorption enthalpy. The carbon capture mechanisms of these site-containing liquid absorbents are also presented. Particular attention has been paid to the latest progress in CO2 capture in multiple-site interactions by amino-free anion-functionalized ionic liquids. In the last section, future directions and prospects for carbon capture by site-containing ionic liquids are outlined. PMID:27243042

  6. Observation of electrodeposited lithium by optical microscope in room temperature ionic liquid-based electrolyte

    NASA Astrophysics Data System (ADS)

    Sano, H.; Sakaebe, H.; Matsumoto, H.

    Room temperature ionic liquids (RTILs) were applied to a lithium (Li) metal battery system, and the behavior of Li electrodeposition on nickel electrodes in RTILs was investigated using in situ optical microscopy with/without an organic additive, vinylene carbonate (VC), in the RTILs. Two RTILs, PP13[TFSA] (N-methyl- N-propylpiperidinium bis(trifluoromethanesulfonyl)amide) and EMI[FSA] (1-ethyl-3-methylimidazolium bis(fluorosulfonyl)amide), were chosen as the base electrolytes. Dendritic particles were obtained in the case of EMI[FSA] with and without VC, and PP13[TFSA] without VC, while non-dendritic fine particles were obtained in the case of PP13[TFSA] with VC.

  7. High Photothermal Activity within Neutral Nickel Dithiolene Complexes Derived from Imidazolium-Based Ionic Liquids.

    PubMed

    Mebrouk, Kenny; Camerel, Franck; Jeannin, Olivier; Heinrich, Benoit; Donnio, Bertrand; Fourmigué, Marc

    2016-02-01

    A new series of nickel N,N'-dialkylimidazolidine-2,4,5-trithione complexes ([Ni(R2timdt)2]) carrying linear or branched carbon chains (R = n-C4H9, n-C8H17, n-C12H25, n-C16H33, 2-ethylhexyl, 2-butyloctyl, phytanyl) have been obtained through an original synthetic pathway starting from easily available imidazolium-based ionic liquids. The chemical structures of these nickel complexes were confirmed by NMR and high-resolution mass spectroscopies as well as by X-ray analysis performed on single crystals. The complexes strongly absorb in the near-IR (NIR) region around 1000 nm, with high extinction coefficients reaching 80 000 M(-1) cm(-1). They are able to efficiently convert NIR light into heat under laser irradiation with very high photothermal conversion efficiencies (around 30%). PMID:26788960

  8. pH-independent optical sensing of heparin based on ionic liquid-capped gold nanoparticles.

    PubMed

    Hemmateenejad, Bahram; Dorostkar, Samira; Shakerizadeh-Shirazi, Fatemeh; Shamsipur, Mojtaba

    2013-09-01

    A simple pH-independent optical method for the sensing of heparin, as a biomedically important polyionic drug, based on aggregation of gold nanoparticles (AuNPs) is described. The polyanionic heparin induces the aggregation of positively charged ionic liquid stabilized AuNPs, which results in a shift in the surface plasmon band and a consequent color change of the AuNPs from red to blue. The color change was monitored using UV-vis spectrophotometry and image analysis methods. The aggregation was confirmed by transmission electron microscopic measurements. The degree of aggregation was found to be proportional to the concentration of the added heparin, allowing its quantitative detection. The change in the absorbance and color-value has been used to monitor the concentration of heparin. This optical method can quantify heparin as low as 0.010 μg mL(-1) and the calibration is linear for a wide range of concentration. PMID:23826612

  9. Cathodic deposition of BiTe as thermoelectric films using choline chloride based ionic liquids

    NASA Astrophysics Data System (ADS)

    Golgovici, Florentina; Visan, Teodor

    2012-06-01

    This paper reports the electrodeposition of BiTe by potential control electrolysis using a ionic liquid based on choline chloride and malonic acid mixture (1:1 moles) in the 25-60°C temperature range. From cyclic voltammetry and impedance experiments carried out in order to characterize the cathodic process on Pt electrode it was found that the deposition of BiTe from electrolytes occurs on a Te-covered Pt substrate at less negative potentials than for deposition of singular Bi or Te films. Nyquist and Bode impedance spectra showed differences in Pt behavior due to its polarization at various cathodic potentials. The morphology and chemical composition of BiTe films deposited on Cu were determined by AFM, SEM and TEM microscopy.

  10. Corrosion of stainless steel battery components by bis(fluorosulfonyl)imide based ionic liquid electrolytes

    NASA Astrophysics Data System (ADS)

    Evans, Tyler; Olson, Jarred; Bhat, Vinay; Lee, Se-Hee

    2014-12-01

    While the anodic behavior of aluminum foil current collectors in imide-based room temperature ionic liquids (RTILs) is relatively well understood, interactions between such RTILs and other passive battery components have not been studied extensively. This study presents the solvent and potential dependent oxidation of SS316 coin-cell components in the N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide (PYR13FSI) RTIL. While this phenomenon prohibits high-voltage cycling of Li(Ni1/3Mn1/3Co1/3)O2 cathodes in SS316 coin-type cells, Al-clad cell components or alternative cell configurations can be utilized to avoid SS316 oxidation-induced cell failure.

  11. Ultrasensitive gaseous NH3 sensor based on ionic liquid-mediated signal-on electrochemiluminescence.

    PubMed

    Chen, Lichan; Huang, Danjun; Zhang, Yuanjin; Dong, Tongqing; Zhou, Chen; Ren, Shuyan; Chi, Yuwu; Chen, Guonan

    2012-08-01

    This work reports that ammonia (NH(3)) can be used as an efficient co-reactant for tris(2,2'-bipyridine)ruthenium(II) (Ru(bpy)(3)(2+)) electrochemiluminescence (ECL) in ionic liquids (ILs), on the basis of which a signal-on ECL sensor for directly detecting gaseous NH(3) has been developed. The NH(3) ECL sensor has a very high sensitivity, with a detection limit of 10 ppt NH(3) (at signal-to-noise ratio of 3) without any preconcentration. The high sensitivity is mainly due to the zero ECL background of Ru(bpy)(3)(2+) in the ILs, strong co-reactant ECL activity of NH(3), and high solubility of NH(3) in imidazolium-based ILs. Additionally, the ECL sensor shows an excellent selectivity against common interfering gases and a wide linear response range from 10 ppt to 10 ppm. PMID:22728516

  12. Bifacial dye-sensitized solar cells based on an ionic liquid electrolyte

    NASA Astrophysics Data System (ADS)

    Ito, Seigo; Zakeeruddin, Shaik M.; Comte, Pascal; Liska, Paul; Kuang, Daibin; Grätzel, Michael

    2008-11-01

    Solar energy is a promising solution to global energy-related problems because it is clean, inexhaustible and readily available. However, the deployment of conventional photovoltaic cells based on silicon is still limited by cost, so alternative, more cost-effective approaches are sought. Here we report a bifacial dye-sensitized solar cell structure that provides high photo-energy conversion efficiency (~6%) for incident light striking its front or rear surfaces. The design comprises a highly stable ruthenium dye (Z907Na) in combination with an ionic-liquid electrolyte and a porous TiO2 layer. The inclusion of a SiO2 layer between the electrodes to prevent generation of unwanted back current and optimization of the thickness of the TiO2 layer are responsible for the enhanced performance.

  13. Novel pyridinium based cobalt carbonyl ionic liquids: synthesis, full characterization, crystal structure and application in catalysis.

    PubMed

    Deng, Fan-Guo; Hu, Bin; Sun, Wei; Chen, Jing; Xia, Chun-Gu

    2007-10-10

    Through an optimized synthetic strategy, a series of novel alkylpyridinium cobalt tetracarbonyl salts, [C(1)Py][Co(CO)(4)] (), [C(4)Py][Co(CO)(4)] () and [C(16)Py][Co(CO)(4)] () (C(n)Py = N-C(n)H(2n+1)-pyridinium), were successfully prepared in good yields, using a water-organic biphasic system. All the three compounds melt well below 100 degrees C and could be classified as ionic liquids. The compounds were fully characterized using IR, UV-Vis, (1)H NMR, (13)C NMR, ESI-MS and elemental analysis, and was structurally characterized by X-ray single crystal analysis. Compound has been found to be an efficient and reusable catalyst for the alkoxycarbonylation of propylene oxide without the aid of a base additive. PMID:17893815

  14. Collective ion diffusion and localized single particle dynamics in pyridinium-based ionic liquids.

    PubMed

    Burankova, Tatsiana; Hempelmann, Rolf; Wildes, Andrew; Embs, Jan P

    2014-12-11

    Quasielastic neutron scattering with polarized neutrons allows for an experimental separation of single-particle and collective processes, as contained in the incoherent and coherent scattering contributions. This technique was used to investigate the dynamical processes in the pyridinium-based ionic liquid 1-butylpyridinium bis(trifluoromethylsulfonyl)-imide. We observed two diffusion processes with different time scales. The slower diffusional process was present in both the coherent and the incoherent contribution, meaning that this process has at least a partial collective nature. The second faster localized process is only present in the incoherent scattering contribution. We conclude that it is a true single-particle process on a shorter time scale. PMID:25387035

  15. An advanced lithium-air battery exploiting an ionic liquid-based electrolyte.

    PubMed

    Elia, G A; Hassoun, J; Kwak, W-J; Sun, Y-K; Scrosati, B; Mueller, F; Bresser, D; Passerini, S; Oberhumer, P; Tsiouvaras, N; Reiter, J

    2014-11-12

    A novel lithium-oxygen battery exploiting PYR14TFSI-LiTFSI as ionic liquid-based electrolyte medium is reported. The Li/PYR14TFSI-LiTFSI/O2 battery was fully characterized by electrochemical impedance spectroscopy, capacity-limited cycling, field emission scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy. The results of this extensive study demonstrate that this new Li/O2 cell is characterized by a stable electrode-electrolyte interface and a highly reversible charge-discharge cycling behavior. Most remarkably, the charge process (oxygen oxidation reaction) is characterized by a very low overvoltage, enhancing the energy efficiency to 82%, thus, addressing one of the most critical issues preventing the practical application of lithium-oxygen batteries. PMID:25329836

  16. Thickness-dependent structural arrangement in nano-confined imidazolium-based ionic liquid films

    SciTech Connect

    Rouha, Michael; Cummings, Peter T.

    2014-12-24

    Here we report that a fundamental understanding of interfacial processes in nano-confined ionic liquids is crucial to increase the performance of modern energy storage devices. It is well-known that interfaces between electrodes and ionic liquids exhibit structures distinct from that of the bulk liquid. Following the recent interest in these systems, we studied the structure of thin ionic liquid films confined in flexible uncharged carbon nano-pores by using fully-atomistic molecular dynamics simulations. We show that the interfacial ions self-assemble into a closely-packed chequerboard-like pattern, formed by both cations and anions in direct contact with the pore wall, and that within this structure we find changes dependent on the thickness of the confined films. At low coverages a dense layer is formed in which both the imidazolium-ring and its alkyl-tail lie parallel to the pore wall. With increasing coverage the alkyl-chains reorient perpendicular to the surface, making space for additional ions until a densified highly ordered layer is formed. This wall-induced self-patterning into interfacial layers with significantly higher than bulk density is consistent with recent experimental and theoretical studies of similar systems. Lastly, this work reveals additional molecular-level details on the effect of the film-thickness on the structure and density of the ionic liquid.

  17. Thickness-dependent structural arrangement in nano-confined imidazolium-based ionic liquid films

    DOE PAGESBeta

    Rouha, Michael; Cummings, Peter T.

    2014-12-24

    Here we report that a fundamental understanding of interfacial processes in nano-confined ionic liquids is crucial to increase the performance of modern energy storage devices. It is well-known that interfaces between electrodes and ionic liquids exhibit structures distinct from that of the bulk liquid. Following the recent interest in these systems, we studied the structure of thin ionic liquid films confined in flexible uncharged carbon nano-pores by using fully-atomistic molecular dynamics simulations. We show that the interfacial ions self-assemble into a closely-packed chequerboard-like pattern, formed by both cations and anions in direct contact with the pore wall, and that withinmore » this structure we find changes dependent on the thickness of the confined films. At low coverages a dense layer is formed in which both the imidazolium-ring and its alkyl-tail lie parallel to the pore wall. With increasing coverage the alkyl-chains reorient perpendicular to the surface, making space for additional ions until a densified highly ordered layer is formed. This wall-induced self-patterning into interfacial layers with significantly higher than bulk density is consistent with recent experimental and theoretical studies of similar systems. Lastly, this work reveals additional molecular-level details on the effect of the film-thickness on the structure and density of the ionic liquid.« less

  18. Factors affecting the stability and performance of ionic liquid-based planar transient photodetectors.

    PubMed

    Dalgleish, Simon; Reissig, Louisa; Hu, Laigui; Matsushita, Michio M; Sudo, Yuki; Awaga, Kunio

    2015-05-12

    A novel planar architecture has been developed for the study of photodetectors utilizing the transient photocurrent response induced by a metal/insulator/semiconductor/metal (MISM) structured device, where the insulator is an ionic liquid (IL-MISM). Using vanadyl 2,3-naphthalocyanine, which absorbs in the communications-relevant near-infrared wavelength region (λ(max,film) ≈ 850 nm), in conjunction with C60 as a bulk heterojunction, the high capacitance of the formed electric double layers at the ionic liquid interfaces yields high charge separation efficiency within the semiconductor layer, and the minimal potential drop in the bulk ionic liquid allows the electrodes to be offset by distances of over 7 mm. Furthermore, the decrease in operational speed with increased electrode separation is beneficial for a clear modeling of the waveform of the photocurrent signal, free from the influence of measurement circuitry. Despite the use of a molecular semiconductor as the active layer in conjunction with a liquid insulating layer, devices with a stability of several days could be achieved, and the operational stability of such devices was shown to be dependent solely on the solubility of the active layer in the ionic liquid, even under atmospheric conditions. Furthermore, the greatly simplified device construction process, which does not rely on transparent electrode materials or direct electrode deposition, provides a highly reproducible platform for the study of the electronic processes within IL-MISM detectors that is largely free from architectural constraints. PMID:25895167

  19. Nuclear Spin Relaxation and Molecular Interactions of a Novel Triazolium-Based Ionic Liquid

    SciTech Connect

    Allen, Jesse J; Schneider, Yanika; Kail, Brian W; Luebke, David R; Nulwala, Hunaid; Damodaran, Krishnan

    2013-04-11

    Nuclear spin relaxation, small-angle X-ray scattering (SAXS), and electrospray ionization mass spectrometry (ESI-MS) techniques are used to determine supramolecular arrangement of 3-methyl-1-octyl-4-phenyl-1H-triazol-1,2,3-ium bis(trifluoromethanesulfonyl)imide [OMPhTz][Tf{sub 2}N], an example of a triazolium-based ionic liquid. The results obtained showed first-order thermodynamic dependence for nuclear spin relaxation of the anion. First-order relaxation dependence is interpreted as through-bond dipolar relaxation. Greater than first-order dependence was found in the aliphatic protons, aromatic carbons (including nearest neighbors), and carbons at the end of the aliphatic tail. Greater than first order thermodynamic dependence of spin relaxation rates is interpreted as relaxation resulting from at least one mechanism additional to through-bond dipolar relaxation. In rigid portions of the cation, an additional spin relaxation mechanism is attributed to anisotropic effects, while greater than first order thermodynamic dependence of the octyl side chain’s spin relaxation rates is attributed to cation–cation interactions. Little interaction between the anion and the cation was observed by spin relaxation studies or by ESI-MS. No extended supramolecular structure was observed in this study, which was further supported by MS and SAXS. nuclear Overhauser enhancement (NOE) factors are used in conjunction with spin–lattice relaxation time (T{sub 1}) measurements to calculate rotational correlation times for C–H bonds (the time it takes for the vector represented by the bond between the two atoms to rotate by one radian). The rotational correlation times are used to represent segmental reorientation dynamics of the cation. A combination of techniques is used to determine the segmental interactions and dynamics of this example of a triazolium-based ionic liquid.

  20. Influence of ester functional groups on the liquid-phase structure and solvation properties of imidazolium-based ionic liquids.

    PubMed

    Pensado, Alfonso S; Pádua, Agílio A H; Costa Gomes, Margarida F

    2011-04-14

    The incorporation of ester functions in the side chains in 1-alkyl-3-methylimidazolium cations seems to increase the biodegradability of these ionic liquids. We study here how the presence of ester functional groups affects the liquid-state structure (namely, the microphase segregation between polar and nonpolar domains in these ionic liquids) and the way in which the solvation of gases can be understood in these solvents. We use molecular simulation to study the structure of the ionic liquids 3-methyl-1-(pentoxycarbonylmethyl)imidazolium octylsulfate, [C(1)COOC(5)C(1)im][C(8)SO(4)]; and 3-methyl-1-(pentoxycarbonylmethyl)imidazolium bis(trifluoromethylsulfonyl)imide, [C(1)COOC(5)C(1)im][NTf(2)] in the liquid phase and to assess the molecular mechanisms of solvation of carbon dioxide and ethane. The presence of ester functions influences the relative size of the polar and nonpolar domains in the ionic liquids, but does not significantly affect the solvation of gases. PMID:21391547

  1. Self-interaction error in DFT-based modelling of ionic liquids.

    PubMed

    Lage-Estebanez, Isabel; Ruzanov, Anton; García de la Vega, José M; Fedorov, Maxim V; Ivaništšev, Vladislav B

    2016-01-21

    The modern computer simulations of potential green solvents of the future, involving the room temperature ionic liquids, heavily rely on density functional theory (DFT). In order to verify the appropriateness of the common DFT methods, we have investigated the effect of the self-interaction error (SIE) on the results of DFT calculations for 24 ionic pairs and 48 ionic associates. The magnitude of the SIE is up to 40 kJ mol(-1) depending on the anion choice. Most strongly the SIE influences the calculation results of ionic associates that contain halide anions. For these associates, the range-separated density functionals suppress the SIE; for other cases, the revPBE density functional with dispersion correction and triple-ζ Slater-type basis is suitable for computationally inexpensive and reasonably accurate DFT calculations. PMID:26690957

  2. Ionic-liquid-based proton conducting membranes for anhydrous H2/Cl2 fuel-cell applications.

    PubMed

    Liu, Sa; Zhou, Li; Wang, Pengjie; Zhang, Fangfang; Yu, Shuchun; Shao, Zhigang; Yi, Baolian

    2014-03-12

    An ionic-liquid-doped poly(benzimidazole) (PBI) proton-conducting membrane for an anhydrous H2/Cl2 fuel cell has been proposed. Compared with other ionic liquids, such as imidazole-type ionic liquids, diethylmethylammonium trifluoromethanesulfonate ([dema][TfO]) showed better electrode reaction kinetics (H2 oxidation and Cl2 reduction reaction at platinum) and was more suitable for a H2/Cl2 fuel cell. PBI polymer and [dema][TfO] were compatible with each other, and the hybrid membranes exhibited high stability and good ionic conductivity, reaching 20.73 mS cm(-1) at 160 °C. We also analyzed the proton-transfer mechanism in this ionic-liquid-based membrane and considered that both proton-hopping and diffusion mechanisms existed. In addition, this composite electrolyte worked well in a H2/Cl2 fuel cell under non-water conditions. This work would give a good path to study the novel membranes for anhydrous H2/Cl2 fuel-cell application. PMID:24490850

  3. FISSION-PRODUCT SEPARATION BASED ON ROOM-TEMPERATURE IONIC LIQUIDS

    EPA Science Inventory

    The objectives of this project are (a) to synthesize new ionic liquids tailored for the extractive separation of Cs + and Sr 2+; (b) to select optimum macrocyclic extractants through studies of complexation of fission products with macrocyclic extractants and transport in new ext...

  4. Effect of unsaturation on the absorption of ethane and ethylene in imidazolium-based ionic liquids.

    PubMed

    Moura, Leila; Mishra, Manas; Bernales, Varinia; Fuentealba, Patricio; Padua, Agilio A H; Santini, Catherine C; Costa Gomes, Margarida F

    2013-06-20

    The influence of the presence of imidazolium side chain unsaturation on the solubility of ethane and ethylene was studied in three ionic liquids: 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide-saturated alkyl side-chain in the cation; 1-methyl-3-(buten-3-yl)imidazolium bis(trifluorosulfonyl)imide-double bond in the side-chain of the cation; and 1-methyl-3-benzylimidazolium bis(trifluorosulfonyl)imide-benzyl group in the side-chain of the cation. The solubility of both gases decreases when the side-chain of the cations is functionalized with an unsaturated group. This can be explained by a less favorable enthalpy of solvation. The difference of solubility between ethane and ethylene can be explained from a balance of enthalpic and entropic factors: for the ionic liquid with the saturated alkyl side-chain and the benzyl-substituted side-chain, it is the favorable entropy of solvation that explains the larger ethylene solubility, whereas in the case of the saturated side-chain, it is the more favorable enthalpy of solvation. Molecular simulation allowed the identification of the mechanisms of solvation and the preferential solvation sites for each gas in the different ionic liquids. Simulations have shown that the entropy of solvation is more favorable when the presence of the gas weakens the cation-anion interactions or when the gas can be solvated near different sites of the ionic liquid. PMID:23713882

  5. Magadiite Templated High Surface Area Graphene-Type Carbons from Metal-Halide based Ionic Liquids

    SciTech Connect

    Fulvio, Pasquale F; Hillesheim, Patrick C; Bauer, John C; Mahurin, Shannon Mark; Dai, Sheng; Arend, Nikolas

    2013-01-01

    Freestanding silicon films with a thickness ranging from 1 nm to several micrometers were prepared by Cat-CVD onto ionic liquid ([BMIM][BF4]) surfaces for the first time. The films, obtained without a solid substrate, can be facilely characterized by TEM and AFM to study the film formation and growth process.

  6. COMMODITY SCALE SYNTHESIS OF 1-METHYLIMIDAZOLE BASED IONIC LIQUIDS USING A SPINNING TUBE-IN-TUBE REACTOR

    EPA Science Inventory

    The continuous large-scale preparation of several 1-methylimidazole based ionic liquids was carried out using a Spinning Tube-in-Tube (STT) reactor (manufactured by Kreido Laboratories). This reactor, which embodies and facilitates the use of Green Chemistry principles and Proce...

  7. Single-material solvent-sensitive actuator from poly(ionic liquid) inverse opals based on gradient dewetting.

    PubMed

    Wu, Hua; Kuang, Minxuan; Cui, Liying; Tian, Di; Wang, Minghui; Luan, Guoyou; Wang, Jingxia; Jiang, Lei

    2016-05-01

    A novel and reversible single-material solvent-sensitive actuator was developed from poly(ionic liquid) inverse opals based on a gradient wetting/dewetting process combining the strong hydrogen bonding interaction between the solvent and polymer. This study will provide an important insight for the design and fabrication of novel-type solvent-actuator materials. PMID:27055537

  8. Novel Fission-Product Separation based on Room-Temperature Ionic Liquids

    SciTech Connect

    Rogers, Robin D.

    2004-12-31

    U.S. DOE's underground storage tanks at Hanford, SRS, and INEEL contain liquid wastes with high concentrations of radioactive cesium-137 and strontium-90. Because the primary chemical components of alkaline supernatants are sodium nitrate and sodium hydroxide, the majority of this could be disposed of as low level waste if radioactive cesium-137 and strontium- 90 could be selectively removed. The underlying goal of this project was to investigate the application of ionic liquids as novel solvents for new solvent extraction processes for separation of cesium-137 and strontium-90 from tank wastes. Ionic liquids are a distinct sub-set of liquids, comprising only of cations and anions they are proving to be increasingly interesting fluids for application in systems from electrochemistry to energetic materials, and are also rapidly establishing their promise as viable media for synthesis and separations operations. Properties including low melting points, electrochemical conductivity, wide liquid ranges, lack of vapor-pressure, and chemical tunability have encouraged researchers to explore the uses of ILs in place of volatile organic solvents. The most promising current developments arise from control of the unique combinations of chemical and physical properties characteristic of ionic liquids.

  9. Rapid and sensitive analysis of microcystins using ionic liquid-based in situ dispersive liquid-liquid microextraction.

    PubMed

    Yu, Honglian; Clark, Kevin D; Anderson, Jared L

    2015-08-01

    Three structurally different ionic liquids (ILs), namely 1-butyl-3-methylimidazolium chloride ([BMIM][Cl]), 1-(6-hydroxyethyl)-3-methylimidazolium chloride ([HeOHMIM][Cl]) and 1-benzyl-3-(2-hydroxyethyl)imidazolium bromide ([BeEOHIM][Br]), were applied as extraction solvents using in situ dispersive liquid-liquid microextraction (in situ DLLME) for the preconcentration of two microcystin variants, microcystin-RR (MC-RR) and microcystin-LR (MC-LR) from aqueous samples. Extraction parameters including sample solution pH, ratio of IL to metathesis reagent, sample volume, IL quantity, and salt concentration were optimized to achieve the best extraction efficiency. The [BeEOHIM][Br] IL, which contains both an aromatic moiety and a hydroxyl group within its chemical structure, exhibited superior extraction efficiency compared to the other two ILs. The analytical performance of the [BeEOHIM][Br] IL as an extraction solvent for in situ DLLME of microcystins was investigated using HPLC-UV and HPLC-MS. The limits of detection (LODs) for MC-RR and MC-LR were 0.7μgL(-1) using UV detection with a linear range from 1 to 50μgL(-1). The separation method was successfully adapted for ESI-MS/SIM detection, wherein the LODs for MC-RR and MC-LR were greatly improved to 0.005 and 0.003μgL(-1), respectively. The accuracy of the method was demonstrated by examining the relative recovery using tap water and river water and produced recoveries ranging from 45.0 to 109.7% and from 46.3 to 103.2%, respectively. PMID:26087964

  10. Improved extraction of fluoroquinolones with recyclable ionic-liquid-based aqueous biphasic systems†

    PubMed Central

    Almeida, Hugo F. D.; Freire, Mara G.; Marrucho, Isabel M.

    2016-01-01

    In the past few years, the improvement of advanced analytical tools allowed to confirm the presence of trace amounts of metabolized and unchanged active pharmaceutical ingredients (APIs) in wastewater treatment plants (WWTPs) as well as in freshwater surfaces. It is known that the continuous contact with APIs, even at very low concentrations (ng L−1–μg L−1), leads to serious human health problems. In this context, this work shows the feasibility of using ionic-liquid-based aqueous biphasic systems (IL-based ABS) in the extraction of quinolones present in aqueous media. In particular, ABS composed of imidazolium- and phosphonium-based ILs and aluminium-based salts (already used in water treatment plants) were evaluated in one-step extractions of six fluoroquinolones (FQs), namely ciprofloxacin, enrofloxacin, moxifloxacin, norfloxacin, ofloxacin and sarafloxacin, and extraction efficiencies up to 98% were obtained. Despite the large interest devoted to IL-based ABS as extractive systems of outstanding performance, their recyclability/reusability has seldomly been studied. An efficient extraction/cleaning process of the IL-rich phase is here proposed by FQs induced precipitation. The recycling of the IL and its further reuse without losses in the ABS extractive performance for FQs were established, as confirmed by the four consecutive removal/extraction cycles evaluated. This novel recycling strategy supports IL-based ABS as sustainable and cost-efficient extraction platforms.

  11. Electrochemical Polishing Applications and EIS of a Vitamin B{sub 4}-Based Ionic Liquid

    SciTech Connect

    Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.; Abdel-Fattah, Tarek M.

    2013-01-01

    Modern particle accelerators require minimal interior surface roughness for Niobium superconducting radio frequency (SRF) cavities. Polishing of the Nb is currently achieved via electrochemical polishing with concentrated mixtures of sulfuric and hydrofluoric acids. This acid-based approach is effective at reducing the surface roughness to acceptable levels for SRF use, but due to acid-related hazards and extra costs (including safe disposal of used polishing solutions), an acid-free method would be preferable. This study focuses on an alternative electrochemical polishing method for Nb, using a novel ionic liquid solution containing choline chloride, also known as Vitamin B{sub 4} (VB{sub 4}). Potentiostatic electrochemical impedance spectroscopy (EIS) was also performed on the VB4-based system. Nb polished using the VB4-based method was found to have a final surface roughness comparable to that achieved via the acid-based method, as assessed by atomic force microscopy (AFM). These findings indicate that acid-free VB{sub 4}-based electrochemical polishing of Nb represents a promising replacement for acid-based methods of SRF cavity preparation.

  12. Atomistic force field for pyridinium-based ionic liquids: reliable transport properties.

    PubMed

    Voroshylova, Iuliia V; Chaban, Vitaly V

    2014-09-11

    Reliable force field (FF) is a central issue in successful prediction of physical chemical properties via computer simulations. This work introduces refined FF parameters for six popular ionic liquids (ILs) of the pyridinium family (butylpyridinium tetrafluoroborate, bis(trifluoromethanesulfonyl)imide, dicyanamide, hexafluorophosphate, triflate, chloride). We elaborate a systematic procedure, which allows accounting for specific cation-anion interactions in the liquid phase. Once these interactions are described accurately, all experimentally determined transport properties can be reproduced. We prove that three parameters per interaction site (atom diameter, depth of potential well, point electrostatic charge) provide a sufficient basis to predict thermodynamics (heat of vaporization, density), structure (radial distributions), and transport (diffusion, viscosity, conductivity) of ILs at room conditions and elevated temperature. The developed atomistic models provide a systematic refinement upon the well-known Canongia Lopes-Pádua (CL&P) FF. Together with the original CL&P parameters the present models foster a computational investigation of ionic liquids. PMID:25144141

  13. Thiophene-based ionic liquids: synthesis, physical properties, self-assembly and oxidative polymerization.

    SciTech Connect

    Burns, C. T.; Lee, S.; Seifert, S.; Firestone, M. A.

    2008-07-01

    Preparation and polymerization of methylimidazolium-based ionic liquids (ILs) that incorporate a thiophene moiety at the terminus of a C{sub 10} alkyl chain are described. Both a bromide and nitrate salt of the amphiphilic thiophene IL self-assembles in water (albeit the nitrate to a lesser extent), adopting columnar mesophases. Polarized optical microscopy and small-angle X-ray scattering (SAXS) studies show that at low water content the IL-water binary mixtures form liquid crystalline mesophases possessing significant short-range ordering due to strong {pi} interactions between adjacent thiophene moieties. At higher water content, the short-range ordering is lost, but long-range ordering persists up to ca. 45% (w/w) water. The chemical oxidative coupling of the nitrate monomer yields a highly water-soluble polymer. Electrochemical studies show that the polymer possesses a high oxidation potential (1.95 V) and thus, is resistant to chemical doping. In dilute aqueous solution, electronic absorption spectroscopy and X-ray scattering show the polymer adopts a random, coil-like conformational state. Slight improvement in the polymer conformation can be achieved by exchange of the counter anion.

  14. Comparable Stability of Hoogsteen and Watson–Crick Base Pairs in Ionic Liquid Choline Dihydrogen Phosphate

    PubMed Central

    Tateishi-Karimata, Hisae; Nakano, Miki; Sugimoto, Naoki

    2014-01-01

    The instability of Hoogsteen base pairs relative to Watson–Crick base pairs has limited biological applications of triplex-forming oligonucleotides. Hydrated ionic liquids (ILs) provide favourable environments for a wide range of chemical reactions and are known to impact the stabilities of Watson–Crick base pairs. We found that DNA triplex formation was significantly stabilized in hydrated choline dihydrogen phosphate as compared with an aqueous buffer at neutral pH. Interestingly, the stability of Hoogsteen base pairs was found to be comparable with that of Watson–Crick base pairs in the hydrated IL. Molecular dynamics simulations of a DNA triplex in the presence of choline ions revealed that the DNA triplex was stabilized because of the binding of choline ion around the third strand in the grooves. Our finding will facilitate the development of new DNA materials. Our data also indicate that triplex formation may be stabilized inside cells where choline ions and their derivatives are abundant in vivo. PMID:24399194

  15. Comparable stability of Hoogsteen and Watson-Crick base pairs in ionic liquid choline dihydrogen phosphate.

    PubMed

    Tateishi-Karimata, Hisae; Nakano, Miki; Sugimoto, Naoki

    2014-01-01

    The instability of Hoogsteen base pairs relative to Watson-Crick base pairs has limited biological applications of triplex-forming oligonucleotides. Hydrated ionic liquids (ILs) provide favourable environments for a wide range of chemical reactions and are known to impact the stabilities of Watson-Crick base pairs. We found that DNA triplex formation was significantly stabilized in hydrated choline dihydrogen phosphate as compared with an aqueous buffer at neutral pH. Interestingly, the stability of Hoogsteen base pairs was found to be comparable with that of Watson-Crick base pairs in the hydrated IL. Molecular dynamics simulations of a DNA triplex in the presence of choline ions revealed that the DNA triplex was stabilized because of the binding of choline ion around the third strand in the grooves. Our finding will facilitate the development of new DNA materials. Our data also indicate that triplex formation may be stabilized inside cells where choline ions and their derivatives are abundant in vivo. PMID:24399194

  16. Key Developments in Ionic Liquid Crystals

    PubMed Central

    Alvarez Fernandez, Alexandra; Kouwer, Paul H. J.

    2016-01-01

    Ionic liquid crystals are materials that combine the classes of liquid crystals and ionic liquids. The first one is based on the multi-billion-dollar flat panel display industry, whilst the latter quickly developed in the past decades into a family of highly-tunable non-volatile solvents. The combination yields materials with a unique set of properties, but also with many challenges ahead. In this review, we provide an overview of the key concepts in ionic liquid crystals, particularly from a molecular perspective. What are the important molecular parameters that determine the phase behavior? How should they be introduced into the molecules? Finally, which other tools does one have to realize specific properties in the material? PMID:27196890

  17. A new dispersive liquid-liquid microextraction using ionic liquid based microemulsion coupled with cloud point extraction for determination of copper in serum and water samples.

    PubMed

    Arain, Salma Aslam; Kazi, Tasneem Gul; Afridi, Hassan Imran; Arain, Mariam Shahzadi; Panhwar, Abdul Haleem; Khan, Naeemullah; Baig, Jameel Ahmed; Shah, Faheem

    2016-04-01

    A simple and rapid dispersive liquid-liquid microextraction procedure based on ionic liquid assisted microemulsion (IL-µE-DLLME) combined with cloud point extraction has been developed for preconcentration copper (Cu(2+)) in drinking water and serum samples of adolescent female hepatitits C (HCV) patients. In this method a ternary system was developed to form microemulsion (µE) by phase inversion method (PIM), using ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([C4mim][PF6]) and nonionic surfactant, TX-100 (as a stabilizer in aqueous media). The Ionic liquid microemulsion (IL-µE) was evaluated through visual assessment, optical light microscope and spectrophotometrically. The Cu(2+) in real water and aqueous acid digested serum samples were complexed with 8-hydroxyquinoline (oxine) and extracted into IL-µE medium. The phase separation of stable IL-µE was carried out by the micellar cloud point extraction approach. The influence of of different parameters such as pH, oxine concentration, centrifugation time and rate were investigated. At optimized experimental conditions, the limit of detection and enhancement factor were found to be 0.132 µg/L and 70 respectively, with relative standard deviation <5%. In order to validate the developed method, certified reference materials (SLRS-4 Riverine water) and human serum (Sero-M10181) were analyzed. The resulting data indicated a non-significant difference in obtained and certified values of Cu(2+). The developed procedure was successfully applied for the preconcentration and determination of trace levels of Cu(2+) in environmental and biological samples. PMID:26761783

  18. Ionic liquid based EDLCs: influence of carbon porosity on electrochemical performance.

    PubMed

    Noofeli, Asa; Hall, Peter J; Rennie, Anthony J R

    2014-01-01

    Electrochemical double layer capacitors (EDLCs) are a category of supercapacitors; devices that store charge at the interface between electrodes and an electrolyte. Currently available commercial devices have a limited operating potential that restricts their energy and power densities. Ionic liquids (ILs) are a promising alternative electrolyte as they generally exhibit greater electrochemical stabilities and lower volatility. This work investigates the electrochemical performance of EDLCs using ILs that combine the bis(trifluoromethanesulfonyl)imide anion with sulfonium and ammonium based cations. Different activated carbon materials were employed to also investigate the influence of varying pore size on electrochemical performance. Electrochemical impedance spectroscopy (EIS) and constant current cycling at different rates were used to assess resistance and specific capacitance. In general, greater specific capacitances and lower resistances were found with the sulfonium based ILs studied, and this was attributed to their smaller cation volume. Comparing electrochemical stabilities indicated that significantly higher operating potentials are possible with the ammonium based ILs. The marginally smaller sulfonium cation performed better with the carbon exhibiting the largest pore width, whereas peak performance of the larger sulfonium cation was associated with a narrower pore size. Considerable differences between the performance of the ammonium based ILs were observed and attributed to differences not only in cation size but also due to the inclusion of a methoxyethyl group. The improved performance of the ether bond containing IL was ascribed to electron donation from the oxygen atom influencing the charge density of the cation and facilitating cation-cation interactions. PMID:25427314

  19. Effect of pyrrolidinium based ionic liquid on the channel form of gramicidin in lipid vesicles.

    PubMed

    Singh, Upendra Kumar; Dohare, Neeraj; Mishra, Prabhash; Singh, Prashant; Bohidar, Himadri B; Patel, Rajan

    2015-08-01

    The present work is focused on the interaction between membrane bound gramicidin and 1-butyl-1-methyl-2-oxopyrrolidinium bromide (BMOP) ionic liquid. Ionic liquids (ILs) are solvents that are often liquid at room temperature and composed of organic cation and appropriate anion. The gramicidin peptide forms prototypical ion channels for cations, which have been extensively used to study the organization, dynamics, and function of membrane spanning channels. The interaction was studied by circular dichroism, steady state, time-resolved fluorescence spectroscopy in combination with dynamic surface tension and field emission scanning electron microscopic methods (FESEM). The results obtained from circular dichroism shows that the BMOP interacts with the channel form of gramicidin in lipid vesicle without any considerable effect on its conformation. The Red-edge excitation shift (REES) also supported the above findings. In addition, the fluorescence studies suggested that BMOP makes ground state complex with ion channel, which was further supported by time resolved measurements. Furthermore, dynamic surface tension analysis shows the faster adsorption of BMOP with membrane bound gramicidin at the air-water interface. Additionally, FESEM results indicated that BMOP forms a film around the membrane bound gramicidin at higher concentration. These results are potentially useful to analyze the effect of ionic liquids on the behaviour of membrane proteins. PMID:26025771

  20. New ionic liquid-based preparative method for diosgenin from Rhizoma dioscoreae nipponicae

    PubMed Central

    Yan, Wang; Ji, Luo; Hang, Song; Shun, Yao

    2013-01-01

    Background: Rhizoma dioscoreae nipponicae is a perennial herb and its roots have been widely used in Traditional Chinese Medicine (TCM). Objective: To develop and optimize the extraction and hydrolysis technology of diosgenin from Rhizoma dioscoreae nipponicae. Materials and Methods: 1-methyl-3-(3-sulfopropyl)-imidazolium hydrogen sulfate ([PSMIM]HSO4), as a kind of functional ionic liquid, replaced inorganic acid, and was used in a one-step ultrasonic extraction and hydrolysis for the preparation of diosgenin (the aglycone of dioscin and an important precursor chemical in the pharmaceutical industry) from Rhizoma dioscoreae nipponicae, for the first time. The effects of various factors were evaluated. The obtained product was studied using high performance liquid chromatography (HPLC). Results: About 6.35 mg of diosgenin could be obtained from 2.0 g of raw material. Reusability and recycling of the ionic liquid were validated with fairly good results. The ionic liquid solution was reused four times, and the final extraction efficiency only decreased by 5%. Conclusion: In virtue of the obvious advantages of the green extraction and catalytic solvent, with further study, it is believed that this new one-step preparative method promises to replace the traditional methods. PMID:23930010

  1. Conductivity Scaling Relationships of Nanostructured Membranes based on Hydrated Protic Polymerized Ionic Liquids: Effect of Domain Spacing

    NASA Astrophysics Data System (ADS)

    Sanoja, Gabriel; Popere, Bhooshan; Beckingham, Bryan; Evans, Christopher; Lynd, Nathaniel; Segalman, Rachel

    Elucidating the relationship between chemical structure, morphology, and ionic conductivity is essential for designing novel materials for electrochemical applications. In this work, the effect of lamellar domain spacing (d) on ionic conductivity (σ) is investigated for a model system of hydrated block copolymer based on a protic polymerized ionic liquid. We present a strategy that allows for the synthesis of a well-defined series of narrowly dispersed PS- b - PIL with constant volume fraction of ionic liquid moieties (fIL ~ 0.39). These materials self-assemble into ordered lamellar morphologies with variable domain spacing (23-59 nm) as demonstrated by SAXS. PS- b - PIL membranes exhibit ionic conductivities above 10-4 S/cm at room temperature, which are independent of domain spacing. The conductivity scaling relationship demonstrated in this work suggests that a mechanically robust membrane can be designed without compromising its ability to transport ions. In addition, PIL-based membranes exhibit lower water uptake (λ = 10) in comparison with many proton-conducting systems reported elsewhere. The low water content of these materials makes them promising candidates for solar-fuels electrochemical devices.

  2. Lithium-sulfur batteries based on nitrogen-doped carbon and an ionic-liquid electrolyte.

    PubMed

    Sun, Xiao-Guang; Wang, Xiqing; Mayes, Richard T; Dai, Sheng

    2012-10-01

    Nitrogen-doped mesoporous carbon (NC) and sulfur were used to prepare an NC/S composite cathode, which was evaluated in an ionic-liquid electrolyte of 0.5 M lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in methylpropylpyrrolidinium bis(trifluoromethane sulfonyl)imide ([MPPY][TFSI]) by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and cycle testing. To facilitate the comparison, a C/S composite based on activated carbon (AC) without nitrogen doping was also fabricated under the same conditions. Compared with the AC/S composite, the NC/S composite showed enhanced activity toward sulfur reduction, as evidenced by the lower onset sulfur reduction potential, higher redox current density in the CV test, and faster charge-transfer kinetics, as indicated by EIS measurements. At room temperature under a current density of 84 mA g(-1) (C/20), the battery based on the NC/S composite exhibited a higher discharge potential and an initial capacity of 1420 mAh g(-1), whereas the battery based on the AC/S composite showed a lower discharge potential and an initial capacity of 1120 mAh g(-1). Both batteries showed similar capacity fading with cycling due to the intrinsic polysulfide solubility and the polysulfide shuttle mechanism; capacity fading can be improved by further cathode modification. PMID:22847977

  3. Properties of Apolar Solutes in Alkyl Imidazolium-Based Ionic Liquids: The Importance of Local Interactions.

    PubMed

    Lesch, Volker; Heuer, Andreas; Holm, Christian; Smiatek, Jens

    2016-02-01

    The solvation and the dynamic properties of apolar model solutes in alkyl imidazolium-based ionic liquids (IL) are studied by using all-atom molecular dynamics simulations. In regards to specific IL effects, we focused on the often used 1-ethyl-3-methyl imidazolium cation in combination with the anions tetrafluoroborate, acetate, and bis(trifluoromethanesulfonyl)imide. Our findings reveal that the size of the anion crucially influences the accumulation behavior of the cations, which results in modified IL solvation properties. Deviations between the different alkyl imidazolium-based IL combinations can be also observed with regard to the results for the radial distribution functions, the number of surrounding molecules, and the molecular orientation. The analysis of the van Hove function further shows pronounced differences in the dynamic behavior of the solutes. The simulations verify that the solute mobilities are mainly influenced by the composition of the local solvent shell and the properties of the underlying Lennard-Jones interactions. Additional simulations with regard to modified short-range dispersion energies for alkyl imidazolium-based ILs validate our conclusions. PMID:26639367

  4. Electrochemical energy storage in montmorillonite K10 clay based composite as supercapacitor using ionic liquid electrolyte.

    PubMed

    Maiti, Sandipan; Pramanik, Atin; Chattopadhyay, Shreyasi; De, Goutam; Mahanty, Sourindra

    2016-02-15

    Exploring new electrode materials is the key to realize high performance energy storage devices for effective utilization of renewable energy. Natural clays with layered structure and high surface area are prospective materials for electrical double layer capacitors (EDLC). In this work, a novel hybrid composite based on acid-leached montmorillonite (K10), multi-walled carbon nanotube (MWCNT) and manganese dioxide (MnO2) was prepared and its electrochemical properties were investigated by fabricating two-electrode asymmetric supercapacitor cells against activated carbon (AC) using 1.0M tetraethylammonium tetrafluroborate (Et4NBF4) in acetonitrile (AN) as electrolyte. The asymmetric supercapacitors, capable of operating in a wide potential window of 0.0-2.7V, showed a high energy density of 171Whkg(-1) at a power density of ∼1.98kWkg(-1). Such high EDLC performance could possibly be linked to the acid-base interaction of K10 through its surface hydroxyl groups with the tetraethylammonium cation [(C2H5)4N(+) or TEA(+)] of the ionic liquid electrolyte. Even at a very high power density of 96.4kWkg(-1), the cells could still deliver an energy density of 91.1Whkg(-1) exhibiting an outstanding rate capability. The present study demonstrates for the first time, the excellent potential of clay-based composites for high power energy storage device applications. PMID:26609925

  5. Lithium-sulfur batteries based on nitrogen-doped carbon and ionic liquid electrolyte

    SciTech Connect

    Sun, Xiao-Guang; Wang, Xiqing; Mayes, Richard T; Dai, Sheng

    2012-01-01

    Nitrogen-doped mesoporous carbon (NC) and sulfur were used to prepare an NC/S composite cathode, which was evaluated in an ionic liquid electrolyte of 0.5 M lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in methylpropylpyrrolidinium bis(trifluoromethane sulfonyl)imide (MPPY.TFSI) by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and cycle testing. To facilitate the comparison, a C/S composite based on activated carbon (AC) without nitrogen doping was also fabricated under the same conditions as those for the NC/S composite. Compared with the AC/S composite, the NC/S composite showed enhanced activity toward sulfur reduction, as evidenced by the early onset sulfur reduction potential, higher redox current density in the CV test, and faster charge transfer kinetics as indicated by EIS measurement. At room temperature under a current density of 84 mA g-1 (C/20), the battery based on the NC/S composite exhibited higher discharge potential and an initial capacity of 1420 mAh g-1 whereas that based on the AC/S composite showed lower discharge potential and an initial capacity of 1120 mAh g-1. Both batteries showed similar capacity fading with cycling due to the intrinsic polysulfide solubility and the polysulfide shuttle mechanism; the capacity fading can be improved by further modification of the cathode.

  6. Enhanced energy transfer efficiency and stability of europium β-diketonate complex in ionic liquid-based lyotropic liquid crystals.

    PubMed

    Yi, Sijing; Wang, Jiao; Chen, Xiao

    2015-08-21

    Luminescent materials from europium β-diketonate complex in ionic liquids (ILs) could achieve enhanced luminescence efficiencies and photostabilities. However, the question of how to provide a feasible and environmentally-friendly way to distribute these lanthanide complexes uniformly and stably within IL-based matrix remains a significant challenge. Here, a soft luminescent material from IL-mediated lyotropic liquid crystals (LLCs) doped with [Bmim][Eu(TTA)4] (Bmim = 1-butyl-3-methyl imidazolium, TTA = 2-thenoyltrifluoroacetone) has been constructed by a convenient self-assembling method. The hexagonal or lamellar LLC phases could be identified by small-angle X-ray scattering (SAXS) measurements. All LLC samples exhibited intense red luminescence upon exposure to ultraviolet radiation. The good dispersibility of the complexes in LLC matrices and their good photostability (as in ILs) was verified by steady-state luminescence spectroscopy. The isolated and unique characteristics of the microenvironment within the LLCs were noteworthy to decrease the nonradiative deactivation of the excited states, thereby allowing more efficient energy transfer and longer lifetimes than those in pure complex or IL solutions. Both the luminescent property and the stability of the LLC materials were different in different phase structures, the complexes behaving better in the lamellar phase than in the hexagonal one. The findings reported herein will not only present an easy way to design novel luminescent lanthanide β-diketonate soft materials, but also provide a useful reference to better understand the LLC phase structure effects on the luminescence properties. PMID:26190789

  7. Ionic liquid-based dispersive liquid-liquid microextraction and enhanced spectrophotometric determination of molybdenum (VI) in water and plant leaves samples by FO-LADS.

    PubMed

    Gharehbaghi, Maysam; Shemirani, Farzaneh

    2011-02-01

    A new simple and rapid ionic liquid-based dispersive liquid-liquid microextraction (IL-DLLME) has been applied to preconcentrate trace levels of molybdenum (VI) as a prior step to its enhanced determination by fiber optic-linear array detection spectrophotometry (FO-LADS). In this method, a small amount of [Hmim][Tf(2)N] (1-hexyl-3-methylimmidazolium bis (trifluormethylsulfonyl) imid) as an extraction solvent was applied to extract molybdenum - pyrogallol red complex, which was formed in an aqueous solution in the presence of N-cetyl-N-N-N-trimethyl ammonium chloride as a sensitizing agent. Under optimum conditions, enhancement factor, detection limit and relative standard deviation (n=5, for 30 μg L(-1) of molybdenum (VI)) in 10 mL water sample were 72.6, 1.43 μg L(-1) and 2.8%, respectively. PMID:21092750

  8. Separation performance of guanidinium-based ionic liquids as stationary phases for gas chromatography.

    PubMed

    Qiao, Lizhen; Lu, Kai; Qi, Meiling; Fu, Ruonong

    2013-02-01

    Room temperature ionic liquids (RTILs) as stationary phases for gas chromatography (GC) have made great achievements in both research and applications over the last decades. Until now, all of the RTIL stationary phases reported have involved imidazolium, ammonium, pyrrolidinium, and phosphonium-based RTILs, and however, no publications are available using guanidinium-based ionic liquids (GBILs) as GC stationary phases except two preliminary reports from our group. In the present work, three hexaalkyl GBILs stationary phases, namely N, N,N',N'-tetramethyl-N″, N″-dioctylguanidinum hexafluophosphate (DOTMG-PF(6)), N,N,N',N'-tetramethyl-N″, N″-dioctylguanidinium bis (trifluoromethylsulfonyl) imide (DOTMG-NTf(2)), and N,N,N',N'-tetraoctyl-N″, N″-dimethylguanidinium bis (trifluoromethylsulfonyl) imide (TODMG-NTf(2)), were synthesized and used as stationary phases for GC separation after they were statically coated onto the inner walls of fused-silica capillary columns. The evaluation of DOTMG-PF(6) and TODMG-NTf(2) as GC stationary phases is reported here for the first time, whereas additional results on the DOTMG-NTf(2) stationary phase are added here on the basis of our previous report. In this work, McReynolds constants and Abraham solvation system constants are used to evaluate the average polarity and the solvation properties of the GBILs stationary phases for GC separation, respectively. The results show that the GBILs stationary phases exhibit medium polarity with an average polarity of 293-390, and that the major molecular interactions of the GBILs with analytes are dipole/polarizable interactions, H-bond basicity and dispersion forces, etc. After this, the separation performance and thermal stability of the GBILs stationary phases were evaluated, showing that these stationary phases achieve excellent separation for analytes of great variety covering hydrocarbons, alcohols, esters, aldehydes, ketones, amines, amides and aromatics, and exhibit

  9. High-performance supercapacitors based on poly(ionic liquid)-modified graphene electrodes.

    PubMed

    Kim, Tae Young; Lee, Hyun Wook; Stoller, Meryl; Dreyer, Daniel R; Bielawski, Christopher W; Ruoff, Rodney S; Suh, Kwang S

    2011-01-25

    We report a high-performance supercapacitor incorporating a poly(ionic liquid)-modified reduced graphene oxide (PIL:RG-O) electrode and an ionic liquid (IL) electrolyte (specifically, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide or EMIM-NTf(2)). PIL:RG-O provides enhanced compatibility with the IL electrolyte, thereby increasing the effective electrode surface area accessible to electrolyte ions. The supercapacitor assembled with PIL:RG-O electrode and EMIM-NTf(2) electrolyte showed a stable electrochemical response up to 3.5 V operating voltage and was capable of yielding a maximum energy density of 6.5 W·h/kg with a power density of 2.4 kW/kg. These results demonstrate the potential of the PIL:RG-O material as an electrode in high-performance supercapacitors. PMID:21142183

  10. Lewis Acidity/Basicity Changes in Imidazolium Based Ionic Liquids Brought About by Impurities.

    PubMed

    Gazitúa, Marcela; Fuentealba, Patricio; Contreras, Renato; Ormazábal-Toledo, Rodrigo

    2015-10-15

    We herein report on the effect that water molecules, present as impurities, in the vicinity of an ionic liquid model structure, may induce on the Lewis acidity/basicity patterns normally observed in these materials. Depending on the position and orientation of water, the Lewis acidity/basicity pattern changes from "normal distribution" (i.e., the basicity located at the anion moiety and the acidity located at the cation fragment) to "bifunctional distribution" (i.e., the acidity and basicity located at the cation moiety). In some specific cases, there appears a third Lewis acidity/basicity distribution, where water may bind both the cation and the anion of the ion pair; a response we tentatively call "amphoteric". These effects are clearly traced to the hydrogen bond formation ability of water to coordinate different regions of pure ionic liquids taken as references. PMID:26403375

  11. Densities, Viscosities and Derived Thermophysical Properties of Water-Saturated Imidazolium-Based Ionic Liquids

    PubMed Central

    Martins, Mónia A. R.; Neves, Catarina M. S. S.; Kurnia, Kiki A.; Carvalho, Pedro J.; Rocha, Marisa A. A.; Santos, Luís M. N. B. F.; Pinho, Simão P.; Freire, Mara G.

    2016-01-01

    In order to evaluate the impact of the alkyl side chain length and symmetry of the cation on the thermophysical properties of water-saturated ionic liquids (ILs), densities and viscosities as a function of temperature were measured at atmospheric pressure and in the (298.15 to 363.15) K temperature range, for systems containing two series of bis(trifluoromethylsulfonyl)imide-based compounds: the symmetric [CnCnim][NTf2] (with n = 1-8 and 10) and asymmetric [CnC1im][NTf2] (with n = 2-5, 7, 9 and 11) ILs. For water-saturated ILs, the density decreases with the increase of the alkyl side chain length while the viscosity increases with the size of the aliphatic tails. The saturation water solubility in each IL was further estimated with a reasonable agreement based on the densities of water-saturated ILs, further confirming that for the ILs investigated the volumetric mixing properties of ILs and water follow a near ideal behaviour. The water-saturated symmetric ILs generally present lower densities and viscosities than their asymmetric counterparts. From the experimental data, the isobaric thermal expansion coefficient and energy barrier were also estimated. A close correlation between the difference in the energy barrier values between the water-saturated and pure ILs and the water content in each IL was found, supporting that the decrease in the viscosity of ILs in presence of water is directly related with the decrease of the energy barrier.

  12. Cellulose-based films prepared directly from waste newspapers via an ionic liquid.

    PubMed

    Xia, Guangmei; Wan, Jiqiang; Zhang, Jinming; Zhang, Xiaoyu; Xu, Lili; Wu, Jin; He, Jiasong; Zhang, Jun

    2016-10-20

    Waste newspapers, composed of cellulose (>60wt%), lignin (∼15wt%), hemicellulose (∼10wt%) and other additives, are one kind of low-cost, easily collected and abundant resources. In order to get value-added products from this waste, in this work an attempt was made to directly convert waste newspapers into cellulose-based films by employing an ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a solvent. Most of the organic substances in this waste were dissolved quickly in AmimCl under mild conditions, and then coagulated and dried. Although containing lignin, hemicellulose and inorganic additives, the regenerated cellulose-based films were smooth, compact and semi-transparent, and exhibited good mechanical properties. If the newspaper/AmimCl solution was filtered to remove undissolved inorganic substances, the regenerated films became transparent and had a tensile strength of 80MPa. Thus, this work provides a new, simple and highly efficient way to achieve a high-valued utilization of waste newspapers for packaging and wrapping. PMID:27474561

  13. Nanoparticle enhanced ionic liquid heat transfer fluids

    DOEpatents

    Fox, Elise B.; Visser, Ann E.; Bridges, Nicholas J.; Gray, Joshua R.; Garcia-Diaz, Brenda L.

    2014-08-12

    A heat transfer fluid created from nanoparticles that are dispersed into an ionic liquid is provided. Small volumes of nanoparticles are created from e.g., metals or metal oxides and/or alloys of such materials are dispersed into ionic liquids to create a heat transfer fluid. The nanoparticles can be dispersed directly into the ionic liquid during nanoparticle formation or the nanoparticles can be formed and then, in a subsequent step, dispersed into the ionic liquid using e.g., agitation.

  14. Ionic liquid electrolyte based on S-propyltetrahydrothiophenium iodide for dye-sensitized solar cells

    SciTech Connect

    Guo, Lei; Pan, Xu; Zhang, Changneng; Liu, Weiqing; Wang, Meng; Fang, Xiaqin; Dai, Songyuan

    2010-03-15

    A new ionic liquid S-propyltetrahydrothiophenium iodide (T{sub 3}I) was developed as the solvent and iodide ion source in electrolyte for dye-sensitized solar cells. The electrochemical behavior of the I{sub 3}{sup -}/I{sup -} redox couple and effect of additives in this ionic liquid system was tested and the results showed that this ionic liquid electrolyte revealed good conducting abilities and potential application for solar devices. The effects of LiI and dark-current inhibitors were investigated. The dye-sensitized solar cell with the electrolyte (0.1 mol L{sup -1} LiI, 0.35 mol L{sup -1} I{sub 2}, 0.5 mol L{sup -1} NMBI in pure T{sub 3}I) gave short-circuit photocurrent density (J{sub sc}) of 11.22 mA cm{sup 2}, open-circuit voltage (V{sub oc}) of 0.61 V and fill factor (FF) of 0.51, corresponding to the photoelectric conversion efficiency ({eta}) of 3.51% under one Sun (AM1.5). (author)

  15. Theoretical study of ionic liquids based on the cholinium cation. Ab initio simulations of their condensed phases.

    PubMed

    Campetella, Marco; Bodo, Enrico; Montagna, Maria; De Santis, Serena; Gontrani, Lorenzo

    2016-03-14

    We have explored by means of ab initio molecular dynamics the homologue series of 11 different ionic liquids based on the combination of the cholinium cation with deprotonated amino acid anions. We present a structural analysis of the liquid states of these compounds as revealed by accurate ab initio computations of the forces. We highlight the persistent structural motifs that see the ionic couple as the basic building block of the liquid whereby a strong hydrogen bonding network substantially determines the short range structural behavior of the bulk state. Other minor docking features of the interaction network are also discovered and described. Special cases along the series such as Cysteine and Phenylalanine are discussed in the view of their peculiar properties due to zwitterion formation and additional long-range structural organization. PMID:26979694

  16. Theoretical study of ionic liquids based on the cholinium cation. Ab initio simulations of their condensed phases

    NASA Astrophysics Data System (ADS)

    Campetella, Marco; Bodo, Enrico; Montagna, Maria; De Santis, Serena; Gontrani, Lorenzo

    2016-03-01

    We have explored by means of ab initio molecular dynamics the homologue series of 11 different ionic liquids based on the combination of the cholinium cation with deprotonated amino acid anions. We present a structural analysis of the liquid states of these compounds as revealed by accurate ab initio computations of the forces. We highlight the persistent structural motifs that see the ionic couple as the basic building block of the liquid whereby a strong hydrogen bonding network substantially determines the short range structural behavior of the bulk state. Other minor docking features of the interaction network are also discovered and described. Special cases along the series such as Cysteine and Phenylalanine are discussed in the view of their peculiar properties due to zwitterion formation and additional long-range structural organization.

  17. The hype with ionic liquids as solvents

    NASA Astrophysics Data System (ADS)

    Kunz, Werner; Häckl, Katharina

    2016-09-01

    In this mini review, we give our personal opinion about the present state of the art concerning Ionic Liquids, proposed as alternative solvents. In particular, we consider their different drawbacks and disadvantages and discuss the critical aspects of the research of Ionic Liquids as solvents. Finally, we point out some aspects on potentially promising Ionic Liquid solvents.

  18. High Performance Electroactive Polymer Actuators Based on Sulfonated Block Copolymers Comprising Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Kim, Onnuri; Park, Moon Jeong

    2015-03-01

    Electroactive polymer (EAP) actuators that show reversible deformation under external electric stimulus have attracted great attention toward a range of biomimetic applications such as microsensors and artificial muscles. Key challenges to advance the technologies can be placed on the achievement of fast response time, low driving voltage, and durable operation in air. In present study, we are motivated to solve these issues by employing self-assembled block copolymers containing ionic liquids (ILs) as polymer layers in the actuator based on knowledge of factors affecting electromechanical properties of actuators. By controlling the block architecture and molecular weight of block copolymers, bending strain and durability were controlled in a straightforward manner. It has also been revealed that the type of IL makes impact on the EAP actuator performance by determining ion migration dynamics. Our actuators demonstrated large bending strains (up to 4%) under low voltages of 1-3V, which far exceeds the best performance of other EAP actuators reported in the literature. To underpin the molecular-level understanding of actuation mechanisms underlying the improved performance, we carried out in situ spectroscopy and in situ scattering experiments under actuation.

  19. Hormetic effect and mechanism of imidazolium-based ionic liquids on the nematode Caenorhabditis elegans.

    PubMed

    Zhu, Chun-Jie; Peng, Yong; Tong, Zhong-Hua; Lu, Li-Ya; Cui, Yin-Hua; Yu, Han-Qing

    2016-08-01

    In the present study, we used Caenorhabditis elegans assay system to investigate in hormetic effects of imidazolium-based bromide Ionic Liquids (ILs) and explored the possible underlying mechanism. Firstly, C. elegans was treated with ILs with different alkyl chain lengths at different concentrations. We found that exposure to ILs at 0.01 mg/L extended the mean lifespan of C. elegans and the ILs with longer alkyl chain showed more obvious effects. To investigate the possible mechanism, the nematodes were exposed to the three ILs at 0.01 mg/L for 2, 5, 7, 9 and 11 days. The levels of reactive oxygen species (ROS) in C. elegans increased significantly when treated for 2 days and then declined gradually compared to those of respective controls as time went on. After exposure for 11 days, the ROS levels and liposuscin accumulation were significantly lower in the treated groups than those of control group. Meanwhile, the expression of aging-related genes sod-5 and daf-16 were both massively up-regulated for the three ILs examined. Our results show that low concentration of ILs exert hormetic effect on C. elegans. ROS generation and expression of aging-related genes may play important roles in the IL-induced hormetic effect on C. elegans. PMID:27209554

  20. Temperature-dependent surface-enrichment effects of imidazolium-based ionic liquids.

    PubMed

    Kolbeck, Claudia; Deyko, Alexey; Matsuda, Takashi; Kohler, Florian T U; Wasserscheid, Peter; Maier, Florian; Steinrück, Hans-Peter

    2013-11-11

    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, [C8 C1 Im]Br, [C8 C1 Im][TfO] and [C8 C1 Im][Tf2 N], no significant differences of the temperature-induced partial loss of surface enrichment are found. Measurements for [C4 C1 Im][TfO], [C8 C1 Im][TfO] and [C18 C1 Im][TfO] indicate a small effect of the chain length. For [C18 C1 Im][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. PMID:24123477

  1. Three-dimensional graphitized carbon nanovesicles for high-performance supercapacitors based on ionic liquids.

    PubMed

    Peng, Chengxin; Wen, Zubiao; Qin, Yao; Schmidt-Mende, Lukas; Li, Chongzhong; Yang, Shihe; Shi, Donglu; Yang, Jinhu

    2014-03-01

    Three-dimensional nanoporous carbon with interconnected vesicle-like pores (1.5-4.2 nm) has been prepared through a low-cost, template-free approach from petroleum coke precursor by KOH activation. It is found that the thin pore walls are highly graphitized and consist of only three to four layers of graphene, which endows the material with an unusually high specific surface area (2933 m(2)  g(-1) ) and good conductivity. With such unique structural characteristics, if used as supercapacitor electrodes in ionic liquid (IL) electrolytes, the graphitized carbon nanovesicle (GCNV) material displays superior performance, such as high energy densities up to 145.9 Wh kg(-1) and a high combined energy-power delivery, and an energy density of 97.6 Wh kg(-1) can be charged in 47 s at 60 °C. This demonstrates that the energy output of the GCNV-based supercapacitors is comparable to that of batteries, and the power output is one order of magnitude higher. Moreover, the synergistic effect of the GCNVs and the IL electrolyte on the extraordinary performance of the GCNV supercapacitors has been analyzed and discussed. PMID:24474720

  2. Dielectric response of imidazolium-based room-temperature ionic liquids.

    PubMed

    Daguenet, Corinne; Dyson, Paul J; Krossing, Ingo; Oleinikova, Alla; Slattery, John; Wakai, Chihiro; Weingärtner, Hermann

    2006-06-29

    We have used microwave dielectric relaxation spectroscopy to study the picosecond dynamics of five low-viscosity, highly conductive room temperature ionic liquids based on 1-alkyl-3-methylimidazolium cations paired with the bis((trifluoromethyl)sulfonyl)imide anion. Up to 20 GHz the dielectric response is bimodal. The longest relaxation component at the time scale of several 100 ps reveals strongly nonexponential dynamics and correlates with the viscosity in a manner consistent with hydrodynamic predictions for the diffusive reorientation of dipolar ions. Methyl substitution at the C2 position destroys this correlation. The time constants of the weak second process at the 20 ps time scale are practically the same for each salt. This intermediate process seems to correlate with similar modes in optical Kerr effect spectra, but its physical origin is unclear. The missing high-frequency portion of the spectra indicates relaxation beyond the upper cutoff frequency of 20 GHz, presumably due to subpicosecond translational and librational displacements of ions in the cage of their counterions. There is no evidence for orientational relaxation of long-lived ion pairs. PMID:16800602

  3. Lignin dissolution in dialkylimidazolium-based ionic liquid-water mixtures.

    PubMed

    Wang, Yantao; Wei, Ligang; Li, Kunlan; Ma, Yingchong; Ma, Ningning; Ding, Shan; Wang, Linlin; Zhao, Deyang; Yan, Bing; Wan, Wenying; Zhang, Qian; Wang, Xin; Wang, Junmei; Li, Hui

    2014-10-01

    Lignin dissolution in dialkylimidazolium-based ionic liquid (IL)-water mixtures (40wt%-100wt% IL content) at 60°C was investigated. The IL content and type are found to considerably affect lignin solubility. For the IL-water mixtures except 1-butyl-3-methylimidazolium tetrafluoroborate ([C4C1im]BF4), the maximum lignin solubility can be achieved at 70wt% IL content. Lignin solubility in IL-water mixtures with different cations follows the order 1-butyl-3-methylimidazolium ([C4C1im](+))>1-hexyl-3-methylimidazolium ([C6C1im](+))>1-ethyl-3-methylimidazolium ([C2C1im](+))>1-octyl-3-methylimidazolium ([C8C1im](+))>1-butyl-3-ethylimidazolium ([C4C2im](+))>1-butyl-3-propylimidazolium ([C4C3im](+)). For IL mixtures with different anions, lignin solubility decreases in the following order: methanesulfonate (MeSO3(-))>acetate (MeCO2(-))>bromide (Br(-))>dibutylphosphate (DBP(-)). Evaluation using the theory of Hansen solubility parameter (HSP) is consistent with the experimental results, suggesting that HSP can aid in finding the appropriate range of IL content for IL-water mixtures. However, HSP cannot be used to evaluate the effect of IL type on lignin solubility. PMID:25164342

  4. Micellization behavior of morpholinium-based amide-functionalized ionic liquids in aqueous media.

    PubMed

    Kamboj, Raman; Bharmoria, Pankaj; Chauhan, Vinay; Singh, Sukhprit; Kumar, Arvind; Mithu, Venus Singh; Kang, Tejwant Singh

    2014-08-26

    Morpholinium-based amide-functionalized ionic liquids (ILs) [C(n)AMorph][Br], where n = 8, 12, and 16, have been synthesized and characterized for their micellization behavior in aqueous medium using a variety of state of the art techniques. The adsorption and micellization behavior of [CnAMorph][Br] ILs at the air-solution interface and in the bulk, respectively, has been found to be much better compared to that observed for nonfunctionalized homologous ILs and conventional cationic surfactants, as shown by the comparatively higher adsorption efficiency, lower surface tension at the critical micelle concentraiton (γ(cmc)), and much lower critical micelle concentration (cmc) for [C(n)AMorph][Br] ILs. Conductivity measurements have been performed to obtain the cmc, degree of counterion binding (β), and standard free energy of micellization (ΔG(m)°). Isothermal titration calorimetry has provided information specifically about the thermodynamics of micellization, whereas steady-state fluorescence has been used to obtain the cmc, micropolarity of the cybotactic region, and aggregation number (N(agg)) of the micelles. Both dynamic light scattering and atomic force microscopy have provided insights into the size and shape of the micelles. 2D (1)H-(1)H nuclear Overhauser effect spectroscopy experiments have provided insights into the structure of the micelle, where [C16AMorph][Br] has shown distinct micellization behavior as compared to [C8AMorph][Br] and [C12AMorph][Br] in corroboration with observations made from other techniques. PMID:25062465

  5. Temperature-induced microstructural changes in ionic liquid-based microemulsions.

    PubMed

    Gao, Yanan; Li, Na; Hilfert, Liane; Zhang, Shaohua; Zheng, Liqiang; Yu, Li

    2009-02-01

    In the present contribution, results concerning the effect of temperature on the nonionic surfactant Triton X-100 based 1-butyl-3-methylimidazolium tetrafluoroborate (bmimBF4)-in-cyclohexane and bmimBF4-in-toluene ionic liquid (IL) reverse microemulsions are reported. Dynamic light scattering (DLS) along with freeze-fracture transmission electron microscopy (FF-TEM) measurements revealed that the sizes of single microemulsion droplets increased with increasing temperature. However, a decreased temperature led to the appearance of droplet clusters, which have also been observed previously when the single microemulsion droplets were swollen by added bmimBF4 to a certain extent (Gao, Y. A.; Vogit, A.; Hilfert, L.; Sundmacher, K. ChemPhysChem, 2008, 9, 1603-1609). Compared to traditional aqueous microemulsions, IL microemulsions revealed relatively high temperature-independence. The droplet-shaped microstructure was always kept in a large range of temperature. The temperature-independence is ascribed to the temperature-insensitive electrostatic attraction between the solubilized bmimBF4 and Triton X-100, which was considered to be the driving force for solubilizing bmimBF4 into the cores of Triton X-100 aggregates. Two-dimensional rotating frame nuclear Overhauser effect (NOE) experiments (ROESY) further confirmed the microstructural change with temperature. PMID:19132875

  6. Free energy of solvation of carbon nanotubes in pyridinium-based ionic liquids.

    PubMed

    Chaban, Vitaly V; Fileti, Eudes Eterno

    2016-07-27

    Numerous prospective applications require the availability of individual carbon nanotubes (CNTs). Pristine CNTs, strongly hydrophobic in nature, are known to be either totally insoluble or poorly dispersible. While it is unlikely to be possible to prepare a real solution of CNTs in any solvent, the ability of certain solvents to maintain dispersions of CNTs for macroscopic times constitutes great research interest. In the present work, we characterize two pyridinium-based ionic liquids (ILs), N-butylpyridinium chloride [BPY][Cl] and N-butylpyridinium bis(trifluoromethanesulfonyl)imide [BPY][TFSI], with respect to their potential to solvate CNTs of different diameters, from the CNT (10,10) to the CNT (25,25). Using a universal methodology, we found that both ILs exhibit essentially the same solvation performance. Solvation of CNTs is strongly prohibited entropically, whereas the energy penalty increases monotonically with the CNT diameter. Weak van der Waals interactions, which guide enthalpy alteration upon the CNT solvation, are unable to compensate for the large entropic penalty from the destruction of the IL-IL electrostatic interactions. The structure of ILs inside and outside CNTs is also discussed. The reported results are necessary for gaining a fundamental understanding of the CNT solvation problems, thereby inspiring the search for more suitable solvents. PMID:27400869

  7. Ionic liquid-based zwitterionic organic polymer monolithic column for capillary hydrophilic interaction chromatography.

    PubMed

    Wang, Tingting; Chen, Yihui; Ma, Junfeng; Zhang, Xiaodan; Zhang, Lihua; Zhang, Yukui

    2015-08-21

    In the current study, a novel ionic liquid-based zwitterionic organic polymer monolithic column was developed by copolymerizing 1-vinyl-3-(butyl-4-sulfonate) imidazolium, acrylamide and N,N'-methylenebisacrylamide in a quaternary porogenic solvent consisting of formamide, dimethyl sulphoxide, polyethylene glycol 8000 and polyethylene glycol 10,000 for capillary hydrophilic interaction chromatography. The monolithic stationary phase was optimized by adjusting the amount of monomer in the polymerization solution along with the composition of porogenic solvent. The optimized monolith exhibited excellent selectivity and favorable retention for nucleosides and benzoic acid derivatives. The primary factors affecting the separation efficiency of the monolithic column (including acetonitrile content, pH, and buffer salt concentration in the mobile phase) have been thoroughly evaluated. Excellent reproducibility of the retention times for five nucleosides was achieved, with relative standard deviations of run-to-run (n = 3), column-to-column (n = 3) and batch-to-batch (n = 3) in the range of 0.18-0.48%, 2.33-4.20% and 3.07-6.50%, respectively. PMID:26114194

  8. Role of alkyl group in the aromatic extraction using pyridinium-based ionic liquids.

    PubMed

    Kim, Min Ji; Shin, Seung Hoon; Kim, Young Jin; Cheong, Minserk; Lee, Je Seung; Kim, Hoon Sik

    2013-11-27

    The performance of N-alkylpyridinium-based ionic liquids with a SCN anion (PyILs) was evaluated for the selective extraction of aromatics from aliphatic hydrocarbons. The aromatic extraction ability of PyILs was greatly enhanced by the presence of a methyl group on the pyridinium ring at the 3- or 4-position, whereas the solubility of the aromatics in the PyILs decreased with increasing the number of methyl groups on the benzene ring. The FT-IR studies revealed that the solubility of an aromatic compound in a PyIL is closely correlated with the degree of aromatic C-H bending frequency shift observed during the dissolution of the aromatic compound in the PyIL: the larger the shift, the higher the solubility. The computational calculations on the dispersion interactions between aromatics and PyILs demonstrated that the anion-aromatic interaction is much more important than the cation-aromatic interaction in determining the aromatic solubility in PyILs, and such anion-aromatic interaction can be enhanced by introducing a methyl group at the carbon atom of the pyridinium ring. PMID:24180561

  9. Assessment of bromide-based ionic liquid toxicity toward aquatic organisms and QSAR analysis.

    PubMed

    Wang, Chao; Wei, Zhongbo; Wang, Liansheng; Sun, Ping; Wang, Zunyao

    2015-05-01

    The toxicities of 24 bromide-based ionic liquids (Br-ILs) towards Vibrio fischeri (V. fischeri) and Daphnia magna (D. magna) were determined. These Br-ILs are composed of a bromide ion and a generic cation (i.e., pyrrolidinium, piperidinium, pyridinium or imidazolium) with different alkyl side chains. QSAR models with relatively high correlation coefficients, R(2), of 0.954 and 0.895 were developed for V. fischeri and D. magna. The model for V. fischeri indicated that the Br-IL toxicity towards V. fischeri was negatively correlated with the energy of the lowest unoccupied molecular orbitals (ELUMO) which reflects the electron affinities (EAs) and positively correlated with the volumes of Br-IL cations. For the D. magna model, the Br-IL toxicity was positively correlated with the dipole moment (μ) and negatively correlated with the total energy (TE) that is highly correlated with the molecular volume (V). For Br-ILs with the same cation ring, the toxicity increased as the length of the alkyl chains increased. For the same alkyl chain length, the toxicity order for V. fischeri was pyridinium>imidazolium>piperidinium>pyrrolidinium, except for those containing octyl side chains, while the toxicity ranking for D. magna was imidazolium~pyridinium>piperidinium>pyrrolidinium. PMID:25682588

  10. A preconcentration method for analysis of neonicotinoids in honey samples by ionic liquid-based cold-induced aggregation microextraction.

    PubMed

    Vichapong, Jitlada; Burakham, Rodjana; Santaladchaiyakit, Yanawath; Srijaranai, Supalax

    2016-08-01

    A preconcentration approach based on ionic liquid-based cold-induced aggregation microextraction for determination of neonicotinoid insecticide residues in honey samples before high-performance liquid chromatographic analysis has been developed. Room temperature ionic liquid [C4MIM][PF6] (extraction solvent) and SDS (emulsifier) was used for extraction of the target analytes. The parameters affecting the extraction efficiency were optimized. The optimum microextraction conditions were 200µL room temperature ionic liquids [C4MIM][PF6] containing 0.05molL(-1) SDS, 0.75g sodium carbonate, vortex agitation speed of 1800rpm for 30s and centrifugation at 3500rpm for 10min. Under optimum conditions, the high enrichment factors of 200 could be obtained, leading to low limit of detection (0.01µgL(-1) for all analytes) with the relative standard deviations lower than 2.68% and 5.38% for retention time and peak area, respectively. Good recoveries for the spiked target neonicotinoids at three different concentrations of honey samples were obtained in 86-100% and relative standard deviations were lower than 8.1%. The results demonstrated that the proposed method can be used as an alternative powerful method for the simultaneous determination of the studied insecticides in real honey samples. PMID:27216676

  11. The effect of C2 substitution on melting point and liquid phase dynamics of imidazolium based-ionic liquids: insights from molecular dynamics simulations

    SciTech Connect

    Zhang, Y; Maginn, EJ

    2012-01-01

    Using molecular dynamics simulations, the melting points and liquid phase dynamic properties were studied for four alkyl-imidazolium-based ionic liquids, 1-n-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]), 1-n-butyl-2,3-dimethylimidazolium hexafluorophosphate ([BMMIM][PF6]), 1-ethyl-3-methylimidazolium hexafluorophosphate ([EMIM][PF6]), and 1-ethyl-2,3-dimethylimidazolium hexafluorophosphate ([EMMIM][PF6]), respectively. Experimentally it has been observed that the substitution of a methyl group for a hydrogen at the C2 position of the cation ring leads to an increase in both the melting point and liquid phase viscosity, contrary to arguments that had been made regarding associations between the ions. The melting points of the four ionic liquids were accurately predicted using simulations, as were the trends in viscosity. The simulation results show that the origin of the effect is mainly entropic, although enthalpy also plays an important role.

  12. Branched isomeric 1,2,3-triazolium-based ionic liquids: new insight into structure-property relationships.

    PubMed

    Lartey, M; Meyer-Ilse, J; Watkins, J D; Roth, E A; Bowser, S; Kusuma, V A; Damodaran, K; Zhou, X; Haranczyk, M; Albenze, E; Luebke, D R; Hopkinson, D; Kortright, J B; Nulwala, H B

    2015-11-28

    A series of four isomeric 1,2,3-triazolium-based ionic liquids (ILs) with vary degree of branching were synthesized and characterized to investigate the effect of ion branching on thermal and physical properties of the resulting IL. It was found that increased branching led to a higher ionicity and higher viscosity. The thermal properties were also altered significantly and spectral changes in the near edge X-ray absorption fine structure (NEXAFS) spectra show that branching affects intermolecular interaction. While the ionicity and viscosity varying linearly with branching, the MDSC and NEXAFS measurements show that the cation shape has a stronger influence on the melting temperature and absorptive properties than the number of branched alkyl substituents. PMID:26486091

  13. Bis(fluoromalonato)borate (BFMB) Anion Based Ionic Liquid As an Additive for Lithium-Ion Battery Electrolytes

    SciTech Connect

    Sun, Xiao-Guang; Liao, Chen; Baggetto, Loic; Guo, Bingkun; Unocic, Raymond R; Veith, Gabriel M; Dai, Sheng

    2014-01-01

    Propylene carbonate (PC) is a good solvent for lithium ion battery applications due to its low melting point and high dielectric constant. However, PC is easily intercalated into graphite causing it to exfoliate, killing its electrochemical performance. Here we report on the synthesis of a new ionic liquid electrolyte based on partially fluorinated borate anion, 1-butyl-1,2-dimethylimidazolium bis(fluoromalonato)borate (BDMIm.BFMB), which can be used as an additive in 1 M LiPF6/PC electrolyte to suppress graphite exfoliation and improve cycling performance. In addition, both PC and BDMIm.BFMB can be used synergistically as additive to 1.0M LiPF6/methyl isopropyl sulfone (MIPS) to dramatically improve its cycling performance. It is also found that the chemistry nature of the ionic liquids has dramatic effect on their role as additive in PC based electrolyte.

  14. Ionic liquid based microemulsion with pharmaceutically accepted components: Formulation and potential applications.

    PubMed

    Moniruzzaman, Muhammad; Kamiya, Noriho; Goto, Masahiro

    2010-12-01

    In this paper, we report a novel ionic liquid-in-oil (IL/o) microemulsion which is able to dissolve pharmaceuticals that are insoluble or sparingly soluble in water and most of pharmaceutical grade organic liquids. Towards this approach, the nanometer-sized ionic liquid droplets in isopropyl myristate (IPM) were formed with a blend of nonionic surfactants, polyoxyethylene sorbitan monooleate (Tween-80), and sorbitan laurate (Span-20). A set of ionic liquids (ILs) was tested as a dispersed phase, and it was observed that ILs possessing coordinating anions which are strong hydrogen bond acceptor were most effective in forming microemulsion droplets. The possible formation mechanism was also studied. Ternary phase behavior study clearly indicated the formation of optically transparent and thermodynamically stable microemulsions with a wide range of IL content. The shape, size and size distribution of the aggregates in microemulsions were characterized using dynamic light scattering (DLS), which demonstrated the formation of spherical micelles in the range of 8-34nm. In order to explore the use of newly developed microemulsion as a potential drug carrier, we have investigated the solubility of some drug molecules (e.g., acyclovir, methotrexate and 1-[(5-(p-nitrophenyl) furfurylidene) amino] hydantoin sodium) that are insoluble or sparingly soluble in most of the conventional solvents. Very significantly, the solubility studies indicated a high degree of solubilization of such drugs in IL microemulsions. We believe that this microemulsion formed with ILs having the unique physical, chemical and biological properties may offer novel opportunities to develop a potential drug delivery carrier for poorly soluble drugs molecules. PMID:20825949

  15. Ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction combined with electrothermal atomic absorption spectrometry for a sensitive determination of cadmium in water samples

    NASA Astrophysics Data System (ADS)

    Li, Shengqing; Cai, Shun; Hu, Wei; Chen, Hao; Liu, Hanlan

    2009-07-01

    A new method was developed for the determination of cadmium in water samples using ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction (IL-based USA-DLLME) followed by electrothermal atomic absorption spectrometry (ETAAS). The IL-based USA-DLLME procedure is free of volatile organic solvents, and there is no need for a dispersive solvent, in contrast to conventional DLLME. The ionic liquid, 1-hexyl-3-methylimidazolium hexafluorophosphate (HMIMPF 6), was quickly disrupted by an ultrasonic probe for 1 min and dispersed in water samples like a cloud. At this stage, a hydrophobic cadmium-DDTC complex was formed and extracted into the fine droplets of HMIMPF 6. After centrifugation, the concentration of the enriched cadmium in the sedimented phase was determined by ETAAS. Some effective parameters of the complex formation and microextraction, such as the concentration of the chelating agent, the pH, the volume of the extraction solvent, the extraction time, and the salt effect, have been optimized. Under optimal conditions, a high extraction efficiency and selectivity were reached for the extraction of 1.0 ng of cadmium in 10.0 mL of water solution employing 73 µL of HMIMPF 6 as the extraction solvent. The enrichment factor of the method is 67. The detection limit was 7.4 ng L - 1 , and the characteristic mass ( m0, 0.0044 absorbance) of the proposed method was 0.02 pg for cadmium (Cd). The relative standard deviation (RSD) for 11 replicates of 50 ng L - 1 Cd was 3.3%. The method was applied to the analysis of tap, well, river, and lake water samples and the Environmental Water Reference Material GSBZ 50009-88 (200921). The recoveries of spiked samples were in the range of 87.2-106%.

  16. Sodium-ion electrolytes based on ionic liquids: a role of cation-anion hydrogen bonding.

    PubMed

    Chaban, Vitaly V; Andreeva, Nadezhda A

    2016-08-01

    Recent success of the sodium-ion batteries fosters an academic interest for their investigation. Room-temperature ionic liquids (RTILs) constitute universal solvents providing non-volatility and non-flammability to electrolytes. In the present work, we consider four families of RTILs as prospective solvents for NaBF4 and NaNO3 with an inorganic salt concentration of 25 and 50 mol%. We propose a methodology to rate RTILs according to their solvation capability using parameters of the computed radial distribution functions. Hydrogen bonds between the cations and the anions of RTILs were found to indirectly favor sodium solvation, irrespective of the particular RTIL and its concentration. The best performance was recorded in the case of cholinium nitrate. The reported observations and correlations of ionic structures and properties offer important assistance to an emerging field of sodium-ion batteries. Graphical Abstract Sodium-ion electrolytes. PMID:27381471

  17. Crosslinked polymer gel electrolytes based on polyethylene glycol methacrylate and ionic liquid for lithium battery applications

    SciTech Connect

    Liao, Chen; Sun, Xiao-Guang; Dai, Sheng

    2013-01-01

    Gel polymer electrolytes were synthesized by copolymerization polyethylene glycol methyl ether methacrylate with polyethylene glycol dimethacrylate in the presence of a room temperature ionic liquid, methylpropylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPY TFSI). The physical properties of gel polymer electrolytes were characterized by thermal analysis, impedance spectroscopy, and electrochemical tests. The ionic conductivities of the gel polymer electrolytes increased linearly with the amount of MPPY TFSI and were mainly attributed to the increased ion mobility as evidenced by the decreased glass transition temperatures. Li||LiFePO4 cells were assembled using the gel polymer electrolytes containing 80 wt% MPPY TFSI via an in situ polymerization method. A reversible cell capacity of 90 mAh g 1 was maintained under the current density of C/10 at room temperature, which was increased to 130 mAh g 1 by using a thinner membrane and cycling at 50 C.

  18. Tetramethylammonium-lactobionate: A novel ionic liquid chiral selector based on saccharides in capillary electrophoresis.

    PubMed

    Zhang, Qi; Du, Yingxiang; Du, Shuaijing; Zhang, Jinjing; Feng, Zijie; Zhang, Yanjie; Li, Xiaoqi

    2015-05-01

    Chiral ionic liquids (ILs) have aroused widespread interest in separation science; however, only a few papers have reported the application of chiral ILs in CE for enantioseparation, and the use of chiral ILs as the sole chiral selector in an electrophoretic or a chromatographic system was reported in only three papers. In this study, we designed a lactobionic acid LA-based IL, tetramethylammonium-lactobionate (TMA-LA), and it is very interesting to find that the chiral separation capability can be remarkably improved when a conventional saccharide chiral selector evolved into an IL chiral selector. A comparative study of the enantiorecognition capability of three separation systems (single LA system, LA + TMA-chloride (TMA-Cl) system, and TMA-LA IL system) was also conducted, and the results showed that the use of TMA-LA IL as the sole chiral selector exhibited a remarkable superiority. A series of parameters affecting the enantioseparation, such as the type and proportion of organic modifier, buffer composition and pH, chiral selector concentration, as well as applied voltage were systematically investigated. The best enantioseparation was obtained at pH 7.6 using a 40 mM borax buffer with 40% v/v methanol, 200 mM TMA-LA, and 20 kV applied voltage. It is the first time that a saccharide-based IL is evaluated as a sole chiral selector in CE, and we hope this study would provide a new direction for the development of novel ILs chiral selectors based on conventional chiral selectors. PMID:25782175

  19. Molecular dynamics simulation of imidazolium-based ionic liquids. I. Dynamics and diffusion coefficient.

    PubMed

    Kowsari, M H; Alavi, Saman; Ashrafizaadeh, Mahmud; Najafi, Bijan

    2008-12-14

    Molecular dynamics simulations are used to study the dynamics and transport properties of 12 room-temperature ionic liquids of the 1-alkyl-3-methylimidazolium [amim](+) (alkyl = methyl, ethyl, propyl, and butyl) family with PF(6)(-), NO(3)(-), and Cl(-) counterions. The explicit atom transferable force field of Canongia Lopes et al. [J. Phys. Chem. B 108, 2038 (2004)] is used in the simulations. In this first part, the dynamics of the ionic liquids are characterized by studying the mean-square displacement (MSD) and the velocity autocorrelation function (VACF) for the centers of mass of the ions at 400 K. Trajectory averaging was employed to evaluate the diffusion coefficients at two temperatures from the linear slope of MSD(t) functions in the range of 150-300 ps and from the integration of the VACF(t) functions at 400 K. Detailed comparisons are made between the diffusion results from the MSD and VACF methods. The diffusion coefficients from the integration of the VACFs are closer to experimental values than the diffusion coefficients calculated from the slope of MSDs. Both methods can show good agreement with experiment in predicting relative trends in the diffusion coefficients and determining the role of the cation and anion structures on the dynamical behavior of this family of ionic liquids. The MSD and self-diffusion of relatively heavier imidazolium cations are larger than those of the lighter anions from the Einstein results, except for the case of [bmim][Cl]. The cationic transference number generally decreases with temperature, in good agreement with experiments. For the same anion, the cationic transference numbers decrease with increasing length of the alkyl chain, and for the same cation, the trends in the cationic transference numbers are [NO(3)](-) < [Cl](-) < [PF(6)](-). The trends in the diffusion coefficient in the series of cations with identical anions are [emim](+) > [pmim](+) > [bmim](+) and those for anions with identical cations are [NO(3

  20. High carbon dioxide solubilities in imidazolium-based ionic liquids and in poly(ethylene glycol) dimethyl ether.

    PubMed

    Revelli, Anne-Laure; Mutelet, Fabrice; Jaubert, Jean-Noël

    2010-10-14

    This work is focused on the possible capture of carbon dioxide using ionic liquids (ILs). Such solvents are gaining special attention because the efficiency of many processes can be enhanced by the judicious manipulation of their properties. The absorption of greenhouse gases can be enhanced by the basic character of the IL. In this work, these characteristics are evaluated through the study of the gas-liquid equilibrium of four imidazolium-based ILs: 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF(4)], 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN], 1,3-dimethylimidazolium methylphosphonate [DMIM][MP], and 1,3-diethoxyimidazolium bis(trifluoromethylsulfonyl)imide [(ETO)(2)IM][Tf(2)N] with CO(2) at temperatures up to 373 K and pressures up to 300 bar. Solubility of carbon dioxide in poly(ethylene glycol) dimethyl ether, component of selexol, was also measured to evaluate the capture's efficiency of ionic liquids. Experimental data indicate that 67 to 123 g of CO(2) can be absorbed per kg of ionic liquid and 198 g per kg of poly(ethylene glycol) dimethyl ether. PMID:20853857

  1. An Electrochemical NO2 Sensor Based on Ionic Liquid: Influence of the Morphology of the Polymer Electrolyte on Sensor Sensitivity

    PubMed Central

    Kuberský, Petr; Altšmíd, Jakub; Hamáček, Aleš; Nešpůrek, Stanislav; Zmeškal, Oldřich

    2015-01-01

    A systematic study was carried out to investigate the effect of ionic liquid in solid polymer electrolyte (SPE) and its layer morphology on the characteristics of an electrochemical amperometric nitrogen dioxide sensor. Five different ionic liquids were immobilized into a solid polymer electrolyte and key sensor parameters (sensitivity, response/recovery times, hysteresis and limit of detection) were characterized. The study revealed that the sensor based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][N(Tf)2]) showed the best sensitivity, fast response/recovery times, and low sensor response hysteresis. The working electrode, deposited from water-based carbon nanotube ink, was prepared by aerosol-jet printing technology. It was observed that the thermal treatment and crystallinity of poly(vinylidene fluoride) (PVDF) in the solid polymer electrolyte influenced the sensitivity. Picture analysis of the morphology of the SPE layer based on [EMIM][N(Tf)2] ionic liquid treated under different conditions suggests that the sensor sensitivity strongly depends on the fractal dimension of PVDF spherical objects in SPE. Their deformation, e.g., due to crowding, leads to a decrease in sensor sensitivity. PMID:26569248

  2. Mechanistic Investigation of Solvent Extraction Based on Anion-Functionalized Ionic Liquids for Selective Separation of Rare-Earth Ions

    SciTech Connect

    Sun, Xiaoqi; Luo, Huimin; Dai, Sheng

    2013-01-01

    In this study, solvation has been found to be a dominant mechanism in a comprehensive ionic liquid based extraction system for rare earth elements (REEs). Trioctylmethylammonium di(2-ethylhexyl)phosphate ([TOMA][DEHP]), an ionic-liquid extractant, was used in 1-alkyl-3-methylimidizolium bis[(trifluoromethyl)sulfonyl]imide ([Cnmim][NTf2], n = 4, 6, 8, 10) and 1-alkyl-3-methylimidizolium bis(perfluoroethanesulfonyl)imide ([Cnmim][BETI], n = 4, 6, 8, 10) for the separation of REEs. Surprisingly, a very similar extraction behavior was observed even as the carbon chain length on the ionic-liquid (IL) cation increased from butyl (C4) to hexyl (C6), to octyl (C8), to decyl (C10). This behavior is in sharp contrast to that exhibited by the conventional neutral extractants, whose extraction efficiencies are strongly dependent on the hydrophobicity of IL cations. Furthermore, the addition of IL cations ([Cnmim]+) or IL anions ([NTf2]- or [BETI]-) to the aqueous phase had little effect on the extraction behavior of the above extraction system, ruling out the strong involvement of the ion-exchange mechanism associated with traditional IL-based extraction systems. Results showed that the extractabilities and selectivities of REEs using [TOMA][DEHP] in [C10mim][NTf2]/[BETI] are several orders of magnitude better than those achieved using conventional organic solvent, diisopropylbenzene (DIPB). This study highlights the potential of developing a comprehensive IL-based extraction strategy for REEs separations.

  3. Up-and-down shaker-assisted ionic liquid-based dispersive liquid-liquid microextraction of benzophenone-type ultraviolet filters.

    PubMed

    Ku, Yu-Chien; Leong, Mei-I; Wang, Wan-Ting; Huang, Shang-Da

    2013-04-01

    Sun protection is an important part of our lives. UV filters are widely used to absorb solar radiation in sunscreens. However, excess UV filters constitute persistent groups of organic micropollutants present in the environment. An environmentally friendly ionic-liquid-based up-and-down shaker-assisted dispersive liquid-liquid microextraction device combined with ultra-performance liquid chromatography coupled with photodiode-array detection has been developed to preconcentrate three UV filters (benzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone) from field water samples. In this method, the optimal conditions for the proposed extraction method were: 40 μL [C8MIM][PF6 ] as extraction solvent and 200 μL methanol as disperser solvent were used to extract the UV filters. After up-and-down shaking for 3 min, the aqueous solution was centrifuged at 5000 rpm speed, then using microtube to collect the settled extraction solvent and using ultra-performance liquid chromatography for further analysis. Quantification results indicated that the linear range was 2-1000 ng/mL. The LOD of this method was in the range 0.2-1.3 ng/mL with r(2) ≥ 0.9993. The relative recovery in studies of different types of field water samples was in the range 92-120%, and the RSD was 2.3-7.1%. The proposed method was also applied to the analysis of field samples. PMID:23495210

  4. Theoretical study for pyridinium-based ionic liquid 1-ethylpyridinium trifluoroacetate: synthesis mechanism, electronic structure, and catalytic reactivity.

    PubMed

    Zhu, Xueying; Cui, Peng; Zhang, Dongju; Liu, Chengbu

    2011-07-28

    By performing density functional theory calculations, we have studied the synthesis mechanism, electronic structure, and catalytic reactivity of a pyridinium-based ionic liquid, 1-ethylpyridinium trifluoroacetate ([epy](+)[CF(3)COO](-)). It is found that the synthesis of the pyridinium salt follows a S(N)2 mechanism. The electronic structural analyses show that multiple H bonds are generally involved in the pyridinium-based ionic liquid, which may play a decisive role for stabilizing the ionic liquid. The cation-anion interaction mainly involves electron transfer between the lone pair of the oxygen atom in the anion and the antibonding orbital of the C*-H bond (C* denotes the carbon atom at the ortho-position of nitrogen atom in the cation). This present work has also given clearly the catalytic mechanism of [epy](+)[CF(3)COO](-) toward to the Diels-Alder (D-A) reaction of acrylonitrile with 2-methyl-1,3-butadiene. Both the cation and anion are shown to play important roles in promoting the D-A reaction. The cation [epy](+), as a Lewis acid, associates the C≡N group by C≡N···H H bond to increase the polarity of the C═C double bond in acrylonitrile, while the anion CF(3)COO(-) links with the methyl group in 2-methyl-1,3-butadiene by C-H···O H bond, which weakens the electron-donating capability of methyl and thereby lowers the energy barrier of the D-A reaction. The present results are expected to provide valuable information for the design and application of pyridinium-based ionic liquids. PMID:21671599

  5. Surface structured platinum electrodes for the electrochemical reduction of carbon dioxide in imidazolium based ionic liquids.

    PubMed

    Hanc-Scherer, Florin A; Montiel, Miguel A; Montiel, Vicente; Herrero, Enrique; Sánchez-Sánchez, Carlos M

    2015-10-01

    The direct CO2 electrochemical reduction on model platinum single crystal electrodes Pt(hkl) is studied in [C2mim(+)][NTf2(-)], a suitable room temperature ionic liquid (RTIL) medium due to its moderate viscosity, high CO2 solubility and conductivity. Single crystal electrodes represent the most convenient type of surface structured electrodes for studying the impact of RTIL ion adsorption on relevant electrocatalytic reactions, such as surface sensitive electrochemical CO2 reduction. We propose here based on cyclic voltammetry and in situ electrolysis measurements, for the first time, the formation of a stable adduct [C2mimH-CO2(-)] by a radical-radical coupling after the simultaneous reduction of CO2 and [C2mim(+)]. It means between the CO2 radical anion and the radical formed from the reduction of the cation [C2mim(+)] before forming the corresponding electrogenerated carbene. This is confirmed by the voltammetric study of a model imidazolium-2-carboxylate compound formed following the carbene pathway. The formation of that stable adduct [C2mimH-CO2(-)] blocks CO2 reduction after a single electron transfer and inhibits CO2 and imidazolium dimerization reactions. However, the electrochemical reduction of CO2 under those conditions provokes the electrochemical cathodic degradation of the imidazolium based RTIL. This important limitation in CO2 recycling by direct electrochemical reduction is overcome by adding a strong acid, [H(+)][NTf2(-)], into solution. Then, protons become preferentially adsorbed on the electrode surface by displacing the imidazolium cations and inhibiting their electrochemical reduction. This fact allows the surface sensitive electro-synthesis of HCOOH from CO2 reduction in [C2mim(+)][NTf2(-)], with Pt(110) being the most active electrode studied. PMID:26307480

  6. Automated evaluation of protein binding affinity of anti-inflammatory choline based ionic liquids.

    PubMed

    Ribeiro, Rosa; Pinto, Paula C A G; Azevedo, Ana M O; Bica, Katharina; Ressmann, Anna K; Reis, Salette; Saraiva, M Lúcia M F S

    2016-04-01

    In this work, an automated system for the study of the interaction of drugs with human serum albumin (HSA) was developed. The methodology was based on the quenching of the intrinsic fluorescence of HSA by binding of the drug to one of its binding sites. The fluorescence quenching assay was implemented in a sequential injection analysis (SIA) system and the optimized assay was applied to ionic liquids based on the association of non-steroidal anti-inflammatory drugs with choline (IL-API). In each cycle, 100 µL of HSA and 100 µL of IL-API (variable concentration) were aspirated at a flow rate of 1 mL min(-1) and then sent through the reaction coil to the detector where the fluorescence intensity was measured. In the optimized conditions the effect of increasing concentrations of choline ketoprofenate and choline naproxenate (and respective starting materials: ketoprofen and naproxen) on the intrinsic fluorescence of HSA was studied and the dissociation constants (Kd) were calculated by means of models of drug-protein binding in the equilibrium. The calculated Kd showed that all the compounds bind strongly to HSA (Kd<100 µmol L(-1)) and that the use of the drugs in the IL format does not affect or can even improve their HSA binding. The obtained results were compared with those provided by a conventional batch assay and the relative errors were lower than 4.5%. The developed SIA methodology showed to be robust and exhibited good repeatability in all the assay conditions (rsd<6.5%). PMID:26838377

  7. Determination of fluoroquinolone antibiotics via ionic-liquid-based, salt-induced, dual microextraction in swine feed.

    PubMed

    Wang, Huili; Gao, Ming; Gao, Jiajia; Yu, Nana; Huang, Hong; Yu, Qing; Wang, Xuedong

    2016-09-01

    In conventional microextraction procedures, the disperser (organic solvent or ionic liquid) is left in the aqueous phase and discarded after finishing the microextraction process. Because the disperser is water-soluble, it results in low extraction recovery for polar compounds. In this investigation, an ionic-liquid-based microextraction (ILBME) was integrated with salting-out assisted liquid-liquid microextraction (SALLME) to build an ionic-liquid-based, salt-induced, dual microextraction (ILSDME) for isolation of five fluoroquinolone antibiotics (FQs) with high polarity (log P, -1.0 to 1.0). The proposed ILSDME method incorporates a dual microextraction by converting the disperser in the ILBME to the extractor in the SALLME. Optimization of key factors was conducted by integrating single-factor experiments and central composite design. The optimized experimental parameters were 80 μL [C8MIM][PF6] as extractor, 505 μL acetone as disperser, pH = 2.0, 4.1 min extraction time, and 4.2 g of Na2SO4. Under optimized conditions, high ERs (90.6-103.2 %) and low LODs (0.07-0.61 μg kg(-1)) were determined for five FQs in swine feed. Experimental precision based on RSDs was 1.4-5.2 % for intra-day and 2.4-6.9 % for inter-day analyses. The combination of ILBME with SALLME increased FQ recoveries by 15-20 % as compared with SALLME, demonstrating that the ILSDME method can enhance extraction efficiency for polar compounds compared to single-step microextraction. Therefore, the ILSDME method developed in this study has wide application for pretreatment of moderately to highly polar pollutants in complex matrices. Graphical Abstract A dual microextraction was developed by integrating ionic-liquid-based microextraction with salting-out assisted liquid-liquid microextraction for isolation of five fluoroquinolone antibiotics (FQs) with high polarity (log P = -1.0 to 1.0). The principle of dual microextraction is based on converting the remaining disperser from

  8. One-step immobilization of antibodies for α-1-fetoprotein immunosensor based on dialdehyde cellulose/ionic liquid composite.

    PubMed

    Shen, Guangyu; Zhang, Xiangyang; Shen, Youming; Zhang, Songbai; Fang, Li

    2015-02-15

    A novel immunosensor for α-1-fetoprotein based on dialdehyde cellulose/ionic liquid composite film as a matrix has been developed. Microcrystalline cellulose was activated by sodium metaperiodate to produce dialdehyde cellulose. Antibodies can be immobilized on the electrode by a one-step method through covalent bonding of the aldehyde groups of dialdehyde cellulose with the amino groups of antibodies, in which no additional chemical cross-linking step is required. Moreover, ionic liquid added can improve the conductivity of the sensing interface and, therefore, can enhance the electrochemical signal. In this work, α-1-fetoprotein was detected within the range from 0.1 to 60ngml(-1) with a detection limit of 0.07ngml(-1) (signal/noise=3). The proposed immunosensor had good specificity and reproducibility. It was used to determine real samples with satisfactory results. PMID:25286306

  9. Ionic liquid-based hydrothermal synthesis of Lu2O3 and Lu2O3:Eu3+ microcrysals

    NASA Astrophysics Data System (ADS)

    Li, Yinyan; Xu, Shiqing

    2016-09-01

    Uniform and well-defined Lu2O3 and Lu2O3:Eu3+ microarchitectures have been successfully synthesized via a green and facile ionic liquid-based hydrothermal method followed by a subsequent calcination process. Novel 3D micro-rodbundles and 1D microrods of Lu2O3 and Lu2O3:Eu3+ were controllably obtained through this method. X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and photoluminescence spectra were used to characterize the micromaterials. The proposed formation mechanisms have been investigated on the basis of a series of SEM studies of the products obtained at different hydrothermal durations. The results indicated that hydrothermal temperature and the ionic liquid-tetrabutylammonium hydroxide were two key factors for the formation as well as the morphology control of the Lu2O3 and Lu2O3:Eu3+ microarchitectures.

  10. Ionic Liquids and Ionizing Radiation: Reactivity of Highly Energetic Species

    SciTech Connect

    Wishart, J.F.

    2010-11-04

    Due to their unique properties, ionic liquids present many opportunities for basic research on the interactions of radiation with materials under conditions not previously available. At the same time, there are practical applied reasons for characterizing, understanding, and being able to predict how ionic-liquid-based devices and industrial-scale systems will perform under conditions of extreme reactivity, including radiation. This perspective discusses current issues in ionic liquid physical chemistry, provides a brief introduction to radiation chemistry, draws attention to some key findings in ionic liquid radiation chemistry, and identifies some current hot topics and new opportunities.

  11. Highly luminescent and color-tunable salicylate ionic liquids

    DOE PAGESBeta

    Campbell, Paul S.; Yang, Mei; Pitz, Demian; Cybinska, Joanna; Mudring, Anja -Verena

    2014-03-11

    High quantum yields of up to 40.5 % can be achieved in salicylate-bearing ionic liquids. A range of these ionic liquids have been synthesized and their photoluminescent properties studied in detail. The differences noted can be related back to the structure of the ionic liquid cation and possible interionic interactions. It is found that shifts of emission, particularly in the pyridinium-based ionic liquids, can be related to cation–anion pairing interactions. Furthermore, facile and controlled emission color mixing is demonstrated through combining different ILs, with emission colors ranging from blue to yellow.

  12. Highly luminescent and color-tunable salicylate ionic liquids.

    PubMed

    Campbell, Paul S; Yang, Mei; Pitz, Demian; Cybinska, Joanna; Mudring, Anja-Verena

    2014-04-14

    High quantum yields of up to 40.5% can be achieved in salicylate-bearing ionic liquids. A range of these ionic liquids have been synthesized and their photoluminescent properties studied in detail. The differences noted can be related back to the structure of the ionic liquid cation and possible interionic interactions. It is found that shifts of emission, particularly in the pyridinium-based ionic liquids, can be related to cation-anion pairing interactions. Facile and controlled emission color mixing is demonstrated through combining different ILs, with emission colors ranging from blue to yellow. PMID:24615781

  13. Simultaneous multicomponent spectrophotometric monitoring of methyl and propyl parabens using multivariate statistical methods after their preconcentration by robust ionic liquid-based dispersive liquid-liquid microextraction

    NASA Astrophysics Data System (ADS)

    Khani, Rouhollah; Ghasemi, Jahan B.; Shemirani, Farzaneh

    2014-03-01

    A powerful and efficient signal-preprocessing technique that combines local and multiscale properties of the wavelet prism with the global filtering capability of orthogonal signal correction (OSC) is applied for pretreatment of spectroscopic data of parabens as model compounds after their preconcentration by robust ionic liquid-based dispersive liquid-liquid microextraction method (IL-DLLME). In the proposed technique, a mixture of a water-immiscible ionic liquid (as extraction solvent) [Hmim][PF6] and disperser solvent is injected into an aqueous sample solution containing one of the IL's ions, NaPF6, as extraction solvent and common ion source. After preconcentration, the absorbance of the extracted compounds was measured in the wavelength range of 200-700 nm. The wavelet orthogonal signal correction with partial least squares (WOSC-PLS) method was then applied for simultaneous determination of each individual compound. Effective parameters, such as amount of IL, volume of the disperser solvent and amount of NaPF6, were inspected by central composite design to identify the most important parameters and their interactions. The effect of pH on the sensitivity and selectivity was studied according to the net analyte signal (NAS) for each component. Under optimum conditions, enrichment factors of the studied compounds were 75 for methyl paraben (MP) and 71 for propyl paraben (PP). Limits of detection for MP and PP were 4.2 and 4.8 ng mL-1, respectively. The root mean square errors of prediction for MP and PP were 0.1046 and 0.1275 μg mL-1, respectively. The practical applicability of the developed method was examined using hygienic, cosmetic, pharmaceutical and natural water samples.

  14. Simultaneous multicomponent spectrophotometric monitoring of methyl and propyl parabens using multivariate statistical methods after their preconcentration by robust ionic liquid-based dispersive liquid-liquid microextraction.

    PubMed

    Khani, Rouhollah; Ghasemi, Jahan B; Shemirani, Farzaneh

    2014-03-25

    A powerful and efficient signal-preprocessing technique that combines local and multiscale properties of the wavelet prism with the global filtering capability of orthogonal signal correction (OSC) is applied for pretreatment of spectroscopic data of parabens as model compounds after their preconcentration by robust ionic liquid-based dispersive liquid-liquid microextraction method (IL-DLLME). In the proposed technique, a mixture of a water-immiscible ionic liquid (as extraction solvent) [Hmim][PF6] and disperser solvent is injected into an aqueous sample solution containing one of the IL's ions, NaPF6, as extraction solvent and common ion source. After preconcentration, the absorbance of the extracted compounds was measured in the wavelength range of 200-700 nm. The wavelet orthogonal signal correction with partial least squares (WOSC-PLS) method was then applied for simultaneous determination of each individual compound. Effective parameters, such as amount of IL, volume of the disperser solvent and amount of NaPF6, were inspected by central composite design to identify the most important parameters and their interactions. The effect of pH on the sensitivity and selectivity was studied according to the net analyte signal (NAS) for each component. Under optimum conditions, enrichment factors of the studied compounds were 75 for methyl paraben (MP) and 71 for propyl paraben (PP). Limits of detection for MP and PP were 4.2 and 4.8 ng mL(-)(1), respectively. The root mean square errors of prediction for MP and PP were 0.1046 and 0.1275 μg mL(-)(1), respectively. The practical applicability of the developed method was examined using hygienic, cosmetic, pharmaceutical and natural water samples. PMID:24317257

  15. Molecular thermodynamic modeling of ionic liquids using the perturbation-based linear Yukawa isotherm regularity.

    PubMed

    Sohrabi Mahboub, Mahdi; Farrokhpour, Hossein

    2016-06-15

    In this paper, we present the results of an extensive study on a novel approach to the molecular modeling of pure ionic liquids (ILs) that incorporates the perturbed thermodynamic linear Yukawa isotherm regularity (LYIR), which is derived based on an effective nearest neighboring pair attractive interaction of the Yukawa potential. The LYIR was used to model the densities of ILs up to high pressures (35 MPa) and in the temperature range 293.15 to 393.15 K. To use the LYIR for ILs, a simple molecular model was proposed to describe their molecular structure, in which they were considered as a liquid consisting of the ion pairs moving together in the fluid, and each ion pair was assumed to be a one-center spherical united atom. The ILs under consideration contained one of the IL cations [C2mim](+), [C4mim](+), [C7mim](+), [C8mim](+), [C3mpy](+), [C3mpip](+), [C3mpyr](+) or [C4mpyr](+), and one of the IL anions [BF4](-), [C(CN)3](-), [CF3SO4](-) or [NTf2](-). The reliability and physical significance of the parameters as well as the proposed molecular model were tested by calculating the densities of pure imidazolium-, pyridinium-, piperidinium- and pyrrolidimium-based ILs. The results showed that the LYIR can be used to predict and reproduce the density of ILs in good agreement with the experimental data. In addition, the LYIR enabled us to determine the physical quantities, such as an effective Yukawa screening length, λ eff, the product of the effective energy well depth and the effective coordination number, (ε eff/k)z eff, the contribution of the non-reference thermal pressure and also the influence of the anionic and cationic structure on the λ eff parameter. The standard deviation of the IL densities predicted in this work is lower than those calculated by the one other important equation of state reported in the literature. PMID:27157142

  16. Molecular thermodynamic modeling of ionic liquids using the perturbation-based linear Yukawa isotherm regularity

    NASA Astrophysics Data System (ADS)

    Sohrabi Mahboub, Mahdi; Farrokhpour, Hossein

    2016-06-01

    In this paper, we present the results of an extensive study on a novel approach to the molecular modeling of pure ionic liquids (ILs) that incorporates the perturbed thermodynamic linear Yukawa isotherm regularity (LYIR), which is derived based on an effective nearest neighboring pair attractive interaction of the Yukawa potential. The LYIR was used to model the densities of ILs up to high pressures (35 MPa) and in the temperature range 293.15 to 393.15 K. To use the LYIR for ILs, a simple molecular model was proposed to describe their molecular structure, in which they were considered as a liquid consisting of the ion pairs moving together in the fluid, and each ion pair was assumed to be a one-center spherical united atom. The ILs under consideration contained one of the IL cations [C2mim]+, [C4mim]+, [C7mim]+, [C8mim]+, [C3mpy]+, [C3mpip]+, [C3mpyr]+ or [C4mpyr]+, and one of the IL anions [BF4]‑, [C(CN)3]‑, [CF3SO4]‑ or [NTf2]‑. The reliability and physical significance of the parameters as well as the proposed molecular model were tested by calculating the densities of pure imidazolium-, pyridinium-, piperidinium- and pyrrolidimium-based ILs. The results showed that the LYIR can be used to predict and reproduce the density of ILs in good agreement with the experimental data. In addition, the LYIR enabled us to determine the physical quantities, such as an effective Yukawa screening length, λ eff, the product of the effective energy well depth and the effective coordination number, (ε eff/k)z eff, the contribution of the non-reference thermal pressure and also the influence of the anionic and cationic structure on the λ eff parameter. The standard deviation of the IL densities predicted in this work is lower than those calculated by the one other important equation of state reported in the literature.

  17. Confined water in imidazolium based ionic liquids: a supramolecular guest@host complex case.

    PubMed

    Zanatta, Marcileia; Girard, Anne-Lise; Marin, Graciane; Ebeling, Gunter; Dos Santos, Francisco P; Valsecchi, Chiara; Stassen, Hubert; Livotto, Paolo R; Lewis, William; Dupont, Jairton

    2016-07-21

    It is well known that the macroscopic physico-chemical properties of ionic liquids (ILs) are influenced by the presence of water that strongly interferes with the supramolecular organization of these fluids. However, little is known about the function of water traces within this confined space and restricted ionic environments, i.e. between cations and anions. Using specially designed ILs namely 1,2,3-trimethyl-1H-imidazol-3-ium imidazol-1-ide (MMMI·Im) and 3-n-butyl-1,2-dimethyl-1H-imidazol-3-ium imidazol-1-ide (BMMI·Im), the structure and function of water have been determined in condensed, solution and gas phases by X-ray diffraction studies, NMR, molecular dynamics simulations (MDS) and DFT calculations. In the solid state the water molecule is trapped inside the ionic network (constituted of contact ion pairs formed by π(+)-π(-) interaction) through strong H-bonds involving the water hydrogens and the nitrogens of two imidazolate anions forming a guest@host supramolecular structure. A similar structural arrangement was corroborated by DFT calculations and MDS. The presence of a guest@host species (H2O@ILpair) is maintained to a great extent even in solution as detected by (1)H-(1)H NOESY-experiments of the ILs dissolved in solvents with low and high dielectric constants. This confined water catalyses the H/D exchange with other substrates containing acidic-H such as chloroform. PMID:27334927

  18. VOC and HAP recovery using ionic liquids

    SciTech Connect

    Michael R. Milota : Kaichang Li

    2007-05-29

    During the manufacture of wood composites, paper, and to a lesser extent, lumber, large amounts of volatile organic compounds (VOCs) such as terpenes, formaldehyde, and methanol are emitted to air. Some of these compounds are hazardous air pollutants (HAPs). The air pollutants produced in the forest products industry are difficult to manage because the concentrations are very low. Presently, regenerative thermal oxidizers (RTOs and RCOs) are commonly used for the destruction of VOCs and HAPs. RTOs consume large amounts of natural gas to heat air and moisture. The combustion of natural gas generates increased CO2 and NOx, which have negative implications for global warming and air quality. The aforementioned problems are addressed by an absorption system containing a room-temperature ionic liquid (RTIL) as an absorbent. RTILs are salts, but are in liquid states at room temperature. RTILs, an emerging technology, are receiving much attention as replacements for organic solvents in industrial processes with significant cost and environmental benefits. Some of these processes include organic synthesis, extraction, and metal deposition. RTILs would be excellent absorbents for exhausts from wood products facilities because of their unique properties: no measurable vapor pressure, high solubility of wide range of organic compounds, thermal stability to 200°C (almost 400°F), and immisciblity with water. Room temperature ionic liquids were tested as possible absorbents. Four were imidizolium-based and were eight phosphonium-based. The imidizolium-based ionic liquids proved to be unstable at the conditions tested and in the presence of water. The phosphonium-based ionic liquids were stable. Most were good absorbents; however, cleaning the contaminates from the ionic liquids was problematic. This was overcome with a higher temperature (120°C) than originally proposed and a very low pressure (1 kPa. Absorption trials were conducted with tetradecy

  19. Speciation analysis of mercury in sediments using ionic-liquid-based vortex-assisted liquid-liquid microextraction combined with high-performance liquid chromatography and cold vapor atomic fluorescence spectrometry.

    PubMed

    Leng, Geng; Chen, Wenjin; Wang, Yong

    2015-08-01

    An improved novel method based on ionic liquid vortex-assisted liquid-liquid microextraction has been developed for the extraction of methylmercury, ethylmercury and inorganic mercury in sediment samples prior to analysis by high-performance liquid chromatography with cold vapor atomic fluorescence spectrometry. In this work, mercury species were firstly complexed with dithizone, and the complexes were extracted into 1-hexyl-3-methylimidazolium hexafluorophosphate. Key factors that affect the extraction efficiency of mercury species, such as type and amount of ionic liquid and chelatants, extraction time, sample pH, salt effect and matrix effect were investigated. Under the optimum conditions, linearity was found in the concentration range from 0.1-70 ng/g. Limits of detection ranged from 0.037-0.061 ng/g. Reproducibility and recoveries were assessed by extracting a series of six independent sediment samples that were spiked with different concentration levels. Finally, the proposed method was successfully applied in analysis of real sediment samples. In this work, ionic liquids vortex-assisted liquid-liquid microextraction was for the first time used for the extraction of mercury species in sediment samples. The proposed method was proved to be much simpler and more rapid, as well as more environmentally friendly and efficient compared with the previous methods. PMID:25998155

  20. Thermophysical properties of aqueous solution of ammonium-based ionic liquids.

    PubMed

    Umapathi, Reddicherla; Attri, Pankaj; Venkatesu, Pannuru

    2014-06-01

    Experimental densities (ρ), ultrasonic sound velocities (u), viscosities (η), and refractive indices (n(D)) of binary mixtures of ammonium-based ionic liquids (ILs) such as diethylammonium acetate (DEAA) [(CH3CH2)2NH][CH3COO], triethylammonium acetate (TEAA) [(CH3CH2)3NH][CH3COO], diethylammonium hydrogen sulfate (DEAS) [(CH3CH2)2NH][HSO4], triethylammonium hydrogen sulfate (TEAS) [(CH3CH2)3NH][HSO4], trimethylammonium acetate (TMAA) [(CH3)3NH][CH3COO], and trimethylammonium hydrogen sulfate (TMAS) [(CH3)3NH][HSO4] with water are reported over the wide composition range at 25 °C under atmospheric pressure. The excess molar volumes (V(E)), deviation in isentropic compressibilities (Δκ(s)), deviation in viscosities (Δη) and deviation in refractive indices (Δn(D)) are calculated from experimental values and are correlated by Redlich-Kister polynomial equations. The V(E) and Δκ(s) values for the aforesaid systems are negative over the entire composition range while the Δη and Δn(D) values are positive under the same experimental conditions. The intermolecular interactions and structural effects were analyzed on the basis of measured and derived properties. A qualitative analysis of the results is discussed in terms of the ion-dipole, ion-pair interactions and hydrogen bonding between ILs and water. Furthermore, the hydrogen bonding features between ILs with water were analyzed by using a molecular modeling program with the help of HyperChem7. PMID:24830564

  1. Evaluation of interaction between imidazolium-based chloride ionic liquids and calf thymus DNA.

    PubMed

    Liu, Huijun; Dong, Ying; Wu, Jian; Chen, Caidong; Liu, Dingdong; Zhang, Qi; Du, Shaoting

    2016-10-01

    With ionic liquids (ILs) being widely used, the toxicity of many ILs has been studied and verified. However the mechanism underlying the interaction between ILs and DNA needs to be investigated. In this study, the interaction of three imidazolium-based ILs ([C8mim]Cl, [C12mim]Cl, and [C16mim]Cl) with calf thymus DNA (ctDNA) was investigated by UV absorption spectroscopy and fluorescence spectroscopy. An intense interaction between [Cnmim]Cl and ctDNA was observed, involving a hypochromic effect or even a hyperchromic effect, in the UV absorption spectrum of ctDNA at 260nm. The Tm of ctDNA increased over 10°C after binding with [Cnmim]Cl, and the KSV values of [Cnmim]Cl-ctDNA quenched by potassium iodide (KI) were lower than those of [Cnmim]Cl. The fluorescence intensity of ctDNA-ethidium bromide (EB) was gradually quenched as the [Cnmim]Cl concentration increased. The results indicated that ctDNA interacted with [Cnmim]Cl through an intercalation binding mode. The mechanism of fluorescence quenching of [Cnmim]Cl with ctDNA involved static quenching. The binding constant between [Cnmim]Cl and ctDNA were 1443, 11169, and 67189, and the number of binding sites were 0.89, 1.10, and 1.27 at 298K, for [C8mim]Cl, [C12mim]Cl, and [C16mim]Cl, respectively. The results indicated that the intercalation binding between the three [Cnmim]Cl and ctDNA increased with increasing IL-alkyl chain length. These results will aid in the understanding of the mechanism of toxicity and of the biologically mediated environmental processes of ILs. PMID:27203596

  2. Application of Ionic Liquids in Hydrometallurgy

    PubMed Central

    Park, Jesik; Jung, Yeojin; Kusumah, Priyandi; Lee, Jinyoung; Kwon, Kyungjung; Lee, Churl Kyoung

    2014-01-01

    Ionic liquids, low temperature molten salts, have various advantages manifesting themselves as durable and environmentally friendly solvents. Their application is expanding into various fields including hydrometallurgy due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, and wide electrochemical potential window. This paper reviews previous literatures and our recent results adopting ionic liquids in extraction, synthesis and processing of metals with an emphasis on the electrolysis of active/light, rare earth, and platinum group metals. Because the research and development of ionic liquids in this area are still emerging, various, more fundamental approaches are expected to popularize ionic liquids in the metal manufacturing industry. PMID:25177864

  3. Application of ionic liquids in hydrometallurgy.

    PubMed

    Park, Jesik; Jung, Yeojin; Kusumah, Priyandi; Lee, Jinyoung; Kwon, Kyungjung; Lee, Churl Kyoung

    2014-01-01

    Ionic liquids, low temperature molten salts, have various advantages manifesting themselves as durable and environmentally friendly solvents. Their application is expanding into various fields including hydrometallurgy due to their unique properties such as non-volatility, inflammability, low toxicity, good ionic conductivity, and wide electrochemical potential window. This paper reviews previous literatures and our recent results adopting ionic liquids in extraction, synthesis and processing of metals with an emphasis on the electrolysis of active/light, rare earth, and platinum group metals. Because the research and development of ionic liquids in this area are still emerging, various, more fundamental approaches are expected to popularize ionic liquids in the metal manufacturing industry. PMID:25177864

  4. Interactions in ion pairs of protic ionic liquids: Comparison with aprotic ionic liquids

    SciTech Connect

    Tsuzuki, Seiji; Shinoda, Wataru; Miran, Md. Shah; Kinoshita, Hiroshi; Yasuda, Tomohiro; Watanabe, Masayoshi

    2013-11-07

    The stabilization energies for the formation (E{sub form}) of 11 ion pairs of protic and aprotic ionic liquids were studied by MP2/6-311G{sup **} level ab initio calculations to elucidate the difference between the interactions of ions in protic ionic liquids and those in aprotic ionic liquids. The interactions in the ion pairs of protic ionic liquids (diethylmethylammonium [dema] and dimethylpropylammonium [dmpa] based ionic liquids) are stronger than those of aprotic ionic liquids (ethyltrimethylammonium [etma] based ionic liquids). The E{sub form} for the [dema][CF{sub 3}SO{sub 3}] and [dmpa][CF{sub 3}SO{sub 3}] complexes (−95.6 and −96.4 kcal/mol, respectively) are significantly larger (more negative) than that for the [etma][CF{sub 3}SO{sub 3}] complex (−81.0 kcal/mol). The same trend was observed for the calculations of ion pairs of the three cations with the Cl{sup −}, BF{sub 4}{sup −}, TFSA{sup −} anions. The anion has contact with the N–H bond of the dema{sup +} or dmpa{sup +} cations in the most stable geometries of the dema{sup +} and dmpa{sup +} complexes. The optimized geometries, in which the anions locate on the counter side of the cations, are 11.0–18.0 kcal/mol less stable, which shows that the interactions in the ions pairs of protic ionic liquids have strong directionality. The E{sub form} for the less stable geometries for the dema{sup +} and dmpa{sup +} complexes are close to those for the most stable etma{sup +} complexes. The electrostatic interaction, which is the major source of the attraction in the ion pairs, is responsible for the directionality of the interactions and determining the magnitude of the interaction energy. Molecular dynamic simulations of the [dema][TFSA] and [dmpa][TFSA] ionic liquids show that the N–H bonds of the cations have contact with the negatively charged (oxygen and nitrogen) atoms of TFSA{sup −} anion, while the strong directionality of the interactions was not suggested from the simulation

  5. Aprotic Heterocyclic Anion Triazolide Ionic Liquids - A New Class of Ionic Liquid Anion Accessed by the Huisgen Cycloaddition Reaction

    SciTech Connect

    Thompson, Robert L; Damodaran, Krishnan; Luebke, David; Nulwala, Hunaid

    2013-06-01

    The triazole core is a highly versatile heterocyclic ring which can be accessed easily with the Cu(I)-catalyzed Huisgen cycloaddition reaction. Herein we present the preparation of ionic liquids that incorporate a 1,2,3-triazolide anion. These ionic liquids were prepared by a facile procedure utilizing a base-labile pivaloylmethyl group at the 1-position, which can act as precursors to 1H- 4-substituted 1,2,3-triazole. These triazoles were then subsequently converted into ionic liquids after deprotonation using an appropriate ionic liquid cation hydroxide. The densities and thermal decompositions of these ionic liquids were measured. These novel ionic liquids have potential applications in gas separations and in metal-free catalysis.

  6. Spectral and physicochemical characterization of dysprosium-based multifunctional ionic liquid crystals.

    PubMed

    Lu, Chengfei; Das, Susmita; Siraj, Noureen; Magut, Paul K S; Li, Min; Warner, Isiah M

    2015-05-21

    We report on the synthesis and characterization of multifunctional ionic liquid crystals (melting points below 100 °C) which possess chirality and fluorescent behavior as well as mesomorphic and magnetic properties. In this regard, (1R,2S)-(-)-N-methylephedrine ((-)MeEph), containing a chiral center, is linked with variable alkyl chain lengths (e.g., 14, 16, and 18 carbons) to yield liquid crystalline properties in the cations of these compounds. A complex counteranion consisting of trivalent dysprosium (Dy(3+)) and thiocyanate ligand (SCN(-)) is employed, where Dy(3+) provides fluorescent and magnetic properties. Examination of differential scanning calorimetry (DSC) and hot-stage polarizing optical microscopy (POM) data confirmed liquid crystalline characteristics in these materials. We further report on phase transitions from solid to liquid crystal states, followed by isotropic liquid states with increasing temperature. These compounds exhibited two characteristic emission peaks in acetonitrile solution and the solid state when excited at λex = 366 nm, which are attributed to transitions from (4)F9/2 to (6)H15/2 and (4)F9/2 to (6)H13/2. The emission intensities of these compounds were found to be very sensitive to the phase. PMID:25901534

  7. Dielectric relaxations of polyether-based polyurethanes containing ionic liquids as antistatic agents.

    PubMed

    Tsurumaki, Akiko; Bertasi, Federico; Vezzù, Keti; Negro, Enrico; Di Noto, Vito; Ohno, Hiroyuki

    2016-01-28

    Dielectric properties of polyurethanes containing poly(propylene oxide) (PO) and poly(ethylene oxide) (EO) units are discussed, along with the results of direct current (DC) measurements and broadband electrical spectroscopy (BES) studies. The dielectric properties of polyether-containing polyurethanes (PUs) are compared to those of PUs containing 1000 ppm of ionic liquids (ILs) as antistatic agents. The effects of the chemical environment of these ILs, including anion-fixed polymers (PU-AF), cation-fixed polymers (PU-CF), and a simple mixture of IL with the PUs (PU-IL), are compared and discussed on the basis of ion mobility. DC measurements suggest that the charge current is attributed not only to the electrode polarization but also to continuous dielectric relaxation. BES studies elucidate that both fast and slow relaxations are taking place in EO-rich domains in pristine PU and PU-AF. The activation energies of the slow relaxation and of the ionic conductivity are similar, suggesting that the ionic conductivity of these materials is attributed to the ion exchange reaction in EO/ion complexes. In contrast, only fast relaxations are observed in the domains mostly comprised of ion-depleted EO in the PUs containing "free" anions, i.e., PU-CF and PU-IL. This suggests that [Tf2N](-) ligands are weakly interacting with the EO chains and contribute effectively to the ion conduction. Thus, enhanced ionic conductivity is observed in PU-CF and PU-IL, yielding sufficient antistatic effects. Taking into account its long shelf life, arising from the lack of IL bleed-out, PU-CF is concluded to be the most promising candidate. PMID:26700822

  8. Layering of [BMIM]+-based ionic liquids at a charged sapphire interface

    NASA Astrophysics Data System (ADS)

    Mezger, Markus; Schramm, Sebastian; Schröder, Heiko; Reichert, Harald; Deutsch, Moshe; De Souza, Emerson J.; Okasinski, John S.; Ocko, Benjamin M.; Honkimäki, Veijo; Dosch, Helmut

    2009-09-01

    The structure of two model room temperature ionic liquids, [BMIM]+[PF6]- and [BMIM]+[BF4]-, near the solid/liquid interface with charged Al2O3(0001) (sapphire) was determined with subnanometer resolution by high energy (72.5 keV) x-ray reflectivity. [BMIM]+[PF6]- exhibits alternately charged, exponentially decaying, near-surface layering. By contrast, the smaller-anion compound, [BMIM]+[BF4]-, shows only a single layer of enhanced electron density at the interface. The different layering behaviors, and their characteristic length scales, correspond well to the different bulk diffraction patterns, also measured in this study. Complementary measurements of the surface and interface energies showed no significant different between the two RTILs. The combined bulk-interface results support the conclusion that the interfacial ordering is dominated by the same electrostatic ion-ion interactions dominating the bulk correlations, with hydrogen bonding and dispersion interactions playing only a minor role.

  9. [Determination of five triazine herbicides in infant milk powder by high performance liquid chromatography coupled with ionic liquid-based homogeneous liquid-liquid microextraction].

    PubMed

    Zhang, Liyuan; Yao, Di; Li, Na; Zhang, Hanqi; Yu, Aimin

    2015-07-01

    A high performance liquid chromatography coupled with homogeneous liquid-liquid microextraction was developed for the determination of five triazine herbicides in infant milk powders. The ionic liquid was used as microextraction solvent. The separation of the herbicides was performed on an Eclipse XDB-C18 column using acetonitrile and water as mobile phases in gradient mode. The effects of homogeneous liquid-liquid extraction conditions on the experimental results were investigated in detail. Under the optimized experimental conditions, the calibration curves for determining the analytes were linear and the correlation coefficients were ≥ 0.9992. The limits of detection for cyanazine, desmetryn, terbumeton, terbuthylazine and dimethametryn were 12.1, 13.8, 11.8, 14.6 and 13.7 μg/kg, respectively. The recoveries of the analytes spiked in four infant milk powders ranged from 92.2% to 103.2% and the relative standard deviations were lower than 6%. This method is sensitive, simple, and suitable for the determination of triazine herbicides in milk powder samples. PMID:26672205

  10. Label-free amperometric immunobiosensor based on a gold colloid and Prussian blue nanocomposite film modified carbon ionic liquid electrode.

    PubMed

    Huang, Ke-Jing; Niu, De-Jun; Sun, Jun-Yong; Zhu, Xiao-Li; Zhu, Jun-Jie

    2010-08-01

    A novel experimental methodology based on a Prussian blue (PB) and gold nanoparticles (AuNPs) modified carbon ionic liquid electrode (CILE) was developed for use in a label-free amperometric immunosensor for the sensitive detection of human immunoglobulin G (HIgG) as a model protein. The CILE was fabricated by using the ionic liquid 1-octyl-3-methylimidazolium hexafluorophosphate as binder. Controllable electrodeposition of PB on the surface of the CILE and coating with 3-aminopropyl triethylene silane (APS) formed a film with high electronic catalytic activity and large surface area for the assembly of AuNPs and further immobilization of HIgG antibody. The electrochemistry of the formed nanocomposite biofilm was investigated by electrochemical techniques including cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy. The HIgG concentration was measured through the decrease of amperometric responses in the corresponding specific binding of antigen and antibody. The decreased differential pulse voltammetric values were proportional to the HIgG concentration in two ranges, 0.05-1.25 ng mL(-1) and 1.25-40 ng mL(-1), with a detection limit of 0.001 ng mL(-1) (S/N = 3). This electrochemical immunoassay combined the specificity of the immunological reaction with the sensitivity of the AuNPs, ionic liquid, and PB amplified electrochemical detection and would therefore be valuable for clinical immunoassays. PMID:20577722

  11. Stability and magnetorheological behaviour of magnetic fluids based on ionic liquids

    NASA Astrophysics Data System (ADS)

    Rodríguez-Arco, Laura; López-López, Modesto T.; Durán, Juan D. G.; Zubarev, Andrey; Chirikov, Dmitrij

    2011-11-01

    This paper reports the preparation of magnetic fluids consisting of magnetite nanoparticles dispersed in an ionic liquid. Different additives were used in order to stabilize the fluids. Colloidal stability was checked by magnetic sedimentation, centrifugation and direct observation. The results of these tests showed that a true ferrofluid was only obtained when the nanoparticles were coated with a layer of surfactant compatible with the ionic liquid. These experiments also showed that stability could not be reached just by electrostatic repulsion. The conclusions of the stability tests were confirmed by calculations of the interparticle energies of interaction. The rheological behaviour of the magnetic fluids upon magnetic field application was also investigated. The experimental magnetoviscous response was fitted by a microstructural model. The model considered that the fluids consisted of two populations of particles, one with a magnetic core diameter of 9 nm, and another with a larger diameter. Upon field application chain-like structures are supposed to be induced. According to estimations particles of 9 nm are too small to aggregate upon field application. The results of the calculations showed that the intensity of the magnetoviscous response depends on the concentration and size of the large particles, and on the thickness of the surfactant layers.

  12. Stability and magnetorheological behaviour of magnetic fluids based on ionic liquids.

    PubMed

    Rodríguez-Arco, Laura; López-López, Modesto T; Durán, Juan D G; Zubarev, Andrey; Chirikov, Dmitrij

    2011-11-16

    This paper reports the preparation of magnetic fluids consisting of magnetite nanoparticles dispersed in an ionic liquid. Different additives were used in order to stabilize the fluids. Colloidal stability was checked by magnetic sedimentation, centrifugation and direct observation. The results of these tests showed that a true ferrofluid was only obtained when the nanoparticles were coated with a layer of surfactant compatible with the ionic liquid. These experiments also showed that stability could not be reached just by electrostatic repulsion. The conclusions of the stability tests were confirmed by calculations of the interparticle energies of interaction. The rheological behaviour of the magnetic fluids upon magnetic field application was also investigated. The experimental magnetoviscous response was fitted by a microstructural model. The model considered that the fluids consisted of two populations of particles, one with a magnetic core diameter of 9 nm, and another with a larger diameter. Upon field application chain-like structures are supposed to be induced. According to estimations particles of 9 nm are too small to aggregate upon field application. The results of the calculations showed that the intensity of the magnetoviscous response depends on the concentration and size of the large particles, and on the thickness of the surfactant layers. PMID:21971064

  13. Full-color tunable photoluminescent ionic liquid crystals based on tripodal pyridinium, pyrimidinium, and quinolinium salts.

    PubMed

    Tanabe, Kana; Suzui, Yuko; Hasegawa, Miki; Kato, Takashi

    2012-03-28

    Color-tunable luminescent ionic liquid crystals have been designed as a new series of luminescent materials. To achieve tuning of emission colors, intramolecular charge transfer (ICT) character has been incorporated into tripodal molecules. A series of the compounds has three chromophores in each molecule, incorporated with both electron-donating moieties such as alkylaminobenzene and alkoxybenzene, and electron-accepting moieties such as pyridinium, pyrimidinium, and quinolinium parts. These C(3)-symmetrical molecules self-assemble into liquid-crystalline (LC) columnar (Col) structures over wide temperature ranges through nanosegregation between ionic moieties and nonionic aliphatic chains. Photoluminescent (PL) emissions of these tripodal molecules are observed in the visible region both in the self-assembled condensed states and in solutions. For example, a pyrimidinium salt with didodecylaminobenzene moieties exhibits yellowish orange emission (λ(em) = 586 nm in a thin film). Multicolor PL emissions are successfully achieved by simple tuning of changing electron-donating and electron-accepting moieties of the compounds, covering the visible region from blue-green to red. It has been revealed that ICT processes in the excited states and weak intermolecular interactions play important roles in the determination of the PL properties of the materials, by measurements of UV-vis absorption and emission spectra, fluorescence lifetimes, and PL quantum yields. PMID:22372372

  14. Radiation Chemistry and Photochemistry of Ionic Liquids

    SciTech Connect

    Wishart, J.F.; Takahaski, K.

    2010-12-01

    As our understanding of ionic liquids and their tunable properties has grown, it is possible to see many opportunities for ionic liquids to contribute to the sustainable use of energy. The potential safety and environmental benefits of ionic liquids, as compared to conventional solvents, have attracted interest in their use as processing media for the nuclear fuel cycle. Therefore, an understanding of the interactions of ionizing radiation and photons with ionic liquids is strongly needed. However, the radiation chemistry of ionic liquids is still a relatively unexplored topic although there has been a significant increase in the number of researchers in the field recently. This article provides a brief introduction to ionic liquids and their interesting properties, and recent advances in the radiation chemistry and photochemistry of ionic liquids. In this article, we will mainly focus on excess electron dynamics and radical reaction dynamics. Because solvation dynamics processes in ionic liquids are much slower than in molecular solvents, one of the distinguishing characteristics is that pre-solvated electrons play an important role in ionic liquid radiolysis. It will be also shown that the reaction dynamics of radical ions is significantly different from that observed in molecular solvents because of the Coulombic screening effects and electrostatic interactions in ionic liquids.

  15. Ionic liquids as surfactants in micellar liquid chromatography.

    PubMed

    Flieger, Jolanta; Siwek, Agata; Pizoń, Magdalena; Czajkowska-Żelazko, Anna

    2013-05-01

    This paper is devoted to application of ionic liquids as surfactants in LC of organic compounds, derivatives of 1,4-thiosemicarbazides. According to HPLC requirements the most advantageous conditions such as transparency for ultraviolet light, low CMC, additional inorganic salt additives, and appropriate organic solvent were established. The CMC was determined using conductivity measurements. Suitability of two different stationary phases: RP-C18 and cyanopropyl bonded phase was examined under micellar conditions. Chosen ionic liquid surfactant was compared to common traditional amphiphilic reagent - SDS. Elaborated on chromatographic micellar conditions were tested as a pilot technique for prediction of distribution coefficients of organic analytes in ionic liquid-based aqueous two-phase system. PMID:23609988

  16. Electrochemical Deposition of Niobium onto the Surface of Copper Using a Novel Choline Chloride-Based Ionic Liquid

    SciTech Connect

    Wixtroma, Alex I.; Buhlera, Jessica E.; Reece, Charles E.; Abdel-Fattah, Tarek M.

    2013-06-01

    Recent research has shown that choline chloride-based solutions can be used to replace acid-based electrochemical polishing solutions. In this study niobium metal was successfully deposited on the surface of copper substrate via electrochemical deposition using a novel choline chloride-based ionic liquid. The niobium metal used for deposition on the Cu had been dissolved in the solution from electrochemical polishing of a solid niobium piece prior to the deposition. The visible coating on the surface of the Cu was analyzed using scanning electron microscopy (SEM) and electron dispersive x-ray spectroscopy (EDX). This deposition method effectively recycles previously dissolved niobium from electrochemical polishing.

  17. Determination of solute partition behavior with room-temperature ionic liquid based micellar gas-liquid chromatography stationary phases using the pseudophase model.

    PubMed

    Lantz, Andrew W; Pino, Verónica; Anderson, Jared L; Armstrong, Daniel W

    2006-05-19

    The use of micelles in ionic liquid based gas-chromatography stationary phases was evaluated using equations derived for a "three-phase" model. This model allows the determination of all three partition coefficients involved in the system, and elucidates the micellar contribution to retention and selectivity. Four types of micellar-ionic liquid columns were examined in this study: 1-butyl-3-methylimidazolium chloride with sodium dodecylsulfate or dioctyl sulfosuccinate, and 1-butyl-3-methylimidazolium hexafluorophosphate with polyoxyethylene-100-stearyl ether or polyoxyethylene-23-lauryl ether. The partition coefficients were measured for a wide range of probe molecules capable of a variety of types and magnitudes of interactions. In general, most probe molecules preferentially partitioned to the micellar pseudophase over the bulk ionic liquid component of the stationary phase. Therefore, addition of surfactant to the stationary phase usually resulted in greater solute retention. It is also shown that the selectivity of the stationary phase is significantly altered by the presence of micelles, either by enhancing or lessening the separation. The effects of surfactant on the interaction parameters of the stationary phase are determined using the Abraham solvation parameter model. The addition of sodium dodecylsulfate and dioctyl sulfosuccinate to 1-butyl-3-methylimidazolium chloride stationary phases generally increased the phase's hydrogen bond basicity and increased the level of dispersion interaction. Polyoxyethylene-100-stearyl ether and polyoxyethylene-23-lauryl ether surfactants, however, enhanced the pi-pi/n-pi, polarizability/dipolarity, and hydrogen bond basicity interactions of 1-butyl-3-methylimidazolium hexafluorophosphate to a greater degree than the ionic surfactants with 1-butyl-3-methylimidazolium chloride. However, these nonionic surfactants appeared to hinder the ability of the stationary phase to interact with solutes via dispersion forces

  18. Rapid Carbonation for Calcite from a Solid-Liquid-Gas System with an Imidazolium-Based Ionic Liquid

    PubMed Central

    Ibrahim, Abdul-Rauf; Vuningoma, Jean Bosco; Huang, Yan; Wang, Hongtao; Li, Jun

    2014-01-01

    Aqueous carbonation of Ca(OH)2 is a complex process that produces calcite with scalenohedral calcite phases and characterized by inadequate carbonate species for effective carbonation due to the poor dissolution of CO2 in water. Consequently, we report a solid-liquid-gas carbonation system with an ionic liquid (IL), 1-butyl-3-methylimidazolium bromide, in view of enhancing the reaction of CO2 with Ca(OH)2. The use of the IL increased the solubility of CO2 in the aqueous environment and enhanced the transport of the reactive species (Ca2+ and CO32−) and products. The presence of the IL also avoided the formation of the CaCO3 protective and passivation layer and ensured high carbonation yields, as well as the production of stoichiometric rhombohedral calcite phases in a short time. PMID:24968273

  19. Magnesium Battery Electrolytes in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Watkins, Tylan Strike

    A lack of adequate energy storage technologies is arguably the greatest hindrance to a modern sustainable energy infrastructure. Chemical energy storage, in the form of batteries, is an obvious solution to the problem. Unfortunately, today's state of the art battery technologies fail to meet the desired metrics for full scale electric grid and/or electric vehicle role out. Considerable effort from scientists and engineers has gone into the pursuit of battery chemistries theoretically capable of far outperforming leading technologies like Li-ion cells. For instance, an anode of the relatively abundant and cheap metal, magnesium, would boost the specific energy by over 4.6 times that of the current Li-ion anode (LiC6). The work presented here explores the compatibility of magnesium electrolytes in TFSI---based ionic liquids with a Mg anode (TFSI = bis(trifluoromethylsulfonyl)imide). Correlations are made between the Mg2+ speciation conditions in bulk solutions (as determined via Raman spectroscopy) and the corresponding electrochemical behavior of the electrolytes. It was found that by creating specific chelating conditions, with an appropriate Mg salt, the desired electrochemical behavior could be obtained, i.e. reversible electrodeposition and dissolution. Removal of TFSI -- contact ion pairs from the Mg2+ solvation shell was found to be essential for reversible electrodeposition. Ionic liquids with polyethylene glycol chains pendent from a parent pyrrolidinium cation were synthesized and used to create the necessary complexes with Mg 2+, from Mg(BH4)2, so that reversible electrodeposition from a purely ionic liquid medium was achieved. The following document discusses findings from several electrochemical experiments on magnesium electrolytes in ionic liquids. Explanations for the failure of many of these systems to produce reversible Mg electrodeposition are provided. The key characteristics of ionic liquid systems that are capable of achieving reversible Mg

  20. Retreating behavior of a charged ionic liquid droplet in a dielectric liquid under electric field

    NASA Astrophysics Data System (ADS)

    Ahn, Myung Mo; Im, Do Jin; Kang, In Seok

    2013-11-01

    Ionic liquids show great promise as excellent solvents or catalysts in energy and biological fields due to their unique chemical and physical properties. The ionic liquid droplets in microfluidic systems can also be used as a potential platform for chemical biological reactions. In order to control electrically the ionic liquid droplets in a microfluidic device, the charging characteristics of ionic liquid droplets need to be understood. In this work, the charging characteristics of various ionic liquids are investigated by using the parallel plate electrodes system. Under normal situation, a charged droplet shows bouncing motion between electrodes continuously. However, for some special ionic liquids, interesting retreating behavior of charged ionic liquid droplet has been observed. This retreating behavior of ionic liquid droplet has been analyzed experimentally by the image analysis and the electrometer signal analysis. Based on the hypothesis of charge leakage of the retreating ionic liquid droplets, FT-IR spectroscopy analysis has also been performed. The retreating behavior of ionic liquid droplet is discussed from the intermolecular point of view according to the species of ionic liquids. This research was supported by grant No. 2013R1A1A2011956 funded by the Ministry of Science, ICT and Future Planning (MSIP) and by grant No. 2013R1A1A2010483 funded by the Ministry of Education, Science and Technology (MEST) through the NRF.

  1. Sugarcane bagasse pretreatment using three imidazolium-based ionic liquids; mass balances and enzyme kinetics

    PubMed Central

    2012-01-01

    Background Effective pretreatment is key to achieving high enzymatic saccharification efficiency in processing lignocellulosic biomass to fermentable sugars, biofuels and value-added products. Ionic liquids (ILs), still relatively new class of solvents, are attractive for biomass pretreatment because some demonstrate the rare ability to dissolve all components of lignocellulosic biomass including highly ordered (crystalline) cellulose. In the present study, three ILs, 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), 1-ethyl-3-methylimidazolium chloride ([C2mim]Cl), 1-ethyl-3-methylimidazolium acetate ([C2mim]OAc) are used to dissolve/pretreat and fractionate sugarcane bagasse. In these IL-based pretreatments the biomass is completely or partially dissolved in ILs at temperatures greater than 130°C and then precipitated by the addition of an antisolvent to the IL biomass mixture. For the first time mass balances of IL-based pretreatments are reported. Such mass balances, along with kinetics data, can be used in process modelling and design. Results Lignin removals of 10% mass of lignin in bagasse with [C4mim]Cl, 50% mass with [C2mim]Cl and 60% mass with [C2mim]OAc, are achieved by limiting the amount of water added as antisolvent to 0.5 water:IL mass ratio thus minimising lignin precipitation. Enzyme saccharification (24 h, 15FPU) yields (% cellulose mass in starting bagasse) from the recovered solids rank as: [C2mim]OAc(83%) > >[C2mim]Cl(53%) = [C4mim]Cl(53%). Composition of [C2mim]OAc-treated solids such as low lignin, low acetyl group content and preservation of arabinosyl groups are characteristic of aqueous alkali pretreatments while those of chloride IL-treated solids resemble aqueous acid pretreatments. All ILs are fully recovered after use (100% mass as determined by ion chromatography). Conclusions In all three ILs regulated addition of water as an antisolvent effected a polysaccharide enriched precipitate since some of the lignin remained dissolved

  2. The Optimization of an Ionic Liquid-Based TALSPEAK-Like Process for Rare Earth Ions Separation

    SciTech Connect

    Dai, Sheng; Sun, Xiaoqi; Luo, Huimin

    2014-01-01

    Five new functionalized ionic liquids (FILs), tetraethylammonium di(2-ethylhexyl)phosphate ([N2222][DEHP]), tetraethylammonium bis(2,4,4-trimethylpentyl)phosphinite ([N2222][BTMPP]), tetraethylammonium bis(2,4,4-trimethylpentyl)dithiophosphinite ([N2222][BTMPDTP]), tetrahexylammonium di(2-ethylhexyl)phosphate ([N6666][DEHP]), and tetraoctylammonium di(2-ethylhexyl)phosphate ([N8888][DEHP]) were synthesized and characterized. These ILs along with two previously synthesized FILs ([N4444][DEHP] & [N1888][DEHP]) were used as ionic extractants and investigated for rare earth elements (REEs) separation in 1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide/bis(perfluoroethanesulfonyl)imide ([C10mim][NTf2]/[BETI]). These FILs as ionic extractants were miscible with [C10mim][NTf2]/[BETI]. We herein report the applications of these FILs in an IL-based TALSPEAK-like process and the optimization of the process by adjusting the cations and anions of the FILs, concentrations of the FILs as ionic extractants in the IL phase, concentrations of diethylenetriamine pentaacetic acid (DTPA) in the aqueous phase, and acidities of the aqueous phase.

  3. Enzyme catalysis with small ionic liquid quantities.

    PubMed

    Fischer, Fabian; Mutschler, Julien; Zufferey, Daniel

    2011-04-01

    Enzyme catalysis with minimal ionic liquid quantities improves reaction rates, stereoselectivity and enables solvent-free processing. In particular the widely used lipases combine well with many ionic liquids. Demonstrated applications are racemate separation, esterification and glycerolysis. Minimal solvent processing is also an alternative to sluggish solvent-free catalysis. The method allows simplified down-stream processing, as only traces of ionic liquids have to be removed. PMID:21107639

  4. Early Events in Ionic Liquid Radiation Chemistry

    SciTech Connect

    Wishart, J.F.; Cook, A.; Rimmer, R.D.; Gohdo, M.

    2010-09-14

    Ionic liquids are interesting and useful materials whose solvation time scales are up to thousands of times longer than in conventional solvents. The extended lifetimes of pre-solvated electrons and other energetic species in ionic liquids has profound consequences for the radiolytic product distributions and reactivity patterns. We use a newly developed, multiplexed variation of pulse-probe spectroscopy to measure the kinetics of the early dynamical and reactive events in ionic liquids.

  5. Inelastic neutron scattering study on boson peaks of imidazolium-based ionic liquids

    DOE PAGESBeta

    Kofu, Maiko; Inamura, Yasuhiro; Podlesnyak, Andrey A.; Ehlers, Georg; Yamamuro, Osamu; Moriya, Yosuke

    2015-07-26

    Low energy excitations of 1-alkyl-3-methylimidazolium ionic liquids (ILs) have been investigated by means of neutron spectroscopy. In the spectra of inelastic scattering, a broad excitation peak referred to as a “boson peak” appeared at 1–3 meV in all of the ILs measured. The intensity of the boson peak was enhanced at the Q positions corresponding to the diffraction peaks, reflecting the in-phase vibrational nature of the boson peak. Furthermore the boson peak energy (EBP) was insensitive to the length of the alkyl-chain but changed depending on the radius of the anion. From the correlation among EBP, the anion radius, andmore » the glass transition temperature Tg, we conclude that both EBP and Tg in ILs are predominantly governed by the inter-ionic Coulomb interaction which is less influenced by the alkyl-chain length. Furthermore, we also found that the EBP is proportional to the inverse square root of the molecular weight as observed in molecular glasses.« less

  6. Inelastic neutron scattering study on boson peaks of imidazolium-based ionic liquids

    SciTech Connect

    Kofu, Maiko; Inamura, Yasuhiro; Podlesnyak, Andrey A.; Ehlers, Georg; Yamamuro, Osamu; Moriya, Yosuke

    2015-07-26

    Low energy excitations of 1-alkyl-3-methylimidazolium ionic liquids (ILs) have been investigated by means of neutron spectroscopy. In the spectra of inelastic scattering, a broad excitation peak referred to as a “boson peak” appeared at 1–3 meV in all of the ILs measured. The intensity of the boson peak was enhanced at the Q positions corresponding to the diffraction peaks, reflecting the in-phase vibrational nature of the boson peak. Furthermore the boson peak energy (EBP) was insensitive to the length of the alkyl-chain but changed depending on the radius of the anion. From the correlation among EBP, the anion radius, and the glass transition temperature Tg, we conclude that both EBP and Tg in ILs are predominantly governed by the inter-ionic Coulomb interaction which is less influenced by the alkyl-chain length. Furthermore, we also found that the EBP is proportional to the inverse square root of the molecular weight as observed in molecular glasses.

  7. Solvation free energies in [bmim]-based ionic liquids: Anion effect toward solvation of amino acid side chain analogues

    NASA Astrophysics Data System (ADS)

    Latif, Muhammad Alif Mohammad; Micaêlo, Nuno; Abdul Rahman, Mohd Basyaruddin

    2014-11-01

    Stochastic molecular dynamics simulations were performed to investigate the solvation free energy of 15 neutral amino acid side chain analogues in aqueous and five, 1-butyl-3-methylimidazolium ([BMIM])-based ionic liquids. The results in aqueous were found highly correlated with previous experimental and simulation data. Meanwhile, [BMIM]-based RTILs showed better solvation thermodynamics than water to an extent that they were capable of solvating molecules immiscible in water. Non-polar analogues showed stronger solvation in hydrophobic RTIL anions such as [PF6]- and [Tf2N]- while polar analogues showed stronger solvation in the more hydrophilic RTIL anions such as [Cl]-, [TfO]- and [BF4]-.

  8. Development of Flexible Micro-Thermo-electrochemical Generators Based on Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Uhl, Stefanie; Laux, Edith; Journot, Tony; Jeandupeux, Laure; Charmet, Jérôme; Keppner, Herbert

    2014-10-01

    The unfavourable relationship between electrical and thermal conductivity limits the choice of solid-state materials for thermoelectric generators (TEG). Among ionic liquids (IOL), it appears that a large variety of thermoelectric (TE) materials with promising high Seebeck coefficients have potential for development. Furthermore, the novel solid-on-liquid deposition technology (SOLID) allows the encapsulation of liquid TE materials to create new, highly integrated TEG devices. Following this vision, this paper studies a large number of IOLs looking at TE-relevant parameters such as thermal and electrical conductivity, Seebeck coefficient and temperature-dependent viscosity. We show that positive and negative Seebeck coefficients can be obtained, depending on the molecular structure and the viscosity of the IOL. The properties of single-junction TEGs are presented in terms of I- V characteristics correlated with the IOL properties. We prove that the limiting effect of conversion efficiency is the current density that can be extracted from a device rather than the Seebeck coefficient.

  9. A New Green Ionic Liquid-Based Corrosion Inhibitor for Steel in Acidic Environments.

    PubMed

    Atta, Ayman M; El-Mahdy, Gamal A; Al-Lohedan, Hamad A; Ezzat, Abdel Rahman O

    2015-01-01

    This work examines the use of new hydrophobic ionic liquid derivatives, namely octadecylammonium tosylate (ODA-TS) and oleylammonium tosylate (OA-TS) for corrosion protection of steel in 1 M hydrochloric acid solution. Their chemical structures were determined from NMR analyses. The surface activity characteristics of the prepared ODA-TS and OA-TS were evaluated from conductance, surface tension and contact angle measurements. The data indicate the presence of a double bond in the chemical structure of OA-TS modified its surface activity parameters. Potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) measurements, scanning electron microscope (SEM), Energy dispersive X-rays (EDX) analysis and contact angle measurements were utilized to investigate the corrosion protection performance of ODA-TS and OA-TS on steel in acidic solution. The OA-TS and ODA-TS compounds showed good protection performance in acidic chloride solution due to formation of an inhibitive film on the steel surface. PMID:26091073

  10. Hydrophilic Ionic Liquids as Ingredients of Gel-Based Dermal Formulations.

    PubMed

    Dobler, Dorota; Schmidts, Thomas; Zinecker, Christina; Schlupp, Peggy; Schäfer, Jens; Runkel, Frank

    2016-08-01

    Ionic liquids (ILs) have several properties that offer many advantages in dermal drug delivery systems. Depending on the chemical structure, ILs can be used for protection against microorganisms, to enhance skin penetration, and as a solvent. In the present work, SEPINEO™ P 600 formulations and hydroxyethylcellulose gels containing the hydrophilic ILs hexylpyridinium chloride, choline dihydrogen phosphate, and 1-ethyl-3-methylimidazolium ethyl sulfate were prepared, and the influence of the ILs on the formulation properties was evaluated. ILs were successfully incorporated into the emulsion structure, resulting in stable formulations. The antimicrobial activity of the ILs was estimated. The minimal inhibitory concentration values for hexylpyridinium chloride are about 2.5 mg/mL. The other two ILs have no antimicrobial activity. Skin penetration enhancement of caffeine, a hydrophilic model substance, was observed in the presence of hexylpyridinium chloride. PMID:27435197

  11. Volumetric properties of binary mixtures of benzene with cyano-based ionic liquids

    NASA Astrophysics Data System (ADS)

    Gonfa, Girma; Bustam, Mohamad Azmi; Moniruzzaman, Muhammad; Murugesan, Thanabalan

    2014-10-01

    The objective of this study is to investigate the volumetric properties of the binary mixtures comprised benzene and two ionic liquids, 1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN]) and 1-butyl-3-methyl- imidazolium dicyanamide ([ BMIM ][ N ( CN )2]( . Densities (ρ) and viscosities (μ) of the binary mixtures were measured over a temperature range of 293.15 to 323.15 K and at atmospheric pressure. Excess molar volumes and viscosity deviations were calculated from the experimental densities and viscosities values. The volumetric properties of the mixtures were changed significantly with the change of compositions and temperatures. It was also found that the value of excess molar volume and viscosity deviations were negative (-ve) over the entire range of compositions. The results have been interpreted in terms of molecular interactions of ILs and benzene.

  12. Membrane separation of ionic liquid solutions

    SciTech Connect

    Campos, Daniel; Feiring, Andrew Edward; Majumdar, Sudipto; Nemser, Stuart

    2015-09-01

    A membrane separation process using a highly fluorinated polymer membrane that selectively permeates water of an aqueous ionic liquid solution to provide dry ionic liquid. Preferably the polymer is a polymer that includes polymerized perfluoro-2,2-dimethyl-1,3-dioxole (PDD). The process is also capable of removing small molecular compounds such as organic solvents that can be present in the solution. This membrane separation process is suitable for drying the aqueous ionic liquid byproduct from precipitating solutions of biomass dissolved in ionic liquid, and is thus instrumental to providing usable lignocellulosic products for energy consumption and other industrial uses in an environmentally benign manner.

  13. Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure

    NASA Astrophysics Data System (ADS)

    Lima, Thamires A.; Paschoal, Vitor H.; Faria, Luiz F. O.; Ribeiro, Mauro C. C.; Giles, Carlos

    2016-06-01

    X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2]. The peak in the diffraction data characteristic of charge ordering in [N1444][NTf2] is shifted to longer distances in comparison to [N1114][NTf2], but the peak characteristic of short-range correlations is shifted in [N1444][NTf2] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N1114]+ and [N1444]+ proposed in this work. The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N1444]+ as to [N1114]+ because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N1114]+ cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N1114][NTf2], whereas polar and non-polar structure factors are essentially the same in [N1444][NTf2]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids.

  14. Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure.

    PubMed

    Lima, Thamires A; Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C; Giles, Carlos

    2016-06-14

    X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2]. The peak in the diffraction data characteristic of charge ordering in [N1444][NTf2] is shifted to longer distances in comparison to [N1114][NTf2], but the peak characteristic of short-range correlations is shifted in [N1444][NTf2] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N1114](+) and [N1444](+) proposed in this work. The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N1444](+) as to [N1114](+) because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N1114](+) cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N1114][NTf2], whereas polar and non-polar structure factors are essentially the same in [N1444][NTf2]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids. PMID:27306015

  15. Ionic liquids--an overview.

    PubMed

    Jenkins, Harry Donald Brooke

    2011-01-01

    A virtually unprecedented exponential burst of activity resulted following the publication, in 1998, of an article by Michael Freeman (Freemantle, M. Chemical & Engineering News, 1998, March 30, 32), which speculated on the role and contribution that ionic liquids (ILs) might make in the future on the development of clean technology. Up until that time only a handful of researchers were routinely engaged in the study of ILs but frenzied activity followed that continues until the present day. Scientists from all disciplines related to Chemistry have now embarked on studies, including theoreticians who are immersed in the aim of improving the "designer role" so that they can tailor ILs to deliver specified properties. This article, whilst not in any sense attempting to be exhaustive, highlights the main features which characterise ILs, presenting these in a form readily assimilated by newcomers to this area of research. An extensive glossary is featured in this article as well as a chronological list which charts the major areas of development. What follows consists of a number of sections briefly describing the role of lLs as solvents, hypergolic fuels, their use in some electrochemical devices such as solar cells and lithium batteries and their use in polymerisation reactions, followed by a concise summary of some of the other roles that they are capable of playing. The role of empirical, volume-based thermodynamics procedures, as well as large scale computational studies on ILs is also highlighted. These developments which are described are remarkable in that they have been achieved in less than a decade and a half although knowledge of these materials has existed for much longer. PMID:22026149

  16. Charge transport in confined ionic liquids

    NASA Astrophysics Data System (ADS)

    Sangoro, Joshua; Iacob, Ciprian; Kipnusu, Wycliffe; Kremer, Friedrich

    2011-03-01

    Charge transport and glassy dynamics in neat and polymerized ionic liquids confined in nanoporous silica are investigated in a wide frequency and temperature ranges by a combination of Broadband Dielectric Spectroscopy and Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR). By applying the Einstein-Smoluchowski relations to the dielectric spectra, diffusion coefficients are obtained in quantitative agreement with independent PFG NMR. The impact of geometrical confinement as well as the pore wall-ionic liquid interactions on the overall ionic mobility is explored for diverse categories of ionic liquids. The results are discussed within the framework of dynamic glass transition assisted charge transport in ionic liquids. Financial support from the Deutsche Forschungsgemeinschaft under the DFG SPP 1191 Priority Program on Ionic Liquids is gratefully acknowledged.

  17. Surfactant-free ionic liquid-based nanofluids with remarkable thermal conductivity enhancement at very low loading of graphene

    PubMed Central

    2012-01-01

    We report for the first time the preparation of highly stable graphene (GE)-based nanofluids with ionic liquid as base fluids (ionic liquid-based nanofluids (Ionanofluids)) without any surfactant and the subsequent investigations on their thermal conductivity, specific heat, and viscosity. The microstructure of the GE and MWCNTs are observed by transmission electron microscope. Thermal conductivity (TC), specific heat, and viscosity of these Ionanofluids were measured for different weight fractions and at varying temperatures, demonstrating that the Ionanofluids exhibit considerably higher TC and lower viscosity than that of their base fluids without significant specific heat decrease. An enhancement in TC by about 15.5% and 18.6% has been achieved at 25 °C and 65 °C respectively for the GE-based nanofluid at mass fraction of as low as 0.06%, which is larger than that of the MWCNT-dispersed nanofluid at the same loading. When the temperature rises, the TC and specific heat of the Ionanofluid increase clearly, while the viscosity decreases sharply. Moreover, the viscosity of the prepared Ionanofluids is lower than that of the base fluid. All these advantages of this new kind of Ionanofluid make it an ideal fluid for heat transfer and thermal storage. PMID:22713249

  18. Electronic absorption spectra of imidazolium-based ionic liquids studied by far-ultraviolet spectroscopy and quantum chemical calculations.

    PubMed

    Tanabe, Ichiro; Kurawaki, Yuji; Morisawa, Yusuke; Ozaki, Yukihiro

    2016-08-10

    Electronic absorption spectra of imidazolium-based ionic liquids were studied by far- and deep-ultraviolet spectroscopy and quantum chemical calculations. The absorption spectra in the 145-300 nm region of imidazolium-based ionic liquids, [Cnmim](+)[BF4](-) (n = 2, 4, 8) and [C4mim](+)[PF6](-), were recorded using our original attenuated total reflectance (ATR) system spectrometer. The obtained spectra had two definitive peaks at ∼160 and ∼210 nm. Depending on the number of carbon atoms in the alkyl side chain, the peak wavelength around 160 nm changed, while that around 210 nm remained at almost the same wavelength. Quantum chemical calculation results based on the time-dependent density functional theory (TD-DFT) also showed the corresponding peak shifts. In contrast, there was almost no significant difference between [C4mim](+)[BF4](-) and [C4mim](+)[PF6](-), which corresponded with our calculations. Therefore, it can be concluded that the absorption spectra in the 145-300 nm region are mainly determined by the cations when fluorine-containing anions are adopted. In addition, upon addition of organic solvent (acetonitrile) to [C4mim](+)[BF4](-), small peak shifts to the longer wavelength were revealed for both peaks at ∼160 and ∼210 nm. The peak shift in the deep-ultraviolet region (≤200 nm) in the presence of the solvent, which indicates the change of electronic states of the ionic liquid, was experimentally observed for the first time by using the ATR spectrometer. PMID:27471106

  19. Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

    NASA Astrophysics Data System (ADS)

    Davidson, Jacob D.; Goulbourne, N. C.

    2011-01-01

    Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an

  20. Ionic liquid tunes microemulsion curvature.

    PubMed

    Liu, Liping; Bauduin, Pierre; Zemb, Thomas; Eastoe, Julian; Hao, Jingcheng

    2009-02-17

    Middle-phase microemulsions formed from cationic dioctadecyldimethylammonium chloride (DODMAC), anionic sodium dodecylsulfate (SDS), n-butanol, and n-heptane were studied. An ionic liquid (IL), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), was employed as the electrolyte in the aqueous media instead of inorganic salts usually used in microemulsion formulation. Studies have been carried out as a function of the concentrations of [bmim][BF4], n-butanol, total surfactant (cDODMAC+SDS), and temperature on the phase behavior and the ultralow interfacial tensions in which the anionic component is present in excess in the catanionic film. Ultralow interfacial tension measurements confirmed the formation of middle-phase microemulsions and the necessary conditions for stabilizing middle-phase microemulsions. Electrical conductivity, small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS) experiments were also performed, indicating that the typical heptane domain size has an average radius of 360 A and the ionic liquid induces softening of the charged catanionic film. Most interestingly, the IL concentration (cIL) is shown to act as an effective interfacial curvature-control parameter, representing a new approach to tuning the formulation of microemulsions and emulsions. The results expand the potential uses of ILs but also point to the design of new ILs that may achieve superefficient control over interfacial and self-assembly systems. PMID:19161325

  1. Design of Phosphonated Imidazolium-Based Ionic Liquids Grafted on γ-Alumina: Potential Model for Hybrid Membranes.

    PubMed

    Pizzoccaro, Marie-Alix; Drobek, Martin; Petit, Eddy; Guerrero, Gilles; Hesemann, Peter; Julbe, Anne

    2016-01-01

    Imidazolium bromide-based ionic liquids bearing phosphonyl groups on the cationic part were synthesized and grafted on γ-alumina (γ-Al₂O₃) powders. These powders were prepared as companion samples of conventional mesoporous γ-alumina membranes, in order to favor a possible transfer of the results to supported membrane materials, which could be used for CO₂ separation applications. Effective grafting was demonstrated using energy dispersive X-ray spectrometry (EDX), N₂ adsorption measurements, fourier transform infrared spectroscopy (FTIR), and special attention was paid to (31)P and (13)C solid state nuclear magnetic resonance spectroscopy (NMR). PMID:27472321

  2. Eco-Friendly Synthesis of a New Class of Pyridinium-Based Ionic Liquids with Attractive Antimicrobial Activity.

    PubMed

    Messali, Mouslim

    2015-01-01

    The present study reports a green synthesis of a new family of ionic liquids (ILs) based on functionalized 4-dimethylaminopyridinium derivatives. The structures of 23 newly synthesized ILs (2-24) were confirmed by FT-IR, (1)H-, (13)C-, (11)B-, (19)F-, and (31)P-NMR spectroscopy and mass spectrometry. The antimicrobial activity of all novel ILs was tested against a panel of bacteria and fungi. The results prove that all tested ILs are effective antibacterial and antifungal agents, especially 4-(dimethylamino)-1-(4-phenoxybutyl) pyridinium derivatives 5 and 19. PMID:26287148

  3. Design of Phosphonated Imidazolium-Based Ionic Liquids Grafted on γ-Alumina: Potential Model for Hybrid Membranes

    PubMed Central

    Pizzoccaro, Marie-Alix; Drobek, Martin; Petit, Eddy; Guerrero, Gilles; Hesemann, Peter; Julbe, Anne

    2016-01-01

    Imidazolium bromide-based ionic liquids bearing phosphonyl groups on the cationic part were synthesized and grafted on γ-alumina (γ-Al2O3) powders. These powders were prepared as companion samples of conventional mesoporous γ-alumina membranes, in order to favor a possible transfer of the results to supported membrane materials, which could be used for CO2 separation applications. Effective grafting was demonstrated using energy dispersive X-ray spectrometry (EDX), N2 adsorption measurements, fourier transform infrared spectroscopy (FTIR), and special attention was paid to 31P and 13C solid state nuclear magnetic resonance spectroscopy (NMR). PMID:27472321

  4. Ionic liquid-based aqueous two-phase system extraction of sulfonamides in milk.

    PubMed

    Shao, Mingyuan; Zhang, Xuli; Li, Na; Shi, Jiayuan; Zhang, Huijie; Wang, Zhibing; Zhang, Hanqi; Yu, Aimin; Yu, Yong

    2014-06-15

    A simple method for the determination of six sulfonamides (SAs) in milk samples was developed. 1-Butyl-3-methylimidazolium tetrafluoroborate and trisodium citrate dihydrate were used to form aqueous two-phase system. The aqueous two phase system was applied to the extraction of the SAs and the determination of the analytes was performed by high-performance liquid chromatography. To achieve optimum extraction performance, several experimental parameters, including the type and the amount of salt, the type and amount of ionic liquid, ultrasonic time and pH of sample solution, were investigated and optimized. Under the optimal experimental conditions, good linearity was observed in the range of 8.55-1036.36ngmL(-1). The limits of detection and quantification were in the range of 2.04-2.84 and 6.73-9.37ngmL(-1), respectively. The present method was successfully applied to the determination of SAs in milk samples, and the recoveries of analytes were in the range of 72.32-108.96% with relative standard deviations ranging from 0.56 to 12.20%. The results showed that the present method was rapid, feasible and environmentally friendly. PMID:24854709

  5. Dynamic Acid/Base Equilibrium in Single Component Switchable Ionic Liquids and Consequences on Viscosity.

    PubMed

    Cantu, David C; Lee, Juntaek; Lee, Mal-Soon; Heldebrant, David J; Koech, Phillip K; Freeman, Charles J; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

    2016-05-01

    The deployment of transformational nonaqueous CO2-capture solvent systems is encumbered by high viscosities even at intermediate uptakes. Using single-molecule CO2 binding organic liquids as a prototypical example, we present key molecular features that control bulk viscosity. Fast CO2-uptake kinetics arise from close proximity of the alcohol and amine sites involved in CO2 binding in a concerted fashion, resulting in a Zwitterion containing both an alkyl-carbonate and a protonated amine. The population of internal hydrogen bonds between the two functional groups determines the solution viscosity. Unlike the ion pair interactions in ionic liquids, these observations are novel and specific to a hydrogen-bonding network that can be controlled by chemically tuning single molecule CO2 capture solvents. We present a molecular design strategy to reduce viscosity by shifting the proton transfer equilibrium toward a neutral acid/amine species, as opposed to the ubiquitously accepted zwitterionic state. The molecular design concepts proposed here are readily extensible to other CO2 capture technologies. PMID:27019342

  6. Ionic liquid-anionic surfactant based aqueous two-phase extraction for determination of antibiotics in honey by high-performance liquid chromatography.

    PubMed

    Yang, Xiao; Zhang, Shaohua; Yu, Wei; Liu, Zhongling; Lei, Lei; Li, Na; Zhang, Hanqi; Yu, Yong

    2014-06-01

    An ionic liquid-anionic surfactant based aqueous two-phase extraction was developed and applied for the extraction of tetracycline, oxytetracycline and chloramphenicol in honey. The honey sample was mixed with Na2EDTA aqueous solution. The sodium dodecyl sulfate, ionic liquid 1-octyl-3-methylimidazolium bromide and sodium chloride were added in the mixture. After the resulting mixture was ultrasonically shaken and centrifuged, the aqueous two phase system was formed and analytes were extracted into the upper phase. The parameters affecting the extraction efficiency, such as the volume of ionic liquid, the category and amount of salts, sample pH value, extraction time and temperature were investigated. The limits of detection of tetracycline, oxytetracycline and chloramphenicol were 5.8, 8.2 and 4.2 μg kg(-1), respectively. When the present method was applied to the analysis of real honey samples, the recoveries of analytes ranged from 85.5 to 110.9% and relative standard deviations were lower than 6.9%. PMID:24767438

  7. Polarity of the interface in ionic liquid in oil microemulsions.

    PubMed

    Andújar-Matalobos, María; García-Río, Luis; López-García, Susana; Rodríguez-Dafonte, Pedro

    2011-11-01

    Ionic liquid based microemulsions were characterized by absorption solvatochromic shifts, (1)H NMR and kinetic measurements in order to investigate the properties of the ionic liquid within the restricted geometry provided by microemulsions and the interactions of the ionic liquid with the interface. Experimental results show a significant difference between the interfaces of normal water and the new ionic liquid microemulsions. Absorption solvatochromic shift experiments and kinetic studies on the aminolysis of 4-nitrophenyl laurate by n-decylamine show that the polarity at the interface of the ionic liquid in oil microemulsions (IL/O) is higher than at the interface of water in oil microemulsions (W/O) despite the fact that the polarity of [bmim][BF(4)(-)] is lower than the polarity of water. (1)H NMR experiments showed that an increase in the ionic liquid content of the microemulsion led to an increase in the interaction between [bmim][BF(4)(-)] and TX-100. The reason for the higher polarity of the microemulsions with the ionic liquid can be explained in terms of the incorporation of higher levels of the ionic liquid at the interface of the microemulsions, as compared to water in the traditional systems. PMID:21820124

  8. Characterization of a novel intrinsic luminescent room-temperature ionic liquid based on [P6,6,6,14 ][ANS].

    PubMed

    Delgado, Joana M; Raymundo, Anabela; Vilarigues, Márcia; Branco, Luís C; Laia, César A T

    2015-01-01

    Intrinsically luminescent room-temperature ionic liquids (RTILs) can be prepared by combining a luminescent anion (more common) or cation with appropriate counter ions, rendering new luminescent soft materials. These RTILs are still new, and many of their photochemical properties are not well known. A novel intrinsic luminescent RTIL based on the 8-anilinonaphthalene-1-sulfonate ([ANS]) anion combined with the trihexyltetradecylphosphonium ([P6,6,6,14 ]) cation was prepared and characterized by spectroscopic techniques. Detailed photophysical studies highlight the influence of the ionic liquid environment on the ANS fluorescence, which together with rheological and (1) H NMR experiments illustrate the effects of both the viscosity and electrostatic interactions between the ions. This material is liquid at room temperature and possesses a glass transition temperature (Tg ) of 230.4 K. The fluorescence is not highly sensitive to factors such as temperature, but owing to its high viscosity, dynamic Stokes shift measurements reveal very slow components for the IL relaxation. PMID:25124894

  9. Ionic liquid-based microwave-assisted extraction of essential oil and biphenyl cyclooctene lignans from Schisandra chinensis Baill fruits.

    PubMed

    Ma, Chun-hui; Liu, Ting-ting; Yang, Lei; Zu, Yuan-gang; Chen, Xiaoqiang; Zhang, Lin; Zhang, Ying; Zhao, Chunjian

    2011-12-01

    Ionic liquid-based microwave-assisted extraction (ILMAE) has been successfully applied in extracting essential oil and four kinds of biphenyl cyclooctene lignans from Schisandra chinensis Baill. 0.25 M 1-lauryl-3-methylimidazolium bromide ionic liquid is selected as solvent. The optimum parameters of dealing with 25.0 g sample are 385 W irradiation power, 40 min microwave extraction time and 1:12 solid-liquid ratio. The yields of essential oil and lignans are 12.12±0.37 ml/kg and 250.2±38.2 mg/kg under the optimum conditions. The composition of the essential oil extracted by hydro-distillation, steam-distillation and ILMAE is analyzed by GC-MS. With ILMAE method, the energy consumption time has not only been shortened to 40 min (hydro-distillation 3.0 h for extracting essential oil and reflux extraction 4.0 h for extracting lignans, respectively), but also the extraction efficiency has been improved (extraction of lignans and distillation of essential oil at the same time) and reduces the environmental pollution. S. chinensis materials treated by different methods are observed by scanning electronic microscopy. Micrographs provide more evidence to prove that ILMAE is a better and faster method. The experimental results also indicate that ILMAE is a simple and efficient technique for sample preparation. PMID:22018714

  10. Extraction of eight triazine and phenylurea herbicides in yogurt by ionic liquid foaming-based solvent floatation.

    PubMed

    Li, Na; Zhang, Rui; Nian, Li; Ren, Ruibing; Wang, Yeqiang; Zhang, Hanqi; Yu, Aimin

    2012-01-27

    The ionic liquid foaming-based solvent floatation (ILF-SF) was developed for extracting triazines and phenylureas from yogurt. These analytes were separated and determined by high performance liquid chromatography. Some experimental parameters, such as the pH value of floatation solution, extraction solvent, kind of ionic liquid and floatation time were investigated and optimized. The mixture of n-propyl alcohol and ethyl acetate was used as extraction solvent and 1-hexyl-3-methylimidazolium hexafluorophosphate was used as foaming agent. The precision and recoveries of eight herbicides vary from 0.17 to 6.90% and from 86.5 to 118.7%, respectively. The detection limits for simeton, simazine, chlortoluron, isoproturon, ametryn, propazine, prometryne and prebane are 0.59, 0.44, 0.44, 0.46, 0.32, 1.01, 0.34 and 0.23 μgL(-1), respectively. The enrichment factors for the solvent floatation range from 11.6 to 18.6 for the eight herbicides. PMID:22218326

  11. Surfactant-based ionic liquids for extraction of phenolic compounds combined with rapid quantification using capillary electrophoresis.

    PubMed

    Huang, Fangzhi; Berton, Paula; Lu, Chengfei; Siraj, Noureen; Wang, Chun; Magut, Paul K S; Warner, Isiah M

    2014-09-01

    A rapid liquid phase extraction employing a novel hydrophobic surfactant-based room temperature ionic liquid (RTIL), tetrabutylphosphonium dioctyl sulfosuccinate ([4C4 P][AOT]), coupled with capillary electrophoretic-UV (CE-UV) detection is developed for removal and determination of phenolic compounds. The long-carbon-chain RTIL used is sparingly soluble in most solvents and can be used to replace volatile organic solvents. This fact, in combination with functional-surfactant-anions, is proposed to reduce the interfacial energy of the two immiscible liquid phases, resulting in highly efficient extraction of analytes. Several parameters that influence the extraction efficiencies, such as extraction time, RTIL type, pH value, and ionic strength of aqueous solutions, were investigated. It was found that, under acidic conditions, most of the investigated phenols were extracted from aqueous solution into the RTIL phase within 12 min. Good linearity was observed over the concentration range of 0.1-80.0 μg/mL for all phenols investigated. The precision of this method, expressed as RSD, was determined to be within 3.4-5.3% range. The LODs (S/N = 3) of the method were in the range of 0.047-0.257 μg/mL. The proposed methodology was successfully applied to determination of phenols in real water samples. PMID:24798689

  12. Ionic liquid-based ultrasound-assisted emulsification microextraction coupled with high performance liquid chromatography for the determination of four fungicides in environmental water samples.

    PubMed

    Liang, Pei; Wang, Fang; Wan, Qin

    2013-02-15

    A highly efficient and environmentally friendly sample preparation method termed ionic liquid-based ultrasound-assisted emulsification microextraction (IL-USAEME) combined with high performance liquid chromatography has been developed for the determination of four fungicides (azoxystrobin, diethofencarb, pyrimethanil and kresoxim-methyl) in water samples. In this novel approach, ionic liquid (IL) was used as extraction solvent in place of the organic solvent used in conventional USAEME assay, and there is no need for using organic dispersive solvent which is typically required in the common dispersive liquid-liquid microextraction method. Various parameters that affect the extraction efficiency, such as the kind and volume of IL, ultrasound emulsification time, extraction temperature and salt addition were investigated and optimized. Under the optimum extraction condition, the linearities of calibration curves were in the range from 3 to 5000 ng mL(-1) for target analytes with the correlation coefficient higher than 0.9992. The enrichment factors and the limits of detection were in the range of 88-137 and 0.73-2.2 ng mL(-1), depending on the analytes. The environmental water samples were successfully analyzed using the proposed method, and the relative recoveries at fortified levels of 50 and 100 ng mL(-1) were in the range of 83.9%-116.2%. PMID:23597988

  13. Quantized friction across ionic liquid thin films.

    PubMed

    Smith, Alexander M; Lovelock, Kevin R J; Gosvami, Nitya Nand; Welton, Tom; Perkin, Susan

    2013-10-01

    Ionic liquids - salts in the liquid state under ambient conditions - are of great interest as precision lubricants. Ionic liquids form layered structures at surfaces, yet it is not clear how this nano-structure relates to their lubrication properties. We measured the friction force between atomically smooth solid surfaces across ionic liquid films of controlled thickness in terms of the number of ion layers. Multiple friction-load regimes emerge, each corresponding to a different number of ion layers in the film. In contrast to molecular liquids, the friction coefficients differ for each layer due to their varying composition. PMID:23942943

  14. Ionic Liquid Membranes for Carbon Dioxide Separation

    SciTech Connect

    Myers, C.R.; Ilconich, J.B.; Luebke, D.R.; Pennline, H.W.

    2008-07-12

    Recent scientific studies are rapidly advancing novel technological improvements and engineering developments that demonstrate the ability to minimize, eliminate, or facilitate the removal of various contaminants and green house gas emissions in power generation. The Integrated Gasification Combined Cycle (IGCC) shows promise for carbon dioxide mitigation not only because of its higher efficiency as compared to conventional coal firing plants, but also due to a higher driving force in the form of high partial pressure. One of the novel technological concepts currently being developed and investigated is membranes for carbon dioxide (CO2) separation, due to simplicity and ease of scaling. A challenge in using membranes for CO2 capture in IGCC is the possibility of failure at elevated temperatures or pressures. Our earlier research studies examined the use of ionic liquids on various supports for CO2 separation over the temperature range, 37°C-300°C. The ionic liquid, 1-hexyl-3methylimidazolium Bis(trifluoromethylsulfonyl)imide, ([hmim][Tf2N]), was chosen for our initial studies with the following supports: polysulfone (PSF), poly(ether sulfone) (PES), and cross-linked nylon. The PSF and PES supports had similar performance at room temperature, but increasing temperature caused the supported membranes to fail. The ionic liquid with the PES support greatly affected the glass transition temperature, while with the PSF, the glass transition temperature was only slightly depressed. The cross-linked nylon support maintained performance without degradation over the temperature range 37-300°C with respect to its permeability and selectivity. However, while the cross-linked nylon support was able to withstand temperatures, the permeability continued to increase and the selectivity decreased with increasing temperature. Our studies indicated that further testing should examine the use of other ionic liquids, including those that form chemical complexes with CO2 based on

  15. Experimental and theoretical enthalpies of formation of glycine-based sulfate/bisulfate amino acid ionic liquids.

    PubMed

    Zhu, Jing-Fang; He, Ling; Zhang, Lei; Huang, Ming; Tao, Guo-Hong

    2012-01-12

    The experimental and theoretical enthalpies of formation of several structural-similar glycine-based sulfate/bisulfate amino acid ionic liquids including glycine sulfate (Gly(2)SO(4), 1), glycine bisulfate (GlyHSO(4), 2), N,N-dimethylglycine sulfate ([DMGly](2)SO(4), 3), N,N-dimethylglycine bisulfate ([DMGly]HSO(4), 4), N,N-dimethylglycine methyl ester sulfate ([DMGlyC(1)](2)SO(4), 5), N,N-dimethylglycine methyl ester bisulfate ([DMGlyC(1)]HSO(4), 6), N,N,N-trimethylglycine methyl ester sulfate ([TMGlyC(1)](2)SO(4), 7), and N,N,N-trimethylglycine methyl ester bisulfate ([TMGlyC(1)]HSO(4), 8) were studied. Their experimental enthalpies of formation were obtained from the corresponding energies of combustion determined by the bomb calorimetry method. The enthalpies of formation of these amino acid ionic liquids are in the range from -1406 kJ mol(-1) to -1128 kJ mol(-1). Systematic theoretical study on these amino acid ionic liquids were performed by quantum chemistry calculation using the Gaussian03 suite of programs. The geometric optimization and the frequency analyses are carried out using the B3LYP method with the 6-31+G** basis set. Their calculated enthalpies of formation were derived from the single point energies carried out with the HF/6-31+G**, B3LYP/6-31+G**, B3LYP/6-311++G**, and MP2/6-311++G** level of theory, respectively. The relevance of experimental and calculated enthalpies of formation was studied. The calculated enthalpies of formation are in good agreement with their experimental data in less than 3% error. PMID:22148242

  16. Influence of process variables on extraction of Cefalexin in a novel biocompatible ionic liquid based-aqueous two phase system.

    PubMed

    Abdolrahimi, Shiva; Nasernejad, Bahram; Pazuki, Gholamreza

    2015-01-01

    Despite the fact that ionic liquid-based aqueous two phase systems (ATPSs) have been widely studied for extraction purposes, the adequacy of biodegradable organic salts as salting out agents has been left unexploited. In this study, we investigated the ability of sodium-based organic salts in the formation of ATPS in the presence of a common ionic liquid, [C4mim]BF4. In the pioneering aspect of this work, Response Surface Methodology (RSM) based on three-variable central composite design (CCD) was employed for determination of the effect of pH and the initial concentration of phase components on the partition coefficient of Cefalexin. Consequently, regression model equations and contour plots were applied to evaluate the effect of system's parameters on biomolecule's extraction. The tie-line (TL) data were determined for each experimental run and their reliability was confirmed by Othmer-Tobias and Bancroft correlations. In order to investigate the salting-out ability the effective excluded volume (EEV) was determined from the binodal data. Furthermore, FTIR spectra confirmed no chemical interactions between Cefalexin and [C4mim]BF4 in the extraction process. The microscopic structure of the top phase was analyzed by DLS, conductivity and TEM in order to investigate the mechanism of extraction. Hydrophobic interaction, the salting-out effect and the aggregation phenomena played the dominant role in the study of the extraction process. PMID:25407265

  17. Ionic liquid-in-oil microemulsions.

    PubMed

    Eastoe, Julian; Gold, Sarah; Rogers, Sarah E; Paul, Alison; Welton, Tom; Heenan, Richard K; Grillo, Isabelle

    2005-05-25

    Phase stability and small-angle neutron scattering (SANS) data show that surfactant-stabilized nanodomains of a typical ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4]) may be dispersed by the nonionic surfactant Triton-X100 in cyclohexane. Analyses of these SANS data are consistent with the formation of ionic liquid-in-oil microemulsion droplets. PMID:15898765

  18. Engineered microorganisms having resistance to ionic liquids

    DOEpatents

    Ruegg, Thomas Lawrence; Thelen, Michael P.

    2016-03-22

    The present invention provides for a method of genetically modifying microorganisms to enhance resistance to ionic liquids, host cells genetically modified in accordance with the methods, and methods of using the host cells in a reaction comprising biomass that has been pretreated with ionic liquids.

  19. Ionic liquid incorporating thiosalicylate for metal removal

    NASA Astrophysics Data System (ADS)

    Wilfred, Cecilia Devi; Mustafa, Fadwa Babiker; Romeli, Fatimah Julia

    2012-09-01

    Ionic liquids are a class of organic molten salts "designer solvents" that are composed totally of anions (inorganic and organic polyatomic) and organic cations. The replacement of volatile organic solvents from a separation process is of utmost importance since the use of a large excess of these solvents is hazardous and creates ecological problem. The new method for metal ion extraction is by using task-specific ionic liquids such as ionic liquids which incorporate thiosalicylate functionality. This paper looks at producing a new cluster of ionic liquids which incorporates thiosalicylate with pyridinium cation. Its thermophysical properties such as density and viscosity in single and binary mixtures are studied. The ionic liquids' capability in metal removal processes is evaluated.

  20. In situ metathesis reaction combined with liquid-phase microextraction based on the solidification of sedimentary ionic liquids for the determination of pyrethroid insecticides in water samples.

    PubMed

    Hu, Lu; Zhang, Panjie; Shan, Wanyu; Wang, Xuan; Li, Songqing; Zhou, Wenfeng; Gao, Haixiang

    2015-11-01

    A novel dispersion liquid-liquid microextraction method based on the solidification of sedimentary ionic liquids (SSIL-DLLME), in which an in situ metathesis reaction forms an ionic liquid (IL) extraction phase, was developed to determine four pyrethroid insecticides (i.e., permethrin, cyhalothrin, fenpropathrin, and transfluthrin) in water followed by separation using high-performance liquid chromatography. In the developed method, in situ DLLME was used to enhance the extraction efficiency and yield. After centrifugation, the extraction solvent, tributyldodecylphosphonium hexafluorophosphate ([P44412][PF6]), was easily collected by solidification in the bottom of the tube. The effects of various experimental parameters, the quantity of tributyldodecylphosphonium bromide ([P44412]Br), the molar ratio of [P44412]Br to potassium hexafluorophosphate (KPF6), the ionic strength, the temperature of the sample solution, and the centrifugation time, were optimized using a Plackett-Burman design to identify the significant factors that affected the extraction efficiency. These significant factors were then optimized using a central composite design. Under the optimized conditions, the recoveries of the four pyrethroid insecticides at four spiked levels ranged from 87.1% to 101.7%, with relative standard deviations (RSDs) ranging from 0.1% to 5.5%. At concentration levels between 1 and 500 µg/L, good linearity was obtained, with coefficients of determination greater than 0.9995. The limits of detection (LODs) for the four pyrethroid insecticides were in the range of 0.71-1.54 µg/L. The developed method was then successfully used for the determination of pyrethroid insecticides in environmental samples. PMID:26452797

  1. Ionic liquids and oligomer electrolytes based on the B(CN)4(-) anion; ion association, physical and electrochemical properties.

    PubMed

    Scheers, Johan; Pitawala, Jagath; Thebault, Frederic; Kim, Jae-Kwang; Ahn, Jou-Hyeon; Matic, Aleksandar; Johansson, Patrik; Jacobsson, Per

    2011-09-01

    The role of B(CN)(4)(-) (Bison) as a component of battery electrolytes is addressed by investigating the ionic conductivity and phase behaviour of ionic liquids (ILs), ion association mechanisms, and the electrochemical stability and cycling properties of LiBison based electrochemical cells. For C(4)mpyrBison and C(2)mimBison ILs, and mixtures thereof, high ionic conductivities (3.4 ≤σ(ion)≤ 18 mS cm(-1)) are measured, which together with the glass transition temperatures (-80 ≤T(g)≤-76 °C) are found to shift systematically for most compositions. Unfortunately, poor solubility of LiBison in these ILs hinders their use as solvents for lithium salts, although good NaBison solubility offers an alternative application in Na(+) conducting electrolytes. The poor IL solubility of LiBison is predicted to be a result of a preferred monodentate ion association, according to first principles modelling, supported by Raman spectroscopy. The solubility is much improved in strongly Li(+) coordinating oligomers, for example polyethylene glycol dimethyl ether (PEGDME), with the practical performance tested in electrochemical cells. The electrolyte is found to be stable in Li/LiFePO(4) coin cells up to 4 V vs. Li and shows promising cycling performance, with a capacity retention of 99% over 22 cycles. PMID:21776511

  2. Applications and Properties of Ionic Liquid- Based Gels and Soft Solid Composites

    NASA Astrophysics Data System (ADS)

    Voss, Bret Alan McGinness

    2011-12-01

    Solid-liquid composites (gels) have a combination of properties that afford new material applications in which high solute diffusion is desirable. These composites have a soft-solid mechanical integrity and will not flow under gravity, but entrain a liquid matrix (i.e. 60-98 mass %) which allows for high diffusion and high reactivity. Room temperature ionic liquid (RTILs) are molten organic salts with a melting point below room temperature and negligible vapor pressure. If the RTILs are used as the liquid component of a gel, then the gel matrix will not evaporate (unlike other organic solvents) and may be used for long term applications. This thesis research applies RTIL gels for two new applications; carbon dioxide/nitrogen separation and chemical warfare agent (CWA) barrier and decontamination. Separating CO2 from the flue gas of coal and gas fired power-plants is an increasingly economically and environmentally important gas separation. In this first study, RTIL gels are cast in a supported membrane and gas permeability and ideal selectivity are measured. The RTIL matrix has an inherent affinity for CO2 and provides a high diffusion, hence high permeability (i.e. 500-700 barrer). The solidifying component is a low molecular-weight organic gelator (LMOG) which through physical bonding interactions (i.e. hydrogen bonding, pi-pi stacking and van der Walls forces) forms an entangled network which provides mechanical stability (i.e. increase trans-membrane pressure required to expel selective material from the support). In these studies two LMOGs and five RTILs are used to make supported gel membranes and determine gas permeability and temperature dependent trends. The second application for RTIL gels is a decontaminating barrier for CWAs and toxic industrial compounds (TICs). In these studies a layer of RTIL gel is applied on top of a substrate contaminated with a CWA simulant (i.e. chloroethylethylsulfide, CEES). The gel performs well as a barrier, preventing CEES

  3. Effectiveness and potential of straw- and wood-based biochars for adsorption of imidazolium-type ionic liquids.

    PubMed

    Shi, Kaishun; Qiu, Yuping; Ben Li; Stenstrom, Michael K

    2016-08-01

    The growing industrial application of imidazolium-type ionic liquids (ITILs) is likely to result in their release to the environment. Water-soluble ITILs are difficult to remove from wastewaters using traditional adsorbents. In this work, we developed different biochars derived from straw and wood (named as SBB and WBB, respectively) to improve the adsorption effectiveness for removal of ITILs from wastewaters. SBB had high O/C element ratio (0.143), while WBB had high ratio of Vmicro/Vtotal (61.5%) compared with commercial activated carbon (AC). Both of them showed greater adsorption of ITILs than AC with different adsorption mechanisms. FTIR spectra revealed that electrostatic interactions were the dominant driving force in SBB adsorption, while high micropore volume promoted adsorption in WBB. The adsorption of [C2mim][BF4] on SBB and WBB was strongly enhanced by trivalent PO4(3-) anions, suggesting that PO4(3-) anions could be used as promoter to increase the removal efficiency of ITILs from wastewater. Using HCl solution (pH=0.5) as regenerant, SBB and WBB were regenerated with nearly 100% recovery of adsorption capacity over ten consecutive adsorption-desorption cycles. Straw-based biochar and wood-based biochar are efficient sorbents for removal of water-soluble ionic liquids from aqueous solutions. PMID:27107176

  4. Isolation of natural red colorants from fermented broth using ionic liquid-based aqueous two-phase systems.

    PubMed

    Ventura, Sónia P M; Santos-Ebinuma, Valéria C; Pereira, Jorge F B; Teixeira, Maria F S; Pessoa, Adalberto; Coutinho, João A P

    2013-05-01

    There is a growing demand for natural colorants. This is prompting the search for new alternative and "benign" separation systems allowing higher recoveries, extraction yields, and selectivities. This work investigates the use of aqueous two-phase systems (ATPS) based on ionic liquids as extraction processes for the recovery of red colorants from the fermented broth of Penicillium purpurogenum DPUA 1275. Several ATPS based on quaternary ammonium and imidazolium were studied in this work aiming at separating the red colorants produced from the remaining colorants and contaminant proteins present in the fermented broth. The results suggest that the red colorants can be isolated by an appropriate manipulation of some of the process conditions, such as the use of quaternary ammonium with short alkyl chains, alkaline media, and short tie-line lengths (extraction point systems with lower concentrations of ionic liquid). These conditions allow large partition coefficients for the red colorants (K red = 24.4 ± 2.3), high protein removal (60.7 ± 2.8 %) and selectivity parameters (S red/prot = 10.05). PMID:23455697

  5. Screen-printed electrode based electrochemical detector coupled with ionic liquid dispersive liquid-liquid microextraction and microvolume back-extraction for determination of mercury in water samples.

    PubMed

    Fernández, Elena; Vidal, Lorena; Martín-Yerga, Daniel; Blanco, María del Carmen; Canals, Antonio; Costa-García, Agustín

    2015-04-01

    A novel approach is presented, whereby gold nanostructured screen-printed carbon electrodes (SPCnAuEs) are combined with in-situ ionic liquid formation dispersive liquid-liquid microextraction (in-situ IL-DLLME) and microvolume back-extraction for the determination of mercury in water samples. In-situ IL-DLLME is based on a simple metathesis reaction between a water-miscible IL and a salt to form a water-immiscible IL into sample solution. Mercury complex with ammonium pyrrolidinedithiocarbamate is extracted from sample solution into the water-immiscible IL formed in-situ. Then, an ultrasound-assisted procedure is employed to back-extract the mercury into 10 µL of a 4 M HCl aqueous solution, which is finally analyzed using SPCnAuEs. Sample preparation methodology was optimized using a multivariate optimization strategy. Under optimized conditions, a linear range between 0.5 and 10 µg L(-1) was obtained with a correlation coefficient of 0.997 for six calibration points. The limit of detection obtained was 0.2 µg L(-1), which is lower than the threshold value established by the Environmental Protection Agency and European Union (i.e., 2 µg L(-1) and 1 µg L(-1), respectively). The repeatability of the proposed method was evaluated at two different spiking levels (3 and 10 µg L(-1)) and a coefficient of variation of 13% was obtained in both cases. The performance of the proposed methodology was evaluated in real-world water samples including tap water, bottled water, river water and industrial wastewater. Relative recoveries between 95% and 108% were obtained. PMID:25640123

  6. Actinide chemistry in ionic liquids.

    PubMed

    Takao, Koichiro; Bell, Thomas James; Ikeda, Yasuhisa

    2013-04-01

    This Forum Article provides an overview of the reported studies on the actinide chemistry in ionic liquids (ILs) with a particular focus on several fundamental chemical aspects: (i) complex formation, (ii) electrochemistry, and (iii) extraction behavior. The majority of investigations have been dedicated to uranium, especially for the 6+ oxidation state (UO2(2+)), because the chemistry of uranium in ordinary solvents has been well investigated and uranium is the most abundant element in the actual nuclear fuel cycles. Other actinides such as thorium, neptunium, plutonium, americium, and curiumm, although less studied, are also of importance in fully understanding the nuclear fuel engineering process and the safe geological disposal of radioactive wastes. PMID:22873132

  7. Lipid Biomembrane in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Yoo, Brian; Jing, Benxin; Shah, Jindal; Maginn, Ed; Zhu, Y. Elaine; Department of Chemical and Biomolecular Engineering Team

    2014-03-01

    Ionic liquids (ILs) have been recently explored as new ``green'' chemicals in several chemical and biomedical processes. In our pursuit of understanding their toxicities towards aquatic and terrestrial organisms, we have examined the IL interaction with lipid bilayers as model cell membranes. Experimentally by fluorescence microscopy, we have directly observed the disruption of lipid bilayer by added ILs. Depending on the concentration, alkyl chain length, and anion hydrophobicity of ILs, the interaction of ILs with lipid bilayers leads to the formation of micelles, fibrils, and multi-lamellar vesicles for IL-lipid complexes. By MD computer simulations, we have confirmed the insertion of ILs into lipid bilayers to modify the spatial organization of lipids in the membrane. The combined experimental and simulation results correlate well with the bioassay results of IL-induced suppression in bacteria growth, thereby suggesting a possible mechanism behind the IL toxicity. National Science Foundation, Center for Research Computing at Notre Dame.

  8. Structural and Electronic Properties of Amino Acid Based Ionic Liquids: A Theoretical Study

    NASA Astrophysics Data System (ADS)

    Wu, Yang; Zhang, Tiantian

    2009-10-01

    The gas-phase ion pairs of the ionic liquids containing 1-ethyl-3-methylimidazolium ([emim]+) and 20 natural amino acids ([AA]-) are studied at the B3LYP/6-311+G (d,p) level. The optimized structures, energies, and natural population analysis are presented and analyzed in terms of their possible correlation with the interaction energies and the H-bond separations. It is found that all the ion pairs of [emim][AA] can form strong H-bond interactions, which are dominated by the side-chain structure and the functional group of amino acid anions. The calculations indicate that an increase of the alkyl side-chain length coincides with a gradual decrease of H-bond energy, while the functional groups lead to the different localized charges on the anions, consequently affecting the electrostatic force. In addition, the intramolecular H bond in [AA]- can weaken the interaction, due to the decrease of the proton-accepting ability of the carbonyl O atoms. The H-bond chemical nature of [emim][AA] is investigated by atoms in molecules and natural bond orbital analyses. The preliminary analysis of 20 kinds of [emim][AA] ion pairs provides some initial hints as to the relationship between the interaction energy and the experimental glass transition temperature.

  9. Tailoring the properties of acetate-based ionic liquids using the tricyanomethanide anion.

    PubMed

    Lepre, L F; Szala-Bilnik, J; Padua, A A H; Traïkia, M; Ando, R A; Costa Gomes, M F

    2016-08-17

    The equilibrium and transport properties of mixtures of two ionic liquids - [C4C1Im][OAc] and [C4C1Im][C(CN)3] - were determined and interpreted at the molecular level using vibration spectroscopy, NMR and molecular dynamics simulation. The non-ideality of the mixtures [C4C1Im][OAc](1-x)[C(CN)3]x was characterized by V(E) = +0.28 cm(3) mol(-1) (293 K, x = 0.65) and H(E) = -2.2 kJ mol(-1) for x = 0.5. These values could be explained by a rearrangement of the hydrogen-bond network of the mixture that favours the interaction of the acetate anion with the imidazolium cation at position C2. The dynamic properties of the mixture are also dramatically influenced by the composition with a decrease of the viscosity and an increase of self-diffusion coefficients of the ions when the amount of tricyanomethanide anion increases in the mixture. PMID:27498753

  10. Aqueous two phase system based on ionic liquid for isolation of quinine from human plasma sample.

    PubMed

    Flieger, J; Czajkowska-Żelazko, A

    2015-01-01

    Aqueous two phase system was applied for selective extraction of quinine from human plasma. Bi-phase was constructed from ionic liquid: butyl-methyl-imidazolium chloride after addition kosmotropic salts K₃PO₄ or KH₂PO₄. Quinine was determined in plasma samples after drinking of tonic containing quinine. Determination was performed by HPLC on 5-μm Zorbax SB-CN column and eluent containing 40% acetonitrile (v/v), 20 mM phosphate buffer at pH 3 and 40 mM NaPF₆ using external standard method. The spectrophotometric detection was set λ=214 nm. Selective fluorescence detection was performed at excitation of 325 nm and emission of 375 nm. Proposed strategy provides suitable sample purification and gives extraction yields in the range of 89-106%. The determination coefficient (R(2)) has a value ≥0.997 in the range of 50-800 ng/ml quinine concentration. The limit of quantification was set at 27.9 ng/ml and the detection limit was found to be 8.4 ng/ml under fluorescence detection. PMID:25053040

  11. High-performance lubricant additives based on modified graphene oxide by ionic liquids.

    PubMed

    Fan, Xiaoqiang; Wang, Liping

    2015-08-15

    Graphene oxide (GO) is a layered material bearing a variety of oxygen-containing functional groups on its basal planes and edges, which allow it as a substrate to conduct a variety of chemical transformations. Here modified graphene oxide (MGO) was prepared using alkyl imidazolium ionic liquids (ILs) (1-butyl-3-methylimidazolium tetrafluoroborate (LB104), 1-butyl-3-methyl imidazolium hexafluorophosphate (LP104) and 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl) amide (LF106)) via epoxide ring-opening reaction, cation-π stacking or van der Waals interactions, with LB104 modified graphene (MG) exfoliated from graphite rod by a moderate electrochemical method as a comparison. The stability and tribological properties of MGO and MG as multialkylated cyclopentanes (MACs) additives were investigated in detail. The results show that GO is converted into graphene through the chemical modification using ILs, and MGO with good dispersion and stability in MACs significantly improves the tribological performance (friction and wear were reduced about 27% and 74% with pure MACs as a comparison, respectively). The excellent tribological properties are attributed to the formation of an ILs-containing graphene-rich tribofilm on the sliding surfaces, which as the third body can prevent the sliding surfaces from straight asperity contact and improve friction reducing and anti-wear behaviors. PMID:25935280

  12. Experiment and DFT studies on radioiodine removal and storage mechanism by imidazolium-based ionic liquid.

    PubMed

    Cao, Bobo; Liu, Shuangyue; Du, Dongmei; Xue, Zhimin; Fu, Hui; Sun, Haitao

    2016-03-01

    In order to remove and store radioactive substances effectively, studies on the mechanisms of radioiodine captured by ionic liquids (ILs) with a fixed cation (1-butyl-3-methyl-imidazolium cation [Bmim]+) were carried out in experimental and theoretical methods. Fourier transform infrared attenuated total reflectance (FT-IR ATR) spectra of 2BP8HQ and ultraviolet-visible (UV/vis) spectroscopy were used to investigate the kinetic process of radioiodine removal by ILs in experiment. Corresponding theoretical investigations on the structures and formation mechanisms of ILs, bare anions and complexes as well as hydrogen bonds was carried using density functional theory. The electrostatic potential was used in configuration design and construction. Charge distribution was used to show the variation of atom charge density, Interaction energy and vibration frequency change were performed to explore possible mechanisms on the halogen bond formation between radioiodine molecule and bare anion or anion in ILs when radioiodine captured by ILs. In order to characterize halogen bonds both natural bond orbital analysis and atoms in molecules analysis were performed. Both experimental and computational results showed that radioiodine could be captured by ILs with a 1:1mol stoichiometry. It was noteworthy that [Bmim][Br], [Bmim][I] and [Bmim][Cl], containing high radioiodine capture efficiency anions, were better candidates in removal and reliable storage of radioiodine for their capture efficiencies of over 80% in 5h. PMID:26774640

  13. Electrodeposition of Nanocrystalline Chromium Coatings Based on 1-Butyl-3-Methylimidazolium-Bromide Ionic Liquid.

    PubMed

    He, Xinkuai; Zhu, Qingyun; Hou, Bailong; Cai, Youxing; Li, Chen; Fu, Liqin; Wu, Luye

    2015-12-01

    The electrochemical behavior of trivalent chromium reduction from 1-butyl-3-methylimidazolium-bromide ([BMIM]Br) ionic liquid is studied. The result of cyclic voltammetry shows that the Cr(III) reduction is irreversible and occurs in two steps, Cr(III)to Cr(II), and Cr(II) to Cr(0), respectively. In the electrochemical impedance spectroscopy measurements, the preferable equivalent circuit is made to fit the experimental data. The effects of electroplating parameters on coating thickness and electrodepositon rate are investigated by potentiostatic method on Cu electrode from Cr(III)-[BMIM]Br solution. The results show that the temperature and depositing potential have great effect on the coating thickness and electrodeposition rate. The surface morphology and composition of deposited Cr are investigated using scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS). SEM analysis shows that chromium electrodeposits obtained on Cu electrodes present a ball-like structure. EDS analysis shows that the coatings are composed of Cr. Moreover, the corrosion resistance of the as-deposited chromium layer is evaluated using polarization curves. The results show that the corrosion resistance of the chromium coatings obtained at higher potential is better. PMID:26682363

  14. Electro-optical phenomena based on ionic liquids in an optofluidic waveguide.

    PubMed

    He, Xiaodong; Shao, Qunfeng; Cao, Pengfei; Kong, Weijie; Sun, Jiqian; Zhang, Xiaoping; Deng, Youquan

    2015-03-01

    An optofluidic waveguide with a simple two-terminal electrode geometry, when filled with an ionic liquid (IL), forms a lateral electric double-layer capacitor under a direct current (DC) electric field, which allows the realization of an extremely high carrier density in the vicinity of the electrode surface and terminals to modulate optical transmission at room temperature under low voltage operation (0 to 4 V). The unique electro-optical phenomenon of ILs was investigated at three wavelengths (663, 1330 and 1530 nm) using two waveguide geometries. Strong electro-optical modulations with different efficiencies were observed at the two near-infrared (NIR) wavelengths, while no detectable modulation was observed at 663 nm. The first waveguide geometry was used to investigate the position-dependent modulation along the waveguide; the strongest modulation was observed in the vicinity of the electrode terminal. The modulation phase is associated with the applied voltage polarity, which increases in the vicinity of the negative electrode and decreases at the positive electrode. The second waveguide geometry was used to improve the modulation efficiency. Meanwhile, the electro-optical modulations of seven ILs were compared at an applied voltage ranging from ±2 V to ±3.5 V. The results reveal that the modulation amplitude and response speed increase with increasing applied voltage, as well as the electrical conductivity of ILs. Despite the fact that the response speed isn't fast due to the high ionic density of ILs, the modulation amplitude can reach up to 6.0 dB when a higher voltage (U = ±3.5 V) is applied for the IL [Emim][BF4]. Finally, the physical explanation of the phenomenon was discussed. The effect of the change in IL structure on the electro-optical phenomena was investigated in another new experiment. The results reveal that the electro-optical phenomenon is probably caused mainly by the change in carrier concentration (ion redistribution near charged

  15. Ionic liquid based lithium battery electrolytes: fundamental benefits of utilising both TFSI and FSI anions?

    PubMed

    Kerner, M; Plylahan, N; Scheers, J; Johansson, P

    2015-07-15

    Several IL based electrolytes with an imidazolium cation (EMI) have been investigated trying to elucidate a possible beneficial effect of mixing FSI and TFSI anions in terms of physico-chemical properties and especially Li(+) solvation. All electrolytes were evaluated in terms of phase transitions, densities and viscosities, thermal stabilities, ionic conductivities and local structure, i.e. charge carriers. The electrolytes with up to 20% of Li-salts showed to be promising for high temperature lithium ion battery application (ca. 100 °C) and a synergetic effect of having mixed anions is discernible with the LiTFSI0.2EMIFSI0.8 electrolyte giving the best overall performance. The determination of the charge carriers revealed the SN to be ca. 2 for all analysed electrolytes, and proved the analysis of the mixed anion electrolytes to be challenging and inherently leads to an ambiguous picture of the Li(+) solvation. PMID:26147418

  16. Local structure formation in alkyl-imidazolium-based ionic liquids as revealed by linear and nonlinear Raman spectroscopy.

    PubMed

    Iwata, Koichi; Okajima, Hajime; Saha, Satyen; Hamaguchi, Hiro-O

    2007-11-01

    We show several pieces of Raman spectroscopic evidence that are indicative of local structure formation in imidazolium-based ionic liquids. Low-frequency Raman spectra of C n mimX, where C n mim stands for 1-alkyl(C n H 2 n+1 )-3-methylimidazolium cation and X represents the anion, exhibit broad bands assignable to collective modes of local structures. Spatial distributions of coherent anti-Stokes Raman scattering (CARS) signals from C n mim[PF 6] are consistent with local structures whose size increases with increasing n. Picosecond Raman spectra of S 1 trans-stilbene as a "picosecond Raman thermometer" show microscopic thermal inhomogeneity ascribable to local structure formation in C 2mimTf 2N and C 4mimTf 2N. We also describe two novel phenomena that we believe are relevant to extraordinary nanoenvironments generated by local structures in a magnetic ionic liquid C 4mim[FeCl 4]. PMID:17963358

  17. Influence of Particle Size Distribution on the Performance of Ionic Liquid-based Electrochemical Double Layer Capacitors

    PubMed Central

    Rennie, Anthony J. R.; Martins, Vitor L.; Smith, Rachel M.; Hall, Peter J.

    2016-01-01

    Electrochemical double layer capacitors (EDLCs) employing ionic liquid electrolytes are the subject of much research as they promise increased operating potentials, and hence energy densities, when compared with currently available devices. Herein we report on the influence of the particle size distribution of activated carbon material on the performance of ionic liquid based EDLCs. Mesoporous activated carbon was ball-milled for increasing durations and the resultant powders characterized physically (using laser diffraction, nitrogen sorption and SEM) and investigated electrochemically in the form of composite EDLC electrodes. A bi-modal particle size distribution was found for all materials demonstrating an increasing fraction of smaller particles with increased milling duration. In general, cell capacitance decreased with increased milling duration over a wide range of rates using CV and galvanostatic cycling. Reduced coulombic efficiency is observed at low rates (<25 mVs−1) and the efficiency decreases as the volume fraction of the smaller particles increases. Efficiency loss was attributed to side reactions, particularly electrolyte decomposition, arising from interactions with the smaller particles. The effect of reduced efficiency is confirmed by cycling for over 15,000 cycles, which has the important implication that diminished performance and reduced cycle life is caused by the presence of submicron-sized particles. PMID:26911531

  18. Influence of Particle Size Distribution on the Performance of Ionic Liquid-based Electrochemical Double Layer Capacitors

    NASA Astrophysics Data System (ADS)

    Rennie, Anthony J. R.; Martins, Vitor L.; Smith, Rachel M.; Hall, Peter J.

    2016-02-01

    Electrochemical double layer capacitors (EDLCs) employing ionic liquid electrolytes are the subject of much research as they promise increased operating potentials, and hence energy densities, when compared with currently available devices. Herein we report on the influence of the particle size distribution of activated carbon material on the performance of ionic liquid based EDLCs. Mesoporous activated carbon was ball-milled for increasing durations and the resultant powders characterized physically (using laser diffraction, nitrogen sorption and SEM) and investigated electrochemically in the form of composite EDLC electrodes. A bi-modal particle size distribution was found for all materials demonstrating an increasing fraction of smaller particles with increased milling duration. In general, cell capacitance decreased with increased milling duration over a wide range of rates using CV and galvanostatic cycling. Reduced coulombic efficiency is observed at low rates (<25 mVs-1) and the efficiency decreases as the volume fraction of the smaller particles increases. Efficiency loss was attributed to side reactions, particularly electrolyte decomposition, arising from interactions with the smaller particles. The effect of reduced efficiency is confirmed by cycling for over 15,000 cycles, which has the important implication that diminished performance and reduced cycle life is caused by the presence of submicron-sized particles.

  19. The interaction of a model active pharmaceutical with cationic surfactant and the subsequent design of drug based ionic liquid surfactants.

    PubMed

    Qamar, Sara; Brown, Paul; Ferguson, Steven; Khan, Rafaqat Ali; Ismail, Bushra; Khan, Abdur Rahman; Sayed, Murtaza; Khan, Asad Muhammad

    2016-11-01

    Interactions of active pharmaceutical ingredients (API) with surfactants remain an important research area due to the need to improve drug delivery systems. In this study, UV-Visible spectrophotometry was used to investigate the interactions between a model low molecular weight hydrophilic drug sodium valproate (SV) and cationic surfactant cetyltrimethylammonium bromide (CTAB). Changes in the spectra of SV were observed in pre- and post-micellar concentrations of CTAB. The binding constant (Kb) values and the number of drug molecules encapsulated per micelle were calculated, which posed the possibility of mixed micelle formation and strong complexation between SV and CTAB. These results were compared to those of a novel room temperature surface active ionic liquid, which was synthesized by the removal of inorganic counterions from a 1:1 mixture of CTAB and SV. In this new compound the drug now constitutes a building block of the carrier and, as such, has considerably different surfactant properties to its building blocks. In addition, enhanced solubility in a range of solvents, including simulated gastric fluid, was observed. The study provides valuable experimental evidence concerning the performance of drug based surfactant ionic liquids and how their chemical manipulation, without altering the architecture of the API, leads to control of surfactant behavior and physicochemical properties. In turn, this should feed through to improved and controlled drug release rates and delivery mechanisms, and the prevention of precipitation or formation of polymorphs typical of crystalline form APIs. PMID:27472069

  20. Influence of Particle Size Distribution on the Performance of Ionic Liquid-based Electrochemical Double Layer Capacitors.

    PubMed

    Rennie, Anthony J R; Martins, Vitor L; Smith, Rachel M; Hall, Peter J

    2016-01-01

    Electrochemical double layer capacitors (EDLCs) employing ionic liquid electrolytes are the subject of much research as they promise increased operating potentials, and hence energy densities, when compared with currently available devices. Herein we report on the influence of the particle size distribution of activated carbon material on the performance of ionic liquid based EDLCs. Mesoporous activated carbon was ball-milled for increasing durations and the resultant powders characterized physically (using laser diffraction, nitrogen sorption and SEM) and investigated electrochemically in the form of composite EDLC electrodes. A bi-modal particle size distribution was found for all materials demonstrating an increasing fraction of smaller particles with increased milling duration. In general, cell capacitance decreased with increased milling duration over a wide range of rates using CV and galvanostatic cycling. Reduced coulombic efficiency is observed at low rates (<25 mVs(-1)) and the efficiency decreases as the volume fraction of the smaller particles increases. Efficiency loss was attributed to side reactions, particularly electrolyte decomposition, arising from interactions with the smaller particles. The effect of reduced efficiency is confirmed by cycling for over 15,000 cycles, which has the important implication that diminished performance and reduced cycle life is caused by the presence of submicron-sized particles. PMID:26911531

  1. Effect of imidazolium-based ionic liquids on bacterial growth inhibition investigated via experimental and QSAR modelling studies.

    PubMed

    Ghanem, Ouahid Ben; Mutalib, M I Abdul; El-Harbawi, Mohanad; Gonfa, Girma; Kait, Chong Fai; Alitheen, Noorjahan Banu Mohamed; Leveque, Jean-Marc

    2015-10-30

    Tuning the characteristics of solvents to fit industrial requirements has currently become a major interest in both academic and industrial communities, notably in the field of room temperature ionic liquids (RTILs), which are considered one of the most promising green alternatives to molecular organic solvents. In this work, several sets of imidazolium-based ionic liquids were synthesized, and their toxicities were assessed towards four human pathogens bacteria to investigate how tunability can affect this characteristic. Additionally, the toxicity of particular RTILs bearing an amino acid anion was introduced in this work. EC50 values (50% effective concentration) were established, and significant variations were observed; although all studied ILs displayed an imidazolium moiety, the toxicity values were found to vary between 0.05 mM for the most toxic to 85.57 mM for the least toxic. Linear quantitative structure activity relationship models were then developed using the charge density distribution (σ-profiles) as molecular descriptors, which can yield accuracies as high as 95%. PMID:25965417

  2. Dendrite-Free Nanocrystalline Zinc Electrodeposition from an Ionic Liquid Containing Nickel Triflate for Rechargeable Zn-Based Batteries.

    PubMed

    Liu, Zhen; Cui, Tong; Pulletikurthi, Giridhar; Lahiri, Abhishek; Carstens, Timo; Olschewski, Mark; Endres, Frank

    2016-02-18

    Metallic zinc is a promising anode material for rechargeable Zn-based batteries. However, the dendritic growth of zinc has prevented practical applications. Herein it is demonstrated that dendrite-free zinc deposits with a nanocrystalline structure can be obtained by using nickel triflate as an additive in a zinc triflate containing ionic liquid. The formation of a thin layer of Zn-Ni alloy (η- and γ-phases) on the surface and in the initial stages of deposition along with the formation of an interfacial layer on the electrode strongly affect the nucleation and growth of zinc. A well-defined and uniform nanocrystalline zinc deposit with particle sizes of about 25 nm was obtained in the presence of Ni(II) . Further, it is shown that the nanocrystalline Zn exhibits a high cycling stability even after 50 deposition/stripping cycles. This strategy of introducing an inorganic metal salt in ionic liquid electrolytes can be considered as an efficient way to obtain dendrite-free zinc. PMID:26822484

  3. Specific solvation interactions of CO2 on acetate and trifluoroacetate imidazolium based ionic liquids at high pressures.

    PubMed

    Carvalho, Pedro J; Alvarez, Víctor H; Schröder, Bernd; Gil, Ana M; Marrucho, Isabel M; Aznar, Martín; Santos, Luís M N B F; Coutinho, João A P

    2009-05-14

    New classes of acidic or basic ionic liquids (ILs) are gaining special attention, since the efficiency of many processes can be enhanced by the judicious manipulation of these properties. The absorption of sour gases can be enhanced by the basic character of the IL. The fluorination of the cation or the anion can also contribute to enhance the gas solubility. In this work these two characteristics are evaluated through the study of the gas-liquid equilibrium of two ionic liquids based on similar anions, 1-butyl-3-methylimidazolium acetate ([C4mim][Ac]) and 1-butyl-3-methylimidazolium trifluoroacetate ([C4mim][TFA]), with carbon dioxide (CO2) at temperatures up to 363 K and pressures up to 76 MPa. The data reported are shown to be thermodynamically consistent. Henry's constants estimated from the experimental data show the solubility of CO2 on the [C4mim][Ac] to be spontaneous unlike in [C4mim][TFA] due to the differences in solvation enthalpies in these systems. Ab initio calculations were performed on simple intermolecular complexes of CO2 with acetate and trifluoroacetate using MP2/6-31G(d) and the G3 and G3MP2 theoretical procedures to understand the interactions between CO2 and the anions. The theoretical study indicates that although both anions exhibit a simultaneous interaction of the two oxygen of the carboxylate group with the CO2, the acetate acts as a stronger Lewis base than the trifluoroacetate. 13C high-resolution and magic angle spinning (HRMAS) NMR spectra provide further evidence for the acid/base solvation mechanism and the stability of the acetate ion on these systems. Further similarities and differences observed between the two anions in what concerns the solvation of CO2 are discussed. PMID:19374423

  4. An electrochemical gas sensor based on paper supported room temperature ionic liquids.

    PubMed

    Dossi, Nicolò; Toniolo, Rosanna; Pizzariello, Andrea; Carrilho, Emanuel; Piccin, Evandro; Battiston, Simone; Bontempelli, Gino

    2012-01-01

    A sensitive and fast-responding membrane-free amperometric gas sensor is described, consisting of a small filter paper foil soaked with a room temperature ionic liquid (RTIL), upon which three electrodes are screen printed with carbon ink, using a suitable mask. It takes advantage of the high electrical conductivity and negligible vapour pressure of RTILs as well as their easy immobilization into a porous and inexpensive supporting material such as paper. Moreover, thanks to a careful control of the preparation procedure, a very close contact between the RTIL and electrode material can be achieved so as to allow gaseous analytes to undergo charge transfer just as soon as they reach the three-phase sites where the electrode material, paper supported RTIL and gas phase meet. Thus, the adverse effect on recorded currents of slow steps such as analyte diffusion and dissolution in a solvent is avoided. To evaluate the performance of this device, it was used as a wall-jet amperometric detector for flow injection analysis of 1-butanethiol vapours, adopted as the model gaseous analyte, present in headspace samples in equilibrium with aqueous solutions at controlled concentrations. With this purpose, the RTIL soaked paper electrochemical detector (RTIL-PED) was assembled by using 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as the wicking RTIL and printing the working electrode with carbon ink doped with cobalt(II) phthalocyanine, to profit from its ability to electrocatalyze thiol oxidation. The results obtained were quite satisfactory (detection limit: 0.5 μM; dynamic range: 2-200 μM, both referring to solution concentrations; correlation coefficient: 0.998; repeatability: ±7% RSD; long-term stability: 9%), thus suggesting the possible use of this device for manifold applications. PMID:22076475

  5. Graphene-based supercapacitors in the parallel-plate electrode configuration: ionic liquids versus organic electrolytes.

    PubMed

    Shim, Youngseon; Kim, Hyung J; Jung, Younjoon

    2012-01-01

    Supercapacitors with two single-sheet graphene electrodes in the parallel plate geometry are studied via molecular dynamics (MD) computer simulations. Pure 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI+BF4-) and a 1.1 M solution of EMI+BF4- in acetonitrile are considered as prototypes of room-temperature ionic liquids (RTILs) and organic electrolytes. Electrolyte structure, charge density and associated electric potential are investigated by varying the charges and separation of the two electrodes. Multiple charge layers formed in the electrolytes in the vicinity of the electrodes are found to screen the electrode surface charge almost completely. As a result, the supercapacitors show nearly an ideal electric double layer behavior, i.e., the electric potential exhibits essentially a plateau behavior in the entire electrolyte region except for sharp changes in screening zones very close to the electrodes. Due to its small size and large charge separation, BF4- is considerably more efficient in shielding electrode charges than EMI+. In the case of the acetonitrile solution, acetonitrile also plays an important role by aligning its dipoles near the electrodes; however, the overall screening mainly arises from ions. Because of the disparity of shielding efficiency between cations and anions, the capacitance of the positively-charged anode is significantly larger than that of the negatively-charged cathode. Therefore, the total cell capacitance in the parallel plate configuration is primarily governed by the cathode. Ion conductivity obtained via the Green-Kubo (GK) method is found to be largely independent of the electrode surface charge. Interestingly, EMI+BF4- shows higher GK ion conductivity than the 1.1 M acetonitrile solution between two parallel plate electrodes. PMID:22455024

  6. Reusable electrochemical sensor for bisphenol A based on ionic liquid functionalized conducting polymer platform.

    PubMed

    Wang, Jhe-Yi; Su, Ya-Ling; Wu, Bo-Hao; Cheng, Shu-Hua

    2016-01-15

    The toxicity of bisphenol A (BPA) has attracted considerable attention, and the reported electrochemical sensors for BPA need further improvement in reusability due to serious surface fouling. In this study, a composite film is designed aiming to provide both an accurate and repeatable platform for BPA determination. The conducting poly(3,4-ethylenedioxythiophene) film (PEDOT) and ionic liquid 1-butyl-3-methylimidazolium bromide (BMIMBr) were modified onto screen-printed carbon electrodes (SPCE) by electropolymerization and drop/spin methods, respectively. The surface characteristics of the composite film were characterized by field emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and surface water contact angle experiments. The composite film-modified electrodes exhibited a linear response to BPA in the range of 0.1-500µM in pH 7.0 phosphate buffer solution (PBS) under optimized flow-injection amperometry. The method sensitivity and detection limit (S/N=3) were 0.2661μA μM(-1) (2.419μA μM(-1)cm(-2)) and 0.02µM, respectively. A relative standard deviation of 1.95% was obtained for 77 successive measurements of 10µM BPA, and the repeatability outperformed previously reported work. The proposed method was applied to detect BPA released from plastic water bottles using the standard addition method, and satisfactory recoveries were obtained. The electrochemical assay was validated by comparison with the chromatographic method, and the results showed good agreement between the two methods. PMID:26592583

  7. Adsorption Kinetics at Silica Gel/Ionic Liquid Solution Interface.

    PubMed

    Flieger, Jolanta; Tatarczak-Michalewska, Małgorzata; Groszek, Anna; Blicharska, Eliza; Kocjan, Ryszard

    2015-01-01

    A series of imidazolium and pyridinium ionic liquids with different anions (Cl(-), Br(-), BF₄(-), PF₆(-)) has been evaluated for their adsorption activity on silica gel. Quantification of the ionic liquids has been performed by the use of RP-HPLC with organic-aqueous eluents containing an acidic buffer and a chaotropic salt. Pseudo-second order kinetic models were applied to the experimental data in order to investigate the kinetics of the adsorption process. The experimental data showed good fitting with this model, confirmed by considerably high correlation coefficients. The adsorption kinetic parameters were determined and analyzed. The relative error between the calculated and experimental amount of ionic liquid adsorbed at equilibrium was within 7%. The effect of various factors such as initial ionic liquid concentration, temperature, kind of solvent, kind of ionic liquid anion and cation on adsorption efficiency were all examined in a lab-scale study. Consequently, silica gel showed better adsorptive characteristics for imidazolium-based ionic liquids with chaotropic anions from aqueous solutions in comparison to pyridinium ionic liquids. The adsorption was found to decrease with the addition of organic solvents (methanol, acetonitrile) but it was not sensitive to the change of temperature in the range of 5-40 °C. PMID:26690392

  8. Ionic liquid-based zinc oxide nanofluid for vortex assisted liquid liquid microextraction of inorganic mercury in environmental waters prior to cold vapor atomic fluorescence spectroscopic detection.

    PubMed

    Amde, Meseret; Liu, Jing-Fu; Tan, Zhi-Qiang; Bekana, Deribachew

    2016-03-01

    Zinc oxide nanofluid (ZnO-NF) based vortex assisted liquid liquid microextraction (ZnO-NF VA-LLME) was developed and employed in extraction of inorganic mercury (Hg(2+)) in environmental water samples, followed by cold vapor atomic fluorescence spectrometry (CV-AFS). Unlike other dispersive liquid liquid microextraction techniques, ZnO-NF VA-LLME is free of volatile organic solvents and dispersive solvent consumption. Analytical signals were obtained without back-extraction from the ZnO-NF phase prior to CV-AFS determination. Some essential parameters of the ZnO-NF VA-LLME and cold vapor generation such as composition and volume of the nanofluid, vortexing time, pH of the sample solution, amount of the chelating agent, ionic strength and matrix interferences have been studied. Under optimal conditions, efficient extraction of 1ng/mL of Hg(2+) in 10mL of sample solution was achieved using 50μL of ZnO-NF. The enrichment factor before dilution, detection limits and limits of quantification of the method were about 190, 0.019 and 0.064ng/mL, respectively. The intra and inter days relative standard deviations (n=8) were found to be 4.6% and 7.8%, respectively, at 1ng/mL spiking level. The accuracy of the current method was also evaluated by the analysis of certified reference materials, and the measured Hg(2+) concentration of GBW08603 (9.6ng/mL) and GBW(E)080392 (8.9ng/mL) agreed well with their certified value (10ng/mL). The method was applied to the analysis of Hg(2+) in effluent, influent, lake and river water samples, with recoveries in the range of 79.8-92.8% and 83.6-106.1% at 1ng/mL and 5ng/mL spiking levels, respectively. Overall, ZnO-NF VA-LLME is fast, simple, cost-effective and environmentally friendly and it can be employed for efficient enrichment of the analyte from various water samples. PMID:26717850

  9. Comparative study of bending characteristics of ionic polymer actuators containing ionic liquids for modeling actuation

    NASA Astrophysics Data System (ADS)

    Kikuchi, Kunitomo; Sakamoto, Takumi; Tsuchitani, Shigeki; Asaka, Kinji

    2011-04-01

    Ionic polymer metal composites (IPMCs) that can operate in air have recently been developed by incorporating an ionic liquid in ionic polymers. To understand transduction in these composites, it is important to determine the role of the ionic liquid in the ionic polymer (Nafion®), to identify the counter cation, and to investigate the interaction of IPMCs with water vapor in the air. We used Fourier-transform infrared spectroscopy to analyze three Nafion® membranes, which were soaked in mixtures of water and an ionic liquid (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIBF4), 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6)). The results demonstrate that only cations (EMI+ and BMI+) in the ionic liquids are taken into the Nafion® membranes as counter ions and that the water content of the membranes in air is less than ˜4% that of Nafion® swollen with water. Based on the experimental results, a transduction model is proposed for an IPMC with an ionic liquid. In this model, bending is caused by local swelling due to the volume effect of the bulky counter cations. This model can explain 30-50% of the experimentally observed bending curvature.

  10. Thermodynamics and micro heterogeneity of ionic liquids.

    PubMed

    Gomes, Margarida F Costa; Lopes, J N Canongia; Padua, A A H

    2010-01-01

    The high degree of organisation in the fluid phase of room-temperature ionic liquids has major consequences on their macroscopic properties, namely on their behaviour as solvents. This nanoscale self-organisation is the result of an interplay between two types of interaction in the liquid phase - Coulomb and van der Waals - that eventually leads to the formation of medium-range structures and the recognition of some ionic liquids as composed of a high-charge density, cohesive network permeated by low-charge density regions.In this chapter, the structure of the ionic liquids will be explored and some of their consequences to the properties of ionic liquids analyzed. PMID:21107797

  11. Ionic liquid lubrication at electrified interfaces

    NASA Astrophysics Data System (ADS)

    Kong, Lingling; Huang, Wei; Wang, Xiaolei

    2016-06-01

    The lubrication performances of ionic liquids at electrified interfaces have been investigated by using a reciprocating sliding tribometer. Experimental results indicated that the lubricity of the confined ionic liquids was markedly affected by the application of external electric field and strong interface electric field strength could result in high friction. The influence was more pronounced for the ionic liquid with a shorter alkyl side chain in particular. The main reason of the friction increment might be ascribed to the electrically influenced surface adsorption where the charged ions were structured to form robust and ordered layers.

  12. [Separation of bases, phenols and pharmaceuticals on ionic liquid-modified silica stationary phase with pure water as mobile phase].

    PubMed

    Wang, Xusheng; Qiu, Hongdeng; Liu, Xia; Jiang, Shengxiang

    2011-03-01

    N-methylimidazolium ionic liquid (IL) -modified silica was prepared with the reaction of 3-chloropropyl modified silica and N-methylimidazole using toluene as solvent. Based on the multiple interactions between N-methylimidazolium IL-modified silica and analytes such as hydrophobic interaction, electrostatic attraction, repulsion interaction, hydrogen-bonding, etc., the bases (cytosine, thymine, 2-aminopyrimidine and 6-chloroguanine), phenols (m-aminophenol, resorcinol and m-nitrophenol) and three pharmaceuticals (moroxydine hydrochloride, acyclovir and cephalexin hydrate) were separated successfully with only pure water as the mobile phase. These chromatographic separations are environmental friendly, economical and convenient, without any organic solvent or buffer additive. The retention mechanism of these samples on the stationary phase was also investigated. PMID:21657060

  13. Isothermal and non-isothermal crystallization kinetics of PVA + ionic liquid [BDMIM][BF4]-based polymeric films

    NASA Astrophysics Data System (ADS)

    Saroj, A. L.; Chaurasia, S. K.; Kataria, Shalu; Singh, R. K.

    2016-06-01

    The effect of ionic liquid (IL), 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BDMIM][BF4], on crystallization behavior of poly(vinyl alcohol) (PVA) has been studied by isothermal and non-isothermal differential scanning calorimetry techniques. The PVA + IL based polymer electrolyte films have been prepared using solution casting technique. To describe the isothermal and non-isothermal crystallization kinetics, several kinetic equations have been employed on PVA + IL based films. There is strong dependence of the peak crystallization temperature (Tc), relative degree of crystallity (Xt), half-time of crystallization (t1/2), crystallization rate constants (Avrami Kt and Tobin AT), and Avrami (n) and Tobin (nT) exponents on the cooling rate and IL loading.

  14. Evaluation of Two Ionic Liquid-Based Epoxies from the MISSE-8 (Materials International Space Station Experiment-8) Sample Carrier

    NASA Technical Reports Server (NTRS)

    Rabenberg, Ellen; Kaukler, William; Grugel, Richard

    2015-01-01

    Two sets of epoxy mixtures, both containing the same ionic liquid (IL) based resin but utilizing two different curing agents, were evaluated after spending more than two years of continual space exposure outside of the International Space Station on the MISSE-8 sample rack. During this period the samples, positioned on nadir side, also experienced some 12,500 thermal cycles between approximately -40?C and +40 C. Initial examination showed some color change, a miniscule weight variance, and no cracks or de-bonding from the sample substrate. Microscopic examination of the surface reveled some slight deformities and pitting. These observations, and others, are discussed in view of the ground-based control samples. Finally, the impetus of this study in terms of space applications is presented.

  15. The effects of ionic liquid on the electrochemical sensing performance of graphene- and carbon nanotube-based electrodes.

    PubMed

    Wang, Chueh-Han; Wu, Cheng-Hung; Wu, Jia-Wun; Lee, Ming-Tsung; Chang, Jeng-Kuei; Ger, Ming-Der; Sun, Chia-Liang

    2013-01-21

    The electrochemical sensing properties of graphene-based and carbon nanotube (CNT)-based electrodes towards ascorbic acid, dopamine, uric acid, and glucose are systematically compared. Nano-sized Pd catalyst particles are uniformly dispersed on both carbon supports using a supercritical fluid deposition technique to increase the sensing performance. The CNT/Pd electrode shows higher detection current than that of the graphene/Pd electrode, which is attributed to the three-dimensional architecture interwoven by the CNTs that creates a larger number of reaction sites. With the incorporation of ionic liquid (IL), the detection sensitivity of the IL/graphene/Pd electrode significantly increases, becoming noticeably higher than that of the IL/CNT/Pd counterpart. The synergistic interactions between graphene and IL that lead to the superior sensing performance are demonstrated and discussed. PMID:23172364

  16. Understanding the mechanism of CO2 capture by 1,3 di-substituted imidazolium acetate based ionic liquids.

    PubMed

    Mao, James X; Steckel, Janice A; Yan, Fangyong; Dhumal, Nilesh; Kim, Hyung; Damodaran, Krishnan

    2016-01-21

    Efficient CO2 capture by ionic liquids needs a thorough understanding of underlying mechanisms of the CO2 interaction with ionic liquids, especially when it involves chemisorption. In this work we have systematically investigated the mechanism of CO2 capture by 1,3 di-substituted imidazolium acetate ionic liquids using density functional theory. Solvent effects are analyzed using QM/MM and QM/QM approaches with the help of molecular dynamics simulations and ONIOM methods. The investigation of different stepwise mechanisms shows that CO2 could be involved in the first step of the reaction mechanism, also a new two-step mechanism is proposed. The final stabilization step is analyzed and pointed out to be responsible for important experimentally-observed features of the reaction. PMID:26687108

  17. Fabrication of core-shell structured magnetic nanocellulose base polymeric ionic liquid for effective biosorption of Congo red dye.

    PubMed

    Beyki, Mostafa Hossein; Bayat, Mehrnoosh; Shemirani, Farzaneh

    2016-10-01

    Ionic liquids are considered to be a class of environmentally friendly compounds as combination of them with bioresource polymeric substances such as; cellulose, constitute emerging coating materials. Biosorption by polymeric ionic liquids exhibits an attractive green way that involves low cost and irrespective of toxicity. As a result, a novel polymeric ionic liquid has been developed by the reaction of one step synthesized Fe3O4-cellulose nanohybrid, epichlorohydrin and 1-methylimidazole and employed as a green sorbent for efficient biosorption of Congo red dye. Effective parameters on dye removing as well as their interactions were determined with response surface methodology (RSM). Congo red adsorption showed fast equilibrium time (11min) with maximum uptake of 131mgg(-1). Isotherm study revealed that Langmuir adsorption model can better describe dye adsorption behavior. Regeneration of the sorbent was performed with a mixture of methanol-acetone-NaOH (3.0molL(-1)) solution. PMID:27372013

  18. Lithium-Air and ionic Liquids

    SciTech Connect

    Kellar, Michael

    2015-09-01

    The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to the typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.

  19. Use of a 4,5-dicyanoimidazolate anion based ionic liquid for the synthesis of iron and silver nanoparticles.

    PubMed

    Mondal, Suvendu Sekhar; Marquardt, Dorothea; Janiak, Christoph; Holdt, Hans-Jürgen

    2016-04-01

    Sixteen new ionic liquids (ILs) with tetraethylammonium, 1-butyl-3-methylimidazolium, 3-methyl-1-octylimidazolium and tetrabutylphosphonium cations paired with 2-substituted 4,5-dicyanoimidazolate anions (substituent at C2 = methyl, trifluoromethyl, pentafluoroethyl, N,N'-dimethyl amino and nitro) have been synthesized and characterized by using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA). The effects of cation and anion type and structure of the resulting ILs, including several room temperature ionic liquids (RTILs), are reflected in the crystallization, melting points and thermal decomposition of the ILs. ILs exhibited large liquid and crystallization ranges and formed glasses on cooling with glass transition temperatures in the range of -22 to -71 °C. We selected one of the newly designed ILs due to its bigger size, compared to the common conventional IL anion and high electron-withdrawing nitrile group leads to an overall stabilization anion that may stabilize the metal nanoparticles. Stable and better separated iron and silver nanoparticles are obtained by the decomposition of corresponding Fe2(CO)9 and AgPF6, respectively, under N2-atmosphere in newly designed nitrile functionalized 4,5-dicyanoimidazolate anion based IL. Very small and uniform size for Fe-nanoparticles of about 1.8 ± 0.6 nm were achieved without any additional stabilizers or capping molecules. Comparatively bigger size of Ag-nanoparticles was obtained through the reduction of AgPF6 by hydrogen gas. Additionally, the AgPF6 precursor was decomposed under microwave irradiation (MWI), fabricating nut-in-shell-like, that is, core-separated-from-shell Ag-nano-structures. PMID:26885778

  20. Thermodynamic modeling of ionic liquid systems: development and detailed overview of novel methodology based on the PC-SAFT.

    PubMed

    Paduszyński, Kamil; Domańska, Urszula

    2012-04-26

    We present the results of an extensive study on a novel approach of modeling ionic liquids (ILs) and their mixtures with molecular compounds, incorporating perturbed-chain statistical associating fluid theory (PC-SAFT). PC-SAFT was used to calculate the thermodynamic properties of different homologous series of ILs based on the bis(trifluormethylsulfonyl)imide anion ([NTf2]). First, pure fluid parameters were obtained for each IL by means of fitting the model predictions to experimental liquid densities over a broad range of temperature and pressure. The reliability and physical significance of the parameters as well as the employed molecular scheme were tested by calculation of density, vapor pressure, and other properties of pure ILs (e.g., critical properties, normal boiling point). Additionally, the surface tension of pure ILs was calculated by coupling the PC-SAFT equation of state with density gradient theory (DGT). All correlated/predicted results were compared with literature experimental or simulation data. Afterward, we attempted to model various thermodynamic properties of some binary systems composed of IL and organic solvent or water. The properties under study were the binary vapor-liquid, liquid-liquid, and solid-liquid equilibria and the excess enthalpies of mixing. To calculate cross-interaction energies we used the standard combining rules of Lorentz-Berthelot, Kleiner-Sadowski, and Wolbach-Sandler. It was shown that incorporation of temperature-dependent binary corrections was required to obtain much more accurate results than in the case of conventional predictions. Binary corrections were adjusted to infinite dilution activity coefficients of a particular solute in a given IL determined experimentally or predicted by means of the modified UNIFAC (Dortmund) group contribution method. We concluded that the latter method allows accurate and reliable calculations of bulk-phase properties in a totally predictive manner. PMID:22469027

  1. Ultrasound-assisted ionic liquid-based dispersive liquid-liquid microextraction for preconcentration of patent blue V and its determination in food samples by UV-visible spectrophotometry.

    PubMed

    Unsal, Yunus Emre; Soylak, Mustafa; Tuzen, Mustafa

    2015-04-01

    Ultrasound-assisted ionic liquid-based dispersive liquid-liquid microextraction procedure (UA-IL-DLLME) was developed for determination of trace levels of patent blue V prior to its determination by UV-visible spectrophotometry. Patent blue V was extracted from 25-mL sample into a 100-μL volume of ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), with the aid of sonication in an ultrasonic bath. Several variables affecting microextraction efficiency were optimized. Under the optimum experimental conditions, the detection limit (3 s) was 0.68 μg L(-1), and the preconcentration factor was 100. The relative standard deviation for six replicate determinations of patent blue V was 4.5%. The method was applied to the determination of patent blue V in food samples. The proposed procedure is effective, very simple, and fast. PMID:25800367

  2. Occupational Exposure to Mercury: Air Exposure Assessment and Biological Monitoring based on Dispersive Ionic Liquid-Liquid Microextraction

    PubMed Central

    SHIRKHANLOO, Hamid; GOLBABAEI, Farideh; HASSANI, Hamid; EFTEKHAR, Farrokh; KIAN, Mohammad Javad

    2014-01-01

    Abstract Background Exposure to mercury (Hg) as a heavy metal can cause health effects. The objective of this study was to assess occupational exposure to Hg in a chlor-alkali petrochemical industry in Iran by determining of Hg concentrations in air, blood and urine samples. Methods The study was performed on 50 exposed subjects and 50 unexposed controls. Air samples were collected in the breathing zone of exposed subjects, using hopcalite sorbents. Analysis was performed using a cold vapor atomic absorption spectrophotometer (CV-AAS) according to NIOSH analytical method 6009. For all participants, blood and urine samples were collected and then transferred into sterile glass tubes. After micro-extraction with ionic liquid and back extraction with nitric acid, Hg concentrations in blood and urine samples were determined by CV-AAS. Results The mean concentration of air Hg was 0.042± 0.003 mg/m3. The mean concentrations of Hg in blood and urine samples of exposed subjects were significantly higher than unexposed controls (22.41± 12.58 versus 1.19± 0.95 μg/l and 30.61± 10.86 versus 1.99± 1.34 μg/g creatinine, respectively). Correlation of air Hg with blood Hg, urine Hg and blood Hg-urine Hg ratio were significant statistically (P< 0.05). Conclusions The values of Hg in blood and urine samples of chlor-alkali workers were considerably high. Correlation coefficients showed that blood Hg and blood Hg-urine Hg ratio are better indicators than urine Hg for assessing occupationally exposed workers in terms of current exposure assessment. PMID:26110150

  3. Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal

    PubMed Central

    Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka

    2014-01-01

    The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes, or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70% molar yield toward citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide. PMID:24790972

  4. Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal

    NASA Astrophysics Data System (ADS)

    Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka

    2014-02-01

    The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70 % molar yield towards citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide.

  5. Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal.

    PubMed

    Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka

    2014-01-01

    The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes, or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70% molar yield toward citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide. PMID:24790972

  6. Confinement of Ionic Liquids in Nanocages: Tailoring the Molecular Sieving Properties of ZIF-8 for Membrane-Based CO2 Capture.

    PubMed

    Ban, Yujie; Li, Zhengjie; Li, Yanshuo; Peng, Yuan; Jin, Hua; Jiao, Wenmei; Guo, Ang; Wang, Po; Yang, Qingyuan; Zhong, Chongli; Yang, Weishen

    2015-12-14

    Fine-tuning of effective pore size of microporous materials is necessary to achieve precise molecular sieving properties. Herein, we demonstrate that room temperature ionic liquids can be used as cavity occupants for modification of the microenvironment of MOF nanocages. Targeting CO2 capture applications, we tailored the effective cage size of ZIF-8 to be between CO2 and N2 by confining an imidazolium-based ionic liquid [bmim][Tf2 N] into ZIF-8's SOD cages by in-situ ionothermal synthesis. Mixed matrix membranes derived from ionic liquid-modified ZIF-8 exhibited remarkable combinations of permeability and selectivity that transcend the upper bound of polymer membranes for CO2 /N2 and CO2 /CH4 separation. We observed an unusual response of the membranes to varying pressure, that is, an increase in the CO2 /CH4 separation factor with pressure, which is highly desirable for practical applications in natural gas upgrading. PMID:26515558

  7. Catalytic reactions in ionic liquids.

    PubMed

    Sheldon, R

    2001-12-01

    The chemical industry is under considerable pressure to replace many of the volatile organic compounds (VOCs) that are currently used as solvents in organic synthesis. The toxic and/or hazardous properties of many solvents, notably chlorinated hydrocarbons, combined with serious environmental issues, such as atmospheric emissions and contamination of aqueous effluents is making their use prohibitive. This is an important driving force in the quest for novel reaction media. Curzons and coworkers, for example, recently noted that rigorous management of solvent use is likely to result in the greatest improvement towards greener processes for the manufacture of pharmaceutical intermediates. The current emphasis on novel reaction media is also motivated by the need for efficient methods for recycling homogeneous catalysts. The key to waste minimisation in chemicals manufacture is the widespread substitution of classical 'stoichiometric' syntheses by atom efficient, catalytic alternatives. In the context of homogeneous catalysis, efficient recycling of the catalyst is a conditio sine qua non for economically and environmentally attractive processes. Motivated by one or both of the above issues much attention has been devoted to homogeneous catalysis in aqueous biphasic and fluorous biphasic systems as well as in supercritical carbon dioxide. Similarly, the use of ionic liquids as novel reaction media may offer a convenient solution to both the solvent emission and the catalyst recycling problem. PMID:12239988

  8. Aggregation Behavior of Imidazolium-Based Surface-Active Ionic Liquids with Photoresponsive Cinnamate Counterions in the Aqueous Solution.

    PubMed

    Bi, Yanhui; Zhao, Liuchen; Hu, Qiongzheng; Gao, Yan'an; Yu, Li

    2015-11-24

    Two imidazolium-based surface active ionic liquids (SAILs) with photoresponsive cinnamate aromatic counterions, viz. 1-dodecyl-3-methylimidazolium cinnamate ([C12mim][CA]) and 1-dodecyl-3-methylimidazolium para-hydroxy-cinnamate ([C12mim][PCA]), were newly synthesized, and their self-assembly behaviors in aqueous solutions were systematically explored. Results of surface tension and conductivity measurements show that both [C12mim][CA] and [C12mim][PCA] display a superior surface activity in aqueous solutions compared to the common imidazolium-based SAIL, 1-dodecyl-3-methylimidazolium bromide (C12mimBr), which implies the incorporation of cinnamate aromatic counterions can promote the micellar formation. Furthermore, [C12mim][CA] shows higher surface activity due to the higher hydrophobicity of its counterion in comparison to [C12mim][PCA] that has a hydroxyl group. Both hexagonal liquid-crystalline phase (H1) and cubic liquid-crystalline phase (V2) were constructed in the [C12mim][CA] aqueous solutions. In contrast, the [C12mim][PCA]/H2O system only exhibits a single hexagonal liquid-crystalline phase (H1) in a broad concentration region. These lyotropic liquid crystal (LLC) phases were comprehensively characterized by polarized optical microscopy (POM), small-angle X-ray scattering (SAXS), and rheometer. Investigation on the temperature-dependent self-assembly nanostructures demonstrates that the higher temperature leads to a looser arrangement. Under UV irradiation, trans-cis photoisomerization of the phenylalkene group results in inferior surface activity of the prepared SAILs in aqueous solution with higher cmc values. Moreover, UV light irradiation induces obvious change of the structural parameters without altering the LLC phases. This work is expected to enrich the investigations of phase behaviors formed in SAILs systems and receive particular attention due to their unique properties and potential applications in drug delivery, biochemistry, materials

  9. Encapsulated ionic liquids (ENILs): from continuous to discrete liquid phase.

    PubMed

    Palomar, Jose; Lemus, Jesus; Alonso-Morales, Noelia; Bedia, Jorge; Gilarranz, Miguel A; Rodriguez, Juan J

    2012-10-14

    Encapsulated ionic liquid (ENIL) material was developed, consisting of ionic liquid (IL) introduced into carbon submicrocapsules. ENILs contain >85% w/w of IL but discretized in submicroscopic encapsulated drops, drastically increasing the surface contact area with respect to the neat fluid. ENIL materials were here tested for gas separation processes, obtaining a drastic increase in mass transfer rate. PMID:22935733

  10. Determination of sunset yellow and tartrazine in food samples by combining ionic liquid-based aqueous two-phase system with high performance liquid chromatography.

    PubMed

    Sha, Ou; Zhu, Xiashi; Feng, Yanli; Ma, Weixing

    2014-01-01

    We proposed a simple and effective method, by coupling ionic liquid-based aqueous two-phase systems (IL-ATPSs) with high performance liquid chromatography (HPLC), for the analysis of determining tartrazine and sunset yellow in food samples. Under the optimized conditions, IL-ATPSs generated an extraction efficiency of 99% for both analytes, which could then be directly analyzed by HPLC without further treatment. Calibration plots were linear in the range of 0.01-50.0 μg/mL for both Ta and SY. The limits of detection were 5.2 ng/mL for Ta and 6.9 ng/mL for SY. This method proves successful for the separation/analysis of tartrazine and sunset yellow in soft drink sample, candy sample, and instant powder drink and leads to consistent results as obtained from the Chinese national standard method. PMID:25538857

  11. Determination of Sunset Yellow and Tartrazine in Food Samples by Combining Ionic Liquid-Based Aqueous Two-Phase System with High Performance Liquid Chromatography

    PubMed Central

    Sha, Ou; Zhu, Xiashi; Feng, Yanli; Ma, Weixing

    2014-01-01

    We proposed a simple and effective method, by coupling ionic liquid-based aqueous two-phase systems (IL-ATPSs) with high performance liquid chromatography (HPLC), for the analysis of determining tartrazine and sunset yellow in food samples. Under the optimized conditions, IL-ATPSs generated an extraction efficiency of 99% for both analytes, which could then be directly analyzed by HPLC without further treatment. Calibration plots were linear in the range of 0.01–50.0 μg/mL for both Ta and SY. The limits of detection were 5.2 ng/mL for Ta and 6.9 ng/mL for SY. This method proves successful for the separation/analysis of tartrazine and sunset yellow in soft drink sample, candy sample, and instant powder drink and leads to consistent results as obtained from the Chinese national standard method. PMID:25538857

  12. Are ionic liquids based on pyrrolidinium imide able to wet separators and electrodes used for Li-ion batteries?

    NASA Astrophysics Data System (ADS)

    Stefan, Claudia Simona; Lemordant, Daniel; Claude-Montigny, Bénédicte; Violleau, David

    Surface free energy and contact angle measurements were conducted with a series of room temperature ionic liquids (RTILs) based on N,N‧-alkyl-pyrrolidinium imide. Wetting characteristics of various separators (Celgard ® and Separion ®) and electrodes (LiCoO 2, Li 4Ti 5O 12 and graphite), commonly used in Li-ion batteries, were performed. Initially, the free surface energies were determined for both smooth polymeric materials, constituent of the separators, and pyrrolidinium RTILs. Experimental results and calculations show that (i) N-methyl-N-pentyl pyrrolidinium imide is the most wetting RTIL whatever the separator used, and that (ii) the separator wettability is one of the most important factor to take into account in electrochemical devices.

  13. A chiral electrochemical sensor for propranolol based on multi-walled carbon nanotubes/ionic liquids nanocomposite.

    PubMed

    Chen, Lisha; Li, Kunlin; Zhu, Hong; Meng, Lingchen; Chen, Jitao; Li, Meixian; Zhu, Zhiwei

    2013-02-15

    A novel chiral electrochemical sensor based on multi-walled carbon nanotubes (MWCNTs)/ionic liquids (ILs) nanocomposite was developed and applied to the enantiomeric recognition of propranolol (PRO). Mechanisms for chiral sensing were discussed in terms of the formation of an efficient chiral nanospace originating from the weak interactions between quasi-chiral MWCNTs and versatile ILs. This work provided new evidence that the electro-oxidation of PRO should result from its hydroxyl group. Herein the ratio of oxidation peak currents, instead of the commonest shift of peak potential, was used to sense the enantiomeric fraction (EF) of (R)-PRO with a linear correlation coefficient of 0.9936. This simple and reliable sensor was successfully applied in an accurate determination of the enantiomeric purity of reagent, as well as the evaluation of waste water treatment efficiency. PMID:23598015

  14. Pyridinium-based Task-specific Ionic Liquid with a Monothioether Group for Selective Extraction of Class b Metal Ions.

    PubMed

    Chayama, Kenji; Sano, Yuki; Iwatsuki, Satoshi

    2015-01-01

    A pyridinium-based task-specific ionic liquid (TSIL) with a monothioether group, [3-TPPy][NTf2], extracted typical class b metal ions, such as Ag(I), Cu(I), Pd(II), and Pt(II), in high selectivity. It was found that the composition ratio of the extracted Ag(I) and Cu(I) species depended on the TSIL concentration, and that TSIL extracted these metal ions through mono-S-coordinated complex formation at low TSIL concentrations. [3-TPPy][NTf2] can be recycled in the extraction-recovery process, which is of a great advantage for practical use in environmentally benign separation methods. PMID:26561253

  15. Steric repulsion as a way to achieve the required stability for the preparation of ionic liquid-based ferrofluids.

    PubMed

    Rodríguez-Arco, Laura; López-López, Modesto T; González-Caballero, Fernando; Durán, Juan D G

    2011-05-01

    With this work we would like to emphasize the necessity of steric repulsion to stabilize novel ionic liquid-based ferrofluids. For this purpose, we prepared a suspension of magnetite nanoparticles coated with a double layer of oleic acid, dispersed in 1-ethyl-3-methylimidazolium ethylsulphate ([EMIM][EtSO(4)]). For comparison, a suspension of bare magnetite nanoparticles in [EMIM][EtSO(4)] was also prepared. The stability of these suspensions was checked by magnetic sedimentation and centrifugation processes. Furthermore, their yield stress was measured as a function of the applied magnetic field, which gave additional information on their stability. The results of these experiments showed that the suspension of bare nanoparticles was rather unstable, whereas the suspension of double layer coated nanoparticles gave rise to a true (stable) ferrofluid. PMID:21345446

  16. Facile synthesis of water-soluble graphene-based composite: Non-covalently functionalized with chitosan-ionic liquid conjugation

    NASA Astrophysics Data System (ADS)

    Li, Pei-Ying; Cheng, Kai-Yu; Zheng, Xiu-Cheng; Liu, Pu; Xu, Xiu-Juan

    2016-05-01

    Chitosan-ionic liquid conjugation (CILC), which was prepared through the reaction of 1-(4-bromobutyl)-3-methylimidazolium bromide (BBMIB) with chitosan, was firstly used to prepare functionalized graphene composite via the chemical reduction of graphene oxide (GO). The obtained water soluble graphene-based composite was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), ultraviolet-visible (UV-Vis) spectroscopy and so on. CILC-RGO showed excellent dispersion stability in water at the concentration of 2.0 mg/mL, which was stable for several months without any precipitate. This may be ascribed to the electrostatic attraction and π-π interaction between CILC and graphene.

  17. Effect of lithium salts addition on the ionic liquid based extraction of essential oil from Farfarae Flos.

    PubMed

    Li, Zhen-Yu; Zhang, Sha-Sha; Jie-Xing; Qin, Xue-Mei

    2015-01-01

    In this study, an ionic liquids (ILs) based extraction approach has been successfully applied to the extraction of essential oil from Farfarae Flos, and the effect of lithium chloride was also investigated. The results indicated that the oil yields can be increased by the ILs, and the extraction time can be reduced significantly (from 4h to 2h), compared with the conventional water distillation. The addition of lithium chloride showed different effect according to the structures of ILs, and the oil yields may be related with the structure of cation, while the chemical compositions of essential oil may be related with the anion. The reduction of extraction time and remarkable higher efficiency (5.41-62.17% improved) by combination of lithium salt and proper ILs supports the suitability of the proposed approach. PMID:25459951

  18. Ionic liquid polyoxometalates as light emitting materials

    SciTech Connect

    Ortiz-acosta, Denisse; Del Sesto, Rico E; Scott, Brian; Bennett, Bryan L; Purdy, Geraldine M; Muenchausen, Ross E; Mc Kigney, Edward; Gilbertson, Robert

    2008-01-01

    The low melting point, negligible vapor pressure, good solubility, and thermal and chemical stability make ionic liquids useful materials for a wide variety of applications. Polyoxometalates are early transition metal oxygen clusters that can be synthesized in many different sizes and with a variety of heterometals. The most attractive feature of POMs is that their physical properties, in particular electrical, magnetic, and optical properties, can be easily modified following known procedures. It has been shown that POMs can exhibit cooperative properties, as superconductivity and energy transfer. POM ionic liquids can be obtained by selecting the appropliate cation. Different alkyl ammonium and alkyl phosphonium salts are being used to produce new POM ionic liquids together with organic or inorganic luminescent centers to design light emitting materials. Ammonium and phosphonium cations with activated, polymerizable groups are being used to further polymerize the ionic liquid into transparent, solid materials with high metal density.

  19. Effects of substituent branching and chirality on the physical properties of ionic liquids based on cationic ruthenium sandwich complexes.

    PubMed

    Higashi, Tomomi; Ueda, Takahiro; Mochida, Tomoyuki

    2016-04-21

    An appropriate understanding of how substituents affect the physical properties of ionic liquids is important for the molecular design of ionic liquids. Toward this end, we investigated how the branching and chirality of substituents affect the physical properties of organometallic ionic liquids. We synthesized a series of ionic liquids bearing a branched or linear alkoxy group with the same number of carbons: [Ru(C5H5)(η(6)-C6H5OR)]X (rac-[1]X: R = -CH(C2H5)(C6H13), [2]X: R = -CH(C4H9)2, [3]X: R = -C9H19), where X = PF6(-), (SO2F)2N(-), and (SO2CF3)2N(-). rac-[1]X are racemic salts. Salts with less symmetrical substituents tend to maintain the liquid state due to suppression of crystallization; crystallization is completely suppressed in most of the rac-[1]X salts and in some of the [2]X salts, whereas not in [3]X salts. The glass-transition temperatures and viscosities of the salts with branched substituents are greater than those with linear substituents. Chiral resolution of rac-[1][PF6] was performed by chiral chromatography. The melting point of rac-[1][PF6] is much lower than that of the enantiopure salt (chiral-[1][PF6]), which we ascribe to the formation of a conglomerate in the solid state. X-ray structure analysis revealed that the solid salts form layered structures. PMID:27004435

  20. MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

    PubMed

    Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

    2013-03-21

    Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results. PMID:23480174

  1. Use of an ionic liquid-based surfactant as pseudostationary phase in the analysis of carbamates by micellar electrokinetic chromatography.

    PubMed

    Tejada-Casado, Carmen; Moreno-González, David; García-Campaña, Ana M; del Olmo-Iruela, Monsalud

    2015-03-01

    The applicability of an ionic liquid-based cationic surfactant 1-dodecyl-3-methyl-imidazolium tetrafluoroborate (C12 MImBF4 ) as pseudostationary phase in MEKC has been evaluated for the analysis of 11 carbamate pesticides (promecarb, carbofuran, metolcarb, fenobucarb, aldicarb, propoxur, asulam, benomyl, carbendazim, ethiofencarb, isoprocarb) in juice samples. Under optimum conditions (separation buffer, 35 mM NaHCO3 and 20 mM C12 MImBF4 , pH 9.0; capillary temperature 25°C; voltage -22 kV) the analysis was carried out in less than 12 min, using hydrodynamic injection (50 mbar for 7.5 s) and detection at 200 nm. For the extraction of these CRBs from juice samples, a dispersive liquid-liquid microextraction (DLLME) procedure has been proposed, by optimization of variables affecting the efficiency of the extraction. Following this treatment, sample throughput was approximately 12 samples per hour, obtaining a preconcentration factor of 20. Matrix-matched calibration curves were established using tomato juice as representative matrix (from 5 to 250 μg/L for CBZ, BY, PX, CF, FEN, ETH, ISP, and 25-250 μg/L for ASL, ALD, PRC, MTL), obtaining quantification limits ranging from 1 to 18 μg/L and recoveries from 70 to 96%, with RSDs lower than 9%. PMID:25546365

  2. Electrotunable Lubricity with Ionic Liquid Nanoscale Films

    PubMed Central

    Fajardo, O. Y.; Bresme, F.; Kornyshev, A. A.; Urbakh, M.

    2015-01-01

    One of the main challenges in tribology is finding the way for an in situ control of friction without changing the lubricant. One of the ways for such control is via the application of electric fields. In this respect a promising new class of lubricants is ionic liquids, which are solvent-free electrolytes, and their properties should be most strongly affected by applied voltage. Based on a minimal physical model, our study elucidates the connection between the voltage effect on the structure of the ionic liquid layers and their lubricating properties. It reveals two mechanisms of variation of the friction force with the surface charge density, consistent with recent AFM measurements, namely via the (i) charge effect on normal and in-plane ordering in the film and (ii) swapping between anion and cation layers at the surfaces. We formulate conditions that would warrant low friction coefficients and prevent wear by resisting “squeezing-out” of the liquid under compression. These results give a background for controllable variation of friction. PMID:25572127

  3. Electrochemical and structural characterization of polymer gel electrolytes based on a PEO copolymer and an imidazolium-based ionic liquid for dye-sensitized solar cells.

    PubMed

    Freitas, Flavio S; de Freitas, Jilian N; Ito, Bruno I; De Paoli, Marco-A; Nogueira, Ana F

    2009-12-01

    Polymer electrolytes based on mixtures of poly(ethylene oxide-co-propylene oxide) and 1-methyl-3-propyl-imidazolium iodide (MPII) were investigated, aiming at their application in dye-sensitized solar cells (DSSC). The interactions between the copolymer and the ionic liquid were analyzed by infrared spectroscopy and (1)H NMR. The results show interactions between the ether oxygen in the polymer and the hydrogen in the imidazolium cations. The ionic conductivities, electrochemical behaviors, and thermal properties of the electrolytes containing different concentrations of MPII were investigated. The electrolyte containing 70 wt % MPII presented the highest ionic conductivity (2.4 x 10(-3) S cm(-1)) and a diffusion coefficient of 1.9 x 10(-7) cm(2) s(-1). The influence of LiI addition to the electrolytes containing different concentrations of MPII was also investigated. The DSSC assembled with the electrolyte containing 70 wt % MPII showed an efficiency of 3.84% at 100 mW cm(-2). The stability of the devices for a period of 30 days was also evaluated using sealed cells. The devices assembled with the electrolyte containing less ionic liquid showed to be more stable. PMID:20356169

  4. The radiation chemistry of ionic liquids: A review

    SciTech Connect

    Mincher, Bruce J.; Wishart, James F.

    2014-07-03

    Ionic liquids have received increasing attention as media for radiochemical separations. Recent literature includes examinations of the efficiencies and mechanisms of the solvent extraction of lanthanides, actinides and fission products into ionic liquid solutions. For radiochemical applications, including as replacement solvents for nuclear fuel reprocessing, a thorough understanding of the radiation chemistry of ionic liquids will be required. Such an understanding can be achieved based on a combination of steady-state radiolysis experiments coupled with post-irradiation product identification and pulse-radiolysis experiments to acquire kinetic information. These techniques allow for the elucidation of radiolytic mechanisms. This contribution reviews the current ionic liquid radiation chemistry literature as it affects separations, with these considerations in mind.

  5. Anomalous Wien Effects in Supercooled Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Patro, L. N.; Burghaus, O.; Roling, B.

    2016-05-01

    We have measured conductivity spectra of several supercooled monocationic and dicationic ionic liquids in the nonlinear regime by applying ac electric fields with large amplitudes up to about 180 kV /cm . Thereby, higher harmonic ac currents up to the 7th order were detected. Our results point to the existence of anomalous Wien effects in supercooled ionic liquids. Most ionic liquids studied here exhibit a conductivity-viscosity relation, which is close to the predictions of the Nernst-Einstein and Stokes-Einstein equations, as observed for classical strong electrolytes like KCl. These "strong" ionic liquids show a much stronger nonlinearity of the conductivity than classical strong electrolytes. On the other hand, the conductivity-viscosity relation of the ionic liquid [P6 ,6 ,6 ,14][Cl ] points to ion association effects. This "weak" ionic liquid shows a strength of the nonlinear effect, which is comparable to classical weak electrolytes. However, the nonlinearity increases quadratically with the field. We suggest that a theory for explaining these anomalies will have to go beyond the level of Coulomb lattice gas models.

  6. Anomalous Wien Effects in Supercooled Ionic Liquids.

    PubMed

    Patro, L N; Burghaus, O; Roling, B

    2016-05-01

    We have measured conductivity spectra of several supercooled monocationic and dicationic ionic liquids in the nonlinear regime by applying ac electric fields with large amplitudes up to about 180  kV/cm. Thereby, higher harmonic ac currents up to the 7th order were detected. Our results point to the existence of anomalous Wien effects in supercooled ionic liquids. Most ionic liquids studied here exhibit a conductivity-viscosity relation, which is close to the predictions of the Nernst-Einstein and Stokes-Einstein equations, as observed for classical strong electrolytes like KCl. These "strong" ionic liquids show a much stronger nonlinearity of the conductivity than classical strong electrolytes. On the other hand, the conductivity-viscosity relation of the ionic liquid [P_{6,6,6,14}][Cl] points to ion association effects. This "weak" ionic liquid shows a strength of the nonlinear effect, which is comparable to classical weak electrolytes. However, the nonlinearity increases quadratically with the field. We suggest that a theory for explaining these anomalies will have to go beyond the level of Coulomb lattice gas models. PMID:27203333

  7. Dual Ionic and Organic Nature of Ionic Liquids.

    PubMed

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids--a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660

  8. Morphology-induced low temperature conductivity in ionic liquids

    NASA Astrophysics Data System (ADS)

    Erbas, Aykut; Olvera de La Cruz, Monica; Olvera de la Cruz Team

    Ionic liquids exhibit nano-scale liquid crystalline order depending on the polymeric details of salt molecules. The resulting morphology and temperature behavior are key factors in determining the room temperature conductivity of ionic liquids. Here we discuss the phase behavior and related ionic conductivities of dry ionic liquids with volume fractions close to unity by using extensive molecular dynamics simulations. Temperature dependence, effective persistence length of tails, and excluded volume symmetry of amphiphilic ionic liquid molecules are investigated in large scale systems with short and long-range electrostatics. Our results suggest that by adjusting stiffness of the amphiphilic molecules and excluded volume interactions, lamellar or interconnected 3D phases can be obtained. Resulting phases have significant effects on the conductive properties. If there is no excluded volume asymmetry along the molecules, mostly lamellar phases with anisotropic conductivities emerge. If the excluded volume interactions become asymmetric, lamellar phases are replaced by interconnected phases consist of charged groups. Within temperature ranges that morphological phases are observed, conductivities exhibit low-temperature maxima in accord with experiments of ionic liquid-based liquid Center of Bio-inspried Energy Center (CBES).

  9. Ultrafast dynamics of pyrrolidinium cation ionic liquids.

    PubMed

    Shirota, Hideaki; Funston, Alison M; Wishart, James F; Castner, Edward W

    2005-05-01

    We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromide P1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-, Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast ( approximately 2 ps) and intermediate (approximately 20 ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750 cm(-1) are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150 cm(-1) are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape. PMID:15918734

  10. Ultrafast dynamics of pyrrolidinium cation ionic liquids

    NASA Astrophysics Data System (ADS)

    Shirota, Hideaki; Funston, Alison M.; Wishart, James F.; Castner, Edward W.

    2005-05-01

    We have investigated the ultrafast molecular dynamics of five pyrrolidinium cation room temperature ionic liquids using femtosecond optical heterodyne-detected Raman-induced Kerr effect spectroscopy. The ionic liquids studied are N-butyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P14+/NTf2-), N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide P1EOE+/NTf2-), N-ethoxyethyl-N-methylpyrrolidinium bromideP1EOE+, and N-ethoxyethyl-N-methylpyrrolidinium dicyanoamide P1EOE+/DCA-). For comparing dynamics among the five ionic liquids, we categorize the ionic liquids into two groups. One group of liquids comprises the three pyrrolidinium cations P14+, P1EOM+, and P1EOE+ paired with the NTf2- anion. The other group of liquids consists of the P1EOE+ cation paired with each of the three anions NTf2-,Br-, and DCA-. The overdamped relaxation for time scales longer than 2 ps has been fit by a triexponential function for each of the five pyrrolidinium ionic liquids. The fast (˜2ps) and intermediate (˜20ps) relaxation time constants vary little among these five ionic liquids. However, the slow relaxation time constant correlates with the viscosity. Thus, the Kerr spectra in the range from 0 to 750cm-1 are quite similar for the group of three pyrrolidinium ionic liquids paired with the NTf2- anion. The intermolecular vibrational line shapes between 0 and 150cm-1 are fit to a multimode Brownian oscillator model; adequate fits required at least three modes to be included in the line shape.

  11. A Sustainable Approach to the Stereoselective Synthesis of Diazaheptacyclic Cage Systems Based on a Multicomponent Strategy in an Ionic Liquid.

    PubMed

    Suresh Kumar, Raju; Almansour, Abdulrahman I; Arumugam, Natarajan; Altaf, Mohammad; Menéndez, José Carlos; Kumar, Raju Ranjith; Osman, Hasnah

    2016-01-01

    The microwave-assisted three-component reactions of 3,5-bis(E)-arylmethylidene]tetrahydro-4(1H)-pyridinones, acenaphthenequinone and cyclic α-amino acids in an ionic liquid, 1-butyl-3-methylimidazolium bromide, occurred through a domino sequence affording structurally intriguing diazaheptacyclic cage-like compounds in excellent yields. PMID:26840282

  12. A cobalt(II) bis(salicylate)-based ionic liquid that shows thermoresponsive and selective water coordination

    SciTech Connect

    Kohno, Y; Cowan, MG; Masuda, M; Bhowmick, I; Shores, MP; Gin, DL; Noble, RD

    2014-01-01

    A metal-containing ionic liquid (MCIL) has been prepared in which the [CoII(salicylate)(2)](2-) anion is able to selectively coordinate two water molecules with a visible colour change, even in the presence of alcohols. Upon moderate heating or placement in vacuo, the hydrated MCIL undergoes reversible thermochromism by releasing the bound water molecules.

  13. Thallium Transfer from Hydrochloric Acid Media into Pure Ionic Liquids.

    PubMed

    Tereshatov, Evgeny E; Boltoeva, Maria Yu; Mazan, Valerie; Volia, Merinda F; Folden, Charles M

    2016-03-10

    Pure hydrophobic ionic liquids are known to extract metallic species from aqueous solutions. In this work we have systematically investigated thallium (Tl) extraction from aqueous hydrochloric acid (HCl) solutions into six pure fluorinated ionic liquids, namely imidazolium- and pyrrolidinium-based ionic liquids with bis(trifluoromethanesulfonyl)imide and bis(fluorosulfonyl)-imide anions. The dependence of the Tl extraction efficiency on the structure and composition of the ionic liquid ions, metal oxidation state, and initial metal and aqueous acid concentrations have been studied. Tl concentrations were on the order of picomolar (analyzed using radioactive tracers) and millimolar (analyzed using inductively coupled plasma mass spectrometry). The extraction of the cationic thallium species Tl(+) is higher for ionic liquids with more hydrophilic cations, while for the TlX(z)(3-z) anionic species (where X = Cl(-) and/or Br(-)), the extraction efficiency is greater for ionic liquids with more hydrophobic cations. The highest distribution value of Tl(III) was approximately 2000. An improved mathematical model based on ion exchange and ion pair formation mechanisms has been developed to describe the coextraction of two different anionic species, and the relative contributions of each mechanism have been determined. PMID:26769597

  14. Ionic Liquids with Ammonium Cations as Lubricants or Additives

    SciTech Connect

    Qu, Jun; Blau, Peter Julian; Dai, Sheng; Luo, Huimin; Truhan, Jr., John J

    2006-01-01

    Friction and wear are estimated to cost 6% of the US gross national product, or around $700 billion annually. A new class of more effective lubricants could lead to huge energy savings. Limited recent literature has suggested potential for using room-temperature ionic liquids as lubricants, however only a few out of millions (or more) of species have been evaluated. Recent ORNL work discovered a new category of ionic liquids with ammonium cations that have demonstrated promising lubricating properties as net lubricants or lubricant additives, particularly in lubricating difficult-to-lubricate metals like aluminum. More than 30% friction reduction has been observed on ammonium-based ionic liquids compared to conventional hydrocarbon oils. The inherent polarity of ionic liquids is believed to provide strong adhesion to contact surfaces and form a boundary lubricating film leading to friction and wear reductions. Other advantages of ionic liquids include (1) negligible volatility, (2) high thermal stability, (3) non-flammability, and (4) better intrinsic properties that eliminate the necessity of many expensive lubricant additives. With very flexible molecular structures, this new class of lubricants, particularly ammonium-based ionic liquids, can be tailored to fit a big variety of applications including but not limited to bearings, combustion engines, MEMS, and metal forming.

  15. TETRAHALOINDATE(III)-BASED IONIC LIQUIDS IN THE COUPLING REACTION OF CARBON DIOXIDE AND EPOXIDES TO GENERATE CYCLIC CARBONATES: H-BONDING AND MECHANISTIC STUDIES

    EPA Science Inventory

    The microwave reactions of InX3 with [Q]Y produce a series of tetrahaloindate(III)-based ionic liquids (ILs) with a general formula of [Q][InX3Y] (Q = imidazolium, phosphonium, ammonium, and pyridinium; X = Cl, Br, I; Y = Cl, Br). The reaction of CO2

  16. Separation of curcuminoids using ionic liquid based aqueous two-phase system coupled with in situ dispersive liquid-liquid microextraction.

    PubMed

    Shu, Yang; Gao, Mingcen; Wang, Xueying; Song, Rusheng; Lu, Jun; Chen, Xuwei

    2016-03-01

    An aqueous two-phase extraction system (ATPS) combined with an in situ dispersive liquid-liquid microextraction (DLLME) method using imidazolium ionic liquids (ILs) for the separation of curcuminoids is developed. The influence of structure of IL, the type of metathesis reagents, and the back extraction agents on the extraction efficiency is investigated. 2.0mg of curcuminoids are extracted by an IL ATPS composed of 0.4g 1,3-diethylimidazolium iodine (EeimI), 0.6g potassium hydrogen phosphate, 1.0g water. Then the bis[(trifluoromethyl)sulfonyl]imide lithium (LiNTf2) aqueous solution is added to the EeimI-rich phase of the ATPS. The water-immiscible ionic liquids, 1,3-diethylimidazole bis[(trifluoromethyl)sulfonyl]imide (EeimNTf2), forms by the metathesis reaction. The in situ DLLME is triggered simultaneously and further purifies the curcuminoids. 92% of EeimI transforms into EeimNTf2 and thus the Eeim(+) cation is used for twice in this method. Finally, 0.1mol/L NaOH aqueous solution is used as the back extraction reagent. The curcuminoids precipitate is achieved with 93% of recovery when the aqueous solution is adjusted to pH 3.0. This ATPS-DLLME method is successfully applied to the separation of curcuminoids from Curcuma Longa (0.96±0.02% of extraction yield, a purity of >51% with respect to the total dry mass of the product). PMID:26717808

  17. Enhanced extraction of proteins using cholinium-based ionic liquids as phase-forming components of aqueous biphasic systems.

    PubMed

    Quental, Maria V; Caban, Magda; Pereira, Matheus M; Stepnowski, Piotr; Coutinho, João A P; Freire, Mara G

    2015-09-01

    Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) are promising platforms for the extraction and purification of proteins. In this work, a series of alternative and biocompatible ABS composed of cholinium-based ILs and polypropylene glycol were investigated. The respective ternary phase diagrams, tie-lines, tie-line lengths and critical points were determined at 25°C. The extraction performance of these systems for commercial bovine serum albumin (BSA) was then evaluated. The stability of BSA at the IL-rich phase was ascertained by size exclusion high-performance liquid chromatography and Fourier transform infrared spectroscopy. Appropriate ILs lead to the complete extraction of BSA for the IL-rich phase, in a single step, while maintaining the protein's native conformation. Furthermore, to evaluate the performance of these systems when applied to real matrices, the extraction of BSA from bovine serum was additionally carried out, revealing that the complete extraction of BSA was maintained and achieved in a single step. The remarkable extraction efficiencies obtained are far superior to those observed with typical polymer-based ABS. Therefore, the proposed ABS may be envisaged as a more effective and biocompatible approach for the separation and purification of other value-added proteins. PMID:25864445

  18. Properties of Water Confined in Ionic Liquids

    PubMed Central

    Saihara, Koji; Yoshimura, Yukihiro; Ohta, Soichi; Shimizu, Akio

    2015-01-01

    The varying states of water confined in the nano-domain structures of typical room temperature ionic liquids (ILs) were investigated by 1H NMR and by measurements of self-diffusion coefficients while systematically varying the IL cations and anions. The NMR peaks for water in BF4-based ILs were clearly split, indicating the presence of two discrete states of confined water (H2O and HOD). Proton and/or deuterium exchange rate among the water molecules was very slowly in the water-pocket. Notably, no significant changes were observed in the chemical shifts of the ILs. Self-diffusion coefficient results showed that water molecules exhibit a similar degree of mobility, although their diffusion rate is one order of magnitude faster than that of the IL cations and anions. These findings provide information on a completely new type of confinement, that of liquid water in soft matter. PMID:26024339

  19. Design of ionic liquids for lipase purification.

    PubMed

    Ventura, Sónia P M; Sousa, Sílvia G; Freire, Mara G; Serafim, Luísa S; Lima, Alvaro S; Coutinho, João A P

    2011-09-15

    Aqueous two-phase systems (ATPS) are considered as efficient downstream processing techniques in the production and purification of enzymes, since they can be considered harmless to biomolecules due to their high water content and due to the possibility of maintaining a neutral pH value in the medium. A recent type of alternative ATPS is based on hydrophilic ionic liquids (ILs) and salting-out inducing salts. The aim of this work was to study the lipase (Candida antarctica lipase B - CaLB) partitioning in several ATPS composed of ionic liquids (ILs) and inorganic salts, and to identify the best IL for the enzyme purification. For that purpose a wide range of IL cations and anions, and some of their combinations were studied. For each system the enzyme partitioning between the two phases was measured and the purification factors and enzyme recoveries were determined. The results indicate that the lipase maximum purification and recovery were obtained for cations with a C(8) side alkyl chain, the [N(CN)(2)] anion and ILs belonging to the pyridinium family. However, the highest purification parameters were observed for 1-methyl-3-octylimidazolium chloride [C(8)mim]Cl, suggesting that the IL extraction capability does not result from a cumulative character of the individual characteristics of ILs. The results indicate that the IL based ATPS have an improved performance in the lipase purification and recovery. PMID:21852207

  20. Stabilization of different conformers of bis(trifluoromethanesulfonyl)imide anion in ammonium-based ionic liquids at low temperatures.

    PubMed

    Vitucci, F M; Trequattrini, F; Palumbo, O; Brubach, J-B; Roy, P; Navarra, M A; Panero, S; Paolone, A

    2014-09-25

    The infrared absorption spectra of two ionic liquids with bis(trifluoromethanesulfonyl)imide (TFSI) as an anion and ammonium with different alkyl chains as cations are reported as a function of temperature. Using the comparison with ab initio calculations of the infrared-active intramolecular vibrations, the experimental lines were ascribed to the various ions composing the ionic liquids. In the liquid state of the samples, both conformers of the TFSI ion are present. In the solid state, however, the two conformers survive in N-trimethyl-N-propylammonium bis(trifluoromethanesulfonyl)imide (TMPA-TFSI), while only cis-TFSI is retained in N-trimethyl-N-hexylammonium bis(trifluoromethanesulfonyl)imide (TMHA-TFSI). We suggest that the longer alkyl chains of the former compound stabilize the less stable conformer of TFSI by means of stronger interactions between anions and cations. PMID:25188394

  1. Ionic liquids behave as dilute electrolyte solutions

    PubMed Central

    Gebbie, Matthew A.; Valtiner, Markus; Banquy, Xavier; Fox, Eric T.; Henderson, Wesley A.; Israelachvili, Jacob N.

    2013-01-01

    We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends. PMID:23716690

  2. Water Contaminant Mitigation in Ionic Liquid Propellant

    NASA Technical Reports Server (NTRS)

    Conroy, David; Ziemer, John

    2009-01-01

    Appropriate system and operational requirements are needed in order to ensure mission success without unnecessary cost. Purity requirements applied to thruster propellants may flow down to materials and operations as well as the propellant preparation itself. Colloid electrospray thrusters function by applying a large potential to a room temperature liquid propellant (such as an ionic liquid), inducing formation of a Taylor cone. Ions and droplets are ejected from the Taylor cone and accelerated through a strong electric field. Electrospray thrusters are highly efficient, precise, scaleable, and demonstrate low thrust noise. Ionic liquid propellants have excellent properties for use as electrospray propellants, but can be hampered by impurities, owing to their solvent capabilities. Of foremost concern is the water content, which can result from exposure to atmosphere. Even hydrophobic ionic liquids have been shown to absorb water from the air. In order to mitigate the risks of bubble formation in feed systems caused by water content of the ionic liquid propellant, physical properties of the ionic liquid EMI-Im are analyzed. The effects of surface tension, material wetting, physisorption, and geometric details of the flow manifold and electrospray emitters are explored. Results are compared to laboratory test data.

  3. Hydroxypropyl Cellulose Based Non-Volatile Gel Polymer Electrolytes for Dye-Sensitized Solar Cell Applications using 1-methyl-3-propylimidazolium iodide ionic liquid

    PubMed Central

    Khanmirzaei, Mohammad Hassan; Ramesh, S.; Ramesh, K.

    2015-01-01

    Gel polymer electrolytes using imidazolium based ionic liquids have attracted much attention in dye-sensitized solar cell applications. Hydroxypropyl cellulose (HPC), sodium iodide (NaI), 1-methyl-3-propylimidazolium iodide (MPII) as ionic liquid (IL), ethylene carbonate (EC) and propylene carbonate (PC) are used for preparation of non-volatile gel polymer electrolyte (GPE) system (HPC:EC:PC:NaI:MPII) for dye-sensitized solar cell (DSSC) applications. The highest ionic conductivity of 7.37 × 10−3 S cm−1 is achieved after introducing 100% of MPII with respect to the weight of HPC. Temperature-dependent ionic conductivity of gel polymer electrolytes is studied in this work. XRD patterns of gel polymer electrolytes are studied to confirm complexation between HPC polymer, NaI and MPII. Thermal behavior of the GPEs is studied using simultaneous thermal analyzer (STA) and differential scanning calorimetry (DSC). DSSCs are fabricated using gel polymer electrolytes and J-V centeracteristics of fabricated dye sensitized solar cells were analyzed. The gel polymer electrolyte with 100 wt.% of MPII ionic liquid shows the best performance and energy conversion efficiency of 5.79%, with short-circuit current density, open-circuit voltage and fill factor of 13.73 mA cm−2, 610 mV and 69.1%, respectively. PMID:26659087

  4. Hydroxypropyl Cellulose Based Non-Volatile Gel Polymer Electrolytes for Dye-Sensitized Solar Cell Applications using 1-methyl-3-propylimidazolium iodide ionic liquid.

    PubMed

    Khanmirzaei, Mohammad Hassan; Ramesh, S; Ramesh, K

    2015-01-01

    Gel polymer electrolytes using imidazolium based ionic liquids have attracted much attention in dye-sensitized solar cell applications. Hydroxypropyl cellulose (HPC), sodium iodide (NaI), 1-methyl-3-propylimidazolium iodide (MPII) as ionic liquid (IL), ethylene carbonate (EC) and propylene carbonate (PC) are used for preparation of non-volatile gel polymer electrolyte (GPE) system (HPC:EC:PC:NaI:MPII) for dye-sensitized solar cell (DSSC) applications. The highest ionic conductivity of 7.37 × 10(-3) S cm(-1) is achieved after introducing 100% of MPII with respect to the weight of HPC. Temperature-dependent ionic conductivity of gel polymer electrolytes is studied in this work. XRD patterns of gel polymer electrolytes are studied to confirm complexation between HPC polymer, NaI and MPII. Thermal behavior of the GPEs is studied using simultaneous thermal analyzer (STA) and differential scanning calorimetry (DSC). DSSCs are fabricated using gel polymer electrolytes and J-V centeracteristics of fabricated dye sensitized solar cells were analyzed. The gel polymer electrolyte with 100 wt.% of MPII ionic liquid shows the best performance and energy conversion efficiency of 5.79%, with short-circuit current density, open-circuit voltage and fill factor of 13.73 mA cm(-2), 610 mV and 69.1%, respectively. PMID:26659087

  5. Hydroxypropyl Cellulose Based Non-Volatile Gel Polymer Electrolytes for Dye-Sensitized Solar Cell Applications using 1-methyl-3-propylimidazolium iodide ionic liquid

    NASA Astrophysics Data System (ADS)

    Khanmirzaei, Mohammad Hassan; Ramesh, S.; Ramesh, K.

    2015-12-01

    Gel polymer electrolytes using imidazolium based ionic liquids have attracted much attention in dye-sensitized solar cell applications. Hydroxypropyl cellulose (HPC), sodium iodide (NaI), 1-methyl-3-propylimidazolium iodide (MPII) as ionic liquid (IL), ethylene carbonate (EC) and propylene carbonate (PC) are used for preparation of non-volatile gel polymer electrolyte (GPE) system (HPC:EC:PC:NaI:MPII) for dye-sensitized solar cell (DSSC) applications. The highest ionic conductivity of 7.37 × 10-3 S cm-1 is achieved after introducing 100% of MPII with respect to the weight of HPC. Temperature-dependent ionic conductivity of gel polymer electrolytes is studied in this work. XRD patterns of gel polymer electrolytes are studied to confirm complexation between HPC polymer, NaI and MPII. Thermal behavior of the GPEs is studied using simultaneous thermal analyzer (STA) and differential scanning calorimetry (DSC). DSSCs are fabricated using gel polymer electrolytes and J-V centeracteristics of fabricated dye sensitized solar cells were analyzed. The gel polymer electrolyte with 100 wt.% of MPII ionic liquid shows the best performance and energy conversion efficiency of 5.79%, with short-circuit current density, open-circuit voltage and fill factor of 13.73 mA cm-2, 610 mV and 69.1%, respectively.

  6. Ionic liquid-based foam flotation followed by solid phase extraction to determine triazine herbicides in corn.

    PubMed

    Zhang, Liyuan; Wang, Zhibing; Li, Na; Yu, Aimin; Zhang, Hanqi

    2014-05-01

    Ionic liquid-based foam flotation followed by solid phase extraction was developed for extraction of eight triazine herbicides, including cyanazine, metribuzin, desmetryn, secbumeton, terbumeton, terbuthylazine, dimethametryn and dipropetryn in corn samples. When the extraction was completed, the analytes were separated from the sample matrix by foam flotation and introduced into the solid phase extraction cartridge. The separation and concentration of target analytes were performed simultaneously. The analytes eluted from the solid phase extraction cartridge were determined by high performance liquid chromatography. The effects of experimental parameters of extraction and flotation were examined. Under the optimized experimental conditions, a good linearity was obtained in the range of 2.50-150 µg/kg. The detection limits of the triazine herbicides were in the range of 0.74-1.62 µg/kg. The present method was successfully applied to the analysis of corn samples. The recoveries ranged from 85.9% to 104.0% and the relative standard deviations were lower than 5.6%. PMID:24720960

  7. Structure and thermal properties of salicylate-based-protic ionic liquids as new heat storage media. COSMO-RS structure characterization and modeling of heat capacities.

    PubMed

    Jacquemin, Johan; Feder-Kubis, Joanna; Zorębski, Michał; Grzybowska, Katarzyna; Chorążewski, Mirosław; Hensel-Bielówka, Stella; Zorębski, Edward; Paluch, Marian; Dzida, Marzena

    2014-02-28

    During this research, we present a study on the thermal properties, such as the melting, cold crystallization, and glass transition temperatures as well as heat capacities from 293.15 K to 323.15 K of nine in-house synthesized protic ionic liquids based on the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate ([H-Im-C1OC(n)][Sal]) with n = 3-11. The 3D structures, surface charge distributions and COSMO volumes of all investigated ions are obtained by combining DFT calculations and the COSMO-RS methodology. The heat capacity data sets as a function of temperature of the 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate are then predicted using the methodology originally proposed in the case of ionic liquids by Ge et al. 3-(Alkoxymethyl)-1H-imidazol-3-ium salicylate based ionic liquids present specific heat capacities higher in many cases than other ionic liquids that make them suitable as heat storage media and in heat transfer processes. It was found experimentally that the heat capacity increases linearly with increasing alkyl chain length of the alkoxymethyl group of 3-(alkoxymethyl)-1H-imidazol-3-ium salicylate as was expected and predicted using the Ge et al. method with an overall relative absolute deviation close to 3.2% for temperatures up to 323.15 K. PMID:24413748

  8. Ionic liquid-based totally organic solvent-free emulsification microextraction coupled with high performance liquid chromatography for the determination of three acaricides in fruit juice.

    PubMed

    Zhang, Jiaheng; Liang, Zhe; Guo, Hao; Gao, Peng; Lu, Runhua; Zhou, Wenfeng; Zhang, Sanbing; Gao, Haixiang

    2013-10-15

    A novel, totally organic solvent-free emulsification microextraction (TEME) technique using ionic liquids (ILs) is proposed in this study. Seven bis(trifluoromethylsulfonyl)imide ionic liquids were synthesized. After comparing the physicochemical properties of the ionic liquids and their application to microextraction experiments, 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C6MIM][NTf2]), which has moderate surface tension and viscosity, was selected as the extraction solvent. The dispersion of ILs and mass transfer were accelerated by ultrasound irradiation and temperature control processes. Therefore, no dispersive organic solvent was needed. Several variables, such as ionic liquid volume, duration of the ultrasound extraction, dispersion temperature, ionic strength and centrifugation time were investigated and optimized. Under the optimum conditions, the calibration curve was linear in the range of 0.1-600 μg L(-1) for chlorfenapyr and fenpyroximate and 0.5-600 μg L(-1) for spirodiclofen, with correlation coefficients of 0.9994-0.9999. The enrichment factors were between 261 and 285. The limits of detection (LODs) were 0.02-0.06 μg L(-1). Real fruit juice samples (at fortified levels of 10 μg L(-1) and 30 μg L(-1)) were successfully analyzed using the proposed method. The relative recoveries and enrichment factors were in the range of 92-104%. PMID:24054632

  9. Predictive thermodynamics for ionic solids and liquids.

    PubMed

    Glasser, Leslie; Jenkins, H Donald Brooke

    2016-08-21

    The application of thermodynamics is simple, even if the theory may appear intimidating. We describe tools, developed over recent years, which make it easy to estimate often elusive thermodynamic parameter values, generally (but not exclusively) for ionic materials, both solid and liquid, as well as for their solid hydrates and solvates. The tools are termed volume-based thermodynamics (VBT) and thermodynamic difference rules (TDR), supplemented by the simple salt approximation (SSA) and single-ion values for volume, Vm, heat capacity, , entropy, , formation enthalpy, ΔfH°, and Gibbs formation energy, ΔfG°. These tools can be applied to provide values of thermodynamic and thermomechanical properties such as standard enthalpy of formation, ΔfH°, standard entropy, , heat capacity, Cp, Gibbs function of formation, ΔfG°, lattice potential energy, UPOT, isothermal expansion coefficient, α, and isothermal compressibility, β, and used to suggest the thermodynamic feasibility of reactions among condensed ionic phases. Because many of these methods yield results largely independent of crystal structure, they have been successfully extended to the important and developing class of ionic liquids as well as to new and hypothesised materials. Finally, these predictive methods are illustrated by application to K2SnCl6, for which known experimental results are available for comparison. A selection of applications of VBT and TDR is presented which have enabled input, usually in the form of thermodynamics, to be brought to bear on a range of topical problems. Perhaps the most significant advantage of VBT and TDR methods is their inherent simplicity in that they do not require a high level of computational expertise nor expensive high-performance computation tools - a spreadsheet will usually suffice - yet the techniques are extremely powerful and accessible to non-experts. The connection between formula unit volume, Vm, and standard thermodynamic parameters represents a

  10. The radiation chemistry of ionic liquids: A review

    DOE PAGESBeta

    Mincher, Bruce J.; Wishart, James F.

    2014-07-03

    Ionic liquids have received increasing attention as media for radiochemical separations. Recent literature includes examinations of the efficiencies and mechanisms of the solvent extraction of lanthanides, actinides and fission products into ionic liquid solutions. For radiochemical applications, including as replacement solvents for nuclear fuel reprocessing, a thorough understanding of the radiation chemistry of ionic liquids will be required. Such an understanding can be achieved based on a combination of steady-state radiolysis experiments coupled with post-irradiation product identification and pulse-radiolysis experiments to acquire kinetic information. These techniques allow for the elucidation of radiolytic mechanisms. This contribution reviews the current ionic liquidmore » radiation chemistry literature as it affects separations, with these considerations in mind.« less

  11. Dual Ionic and Organic Nature of Ionic Liquids

    PubMed Central

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660

  12. Dual Ionic and Organic Nature of Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs.

  13. An ether-functionalised cyclic sulfonium based ionic liquid as an electrolyte for electrochemical double layer capacitors

    NASA Astrophysics Data System (ADS)

    Neale, Alex R.; Murphy, Sinead; Goodrich, Peter; Schütter, Christoph; Hardacre, Christopher; Passerini, Stefano; Balducci, Andrea; Jacquemin, Johan

    2016-09-01

    A novel cyclic sulfonium cation-based ionic liquid (IL) with an ether-group appendage and the bis{(trifluoromethyl)sulfonyl}imide anion was synthesised and developed for electrochemical double layer capacitor (EDLC) testing. The synthesis and chemical-physical characterisation of the ether-group containing IL is reported in parallel with a similarly sized alkyl-functionalised sulfonium IL. Results of the chemical-physical measurements demonstrate how important transport properties, i.e. viscosity and conductivity, can be promoted through the introduction of the ether-functionality without impeding thermal, chemical or electrochemical stability of the IL. Although the apparent transport properties are improved relative to the alkyl-functionalised analogue, the ether-functionalised sulfonium cation-based IL exhibits moderately high viscosity, and poorer conductivity, when compared to traditional EDLC electrolytes based on organic solvents (propylene carbonate and acetonitrile). Electrochemical testing of the ether-functionalised sulfonium IL was conducted using activated carbon composite electrodes to inspect the performance of the IL as a solvent-free electrolyte for EDLC application. Good cycling stability was achieved over the studied range and the performance was comparable to other solvent-free, IL-based EDLC systems. Nevertheless, limitations of the attainable performance are primarily the result of sluggish transport properties and a restricted operative voltage of the IL, thus highlighting key aspects of this field which require further attention.

  14. Morphological and electromechanical characterization of ionic liquid/Nafion polymer composites

    NASA Astrophysics Data System (ADS)

    Bennett, Matthew; Leo, Donald

    2005-05-01

    Ionic liquids have shown promise as replacements for water in ionic polymer transducers. Ionic liquids are non-volatile and have a larger electrochemical stability window than water. Therefore, transducers employing ionic liquids can be operated for long periods of time in air and can be actuated with higher voltages. Furthermore, transducers based on ionic liquids do not exhibit the characteristic back relaxation that is common with water-swollen materials. However, the physics of transduction in the ionic liquid-swollen materials is not well understood. In this paper, the morphology of Nafion/ionic liquid composites is characterized using small-angle X-ray scattering (SAXS). The electromechanical transduction behavior of the composites is also investigated. For this testing, five different counterions and two ionic liquids are used. The results reveal that both the morphology and transduction performance of the composites is affected by the identity of the ionic liquid, the cation, and the swelling level of ionic liquid within the membrane. Specifically, speed of response is found to be lower for the membranes that were exchanged with the smaller lithium and potassium ions. The response speed is also found to increase with increased content of ionic liquid. Furthermore, for the two ionic liquids studied, the actuators swollen with the less viscous ionic liquid exhibited a slower response. The slower speed of response corresponds to less contrast between the ionically conductive phase and the inert phase of the polymer. This suggests that disruption of the clustered morphology in the ionic liquid-swollen membranes as compared to water-swollen membranes attenuates ion mobility within the polymer. This attenuation is attributed to swelling of the non-conductive phase by the ionic liquids.

  15. Nonlinear capacitance and electrochemical response of ionic liquid-ionic polymers

    NASA Astrophysics Data System (ADS)

    Davidson, Jacob D.; Goulbourne, N. C.

    2011-04-01

    In this paper we present a physics-based model for the electrochemical response of ionic liquid-ionic polymer transducers (IPTs) and show how the mobile ionic liquid ions influence the charging characteristics and actuation performance of a device. It is assumed that a certain fraction of the ionic liquid ions exist as "free," making for a total of 3 mobile ions. This leads to predictions of distinctly different charging characteristics for ionic liquid versus water-based IPTs, since for the latter there is only a single mobile ion. The large ionic liquid ions are modeled by including steric effects in a set of modified Nernst-Planck/Poisson equations, and the resulting system of equations is solved using the method of matched asymptotic expansions (MAE). The inclusion of steric effects allows for a realistic description of boundary layer composition near actuator operating voltages (~1 V). Analytical expressions for the charge transferred and differential capacitance are derived as a function of the fraction of free ionic liquid ions, influence of steric effects in formation of the electric double layer, and applied voltage. It is shown that the presence of free ionic liquid ions tends to increase the overall amount of charge transferred, and also leads to a nonmonotonic capacitance-voltage curve. We suggest that these results could be used to experimentally identify the extent of free ionic liquid ion movement and to test the validity of the assumptions made in the underlying theory. A comparison with numerical results shows that while the MAE solution procedure gives valid results for capacitance and charge transferred, it cannot predict the dynamic response due to the presence of multiple time scales in the current decay. This is in contrast to previous results in analyzing water-based IPTs, where the MAE solution is in good agreement with numerical results at all times and applied voltages due to the presence of only a single mobile ion. By examining the

  16. Ionic Liquid Extractions of Soil Organic Matter

    NASA Astrophysics Data System (ADS)

    Patti, Antonio; Macfarlane, Douglas; Clarke, Michael

    2010-05-01

    A large range of ionic liquids with the ability to dissolve different classes of natural biopolymers (e.g. cellulose, lignin, protein) have been reported in the literature. These have the potential to isolate different fractions of soil organic matter, thus yielding novel information that is not available through other extraction procedures. The ionic liquids dimethylammonium dimethylcarbamate (DIMCARB), alkylbenzenesulfonate and 1-butyl-3methylimidazolium chloride (Bmim Cl) can solubilise selected components of soil organic matter. Soil extractions with these materials showed that the organic matter recovered showed chemical properties that were consistent with humic substances. These extracts had a slightly different organic composition than the humic acids extracted using the traditional International Humic Substances Society (IHSS) method. The ionic liquids also solubilised some inorganic matter from the soil. Humic acids recovered with alkali were also partially soluble in the ionic liquids. DIMCARB appeared to chemically interfere with organic extract, increasing the level of nitrogen in the sample. It was concluded that the ionic liquid Bmim Cl may function as a useful solvent for SOM, and may be used to recover organic matter of a different character to that obtained with alkali

  17. Selective ionic liquid ferrofluid based dispersive-solid phase extraction for simultaneous preconcentration/separation of lead and cadmium in milk and biological samples.

    PubMed

    Fasih Ramandi, Negin; Shemirani, Farzaneh

    2015-01-01

    For the first time, a selective ionic liquid ferrofluid has been used in dispersive solid phase extraction (IL-FF-D-SPE) for simultaneous preconcentration and separation of lead and cadmium in milk and biological samples combined with flame atomic absorption spectrometry. To improve the selectivity of the ionic liquid ferrofluid, the surface of TiO2 nanoparticles with a magnetic core as sorbent was modified by loading 1-(2-pyridylazo)-2-naphtol. Due to the rapid injection of an appropriate amount of ionic liquid ferrofluid into the aqueous sample by a syringe, extraction can be achieved within a few seconds. In addition, based on the attraction of the ionic liquid ferrofluid to a magnet, no centrifugation step is needed for phase separation. The experimental parameters of IL-FF-D-SPE were optimized using a Box-Behnken design (BBD) after a Plackett-Burman screening design. Under the optimum conditions, the relative standard deviations of 2.2% and 2.4% were obtained for lead and cadmium, respectively (n=7). The limit of detections were 1.21 µg L(-1) for Pb(II) and 0.21 µg L(-1) for Cd(II). The preconcentration factors were 250 for lead and 200 for cadmium and the maximum adsorption capacities of the sorbent were 11.18 and 9.34 mg g(-1) for lead and cadmium, respectively. PMID:25281121

  18. Rotational diffusion of neutral and charged solutes in 1-butyl-3-methylimidazolium-based ionic liquids: influence of the nature of the anion on solute rotation.

    PubMed

    Karve, Lalita; Dutt, G B

    2012-02-16

    Temperature-dependent fluorescence anisotropies of two organic solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and rhodamine 110 (R110), have been measured in 1-butyl-3-methylimidazolium ([bmim(+)])-based ionic liquids containing the anions hexafluorophosphate ([PF(6)(-)]), bis(trifluoromethylsulfonyl)imide ([Tf(2)N(-)]), tetrafluoroborate ([BF(4)(-)]), trifluoromethanesulfonate ([TfO(-)]), and nitrate ([NO(3)(-)]). This data has been used in conjunction with the recently published results (Dutt, G. B. J. Phys. Chem. B2010, 114, 8971) for the same solutes in [bmim(+)] tris(pentafluoroethyl)trifluorophosphate ([FAP(-)]) to understand the influence of various anions on solute rotation. The boundary condition parameter C(obs), which has been obtained from the analysis of the data using Stokes-Einstein-Debye hydrodynamic theory, for the neutral solute DMDPP is more or less the same in all the ionic liquids. Moreover, C(obs) values are close to the predictions of slip boundary condition, which indicates that solvent viscosity alone governs the rotation of DMDPP. In contrast, for R110, which experiences specific interactions with the anions of the ionic liquids, the C(obs) values are close to stick hydrodynamics. It has also been noticed that the C(obs) values vary with the nature of the anion and this variation correlates with the hydrogen bond basicities of the anions of the ionic liquids. PMID:22233259

  19. Bacillus coagulans tolerance to 1-ethyl-3-methylimidazolium-based ionic liquids in aqueous and solid-state thermophilic culture.

    PubMed

    Simmons, Christopher W; Reddy, Amitha P; Vandergheynst, Jean S; Simmons, Blake A; Singer, Steven W

    2014-01-01

    The use of ionic liquids (ILs) to disrupt the recalcitrant structure of lignocellulose and make polysaccharides accessible to hydrolytic enzymes is an emerging technology for biomass pretreatment in lignocellulosic biofuel production. Despite efforts to reclaim and recycle IL from pretreated biomass, residual IL can be inhibitory to microorganisms used for downstream fermentation. As a result, pathways for IL tolerance are needed to improve the activity of fermentative organisms in the presence of IL. In this study, microbial communities from compost were cultured under high-solids and thermophilic conditions in the presence of 1-ethyl-3-methylimidazolium-based ILs to enrich for IL-tolerant microorganisms. A strain of Bacillus coagulans isolated from an IL-tolerant community was grown in liquid and solid-state culture in the presence of the ILs 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) or 1-ethyl-3-methylimidazolium chloride ([C2mim][Cl]) to gauge IL tolerance. Viability and respiration varied with the concentration of IL applied and the type of IL used. B. coagulans maintained growth and respiration in the presence of 4 wt% IL, a concentration similar to that present on IL-pretreated biomass. In the presence of both [C2mim][OAc] and [C2mim][Cl] in liquid culture, B. coagulans grew at a rate approximately half that observed in the absence of IL. However, in solid-state culture, the bacteria were significantly more tolerant to [C2mim][Cl] compared with [C2mim][OAc]. B. coagulans tolerance to IL under industrially relevant conditions makes it a promising bacterium for understanding mechanisms of IL tolerance and discovering IL tolerance pathways for use in other microorganisms, particularly those used in bioconversion of IL-pretreated plant biomass. PMID:24376258

  20. 3-V Solid-State Flexible Supercapacitors with Ionic-Liquid-Based Polymer Gel Electrolyte for AC Line Filtering.

    PubMed

    Kang, Yu Jin; Yoo, Yongju; Kim, Woong

    2016-06-01

    State-of-the-art solid-state flexible supercapacitors with sufficiently fast response speed for AC line filtering application suffer from limited energy density. One of the main causes of the low energy density is the low cell voltage (1 V), which is limited by aqueous-solution-based gel electrolytes. In this work, we demonstrate for the first time a 3-V flexible supercapacitor for AC line filtering based on an ionic-liquid-based polymer gel electrolyte and carbon nanotube electrode material. The flexible supercapacitor exhibits an areal energy density that is more than 20 times higher than that of the previously demonstrated 1-V flexible supercapacitor (0.66 vs 0.03 μWh/cm(2)) while maintaining excellent capacitive behavior at 120 Hz. The supercapacitor shows a maximum areal power density of 1.5 W/cm(2) and a time constant of 1 ms. The improvement of the cell voltage while maintaining the fast-response capability greatly improves the potential of supercapacitors for high-frequency applications in wearable and/or portable electronics. PMID:27167760

  1. Ionic liquid-based aqueous biphasic systems as a versatile tool for the recovery of antioxidant compounds.

    PubMed

    Santos, João H; e Silva, Francisca A; Ventura, Sónia P M; Coutinho, João A P; de Souza, Ranyere L; Soares, Cleide M F; Lima, Álvaro S

    2015-01-01

    The comparative evaluation of distinct types of ionic liquid-based aqueous biphasic systems (IL-ABS) and more conventional polymer/salt-based ABS to the extraction of two antioxidants, eugenol and propyl gallate, is focused. In a first approach, IL-ABS composed of ILs and potassium citrate (C6H5K3O7/C6H8O7) buffer at pH 7 were applied to the extraction of two antioxidants, enabling the assessment of the impact of IL cation core on the extraction. The second approach uses ABS composed of polyethylene glycol (PEG) and potassium phosphate (K2HPO4/KH2PO4) buffer at pH 7 with imidazolium-based ILs as adjuvants. Their application to the extraction of the compounds allowed the investigation of the impact of the presence/absence of IL, the PEG molecular weight, and the alkyl side chain length of the imidazolium cation on the partition. It is possible to maximize the extractive performance of both antioxidants up to 100% using both types of IL-ABS. The IL enhances the performance of ABS technology. The data puts in evidence the pivotal role of the appropriate selection of the ABS components and design to develop a successful extractive process, from both environmental and performance points of view. PMID:25311237

  2. High-Permeance Room-Temperature Ionic-Liquid-Based Membranes for CO2/N-2 Separation

    SciTech Connect

    Zhou, JS; Mok, MM; Cowan, MG; McDanel, WM; Carlisle, TK; Gin, DL; Noble, RD

    2014-12-24

    We have developed and fabricated thin-film composite (TFC) membranes with an active layer consisting of a room-temperature ionic liquid/polymerized (room-temperature ionic liquid) [i.e., (RTIL)/poly(RTIL)] composite material. The resulting membrane has a CO2 permeance of 6100 +/- 400 GPU (where 1 GPU = 10(-6) cm(3)/(cm(2) s cmHg)) and an ideal CO2/N-2 selectivity of 22 +/- 2. This represents a new membrane with state-of-the-art CO2 permeance and good CO2/N-2 selectivity. To our knowledge, this is the first example of a TFC gas separation membrane composed of an RTIL-containing active layer.

  3. Enzyme activity in dialkyl phosphate ionic liquids.

    PubMed

    Thomas, Marie F; Li, Luen-Luen; Handley-Pendleton, Jocelyn M; van der Lelie, Daniel; Dunn, John J; Wishart, James F

    2011-12-01

    The activity of four metagenomic enzymes and an enzyme cloned from the straw mushroom, Volvariella volvacea were studied in the following ionic liquids, 1,3-dimethylimidazolium dimethyl phosphate, [mmim][dmp], 1-ethyl-3-methylimidazolium dimethyl phosphate, [emim][dmp], 1-ethyl-3-methylimidazolium diethyl phosphate, [emim][dep] and 1-ethyl-3-methylimidazolium acetate, [emim][OAc]. Activity was determined by analyzing the hydrolysis of para-nitrobenzene carbohydrate derivatives. In general, the enzymes were most active in the dimethyl phosphate ionic liquids, followed by acetate. Generally speaking, activity decreased sharply for concentrations of [emim][dep] above 10% v/v, while the other ionic liquids showed less impact on activity up to 20% v/v. PMID:22001053

  4. Enzyme activity in dialkyl phosphate ionic liquids

    SciTech Connect

    Thomas, M.F.; Dunn, J.; Li, L.-L.; Handley-Pendleton, J. M.; van der lelie, D.; Wishart, J. F.

    2011-12-01

    The activity of four metagenomic enzymes and an enzyme cloned from the straw mushroom, Volvariellavolvacea were studied in the following ionic liquids, 1,3-dimethylimidazolium dimethyl phosphate, [mmim][dmp], 1-ethyl-3-methylimidazolium dimethyl phosphate, [emim][dmp], 1-ethyl-3-methylimidazolium diethyl phosphate, [emim][dep] and 1-ethyl-3-methylimidazolium acetate, [emim][OAc]. Activity was determined by analyzing the hydrolysis of para-nitrobenzene carbohydrate derivatives. In general, the enzymes were most active in the dimethyl phosphate ionic liquids, followed by acetate. Generally speaking, activity decreased sharply for concentrations of [emim][dep] above 10% v/v, while the other ionic liquids showed less impact on activity up to 20% v/v.

  5. Desulfurization of oxidized diesel using ionic liquids

    NASA Astrophysics Data System (ADS)

    Wilfred, Cecilia D.; Salleh, M. Zulhaziman M.; Mutalib, M. I. Abdul

    2014-10-01

    The extraction of oxidized sulfur compounds from diesel were carried out using ten types of ionic liquids consisting of different cation and anion i.e. 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazoium thiocyanate, 1-butyl-3-methylimidazoium dicyanamide, 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazoliumhexafluorophosphate, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate, trioctylmethylammonium chloride, 1-propionitrile-3-butylimidazolium thiocyanate, 1-propionitrile-3-butylimidazolium dicyanamide and 1-butyl-6-methylquinolinium dicyanamide. The oxidation of diesel was successfully done using phosphotungstic acid as the catalyst, hydrogen peroxide (H2O2) as the oxidant and trioctylmethylammonium chloride as the phase transfer agent. The oxidation of diesel changes the sulfur compounds into sulfone which increases its polarity and enhances the ionic liquid's extraction performance. Result showed that ionic liquid [C4mquin][N(CN)2] performed the highest sulfur removal (91% at 1:5 diesel:IL ratio) compared to the others.

  6. TETRAALKYLPHOSPHONIUM POLYOXOMETALATES AS NOVEL IONIC LIQUIDS.

    SciTech Connect

    DIETZ,M.L.; RICKERT, P.G.; ANTONIO, M.R.; FIRESTONE, M.A.; WISHART, J.F.; SZREDER, T.

    2007-11-30

    The pairing of a Lindqvist or Keggin polyoxometalate (POM) anion with an appropriate tetraalkylphosphonium cation, [R{sub 3}R{prime}P]{sup +}, has been shown to yield an original family of ionic liquids (POM-ILs), among them salts liquid at or near ambient temperature. The physicochemical properties of several such 'inorganic liquids', in particular their thermal properties, suggests the possible application of these compounds as robust, thermally-stable solvents for liquid-liquid extraction. A preliminary evaluation of the potential of POM-ILs in this application is presented.

  7. Selective extraction and determination of vitamin B12 in urine by ionic liquid-based aqueous two-phase system prior to high-performance liquid chromatography.

    PubMed

    Berton, Paula; Monasterio, Romina P; Wuilloud, Rodolfo G

    2012-08-15

    A rapid and simple extraction technique based on aqueous two-phase system (ATPS) was developed for separation and enrichment of vitamin B(12) in urine samples. The proposed ATPS-based method involves the application of the hydrophilic ionic liquid (IL) 1-hexyl-3-methylimidazolium chloride and K(2)HPO(4). After the extraction procedure, the vitamin B(12)-enriched IL upper phase was directly injected into the high performance liquid chromatography (HPLC) system for analysis. All variables influencing the IL-based ATPS approach (e.g., the composition of ATPS, pH and temperature values) were evaluated. The average extraction efficiency was 97% under optimum conditions. Only 5.0 mL of sample and a single hydrolysis/deproteinization/extraction step were required, followed by direct injection of the IL-rich upper phase into HPLC system for vitamin B(12) determination. A detection limit of 0.09 μg mL(-1), a relative standard deviation (RSD) of 4.50% (n=10) and a linear range of 0.40-8.00 μg mL(-1) were obtained. The proposed green analytical procedure was satisfactorily applied to the analysis of samples with highly complex matrices, such as urine. Finally, the IL-ATPS technique could be considered as an efficient tool for the water-soluble vitamin B(12) extraction. PMID:22841117

  8. Choline chloride based ionic liquid analogues as tool for the fabrication of agar films with improved mechanical properties.

    PubMed

    Sousa, Ana M M; Souza, Hiléia K S; Latona, Nicholas; Liu, Cheng-Kung; Gonçalves, Maria P; Liu, LinShu

    2014-10-13

    In the present paper, we test the suitability of ChCl/urea (DES-U) and ChCl/glycerol (DES-G) eutectic mixtures, each one prepared at 1:2 molar ratio, for the production of agar films. A three-step process is proposed: pre-solubilization of polymer in DES followed by compression-molding and subsequent drying. The mechanical properties, water resistance and microstructure of the films were evaluated at different polymer concentrations (i.e. 2-6%, w/w). DES-U showed by far, the best film forming ability. Agreeing with the diffusion and SEM data, films with the best mechanical properties were found at the lowest and highest agar concentrations (tensile strengths of 24.2-42 MPa and elongations of 15.4-38.9%). The water sorption and contact angle studies suggested increased hydrophilicity for the film containing the lowest concentration of agar. The use of choline chloride based ionic liquid analogues as solvent and plasticizer might be a promising tool for the development of new non-aqueous materials based on seaweed polysaccharides. PMID:25037344

  9. Pharmacological performance of novel poly-(ionic liquid)-grafted chitosan-N-salicylidene Schiff bases and their complexes.

    PubMed

    Elshaarawy, Reda F M; Refaee, Ayaat A; El-Sawi, Emtithal A

    2016-08-01

    In our endeavor to develop a new class of pharmacological candidates with antimicrobial and anticancer efficacy, a series of biopolymeric chitosan Schiff bases bearing salicylidene ionic liquid (IL-Sal) brushes (ILCSB1-3, poly-(GlcNHAc-GlcNH2-(GlcN-Sal-IL)) was successfully synthesized by adopting efficient synthetic routes. Unfortunately, metalation trials of these biopolymeric Schiff bases afford the corresponding Ag(I)/M(II) complexes (where M=Co, Pd). These designed architectures were structurally characterized and pharmacologically evaluated for their in vitro antimicrobial, against common bacterial and fungal pathogens, and anticancer activities against human colon carcinoma (HCT-116) cell line. In conclusion functionalization of chitosan with IL-Sal brushes coupled with metalation of formed ILCSBs were synergistically enhanced its antimicrobial and antitumor properties to a great extent. Noteworthy, Ag-ILCSB2 (IC50=9.13μg/mL) was ca. 5-fold more cytotoxic against HCT-116 cell line than ILCSB2 (IC50=43.30μg/mL). PMID:27112887

  10. Structure of room temperature ionic liquids.

    PubMed

    Yethiraj, Arun

    2016-10-19

    The structure of room temperature ionic liquids is studied using molecular dynamics simulations and integral equation theory. Three ionic liquids 1-alkyl-3-methylimidazolium hexfluorophosphate, [C n MIM] [PF6], for n  =  1, 4, and 8, are studied using a united atom model of the ions. The primary interest is a study of the pair correlation functions and a test of the reference interaction site model theory. There is liquid-like ordering in the liquid that arises from electrostatic attractions and steric packing considerations. The theory is not in quantitative agreement with the simulation results and underestimates the degree of liquid-like order. A pre-peak in the static structure factor is seen in both simulations and theory, suggesting that this is a geometric effect arising from a packing of the alkyl chains. PMID:27546807

  11. Electroless deposition of metallic silver from a choline chloride-based ionic liquid: a study using acoustic impedance spectroscopy, SEM and atomic force microscopy.

    PubMed

    Abbott, Andrew P; Nandhra, Satvinder; Postlethwaite, Stella; Smith, Emma L; Ryder, Karl S

    2007-07-28

    In this paper, we describe the first example of a sustained galvanic coating deposited on a surface from a non-aqueous liquid. We present the surface characterization of electroless silver deposits on copper substrates from a solution of Ag(+) ions in an ionic liquid based on a choline chloride (ChCl) eutectic. Through a study of these deposits and the mechanism of formation using acoustic impedance spectroscopy (QCM), probe microscopy (AFM) and electron microscopy (SEM/EDX), we demonstrate that sustained growth of the silver deposit is facilitated by the porous nature of the silver. This is in contrast to the dip-coating reaction of silver ions in aqueous media, where the reaction stops when surface coverage is reached. Electroless silver deposits of up to several microns have been obtained by dip coating in ionic liquids without the use of catalysts of strong inorganic acids. PMID:17622408

  12. Enhanced extraction of bovine serum albumin with aqueous biphasic systems of phosphonium- and ammonium-based ionic liquids.

    PubMed

    Pereira, Matheus M; Pedro, Sónia N; Quental, Maria V; Lima, Álvaro S; Coutinho, João A P; Freire, Mara G

    2015-07-20

    Novel aqueous biphasic systems (ABS) composed of phosphonium- or ammonium-based ionic liquids (ILs), combined with a buffered aqueous solution of potassium citrate/citric acid (pH=7.0), were investigated for the extraction of proteins. For that purpose, the phase diagrams, tie-lines and tie-line lengths were determined at 25 °C, and the performance of these ABS for the extraction of bovine serum albumin (BSA) was then evaluated. The obtained results reveal that, with the exception of the more hydrophobic ILs, most of the systems investigated allow the complete extraction of BSA for the IL-rich phase in a single-step. These remarkable extraction efficiencies are far superior to those afforded by more conventional extraction systems previously reported. The composition of the biphasic systems, i.e., the amount of phase-forming components, was also investigated aiming at reducing the overall costs of the process without losing efficiency on the protein extraction. It is shown that the extraction efficiencies of BSA are maintained at 100% up to high protein concentrations (at least up to 10 g L(-1)). The recovery of the BSA from the IL-rich phase by dialysis is also shown in addition to the demonstration of the IL recyclability and reusability, at least for 3 times. In the sequential three-step extractions (BSA recovery/IL reusability), the extraction efficiencies of BSA for the IL-rich phase were maintained at 100%. For the improved ABS, the preservation of the protein native conformation was confirmed by Size Exclusion High-Performance Liquid Chromatography (used also as the quantification method) and by Fourier Transform Infra-Red spectroscopy. According to the results herein reported, ABS composed of phosphonium- or ammonium-based ILs and a biodegradable organic salt represent an alternative and remarkable platform for the extraction of BSA and may be extended to other proteins of interest. PMID:25865275

  13. Cholinium-amino acid based ionic liquids: a new method of synthesis and physico-chemical characterization.

    PubMed

    De Santis, Serena; Masci, Giancarlo; Casciotta, Francesco; Caminiti, Ruggero; Scarpellini, Eleonora; Campetella, Marco; Gontrani, Lorenzo

    2015-08-28

    In the present work we report the synthesis and physico-chemical characterization in terms of the viscosity and density of a wide series of cholinium-amino acid based room temperature ionic liquids ([Ch][AA] RTILs). 18 different amino acids were used to obtain 14 room temperature ILs. Among the most common AAs, only valine did not form an RTIL but it is a liquid above 80 °C. With respect to the methods reported in the literature we propose a synthesis based on potentiometric titration which has several advantages such as shorter preparation time, stoichiometry within ±1%, very high yields (close to 100%), high reproducibility, and no use of organic solvents, thus being more environmentally friendly. We tried to prepare dianionic ILs with some AAs with two potentially ionisable groups but in all cases the salts were solids at room temperature. All the ILs were characterized by (1)H NMR to confirm the stoichiometry. Physico-chemical properties such as density, viscosity, refractive index and conductivity were measured as a function of temperature and correlated with empirical equations. The values were compared with the data already reported in the literature for some [Ch][AA] ILs. The thermal expansion coefficient αp and the molar volume Vm were also calculated from the experimental density values. Due to the high number of AAs explored and their structural heterogeneity we have been able to find some interesting correlations between the data obtained and the structural features of the AAs in terms of the alkyl chain length, hydrogen bonding ability, stacking and cyclization. Some parameters were also found to be in good agreement with those reported for other ILs. We think that these data can give an important contribution to the understanding of the structure-property relationship of ILs because they focused on the structural effect of the anions, while most data in the literature are focussed on the cations. PMID:26206450

  14. Predictive model for ionic liquid extraction solvents for rare earth elements

    NASA Astrophysics Data System (ADS)

    Grabda, Mariusz; Oleszek, Sylwia; Panigrahi, Mrutyunjay; Kozak, Dmytro; Eckert, Franck; Shibata, Etsuro; Nakamura, Takashi

    2015-12-01

    The purpose of our study was to select the most effective ionic liquid extraction solvents for dysprosium (III) fluoride using a theoretical approach. Conductor-like Screening Model for Real Solvents (COSMO-RS), based on quantum chemistry and the statistical thermodynamics of predefined DyF3-ionic liquid systems, was applied to reach the target. Chemical potentials of the salt were predicted in 4,400 different ionic liquids. On the base of these predictions set of ionic liquids' ions, manifesting significant decrease of the chemical potentials, were selected. Considering the calculated physicochemical properties (hydrophobicity, viscosity) of the ionic liquids containing these specific ions, the most effective extraction solvents for liquid-liquid extraction of DyF3 were proposed. The obtained results indicate that the COSMO-RS approach can be applied to quickly screen the affinity of any rare earth element for a large number of ionic liquid systems, before extensive experimental tests.

  15. Unravelling nanoconfined films of ionic liquids

    SciTech Connect

    Lee, Alpha A.; Vella, Dominic; Goriely, Alain; Perkin, Susan

    2014-09-07

    The confinement of an ionic liquid between charged solid surfaces is treated using an exactly solvable 1D Coulomb gas model. The theory highlights the importance of two dimensionless parameters: the fugacity of the ionic liquid, and the electrostatic interaction energy of ions at closest approach, in determining how the disjoining pressure exerted on the walls depends on the geometrical confinement. Our theory reveals that thermodynamic fluctuations play a vital role in the “squeezing out” of charged layers as the confinement is increased. The model shows good qualitative agreement with previous experimental data, with all parameters independently estimated without fitting.

  16. Determination of trace mercury in water based on N-octylpyridinium ionic liquids preconcentration and stripping voltammetry.

    PubMed

    Li, Zhenhan; Xia, Shanhong; Wang, Jinfen; Bian, Chao; Tong, Jianhua

    2016-01-15

    A novel method for determination of trace mercury in water is developed. The method is performed by extracting mercury firstly with ionic liquids (ILs) and then detecting the concentration of mercury in organic media with anodic stripping voltammetry. Liquid-liquid extraction of mercury(II) ions by four ionic liquids with N-octylpyridinium cations ([OPy](+)) was studied. N-octylpyridinium tetrafluoroborate and N-octylpyridinium trifluoromethylsulfonate were found to be efficient and selective extractant for mercury. Temperature controlled dispersive liquid phase microextraction (TC-DLPME) technique was utilized to improve the performance of preconcentration. After extraction, precipitated IL was diluted by acetonitrile buffer and mercury was detected by differential pulse stripping voltammetry (DPSV) with gold disc electrode. Mercury was enriched by 17 times while interfering ions were reduced by two orders of magnitude in the organic media under optimum condition. Sensitivity and selectivity for electrochemical determination of mercury were improved by using the proposed method. Tap, pond and waste water samples were analyzed with recoveries ranging from 81% to 107% and detection limit of 0.05 μg/L. PMID:26364269

  17. Trace element partitioning between ionic crystal and liquid

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Philpotts, J. A.; Yin, L.

    1978-01-01

    The partitioning of trace elements between ionic crystals and the melt has been correlated with lattice energy of the host. The solid-liquid partition coefficient has been expressed in terms of the difference in relative ionic radius of the trace element and the homogeneous and heterogeneous strain of the host lattice. Predictions based on this model appear to be in general agreement with data for alkali nitrates and for rare-earth elements in natural garnet phenocrysts.

  18. Using glucaminium-based ionic liquids for improving the separation of 2-aminopyrimidine-5-ylboronic acid and its pinacol ester by high performance liquid chromatography.

    PubMed

    Joshi, Manishkumar D; Li, Tianhao; Zhong, Qiqing; Anderson, Jared L

    2013-09-20

    A reversed-phase high performance liquid chromatography (HPLC) method is described for the determination of boronic acids that are commonly present as impurities in pinacolboronate ester reagents. Boronic acids and their pinacolboronate esters are key reagents in the Suzuki-Miyaura coupling reaction. The retention of hydrophilic boronic acids in reversed-phase chromatography is often a challenge, especially in very high pH mobile phases, which are needed to mitigate the on-column degradation of pinacolboronate esters. In this study, a hydrophilic boronic acid, 2-aminopyrimidine-5-ylboronic acid, was complexed with specifically functionalized glucaminium-based ionic liquids that were added to the diluent. The two glucaminium-based ILs possess cis-diol moieties that are capable of forming complexes with boronic acids. In addition, aromatic functional groups within the glucaminium cation allow strong π-π interactions with the polymeric stationary phase. Using this approach, the limit of detection for 2-aminopyrimidine-5-ylboronic acid was found to be 3-4μM. The quantification of 2-aminopyrimidine-5-ylboronic acid within a 2-aminopyrimidine-5-pinacolboronate ester sample was successfully achieved using this method. PMID:23958694

  19. Cationic Ionic Liquids Organic Ligands Based Metal-Organic Frameworks for Fabrication of Core-Shell Microspheres for Hydrophilic Interaction Liquid Chromatography.

    PubMed

    Dai, Qian; Ma, Junqian; Ma, Siqi; Wang, Shengyu; Li, Lijun; Zhu, Xianghui; Qiao, Xiaoqiang

    2016-08-24

    In this study, new metal-organic frameworks (MOFs) nanocrystals modified SiO2 core-shell microspheres were designed with cationic ionic liquids (ILs) 1,3-bis(4-carboxybutyl)imidazolium bromide (ILI) as organic ligands. By further adjustment the growth cycles, the new ILI-01@SiO2 core-shell stationary phase was facilely fabricated. The developed stationary phase was respectively characterized via element analysis, thermogravimetric analysis, scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectrometry. Because the introduction of cationic imidazolium-based ILs ILI for fabrication of the MOFs nanocrystals shell, the new stationary phase exhibits the retention mechanism of hydrophilic interaction liquid chromatography (HILIC). Many polar samples, such as amides, vitamins, nucleic acid bases, and nucleosides, were utilized to investigate the performance of the prepared ILI-01@SiO2 column. Compared to the conventional aminosilica column, the new ILI-01@SiO2 column displays high separation selectivity in a shorter separation time. Furthermore, the new ILI-01@SiO2 column was also used for detection of illegal melamine addition in the baby formula. All the above results demonstrate the new ILI-01@SiO2 core-shell stationary phase is of good potentials for high-selectivity separation the polar samples. PMID:27483161

  20. High-Surface-Area CO2 Sponge: High Performance CO2 Scrubbing Based on Hollow Fiber-Supported Designer Ionic Liquid Sponges

    SciTech Connect

    2010-09-01

    IMPACCT Project: The team from ORNL and Georgia Tech is developing a new technology that will act like a sponge, integrating a new, alcohol-based ionic liquid into hollow fibers (magnified image, right) to capture CO2 from the exhaust produced by coal-fired power plants. Ionic liquids, or salts that exist in liquid form, are promising materials for carbon capture and storage, but their tendency to thicken when combined with CO2 limits their efficiency and poses a challenge for their development as a cost-effective alternative to current-generation solutions. Adding alcohol to the mix limits this tendency to thicken in the presence of CO2 but can also make the liquid more likely to evaporate, which would add significantly to the cost of CO2 capture. To solve this problem, ORNL is developing new classes of ionic liquids with high capacity for absorbing CO2. ORNL’s sponge would reduce the cost associated with the energy that would need to be diverted from power plants to capture CO2 and release it for storage.

  1. Analysis of the driving force that rule the stability of lysozyme in alkylammonium-based ionic liquids.

    PubMed

    Bisht, Meena; Kumar, Awanish; Venkatesu, Pannuru

    2015-11-01

    Ionic liquids (ILs) have found various applications in the field of biotechnology that involves protein extraction from the aqueous phase. However, the stability of biomolecules in ILs is still unpredictable. Therefore, this work aims to understand the effect of ammonium-based ILs with a fixed (trifluoromethylsulfonyl)imide [NTf2](-) anion and variable ammonium cations such as butyltrimethylammonium (IL-1), ethyldimethylpropylammonium (IL-2), diethylmethyl(2-methoxyethyl)ammonium (IL-3) and methyl-trioctylammonium (IL-4) on the stability of lysozyme. The spectroscopic analysis (UV, fluorescence and circular dichroism (CD)) revealed the existence of native structure of lysozyme in the presence of ILs at 25°C. Evidently, the presence of α-helix structure in lysozyme was confirmed using CD spectroscopy. In contrary, the thermal stability of the protein gradually decreased with increase in the concentration of the ILs. This was due to the strong favorable interactions of the ILs with the amino acid residues of the protein. Further, Nile red fluorescence revealed existence of the hydrophobic interactions between ILs and the lysozyme. Hence, due to its immense hydrophobic character, IL-4 thereby, decreased the catalytic activity and stability of the lysozyme to a greater extent. PMID:26410812

  2. Room-temperature ionic liquid assisted fabrication of sensitive electrochemical immunosensor based on ordered macroporous gold film.

    PubMed

    Chen, Xiaojun; Zhou, Jinjun; Xuan, Jie; Yan, Wei; Jiang, Li-Ping; Zhu, Jun-Jie

    2010-10-01

    A novel label-free highly sensitive electrochemical impedance spectroscopy (EIS) immunosensor was fabricated based on the highly ordered macroporous gold film (HOMGF) in the presence of room-temperature ionic liquid (IL) for the detection of human Apolipoprotein B-100 (ApoB-100). The antibody of ApoB-100 (Ab) was adsorbed directly onto the HOMGF electrode surface and maintained its bioactivity. After the residual active sites at the electrode were passivated by BSA, the mixture of BMIm(+)BF(4)(-) and silica sol was dropped onto the electrode to entrap the adsorbed Ab and BSA molecules firmly. The addition of IL could prevent the inactivation of Ab by releasing alcohol during the sol-gel process, and the conductivity of the IL-gel membrane was increased. Of particular interest is the fact that the fabricated immunosensor could be used at 60 °C. This could be attributed to the interconnected porosity of the IL-gel membrane, which can prevent Ab from unfolding and losing its bioactivities. The immunosensor also exhibited a highly sensitive response to ApoB-100 with the lowest concentration of 5 fg mL(-1). The detection of ApoB-100 levels in five sera samples obtained from hospital showed acceptable accuracy with that using commercial immunonephelometry method. PMID:20694205

  3. Electrodeposition mechanism and characterization of Ni-Cu alloy coatings from a eutectic-based ionic liquid

    NASA Astrophysics Data System (ADS)

    Wang, Shaohua; Guo, Xingwu; Yang, Haiyan; Dai, JiChun; Zhu, Rongyu; Gong, Jia; Peng, Liming; Ding, Wenjiang

    2014-01-01

    The electrodeposition mechanism, microstructures and corrosion resistances of Ni-Cu alloy coatings on Cu substrate were investigated in a choline chloride-urea (1:2 molar ratio) eutectic-based ionic liquid (1:2 ChCl-urea IL) containing nickel and copper chlorides. Cyclic voltammetry showed that the onset reduction potentials for Cu (˜-0.32 V) and for Ni (˜-0.47 V) were close to each other, indicating that Ni-Cu co-deposition could be easily achieved in the absence of complexing agent which was indispensable in aqueous plating electrolyte. Chronoamperometric investigations revealed that Ni-Cu deposits followed the three-dimensional instantaneous nucleation/growth mechanism, thus producing a solid solution. The compositions, microstructures and corrosion resistances of Ni-Cu alloy coatings were significantly dependent on the deposition current densities. Ni-Cu alloy coatings were α-Ni(Cu) solid solutions, and the coating containing ˜17.6 at.% Cu exhibited the best corrosion resistance because of its dense and crack-free structure.

  4. One-pot transformation of cellobiose to formic acid and levulinic acid over ionic-liquid-based polyoxometalate hybrids.

    PubMed

    Li, Kaixin; Bai, Linlu; Amaniampong, Prince Nana; Jia, Xinli; Lee, Jong-Min; Yang, Yanhui

    2014-09-01

    Currently, levulinic acid (LA) and formic acid (FA) are considered as important carbohydrates for the production of value-added chemicals. Their direct production from biomass will open up a new opportunity for the transformation of biomass resource to valuable chemicals. In this study, one-pot transformation of cellobiose into LA and FA was demonstrated, using a series of multiple-functional ionic liquid-based polyoxometalate (IL-POM) hybrids as catalytic materials. These IL-POMs not only markedly promoted the production of valuable chemicals including LA, FA and monosaccharides with high selectivities, but also provided great convenience of the recovery and the reuse of the catalytic materials in an environmentally friendly manner. Cellobiose conversion of 100%, LA selectivity of 46.3%, and FA selectivity of 26.1% were obtained at 423 K and 3 MPa for 3 h in presence of oxygen. A detailed catalytic mechanism for the one-pot transformation of cellobiose was also presented. PMID:25110998

  5. The effect of cation structure on the mesophase architecture of self-assembled and polymerized imidazolium-based ionic liquids.

    SciTech Connect

    Batra, D.; Seifert, S.; Firestone, M. A.; Materials Science Division

    2007-01-01

    The binary phase behavior of a series of imidazolium-based ionic liquids (ILs) has been investigated. In particular, the effect of two structural modifications of the imidazolium cation, alkyl chain length, and the introduction of a polymerizable acryloyl group at the alkyl chain terminus, has been studied using small angle X-ray scattering. Upon increasing water content, the non-polymerizable IL, 1-decyl-3-methylimidazolium chloride, adopts mesophase structures of predominately two-dimensional (2D) hexagonal symmetry, including structures intermediate in character between lamellae and 2D hexagonal micelles. Introduction of a photopolymerizable acryloyl functional group to form 1-(10-(acryloyloxy)decyl)-3-methylimidazolium chloride produces a rod-coil IL cation that yields self-assembled mesophases in which the formation of tetragonal morphologies is favored. Covalent linking of the IL cations by UV-induced polymerization converts the lyotropic mesophase into three-dimensional biocontinuous chemical gels. Reducing the alkyl chain length, as in the polymerizable IL cation 1-(8-(acryloyloxy)octyl)-3-methylimidazolium chloride, severely reduces the self-assembled mesophase order, and triggers the formation of only weakly ordered one-dimensional lamellar structures.

  6. A new coupling of ionic liquid based-single drop microextraction with tungsten coil electrothermal atomic absorption spectrometry

    NASA Astrophysics Data System (ADS)

    Wen, Xiaodong; Deng, Qingwen; Wang, Jiwei; Yang, Shengchun; Zhao, Xia

    2013-03-01

    In this work, an improved method of ionic liquid based-single drop microextraction (IL-SDME) preconcentration was firstly coupled with tungsten coil electrothermal atomic absorption spectrometry (W-coil ET-AAS) detection. The new coupling was developed and applied for the determination of ultra-trace cadmium. Experimental parameters influencing the performance of IL-SDME as well as instrumental conditions were studied systematically, including IL-drop volume, chelating agent concentration, pH, stirring rate and time, heating program of W-coil ET-AAS, flow rate of carrier gas. Under the optimal conditions, the limit of detection (LOD) for cadmium was 0.015 μg L-1 (sampling amount on W-coil was 10 μL). The sensitivity enhancement factor was 42, while the improvement factor of LOD was 33. The established method was applied to determine cadmium in standard reference materials of rice and real water samples successfully. The developed IL-SDME-W-coil ET-AAS coupling represents a simple, green and highly sensitive method for cadmium determination.

  7. Catalytic activities of fungal oxidases in hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate-based microemulsion.

    PubMed

    Zhou, Gui-Ping; Zhang, Yun; Huang, Xi-Rong; Shi, Chuan-Hong; Liu, Wei-Feng; Li, Yue-Zhong; Qu, Yin-Bo; Gao, Pei-Ji

    2008-10-01

    For hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF(6)]), an H(2)O-in-[BMIM][PF(6)] microemulsion could be formed in the presence of nonionic surfactant Triton X-100 (TX-100). In such a medium, both lignin peroxidase (LiP) and laccase could express their catalytic activity with the optimum molar ratio of H(2)O to TX-100 at 8.0 for LiP and >20 for laccase, and the optimum pH values at 3.2 for LiP and 4.2 for laccase, respectively. As compared with pure or water saturated [BMIM][PF(6)], in which the two oxidases had negligible catalytic activity due to the strong inactivating effect of [BMIM][PF(6)] on both enzymes, the use of the [BMIM][PF(6)]-based microemulsion had some advantages. Not only the catalytic activities of both fungal oxidases greatly enhanced, but also the apparent viscosity of the medium decreased. PMID:18602799

  8. Novel multifunctional nanofibers based on thermoplastic polyurethane and ionic liquid: towards antibacterial, anti-electrostatic and hydrophilic nonwovens by electrospinning.

    PubMed

    Xing, Chenyang; Guan, Jipeng; Chen, Zhouli; Zhu, Yu; Zhang, Bowu; Li, Yongjin; Li, Jingye

    2015-03-13

    Novel antibacterial, anti-electrostatic, and hydrophilic nanofibers based on a blend containing thermoplastic polyurethane (TPU) and a room-temperature ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], were fabricated by electrospinning. We investigated the effect of the IL on the morphology and the physical properties of the TPU nanofibers. Nanofibers with a 'bead-on-string' morphology were obtained by electrospinning from a neat TPU solution. The incorporation of the IL, at levels as low as 1 wt%, largely suppressed the formation of beads during electrospinning, and homogeneous nanofibers were obtained. The as-spun TPU/IL composite nanofibers showed significant activity against both Escherichia coli (E coli) and Staphylococcus aureus (S. aureus), with antibacterial activities of more than four and three, respectively. This means that the antibacterial efficiencies of TPU/IL composite nanofibers toward E coli and S. aureus are 99.99% and 99.9%, respectively. Moreover, nonwoven fabrics derived from the electrospun TPU/IL composite nanofibers exhibit better stretchability, elasticity, and higher electrical conductivity compared to those made using neat TPU without an IL. Additionally, the incorporation of the IL leads to a hydrophilic surface for the TPU/IL composite nanofibers compared to hydrophobic neat TPU nanofibers. These multifunctional nanofibers with excellent antibacterial, anti-electrostatic, and mechanical properties and improved hydrophilicity are promising candidates for biomedical and wastewater treatment applications. PMID:25686531

  9. Structural insights into the effect of cholinium-based ionic liquids on the critical micellization temperature of aqueous triblock copolymers.

    PubMed

    Khan, Imran; Umapathi, Reddicherla; Neves, Márcia C; Coutinho, João A P; Venkatesu, Pannuru

    2016-03-16

    Symmetrical poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEG-PPG-PEG) triblock copolymer with 82.5% PEG as the hydrophilic end blocks, and PPG as the hydrophobic middle block, was chosen to study the effect of ionic liquids (ILs) on the critical micellization temperature (CMT) of block copolymers in aqueous solution. In the present work, cholinium-based ILs were chosen to explore the effect of the anions on the copolymer CMT using fluorescence spectroscopy, dynamic light scattering (DLS), viscosity (η), FT-IR spectroscopy, nuclear magnetic resonance (NMR), and direct visualization of the various self-assembled nanostructures by scanning electron microscopy (SEM). The result suggests that ILs have the ability to decrease the CMT of the aqueous copolymer solution which is dependent on the nature of the anions of the ILs. The present study reveals that the hydrophobic part PPG of the copolymer has more influence on this behavior than the PEG hydrophilic part. PMID:26700649

  10. Correlation between Soft X-ray Absorption and Emission Spectra of the Nitrogen Atoms within Imidazolium-Based Ionic Liquids.

    PubMed

    Horikawa, Yuka; Tokushima, Takashi; Takahashi, Osamu; Hoke, Hiroshi; Takamuku, Toshiyuki

    2016-08-01

    Soft X-ray absorption spectroscopy (XAS) has been performed on the N K-edge of two imidazolium-based ionic liquids (ILs), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([C2mim][TFSA]) and 1-ethyl-3-methylimidazolium bromide ([C2mim][Br]), to clarify the electronic structures of the ILs. Soft X-ray emission spectroscopy (XES) has also been applied to the ILs by excitation at various X-ray energies according to the XAS spectra. It was possible to fully associate the XAS peaks with the XES peaks. Additionally, both XAS and XES spectra of the ILs were well reproduced by the theoretical spectra for a single-molecule model on [C2mim](+) and [TFSA](-) using density functional theory. The assignments for the XAS and XES peaks of the ILs were accomplished from both experimental and theoretical approaches. The theoretical XAS and XES spectra of [C2mim](+) and [TFSA](-) did not significantly depend on the conformations of the ions. The reproducibility of the theoretical spectra for the single-molecule model suggested that the interactions between the cations and anions are very weak in the ILs, thus scarcely influencing the electronic structures of the nitrogen atoms. PMID:27388151

  11. Structure, thermodynamic and transport properties of imidazolium-based bis(trifluoromethylsulfonyl)imide ionic liquids from molecular dynamics simulations

    NASA Astrophysics Data System (ADS)

    Androulaki, Eleni; Vergadou, Niki; Ramos, Javier; Economou, Ioannis G.

    2012-06-01

    Molecular dynamics (MD) simulations have been performed in order to investigate the properties of [C n mim+][Tf2N-] (n = 4, 8, 12) ionic liquids (ILs) in a wide temperature range (298.15-498.15 K) and at atmospheric pressure (1 bar). A previously developed methodology for the calculation of the charge distribution that incorporates ab initio quantum mechanical calculations based on density functional theory (DFT) was used to calculate the partial charges for the classical molecular simulations. The wide range of time scales that characterize the segmental dynamics of these ILs, especially at low temperatures, required very long MD simulations, on the order of several tens of nanoseconds, to calculate the thermodynamic (density, thermal expansion, isothermal compressibility), structural (radial distribution functions between the centers of mass of ions and between individual sites, radial-angular distribution functions) and dynamic (relaxation times of the reorientation of the bonds and the torsion angles, self-diffusion coefficients, shear viscosity) properties. The influence of the temperature and the cation's alkyl chain length on the above-mentioned properties was thoroughly investigated. The calculated thermodynamic (primary and derivative) and structural properties are in good agreement with the experimental data, while the extremely sluggish dynamics of the ILs under study renders the calculation of their transport properties a very complicated and challenging task, especially at low temperatures.

  12. Novel multifunctional nanofibers based on thermoplastic polyurethane and ionic liquid: towards antibacterial, anti-electrostatic and hydrophilic nonwovens by electrospinning

    NASA Astrophysics Data System (ADS)

    Xing, Chenyang; Guan, Jipeng; Chen, Zhouli; Zhu, Yu; Zhang, Bowu; Li, Yongjin; Li, Jingye

    2015-03-01

    Novel antibacterial, anti-electrostatic, and hydrophilic nanofibers based on a blend containing thermoplastic polyurethane (TPU) and a room-temperature ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], were fabricated by electrospinning. We investigated the effect of the IL on the morphology and the physical properties of the TPU nanofibers. Nanofibers with a ‘bead-on-string’ morphology were obtained by electrospinning from a neat TPU solution. The incorporation of the IL, at levels as low as 1 wt%, largely suppressed the formation of beads during electrospinning, and homogeneous nanofibers were obtained. The as-spun TPU/IL composite nanofibers showed significant activity against both Escherichia coli (E coli) and Staphylococcus aureus (S. aureus), with antibacterial activities of more than four and three, respectively. This means that the antibacterial efficiencies of TPU/IL composite nanofibers toward E coli and S. aureus are 99.99% and 99.9%, respectively. Moreover, nonwoven fabrics derived from the electrospun TPU/IL composite nanofibers exhibit better stretchability, elasticity, and higher electrical conductivity compared to those made using neat TPU without an IL. Additionally, the incorporation of the IL leads to a hydrophilic surface for the TPU/IL composite nanofibers compared to hydrophobic neat TPU nanofibers. These multifunctional nanofibers with excellent antibacterial, anti-electrostatic, and mechanical properties and improved hydrophilicity are promising candidates for biomedical and wastewater treatment applications.

  13. Lithium ion conducting PVdF-HFP composite gel electrolytes based on N-methoxyethyl- N-methylpyrrolidinium bis(trifluoromethanesulfonyl)-imide ionic liquid

    NASA Astrophysics Data System (ADS)

    Ferrari, S.; Quartarone, E.; Mustarelli, P.; Magistris, A.; Fagnoni, M.; Protti, S.; Gerbaldi, C.; Spinella, A.

    Blends of PVdF-HFP and ionic liquids (ILs) are interesting for application as electrolytes in plastic Li batteries. They combine the advantages of the gel polymer electrolytes (GPEs) swollen by conventional organic liquid electrolytes with the nonflammability, and high thermal and electrochemical stability of ILs. In this work we prepared and characterized PVdF-HFP composite membranes swollen with a solution of LiTFSI in ether-functionalized pyrrolidinium-imide ionic liquid (PYRA 12O1TFSI). The membranes were filled in with two different types of silica: (i) mesoporous SiO 2 (SBA-15) and (ii) a commercial nano-size one (HiSil™ T700). The ionic conductivity and the electrochemical properties of the gel electrolytes were studied in terms of the nature of the filler. The thermal and the transport properties of the composite membranes are similar. In particular, room temperature ionic conductivities higher than 0.25 mS cm -1 are easily obtained at defined filler contents. However, the mesoporous filler guarantees higher lithium transference numbers, a more stable electrochemical interface and better cycling performances. Contrary to the HiSil™-based membrane, the Li/LiFePO 4 cells with PVdF-HFP/PYRA 12O1TFSI-LiTFSI films containing 10 wt% of SBA-15 show good charge/discharge capacity, columbic efficiency close to unity, and low capacity losses at medium C-rates during 180 cycles.

  14. Novel polymer electrolytes based on thermoplastic polyurethane and ionic liquid/lithium bis(trifluoromethanesulfonyl)imide/propylene carbonate salt system

    NASA Astrophysics Data System (ADS)

    Lavall, R. L.; Ferrari, S.; Tomasi, C.; Marzantowicz, M.; Quartarone, E.; Magistris, A.; Mustarelli, P.; Lazzaroni, S.; Fagnoni, M.

    Polymer electrolytes were prepared from thermoplastic polyurethane with addition of mixture of ionic liquid N-ethyl(methylether)-N-methylpyrrolidinium trifluoromethanesulfonimmide (PYRA 12O1TFSI), lithium bis(trifluoromethanesulfoneimide) salt and propylene carbonate. The electrolytes characterization was performed by thermogravimetric analysis, differential scanning calorimetry and scanning electron microscopy. The electrical properties were investigated in detail by impedance spectroscopy with the aid of equivalent circuit fitting of the impedance spectra. A model describing temperature evolution of ionic conductivity and the properties of electrolyte/blocking electrode interface was developed. The electrochemical stability of the electrolytes was studied by linear voltammetry. Our results indicate that the studied electrolytes have good self-standing characteristics, and also a sufficient level of thermal stability and a fairly good electrochemical window. The ionic conductivity increases with increasing amount of mixture, and the character of temperature dependence of conductivity indicates decoupling of ion transport from polymer matrix. For studied system, the highest value of ionic conductivity measured at room temperature was 10 -4 S cm -1.

  15. Ionic liquid-based aqueous two-phase system, a sample pretreatment procedure prior to high-performance liquid chromatography of opium alkaloids.

    PubMed

    Li, Shehong; He, Chiyang; Liu, Huwei; Li, Kean; Liu, Feng

    2005-11-01

    An ionic liquid, 1-butyl-3-methylimidazolium chloride ([C4 mim]Cl)/salt aqueous two-phase systems (ATPS) was presented as a simple, rapid and effective sample pretreatment technique coupled with high-performance liquid chromatography (HPLC) for analysis of the major opium alkaloids in Pericarpium papaveris. To find optimal conditions, the partition behaviors of codeine and papaverine in ionic liquid/salt aqueous two-phase systems were investigated. Various factors were considered systematically, and the results indicated that both the pH value and the salting-out ability of salt had great influence on phase separation. The recoveries of codeine and papaverine were 90.0-100.2% and 99.3-102.0%, respectively, from aqueous samples of P. papaveris by the proposed method. PMID:16143571

  16. Preparation of AgX (X = Cl, I) nanoparticles using ionic liquids

    NASA Astrophysics Data System (ADS)

    Rodil, Eva; Aldous, Leigh; Hardacre, Christopher; Lagunas, M. Cristina

    2008-03-01

    Nanoparticles of silver halides have been prepared by mixing silver halide powder with a single liquid phase consisting of an ionic liquid, isooctane, n-decanol and water. Much higher nanoparticle concentrations may be formed with ionic liquids using this new simple method than are found with conventionally applied surfactants. This method also emphasizes the applicability of ionic liquids as versatile components in microemulsions and as solvents for the synthesis of nanomaterials. The effect on the nanoparticles of changing the composition of the liquid mixtures and the nature of the ionic liquid is analysed. High nanoparticle concentrations were only found with chloride based ionic liquids, indicating the importance of the ionic liquid anion in the mechanism of the reaction.

  17. Sensitive determination of estrogens in environmental waters treated with polymeric ionic liquid-based stir cake sorptive extraction and liquid chromatographic analysis.

    PubMed

    Chen, Lei; Mei, Meng; Huang, Xiaojia; Yuan, Dongxing

    2016-05-15

    A simple, sensitive and environmentally friendly method using polymeric ionic liquid-based stir cake sorptive extraction followed by high performance liquid chromatography with diode array detection (HPLC/DAD) has been developed for efficient quantification of six selected estrogens in environmental waters. To extract trace estrogens effectively, a poly (1-ally-3-vinylimidazolium chloride-co-ethylene dimethacrylate) monolithic cake was prepared and used as the sorbent of stir cake sorptive extraction (SCSE). The effects of preparation conditions of sorbent and extraction parameters of SCSE for estrogens were investigated and optimized. Under optimal conditions, the developed method showed satisfactory analytical performance for targeted analytes. Low limits of detection (S/N=3) and quantification limits (S/N=10) were achieved within the range of 0.024-0.057µg/L and 0.08-0.19µg/L, respectively. Good linearity of method was obtained for analytes with the correlation coefficients (R(2)) above 0.99. At the same time, satisfactory method repeatability and reproducibility was achieved in terms of intra- and inter-day precisions, respectively. Finally, the established SCSE-HPLC/DAD method was successfully applied for the determination of estrogens in different environmental water samples. Recoveries obtained for the determination of estrogens in spiked samples ranged from 71.2% to 108%, with RSDs below 10% in all cases. PMID:26992499

  18. Rapid quantification of imidazolium-based ionic liquids by hydrophilic interaction liquid chromatography: Methodology and an investigation of the retention mechanisms.

    PubMed

    Hawkins, Cory A; Rud, Anna; Guthrie, Margaret L; Dietz, Mark L

    2015-06-26

    The separation of nine N,N'-dialkylimidazolium-based ionic liquids (ILs) by an isocratic hydrophilic interaction high-performance liquid chromatographic method using an unmodified silica column was investigated. The chosen analytical conditions using a 90:10 acetonitrile-ammonium formate buffer mobile phase on a high-purity, unmodified silica column were found to be efficient, robust, and sensitive for the determination of ILs in a variety of solutions. The retention window (k' = 2-11) was narrower than that of previous methods, resulting in a 7-min runtime for the nine IL homologues. The lower limit of quantification of the method, 2-3 μmol L(-1), was significantly lower than those reported previously for HPLC-UV methods. The effects of systematically modifying the IL cation alkyl chain length, column temperature, and mobile-phase water and buffer content on solute retention were examined. Cation exchange was identified as the dominant retention mechanism for most of the solutes, with a distinct (single methylene group) transition to a dominant partitioning mode at the highest solute polarity. PMID:25979537

  19. Ionic liquids based on phosphonium cations as neat lubricants or lubricant additives for a steel/steel contact.

    PubMed

    Otero, Inés; López, Enriqueta R; Reichelt, Manuela; Villanueva, María; Salgado, Josefa; Fernández, Josefa

    2014-08-13

    After doing several miscibility essays with eight ionic liquids (ILs) and four base oils, the ILs tri(butyl)ethylphosphonium diethylphosphate [P4,4,4,2][C2C2PO4] and trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate [P6,6,6,14][(C2F5)3PF3] were selected to be studied as lubricant additives. The neat IL [P4,4,4,2][C2C2PO4], the base oils, and several blends were characterized in terms of density, viscosity, and thermal stability. The tribological performance of the miscible base oil/IL blends (1 wt %) and the neat [P4,4,4,2][C2C2PO4] were evaluated for the lubrication of an AISI 420 steel-100Cr6 steel contact pair. The friction coefficients and wear volumes obtained are also compared with those corresponding to the pure base oils and their mixtures with conventional additive zinc dialkyldithiophosphate (ZDDP). As neat lubricants, [P4,4,4,2][C2C2PO4] showed the best antifriction ability, whereas in terms of wear, better results were obtained with [P6,6,6,14][(C2F5)3PF3]. However, higher improvements in both friction and wear were found for blends containing [P4,4,4,2][C2C2PO4]. XPS analyses of the worn surfaces lubricated with these mixtures indicated the presence of phosphorus in the tribofilm formed on the wear track. However, this compound was slightly detected on tribosamples lubricated with blends containing [P6,6,6,14][(C2F5)3PF3]. PMID:25046076

  20. EXPEDITIOUS SYNTHESIS OF IONIC LIQUIDS USING ULTRASOUND AND MICROWAVE IRRADIATION

    EPA Science Inventory

    Environmentally friendlier preparations of ionic liquids have been developed that proceed expeditiously under the influence of microwave or ultrasound irradiation conditions using neat reactants, alkylimidazoles and alkyl halides. A number of useful ionic liquids have been prepar...