Highly selective separation of carbon dioxide from nitrogen and methane by nitrile/glycol-difunctionalized ionic liquids in supported ionic liquid membranes (SILMs).

PubMed

Hojniak, Sandra D; Silverwood, Ian P; Khan, Asim Laeeq; Vankelecom, Ivo F J; Dehaen, Wim; Kazarian, Sergei G; Binnemans, Koen

2014-07-03

Novel difunctionalized ionic liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic liquid membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature liquidity of the pyrrolidinium and imidazolium ILs, the two classes of ILs benefit from the presence of a nitrile group in different ways. The difunctionalized pyrrolidinium ILs exhibit an increase in CO2 permeance, whereas the permeances of the contaminant gases rise negligibly, resulting in high gas separation selectivities. In the imidazolium ILs, the presence of a nitrile group does not always increase the CO2 permeance nor does it increase the CO2 solubility, as showed in situ by the ATR-FTIR spectroscopic method. High selectivity of these ILs is caused by the considerably reduced permeances of N2 and CH4, most likely due to the ability of the -CN group to reject the nonpolar contaminant gases. Apart from the CO2 solubility, IL-CO2 interactions and IL swelling were studied with the in situ ATR-FTIR spectroscopy. Different strengths of the IL-CO2 interactions were found to be the major difference between the two classes of ILs. The difunctionalized ILs interacted stronger with CO2 than the glycol-functionalized ILs, as manifested in the smaller bandwidths of the bending mode band of CO2 for the latter.

A structural, functional, and computational analysis suggests pore flexibility as the base for the poor selectivity of CNG channels

PubMed Central

Napolitano, Luisa Maria Rosaria; Bisha, Ina; De March, Matteo; Marchesi, Arin; Arcangeletti, Manuel; Demitri, Nicola; Mazzolini, Monica; Rodriguez, Alex; Magistrato, Alessandra; Onesti, Silvia; Laio, Alessandro; Torre, Vincent

2015-01-01

Cyclic nucleotide-gated (CNG) ion channels, despite a significant homology with the highly selective K+ channels, do not discriminate among monovalent alkali cations and are permeable also to several organic cations. We combined electrophysiology, molecular dynamics (MD) simulations, and X-ray crystallography to demonstrate that the pore of CNG channels is highly flexible. When a CNG mimic is crystallized in the presence of a variety of monovalent cations, including Na+, Cs+, and dimethylammonium (DMA+), the side chain of Glu66 in the selectivity filter shows multiple conformations and the diameter of the pore changes significantly. MD simulations indicate that Glu66 and the prolines in the outer vestibule undergo large fluctuations, which are modulated by the ionic species and the voltage. This flexibility underlies the coupling between gating and permeation and the poor ionic selectivity of CNG channels. PMID:26100907

A structural, functional, and computational analysis suggests pore flexibility as the base for the poor selectivity of CNG channels.

PubMed

Napolitano, Luisa Maria Rosaria; Bisha, Ina; De March, Matteo; Marchesi, Arin; Arcangeletti, Manuel; Demitri, Nicola; Mazzolini, Monica; Rodriguez, Alex; Magistrato, Alessandra; Onesti, Silvia; Laio, Alessandro; Torre, Vincent

2015-07-07

Cyclic nucleotide-gated (CNG) ion channels, despite a significant homology with the highly selective K(+) channels, do not discriminate among monovalent alkali cations and are permeable also to several organic cations. We combined electrophysiology, molecular dynamics (MD) simulations, and X-ray crystallography to demonstrate that the pore of CNG channels is highly flexible. When a CNG mimic is crystallized in the presence of a variety of monovalent cations, including Na(+), Cs(+), and dimethylammonium (DMA(+)), the side chain of Glu66 in the selectivity filter shows multiple conformations and the diameter of the pore changes significantly. MD simulations indicate that Glu66 and the prolines in the outer vestibule undergo large fluctuations, which are modulated by the ionic species and the voltage. This flexibility underlies the coupling between gating and permeation and the poor ionic selectivity of CNG channels.

Toxicity of ionic liquids: eco(cyto)activity as complicated, but unavoidable parameter for task-specific optimization.

PubMed

Egorova, Ksenia S; Ananikov, Valentine P

2014-02-01

Rapid progress in the field of ionic liquids in recent decades led to the development of many outstanding energy-conversion processes, catalytic systems, synthetic procedures, and important practical applications. Task-specific optimization emerged as a sharpening stone for the fine-tuning of structure of ionic liquids, which resulted in unprecedented efficiency at the molecular level. Ionic-liquid systems showed promising opportunities in the development of green and sustainable technologies; however, the chemical nature of ionic liquids is not intrinsically green. Many ionic liquids were found to be toxic or even highly toxic towards cells and living organisms. In this Review, we show that biological activity and cytotoxicity of ionic liquids dramatically depend on the nature of a biological system. An ionic liquid may be not toxic for particular cells or organisms, but may demonstrate high toxicity towards another target present in the environment. Thus, a careful selection of biological activity data is a must for the correct assessment of chemical technologies involving ionic liquids. In addition to the direct biological activity (immediate response), several indirect effects and aftereffects are of primary importance. The following principal factors were revealed to modulate toxicity of ionic liquids: i) length of an alkyl chain in the cation; ii) degree of functionalization in the side chain of the cation; iii) anion nature; iv) cation nature; and v) mutual influence of anion and cation. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium-Sulfur Batteries.

PubMed

Ward, Ashleigh L; Doris, Sean E; Li, Longjun; Hughes, Mark A; Qu, Xiaohui; Persson, Kristin A; Helms, Brett A

2017-05-24

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device's active materials when they enter the membrane's pore. This transformation has little influence on the membrane's ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development.

Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium–Sulfur Batteries

PubMed Central

2017-01-01

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium–sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development. PMID:28573201

Application of Ionic Liquids in Amperometric Gas Sensors.

PubMed

Gębicki, Jacek; Kloskowski, Adam; Chrzanowski, Wojciech; Stepnowski, Piotr; Namiesnik, Jacek

2016-01-01

This article presents an analysis of available literature data on metrological parameters of the amperometric gas sensors containing ionic liquids as an electrolyte. Four mechanism types of signal generation in amperometric sensors with ionic liquid are described. Moreover, this article describes the influence of selected physico-chemical properties of the ionic liquids on the metrological parameters of these sensors. Some metrological parameters are also compared for amperometric sensors with GDE and SPE electrodes and with ionic liquids for selected analytes.

Non-ionic detergents facilitate non-specific binding of M13 bacteriophage to polystyrene surfaces.

PubMed

Hakami, Abdulrahim R; Ball, Jonathan K; Tarr, Alexander W

2015-09-01

Phage-displayed random peptide libraries are widely used for identifying peptide interactions with proteins and other substrates. Selection of peptide ligands involves iterative rounds of affinity enrichment. The binding properties of the selected phage clones are routinely tested using immunoassay after propagation to high titre in a bacterial host and precipitation using polyethylene glycol (PEG) and high salt concentration. These immunoassays can suffer from low sensitivity and high background signals. Polysorbate 20 (Tween(®) 20) is a non-ionic detergent commonly used in immunoassay washing buffers to reduce non-specific binding, and is also used as a blocking reagent. We have observed that Tween 20 enhances non-specific M13 library phage binding in a peptide-independent manner. Other non-ionic detergents were also found to promote significant, dose-dependent non-specific phage binding in ELISA. This effect was not observed for assays using phage concentrated by ultracentrifugation, suggesting that interactions occur between detergents and the PEG-precipitated phage, irrespective of the displayed peptide motif. This artefact may impact on successful affinity selection of peptides from phage-display libraries. We propose alternative methods for screening phage libraries for identifying binding interactions with target ligands. Copyright © 2015 Elsevier B.V. All rights reserved.

Advances in the analysis of biological samples using ionic liquids.

PubMed

Clark, Kevin D; Trujillo-Rodríguez, María J; Anderson, Jared L

2018-02-12

Ionic liquids are a class of solvents and materials that hold great promise in bioanalytical chemistry. Task-specific ionic liquids have recently been designed for the selective extraction, separation, and detection of proteins, peptides, nucleic acids, and other physiologically relevant analytes from complex biological samples. To facilitate rapid bioanalysis, ionic liquids have been integrated in miniaturized and automated procedures. Bioanalytical separations have also benefited from the modification of nonspecific magnetic materials with ionic liquids or the implementation of ionic liquids with inherent magnetic properties. Furthermore, the direct detection of the extracted molecules in the analytical instrument has been demonstrated with structurally tuned ionic liquids and magnetic ionic liquids, providing a significant advantage in the analysis of low-abundance analytes. This article gives an overview of these advances that involve the application of ionic liquids and derivatives in bioanalysis. Graphical abstract Ionic liquids, magnetic ionic liquids, and ionic liquid-based sorbents are increasing the speed, selectivity, and sensitivity in the analysis of biological samples.

Improvement of imprinting effect of ionic liquid molecularly imprinted polymers by use of a molecular crowding agent.

PubMed

Jia, Man; Yang, Jian; Sun, Ya Kun; Bai, Xi; Wu, Tao; Liu, Zhao Sheng; Aisa, Haji Akber

2018-01-01

We aimed to improve the imprinting effect of ionic liquid molecularly imprinted polymers (MIPs) by use of a molecular crowding agent. The ionic liquid 1-vinyl-3-ethylimidazolium tetrafluoroborate ([VEIm][BF 4 ]) was used as the functional monomer and aesculetin was used as the template molecule in a crowding environment, which was made up of a tetrahydrofuran solution of polystyrene. The ionic liquid MIPs that were prepared in the crowding environment displayed an enhanced imprinting effect. NMR peak shifts of active hydrogen of aesculetin suggested that interaction between the functional monomer and the template could be increased by the use of a crowding agent in the self-assembly process. The retention and selectivity of aesculetin were affected greatly by high molecular crowding, the amount of high molecular weight crowding agent, and the ratio of [VEIm][BF 4 ] to aesculetin. The optimal MIPs were used as solid-phase extraction sorbents to extract aesculetin from Cichorium glandulosum. A calibration curve was obtained with aesculetin concentrations from 0.0005 to 0.05 mg mL -1 (correlation coefficient R 2 of 0.9999, y = 1519x + 0.0923). The limit of quantification was 0.12 μg mL -1 , and the limit of detection was 0.05 μg mL -1 . The absolute recovery of aesculetin was (80 ± 2)% (n = 3), and the purity of aesculetin was (92 ± 0.5)% (n = 5). As a conclusion, molecular crowding is an effective approach to obtain ionic liquid MIPs with high selectivity even in a polar solvent environment.

Ionic liquids: solvents and sorbents in sample preparation.

PubMed

Clark, Kevin D; Emaus, Miranda N; Varona, Marcelino; Bowers, Ashley N; Anderson, Jared L

2018-01-01

The applications of ionic liquids (ILs) and IL-derived sorbents are rapidly expanding. By careful selection of the cation and anion components, the physicochemical properties of ILs can be altered to meet the requirements of specific applications. Reports of IL solvents possessing high selectivity for specific analytes are numerous and continue to motivate the development of new IL-based sample preparation methods that are faster, more selective, and environmentally benign compared to conventional organic solvents. The advantages of ILs have also been exploited in solid/polymer formats in which ordinarily nonspecific sorbents are functionalized with IL moieties in order to impart selectivity for an analyte or analyte class. Furthermore, new ILs that incorporate a paramagnetic component into the IL structure, known as magnetic ionic liquids (MILs), have emerged as useful solvents for bioanalytical applications. In this rapidly changing field, this Review focuses on the applications of ILs and IL-based sorbents in sample preparation with a special emphasis on liquid phase extraction techniques using ILs and MILs, IL-based solid-phase extraction, ILs in mass spectrometry, and biological applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent advances in the use of ionic liquids for electrochemical sensing.

PubMed

Silvester, Debbie S

2011-12-07

Ionic Liquids are salts that are liquid at (or just above) room temperature. They possess several advantageous properties (e.g. high intrinsic conductivity, wide electrochemical windows, low volatility, high thermal stability and good solvating ability), which make them ideal as non-volatile electrolytes in electrochemical sensors. This mini-review article describes the recent uses of ionic liquids in electrochemical sensing applications (covering the last 3 years) in the context of voltammetric sensing at solid/liquid, liquid/liquid interfaces and carbon paste electrodes, as well as their use in gas sensing, ion-selective electrodes, and for detecting biological molecules, explosives and chemical warfare agents. A comment on the future direction and challenges in this field is also presented.

Ionic liquid-impregnated agarose film two-phase micro-electrodriven membrane extraction (IL-AF-μ-EME) for the analysis of antidepressants in water samples.

PubMed

Mohamad Hanapi, Nor Suhaila; Sanagi, Mohd Marsin; Ismail, Abd Khamim; Wan Ibrahim, Wan Aini; Saim, Nor'ashikin; Wan Ibrahim, Wan Nazihah

2017-03-01

The aim of this study was to investigate and apply supported ionic liquid membrane (SILM) in two-phase micro-electrodriven membrane extraction combined with high performance liquid chromatography-ultraviolet detection (HPLC-UV) for pre-concentration and determination of three selected antidepressant drugs in water samples. A thin agarose film impregnated with 1-hexyl-3-methylimidazolium hexafluorophosphate, [C 6 MIM] [PF 6 ], was prepared and used as supported ionic liquid membrane between aqueous sample solution and acceptor phase for extraction of imipramine, amitriptyline and chlorpromazine. Under the optimized extraction conditions, the method provided good linearity in the range of 1.0-1000μgL -1 , good coefficients of determination (r 2 =0.9974-0.9992) and low limits of detection (0.1-0.4μgL -1 ). The method showed high enrichment factors in the range of 110-150 and high relative recoveries in the range of 88.2-111.4% and 90.9-107.0%, for river water and tap water samples, respectively with RSDs of ≤7.6 (n=3). This method was successfully applied to the determination of the drugs in river and tap water samples. It is envisaged that the SILM improved the perm-selectivity by providing a pathway for targeted analytes which resulted in rapid extraction with high degree of selectivity and high enrichment factor. Copyright © 2017 Elsevier B.V. All rights reserved.

Study of surface-bonded dicationic ionic liquids as stationary phases for hydrophilic interaction chromatography.

PubMed

Qiao, Lizhen; Li, Hua; Shan, Yuanhong; Wang, Shuangyuan; Shi, Xianzhe; Lu, Xin; Xu, Guowang

2014-02-21

In the present study, several geminal dicationic ionic liquids based on 1,4-bis(3-allylimidazolium)butane and 1,8-bis(3-allylimidazolium)octane in combination with different anions bromide and bis(trifluoromethanesulphonyl)imide were prepared and then bonded to the surface of 3-mercaptopropyl modified silica materials through the "thiol-ene" click chemistry as stationary phases for hydrophilic interaction chromatography (HILIC). Compared with their monocationic analogues, the dicationic ionic liquids stationary phases presented effective retention and good selectivity for typical hydrophilic compounds under HILIC mode with the column efficiency as high as 130,000 plates/m. Moreover, the influence of different alkyl chain spacer between dications and combined anions on the retention behavior and selectivity of the dicationic ionic liquids stationary phases under HILIC mode was displayed. The results indicated that the longer linkage chain would decrease the hydrophilicity and retention on the dicationic ionic liquid stationary phase, and while differently combined anions had no difference due to the exchangeability under the common HILIC mobile phase with buffer salt. Finally, the retention mechanism was investigated by evaluating the effect of chromatographic factors on retention, including the water content in the mobile phase, the mobile phase pH and buffer salt concentration. The results showed that the dicationic ionic liquids stationary phases presented a mixed-mode retention behavior with HILIC mechanism and anion exchange. Copyright © 2014 Elsevier B.V. All rights reserved.

Thermoelectric Generators Based on Ionic Liquids

NASA Astrophysics Data System (ADS)

Laux, Edith; Uhl, Stefanie; Jeandupeux, Laure; López, Pilar Pérez; Sanglard, Pauline; Vanoli, Ennio; Marti, Roger; Keppner, Herbert

2018-03-01

Looking at energy harvesting using body or waste heat for portable electronic or on-board devices, Ionic liquids are interesting candidates as thermoactive materials in thermoelectric generators (TEGs) because of their outstanding properties. Two different kinds of ionic liquid, with alkylammonium and choline as cations, were studied, whereby different anions and redox couples were combined. This study focussed on the intention to find non-hazardous and environmentally friendly ionic liquids for TEGs to be selected among the thousands that can potentially be used. Seebeck coefficients (SEs) as high as - 15 mV/K were measured, in a particular case for an electrode temperature difference of 20 K. The bottleneck of our TEG device is still the abundance of negative SE liquids matching the internal resistance with the existing positive SE-liquids at series connections. In this paper, we show further progress in finding increased negative SE liquids. For current extraction from the TEG, the ionic liquid must be blended with a redox couple, allowing carrier exchange in a cyclic process under a voltage which is incuced by the asymmetry of the generator in terms of hot and cold electrodes. In our study, two types of redox pairs were tested. It was observed that a high SE of an ionic liquid/redox blend is not a sufficient condition for high power output. It appears that more complex effects between the ionic liquid and the electrode determine the magnitude of the final current/power output. The physico-chemical understanding of such a TEG cell is not yet available.

Thermoelectric Generators Based on Ionic Liquids

NASA Astrophysics Data System (ADS)

Laux, Edith; Uhl, Stefanie; Jeandupeux, Laure; López, Pilar Pérez; Sanglard, Pauline; Vanoli, Ennio; Marti, Roger; Keppner, Herbert

2018-06-01

Looking at energy harvesting using body or waste heat for portable electronic or on-board devices, Ionic liquids are interesting candidates as thermoactive materials in thermoelectric generators (TEGs) because of their outstanding properties. Two different kinds of ionic liquid, with alkylammonium and choline as cations, were studied, whereby different anions and redox couples were combined. This study focussed on the intention to find non-hazardous and environmentally friendly ionic liquids for TEGs to be selected among the thousands that can potentially be used. Seebeck coefficients (SEs) as high as - 15 mV/K were measured, in a particular case for an electrode temperature difference of 20 K. The bottleneck of our TEG device is still the abundance of negative SE liquids matching the internal resistance with the existing positive SE-liquids at series connections. In this paper, we show further progress in finding increased negative SE liquids. For current extraction from the TEG, the ionic liquid must be blended with a redox couple, allowing carrier exchange in a cyclic process under a voltage which is incuced by the asymmetry of the generator in terms of hot and cold electrodes. In our study, two types of redox pairs were tested. It was observed that a high SE of an ionic liquid/redox blend is not a sufficient condition for high power output. It appears that more complex effects between the ionic liquid and the electrode determine the magnitude of the final current/power output. The physico-chemical understanding of such a TEG cell is not yet available.

ENZYMATIC POLYMERIZATION OF PHENOLS IN ROOM TEMPERATURE IONIC LIQUIDS

PubMed Central

Eker, Bilge; Zagorevski, Dmitri; Zhu, Guangyu; Linhardt, Robert J.; Dordick, Jonathan S.

2009-01-01

Soybean peroxidase (SBP) was used to catalyze the polymerization of phenols in room-temperature ionic liquids (RTILs). Phenolic polymers with number average molecular weights ranging from 1200 to 4100 D were obtained depending on the composition of the reaction medium and the nature of the phenol. Specifically, SBP was highly active in methylimidazolium-containing RTILs, including 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM(BF4)), and 1-butyl-3-methylpyridinium tetrafluoroborate (BMPy(BF4)) with the ionic liquid content as high as 90% (v/v); the balance being aqueous buffer. Gel permeation chromatography and MALDI-TOF analysis indicated that higher molecular weight polymers can be synthesized in the presence of higher RTIL concentrations, with selective control over polymer size achieved by varying the RTIL concentration. The resulting polyphenols exhibited high thermostability and possessed thermosetting properties. PMID:20161409

Synthesis of 5-(hydroxymethyl)furfural in ionic liquids: paving the way to renewable chemicals.

PubMed

Ståhlberg, Tim; Fu, Wenjing; Woodley, John M; Riisager, Anders

2011-04-18

The synthesis of 5-(hydroxymethyl)furfural (HMF) in ionic liquids is a field that has grown rapidly in recent years. Unique dissolving properties for crude biomass in combination with a high selectivity for HMF formation from hexose sugars make ionic liquids attractive reaction media for the production of chemicals from renewable resources. A wide range of new catalytic systems that are unique for the transformation of glucose and fructose to HMF in ionic liquids has been found. However, literature examples of scale-up and process development are still scarce, and future research needs to complement the new chemistry with studies on larger scales in order to find economically and environmentally feasible processes for HMF production in ionic liquids. This Minireview surveys important progress made in catalyst development for the synthesis of HMF in ionic liquids, and proposes future research directions in process technology. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of ionic liquid stationary phases for one dimensional gas chromatography-mass spectrometry and comprehensive two dimensional gas chromatographic analyses of fatty acids in marine biota.

PubMed

Gu, Qun; David, Frank; Lynen, Frédéric; Vanormelingen, Pieter; Vyverman, Wim; Rumpel, Klaus; Xu, Guowang; Sandra, Pat

2011-05-20

Ionic liquid stationary phases were tested for one dimensional gas chromatography-mass spectrometry (GC-MS) and comprehensive two dimensional gas chromatography (GC×GC) of fatty acid methyl esters from algae. In comparison with polyethylene glycol and cyanopropyl substituted polar stationary phases, ionic liquid stationary phases SLB-IL 82 and SLB-IL 100 showed comparable resolution, but lower column bleeding with MS detection, resulting in better sensitivity. The selectivity and polarity of the ionic liquid phases are similar to a highly polar biscyanopropyl-silicone phase (e.g. HP-88). In GC×GC, using an apolar polydimethyl siloxane×polar ionic liquid column combination, an excellent group-type separation of fatty acids with different carbon numbers and number of unsaturations was obtained, providing information that is complementary to GC-MS identification. Copyright © 2011 Elsevier B.V. All rights reserved.

Tuning transport selectivity of ionic species by phosphoric acid gradient in positively charged nanochannel membranes.

PubMed

Yang, Meng; Yang, Xiaohai; Wang, Kemin; Wang, Qing; Fan, Xin; Liu, Wei; Liu, Xizhen; Liu, Jianbo; Huang, Jin

2015-02-03

The transport of ionic species through a nanochannel plays important roles in fundamental research and practical applications of the nanofluidic device. Here, we demonstrated that ionic transport selectivity of a positively charged nanochannel membrane can be tuned under a phosphoric acid gradient. When phosphoric acid solution and analyte solution were connected by the positively charged nanochannel membrane, the faster-moving analyte through the positively charged nanochannel membrane was the positively charged dye (methylviologen, MV(2+)) instead of the negatively charged dye (1,5-naphthalene disulfonate, NDS(2-)). In other words, a reversed ion selectivity of the nanochannel membranes can be found. It can be explained as a result of the combination of diffusion, induced electroosmosis, and induced electrophoresis. In addition, the influencing factors of transport selectivity, including concentration of phosphoric acid, penetration time, and volume of feed solution, were also investigated. The results showed that the transport selectivity can further be tuned by adjusting these factors. As a method of tuning ionic transport selectivity by establishing phosphoric acid gradient, it will be conducive to improving the separation of ionic species.

Ceramic membranes for catalytic membrane reactors with high ionic conductivities and low expansion properties

DOEpatents

Mackay, Richard; Sammells, Anthony F.

2000-01-01

Ceramics of the composition: Ln.sub.x Sr.sub.2-x-y Ca.sub.y B.sub.z M.sub.2-z O.sub.5+.delta. where Ln is an element selected from the fblock lanthanide elements and yttrium or mixtures thereof; B is an element selected from Al, Ga, In or mixtures thereof; M is a d-block transition element of mixtures thereof; 0.01.ltoreq.x.ltoreq.1.0; 0.01.ltoreq.y.ltoreq.0.7; 0.01.ltoreq.z.ltoreq.1.0 and .delta. is a number that varies to maintain charge neutrality are provided. These ceramics are useful in ceramic membranes and exhibit high ionic conductivity, high chemical stability under catalytic membrane reactor conditions and low coefficients of expansion. The materials of the invention are particularly useful in producing synthesis gas.

Highly stable ionic-covalent cross-linked sulfonated poly(ether ether ketone) for direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Lei, Linfeng; Zhu, Xingye; Xu, Jianfeng; Qian, Huidong; Zou, Zhiqing; Yang, Hui

2017-05-01

A novel ionic cross-linked sulfonated poly(ether ether ketone) containing equal content of sulfonic acid and pendant tertiary amine groups (TA-SPEEK) has been initially synthesized for the application in direct methanol fuel cells (DMFCs). By adjusting the ratio of p-xylene dibromide to tertiary amine groups of TA-SPEEK, a series of ionic-covalent cross-linked membranes (C-SPEEK-x) with tunable degree of cross-linking are prepared. Compared with the pristine membrane, the ionic and ionic-covalent cross-linked proton exchange membranes (PEMs) exhibit reduced methanol permeability and improved mechanical properties, dimensional and oxidative stability. The proton conductivity and methanol selectivity of protonated TA-SPEEK and C-SPEEK-x at 25 °C is up to 0.109 S cm-1 and 3.88 × 105 S s cm-3, respectively, which are higher than that of Nafion 115. The DMFC incorporating C-SPEEK-25 exhibits a maximum power density as high as 35.3 mW cm-2 with 4 M MeOH at 25 °C (31.8 mW cm-2 for Nafion 115). Due to the highly oxidative stability of the membrane, no obvious performance degradation of the DMFC is observed after more than 400 h operation, indicating such cost-effective ionic-covalent cross-linked membranes have substantial potential as alternative PEMs for DMFC applications.

Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries

DOE PAGES

Ward, Ashleigh L.; Doris, Sean E.; Li, Longjun; ...

2017-04-27

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Ashleigh L.; Doris, Sean E.; Li, Longjun

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

On the chemical stabilities of ionic liquids.

PubMed

Sowmiah, Subbiah; Srinivasadesikan, Venkatesan; Tseng, Ming-Chung; Chu, Yen-Ho

2009-09-25

Ionic liquids are novel solvents of interest as greener alternatives to conventional organic solvents aimed at facilitating sustainable chemistry. As a consequence of their unusual physical properties, reusability, and eco-friendly nature, ionic liquids have attracted the attention of organic chemists. Numerous reports have revealed that many catalysts and reagents were supported in the ionic liquid phase, resulting in enhanced reactivity and selectivity in various important reaction transformations. However, synthetic chemists cannot ignore the stability data and intermolecular interactions, or even reactions that are directly applicable to organic reactions in ionic liquids. It is becoming evident from the increasing number of reports on use of ionic liquids as solvents, catalysts, and reagents in organic synthesis that they are not totally inert under many reaction conditions. While in some cases, their unexpected reactivity has proven fortuitously advantageous in others is has been a problem, it is imperative that when selecting an ionic liquid for a particular synthetic application, attention be paid to its compatibility with the reaction conditions. Even though, more than 200 room temperature ionic liquids are known, only a few reports have commented their effects on reaction mechanisms or rate/stability. Therefore, rather than attempting to give a comprehensive overview of ionic liquid chemistry, this review focuses on the non-innocent nature of ionic liquids, with a decided emphasis to clearly illuminate the ability of ionic liquids to affect the mechanistic aspects of some organic reactions thereby affecting and promoting the yield and selectivity.

Mesoporous poly(ionic liquid) supported palladium(II) catalyst for oxidative coupling of benzene under atmospheric oxygen

NASA Astrophysics Data System (ADS)

Liu, Yangqing; Wang, Kai; Hou, Wei; Shan, Wanjian; Li, Jing; Zhou, Yu; Wang, Jun

2018-01-01

Multi-functional mesoporous poly(ionic liquid) (MPIL) containing pyridine-based ionic liquid (IL) moieties and adjacent double sbnd COOH groups was synthesized through the free radical copolymerization of IL monomer N-propane sulfonate-4-vinylpyridine, maleic anhydride and divinylbenzene. Palladium(II) species were anchored on this MPIL support, affording the first efficient heterogeneous catalyst for the oxidative coupling of benzene to biphenyl under atmospheric oxygen at low temperature. The biphenyl yield of 15.0% (selectivity: 98.5%, turnover number: 62) was even higher than the one over the homogeneous counterpart palladium acetate. The catalyst can be facilely separated and reused. The IL moiety in the polymeric framework endowed the formation of immobilized palladium(II) species with high electrophilicity, which responds to the high performance.

Ionic liquids as transesterification catalysts: applications for the synthesis of linear and cyclic organic carbonates

PubMed Central

Perosa, Alvise; Guidi, Sandro; Cattelan, Lisa

2016-01-01

Summary The use of ionic liquids (ILs) as organocatalysts is reviewed for transesterification reactions, specifically for the conversion of nontoxic compounds such as dialkyl carbonates to both linear mono-transesterification products or alkylene carbonates. An introductory survey compares pros and cons of classic catalysts based on both acidic and basic systems, to ionic liquids. Then, innovative green syntheses of task-specific ILs and their representative applications are introduced to detail the efficiency and highly selective outcome of ILs-catalyzed transesterification reactions. A mechanistic hypothesis is discussed by the concept of cooperative catalysis based on the dual (electrophilic/nucleophilic) activation of reactants. PMID:27829898

Porous dendritic copper: an electrocatalyst for highly selective CO2 reduction to formate in water/ionic liquid electrolyte.

PubMed

Huan, Tran Ngoc; Simon, Philippe; Rousse, Gwenaëlle; Génois, Isabelle; Artero, Vincent; Fontecave, Marc

2017-01-01

Copper is currently extensively studied because it provides promising electrodes for carbon dioxide electroreduction. The original combination, reported here, of a nanostructured porous dendritic Cu-based material, characterized by electron microcopy (SEM, TEM) and X-ray diffraction methods, and a water/ionic liquid mixture as the solvent, contributing to CO 2 solubilization and activation, results in a remarkably efficient (large current densities at low overpotentials), stable and selective (large faradic yields) electrocatalytic system for the conversion of CO 2 into formic acid, a product with a variety of uses. These results provide new directions for the further improvement of Cu electrodes.

Innovative polymer nanocomposite electrolytes: nanoscale manipulation of ion channels by functionalized graphenes.

PubMed

Choi, Bong Gill; Hong, Jinkee; Park, Young Chul; Jung, Doo Hwan; Hong, Won Hi; Hammond, Paula T; Park, Hoseok

2011-06-28

The chemistry and structure of ion channels within the polymer electrolytes are of prime importance for studying the transport properties of electrolytes as well as for developing high-performance electrochemical devices. Despite intensive efforts on the synthesis of polymer electrolytes, few studies have demonstrated enhanced target ion conduction while suppressing unfavorable ion or mass transport because the undesirable transport occurs through an identical pathway. Herein, we report an innovative, chemical strategy for the synthesis of polymer electrolytes whose ion-conducting channels are physically and chemically modulated by the ionic (not electronic) conductive, functionalized graphenes and for a fundamental understanding of ion and mass transport occurring in nanoscale ionic clusters. The functionalized graphenes controlled the state of water by means of nanoscale manipulation of the physical geometry and chemical functionality of ionic channels. Furthermore, the confinement of bound water within the reorganized nanochannels of composite membranes was confirmed by the enhanced proton conductivity at high temperature and the low activation energy for ionic conduction through a Grotthus-type mechanism. The selectively facilitated transport behavior of composite membranes such as high proton conductivity and low methanol crossover was attributed to the confined bound water, resulting in high-performance fuel cells.

Ionic liquid containing hydroxamate and N-alkyl sulfamate ions

DOEpatents

Friesen, Cody A.; Wolfe, Derek; Johnson, Paul Bryan

2016-03-15

Embodiments of the invention are related to ionic liquids and more specifically to ionic liquids used in electrochemical metal-air cells in which the ionic liquid includes a cation and an anion selected from hydroxamate and/or N-alkyl sulfamate anions.

Experimental and computational study on the properties of pure and water mixed 1-ethyl-3-methylimidazolium L-(+)-lactate ionic liquid.

PubMed

Aparicio, Santiago; Alcalde, Rafael; Atilhan, Mert

2010-05-06

Ionic liquids have attracted great attention, from both industry and academe, as alternative fluids for a large collection of applications. Although the term green is used frequently to describe ionic liquids in general, it is obvious that it cannot be applied to the huge quantity of possible ionic liquids, and thus, those with adequate environmental and technological profiles must be selected for further and deeper studies, from both basic science and applied approaches. In this work, 1-ethyl-3-methylimidazolium L-(+)-lactate ionic liquid is studied, because of its remarkable properties, through a wide-ranging approach considering thermophysical, spectroscopic, and computational tools, to gain a deeper insight into its complex liquid structure, both pure and mixed with water, thus implying the main factors that would control the technological applications that could be designed using this fluid. The reported results shows a strongly structured pure ionic liquid, in which hydrogen bonding, because of the hydroxyl group of the lactate anion, develops a remarkable role, together with Coulombic forces to determine the fluid's behavior. Upon mixing with water, the ionic liquid retains its structure up to very high dilution levels, with the effect of the ionic liquid on the water structure being very large, even for very low ionic liquid mole fractions. Thus, in water solution, the studied ionic liquid evolves from noninteracting ions solvated by water molecules toward large interacting structures with increasing ionic liquid content.

ORGANIC-HIGH IONIC STRENGTH AQUEOUS SOLVENT SYSTEMS FOR SPIRAL COUNTER-CURRENT CHROMATOGRAPHY: GRAPHIC OPTIMIZATION OF PARTITION COEFFICIENT

PubMed Central

Zeng, Yun; Liu, Gang; Ma, Ying; Chen, Xiaoyuan; Ito, Yoichiro

2012-01-01

A new series of organic-high ionic strength aqueous two-phase solvents systems was designed for separation of highly polar compounds by spiral high-speed counter-current chromatography. A total of 21 solvent systems composed of 1-butanol-ethanol-saturated ammonium sulfate-water at various volume ratios are arranged according to an increasing order of polarity. Selection of the two-phase solvent system for a single compound or a multiple sample mixture can be achieved by two steps of partition coefficient measurements using a graphic method. The capability of the method is demonstrated by optimization of partition coefficient for seven highly polar samples including tartrazine (K=0.77), tryptophan (K=1.00), methyl green (K= 0.93), tyrosine (0.81), metanephrine (K=0.89), tyramine (K=0.98), and normetanephrine (K=0.96). Three sulfonic acid components in D&C Green No. 8 were successfully separated by HSCCC using the graphic selection of the two-phase solvent system. PMID:23467197

Extraction and Chromatographic Determination of Shikimic Acid in Chinese Conifer Needles with 1-Benzyl-3-methylimidazolium Bromide Ionic Liquid Aqueous Solutions

PubMed Central

Chen, Fengli; Hou, Kexin; Li, Shuangyang; Zu, Yuangang; Yang, Lei

2014-01-01

An ionic liquids-based ultrasound-assisted extraction (ILUAE) method was successfully developed for extracting shikimic acid from conifer needles. Eleven 1-alkyl-3-methylimidazolium ionic liquids with different cations and anions were investigated and 1-benzyl-3-methylimidazolium bromide solution was selected as the solvent. The conditions for ILUAE, including the ionic liquid concentration, ultrasound power, ultrasound time, and liquid-solid ratio, were optimized. The proposed method had good recovery (99.37%–100.11%) and reproducibility (RSD, n = 6; 3.6%). ILUAE was an efficient, rapid, and simple sample preparation technique that showed high reproducibility. Based on the results, a number of plant species, namely, Picea koraiensis, Picea meyeri, Pinus elliottii, and Pinus banksiana, were identified as among the best resources of shikimic acid. PMID:24782942

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

Scalable Graphene-Based Membranes for Ionic Sieving with Ultrahigh Charge Selectivity.

PubMed

Hong, Seunghyun; Constans, Charlotte; Surmani Martins, Marcos Vinicius; Seow, Yong Chin; Guevara Carrió, Juan Alfredo; Garaj, Slaven

2017-02-08

Nanostructured graphene-oxide (GO) laminate membranes, exhibiting ultrahigh water flux, are excellent candidates for next generation nanofiltration and desalination membranes, provided the ionic rejection could be further increased without compromising the water flux. Using microscopic drift-diffusion experiments, we demonstrated the ultrahigh charge selectivity for GO membranes, with more than order of magnitude difference in the permeabilities of cationic and anionic species of equivalent hydration radii. Measuring diffusion of a wide range of ions of different size and charge, we were able to clearly disentangle different physical mechanisms contributing to the ionic sieving in GO membranes: electrostatic repulsion between ions and charged chemical groups; and the compression of the ionic hydration shell within the membrane's nanochannels, following the activated behavior. The charge-selectivity allows us to rationally design membranes with increased ionic rejection and opens up the field of ion exchange and electrodialysis to the GO membranes.

Kamlet-Taft solvent parameters, NMR spectroscopic analysis and thermoelectrochemistry of lithium-glyme solvate ionic liquids and their dilute solutions.

PubMed

Black, Jeffrey J; Dolan, Andrew; Harper, Jason B; Aldous, Leigh

2018-06-06

Solvate ionic liquids are a relatively new class of liquids produced by combining a coordinating solvent with a salt. They have a variety of uses and their suitability for such depends upon the ratio of salt to coordinating solvent. This work investigates the Kamlet-Taft solvent parameters of, NMR chemical shifts of nuclei in, and thermoelectrochemistry of a selected set of solvate ionic liquids produced from glymes (methyl terminated oligomers of ethylene glycol) and lithium bis(trifluoromethylsulfonyl)imide at two different compositions. The aim is to improve the understanding of the interactions occurring in these ionic liquids to help select suitable solvate ionic liquids for future applications.

Lyotropic Phase Behavior of Polybutadiene-Poly(ethylene oxide) Diblock Copolymers in Ionic Liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Simone, Peter M.; Lodge, Timothy P.

2008-08-26

The lyotropic phase behavior of three poly(1,2-butadiene-b-ethylene oxide) diblock copolymers (PB-PEO) with different monomer volume fractions has been studied in two different ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF{sub 6}]), across the complete concentration range. The ordered microstructures present in the solutions were characterized via small-angle X-ray scattering (SAXS). The phase diagrams for the PB-PEO/ionic liquid solutions include regions corresponding to the classical copolymer microstructures: body-centered-cubic lattices of spheres, hexagonally ordered cylinders, and lamellae. Additionally, the phase diagrams also include wide regions of coexisting microstructures and regions apparently corresponding to a disordered network microstructure. The phase behavior ofmore » the PB-PEO copolymers in both ionic liquids was comparable to their previously reported aqueous solution behavior. The temperature dependence of the phase diagrams was very modest, indicative of a highly segregated system. The level of solvent selectivity was also investigated via cryogenic transmission electron microscopy (cryo-TEM) on dilute solutions. On the basis of the morphology of the dilute solution copolymer aggregate structures in the ionic liquid solvents, and on the structural length scales of the concentrated solutions, it was concluded that for PB-PEO [BMI][PF{sub 6}] behaves as a more selective solvent than [EMI][TFSI].« less

Ionic liquid thermal stabilities: decomposition mechanisms and analysis tools.

PubMed

Maton, Cedric; De Vos, Nils; Stevens, Christian V

2013-07-07

The increasing amount of papers published on ionic liquids generates an extensive quantity of data. The thermal stability data of divergent ionic liquids are collected in this paper with attention to the experimental set-up. The influence and importance of the latter parameters are broadly addressed. Both ramped temperature and isothermal thermogravimetric analysis are discussed, along with state-of-the-art methods, such as TGA-MS and pyrolysis-GC. The strengths and weaknesses of the different methodologies known to date demonstrate that analysis methods should be in line with the application. The combination of data from advanced analysis methods allows us to obtain in-depth information on the degradation processes. Aided with computational methods, the kinetics and thermodynamics of thermal degradation are revealed piece by piece. The better understanding of the behaviour of ionic liquids at high temperature allows selective and application driven design, as well as mathematical prediction for engineering purposes.

Selective separation of americium from europium using 2,9-bis(triazine)-1,10-phenanthrolines in ionic liquids: a new twist on an old story

DOE Office of Scientific and Technical Information (OSTI.GOV)

Williams, Neil J.; Dehaudt, Jeremy; Bryantsev, Vyacheslav S.

Bis-triazine phenanthrolines have shown great promise for f-block metal separations, attributable to their highly preorganized structure, nitrogen donors, and more enhanced covalent bonding with actinides over lanthanides. However, their limited solubility in traditional solvents remains a technological bottleneck. Here in this paper we report our recent work using a simple 2,9-bis(triazine)-1,10-phenanthroline (Me-BTPhen) dissolved in an ionic liquid (IL), demonstrating the efficacy of IL extraction systems for the selective separation of americium from europium, achieving separation factors in excess of 7500 and selectively removing up to 99% of the americium. Characterization of the coordination environment was performed using a combination ofmore » X-ray absorption fine structure spectroscopy (XAFS) and density functional theory (DFT) calculations.« less

Selective separation of americium from europium using 2,9-bis(triazine)-1,10-phenanthrolines in ionic liquids: a new twist on an old story

DOE PAGES

Williams, Neil J.; Dehaudt, Jeremy; Bryantsev, Vyacheslav S.; ...

2017-02-10

Bis-triazine phenanthrolines have shown great promise for f-block metal separations, attributable to their highly preorganized structure, nitrogen donors, and more enhanced covalent bonding with actinides over lanthanides. However, their limited solubility in traditional solvents remains a technological bottleneck. Here in this paper we report our recent work using a simple 2,9-bis(triazine)-1,10-phenanthroline (Me-BTPhen) dissolved in an ionic liquid (IL), demonstrating the efficacy of IL extraction systems for the selective separation of americium from europium, achieving separation factors in excess of 7500 and selectively removing up to 99% of the americium. Characterization of the coordination environment was performed using a combination ofmore » X-ray absorption fine structure spectroscopy (XAFS) and density functional theory (DFT) calculations.« less

Directed Synthesis of Nanoporous Carbons from Task-Specific Ionic Liquid Precursors for the Adsorption of CO 2

DOE PAGES

Mahurin, Shannon M.; Fulvio, Pasquale F.; Hillesheim, Patrick C.; ...

2014-07-31

Postcombustion CO 2 capture has become a key component of greenhouse-gas reduction as anthropogenic emissions continue to impact the environment. In this paper, we report a one-step synthesis of porous carbon materials using a series of task-specific ionic liquids for the adsorption of CO 2. By varying the structure of the ionic liquid precursor, we were able to control pore architecture and surface functional groups of the carbon materials in this one-step synthesis process leading to adsorbents with high CO 2 sorption capacities (up to 4.067 mmol g -1) at 0 °C and 1 bar. Finally, added nitrogen functional groupsmore » led to high CO 2/N 2 adsorption-selectivity values ranging from 20 to 37 whereas simultaneously the interaction energy was enhanced relative to carbon materials with no added nitrogen.« less

Predictive model for ionic liquid extraction solvents for rare earth elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grabda, Mariusz; Oleszek, Sylwia; Institute of Environmental Engineering of the Polish Academy of Sciences, ul. M. Sklodowskiej-Curie 34, 41-819, Zabrze

2015-12-31

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 DyF{sub 3}-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 effectivemore » extraction solvents for liquid-liquid extraction of DyF{sub 3} 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.« less

A Molecular Dynamics Study on Selective Cation Depletion from an Ionic Liquid Droplet under an Electric Field

NASA Astrophysics Data System (ADS)

Yang, Yudong; Ahn, Myungmo; Im, Dojin; Oh, Jungmin; Kang, Inseok

2017-11-01

General electrohydrodynamic behavior of ionic liquid droplets under an electric field is investigated using MD simulations. Especially, a unique behavior of ion depletion of an ionic liquid droplet under a uniform electric field is studied. Shape deformation due to electric stress and ion distributions inside the droplet are calculated to understand the ionic motion of imidazolium-based ionic liquid droplets with 200 ion pairs of 2 kinds of ionic liquids: EMIM-NTf2 and EMIM-ES. The intermolecular force between cations and anions can be significantly different due to the nature of the structure and charge distribution of the ions. Together with an analytical interpretation of the conducting droplet in an electric field, the MD simulation successfully explains the mechanism of selective ion depletion of an ionic liquid droplet in an electric field. The selective ion depletion phenomenon has been adopted to explain the experimentally observed retreating motion of a droplet in a uniform electric field. The effect of anions on the cation depletion phenomenon can be accounted for from a direct approach to the intermolecular interaction. This research was supproted by the National Research Foundation of Korea (NRF) Grant funded by the Korea government (MSIP) (No. 2017R1D1A1B05035211).

A controllable molecular sieve for Na+ and K+ ions.

PubMed

Gong, Xiaojing; Li, Jichen; Xu, Ke; Wang, Jianfeng; Yang, Hui

2010-02-17

The selective rate of specific ion transport across nanoporous material is critical to biological and nanofluidic systems. Molecular sieves for ions can be achieved by steric and electrical effects. However, the radii of Na(+) and K(+) are quite similar; they both carry a positive charge, making them difficult to separate. Biological ionic channels contain precisely arranged arrays of amino acids that can efficiently recognize and guide the passage of K(+) or Na(+) across the cell membrane. However, the design of inorganic channels with novel recognition mechanisms that control the ionic selectivity remains a challenge. We present here a design for a controllable ion-selective nanopore (molecular sieve) based on a single-walled carbon nanotube with specially arranged carbonyl oxygen atoms modified inside the nanopore, which was inspired by the structure of potassium channels in membrane spanning proteins (e.g., KcsA). Our molecular dynamics simulations show that the remarkable selectivity is attributed to the hydration structure of Na(+) or K(+) confined in the nanochannels, which can be precisely tuned by different patterns of the carbonyl oxygen atoms. The results also suggest that a confined environment plays a dominant role in the selectivity process. These studies provide a better understanding of the mechanism of ionic selectivity in the KcsA channel and possible technical applications in nanotechnology and biotechnology, including serving as a laboratory-in-nanotube for special chemical interactions and as a high-efficiency nanodevice for purification or desalination of sea and brackish water.

Poly(ionic liquid) based chemosensors for detection of basic amino acids in aqueous medium

NASA Astrophysics Data System (ADS)

Li, Xinjuan; Wang, Kai; Ma, Nana; Jia, Xianbin

2017-09-01

Naked-eye detection of amino acids in water is of great significance in the field of bio-analytical applications. Herein, polymerized ionic liquids (PILs) with controlled chain length structures were synthesized via reversible addition-fragmentation chain-transfer (RAFT) polymerization and post-quaternization approach. The amino acids recognition performance of PILs with different alkyl chain lengths and molecular weights was evaluated by naked-eye color change and ultraviolet-visible (UV-vis) spectral studies. These PILs were successfully used for highly sensitive and selective detection of Arg, Lys and His in water. The recognition performance was improved effectively with increased molecular weight of PILs. The biosensitivity of the PILs in water was strongly dependent on their aggregation effect and polarization effect. Highly sensitive and selective detection of amino acids was successfully accomplished by introducing positively charged pyridinium moieties and controlled RAFT radical polymerization.

Extraction of organic compounds with room temperature ionic liquids.

PubMed

Poole, Colin F; Poole, Salwa K

2010-04-16

Room temperature ionic liquids are novel solvents with a rather specific blend of physical and solution properties that makes them of interest for applications in separation science. They are good solvents for a wide range of compounds in which they behave as polar solvents. Their physical properties of note that distinguish them from conventional organic solvents are a negligible vapor pressure, high thermal stability, and relatively high viscosity. They can form biphasic systems with water or low polarity organic solvents and gases suitable for use in liquid-liquid and gas-liquid partition systems. An analysis of partition coefficients for varied compounds in these systems allows characterization of solvent selectivity using the solvation parameter model, which together with spectroscopic studies of solvent effects on probe substances, results in a detailed picture of solvent behavior. These studies indicate that the solution properties of ionic liquids are similar to those of polar organic solvents. Practical applications of ionic liquids in sample preparation include extractive distillation, aqueous biphasic systems, liquid-liquid extraction, liquid-phase microextraction, supported liquid membrane extraction, matrix solvents for headspace analysis, and micellar extraction. The specific advantages and limitations of ionic liquids in these studies is discussed with a view to defining future uses and the need not to neglect the identification of new room temperature ionic liquids with physical and solution properties tailored to the needs of specific sample preparation techniques. The defining feature of the special nature of ionic liquids is not their solution or physical properties viewed separately but their unique combinations when taken together compared with traditional organic solvents. Copyright 2009 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babucci, Melike; Fang, Chia -Yu; Hoffman, Adam S.

1,3-Dialkylimidazolium ionic liquid coatings act as electron donors, increasing the selectivity for partial hydrogenation of 1,3-butadiene catalyzed by iridium complexes supported on high-surface-area γ-Al 2O 3. High-energy-resolution fluorescence detection X-ray absorption near-edge structure (HERFD XANES) measurements quantify the electron donation and are correlated with the catalytic activity and selectivity. Furthermore, the results demonstrate broad opportunities to tune electronic environments and catalytic properties of atomically dispersed supported metal catalysts.

Ion distribution and selectivity of ionic liquids in microporous electrodes.

PubMed

Neal, Justin N; Wesolowski, David J; Henderson, Douglas; Wu, Jianzhong

2017-05-07

The energy density of an electric double layer capacitor, also known as supercapacitor, depends on ion distributions in the micropores of its electrodes. Herein we study ion selectivity and partitioning of symmetric, asymmetric, and mixed ionic liquids among different pores using the classical density functional theory. We find that a charged micropore in contact with mixed ions of the same valence is always selective to the smaller ions, and the ion selectivity, which is strongest when the pore size is comparable to the ion diameters, drastically falls as the pore size increases. The partitioning behavior in ionic liquids is fundamentally different from those corresponding to ion distributions in aqueous systems whereby the ion selectivity is dominated by the surface energy and entropic effects insensitive to the degree of confinement.

Implementation of perturbed-chain statistical associating fluid theory (PC-SAFT), generalized (G)SAFT+cubic, and cubic-plus-association (CPA) for modeling thermophysical properties of selected 1-alkyl-3-methylimidazolium ionic liquids in a wide pressure range.

PubMed

Polishuk, Ilya

2013-03-14

This study is the first comparative investigation of predicting the isochoric and the isobaric heat capacities, the isothermal and the isentropic compressibilities, the isobaric thermal expansibilities, the thermal pressure coefficients, and the sound velocities of ionic liquids by statistical associating fluid theory (SAFT) equation of state (EoS) models and cubic-plus-association (CPA). It is demonstrated that, taking into account the high uncertainty of the literature data (excluding sound velocities), the generalized for heavy compounds version of SAFT+Cubic (GSAFT+Cubic) appears as a robust estimator of the auxiliary thermodynamic properties under consideration. In the case of the ionic liquids the performance of PC-SAFT seems to be less accurate in comparison to ordinary compounds. In particular, PC-SAFT substantially overestimates heat capacities and underestimates the temperature and pressure dependencies of sound velocities and compressibilities. An undesired phenomenon of predicting high fictitious critical temperatures of ionic liquids by PC-SAFT should be noticed as well. CPA is the less accurate estimator of the liquid phase properties, but it is advantageous in modeling vapor pressures and vaporization enthalpies of ionic liquids. At the same time, the preliminary results indicate that the inaccuracies in predicting the deep vacuum vapor pressures of ionic liquids do not influence modeling of phase equilibria in their mixtures at much higher pressures.

Application of ionic liquids in liquid chromatography and electrodriven separation.

PubMed

Huang, Yi; Yao, Shun; Song, Hang

2013-08-01

Ionic liquids (ILs) are salts in the liquid state at ambient temperature, which are nonvolatile, nonflammable with high thermal stability and dissolve easily for a wide range of inorganic and organic materials. As a kind of potential green solvent, they show high efficiency and selectivity in the field of separation research, especially in instrumental analysis. Thus far, ILs have been successfully applied by many related researchers in high-performance liquid chromatography and capillary electrophoresis as chromatographic stationary phases, mobile phase additives or electroosmotic flow modifiers. This paper provides a detailed review of these applications in the study of natural products, foods, drugs and other fine chemicals. Furthermore, the prospects of ILs in liquid chromatographic and electrodriven techniques are discussed.

Modeling electrokinetics in ionic liquids: General

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Chao; Bao, Jie; Pan, Wenxiao

2017-04-07

Using direct numerical simulations we provide a thorough study on the electrokinetics of ionic liquids. In particular, the modfied Poisson-Nernst-Planck (MPNP) equations are solved to capture the crowding and overscreening effects that are the characteristics of an ionic liquid. For modeling electrokinetic flows in an ionic liquid, the MPNP equations are coupled with the Navier-Stokes equations to study the coupling of ion transport, hydrodynamics, and electrostatic forces. Specifically, we consider the ion transport between two parallel plates, charging dynamics in a 2D straight-walled pore, electro-osmotic ow in a nano-channel, electroconvective instability on a plane ion-selective surface, and electroconvective ow onmore » a curved ion-selective surface. We discuss how the crowding and overscreening effects and their interplay affect the electrokinetic behaviors of ionic liquids in these application problems.« less

Ionic calcium determination in skim milk with molecular probes and front-face fluorescence spectroscopy: simple linear regression.

PubMed

Gangidi, R R; Metzger, L E

2006-11-01

The purpose of this study was to determine if the ionic calcium content of skim milk could be determined using molecular probes and front-face fluorescence spectroscopy. Current methods for determining ionic calcium are not sensitive, overestimate ionic calcium, or require complex procedures. Molecular probes designed specifically for measuring ionic calcium could potentially be used to determine the ionic calcium content of skim milk. The goal of the current study was to develop foundation methods for future studies to determine ionic calcium directly in skim milk and other dairy products with molecular probes and fluorescence spectroscopy. In this study, the effect of pH on calcium-sensitive fluorescent probe (Rhod-5N and Fluo-5N) performance using various concentrations of skim milk was determined. The pH of diluted skim milk (1.9 to 8.9% skim milk), was adjusted to either 6.2 or 7.0, after which the samples were analyzed with fluorescent probes (1 microM) and front-face fluorescence spectroscopy. The ionic calcium content of each sample was also determined using a calcium ion-selective electrode. The results demonstrated that the ionic calcium content of each sample was highly correlated (R2 > 0.989) with the fluorescence intensities of the probe-calcium adduct using simple linear regression. Higher than suggested ionic calcium contents of 1,207 and 1,973 microM were determined with the probes (Fluo-5N and Rhod-5N) in diluted skim milk with pH 7.0 and 6.2, respectively. The fluorescence intensity of the probe-calcium adduct decreased with a decrease in pH for the same ionic calcium concentration. This study demonstrates that Fluo-5N and Rhod-5N can be used to determine the ionic-calcium content of diluted milk with front-face fluorescence spectroscopy. Furthermore, these probes may also have the potential to determine the ionic calcium content of undiluted skim milk.

Ionic Association Ion-Selective Electrode Experiment.

ERIC Educational Resources Information Center

Emara, Mostafa M.; And Others

1979-01-01

Describes an experiment that, using a commercially available solid-state selective electrode in conjunction with a pH-meter, determines the stability constants of sodium sulfate while varying the ionic strength of the media using sodium chloride. Detailed reproducible procedures of both the measurements and calculations are described. (BT)

A Comparison of Two Methods of Teaching Molecular Architecture to High School Chemistry Students.

ERIC Educational Resources Information Center

Halsted, Douglas Alan

This investigation explored the question of how high school chemistry students best learn three-dimensional molecular, ionic, and metallic structures in CHEM Study (Freeman, 1963). The experimenter compared the achievement, attitude, and instructional preferences of 110 randomly selected students taught by two different methods: (1) student…

A Phosphine-mediated Synthesis of 2,3,4,5-tetra-substituted N-hydroxypyrroles from α-oximino Ketones and Dialkyl Acetylenedicarboxylates Under Ionic Liquid Green-media.

PubMed

Shahvelayati, Ashraf S; Ghazvini, Maryam; Yadollahzadeh, Khadijeh; Delbari, Akram S

2018-01-01

The development of multicomponent reactions (MCRs) in the presence of task-specific ionic liquids (ILs), used not only as environmentally benign reaction media, but also as catalysts, is a new approach that meet with the requirements of sustainable chemistry. In recent years, the use of ionic liquids as a green media for organic synthesis has become a chief study area. This is due to their unique properties such as non-volatility, non-flammability, chemical and thermal stability, immiscibility with both organic compounds and water and recyclability. Ionic liquids are used as environmentally friendly solvents instead of hazardous organic solvents. We report the condensation reaction between α-oximinoketone and dialkyl acetylene dicarboxylate in the presence of triphenylphosphine to afford substituted pyrroles under ionic liquid conditions in good yields. Densely functionalized pyrroles was easily prepared from reaction of α-oximinoketones, dialkyl acetylene dicarboxylate in the presence of triphenylphosphine in a quantitative yield under ionic liquid conditions at room temperature. In conclusion, ionic liquids are indicated as a useful and novel reaction medium for the selective synthesis of functionalized pyrroles. This reaction medium can replace the use of hazardous organic solvents. Easy work-up, synthesis of polyfunctional compounds, decreased reaction time, having easily available-recyclable ionic liquids, and good to high yields are advantages of present method. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Ionic Liquids as the MOFs/Polymer Interfacial Binder for Efficient Membrane Separation.

PubMed

Lin, Rijia; Ge, Lei; Diao, Hui; Rudolph, Victor; Zhu, Zhonghua

2016-11-23

Obtaining strong interfacial affinity between filler and polymer is critical to the preparation of mixed matrix membranes (MMMs) with high separation efficiency. However, it is still a challenge for micron-sized metal organic frameworks (MOFs) to achieve excellent compatibility and defect-free interface with polymer matrix. Thin layer of ionic liquid (IL) was immobilized on micron-sized HKUST-1 to eliminate the interfacial nonselective voids in MMMs with minimized free ionic liquid (IL) in polymer matrix, and then the obtained IL decorated HKUST-1 was incorporated into 4,4'-(hexafluoroisopropylidene)diphthalic anhydride-2,3,5,6-tetramethyl-1,3-phenyldiamine (6FDA-Durene) to fabricate MMMs. Acting as a filler/polymer interfacial binder, the favorable MOF/IL and IL/polymer interaction can facilitate the enhancement of MOF/polymer affinity. Compared to MMM with only HKUST-1 incorporation, MMM with IL decorated HKUST-1 succeeded in restricting the formation of nonselective interfacial voids, leading to an increment in CO 2 selectivity. The IL decoration method can be an effective approach to eliminate interfacial voids in MMMs, extending the filler selection to a wide range of large-sized fillers.

Dramatic pressure-sensitive ion conduction in conical nanopores.

PubMed

Jubin, Laetitia; Poggioli, Anthony; Siria, Alessandro; Bocquet, Lydéric

2018-04-17

Ion transporters in Nature exhibit a wealth of complex transport properties such as voltage gating, activation, and mechanosensitive behavior. When combined, such processes result in advanced ionic machines achieving active ion transport, high selectivity, or signal processing. On the artificial side, there has been much recent progress in the design and study of transport in ionic channels, but mimicking the advanced functionalities of ion transporters remains as yet out of reach. A prerequisite is the development of ionic responses sensitive to external stimuli. In the present work, we report a counterintuitive and highly nonlinear coupling between electric and pressure-driven transport in a conical nanopore, manifesting as a strong pressure dependence of the ionic conductance. This result is at odds with standard linear response theory and is akin to a mechanical transistor functionality. We fully rationalize this behavior on the basis of the coupled electrohydrodynamics in the conical pore by extending the Poisson-Nernst-Planck-Stokes framework. The model is shown to capture the subtle mechanical balance occurring within an extended spatially charged zone in the nanopore. The pronounced sensitivity to mechanical forcing offers leads in tuning ion transport by mechanical stimuli. The results presented here provide a promising avenue for the design of tailored membrane functionalities.

Construction of a carbon ionic liquid paste electrode based on multi-walled carbon nanotubes-synthesized Schiff base composite for trace electrochemical detection of cadmium.

PubMed

Afkhami, Abbas; Khoshsafar, Hosein; Bagheri, Hasan; Madrakian, Tayyebeh

2014-02-01

A simple, highly sensitive and selective carbon nanocomposite electrode has been developed for the electrochemical trace determination of cadmium. This sensor was designed by incorporation of multi-walled carbon nanotubes (MWCNTs) and a new synthesized Schiff base into the carbon paste ionic liquid electrode (CPE(IL)) which provides remarkably improved sensitivity and selectivity for the electrochemical stripping assay of Cd(II). The detection limit of the method was found to be 0.08 μg L(-1) (S/N=3) that is lower than the maximum contaminant level of Cd(II) allowed by the Environmental Protection Agency (EPA) in standard drinking waters. The proposed electrode exhibits good applicability for monitoring Cd(II) in various real samples. © 2013.

Ionic Liquid-Hybrid Molecularly Imprinted Material-Filter Solid-Phase Extraction Coupled with HPLC for Determination of 6-Benzyladenine and 4-Chlorophenoxyacetic Acid in Bean Sprouts.

PubMed

Han, Yehong; Yang, Chunliu; Zhou, Yang; Han, Dandan; Yan, Hongyuan

2017-03-01

A new method involving ionic liquid-hybrid molecularly imprinted material-filter solid-phase extraction coupled to high-performance liquid chromatography (IL-HIM-FSPE-HPLC) was developed for the simultaneous isolation and determination of 6-benzyladenine (6-BA) and 4-chlorophenoxyacetic acid (4-CPA) in bean sprouts. Sample preconcentration was performed using a modified filter, with the new IL-HIM as the adsorbent, which shows double adsorption. The first adsorption involves special recognition of molecular imprinting, and the second involves ion exchange and electrostatic attraction caused by the ionic liquid. This method combines the advantages of ionic liquids, hybrid materials, and molecularly imprinted polymers and was successfully applied to determine 6-BA and 4-CPA in bean sprouts. The adsorption of 6-BA to IL-HIM is based on selective imprinted recognition, whereas the adsorption of 4-CPA is mainly dependent on ion-exchange interactions.

Fabrication of an ionic-liquid-based polymer monolithic column and its application in the fractionation of proteins from complex biosamples.

PubMed

Zhang, Doudou; Zhang, Qian; Bai, Ligai; Han, Dandan; Liu, Haiyan; Yan, Hongyuan

2018-05-01

An ionic-liquid-based polymer monolithic column was synthesized by free radical polymerization within the confines of a stainless-steel column (50 mm × 4.6 mm id). In the processes, ionic liquid and stearyl methacrylate were used as dual monomers, ethylene glycol dimethacrylate as the cross-linking agent, and polyethylene glycol 200 and isopropanol as co-porogens. Effects of the prepolymerization solution components on the properties of the resulting monoliths were studied in detail. Scanning electron microscopy, nitrogen adsorption-desorption measurements, and mercury intrusion porosimetry were used to investigate the morphology and pore size distribution of the prepared monoliths, which showed that the homemade ionic-liquid-based monolith column possessed a relatively uniform macropore structure with a total macropore specific surface area of 44.72 m 2 /g. Compared to a non-ionic-liquid-based monolith prepared under the same conditions, the ionic-liquid-based monolith exhibited excellent selectivity and high performance for separating proteins from complex biosamples, such as egg white, snailase, bovine serum albumin digest solution, human plasma, etc., indicating promising applications in the fractionation and analysis of proteins from the complex biosamples in proteomics research. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application and recovery of ionic liquids in the preparative separation of four flavonoids from Rhodiola rosea by on-line three-dimensional liquid chromatography.

PubMed

Ma, Shufeng; Hu, Liming; Ma, Chaoyang; Lv, Wenping; Wang, Hongxin

2014-09-01

A novel on-line three-dimensional liquid chromatography method was developed to separate four main flavonoids from Rhodiola rosea. Ethyl acetate/0.5 mol/L ionic liquid 1-butyl-3-methylimidazolium chloride aqueous solution was selected as the solvent system. In the first-dimension separation, the target flavonoids were entrapped and subsequently desorbed into the second-dimension high-speed countercurrent chromatographic column for separation. In the third-dimension chromatography, the residual ionic liquid in the four separated flavonoids was removed and the used ionic liquid was recovered. As a result, 35.1 mg of compound 1, 20.4 mg of compound 2, 8.5 mg of compound 3, and 10.6 mg of compound 4 were obtained from 1.53 g R. rosea extract. They were identified as rhodiosin, rhodionin, herbacetin, and kaempferol, respectively. The recovery of ionic liquid reached 99.1% of the initial amount. The results showed that this method is a powerful technology for the separation of R. rosea flavonoids and that the ionic-liquid-based solvent system has advantages over traditional solvent systems in renewable and environmentally friendly properties. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraction of ranitidine and nizatidine with using imidazolium ionic liquids prior spectrophotometric and chromatographic detection.

PubMed

Kiszkiel, Ilona; Starczewska, Barbara; Leśniewska, Barbara; Późniak, Patrycja

2015-03-15

A new extraction medium was proposed for liquid-liquid extraction of the histamine H2 receptor antagonists ranitidine (RNT) and nizatidine (NZT). The ionic liquids with low vapor pressure and favorable solvating properties for a range of compounds such as 1-butyl-3-methylimidazolium hexafluorophosphate [C4mim][PF6] and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C4mim][Tf2N] were tested for isolation of analytes. The extraction parameters of RNT and NZT, namely, amount of ionic liquid, pH of sample solution, shaking and centrifugation time were optimized. The isolation processes were performed with 1 mL of the ionic liquids. The extracted samples (pH values near 4) were shaken at 1750 rpm. The influence of interfering substances on the efficiency of extraction process was also studied. Methods for the histamine H2 receptor antagonists (ranitidine and nizatidine) determination after their separation using imidazolium ionic liquids by high performance liquid chromatography (HPLC) combined with UV spectrophotometry were developed. The application of ionic liquids in extraction step allows for selective isolation of analytes from aqueous matrices and their preconcentration. The above methods were applied to the determination of RNT and NZT in environmental samples (river water and wastewater after treatment). Copyright © 2014 Elsevier B.V. All rights reserved.

Ultrahigh-throughput exfoliation of graphite into pristine 'single-layer' graphene using microwaves and molecularly engineered ionic liquids.

PubMed

Matsumoto, Michio; Saito, Yusuke; Park, Chiyoung; Fukushima, Takanori; Aida, Takuzo

2015-09-01

Graphene has shown much promise as an organic electronic material but, despite recent achievements in the production of few-layer graphene, the quantitative exfoliation of graphite into pristine single-layer graphene has remained one of the main challenges in developing practical devices. Recently, reduced graphene oxide has been recognized as a non-feasible alternative to graphene owing to variable defect types and levels, and attention is turning towards reliable methods for the high-throughput exfoliation of graphite. Here we report that microwave irradiation of graphite suspended in molecularly engineered oligomeric ionic liquids allows for ultrahigh-efficiency exfoliation (93% yield) with a high selectivity (95%) towards 'single-layer' graphene (that is, with thicknesses <1 nm) in a short processing time (30 minutes). The isolated graphene sheets show negligible structural deterioration. They are also readily redispersible in oligomeric ionic liquids up to ~100 mg ml(-1), and form physical gels in which an anisotropic orientation of graphene sheets, once induced by a magnetic field, is maintained.

Use of ionic liquids as stationary phases in hyphenated gas chromatography techniques.

PubMed

Ragonese, Carla; Sciarrone, Danilo; Tranchida, Peter Quinto; Dugo, Paola; Mondello, Luigi

2012-09-14

In the past decades a consistent number of ionic liquids have been specifically synthesized and evaluated as stationary phase in gas chromatography. Ionic liquid, also defined as "molten salts", are a class of organic non-molecular solvents liquid at room temperature (RTILs) that satisfy most of the requirements of a GC stationary phase, among which a high viscosity, the possibility to tune the selectivity (by changing the cation-anion combination) and a high thermal stability. The choice of the proper stationary phase plays a key role in the improvement/optimization of a GC method, and although the use of IL as stationary phases is still not well-established, the general interest in their applications has greatly increased, thanks to their particular properties. The present contribution provides an overview on recent evaluations and applications of IL stationary phases, focusing in particular on the use of these novel tools in hyphenated GC-based techniques. Copyright © 2012 Elsevier B.V. All rights reserved.

Growth-induced anisotropy in bismuth - Rare-earth iron garnets

NASA Technical Reports Server (NTRS)

Fratello, V. J.; Slusky, S. E. G.; Brandle, C. D.; Norelli, M. P.

1986-01-01

The bismuth-doped rare-earth iron garnets, (R3-x-yBixPby)Fe5O12 (Bi:RIG, R = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y), were prepared under constant growth conditions to investigate the influence of ionic species on the bismuth-based growth-induced uniaxial anisotropy K(u) exp g. The effect of ionic species on growth-induced anisotropy in Bi:RIG was not consistent with the ionic size model of site ordering. In particular, Bi:SmIG, Bi:EuIG, and Bi:TbIG displayed high growth-induced anisotropies, up to 331,000 erg/cu cm at room temperature for x of about 0.5. The temperature dependence of these K(u) exp gs was somewhat higher than that of the well studied Bi:YIG. The site ordering of Bi can be modeled by assuming that small, low-oxygen-coordination BiOw exp +3-2 w melt complexes have a strong site selectivity for small, high-oxygen coordination sites at the growth interface.

Dynamic Charge Storage in Ionic Liquids-Filled Nanopores: Insight from a Computational Cyclic Voltammetry Study.

PubMed

He, Yadong; Huang, Jingsong; Sumpter, Bobby G; Kornyshev, Alexei A; Qiao, Rui

2015-01-02

Understanding the dynamic charge storage in nanoporous electrodes with room-temperature ionic liquid electrolytes is essential for optimizing them to achieve supercapacitors with high energy and power densities. Herein, we report coarse-grained molecular dynamics simulations of the cyclic voltammetry of supercapacitors featuring subnanometer pores and model ionic liquids. We show that the cyclic charging and discharging of nanopores are governed by the interplay between the external field-driven ion transport and the sloshing dynamics of ions inside of the pore. The ion occupancy along the pore length depends strongly on the scan rate and varies cyclically during charging/discharging. Unlike that at equilibrium conditions or low scan rates, charge storage at high scan rates is dominated by counterions while the contribution by co-ions is marginal or negative. These observations help explain the perm-selective charge storage observed experimentally. We clarify the mechanisms underlying these dynamic phenomena and quantify their effects on the efficiency of the dynamic charge storage in nanopores.

Pharmacological and ionic characterizations of the muscarinic receptors modulating (/sup 3/H)acetylcholine release from rat cortical synaptosomes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, E.M.; Otero, D.H.

The muscarinic receptors that modulate acetylcholine release from rat cortical synaptosomes were characterized with respect to sensitivity to drugs that act selectively at M1 or M2 receptor subtypes, as well as to changes in ionic strength and membrane potential. The modulatory receptors appear to be of the M2 type, since they are activated by carbachol, acetylcholine, methacholine, oxotremorine, and bethanechol, but not by pilocarpine, and are blocked by atropine, scopolamine, and gallamine (at high concentrations), but not by pirenzepine or dicyclomine. The ED50S for carbachol, acetylcholine, and oxotremorine are less than 10 microM, suggesting that the high affinity state ofmore » the receptor is functional. High ionic strength induced by raising the NaCl concentration has no effect on agonist (oxotremorine) potency, but increases the efficacy of this compound, which disagrees with receptor-binding studies. On the other hand, depolarization with either KCl or with veratridine (20 microM) reduces agonist potencies by approximately an order of magnitude, suggesting a potential mechanism for receptor regulation.« less

Protein Self-Assemblies That Can Generate, Hold, and Discharge Electric Potential in Response to Changes in Relative Humidity.

PubMed

Carter, Nathan A; Grove, Tijana Z

2018-05-30

Generation of electric potential upon external stimulus has attracted much attention for the development of highly functional sensors and devices. Herein, we report large-displacement, fast actuation in the self-assembled engineered repeat protein Consensus Tetratricopeptide Repeat protein (CTPR18) materials. The ionic nature of the CTPR18 protein coupled to the long-range alignment upon self-assembly results in the measured conductivity of 7.1 × 10 -2 S cm -1 , one of the highest reported for protein materials. The change of through-thickness morphological gradient in the self-assembled materials provides the means to select between faster, highly water-sensitive actuation or vastly increased mechanical strength. Tuning of the mode of motion, e.g., bending, twisting, and folding, is achieved by changing the morphological director. We further show that the highly ionic character of CTPR18 gives rise to piezo-like behavior in these materials, exemplified by low-voltage, ionically driven actuation and mechanically driven generation/discharge of voltage. This work contributes to our understanding of the emergence of stimuli-responsiveness in biopolymer assemblies.

A "by-productless" cellulose foaming agent for use in imidazolium ionic liquids.

PubMed

Scott, Janet L; Unali, Gianfranco; Perosa, Alvise

2011-03-14

Cellulose foams, or sponges, are produced from solutions in ionic liquids by the aqueous acid mediated decomposition of 1-alkyl-3-methylimidazolium-2-carboxylates, where the alkyl group and acid may be selected such that the by-product is the ionic liquid solvent: a by-productless foaming.

Enzymatically active high-flux selectively gas-permeable membranes

DOEpatents

Jiang, Ying-Bing; Cecchi, Joseph L.; Rempe, Susan; FU, Yaqin; Brinker, C. Jeffrey

2016-01-26

An ultra-thin, catalyzed liquid transport medium-based membrane structure fabricated with a porous supporting substrate may be used for separating an object species such as a carbon dioxide object species. Carbon dioxide flux through this membrane structures may be several orders of magnitude higher than traditional polymer membranes with a high selectivity to carbon dioxide. Other gases such as molecular oxygen, molecular hydrogen, and other species including non-gaseous species, for example ionic materials, may be separated using variations to the membrane discussed.

Glass electrolyte composition

DOEpatents

Kucera, Gene H.; Roche, Michael F.

1985-01-01

An ionically conductive glass is disclosed for use as electrolyte in a high temperature electrochemical cell, particularly a cell with sodium anode and sulfur cathode. The glass includes the constituents Na.sub.2 O, ZrO.sub.2, Al.sub.2 O.sub.3 and SiO.sub.2 in selected proportions to be a single phase solid solution substantially free of crystalline regions and undissolved constituents. Other advantageous properties are an ionic conductivity in excess of 2.times.10.sup.-3 (ohm-cm).sup.-1 at 300.degree. C. and a glass transition temperature in excess of 500.degree. C.

Glass electrolyte composition

DOEpatents

Kucera, G.H.; Roche, M.F.

1985-01-08

An ionically conductive glass is disclosed for use as electrolyte in a high temperature electrochemical cell, particularly a cell with sodium anode and sulfur cathode. The glass includes the constituents Na/sub 2/O, ZrO/sub 2/, Al/sub 2/O/sub 3/ and SiO/sub 2/ in selected proportions to be a single phase solid solution substantially free of crystalline regions and undissolved constituents. Other advantageous properties are an ionic conductivity in excess of 2 x 10/sup -3/ (ohm-cm)/sup -1/ at 300/sup 0/C and a glass transition temperature in excess of 500/sup 0/C.

An adaptive self-healing ionic liquid nanocomposite membrane for olefin-paraffin separations.

PubMed

Pitsch, Fee; Krull, Florian F; Agel, Friederike; Schulz, Peter; Wasserscheid, Peter; Melin, Thomas; Wessling, Matthias

2012-08-16

An adaptive self-healing ionic liquid nanocomposite membrane comprising a multi-layer support structure hosting the ionic salt [Ag](+) [Tf(2) N](-) is used for the separation of the olefin propylene and the paraffin propane. The ionic salt renders liquid like upon complexation with propylene, resulting in facilitated transport of propylene over propane at benchmark-setting selectivity and permeance levels. The contacting with acetylene causes the ionic salt to liquefy without showing evidence of forming explosive silver acetylide. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical and thermal stability of N-heterocyclic ionic liquids in catalytic C-H activation reactions.

PubMed

Chen, Guanyi; Kang, Shujuan; Ma, Qisheng; Chen, Weiqun; Tang, Yongchun

2014-11-01

(1)H-NMR spectrum analyses are applied to study the chemical and thermal stability of selected N-heterocyclic ionic liquids within the reaction system that can highly efficiently activate a C-H bond of methane and convert it into the C-O bond in methanol. Our results indicate that under such reaction conditions involving using a powerful Pt-based catalyst and strong acidic solvent, the aromatic ring of an imidazolium cation becomes unstable generating an ammonium ion (NH(4)(+)). Our results also suggest that the instability of the imidazolium ring is more chemically (participation in reactions) than thermally based. Modifications of the aromatic ring structure such as pyrazolium and triazolium cations can increase the chemical/thermal stability of ionic liquids under these reaction conditions. Copyright © 2014 John Wiley & Sons, Ltd.

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes.

PubMed

Akhmetshina, Alsu A; Davletbaeva, Ilsiya M; Grebenschikova, Ekaterina S; Sazanova, Tatyana S; Petukhov, Anton N; Atlaskin, Artem A; Razov, Evgeny N; Zaripov, Ilnaz I; Martins, Carla F; Neves, Luísa A; Vorotyntsev, Ilya V

2015-12-30

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf₂N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N₂, NH₃, H₂S, and CO₂ gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF₆] and [emim][Tf₂N]. The modification of SILMs by nanosize silica particles leads to an increase of NH₃ separation relatively to CO₂ or H₂S.

A Highly Aromatic and Sulfonated Ionomer for High Elastic Modulus Ionic Polymer Membrane Micro-Actuators

DTIC Science & Technology

2012-05-01

fluorophenyl)sulfone (DPA-PS:BP) is investigated for ionic polymer actuators. The uniqueness of DPA-PS:BP is that it can have a high ionic liquid (IL... ionic liquid Q M Zhang, Gokhan Hatipoglu, Yang Liu, Ran Zhao, Mitra Yoonessi, Dean M Tigelaar, Srinivas Tadigadapa Virginia Polytechnic Institute...DPA-PS:BP) is investigated for ionic polymer actuators. The uniqueness of DPA-PS:BP is that it can have a high ionic liquid (IL) uptake and

A coated-wire ion-selective electrode for ionic calcium measurements

NASA Technical Reports Server (NTRS)

Hines, John W.; Arnaud, Sara; Madou, Marc; Joseph, Jose; Jina, Arvind

1991-01-01

A coated-wire ion-selective electrode for measuring ionic calcium was developed, in collaboration with Teknektron Sensor Development Corporation (TSDC). This coated wire electrode sensor makes use of advanced, ion-responsive polyvinyl chloride (PVC) membrane technology, whereby the electroactive agent is incorporated into a polymeric film. The technology greatly simplifies conventional ion-selective electrode measurement technology, and is envisioned to be used for real-time measurement of physiological and environment ionic constituents, initially calcium. A primary target biomedical application is the real-time measurement of urinary and blood calcium changes during extended exposure to microgravity, during prolonged hospital or fracture immobilization, and for osteoporosis research. Potential advanced life support applications include monitoring of calcium and other ions, heavy metals, and related parameters in closed-loop water processing and management systems. This technology provides a much simplified ionic calcium measurement capability, suitable for both automated in-vitro, in-vivo, and in-situ measurement applications, which should be of great interest to the medical, scientific, chemical, and space life sciences communities.

Dissection of specific binding of HIV-1 Gag to the 'packaging signal' in viral RNA.

PubMed

Comas-Garcia, Mauricio; Datta, Siddhartha Ak; Baker, Laura; Varma, Rajat; Gudla, Prabhakar R; Rein, Alan

2017-07-20

Selective packaging of HIV-1 genomic RNA (gRNA) requires the presence of a cis -acting RNA element called the 'packaging signal' (Ψ). However, the mechanism by which Ψ promotes selective packaging of the gRNA is not well understood. We used fluorescence correlation spectroscopy and quenching data to monitor the binding of recombinant HIV-1 Gag protein to Cy5-tagged 190-base RNAs. At physiological ionic strength, Gag binds with very similar, nanomolar affinities to both Ψ-containing and control RNAs. We challenged these interactions by adding excess competing tRNA; introducing mutations in Gag; or raising the ionic strength. These modifications all revealed high specificity for Ψ. This specificity is evidently obscured in physiological salt by non-specific, predominantly electrostatic interactions. This nonspecific activity was attenuated by mutations in the MA, CA, and NC domains, including CA mutations disrupting Gag-Gag interaction. We propose that gRNA is selectively packaged because binding to Ψ nucleates virion assembly with particular efficiency.

Crosslinked structurally-tuned polymeric ionic liquids as stationary phases for the analysis of hydrocarbons in kerosene and diesel fuels by comprehensive two-dimensional gas chromatography.

PubMed

Zhang, Cheng; Park, Rodney A; Anderson, Jared L

2016-04-01

Structurally-tuned ionic liquids (ILs) have been previously applied as the second dimension column in comprehensive two-dimensional gas chromatography (GC×GC) and have demonstrated high selectivity in the separation of individual aliphatic hydrocarbons from other aliphatic hydrocarbons. However, the maximum operating temperatures of these stationary phases limit the separation of analytes with high boiling points. In order to address this issue, a series of polymeric ionic liquid (PIL)-based stationary phases were prepared in this study using imidazolium-based IL monomers via in-column free radical polymerization. The IL monomers were functionalized with long alkyl chain substituents to provide the needed selectivity for the separation of aliphatic hydrocarbons. Columns were prepared with different film thicknesses to identify the best performing stationary phase for the separation of kerosene. The bis[(trifluoromethyl)sulfonyl]imide ([NTf2](-))-based PIL stationary phase with larger film thickness (0.28μm) exhibited higher selectivity for aliphatic hydrocarbons and showed a maximum allowable operating temperature of 300°C. PIL-based stationary phases containing varied amount of IL-based crosslinker were prepared to study the effect of the crosslinker on the selectivity and thermal stability of the resulting stationary phase. The optimal resolution of aliphatic hydrocarbons was achieved when 50% (w/w) of crosslinker was incorporated into the PIL-based stationary phase. The resulting stationary phase exhibited good selectivity for different groups of aliphatic hydrocarbons even after being conditioned at 325°C. Finally, the crosslinked PIL-based stationary phase was compared with SUPELCOWAX 10 and DB-17 columns for the separation of aliphatic hydrocarbons in diesel fuel. Better resolution of aliphatic hydrocarbons was obtained when employing the crosslinked PIL-based stationary phase as the second dimension column. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of High-pH and High-Ionic-Strength Groundwater on Iodide, Pertechnetate, and Selenate Sorption to Hanford Sediments: Final Report for Subtask 3a

DOE Office of Scientific and Technical Information (OSTI.GOV)

DI Kaplan; KE Parker; RD Orr

1998-10-14

As part of the Immobilized Low-Activity Waste-Performance Assessment three experiments were conducted to evaluate the effect of the expected near-field chemistry on the sorption of iodide, selenate, and pertechnetate onto a sediment obtained from the Hanford Site. These experiments were performed in fiscal year 1998 at the Pacific Northwest National Laboratory.' During these experiments, attention was directed at the identification of the chemical mechanisms controlling the sorption processes to provide technical defensibility for the selection of the distribution coefficients (IQ to be used in the remainder of the performance assessment. It was found, during the conduct of the experiments, thatmore » selenium and technetium I&s increased as ionic strength increased. The cause for this is most likely to be that the higher ionic strength caused the double layer around the particles to decrease, thereby permitting greater interaction with the mineral surfaces. Further, the pH level had an effect on the sorption of these anions. These are the first-ever experiments conducted with Hanford Site sediment in which the IQ were measured as a function of ionic strength and pH. Overall, the observed trends were consistent with more generalized geochemical principles. One of the most important contributions of these experiments was that they quantified the & changes induced by variations in ionic strength and pH that are expected to exist in the near field.« less

A green separation strategy for neodymium (III) from cobalt (II) and nickel (II) using an ionic liquid-based aqueous two-phase system.

PubMed

Chen, Yuehua; Wang, Huiyong; Pei, Yuanchao; Wang, Jianji

2018-05-15

It is significant to develop sustainable strategies for the selective separation of rare earth from transition metals from fundamental and practical viewpoint. In this work, an environmentally friendly solvent extraction approach has been developed to selectively separate neodymium (III) from cobalt (II) and nickel (II) by using an ionic liquid-based aqueous two phase system (IL-ATPS). For this purpose, a hydrophilic ionic liquid (IL) tetrabutylphosphonate nitrate ([P 4444 ][NO 3 ]) was prepared and used for the formation of an ATPS with NaNO 3 . Binodal curves of the ATPSs have been determined for the design of extraction process. The extraction parameters such as contact time, aqueous phase pH, content of phase-formation components of NaNO 3 and the ionic liquid have been investigated systematically. It is shown that under optimal conditions, the extraction efficiency of neodymium (III) is as high as 99.7%, and neodymium (III) can be selectively separated from cobalt (II) and nickel (II) with a separation factor of 10 3 . After extraction, neodymium (III) can be stripped from the IL-rich phase by using dilute aqueous sodium oxalate, and the ILs can be quantitatively recovered and reused in the next extraction process. Since [P 4444 ][NO 3 ] works as one of the components of the ATPS and the extractant for the neodymium, no organic diluent, extra etractant and fluorinated ILs are used in the separation process. Thus, the strategy described here shows potential in green separation of neodymium from cobalt and nickel by using simple IL-based aqueous two-phase system. Copyright © 2018 Elsevier B.V. All rights reserved.

Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

PubMed

Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

2013-06-15

The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis of thermo-responsive bovine hemoglobin imprinted nanoparticles by combining ionic liquid immobilization with aqueous precipitation polymerization.

PubMed

Wang, Yongmei; Yang, Chongchong; Sun, Yan; Qiu, Fengtao; Xiang, Yang; Fu, Guoqi

2018-02-01

Surface molecular imprinting over functionalized nanoparticles has proved to be an effective approach for construction of artificial nanomaterials for protein recognition. Herein, we report a strategy for synthesis of core-shell protein-imprinted nanoparticles by the functionalization of nano-cores with ionic liquids followed by aqueous precipitation polymerization to build thermo-responsive imprinted polymer nano-shells. The immobilized ionic liquids can form multiple interactions with the protein template. The polymerization process can produce thermo-reversible physical crosslinks, which are advantageous to enhancing imprinting and facilitating template removal. With bovine hemoglobin as a model template, the imprinted nanoparticles showed temperature-sensitivity in both dispersion behaviors and rebinding capacities. Compared with the ionic-liquid-modified core nanoparticles, the imprinted particles exhibited greatly increased selectivity and two orders of magnitude higher binding affinity for the template protein. The imprinted nanoparticles achieved relatively high imprinting factor up to 5.0 and specific rebinding capacity of 67.7 mg/g, respectively. These nanoparticles also demonstrated rapid rebinding kinetics and good reproducibility after five cycles of adsorption-regeneration. Therefore, the presented approach may be viable for the fabrication of high-performance protein-imprinted nanoparticles with temperature sensitivity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective and Responsive Nanopore-Filled Membranes

DTIC Science & Technology

2011-03-14

Materials Science and Engineering Poster Competition 15. Chen, H.; Elabd, Y.A. Ionic Liquid Polymers: Electrospinning and Solution Properties. Fall...hydrophilic ionic polymer gels within a hydrophobic polymer host matrix. The specific tasks of this project include (1) synthesizing stimuli...on polymer-polymer nanocomposites of hydrophilic ionic polymer gels within a hydrophobic polymer host matrix. The specific tasks of this project

Anisotropic amplification of proton transport in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Thimmappa, Ravikumar; Fawaz, Mohammed; Devendrachari, Mruthyunjayachari Chattanahalli; Gautam, Manu; Kottaichamy, Alagar Raja; Shafi, Shahid Pottachola; Thotiyl, Musthafa Ottakam

2017-07-01

Though graphene oxide (GO) membrane shuttles protons under humid conditions, it suffer severe disintegration and anhydrous conditions lead to abysmal ionic conductivity. The trade-off between mechanical integrity and ionic conductivity challenge the amplification of GO's ionic transport under anhydrous conditions. We show anisotropic amplification of GO's ionic transport with a selective amplification of in plane contribution under anhydrous conditions by doping it with a plant extract, phytic acid (PA). The hygroscopic nature of PA stabilized interlayer water molecules and peculiar geometry of sbnd OH functionalities around saturated hydrocarbon ring anisotropically enhanced ionic transport amplifying the fuel cell performance metrics.

High-flux ionic diodes, ionic transistors and ionic amplifiers based on external ion concentration polarization by an ion exchange membrane: a new scalable ionic circuit platform.

PubMed

Sun, Gongchen; Senapati, Satyajyoti; Chang, Hsueh-Chia

2016-04-07

A microfluidic ion exchange membrane hybrid chip is fabricated using polymer-based, lithography-free methods to achieve ionic diode, transistor and amplifier functionalities with the same four-terminal design. The high ionic flux (>100 μA) feature of the chip can enable a scalable integrated ionic circuit platform for micro-total-analytical systems.

Solvent extraction separation of Th-227 and Ac-225 in room temperature ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bell, Jason R; Boll, Rose Ann; Dai, Sheng

2012-01-01

The solvent extractions of Th-227 and Ac-225 from the aqueous phase into ionic liquids (ILs) were investigated by using N,N,N ,N - tetraoctyldiglycolamide (TODGA) or di(2-ethylhexyl)phosphoric acid (HDEHP) as an extractant. Four ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]), 1-butyl-3-methylimidazolium bis(perfluoroethanesulfonyl)imide ([C4mim][BETI]), 1-butyl-2,3-trimethyleneimidazolium (trifluoromethanesulfonyl)imide [BuI5][NTf2], and 1-benzyl pyridinium bis(trifluoromethanesulfonyl)imide ([PhCH2Py][NTf2]) were used as extraction solvents for separation of Th-227 and Ac-225 in this study. Excellent extraction efficiencies and selectivities were found for Th-227/Ac-225 when HDEHP was used as an extractant in these ionic liquids. The effects of different extractant concentrations in ionic liquids and acidities of the aqueous phase on extraction efficienciesmore » and selectivities of Th-227/Ac-225 are also presented in this article.« less

Quantitative and qualitative optimization of allergen extraction from peanut and selected tree nuts. Part 2. Optimization of buffer and ionic strength using a full factorial experimental design.

PubMed

L'Hocine, Lamia; Pitre, Mélanie

2016-03-01

A full factorial design was used to assess the single and interactive effects of three non-denaturing aqueous (phosphate, borate, and carbonate) buffers at various ionic strengths (I) on allergen extractability from and immunoglobulin E (IgE) immunoreactivity of peanut, almond, hazelnut, and pistachio. The results indicated that the type and ionic strength of the buffer had different effects on protein recovery from the nuts under study. Substantial differences in protein profiles, abundance, and IgE-binding intensity with different combinations of pH and ionic strength were found. A significant interaction between pH and ionic strength was observed for pistachio and almond. The optimal buffer system conditions, which maximized the IgE-binding efficiency of allergens and provided satisfactory to superior protein recovery yield and profiles, were carbonate buffer at an ionic strength of I=0.075 for peanut, carbonate buffer at I=0.15 for almond, phosphate buffer at I=0.5 for hazelnut, and borate at I=0.15 for pistachio. The buffer type and its ionic strength could be manipulated to achieve the selective solubility of desired allergens. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions† †Electronic supplementary information (ESI) available: Formulae for calculating aggregation parameters and fitting of kinetic constants and copies of NMR spectra. See DOI: 10.1039/c6cp00493h Click here for additional data file.

PubMed Central

Cognigni, Alice; Gaertner, Peter; Zirbs, Ronald; Peterlik, Herwig; Prochazka, Katharina; Schröder, Christian

2016-01-01

A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle concentration (CMC) and to provide aggregation parameters. The determination of surface activity and aggregation properties of amphiphilic ionic liquids was accompanied by SAXS studies on selected surface-active ionic liquids. The application of these surface-active ionic liquids with different anions was tested in nucleophilic substitution reactions for the degradation of organophosphorus compounds. Kinetic studies via UV-Vis spectrophotometry showed a strong acceleration of the reaction in the micellar system compared to pure water. In addition, an influence of the anion was observed, resulting in a correlation between the anion binding to the micelle and the reaction rate constants, indicating that the careful choice of the surface-active ionic liquid can considerably affect the outcome of reactions. PMID:27121134

A cobalt(II) bis(salicylate)-based ionic liquid that shows thermoresponsive and selective water coordination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kohno, Y; Cowan, MG; Masuda, M

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.

Covalently bonded ionic liquid onto cellulose for fast adsorption and efficient separation of Cr(VI): Batch, column and mechanism investigation.

PubMed

Dong, Zhen; Zhao, Long

2018-06-01

Combining the advantages of both cellulose and ionic liquid, ionic liquid functionalized cellulose (ILFC) as adsorbent was prepared through radiation grafting glycidyl methacrylate onto cellulose microsphere following by reaction with ionic liquid 1-aminopropyl-3-methyl imidazolium nitrate. Its adsorption properties towards Cr(VI) were investigated in batch and column experiments. In batch experiments, the adsorption kinetics was well fitted with pseudo-second-order mode with equilibrium time of 2 h and the adsorption capacity reached 181.8 mg/g at pH 2 calculated from Langmuir model. In fixed column, both Yoon-Nelson and Thomas models gave satisfactory fit to experimental data and breakthrough curves, and equilibrium adsorption capacity calculated by Thomas model was 161.0 mg/g. Moreover, ILFC exhibited high selectivity towards Cr(VI) even in synthetic chrome-plating wastewater. Besides, adsorption/desorption test revealed ILFC can be regenerated and reused several times without obvious decrease in adsorbed amount. The adsorption process was demonstrated to anion exchange-reduction mechanism via XPS analysis. Copyright © 2018 Elsevier Ltd. All rights reserved.

Absorption Refrigeration Cycles with Ammonia-Ionic Liquid Working Pairs Studied by Molecular Simulation.

PubMed

Becker, Tim M; Wang, Meng; Kabra, Abhishek; Jamali, Seyed Hossein; Ramdin, Mahinder; Dubbeldam, David; Infante Ferreira, Carlos A; Vlugt, Thijs J H

2018-04-18

For absorption refrigeration, it has been shown that ionic liquids have the potential to replace conventional working pairs. Due to the huge number of possibilities, conducting lab experiments to find the optimal ionic liquid is infeasible. Here, we provide a proof-of-principle study of an alternative computational approach. The required thermodynamic properties, i.e., solubility, heat capacity, and heat of absorption, are determined via molecular simulations. These properties are used in a model of the absorption refrigeration cycle to estimate the circulation ratio and the coefficient of performance. We selected two ionic liquids as absorbents: [emim][Tf 2 N], and [emim][SCN]. As refrigerant NH 3 was chosen due to its favorable operating range. The results are compared to the traditional approach in which parameters of a thermodynamic model are fitted to reproduce experimental data. The work shows that simulations can be used to predict the required thermodynamic properties to estimate the performance of absorption refrigeration cycles. However, high-quality force fields are required to accurately predict the cycle performance.

Absorption Refrigeration Cycles with Ammonia–Ionic Liquid Working Pairs Studied by Molecular Simulation

PubMed Central

2018-01-01

For absorption refrigeration, it has been shown that ionic liquids have the potential to replace conventional working pairs. Due to the huge number of possibilities, conducting lab experiments to find the optimal ionic liquid is infeasible. Here, we provide a proof-of-principle study of an alternative computational approach. The required thermodynamic properties, i.e., solubility, heat capacity, and heat of absorption, are determined via molecular simulations. These properties are used in a model of the absorption refrigeration cycle to estimate the circulation ratio and the coefficient of performance. We selected two ionic liquids as absorbents: [emim][Tf2N], and [emim][SCN]. As refrigerant NH3 was chosen due to its favorable operating range. The results are compared to the traditional approach in which parameters of a thermodynamic model are fitted to reproduce experimental data. The work shows that simulations can be used to predict the required thermodynamic properties to estimate the performance of absorption refrigeration cycles. However, high-quality force fields are required to accurately predict the cycle performance. PMID:29749996

Recent progress on exploring exceptionally high and anisotropic H+/OH– ion conduction in two-dimensional materials

PubMed Central

Sun, Pengzhan; Sasaki, Takayoshi

2017-01-01

Ion conducting membranes/electrolytes have been employed extensively in some important industrial and biological systems, especially in fuel cells, water electrolyzers, gas separation, sensors and biological selective ion transport, acting as one of the core components and sometimes directly determining the device performance. However, the traditional polymeric proton exchange membranes (PEMs)/anion exchange membranes (AEMs) suffer from highly toxic preparation procedures, poor thermal and chemical stabilities, and unsatisfactory ion conductivities. This has triggered researchers worldwide to explore alternative inorganic building blocks with high ion conductivities and stabilities from the new materials library, hoping to solve the above long-lasting problems. The recent burgeoning research on two-dimensional (2D) materials has unveiled exceptionally high ionic conductivities, which raises the feasibility of fabricating high-performance nanosheet-based ion conductors/membranes. In this perspective, the recent advances in measuring and understanding the exceptionally high and anisotropic H+/OH– ion conductivities of representative 2D materials, e.g. graphene oxide (GO), vermiculite and layered double hydroxide (LDH) nanosheets, are reviewed. In particular, regarding the anisotropic ionic conduction in 2D nanosheets, possible design strategies and technological innovations for fabricating macroscopic nanosheet-based ionic conductors/membranes are proposed for maximizing the high in-plane conduction, which may serve to guide future development of high-performance industrial and biological systems relying on H+/OH– conducting membranes. PMID:29629071

Recent progress on exploring exceptionally high and anisotropic H+/OH- ion conduction in two-dimensional materials.

PubMed

Sun, Pengzhan; Ma, Renzhi; Sasaki, Takayoshi

2018-01-07

Ion conducting membranes/electrolytes have been employed extensively in some important industrial and biological systems, especially in fuel cells, water electrolyzers, gas separation, sensors and biological selective ion transport, acting as one of the core components and sometimes directly determining the device performance. However, the traditional polymeric proton exchange membranes (PEMs)/anion exchange membranes (AEMs) suffer from highly toxic preparation procedures, poor thermal and chemical stabilities, and unsatisfactory ion conductivities. This has triggered researchers worldwide to explore alternative inorganic building blocks with high ion conductivities and stabilities from the new materials library, hoping to solve the above long-lasting problems. The recent burgeoning research on two-dimensional (2D) materials has unveiled exceptionally high ionic conductivities, which raises the feasibility of fabricating high-performance nanosheet-based ion conductors/membranes. In this perspective, the recent advances in measuring and understanding the exceptionally high and anisotropic H + /OH - ion conductivities of representative 2D materials, e.g. graphene oxide (GO), vermiculite and layered double hydroxide (LDH) nanosheets, are reviewed. In particular, regarding the anisotropic ionic conduction in 2D nanosheets, possible design strategies and technological innovations for fabricating macroscopic nanosheet-based ionic conductors/membranes are proposed for maximizing the high in-plane conduction, which may serve to guide future development of high-performance industrial and biological systems relying on H + /OH - conducting membranes.

Nanoarchitecture Control Enabled by Ionic Liquids

NASA Astrophysics Data System (ADS)

Murdoch, Heather A.; Limmer, Krista R.; Labukas, Joseph P.

2017-04-01

Ionic liquids have many advantages over traditional aqueous electrosynthesis for fabrication of functional nanoarchitectures, including enabling the integration of nanoparticles into traditional coatings, superhydrophobicity, nanofoams, and other hierarchical structures. Shape and size control through ionic liquid selection and processing conditions can synthesize nanoparticles and nanoarchitectures without the use of capping agents, surfactants, or templates that are often deleterious to the functionality of the resultant system. Here we give a brief overview of some recent and interesting applications of ionic liquids to the synthesis of nanoparticles and nanoarchitectures.

Analysis of essential oils and fragrances with a new generation of highly inert gas chromatographic columns coated with ionic liquids.

PubMed

Cagliero, Cecilia; Bicchi, Carlo; Cordero, Chiara; Liberto, Erica; Rubiolo, Patrizia; Sgorbini, Barbara

2017-04-28

In the fields of essential oils and fragrances, samples often consist of mixtures of compounds with similar structural and physical characteristics (e.g. mono- and sesquiterpenoids), whose correct identification closely depends on the synergic combination of chromatographic and mass spectral data. This sample complexity means that new GC stationary phases with different selectivities are continually being investigated. Ionic liquids (ILs) are of great interest as GC stationary phases in this field because of their selectivity (significantly different than that of currently phases) and their high temperature stability. A first generation of IL GC columns was found to be competitive when applied to these field, in terms of selectivity and efficiency, compared to conventional columns (polydimethylsiloxane, (e.g. OV-1), methyl-polysiloxane 5%-phenyl (e.g. SE-52), 7%-cyanopropyl, 7%-phenyl polysiloxane (e.g. OV-1701), and polyethylen glycol (e.g. PEG-20M). However, these columns showed significant activity towards polar or active analytes, which primarily affected their quantitative performance. A new generation of highly-inactive columns coated with three of the most widely-used ionic liquid GC stationary phases has recently been introduced; these phases are SLB-IL60i (1,12-di(tripropylphosphonium) dodecane bis(trifluoromethylsulfonyl) imide [NTf 2 ], SLB-IL76i (tri-(tripropylphosphonium-hexanamido)-triethylamine [NTf 2 ]), and SLB-IL111i (1,5-di (2,3-dimethyllimidazolium) pentane [NTf 2 ]). This study carefully tested the new inert IL columns, in view of their routine application in the fragrance and essential oil fields. They were found to have unusually high selectivity, comparable to that of first-generation IL columns, while their inertness and efficiency were competitive with those of currently-used conventional columns. The IL column performance of first and second generations was compared, through the quali-quantitative analysis of components in a group of different complexity samples; these included the Grob test, a standard mixture of "suspected" skin allergens, and the essential oils of chamomile and sandalwood. Copyright © 2017 Elsevier B.V. All rights reserved.

High-flux ionic diodes, ionic transistors and ionic amplifiers based on external ion concentration polarization by an ion exchange membrane: a new scalable ionic circuit platform†

PubMed Central

Sun, Gongchen; Senapati, Satyajyoti

2016-01-01

A microfluidic-ion exchange membrane hybrid chip is fabricated by polymer-based, lithography-free methods to achieve ionic diode, transistor and amplifier functionalities with the same four-terminal design. The high ionic flux (> 100 μA) feature of the chip can enable a scalable integrated ionic circuit platform for micro-total-analytical systems. PMID:26960551

Sodiated Sugar Structures: Cryogenic Ion Vibrational Spectroscopy of Na^+(GLUCOSE) Adducts

NASA Astrophysics Data System (ADS)

Voss, Jonathan; Kregel, Steven J.; Fischer, Kaitlyn C.; Garand, Etienne

2017-06-01

The recent discovery that ionic liquids help facilitate the dissolution of cellulose has renewed interest in understanding how ionic species interact with carbohydrates. Here we present infrared spectra in the 2800 - 3800 \\wn range of gas-phase mass-selected Na^+(Glucose) adducts. These adducts are further probed with IR-dip spectroscopy to yield conformer specific spectra of at least seven unique species. The relative abundances of conformers show that gas-phase interconversion barriers are sufficiently high to preserve the solution-phase populations. Additionally, our results demonstrate that mM concentrations of NaCl do not strongly perturb the anomeric ratio of glucose in solution.

[Architecture of receptor-operated ionic channels of biological membranes].

PubMed

Bregestovski, P D

2011-01-01

Ion channels of biological membranes are the key proteins, which provide bioelectric functioning of living systems. These proteins are homo- or heterooligomers assembled from several identical or different subunits. Understanding the architectural organization and functioning of ion channels has been significantly extended due to resolving the crystal structure of several types of voltage-gated and receptor-operated channels. This review summarizes the information obtained from crystal structures of potassium, nicotinic acetylcholine receptor, P2X, and other ligand-gated ion channels. Despite the differences in the function, topology, ionic selectivity, and the subunit stoichiometry, a high similarity in the principles of organization of these macromolecular complexes has been revealed.

Separation and purification of thymopentin with molecular imprinting membrane by solid phase extraction disks.

PubMed

Wang, Chaoli; Hu, Xiaoling; Guan, Ping; Wu, Danfeng; Qian, Liwei; Li, Ji; Song, Renyuan

2015-01-01

The synthesis and performance of molecularly imprinted membranes (MIMs) as a solid phase extraction packing materials for the separation and purification of thymopentin from crude samples was described. In order to increase structural selectivity and imprinting efficiency, surface-initiated ATRP and ionic liquid (1-vinyl-3-ethyl acetate imidazolium chloride) were used to prepare molecularly imprinting membranes. The results demonstrated that solid phase extraction disks stuffed by MIMs with ionic liquids as functional monomer demonstrated high isolation and purification of performance to the thymopentin. The molecular recognition of thymopentin was analyzed by using molecular modeling software. Copyright © 2014 Elsevier B.V. All rights reserved.

Application of ionic liquids based microwave-assisted simultaneous extraction of carnosic acid, rosmarinic acid and essential oil from Rosmarinus officinalis.

PubMed

Liu, Tingting; Sui, Xiaoyu; Zhang, Rongrui; Yang, Lei; Zu, Yuangang; Zhang, Lin; Zhang, Ying; Zhang, Zhonghua

2011-11-25

An ionic liquid based microwave-assisted simultaneous extraction and distillation (ILMSED) method has been developed for the effective extraction of carnosic acid (CA), rosmarinic acid (RA) and essential oil (EO) from Rosmarinus officinalis. A series of 1-alkyl-3-methylimidazolium ionic liquids differing in composition of anion and cation were evaluated for extraction yield in this work. The results obtained indicated that the anions and cations of ionic liquids had influences on the extraction of CA and RA, 1.0M 1-octyl-3-methylimidazolium bromide ([C8mim]Br) solution was selected as solvent. In addition, the ILMSED procedures for the three target ingredients were optimized and compared with other conventional extraction techniques. ILMSED gave the best result due to the highest extraction yield within the shortest extraction time for CA and RA. The novel process developed offered advantages in term of yield and selectivity of EO and shorter isolation time (20 min in comparison of 4h of hydrodistillation), and provides a more valuable EO (with high amount of oxygenated compounds). The microstructures and chemical structures of rosemary samples before and after extraction were also investigated. Moreover, the proposed method was validated by the stability, repeatability and recovery experiments. The results indicated that the developed ILMSED method provided a good alternative for the both extraction of non-volatile compounds (CA and RA) and EO from rosemary as well as other herbs. Copyright © 2011 Elsevier B.V. All rights reserved.

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes

PubMed Central

Akhmetshina, Alsu A.; Davletbaeva, Ilsiya M.; Grebenschikova, Ekaterina S.; Sazanova, Tatyana S.; Petukhov, Anton N.; Atlaskin, Artem A.; Razov, Evgeny N.; Zaripov, Ilnaz I.; Martins, Carla F.; Neves, Luísa A.; Vorotyntsev, Ilya V.

2015-01-01

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N2, NH3, H2S, and CO2 gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF6] and [emim][Tf2N]. The modification of SILMs by nanosize silica particles leads to an increase of NH3 separation relatively to CO2 or H2S. PMID:26729177

Anion channels in the sea urchin sperm plasma membrane.

PubMed

Morales, E; de la Torre, L; Moy, G W; Vacquier, V D; Darszon, A

1993-10-01

Ionic fluxes in sea urchin sperm plasma membrane regulate cell motility and the acrosome reaction (AR). Although cationic channels mediate some of the ionic movements, little is known about anion channels in these cells. The fusion of sperm plasma membranes into lipid bilayers allowed identification of a 150 pS anion channel. This anion channel was enriched from detergent-solubilized sperm plasma membranes using a wheat germ agglutinin Sepharose column. Vesicles formed from this preparation were fused into black lipid membranes (BLM), yielding single channel anion-selective activity with the properties of those found in the sperm membranes. The following anion selectivity sequence was found: NO3- > CNS- > Br- > Cl-. This anion channel has a high open probability at the holding potentials tested, it is partially blocked by 4,4'-diisothiocyano-2,2'-stilbendisulfonic acid (DIDS), and it often displays substates. The sperm AR was also inhibited by DIDS.

Evaluation of Adsorption Characteristics of a Fibrous Adsorbent Containing Zwitter-Ionic Functional Group, Targeting Organic Acids.

PubMed

Nakazawa, Akira; Tang, Ning; Inoue, Yoshinori; Kamichatani, Waka; Katoh, Toshifumi; Saito, Mitsuru; Obara, Kenji; Toriba, Akira; Hayakawa, Kazuichi

2017-01-01

Diallylamine-maleic acid copolymer (DAM)-nonwoven fabric (DAM-f), a fibrous adsorbent, contains DAM with zwitter-ionic functional groups and forms a hydration layer on the surface. The aim of this report was to evaluate the adsorption selectivity of DAM-f to semi-volatile organic acid (C1-C5). In the aqueous phase, formic acid dissolved in the hydration layer bound to the imino group of DAM-f due to anion exchange interaction. In the gas phase, the adsorption amounts of organic acids increased with the exposure time. Moreover, the adsorption rate constants correlated with the air/water partition coefficients (log K aw ) for formic acid, propionic acid, butyric acid, valeric acid and isovaleric acid, except for acetic acid. These results indicate that DAM-f is highly selective to hydrophilic compounds which easily move from the air to the hydration layer of DAM-f.

Ultrahigh-throughput exfoliation of graphite into pristine ‘single-layer’ graphene using microwaves and molecularly engineered ionic liquids

NASA Astrophysics Data System (ADS)

Matsumoto, Michio; Saito, Yusuke; Park, Chiyoung; Fukushima, Takanori; Aida, Takuzo

2015-09-01

Graphene has shown much promise as an organic electronic material but, despite recent achievements in the production of few-layer graphene, the quantitative exfoliation of graphite into pristine single-layer graphene has remained one of the main challenges in developing practical devices. Recently, reduced graphene oxide has been recognized as a non-feasible alternative to graphene owing to variable defect types and levels, and attention is turning towards reliable methods for the high-throughput exfoliation of graphite. Here we report that microwave irradiation of graphite suspended in molecularly engineered oligomeric ionic liquids allows for ultrahigh-efficiency exfoliation (93% yield) with a high selectivity (95%) towards ‘single-layer’ graphene (that is, with thicknesses <1 nm) in a short processing time (30 minutes). The isolated graphene sheets show negligible structural deterioration. They are also readily redispersible in oligomeric ionic liquids up to ~100 mg ml-1, and form physical gels in which an anisotropic orientation of graphene sheets, once induced by a magnetic field, is maintained.

Solid-State Ionic Diodes Demonstrated in Conical Nanopores

DOE PAGES

Plett, Timothy S.; Cai, Wenjia; Le Thai, Mya; ...

2017-02-27

Ionic transport at the nanoscale features phenomena that are not observed in larger systems. Nonlinear current–voltage curves characteristic of ionic diodes as well as ion selectivity are examples of effects observed at the nanoscale. Many man-made nanopore systems are inspired by biological channels in a cell membrane, thus measurements are often performed in aqueous solutions. Consequently, much less is known about ionic transport in nonaqueous systems, especially in solid-state electrolytes. Here we show ionic transport through single pores filled with gel electrolyte of poly(methyl methacrylate) (PMMA) doped with LiClO 4 in propylene carbonate. The system has no liquid interface andmore » the ionic transport occurs through the porous gel structure. We demonstrate that a conically shaped nanopore filled with the gel rectifies the current and works as a solid-state ionic diode.« less

Role of Heavy Meromyosin in Heat-Induced Gelation in Low Ionic Strength Solution Containing L-Histidine.

PubMed

Hayakawa, Toru; Yoshida, Yuri; Yasui, Masanori; Ito, Toshiaki; Wakamatsu, Jun-ichi; Hattori, Akihito; Nishimura, Takanori

2015-08-01

The gelation of myosin has a very important role in meat products. We have already shown that myosin in low ionic strength solution containing L-histidine forms a transparent gel after heating. To clarify the mechanism of this unique gelation, we investigated the changes in the nature of myosin subfragments during heating in solutions with low and high ionic strengths with and without L-histidine. The hydrophobicity of myosin and heavy meromyosin (HMM) in low ionic strength solution containing L-histidine was lower than in high ionic strength solution. The SH contents of myosin and HMM in low ionic strength solution containing l-histidine did not change during the heating process, whereas in high ionic strength solution they decreased slightly. The heat-induced globular masses of HMM in low ionic strength solution containing L-histidine were smaller than those in high ionic strength solution. These findings suggested that the polymerization of HMM molecules by heating was suppressed in low ionic strength solution containing L-histidine, resulting in formation of the unique gel. © 2015 Institute of Food Technologists®

Ion-Gated Gas Separation through Porous Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tian, Ziqi; Mahurin, Shannon M.; Dai, Sheng

Porous graphene holds great promise as an atom-thin, high-permeance membrane for gas separation, but to precisely control the pore size at three to five angstroms proves challenging. Here we propose an ion-gated graphene membrane comprising a monolayer of ionic liquid coated porous graphene to dynamically modulate the pore size to achieve selective gas separation. This approach enables the otherwise non-selective large pores on the order of 1 nm in size to be selective for gases whose diameters range from three to four angstroms. We show from molecular dynamics simulations that CO 2, N 2 and CH 4 all can permeatemore » through a 1-nm pore in graphene without any selectivity. But when a monolayer of [emim][BF 4] is deposited on the porous graphene, CO 2 has much higher permeance than the other two gases. We find that the anion dynamically modulates the pore size by hovering above the pore and provides affinity for CO 2 while the larger cation (which cannot go through the pore) holds the anion in place via electrostatic attraction. This composite membrane is especially promising for CO 2/CH 4 separation, with a CO 2/CH 4 selectivity of about 42 and CO 2 permeance ~105 GPU (gas permeation unit). We further demonstrate that selectivity and permeance can be tuned by the anion size. The present work points toward a promising direction of using the atom-thin ionic-liquid/porous-graphene hybrid membrane for high-permeance, selective gas separation that allows a greater flexibility in substrate pore size control.« less

Ion-Gated Gas Separation through Porous Graphene

DOE PAGES

Tian, Ziqi; Mahurin, Shannon M.; Dai, Sheng; ...

2017-02-10

Porous graphene holds great promise as an atom-thin, high-permeance membrane for gas separation, but to precisely control the pore size at three to five angstroms proves challenging. Here we propose an ion-gated graphene membrane comprising a monolayer of ionic liquid coated porous graphene to dynamically modulate the pore size to achieve selective gas separation. This approach enables the otherwise non-selective large pores on the order of 1 nm in size to be selective for gases whose diameters range from three to four angstroms. We show from molecular dynamics simulations that CO 2, N 2 and CH 4 all can permeatemore » through a 1-nm pore in graphene without any selectivity. But when a monolayer of [emim][BF 4] is deposited on the porous graphene, CO 2 has much higher permeance than the other two gases. We find that the anion dynamically modulates the pore size by hovering above the pore and provides affinity for CO 2 while the larger cation (which cannot go through the pore) holds the anion in place via electrostatic attraction. This composite membrane is especially promising for CO 2/CH 4 separation, with a CO 2/CH 4 selectivity of about 42 and CO 2 permeance ~105 GPU (gas permeation unit). We further demonstrate that selectivity and permeance can be tuned by the anion size. The present work points toward a promising direction of using the atom-thin ionic-liquid/porous-graphene hybrid membrane for high-permeance, selective gas separation that allows a greater flexibility in substrate pore size control.« less

Geometry effect on electrokinetic flow and ionic conductance in pH-regulated nanochannels

NASA Astrophysics Data System (ADS)

Sadeghi, Morteza; Saidi, Mohammad Hassan; Moosavi, Ali; Sadeghi, Arman

2017-12-01

Semi-analytical solutions are obtained for the electrical potential, electroosmotic velocity, ionic conductance, and surface physicochemical properties associated with long pH-regulated nanochannels of arbitrary but constant cross-sectional area. The effects of electric double layer overlap, multiple ionic species, and surface association/dissociation reactions are all taken into account, assuming low surface potentials. The method of analysis includes series solutions which the pertinent coefficients are obtained by applying the wall boundary conditions using either of the least-squares or point matching techniques. Although the procedure is general enough to be applied to almost any arbitrary cross section, nine nanogeometries including polygonal, trapezoidal, double-trapezoidal, rectangular, elliptical, semi-elliptical, isosceles triangular, rhombic, and isotropically etched profiles are selected for presentation. For the special case of an elliptic cross section, full analytical solutions are also obtained utilizing the Mathieu functions. We show that the geometrical configuration plays a key role in determination of the ionic conductance, surface charge density, electrical potential and velocity fields, and proton enhancement. In this respect, the net electric charge and convective ionic conductance are higher for channels of larger perimeter to area ratio, whereas the opposite is true for the average surface charge density and mean velocity; the geometry impact on the two latest ones, however, vanishes if the background salt concentration is high enough. Moreover, we demonstrate that considering a constant surface potential equal to the average charge-regulated potential provides sufficiently accurate results for smooth geometries such as an ellipse at medium-high aspect ratios but leads to significant errors for geometries having narrow corners such as a triangle.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G.; Eckert, Charles A.; Liotta, Charles L.; Heldebrant, David J.

2013-08-20

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G [Kingston, CA; Eckert, Charles A [Atlanta, GA; Liotta, Charles L [Atlanta, GA; Heldebrant, David J [Richland, WA

2011-07-19

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G; Eckert, Charles A; Liotta, Charles L; Heldebrant, David J

2014-04-29

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

High-capacity NO2 denuder systems operated at various temperatures (298-473 K).

PubMed

Wolf, Jan-Christoph; Niessner, Reinhard

2012-12-01

In this study, we investigated several coatings for high-temperature, high-capacity, and high-efficiency denuder-based NO(2) removal, with the scope to face the harsh conditions and requirements of automotive exhaust gas sampling. As first coating, we propose a potassium iodide (KI)/polyethylene glycol coating with a high removal efficiency (ε > 98%) for about 2 h and 50 ppm NO(2) at room temperature (298 K). At elevated temperatures (423 K), the initial capacity (100 ppmh) is decreased to 15 ppmh. Furthermore, this is the first proposal of the ionic liquid methyl-butyl-imidazolium iodide ([BMIm(+)][I(-)]) as denuder coating material. At room temperature, this ionic liquid exhibits far greater capacity (300 ppmh) and NO(2) removal efficiency (ε > 99.9%) than KI. Nevertheless, KI exhibits a slightly (~10%) higher capacity at elevated temperatures than [BMIm(+)][I(-)]. Both coatings presented are suitable for applications requiring selective denuding of NO(2) at temperatures up to 423 K.

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.

The effect of varying the anion of an ionic liquid on the solvent effects on a nucleophilic aromatic substitution reaction.

PubMed

Hawker, Rebecca R; Haines, Ronald S; Harper, Jason B

2018-05-09

A variety of ionic liquids, each containing the same cation but a different anion, were examined as solvents for a nucleophilic aromatic substitution reaction. Varying the proportion of ionic liquid was found to increase the rate constant as the mole fraction of ionic liquid increased demonstrating that the reaction outcome could be controlled through varying the ionic liquid. The solvent effects were correlated with the hydrogen bond accepting ability (β) of the ionic liquid anion allowing for qualitative prediction of the effect of changing this component of the solute. To determine the microscopic origins of the solvent effects, activation parameters were determined through temperature-dependent kinetic analyses and shown to be consistent with previous studies. With the knowledge of the microscopic interactions in solution, an ionic liquid was rationally chosen to maximise rate enhancement demonstrating that an ionic solvent can be selected to control reaction outcome for this reaction type.

[Evaluation of chromatographic performance of polymerized ionic liquid stationary phase for capillary gas chromatography].

PubMed

Chen, Xiaoyan; Lu, Kai; Qi, Meiling; Fu, Ruonong

2009-11-01

The selectivity and thermal stability of ionic liquids as the stationary phases for capillary gas chromatography (CGC) have attracted much attention of researchers in recent years. In this study, 1-vinyl-3-benzyl imidazolium-bis(trifluoromethane-sulphonyl)imidate (VBIm-NTf2) was synthesized and polymerized (PVBIm-NTf2) in a CGC column. In comparison with VBIm-NTf2, PVBIm-NTf2 exhibits much better thermal stability and chromatographic selectivity, and achieves satisfactory resolution for Grob test mixture, alcohols mixture, esters mixture and aromatics mixture with narrow and symmetric peak shapes. The satisfactory resolution and selectivity of the polymerized column still remain after conditioned at 250 degrees C for 6 h. Additionally, the Abraham solvation parameters of PVBIm-NTf2 were determined and the interactions between the stationary phase and solutes were elucidated. The present work demonstrates that the polymerization is an effective way to improve the selectivity and thermal stability of common ionic liquids as CGC stationary phases.

Ionic Liquids in Selective Oxidation: Catalysts and Solvents.

PubMed

Dai, Chengna; Zhang, Jie; Huang, Chongpin; Lei, Zhigang

2017-05-24

Selective oxidation has an important role in environmental and green chemistry (e.g., oxidative desulfurization of fuels and oxidative removal of mercury) as well as chemicals and intermediates chemistry to obtain high-value-added special products (e.g., organic sulfoxides and sulfones, aldehydes, ketones, carboxylic acids, epoxides, esters, and lactones). Due to their unique physical properties such as the nonvolatility, thermal stability, nonexplosion, high polarity, and temperature-dependent miscibility with water, ionic liquids (ILs) have attracted considerable attention as reaction solvents and media for selective oxidations and are considered as green alternatives to volatile organic solvents. Moreover, for easy separation and recyclable utilization, IL catalysts have attracted unprecedented attention as "biphasic catalyst" or "immobilized catalyst" by immobilizing metal- or nonmetal-containing ILs onto mineral or polymer supports to combine the unique properties of ILs (chemical and thermal stability, capacity for extraction of polar substrates and reaction products) with the extended surface of the supports. This review highlights the most recent outcomes on ILs in several important typical oxidation reactions. The contents are arranged in the series of oxidation of sulfides, oxidation of alcohols, epoxidation of alkenes, Baeyer-Villiger oxidation reaction, oxidation of alkanes, and oxidation of other compounds step by step involving ILs as solvents, catalysts, reagents, or their combinations.

Potential use of ionic species for identifying source land-uses of stormwater runoff.

PubMed

Lee, Dong Hoon; Kim, Jin Hwi; Mendoza, Joseph A; Lee, Chang-Hee; Kang, Joo-Hyon

2017-02-01

Identifying critical land-uses or source areas is important to prioritize resources for cost-effective stormwater management. This study investigated the use of information on ionic composition as a fingerprint to identify the source land-use of stormwater runoff. We used 12 ionic species in stormwater runoff monitored for a total of 20 storm events at five sites with different land-use compositions during the 2012-2014 wet seasons. A stepwise forward discriminant function analysis (DFA) with the jack-knifed cross validation approach was used to select ionic species that better discriminate the land-use of its source. Of the 12 ionic species, 9 species (K + , Mg 2+ , Na + , NH 4 + , Br - , Cl - , F - , NO 2 - , and SO 4 2- ) were selected for better performance of the DFA. The DFA successfully differentiated stormwater samples from urban, rural, and construction sites using concentrations of the ionic species (70%, 95%, and 91% of correct classification, respectively). Over 80% of the new data cases were correctly classified by the trained DFA model. When applied to data cases from a mixed land-use catchment and downstream, the DFA model showed the greater impact of urban areas and rural areas respectively in the earlier and later parts of a storm event.

Microscopic characterization of tension wood cell walls of Japanese beech (Fagus crenata) treated with ionic liquids.

PubMed

Kanbayashi, Toru; Miyafuji, Hisashi

2016-09-01

Tension wood that is an abnormal part formed in angiosperms has been barely used for wood industry. In this study, to utilize the tension wood effectively by means of liquefaction using ionic liquid, we performed morphological and topochemical determination of the changes in tension wood of Japanese beech (Fagus crenata) during ionic liquid treatment at the cellular level using light microscopy, scanning electron microscopy and confocal Raman microscopy. Ionic liquid treatment induced cell wall swelling in tension wood. Changes in the tissue morphology treated with ionic liquids were different between normal wood and tension wood, moreover the types of ionic liquids. The ionic liquid 1-ethyl-3-methylimidazolium chloride liquefied gelatinous layers rapidly, whereas 1-ethylpyridinium bromide liquefied slowly but delignified selectively. These novel insights into the deconstruction behavior of tension wood cell walls during ionic liquid treatment provide better understanding of the liquefaction mechanism. The obtained knowledge will contribute to development of an effective chemical processing of tension wood using ionic liquids and lead to efficient use of wood resources. Copyright © 2016 Elsevier Ltd. All rights reserved.

Super non-linear RRAM with ultra-low power for 3D vertical nano-crossbar arrays.

PubMed

Luo, Qing; Xu, Xiaoxin; Liu, Hongtao; Lv, Hangbing; Gong, Tiancheng; Long, Shibing; Liu, Qi; Sun, Haitao; Banerjee, Writam; Li, Ling; Gao, Jianfeng; Lu, Nianduan; Liu, Ming

2016-08-25

Vertical crossbar arrays provide a cost-effective approach for high density three-dimensional (3D) integration of resistive random access memory. However, an individual selector device is not allowed to be integrated with the memory cell separately. The development of V-RRAM has impeded the lack of satisfactory self-selective cells. In this study, we have developed a high performance bilayer self-selective device using HfO2 as the memory switching layer and a mixed ionic and electron conductor as the selective layer. The device exhibits high non-linearity (>10(3)) and ultra-low half-select leakage (<0.1 pA). A four layer vertical crossbar array was successfully demonstrated based on the developed self-selective device. High uniformity, ultra-low leakage, sub-nA operation, self-compliance, and excellent read/write disturbance immunity were achieved. The robust array level performance shows attractive potential for low power and high density 3D data storage applications.

Advances in QSPR/QSTR models of ionic liquids for the design of greener solvents of the future.

PubMed

Das, Rudra Narayan; Roy, Kunal

2013-02-01

In order to protect the life of all creatures living in the environment, the toxicity arising from various hazardous chemicals must be controlled. This imposes a serious responsibility on different chemical, pharmaceutical, and other biological industries to produce less harmful chemicals. Among various international initiatives on harmful aspects of chemicals, the 'Green Chemistry' ideology appears to be one of the most highlighted concepts that focus on the use of eco-friendly chemicals. Ionic liquids are a comparatively new addition to the huge garrison of chemical compounds released from the industry. Extensive research on ionic liquids in the past decade has shown them to be highly useful chemicals with a good degree of thermal and chemical stability, appreciable task specificity and minimal environmental release resulting in a notion of 'green chemical'. However, studies have also shown that ionic liquids are not intrinsically non-toxic agents and can pose severe degree of toxicity as well as the risk of bioaccumulation depending upon their structural components. Moreover, ionic liquids possess issues of waste generation during synthesis as well as separation problems. Predictive quantitative structure-activity relationship (QSAR) models constitute a rational opportunity to explore the structural attributes of ionic liquids towards various physicochemical and toxicological endpoints and thereby leading to the design of environmentally more benevolent analogues with higher process selectivity. Such studies on ionic liquids have been less extensive compared to other industrial chemicals. The present review attempts to summarize different QSAR studies performed on these chemicals and also highlights the safety, health and environmental issues along with the application specificity on the dogma of 'green chemistry'.

Poly(ionic liquid)/Ionic Liquid Ion-Gels with High "Free" Ionic Liquid Content: Platform Membrane Materials for CO2/Light Gas Separations.

PubMed

Cowan, Matthew G; Gin, Douglas L; Noble, Richard D

2016-04-19

The recycling or sequestration of carbon dioxide (CO2) from the waste gas of fossil-fuel power plants is widely acknowledged as one of the most realistic strategies for delaying or avoiding the severest environmental, economic, political, and social consequences that will result from global climate change and ocean acidification. For context, in 2013 coal and natural gas power plants accounted for roughly 31% of total U.S. CO2 emissions. Recycling or sequestering this CO2 would reduce U.S. emissions by ca. 1800 million metric tons-easily meeting the U.S.'s currently stated CO2 reduction targets of ca. 17% relative to 2005 levels by 2020. This situation is similar for many developed and developing nations, many of which officially target a 20% reduction relative to 1990 baseline levels by 2020. To make CO2 recycling or sequestration processes technologically and economically viable, the CO2 must first be separated from the rest of the waste gas mixture-which is comprised mostly of nitrogen gas and water (ca. 85%). Of the many potential separation technologies available, membrane technology is particularly attractive due to its low energy operating cost, low maintenance, smaller equipment footprint, and relatively facile retrofit integration with existing power plant designs. From a techno-economic standpoint, the separation of CO2 from flue gas requires membranes that can process extremely high amounts of CO2 over a short time period, a property defined as the membrane "permeance". In contrast, the membrane's CO2/N2 selectivity has only a minor effect on the overall cost of some separation processes once a threshold permeability selectivity of ca. 20 is reached. Given the above criteria, the critical properties when developing membrane materials for postcombustion CO2 separation are CO2 permeability (i.e., the rate of CO2 transport normalized to the material thickness), a reasonable CO2/N2 selectivity (≥20), and the ability to be processed into defect-free thin-films (ca. 100-nm-thick active layer). Traditional polymeric membrane materials are limited by a trade-off between permeability and selectivity empirically described by the "Robeson upper bound"-placing the desired membrane properties beyond reach. Therefore, the investigation of advanced and composite materials that can overcome the limitations of traditional polymeric materials is the focus of significant academic and industrial research. In particular, there has been substantial work on ionic-liquid (IL)-based materials due to their gas transport properties. This review provides an overview of our collaborative work on developing poly(ionic liquid)/ionic liquid (PIL/IL) ion-gel membrane technology. We detail developmental work on the preparation of PIL/IL composites and describe how this chemical technology was adapted to allow the roll-to-roll processing and preparation of membranes with defect-free active layers ca. 100 nm thick, CO2 permeances of over 6000 GPU, and CO2/N2 selectivity of ≥20-properties with the potential to reduce the cost of CO2 removal from coal-fired power plant flue gas to ca. $15 per ton of CO2 captured. Additionally, we examine the materials developments that have produced advanced PIL/IL composite membranes. These advancements include cross-linked PIL/IL blends, step-growth PIL/IL networks with facilitated transport groups, and PIL/IL composites with microporous additives for CO2/CH4 separations.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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 cationsmore » 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.« less

Surface deformation and shear flow in ligand mediated cell adhesion.

PubMed

Sircar, Sarthok; Roberts, Anthony J

2016-10-01

We present a unified, multiscale model to study the attachment/detachment dynamics of two deforming, charged, near spherical cells, coated with binding ligands and subject to a slow, homogeneous shear flow in a viscous, ionic fluid medium. The binding ligands on the surface of the cells experience both attractive and repulsive forces in an ionic medium and exhibit finite resistance to rotation via bond tilting. The microscale drag forces and couples describing the fluid flow inside the small separation gap between the cells, are calculated using a combination of methods in lubrication theory and previously published numerical results. For a selected range of material and fluid parameters, a hysteretic transition of the sticking probability curves (i.e., the function [Formula: see text]) between the adhesion phase (when [Formula: see text]) and the fragmentation phase (when [Formula: see text]) is attributed to a nonlinear relation between the total nanoscale binding forces and the separation gap between the cells. We show that adhesion is favoured in highly ionic fluids, increased deformability of the cells, elastic binders and a higher fluid shear rate (until a critical threshold value of shear rate is reached). Within a selected range of critical shear rates, the continuation of the limit points (i.e., the turning points where the slope of [Formula: see text] changes sign) predict a bistable region, indicating an abrupt switching between the adhesion and the fragmentation regimes. Although, bistability in the adhesion-fragmentation phase diagram of two deformable, charged cells immersed in an ionic aqueous environment has been identified by some in vitro experiments, but until now, has not been quantified theoretically.

Heat-induced gelation of myosin in a low ionic strength solution containing L-histidine.

PubMed

Hayakawa, T; Yoshida, Y; Yasui, M; Ito, T; Iwasaki, T; Wakamatsu, J; Hattori, A; Nishimura, T

2012-01-01

Binding properties are important for meat products and are substantially derived from the heat-induced gelation of myosin. We have shown that myosin is solubilized in a low ionic strength solution containing L-histidine. To clarify its processing characteristics, we investigated properties and structures of heat-induced gels of myosin solubilized in a low ionic strength solution containing L-histidine. Myosin in a low ionic strength solution formed transparent gels at 40-50°C, while myosin in a high ionic strength solution formed opaque gels at 60-70°C. The gel of myosin in a low ionic strength solution with L-histidine showed a fine network consisting of thin strands and its viscosity was lower than that of myosin in a high ionic strength solution at 40-50°C. The rheological properties of heat-induced gels of myosin at low ionic strength are different from those at high ionic strength. This difference might be caused by structural changes in the rod region of myosin in a low ionic strength solution containing L-histidine. Copyright © 2011 Elsevier Ltd. All rights reserved.

Sub-0.5 V Highly Stable Aqueous Salt Gated Metal Oxide Electronics

PubMed Central

Park, Sungjun; Lee, SeYeong; Kim, Chang-Hyun; Lee, Ilseop; Lee, Won-June; Kim, Sohee; Lee, Byung-Geun; Jang, Jae-Hyung; Yoon, Myung-Han

2015-01-01

Recently, growing interest in implantable bionics and biochemical sensors spurred the research for developing non-conventional electronics with excellent device characteristics at low operation voltages and prolonged device stability under physiological conditions. Herein, we report high-performance aqueous electrolyte-gated thin-film transistors using a sol-gel amorphous metal oxide semiconductor and aqueous electrolyte dielectrics based on small ionic salts. The proper selection of channel material (i.e., indium-gallium-zinc-oxide) and precautious passivation of non-channel areas enabled the development of simple but highly stable metal oxide transistors manifested by low operation voltages within 0.5 V, high transconductance of ~1.0 mS, large current on-off ratios over 107, and fast inverter responses up to several hundred hertz without device degradation even in physiologically-relevant ionic solutions. In conjunction with excellent transistor characteristics, investigation of the electrochemical nature of the metal oxide-electrolyte interface may contribute to the development of a viable bio-electronic platform directly interfacing with biological entities in vivo. PMID:26271456

Characterization of the aroma profile of novel Brazilian wines by solid-phase microextraction using polymeric ionic liquid sorbent coatings.

PubMed

Crucello, Juliana; Miron, Luiz F O; Ferreira, Victor H C; Nan, He; Marques, Marcia O M; Ritschel, Patricia S; Zanus, Mauro C; Anderson, Jared L; Poppi, Ronei J; Hantao, Leandro W

2018-05-28

In this study, a series of polymeric ionic liquid (PIL) sorbent coatings is evaluated for the extraction of polar volatile organic compounds (VOCs) from Brazilian wines using headspace solid-phase microextraction (HS-SPME), including samples from 'Isabella' and 'BRS Magna' cultivars-the latter was recently introduced by the Brazilian Agricultural Research Corporation - National Grape & Wine Research Center. The structurally tuned SPME coatings were compared to the commercial SPME phases, namely poly(acrylate) (PA) and divinylbenzene/carboxen/poly(dimethylsiloxane) (DVB/CAR/PDMS). The separation, detection and identification of the aroma profiles were obtained using comprehensive two-dimensional gas chromatography mass spectrometry (GC×GC-MS). The best performing PIL-based SPME fiber, namely 1-hexadecyl-3-vinylimidazolium bis[(trifluoromethyl)sulfonyl]imide with 1,12-di(3-vinylimidazolium)dodecane dibis[(trifluoromethyl)sulfonyl]imide incorporated cross-linker supported on an elastic nitinol wire, exhibited superior performance to DVB/CAR/PDMS regarding the average number of extracted peaks and extracted more polar analytes providing additional insight into the aroma profile of 'BRS Magna' wines. Four batches of wine were evaluated, namely 'Isabella' and 'BRS Magna' vintages 2015 and 2016, using highly selective PIL-based SPME coatings and enabled the detection of 350+ peaks. Furthermore, this is the first report evaluating the aroma of 'BRS Magna' wines. A hybrid approach that combined pixel-based Fisher ratio and peak table-based data comparison was used for data handling. This proof-of-concept experiment provided reliable and statistically valid distinction of wines that may guide regulation agencies to create high sample throughput protocols to screen wines exported by Brazilian vintners. Graphical abstract Highly selective extraction of wine aroma using polymeric ionic liquid.

Hollow porous ionic liquids composite polymers based solid phase extraction coupled online with high performance liquid chromatography for selective analysis of hydrophilic hydroxybenzoic acids from complex samples.

PubMed

Dai, Xingping; Wang, Dongsheng; Li, Hui; Chen, Yanyi; Gong, Zhicheng; Xiang, Haiyan; Shi, Shuyun; Chen, Xiaoqing

2017-02-10

Polar and hydrophilic properties of hydroxybenzoic acids usually made them coelute with interferences in high performance liquid chromatography (HPLC) analysis. Then selective analysis of them was necessary. Herein, hollow porous ionic liquids composite polymers (PILs) based solid phase extraction (SPE) was firstly fabricated and coupled online with HPLC for selective analysis of hydroxybenzoic acids from complex matrices. Hollow porous PILs were firstly synthesized using Mobil Composition of Matter No. 48 (MCM-48) spheres as sacrificial support, 1-vinyl-3-methylimidazolium chloride (VMIM + Cl - ) as monomer, and ethylene glycol dimethacrylate (EGDMA) as cross-linker. Various parameters affecting synthesis, adsorption and desorption behaviors were investigated and optimized. Steady-state adsorption studies showed the resulting hollow porous PILs exhibited high adsorption capacity, fast adsorption kinetics, and excellent specific adsorption. Subsequently, the application of online SPE system was studied by selective analysis of protocatechuic acid (PCA), 4-hydroxybenzoic acid (4-HBA), and vanillic acid (VA) from Pollen Typha angustifolia. The obtained limit of detection (LOD) varied from 0.002 to 0.01μg/mL, the linear range (0.05-5.0μg/mL) was wide with correlation coefficient (R) from 0.9982 to 0.9994, and the average recoveries at three spiking levels ranged from 82.7 to 102.4%, with column-to-column relative standard deviation (RSD) below 8.1%. The proposed online method showed good accuracy, precision, specificity and convenience, which opened up a universal and efficient route for selective analysis of hydroxybenzoic acids from complex samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Designing Ionic Liquids for CO2 Capture: What’s the role for computation?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brennecke, Joan F.

Presentation on the computational aspects of ionic liquid selection for carbon dioxide capture to the conference attendees at the New Vistas in Molecular Thermodynamics: Experimentation, Molecular Modeling, and Inverse Design, Berkeley, CA, January 7 through 9, 2018

SELECTIVE OXIDATION OF STYRENE TO ACETOPHENONE IN PRESENCE OF IONIC LIQUIDS

EPA Science Inventory

Palladium-catalyzed oxidation of styrene (Wacker reaction) in the presence of 1,3-dialkylimidazolium cation based ionic liquids is described. The effect of temperature, use of co-catalyst, and recyclability aspects for the generation of carbonyl compounds using environmentally de...

Immobilization of Moniliella spathulata R25L270 Lipase on Ionic, Hydrophobic and Covalent Supports: Functional Properties and Hydrolysis of Sardine Oil.

PubMed

Souza, Lívia T de A; Moreno-Perez, Sonia; Fernández Lorente, Gloria; Cipolatti, Eliane P; de Oliveira, Débora; Resende, Rodrigo R; Pessela, Benevides C

2017-09-25

The oleaginous yeast Moniliella spathulata R25L270 was the first yeast able to grow and produce extracellular lipase using Macaúba ( Acrocomia aculeate ) cake as substrate. The novel lipase was recently identified, and presented promising features for biotechnological applications. The M. spathulata R25L270 lipase efficiently hydrolyzed vegetable and animal oils, and showed selectivity for generating cis -5,8,11,15,17-eicosapentaenoic acid from sardine oil. The enzyme can act in a wide range of temperatures (25-48 °C) and pH (6.5-8.4). The present study deals with the immobilization of M. spathulata R25L270 lipase on hydrophobic, covalent and ionic supports to select the most active biocatalyst capable to obtain omega-3 fatty acids (PUFA) from sardine oil. Nine immobilized agarose derivatives were prepared and biochemically characterized for thermostability, pH stability and catalytic properties (K M and V max ). Ionic supports improved the enzyme-substrate affinity; however, it was not an effective strategy to increase the M. spathulata R25L270 lipase stability against pH and temperature. Covalent support resulted in a biocatalyst with decreased activity, but high thermostability. The enzyme was most stabilized when immobilized on hydrophobic supports, especially Octyl-Sepharose. Compared with the free enzyme, the half-life of the Octyl-Sepharose derivative at 60 °C increased 10-fold, and lipase stability under acidic conditions was achieved. The Octyl-Sepharose derivative was selected to obtain omega-3 fatty acids from sardine oil, and the maximal enzyme selectivity was achieved at pH 5.0.

Application of ionic liquids in electrochemical sensing systems.

PubMed

Shiddiky, Muhammad J A; Torriero, Angel A J

2011-01-15

Since 1992, when the room temperature ionic liquids (ILs) based on the 1-alkyl-3-methylimidazolium cation were reported to provide an attractive combination of an electrochemical solvent and electrolyte, ILs have been widely used in electrodeposition, electrosynthesis, electrocatalysis, electrochemical capacitor, and lithium batteries. However, it has only been in the last few years that electrochemical biosensors based on carbon ionic liquid electrodes (CILEs) and IL-modified macrodisk electrodes have been reported. However, there are still a lot of challenges in achieving IL-based sensitive, selective, and reproducible biosensors for high speed analysis of biological and environmental compounds of interest. This review discusses the principles of operation of electrochemical biosensors based on CILEs and IL/composite-modified macrodisk electrodes. Subsequently, recent developments and major strategies for enhancing sensing performance are discussed. Key challenges and opportunities of IL-based biosensors to further development and use are considered. Emphasis is given to direct electron-transfer reaction and electrocatalysis of hemeproteins and enzyme-modified composite electrodes. Copyright © 2010 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ertem, S. Piril; Caire, Benjamin R.; Tsai, Tsung-Han

Anion exchange membranes (AEMs) are a promising class of materials for applications that require selective ion transport, such as fuel cells, water purification, and electrolysis devices. Studies of structure–morphology–property relationships of ion-exchange membranes revealed that block copolymers exhibit improved ion conductivity and mechanical properties due to their microphase-separated morphologies with well-defined ionic domains. While most studies focused on symmetric diblock or triblock copolymers, here, the first example of a midblock quaternized pentablock AEM is presented. A symmetric ABCBA pentablock copolymer was functionalized to obtain a midblock brominated polymer. Solution cast films were then quaternized to obtain AEMs with resulting ionmore » exchange capacities (IEC) ranging from 0.4 to 0.9 mmol/g. Despite the relatively low IEC, the polymers were highly conductive (up to 60 mS/cm Br2 at 90 8C and 95%RH) with low water absorption (<25 wt %) and maintained adequate mechanical properties in both dry and hydrated conditions. Xray scattering and transmission electron microscopy (TEM) revealed formation of cylindrical non-ionic domains in a connected ionic phase.« less

Ionic liquid-based single-drop microextraction/gas chromatographic/mass spectrometric determination of benzene, toluene, ethylbenzene and xylene isomers in waters.

PubMed

Aguilera-Herrador, Eva; Lucena, Rafael; Cárdenas, Soledad; Valcárcel, Miguel

2008-08-01

The direct coupling between ionic liquid-based single-drop microextraction and gas chromatography/mass spectrometry is proposed for the rapid and simple determination of benzene, toluene, ethylbenzene and xylenes isomers (BTEX) in water samples. The extraction procedure exploits not only the high affinity of the selected ionic liquid (1-methyl-3-octyl-imidazolium hexaflourophosphate) to these aromatic compounds but also its special properties like viscosity, low vapour pressure and immiscibility with water. All the variables involved in the extraction process have been studied in depth. The developed method allows the determination of these single-ring compounds in water under the reference concentration level fixed by the international legislation. In this case, limits of detection were in the range 20 ng L(-1) (obtained for benzene) and 91 ng L(-1) (for o-xylene). The repeatability of the proposed method, expressed as RSD (n=5), varied between 3.0% (o-xylene) and 5.2% (toluene).

Metallosalen-Based Ionic Porous Polymers as Bifunctional Catalysts for the Conversion of CO2 into Valuable Chemicals.

PubMed

Luo, Rongchang; Chen, Yaju; He, Qian; Lin, Xiaowei; Xu, Qihang; He, Xiaohui; Zhang, Wuying; Zhou, Xiantai; Ji, Hongbing

2017-04-10

A series of new metallosalen-based ionic porous organic polymers (POPs) were synthesized for the first time using a simple unique strategy based on the free-radical copolymerization reaction. Various techniques were used to characterize the physicochemical properties of these catalysts. These well-designed materials endowed high surface area, hierarchical porous structures, and enhanced CO 2 /N 2 adsorptive selectivity. Moreover, these POPs having both metal centers (Lewis acid) and ionic units (nucleophile) could serve as bifunctional catalysts in the catalytic conversion of CO 2 into high value-added chemicals without any additional co-catalyst under mild and solvent-free conditions, for example, CO 2 /epoxides cycloaddition and Nformylation of amines from CO 2 and hydrosilanes. The results demonstrated that the irregular porous structure was very favorable for the diffusion of substrates and products, and the microporous structural property resulted in the enrichment of CO 2 near the catalytic centers in the CO 2 -involved transformations. Additionally, the superhydrophobic property could not only enhance the chemoselectivity of products but also promote the stability and recyclability of catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Functionalized MIL-101 with imidazolium-based ionic liquids for the cycloaddition of CO2 and epoxides under mild condition

NASA Astrophysics Data System (ADS)

Liu, Dan; Li, Gang; Liu, Haiou

2018-01-01

A kind of multi-functional sites metal-organic framework (MOF) composite (MIL-101-IMBr) was successfully prepared by post-synthesis modification of MIL-101 with imidazolium-based ionic liquids. The ionic liquids not only functionalize as basic sites but also provide halide anions, which serve as a nucleophile in cycloaddition reaction. The prepared functional MOF materials were characterized by X-ray diffraction, fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, N2 adsorption-desorption and CO2 temperature programmed desorption. The results of fourier transform infrared spectroscopy and energy dispersive spectroscopy show that the MIL-101-IMBr composite was successfully synthesized. The N2 adsorption-desorption results clearly demonstrated that the modified composites still preserve high BET surface area and total pore volume. The composite exhibits high catalytic activity for the cycloaddition of CO2 with epoxides under mild and co-catalyst free conditions. The conversion of propylene oxide was 95.8% and the selectivity of cyclic carbonate was 97.6% under 0.8 MPa at 80 °C for 4 h. Moreover, the catalyst can be used for at least five times.

Ru-Catalyzed Estragole Isomerization under Homogeneous and Ionic Liquid Biphasic Conditions

PubMed Central

2017-01-01

The isomerization of estragole to trans-anethole is an important reaction and is industrially performed using an excess of NaOH or KOH in ethanol at high temperatures with very low selectivity. Simple Ru-based transition-metal complexes, under homogeneous, ionic liquid (IL)-supported (biphasic) and “solventless” conditions, can be used for this reaction. The selectivity of this reaction is more sensitive to the solvent/support used than the ligands associated with the metal catalyst. Thus, under the optimized reaction conditions, 100% conversion can be achieved in the estragole isomerization, using as little as 4 × 10–3 mol % (40 ppm) of [RuHCl(CO)(PPh3)3] in toluene, reflecting a total turnover number (TON) of 25 000 and turnover frequencies (TOFs) of up to 500 min–1 at 80 °C. Using a dimeric Ru precursor, [RuCl(μ-Cl)(η3:η3-C10H16)]2, in ethanol associated with P(OEt)3, a TON of 10 000 and a TOF of 125 min–1 are obtained with 100% conversion and 99% selectivity. These two Ru catalytic systems can be transposed to biphasic IL systems by using ionic-tagged P-ligands such as 1-(3-(diphenylphosphanyl)propyl)-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl)imide immobilized in 1-(3-hydroxypropyl)-2,3-dimethylimidazolium bis(trifluoromethanesulfonyl) imide with up to 99% selectivity and almost complete estragole conversion. However, the reaction is much slower than that performed under solventless or homogeneous conditions. The use of ionic-tagged ligands significantly reduces the Ru leaching to the organic phase, compared to that in reactions performed under homogeneous conditions, where the catalytic system loses catalytic performance after the second recycling. Detailed kinetic investigations of the reaction catalyzed by [RuHCl(CO)(PPh3)3] indicate that a simplified kinetic model (a monomolecular reversible first-order reaction) is adequate for fitting the homogeneous reaction at 80 °C and under biphasic conditions. However, the kinetics of the reaction are better described if all of the elementary steps are taken into consideration, especially at 40 °C. PMID:28393133

Statistical Determinants of Selective Ionic Complexation: Ions in Solvent, Transport Proteins, and Other “Hosts”

PubMed Central

Bostick, David L.; Brooks, Charles L.

2009-01-01

To provide utility in understanding the molecular evolution of ion-selective biomembrane channels/transporters, globular proteins, and ionophoric compounds, as well as in guiding their modification and design, we present a statistical mechanical basis for deconstructing the impact of the coordination structure and chemistry of selective multidentate ionic complexes. The deconstruction augments familiar ideas in liquid structure theory to realize the ionic complex as an open ion-ligated system acting under the influence of an “external field” provided by the host (or surrounding medium). Using considerations derived from this basis, we show that selective complexation arises from exploitation of a particular ion's coordination preferences. These preferences derive from a balance of interactions much like that which dictates the Hofmeister effect. By analyzing the coordination-state space of small family IA and VIIA ions in simulated fluid media, we derive domains of coordinated states that confer selectivity for a given ion upon isolating and constraining particular attributes (order parameters) of a complex comprised of a given type of ligand. We demonstrate that such domains may be used to rationalize the ion-coordinated environments provided by selective ionophores and biological ion channels/transporters of known structure, and that they can serve as a means toward deriving rational design principles for ion-selective hosts. PMID:19486671

An Overview of Novel Power Sources for Advanced Munitions

DTIC Science & Technology

2009-04-27

selected gas when desired. Prevention of rapid heat loss is a critical factor in prolonging operating lifetime as molten salt thermal batteries...4c. A higher number of end heat pellets not only provides more heat for bringing the battery internals above the eutectic point of the electrolyte but...maintenance. Finally, the combination of high vapor pressure and high ionic salt content typically found in catholyte formulations has caused foul- ing

Incorporation of ionic liquid into porous polymer monoliths to enhance the separation of small molecules in reversed-phase high-performance liquid chromatography.

PubMed

Wang, Jiafei; Bai, Ligai; Wei, Zhen; Qin, Junxiao; Ma, Yamin; Liu, Haiyan

2015-06-01

An ionic liquid was incorporated into the porous polymer monoliths to afford stationary phases with enhanced chromatographic performance for small molecules in reversed-phase high-performance liquid chromatography. The effect of the ionic liquid in the polymerization mixture on the performance of the monoliths was studied in detail. While monoliths without ionic liquid exhibited poor resolution and low efficiency, the addition of ionic liquid to the polymerization mixture provides highly increased resolution and high efficiency. The chromatographic performances of the monoliths were demonstrated by the separations of various small molecules including aromatic hydrocarbons, isomers, and homologues using a binary polar mobile phase. The present column efficiency reached 27 000 plates/m, which showed that the ionic liquid monoliths are alternative stationary phases in the separation of small molecules by high-performance liquid chromatography. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic conduction in sodium azide under high pressure: Experimental and theoretical approaches

NASA Astrophysics Data System (ADS)

Wang, Qinglin; Ma, Yanzhang; Sang, Dandan; Wang, Xiaoli; Liu, Cailong; Hu, Haiquan; Wang, Wenjun; Zhang, Bingyuan; Fan, Quli; Han, Yonghao; Gao, Chunxiao

2018-04-01

Alkali metal azides can be used as starting materials for the synthesis of polymeric nitrogen, a potential material of high energy density. In this letter, we report the ionic transport behavior in sodium azide under high pressure by in situ impedance spectroscopy and density functional theory calculations. The ionic transportation consists of ion transfer and Warburg diffusion processes. The ionic migration channels and barrier energy were given for the high-pressure phases. The enhanced ionic conductivity of the γ phase with pressure is because of the formation of space charge regions in the grain boundaries. This ionic conduction and grain boundary effect in NaN3 under pressures could shed light on the better understanding of the conduction mechanism of alkali azides and open up an area of research for polymeric nitrogen in these compounds and other high-energy-density polynitrides.

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. Copyright © 2014 Elsevier B.V. All rights reserved.

Matrine- and oxymatrine-imprinted monodisperse polymers prepared by precipitation polymerization and their applications for the selective extraction of matrine-type alkaloids from Sophora flavescens Aiton.

PubMed

Funaya, Noriko; Haginaka, Jun

2012-07-27

Matrine (MT)- and oxymatrine (OMT)-imprinted monodisperse polymers have been prepared by precipitation polymerization. The prepared molecularly imprinted polymers (MIPs) for MT and OMT, MIP(MT) and MIP(OMT), were monodispersed microspheres of 3.3 and 3.9 μm in diameter, respectively. Binding experiments and Scatchard analyses revealed that two classes of binding sites were formed on MIP(MT) and MIP(OMT). In addition to shape recognition, ionic and hydrophobic interactions seemed to affect the retention and recognition of MT and OMT on MIP(MT) and MIP(OMT), respectively, in low acetonitrile content, and ionic and hydrophilic interactions affected these properties in high acetonitrile content. MIP(MT) was used to selectively extract MT and sophocarpine (13,14-dehydromatrine) from Sophora flavescens root, while MIP(OMT) was used to extract OMT and oxysophocarpine (13,14-dehydrooxymatrine). Copyright © 2012 Elsevier B.V. All rights reserved.

Effect of addition of Proline, ionic liquid [Choline][Pro] on CO2 separation properties of poly(amidoamine) dendrimer / poly(ethylene glycol) hybrid membranes

NASA Astrophysics Data System (ADS)

Duan, S. H.; Kai, T.; Chowdhury, F. A.; Taniguchi, I.; Kazama, S.

2018-01-01

Poly(amidoamine) (PAMAM) dendrimers were incorporated into cross-linked poly(ethylene glycol) (PEGDMA) matrix to improve carbon dioxide (CO2) separation performance at elevated pressures. In our previous studies, PAMAM/PEGDMA hybrid membranes showed high CO2 separation properties from CO2/H2 mixed gases. In this study, proline, choline and ionic liquid [Choline][Pro] compounds were selected as rate promoters that were used to prepare PAMAM/PEGDMA hybrid membranes. The effect of addition of proline, choline, IL [Choline][Pro] on separation performance of PAMAM/PEGDMA) hybrid membranes for CO2/H2 separation was investigated. Amino acid proline, choline, and IL [Choline][Pro] were used to promote CO2 and amine reaction. With the addition of [Choline][Pro] into PAMAM/PEG membrane, CO2 permeance of PAMAM/PEG hybrid membranes are increased up to 46% without any change of selectivity of membrane for CO2.

Superbase-derived protic ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

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.

A physicochemical investigation of ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4sc02931c Click here for additional data file.

PubMed Central

Clough, Matthew T.; Crick, Colin R.; Gräsvik, John; Niedermeyer, Heiko; Whitaker, Oliver P.

2015-01-01

Ionic liquids have earned the reputation of being ‘designer solvents’ due to the wide range of accessible properties and the degree of fine-tuning afforded by varying the constituent ions. Mixtures of ionic liquids offer the opportunity for further fine-tuning of properties. A broad selection of common ionic liquid cations and anions are employed to create a sample of binary and reciprocal binary ionic liquid mixtures, which are analysed and described in this paper. Physical properties such as the conductivity, viscosity, density and phase behaviour (glass transition temperatures) are examined. In addition, thermal stabilities of the mixtures are evaluated. The physical properties examined for these formulations are found to generally adhere remarkably closely to ideal mixing laws, with a few consistent exceptions, allowing for the facile prediction and control of properties of ionic liquid mixtures. PMID:29560198

Capillary-valve-based fabrication of ion-selective membrane junction for electrokinetic sample preconcentration in PDMS chip.

PubMed

Liu, Vincent; Song, Yong-Ak; Han, Jongyoon

2010-06-07

In this paper, we report a novel method for fabricating ion-selective membranes in poly(dimethylsiloxane) (PDMS)/glass-based microfluidic preconcentrators. Based on the concept of capillary valves, this fabrication method involves filling a lithographically patterned junction between two microchannels with an ion-selective material such as Nafion resin; subsequent curing results in a high aspect-ratio membrane for use in electrokinetic sample preconcentration. To demonstrate the concentration performance of this high-aspect-ratio, ion-selective membrane, we integrated the preconcentrator with a surface-based immunoassay for R-Phycoerythrin (RPE). Using a 1x PBS buffer system, the preconcentrator-enhanced immunoassay showed an approximately 100x improvement in sensitivity within 30 min. This is the first time that an electrokinetic microfluidic preconcentrator based on ion concentration polarization (ICP) has been used in high ionic strength buffer solutions to enhance the sensitivity of a surface-based immunoassay.

Room-temperature ionic liquids: slow dynamics, viscosity, and the red edge effect.

PubMed

Hu, Zhonghan; Margulis, Claudio J

2007-11-01

Ionic liquids (ILs) have recently attracted significant attention from academic and industrial sources. This is because, while their vapor pressures are negligible, many of them are liquids at room temperature and can dissolve a wide range of polar and nonpolar organic and inorganic molecules. In this Account, we discuss the progress of our laboratory in understanding the dynamics, spectroscopy, and fluid dynamics of selected imidazolium-based ILs using computational and analytical tools that we have recently developed. Our results indicate that the red edge effect, the non-Newtonian behavior, and the existence of locally heterogeneous environments on a time scale relevant to chemical and photochemical reactivity are closely linked to the viscosity and highly structured character of these liquids.

One-step synthesis of highly efficient nanocatalysts on the supports with hierarchical pores using porous ionic liquid-water gel.

PubMed

Kang, Xinchen; Zhang, Jianling; Shang, Wenting; Wu, Tianbin; Zhang, Peng; Han, Buxing; Wu, Zhonghua; Mo, Guang; Xing, Xueqing

2014-03-12

Stable porous ionic liquid-water gel induced by inorganic salts was created for the first time. The porous gel was used to develop a one-step method to synthesize supported metal nanocatalysts. Au/SiO2, Ru/SiO2, Pd/Cu(2-pymo)2 metal-organic framework (Cu-MOF), and Au/polyacrylamide (PAM) were synthesized, in which the supports had hierarchical meso- and macropores, the size of the metal nanocatalysts could be very small (<1 nm), and the size distribution was very narrow even when the metal loading amount was as high as 8 wt %. The catalysts were extremely active, selective, and stable for oxidative esterification of benzyl alcohol to methyl benzoate, benzene hydrogenation to cyclohexane, and oxidation of benzyl alcohol to benzaldehyde because they combined the advantages of the nanocatalysts of small size and hierarchical porosity of the supports. In addition, this method is very simple.

First application of supported ionic liquid phase (SILP) catalysis for continuous methanol carbonylation.

PubMed

Riisager, Anders; Jørgensen, Betina; Wasserscheid, Peter; Fehrmann, Rasmus

2006-03-07

A solid, silica-supported ionic liquid phase (SILP) rhodium iodide Monsanto-type catalyst system, [BMIM][Rh(CO)2I2]-[BMIM]I-SiO2, exhibits excellent activity and selectivity towards acetyl products in fixed-bed, continuous gas-phase methanol carbonylation.

The effects of high concentrations of ionic liquid on GB1 protein structure and dynamics probed by high-resolution magic-angle-spinning NMR spectroscopy.

PubMed

Warner, Lisa; Gjersing, Erica; Follett, Shelby E; Elliott, K Wade; Dzyuba, Sergei V; Varga, Krisztina

2016-12-01

Ionic liquids have great potential in biological applications and biocatalysis, as some ionic liquids can stabilize proteins and enhance enzyme activity, while others have the opposite effect. However, on the molecular level, probing ionic liquid interactions with proteins, especially in solutions containing high concentration of ionic liquids, has been challenging. In the present work the 13 C, 15 N-enriched GB1 model protein was used to demonstrate applicability of high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy to investigate ionic liquid - protein interactions. Effect of an ionic liquid (1-butyl-3-methylimidazolium bromide, [C 4 -mim]Br) on GB1was studied over a wide range of the ionic liquid concentrations (0.6 to 3.5 M, which corresponds to 10%-60% v/v). Interactions between GB1 and [C 4 -mim]Br were observed from changes in the chemical shifts of the protein backbone as well as the changes in 15 N ps-ns dynamics and rotational correlation times. Site-specific interactions between the protein and [C 4 -mim]Br were assigned using 3D methods under HR-MAS conditions. Thus, HR-MAS NMR is a viable tool that could aid in elucidation of the molecular mechanism of ionic liquid - protein interactions.

Solute-Gas Equilibria in Multi-Organic Aqueous Systems

DTIC Science & Technology

1981-11-30

THIS PAGK(*7@nDae~ Kht.Eero*g) Block 20 (cont.) --z Henry’s constants for selected organic solvents were determined at ionic strengths up to 1.0 M (KC1...equili- brium, batch stripping reactor. Data were fit to a regression equation. Henry’s constants for selected organic solvents were determined at ionic...organic systems. The presence of additional or- ganics (some perhaps not even strippable ) likely to be found along with a particular volatile should be

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

NASA Astrophysics Data System (ADS)

Hoarfrost, Megan Lane

Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

Dissolution and fractionation of nut shells in ionic liquids.

PubMed

Carneiro, Aristides P; Rodríguez, Oscar; Macedo, Eugénia A

2017-03-01

The aim of this work was to study the dissolution of raw peanut and chestnut shells in ionic liquids. Dissolution of raw biomass up to 7wt% was achieved under optimized operatory conditions. Quantification of polysaccharides dissolved through quantitative 13 Cq NMR revealed extractions of the cellulosic material to ionic liquids as high as 87%. Regeneration experiments using an antisolvent mixture allowed to recover the cellulosic material and the ionic liquid. The overall mass balance presented very low loss rates (<8%), recoveries of 75% and 95% of cellulosic material from peanut and chestnut shells, respectively, and the recovery of more than 95% of the ionic liquid in both cases. These results show the high potential of using nut shells and ionic liquids for biorefining purposes. Moreover, high recovery of ionic liquids favors the process from an economical point of view. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling electrokinetics in ionic liquids: General

DOE PAGES

Wang, Chao; Bao, Jie; Pan, Wenxiao; ...

2017-04-01

Using direct numerical simulations, we provide a thorough study regarding the electrokinetics of ionic liquids. In particular, modified Poisson–Nernst–Planck equations are solved to capture the crowding and overscreening effects characteristic of an ionic liquid. For modeling electrokinetic flows in an ionic liquid, the modified Poisson-Nernst-Planck equations are coupled with Navier–Stokes equations to study the coupling of ion transport, hydrodynamics, and electrostatic forces. Specifically, we consider the ion transport between two parallel charged surfaces, charging dynamics in a nanopore, capacitance of electric double-layer capacitors, electroosmotic flow in a nanochannel, electroconvective instability on a plane ion-selective surface, and electroconvective flow on amore » curved ionselective surface. Lastly, we also discuss how crowding and overscreening and their interplay affect the electrokinetic behaviors of ionic liquids in these application problems.« less

Ionic liquids containing symmetric quaternary phosphonium cations and phosphorus-containing anions, and their use as lubricant additives

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, Jun; Luo, Huimin

An ionic liquid composition having the following generic structural formula: ##STR00001## wherein R 1, R 2, R 3, and R 4 are equivalent and selected from hydrocarbon groups containing at least three carbon atoms, and X - is a phosphorus-containing anion, particularly an organophosphate, organophosphonate, or organophosphinate anion, or a thio-substituted analog thereof containing hydrocarbon groups with at least three carbon atoms. Also described are lubricant compositions comprising the above ionic liquid and a base oil, wherein the ionic liquid is dissolved in the base oil. Further described are methods for applying the ionic liquid or lubricant composition onto amore » mechanical device for which lubrication is beneficial, with resulting improvement in friction reduction, wear rate, and/or corrosion inhibition.« less

Promising Cell Configuration for Next-Generation Energy Storage: Li2S/Graphite Battery Enabled by a Solvate Ionic Liquid Electrolyte.

PubMed

Li, Zhe; Zhang, Shiguo; Terada, Shoshi; Ma, Xiaofeng; Ikeda, Kohei; Kamei, Yutaro; Zhang, Ce; Dokko, Kaoru; Watanabe, Masayoshi

2016-06-29

Lithium-ion sulfur batteries with a [graphite|solvate ionic liquid electrolyte|lithium sulfide (Li2S)] structure are developed to realize high performance batteries without the issue of lithium anode. Li2S has recently emerged as a promising cathode material, due to its high theoretical specific capacity of 1166 mAh/g and its great potential in the development of lithium-ion sulfur batteries with a lithium-free anode such as graphite. Unfortunately, the electrochemical Li(+) intercalation/deintercalation in graphite is highly electrolyte-selective: whereas the process works well in the carbonate electrolytes inherited from Li-ion batteries, it cannot take place in the ether electrolytes commonly used for Li-S batteries, because the cointercalation of the solvent destroys the crystalline structure of graphite. Thus, only very few studies have focused on graphite-based Li-S full cells. In this work, simple graphite-based Li-S full cells were fabricated employing electrolytes beyond the conventional carbonates, in combination with highly loaded Li2S/graphene composite cathodes (Li2S loading: 2.2 mg/cm(2)). In particular, solvate ionic liquids can act as a single-phase electrolyte simultaneously compatible with both the Li2S cathode and the graphite anode and can further improve the battery performance by suppressing the shuttle effect. Consequently, these lithium-ion sulfur batteries show a stable and reversible charge-discharge behavior, along with a very high Coulombic efficiency.

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

DOE PAGES

Fang, Youxing; Jiang, Xueguang; Dai, Sheng; ...

2015-07-14

A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl 3 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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fang, Youxing; Jiang, Xueguang; Dai, Sheng

A new kind of ionic liquid based on complexation of dipropyl sulfide (DPS) and AlCl 3 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.

Ionic cross-linked polyether and silica gel mixed matrix membranes for CO 2 separation from flue gas

DOE PAGES

Sekizkardes, Ali K.; Zhou, Xu; Nulwala, Hunaid B.; ...

2017-09-22

Mixed matrix membranes (MMMs) were prepared by incorporating 10 wt%, 20 wt% and 30 wt% silica gel filler particles into novel ionic cross-linked polyether (IXPE) polymers. Porous silica gel has the advantage of high surface area that can increase the free volume and permeability in a polymer film while also being commercially available and low cost. The MMMs featured high chemical and thermal stability as well as a modest improvement in storage modulus. These features are due to the excellent interfacial interaction between silica gel filler particles and the polymer matrix. Increasing the loading of silica gel particles in MMMsmore » resulted in higher permeability up to 120 Barrer for CO 2, which is about 40% higher than the neat polymer matrix. Finally, most importantly, the MMMs maintained a very high CO 2/N 2 selectivity performance of around 41 for all particle loadings that were tested.« less

EFFECTS OF PH, SOLID/SOLUTION RATIO, IONIC STRENGTH, AND ORGANIC ACIDS ON PB AND CD SOPRTION ON KAOLINITE

EPA Science Inventory

Potentiometric and ion-selective electrode titrations together with batch sorption/desorption experiments, were performed to explain the aqueous and surface complexation reactions between kaolinite, Pb, Cd and three organic acids. Variables included pH, ionic strength, metal conc...

Weakening of ion-channel interactions of Na+ and Li+ in acetylcholine-receptor channels of frog skeletal muscle with an increase in agonist concentration.

PubMed

Manthey, A A

1998-05-01

The possibility that increases in agonist concentration beyond threshold levels may force changes in the character of high-conductance open states of skeletal muscle nicotinic acetylcholine receptor channels (nAChR) was examined by seeing whether differences in several critical ionic properties of nAChR currents could be detected with changes in agonist level. Single- and bi-ionic whole-cell currents of Na+ and Li+ in voltage-clamped frog (Rana pipiens) muscle fibers were measured during local superfusion of endplates with carbamylcholine (carb) at concentrations of 54 microm (low-carb) and 270 microM (high-carb). Three ionic properties that would be affected by changes in the open-state configuration of channel subunits were tested. First, ion-saturation characteristics. Peak Na+ and Li+ currents in low-carb trials showed sublinear dependence on ion concentrations from 0 to 60 mM with Km values of 78 (Na+) and 49 (Li+) mM and a power function slope of 0. 75 on double-log plot. In contrast, the concentration dependence of Na+ and Li+ currents in high-carb tests was linear through the origin with a power function slope of 1.02. Second, Na+/Li+ selectivity. The ratio of peak Na+ and Li+ currents in low-carb tests varied from 1.86 to 2.28 for ion concentrations of from 20 to 60 mM [mean = 2.02 +/- 0.06 (SEM)] whereas the ratio for high-carb trials ranged from only 1.29 to 1.52 [mean = 1.42 +/- 0.40 (SEM)]. Third, competitive interactions of Na+ and Li+ currents. Equimolar mixtures of Na+ and Li+ in low-carb tests produced bi-ionic inward currents which were never larger than the single-ion Na+ current alone, but bi-ionic currents at the high-carb level were always greater than the single-ion Na+ current, approximating the sum of the single-ion Na+ and Li+ currents in most cases. The results are consistent with a decrease in ion-channel binding at the high-carb level and support the possibility of agonist-induced changes in the high-conductance open-state configuration of nAChR subunits which result in a weakening of constraints on cation movements through the channel.

Studies on the movements of ionic selectivity, compatible solutes, and intracellular ions caused in the leaves of spinach (Spinacia oleracea L.) plants cultured in a nutrient solution with seawater.

PubMed

Sun, Jin; Jia, Yongxia; Guo, Shirong; Chen, Lifang

2010-01-01

Analyses of ionic selectivity, compatible solutes, and intracellular ions in the leaves of spinach (Spinacia oleracea L.) plants cultured in the Hoagland's nutrient solution with or.without seawater (40%) were carried out using two cultivars--the Helan No.3 (seawater tolerant) and the Yuanye (seawater sensitive). When both cultivars were subjected to seawater stress, the leaves of the Helan No. 3 spinach preferred potassium (K+), calcium (Ca2+), magnesium (Mg2+), and sulfate (SO4(2-)) over sodium (Na+) and chlorine (Cl-) to keep high ratios of K/Na, Mg/Na, Ca/Na, and SO4(2-)/Cl- compared with the Yanye spinach. Moreover, those of the Helan No. 3 spinach under the seawater stress showed high efficiency of accumulation of compatible solutes (sugars and proline), low degradation of proteins, and suppression of free amino acids. However, the activities of plasma membrane H+ -ATPase and tonoplast H+ -ATPase in the leaves of spinach with the stress were enhanced. Taken together, the Helan No. 3 spinach under the seawater stress seems to acquire a high tolerance to the seawater salinity by inducing a high ion uptake, low concentration of Na+ and Cl-, efficient accumulation of compatible solutes, low decomposition of proteins, and suppression of free amino acids in the leaves.

Evaluation of ionic air purifiers for reducing aerosol exposure in confined indoor spaces.

PubMed

Grinshpun, S A; Mainelis, G; Trunov, M; Adhikari, A; Reponen, T; Willeke, K

2005-08-01

Numerous techniques have been developed over the years for reducing aerosol exposure in indoor air environments. Among indoor air purifiers of different types, ionic emitters have gained increasing attention and are presently used for removing dust particles, aeroallergens and airborne microorganisms from indoor air. In this study, five ionic air purifiers (two wearable and three stationary) that produce unipolar air ions were evaluated with respect to their ability to reduce aerosol exposure in confined indoor spaces. The concentration decay of respirable particles of different properties was monitored in real time inside the breathing zone of a human manikin, which was placed in a relatively small (2.6 m3) walk-in chamber during the operation of an ionic air purifier in calm air and under mixing air condition. The particle removal efficiency as a function of particle size was determined using the data collected with a size-selective optical particle counter. The removal efficiency of the more powerful of the two wearable ionic purifiers reached about 50% after 15 min and almost 100% after 1.5 h of continuous operation in the chamber under calm air conditions. In the absence of external ventilation, air mixing, especially vigorous one (900 CFM), enhanced the air cleaning effect. Similar results were obtained when the manikin was placed inside a partial enclosure that simulated an aircraft seating configuration. All three stationary ionic air purifiers tested in this study were found capable of reducing the aerosol concentration in a confined indoor space. The most powerful stationary unit demonstrated an extremely high particle removal efficiency that increased sharply to almost 90% within 5-6 min, reaching about 100% within 10-12 min for all particle sizes (0.3-3 microm) tested in the chamber. For the units of the same emission rate, the data suggest that the ion polarity per se (negative vs. positive) does not affect the performance but the ion emission rate does. The effects of particle size (within the tested range) and properties (NaCl, PSL, Pseudomonas fluorescens bacteria) as well as the effects of the manikin's body temperature and its breathing on the ionic purifier performance were either small or insignificant. The data suggest that the unipolar ionic air purifiers are particularly efficient in reducing aerosol exposure in the breathing zone when used inside confined spaces with a relatively high surface-to-volume ratio. Ionic air purifiers have become increasingly popular for removing dust particles, aeroallergens and airborne microorganisms from indoor air in various settings. While the indoor air cleaning effect, resulting from unipolar and bipolar ion emission, has been tested by several investigators, there are still controversial claims (favorable and unfavorable) about the performance of commercially available ionic air purifiers. Among the five tested ionic air purifiers (two wearable and three stationary) producing unipolar air ions, the units with a higher ion emission rate provided higher particle removal efficiency. The ion polarity (negative vs. positive), the particle size (0.3-3 microm) and properties (NaCl, PSL, Pseudomonas fluorescens bacteria), as well as the body temperature and breathing did not considerable affected the ionization-driven particle removal. The data suggest that the unipolar ionic air purifiers are particularly efficient in reducing aerosol exposure in the breathing zone when they are used inside confined spaces with a relatively high surface-to-volume ratio (such as automobile cabins, aircraft seating areas, bathrooms, cellular offices, small residential rooms, and animal confinements). Based on our experiments, we proposed that purifiers with a very high ion emission rate be operated in an intermittent mode if used indoors for extended time periods. As the particles migrate to and deposit on indoor surfaces during the operation of ionic air purifiers, some excessive surface contamination may occur, which introduces the need of periodic cleaning these surfaces.

Polyelectrolyte layer-by-layer deposition in cylindrical nanopores.

PubMed

Lazzara, Thomas D; Lau, K H Aaron; Abou-Kandil, Ahmed I; Caminade, Anne-Marie; Majoral, Jean-Pierre; Knoll, Wolfgang

2010-07-27

Layer-by-layer (LbL) deposition of polyelectrolytes within nanopores in terms of the pore size and the ionic strength was experimentally studied. Anodic aluminum oxide (AAO) membranes, which have aligned, cylindrical, nonintersecting pores, were used as a model nanoporous system. Furthermore, the AAO membranes were also employed as planar optical waveguides to enable in situ monitoring of the LbL process within the nanopores by optical waveguide spectroscopy (OWS). Structurally well-defined N,N-disubstituted hydrazine phosphorus-containing dendrimers of the fourth generation, with peripherally charged groups and diameters of approximately 7 nm, were used as the model polyelectrolytes. The pore diameter of the AAO was varied between 30-116 nm and the ionic strength was varied over 3 orders of magnitude. The dependence of the deposited layer thickness on ionic strength within the nanopores is found to be significantly stronger than LbL deposition on a planar surface. Furthermore, deposition within the nanopores can become inhibited even if the pore diameter is much larger than the diameter of the G4-polyelectrolyte, or if the screening length is insignificant relative to the dendrimer diameter at high ionic strengths. Our results will aid in the template preparation of polyelectrolyte multilayer nanotubes, and our experimental approach may be useful for investigating theories regarding the partitioning of nano-objects within nanopores where electrostatic interactions are dominant. Furthermore, we show that the enhanced ionic strength dependence of polyelectrolyte transport within the nanopores can be used to selectively deposit a LbL multilayer atop a nanoporous substrate.

Measuring the proton selectivity of graphene membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walker, Michael I.; Keyser, Ulrich F., E-mail: ufk20@cam.ac.uk; Braeuninger-Weimer, Philipp

2015-11-23

By systematically studying the proton selectivity of free-standing graphene membranes in aqueous solutions, we demonstrate that protons are transported by passing through defects. We study the current-voltage characteristics of single-layer graphene grown by chemical vapour deposition (CVD) when a concentration gradient of HCl exists across it. Our measurements can unambiguously determine that H{sup +} ions are responsible for the selective part of the ionic current. By comparing the observed reversal potentials with positive and negative controls, we demonstrate that the as-grown graphene is only weakly selective for protons. We use atomic layer deposition to block most of the defects inmore » our CVD graphene. Our results show that a reduction in defect size decreases the ionic current but increases proton selectivity.« less

Insulated Conducting Cantilevered Nanotips and Two-Chamber Recording System for High Resolution Ion Sensing AFM

PubMed Central

Meckes, Brian; Arce, Fernando Teran; Connelly, Laura S.; Lal, Ratnesh

2014-01-01

Biological membranes contain ion channels, which are nanoscale pores allowing controlled ionic transport and mediating key biological functions underlying normal/abnormal living. Synthetic membranes with defined pores are being developed to control various processes, including filtration of pollutants, charge transport for energy storage, and separation of fluids and molecules. Although ionic transport (currents) can be measured with single channel resolution, imaging their structure and ionic currents simultaneously is difficult. Atomic force microscopy enables high resolution imaging of nanoscale structures and can be modified to measure ionic currents simultaneously. Moreover, the ionic currents can also be used to image structures. A simple method for fabricating conducting AFM cantilevers to image pore structures at high resolution is reported. Tungsten microwires with nanoscale tips are insulated except at the apex. This allows simultaneous imaging via cantilever deflections in normal AFM force feedback mode as well as measuring localized ionic currents. These novel probes measure ionic currents as small as picoampere while providing nanoscale spatial resolution surface topography and is suitable for measuring ionic currents and conductance of biological ion channels. PMID:24663394

The effects of high concentrations of ionic liquid on GB1 protein structure and dynamics probed by high-resolution magic-angle-spinning NMR spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Warner, Lisa; Gjersing, Erica; Follett, Shelby E.

Ionic liquids have great potential in biological applications and biocatalysis, as some ionic liquids can stabilize proteins and enhance enzyme activity, while others have the opposite effect. However, on the molecular level, probing ionic liquid interactions with proteins, especially in solutions containing high concentrations of ionic liquids, has been challenging. In the present work the 13C, 15N-enriched GB1 model protein was used to demonstrate applicability of high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy to investigate ionic liquid-protein interactions. Effect of an ionic liquid (1-butyl-3-methylimidazolium bromide, [C 4-mim]Br) on GB1was studied over a wide range of the ionic liquid concentrations (0.6-3.5 M, whichmore » corresponds to 10-60% v/v). Interactions between GB1 and [C 4-mim]Br were observed from changes in the chemical shifts of the protein backbone as well as the changes in 15N ps-ns dynamics and rotational correlation times. Site-specific interactions between the protein and [C 4-mim]Br were assigned using 3D methods under HR-MAS conditions. Furthermore, HR-MAS NMR is a viable tool that could aid in elucidation of molecular mechanisms of ionic liquid-protein interactions.« less

The effects of high concentrations of ionic liquid on GB1 protein structure and dynamics probed by high-resolution magic-angle-spinning NMR spectroscopy

DOE PAGES

Warner, Lisa; Gjersing, Erica; Follett, Shelby E.; ...

2016-08-11

Ionic liquids have great potential in biological applications and biocatalysis, as some ionic liquids can stabilize proteins and enhance enzyme activity, while others have the opposite effect. However, on the molecular level, probing ionic liquid interactions with proteins, especially in solutions containing high concentrations of ionic liquids, has been challenging. In the present work the 13C, 15N-enriched GB1 model protein was used to demonstrate applicability of high-resolution magic-angle-spinning (HR-MAS) NMR spectroscopy to investigate ionic liquid-protein interactions. Effect of an ionic liquid (1-butyl-3-methylimidazolium bromide, [C 4-mim]Br) on GB1was studied over a wide range of the ionic liquid concentrations (0.6-3.5 M, whichmore » corresponds to 10-60% v/v). Interactions between GB1 and [C 4-mim]Br were observed from changes in the chemical shifts of the protein backbone as well as the changes in 15N ps-ns dynamics and rotational correlation times. Site-specific interactions between the protein and [C 4-mim]Br were assigned using 3D methods under HR-MAS conditions. Furthermore, HR-MAS NMR is a viable tool that could aid in elucidation of molecular mechanisms of ionic liquid-protein interactions.« less

Molecular and ionic mimicry and the transport of toxic metals

PubMed Central

Bridges, Christy C.; Zalups, Rudolfs K.

2008-01-01

Despite many scientific advances, human exposure to, and intoxication by, toxic metal species continues to occur. Surprisingly, little is understood about the mechanisms by which certain metals and metal-containing species gain entry into target cells. Since there do not appear to be transporters designed specifically for the entry of most toxic metal species into mammalian cells, it has been postulated that some of these metals gain entry into target cells, through the mechanisms of ionic and/or molecular mimicry, at the site of transporters of essential elements and/or molecules. The primary purpose of this review is to discuss the transport of selective toxic metals in target organs and provide evidence supporting a role of ionic and/or molecular mimicry. In the context of this review, molecular mimicry refers to the ability of a metal ion to bond to an endogenous organic molecule to form an organic metal species that acts as a functional or structural mimic of essential molecules at the sites of transporters of those molecules. Ionic mimicry refers to the ability of a cationic form of a toxic metal to mimic an essential element or cationic species of an element at the site of a transporter of that element. Molecular and ionic mimics can also be sub-classified as structural or functional mimics. This review will present the established and putative roles of molecular and ionic mimicry in the transport of mercury, cadmium, lead, arsenic, selenium, and selected oxyanions in target organs and tissues. PMID:15845419

Molecular and ionic mimicry and the transport of toxic metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bridges, Christy C.; Zalups, Rudolfs K.

Despite many scientific advances, human exposure to, and intoxication by, toxic metal species continues to occur. Surprisingly, little is understood about the mechanisms by which certain metals and metal-containing species gain entry into target cells. Since there do not appear to be transporters designed specifically for the entry of most toxic metal species into mammalian cells, it has been postulated that some of these metals gain entry into target cells, through the mechanisms of ionic and/or molecular mimicry, at the site of transporters of essential elements and/or molecules. The primary purpose of this review is to discuss the transport ofmore » selective toxic metals in target organs and provide evidence supporting a role of ionic and/or molecular mimicry. In the context of this review, molecular mimicry refers to the ability of a metal ion to bond to an endogenous organic molecule to form an organic metal species that acts as a functional or structural mimic of essential molecules at the sites of transporters of those molecules. Ionic mimicry refers to the ability of a cationic form of a toxic metal to mimic an essential element or cationic species of an element at the site of a transporter of that element. Molecular and ionic mimics can also be sub-classified as structural or functional mimics. This review will present the established and putative roles of molecular and ionic mimicry in the transport of mercury, cadmium, lead, arsenic, selenium, and selected oxyanions in target organs and tissues.« less

Effect of ionic radii on the Curie temperature in Ba1-x-ySrxCayTiO3 compounds.

PubMed

Berenov, A; Le Goupil, F; Alford, N

2016-06-21

A series of Ba1-x-ySrxCayTiO3 compounds were prepared with varying average ionic radii and cation disorder on A-site. All samples showed typical ferroelectric behavior. A simple empirical equation correlated Curie temperature, TC, with the values of ionic radii of A-site cations. This correlation was related to the distortion of TiO6 octahedra observed during neutron diffraction studies. The equation was used for the selection of compounds with predetermined values of TC. The effects of A-site ionic radii on the temperatures of phase transitions in Ba1-x-ySrxCayTiO3 were discussed.

Ionic liquid electrolytes for dye-sensitized solar cells.

PubMed

Gorlov, Mikhail; Kloo, Lars

2008-05-28

The potential of room-temperature molten salts (ionic liquids) as solvents for electrolytes for dye-sensitized solar cells has been investigated during the last decade. The non-volatility, good solvent properties and high electrochemical stability of ionic liquids make them attractive solvents in contrast to volatile organic solvents. Despite this, the relatively high viscosity of ionic liquids leads to mass-transport limitations. Here we review recent developments in the application of different ionic liquids as solvents or components of liquid and quasi-solid electrolytes for dye-sensitized solar cells.

Highly luminescent and color-tunable salicylate ionic liquids

DOE PAGES

Campbell, Paul S.; Yang, Mei; Pitz, Demian; ...

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.

Toxicity evaluation of selected ammonium-based ionic liquid forms with MCPP and dicamba moieties on Pseudomonas putida.

PubMed

Piotrowska, Aleksandra; Syguda, Anna; Wyrwas, Bogdan; Chrzanowski, Łukasz; Heipieper, Hermann J

2017-01-01

Combination of the hydrophilic herbicidal anion with hydrophobic, antimicrobial ammonium cation allows to obtain compounds in ionic liquid form with better properties then conventional herbicides. Both cation and anion can be modified by selection of herbicide and the length of alkyl chains in cation structure. However the knowledge of their potential toxic effects are still limited. Furthermore, the relation between hydrophobicity associated with the length of alkyl chains and toxicity for ionic liquids has not been thoroughly studied. Therefore we investigated toxic effects of herbicidal ionic liquid forms on growth inhibition, given as EC 50, of the common soil bacterium Pseudomonas putida. We thereby concentrated on quaternary ammonium salts. Analyzed compounds were composed of dicamba or MCPP moieties and cation with various alkyl chain lengths (n = 6,8,10) We compared them with commercial herbicides, and ammonium-based ionic liquids with neutral anion (Br - ). In addition, cis-trans isomerisation of unsaturated membrane fatty acids in Pseudomonas putida was applied as the proxy for toxicity and membrane activity. We showed that toxicity increased with the length of alkyl chains. However, this correlation is only valid for six and eight carbon atom in alkyl chains, where for n = 10 the EC 50 values rise by one order of magnitude. In our studies, the herbicidal ionic liquids [C 10 ,C 10 ,C 1 ,C 1 N][MCPP] and [C 10 ,C 10 ,C 1 ,C 1 N][dicamba] showed the lowest toxicity among analyzed quaternary ammonium salts and comparable toxicity with corresponding herbicides. No clear increase in toxicity could be followed by changing the anion moieties for ammonium-based ionic liquid forms. Copyright © 2016 Elsevier Ltd. All rights reserved.

Annual Report - Compatibility of ZDDP and ionic liquid anti-wear additives with hard coatings for engine lubrications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu, Jun; Zhou, Yan; Leonard, Donovan N

The objectives for this considerations described here are to; investigate the compatibility of engine lubricant antiwear (AW) additives, specifically conventional zinc dialkyldithiophosphate (ZDDP) and newly developed ionic liquids (ILs), with selected commercial hard coatings, and provide fundamental understanding to guide future development of engine lubricants.

Characterization of Highly Sulfonated SIBS Polymer Partially Neutralized With Mg(+2) Cations

DTIC Science & Technology

2008-08-01

protective clothing, block copolymer ionomer membranes emerge. They are highly ordered sequence of both ionic and nonionic blocks, in which the ionic ...incorporated into the ionic polymer. Fourier-transform infrared spectroscopy results revealed that a significant amount of ordering occurred as a result on...increasing Mg content. This band indicates Mg complexation formed when two or more sulfonate groups ionically bonded to the Mg+2 cation

Understanding and modulating opalescence and viscosity in a monoclonal antibody formulation

PubMed Central

Salinas, Branden A; Sathish, Hasige A; Bishop, Steven M; Harn, Nick; Carpenter, John F; Randolph, Theodore W

2014-01-01

Opalescence and high viscosities can pose challenges for high concentration formulation of antibodies. Both phenomena result from protein-protein intermolecular interactions that can be modulated with solution ionic strength. We studied a therapeutic monoclonal antibody that exhibits high viscosity in solutions at low ionic strength (~20 centipoise (cP) at 90 mg/mL and 23°C) and significant opalescence at isotonic ionic strength (approximately 100 nephelometric turbidity units at 90 mg/mL and 23°C). The intermolecular interactions responsible for these effects were characterized using membrane osmometry, static light scattering and zeta potential measurements. The net protein-protein interactions were repulsive at low ionic strength (~4 mM) and attractive at isotonic ionic strengths. The high viscosities are attributed to electroviscous forces at low ionic strength and the significant opalescence at isotonic ionic strength is correlated with attractive antibody interactions. Furthermore there appears to be a connection to critical phenomena and it is suggested that the extent of opalescence is dependent on the proximity to the critical point. We demonstrate that by balancing the repulsive and attractive forces via intermediate ionic strengths and by increasing the mAb concentration above the apparent critical concentration both opalescence and viscosity can be simultaneously minimized. PMID:19475558

Theoretical Study of Renewable Ionic Liquids in the Pure State and with Graphene and Carbon Nanotubes.

PubMed

García, Gregorio; Atilhan, Mert; Aparicio, Santiago

2015-09-17

The N-ethyl-N-(furan-2-ylmethyl)ethanaminium dihydrogen phosphate ionic liquid was studied as a model of ionic liquids which can be produced from totally renewable sources. A computational study using both molecular dynamics and density functional theory methods was carried out. The properties, structuring, and intermolecular interactions (hydrogen bonding) of this fluid in the pure state were studied as a function of pressure and temperature. Likewise, the adsorption on graphene and the confinement between graphene sheets was also studied. The solvation of single walled carbon nanotubes in the selected ionic liquid was analyzed together with the behavior of ions confined inside these nanotubes. The reported results show remarkable properties for this fluid, which show that many of the most relevant properties of ionic liquids and their ability to interact with carbon nanosystems may be maintained and even improved using new families of renewable compounds instead of classic types of ionic liquids with worse environmental, toxicological, and economical profiles.

Application of quartz crystal microbalance to study the impact of pH and ionic strength on protein-silicone oil interactions.

PubMed

Dixit, Nitin; Maloney, Kevin M; Kalonia, Devendra S

2011-06-30

In this study, we have used quartz crystal microbalance (QCM) to quantitate the adsorption of a protein on silicone oil coated surfaces as a function of protein concentration, pH and ionic strength using a 5 MHz quartz crystal. Protein adsorption isotherms were generated at different solution pH and ionic strengths. Surface saturation concentrations were selected from adsorption isotherms and used to generate adsorption profiles from pH 3.0 to 9.0, and at ionic strengths of 10 mM and 150 mM. At low ionic strength (10mM) and pH 5.0 (close to the isoelectric point of the protein), maximum adsorption of protein to the silicone oil surface was observed. At higher ionic strength (150 mM), no significant pH influence on adsorption was observed. QCM could be used as a reliable technique to study the binding of proteins to silicone oil coated surfaces. Copyright © 2011 Elsevier B.V. All rights reserved.

Hybrid Encapsulated Ionic Liquids for Post-Combustion Carbon Dioxide (CO 2) Capture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brennecke, Joan; Degnan, Thomas; McCready, Mark

Ionic liquids (ILs) and Phase Change Ionic Liquids (PCILs) are excellent materials for selective removal of carbon dioxide from dilute post-combustion streams. However, they are typically characterized as having high viscosities, which impairs their effectiveness due to mass transfer limitations, caused by the high viscosities. In this project, we are examining the benefits of encapsulating ILs and PCILs in thin polymeric shells to produce particles of approximately 100 to 600 μm in diameter that can be used in a fluidized bed absorber. The particles are produced by microencapsulation of the ILs and PCILs in CO 2-permeable polymer shells. Here wemore » report on the synthesis of the IL and PCIL materials, measurements of thermophysical properties including CO 2 capacity and reprotonation equilibrium and kinetics, encapsulation of the ILs and PCILs, mechanical and thermodynamic testing of the encapsulated materials, development of a rate based model of the absorber, and the design of a laboratory scale unit to test the encapsulated particles for CO 2 capture ability and efficiency. We show that the IL/PCIL materials can be successfully encapsulated, that they retain CO 2 uptake capacity, and that the uptake rates are increased relative to a stagnant sample of IL liquid or PCIL powder.« less

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.

Study, selection, and preparation of solid cationic conductors

NASA Technical Reports Server (NTRS)

Roth, W. L.; Mitoff, S. P.; King, R. N.

1972-01-01

Crystal chemical principles and transport theory were used to predict structures and specific compounds which might find application as solid electrolytes in rechargeable high energy and high power density batteries operating at temperatures less than 200 C. More than twenty compounds were synthesized or obtained and screened by nuclear magnetic resonance and conductivity. Many were densified by sintering or hot pressing. Encouraging results were obtained for nine of these materials but none have yet been good ionic conductors at low temperature.

Evaluation of local anesthetic effects of Lidocaine-Ibuprofen ionic liquid stabilized silver nanoparticles in Male Swiss mice.

PubMed

Jiang, Qiliang; Yu, Shashuang; Li, Xingwang; Ma, Chuangen; Li, Aixiang

2018-01-01

A simple approach for the synthesis of Lidocaine-Ibuprofen ionic liquid stabilized silver nanoparticles (IL-AgNPs) was reported in this work. The shape, size and surface morphology of the Lidocaine-Ibuprofen ionic liquid stabilized AgNPs were characterized by using spectroscopic and microscopic techniques such as Ultraviolet-visible spectroscopy (UV-Visible), X-ray diffraction (XRD) analysis, Selected area electron diffraction (SAED), Transmission electron microscopy (TEM). TEM analysis showed the formation of 20-30nm size of IL-AgNPs with very clear lattice fringes. SAED pattern confirmed the highly crystalline nature of fabricated IL stabilized AgNPs. EDS results confirmed the formation of nanosilver. The fabricated IL-AgNPs were studied for their local anesthetic effect in rats. The results of local anesthetic effect showed that the time for onset of action by IL-AgNPs is 10min, which is significantly higher than that for EMLA. Further, tactile test results confirmed the stronger and faster local anesthetic effect of IL-AgNPs when compared to that of EMLA. Copyright © 2017. Published by Elsevier B.V.

Reactions of Ions with Ionic Liquid Vapors by Selected-Ion Flow Tube Mass Spectrometry

DTIC Science & Technology

2011-03-29

Emel’yanenko, V. N.; Verevkin, S. P.; Heintz, A.; Corfield, J.-A.; Deyko, A.; Lovelock , K. R. J.; Licence, P.; Jones, R. G. Pyrrolidinium- Based Ionic...112, 11734–11742. (2) Lovelock , K. R. J.; Deyko, A.; Licence, P.; Jones, R. G. Vaporisa- tion of an Ionic Liquid Near Room Temperature. Phys. Chem...Relevance of pKa from Aqueous Solutions. J. Am. Chem. Soc. 2003, 125, 15411–15419. (15) Armstrong, J. P.; Hurst, C.; Jones, R. G.; Licence, P.; Lovelock , K

Ionic Liquids as a Basis Context for Developing High school Chemistry Teaching Materials

NASA Astrophysics Data System (ADS)

Hernani; Mudzakir, A.; Sumarna, O.

2017-02-01

This research aims to produce a map of connectedness highschool chemical content with the context of the modern chemical materials applications based on ionic liquids. The research method is content analysis of journal articles related to the ionic liquid materials and the textbooks of high school chemistry and textbooks of general chemistry at the university. The instrument used is the development format of basic text that connect and combine content and context. The results showed the connectedness between: (1) the context lubricants ionic liquid with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, the elements of main group, the elements of transition group, and the classification of macromolecules; (2) the context of fuel cell electrolite with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, Volta cell, and electrolysis cell; (3) the contect of nanocellulose with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, colloid, carbon compound, and the classification of macromolecules; and (4) the context of artificial muscle system with the content of ionic bond, covalent bond, metal bonding, interaction between the particles of matter, hydrocarbons, electrolytes and non-electrolytes, and the classification of macromolecules. Based on the result of this content analysis, the context of ionic liquid is predicted can be utilized for the enrichment of high school chemistry and has the potential to become teaching material’s context of high school chemistry in the future.

Development of safe, green and high performance ionic liquids-based batteries (ILLIBATT project)

NASA Astrophysics Data System (ADS)

Balducci, A.; Jeong, S. S.; Kim, G. T.; Passerini, S.; Winter, M.; Schmuck, M.; Appetecchi, G. B.; Marcilla, R.; Mecerreyes, D.; Barsukov, V.; Khomenko, V.; Cantero, I.; De Meatza, I.; Holzapfel, M.; Tran, N.

This manuscript presents the work carried out within the European project ILLIBATT, which was dedicated to the development of green, safe and high performance ionic liquids-based lithium batteries. Different types of ionic liquids-based electrolytes were developed in the project, based on different ionic liquids and polymers. Using these electrolytes, the performance of several anodic and cathodic materials has been tested and promising results have been obtained. Also, electrodes were formulated using water soluble binders. Using these innovative components, lithium-ion and lithium-metal battery prototypes (0.7-0.8 Ah) have been assembled and cycled between 100% and 0% SOC. The results of these tests showed that such ionic liquids-based prototypes are able to display high capacity, high coulombic efficiency and high cycle life. Moreover, safety tests showed that the introduction of these alternative electrolytes positively contribute to the safety of the batteries.

Highly efficient conductivity modulation of cinnamate-based light-responsive ionic liquids in aqueous solutions.

PubMed

Yang, Jie; Wang, Huiyong; Wang, Jianji; Zhang, Yue; Guo, Zhongjia

2014-12-11

A new class of cinnamate-based light-responsive ionic liquids was synthesized and characterized, and these ionic liquids with longer alkyl chains showed a remarkable increase in ionic conductivity under UV light irradiation in aqueous solutions.

Recent advances in the applications of ionic liquids in protein stability and activity: a review.

PubMed

Patel, Rajan; Kumari, Meena; Khan, Abbul Bashar

2014-04-01

Room temperatures ionic liquids are considered as miraculous solvents for biological system. Due to their inimitable properties and large variety of applications, they have been widely used in enzyme catalysis and protein stability and separation. The related information present in the current review is helpful to the researchers working in the field of biotechnology and biochemistry to design or choose an ionic liquid that can serve as a noble and selective solvent for any particular enzymatic reaction, protein preservation and other protein based applications. We have extensively analyzed the methods used for studying the protein-IL interaction which is useful in providing information about structural and conformational dynamics of protein. This can be helpful to develop and understanding about the effect of ionic liquids on stability and activity of proteins. In addition, the affect of physico-chemical properties of ionic liquids, viz. hydrogen bond capacity and hydrophobicity on protein stability are discussed.

Waste separation and pretreatment using crystalline silicotitanate ion exchangers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tadros, M.E.; Miller, J.E.; Anthony, R.G.

1997-10-01

A new class of inorganic ion exchangers called crystalline silicotitanates (CSTs) has been developed jointly by Sandia National Laboratories and Texas A&M University to selectively remove Cs and other radionuclides from a wide spectrum of radioactive defense wastes. The CST exhibits high selectivity and affinity for Cs and Sr under a wide range of conditions. Tests show it can remove part-per-million concentrations of Cs{sup +} from highly alkaline, high-sodium simulated radioactive waste solutions modeled after those at Hanford, Oak Ridge, and Savannah River. The materials exhibit ion exchange properties based on ionic size selectivity. Specifically, crystalline lattice spacing is controlledmore » to be highly selective for Cs ions even in waste streams containing very high (5 to 10 M) concentrations of sodium. The CST technology is being demonstrated with actual waste at several DOE facilities. The use of inorganic ion exchangers. The inorganics are more resistant to chemical, thermal, and radiation degradation. Their high selectivities result in more efficient operations offering the possibility of a simple single-pass operation. In contrast, regenerable organic ion exchangers require additional processing equipment to handle the regeneration liquids and the eluant with the dissolved Cs.« less

Pressure Swing Absorption Device and Process for Separating CO{sub 2} from Shifted Syngas and its Capture for Subsequent Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sirkar, Kamalesh; Jie, Xingming; Chau, John

Using the ionic liquid (IL) 1-butyl-3-methylimidazolium dicyanamide ([bmim][DCA]) as the absorbent on the shell side of a membrane module containing either a porous hydrophobized ceramic tubule or porous hydrophobized polyether ether ketone (PEEK) hollow fiber membranes, studies for CO{sub 2} removal from hot simulated pre-combustion shifted syngas were carried out by a novel pressure swing membrane absorption (PSMAB) process. Helium was used as a surrogate for H{sub 2} in a simulated shifted syngas with CO{sub 2} around 40% (dry gas basis). In this cyclic separation process, the membrane module was used to achieve non-dispersive gas absorption from a high-pressure feedmore » gas (689-1724 kPag; 100-250 psig) at temperatures between 25-1000C into a stationary absorbent liquid on the module shell side during a certain part of the cycle followed by among other cycle steps controlled desorption of the absorbed gases from the liquid in the rest of the cycle. Two product streams were obtained, one He-rich and the other CO{sub 2}-rich. Addition of polyamidoamine (PAMAM) dendrimer of generation 0 to IL [bmim][DCA] improved the system performance at higher temperatures. The solubilities of CO{sub 2} and He were determined in the ionic liquid with or without the dendrimer in solution as well as in the presence or absence of moisture; polyethylene glycol (PEG) 400 was also studied as a replacement for the IL. The solubility selectivity of the ionic liquid containing the dendrimer for CO{sub 2} over helium was considerably larger than that for the pure ionic liquid. The solubility of CO{sub 2} and CO{sub 2}-He solubility selectivity of PEG 400 and a solution of the dendrimer in PEG 400 were higher than the corresponding ones in the IL, [bmim][DCA]. A mathematical model was developed to describe the PSMAB process; a numerical solution of the governing equations described successfully the observed performance of the PSMAB process for the pure ionic liquid-based system.« less

Ionic Conductivity and Air Stability of Al-Doped Li₇La₃Zr₂O₁₂ Sintered in Alumina and Pt Crucibles.

PubMed

Xia, Wenhao; Xu, Biyi; Duan, Huanan; Guo, Yiping; Kang, Hongmei; Li, Hua; Liu, Hezhou

2016-03-02

Li7La3Zr2O12 (LLZO) is a promising electrolyte material for all-solid-state battery due to its high ionic conductivity and good stability with metallic lithium. In this article, we studied the effect of crucibles on the ionic conductivity and air stability by synthesizing 0.25Al doped LLZO pellets in Pt crucibles and alumina crucibles, respectively. The results show that the composition and microstructure of the pellets play important roles influencing the ionic conductivity, relative density, and air stability. Specifically, the 0.25Al-LLZO pellets sintered in Pt crucibles exhibit a high relative density (∼96%) and high ionic conductivity (4.48 × 10(-4) S cm(-1)). The ionic conductivity maintains 3.6 × 10(-4) S cm(-1) after 3-month air exposure. In contrast, the ionic conductivity of the pellets from alumina crucibles is about 1.81 × 10(-4) S cm(-1) and drops to 2.39 × 10(-5) S cm(-1) 3 months later. The large grains and the reduced grain boundaries in the pellets sintered in Pt crucibles are favorable to obtain high ionic conductivity and good air stability. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy results suggest that the formation of Li2CO3 on the pellet surface is probably another main reason, which is also closely related to the relative density and the amount of grain boundary within the pellets. This work stresses the importance of synthesis parameters, crucibles included, to obtain the LLZO electrolyte with high ionic conductivity and good air stability.

Determination of Inorganic Ion Profiles of Illicit Drugs by Capillary Electrophoresis.

PubMed

Evans, Elizabeth; Costrino, Carolina; do Lago, Claudimir L; Garcia, Carlos D; Roux, Claude; Blanes, Lucas

2016-11-01

A portable capillary electrophoresis instrument with dual capacitively coupled contactless conductivity detection (C 4 D) was used to determine the inorganic ionic profiles of three pharmaceutical samples and precursors of two illicit drugs (contemporary samples of methylone and para-methoxymethamphetamine). The LODs ranged from 0.10 μmol/L to 1.25 μmol/L for the 10 selected cations, and from 0.13 μmol/L to 1.03 μmol/L for the eight selected anions. All separations were performed in less than 6 min with migration times and peak area RSD values ranging from 2 to 7%. The results demonstrate the potential of the analysis of inorganic ionic species to aid in the identification and/or differentiation of unknown tablets, and real samples found in illicit drug manufacture scenarios. From the resulting ionic fingerprint, the unknown tablets and samples can be further classified. © 2016 American Academy of Forensic Sciences.

Altered ion channel conductance and ionic selectivity induced by large imposed membrane potential pulse.

PubMed Central

Chen, W; Lee, R C

1994-01-01

The effects of large magnitude transmembrane potential pulses on voltage-gated Na and K channel behavior in frog skeletal muscle membrane were studied using a modified double vaseline-gap voltage clamp. The effects of electroconformational damage to ionic channels were separated from damage to lipid bilayer (electroporation). A 4 ms transmembrane potential pulse of -600 mV resulted in a reduction of both Na and K channel conductivities. The supraphysiologic pulses also reduced ionic selectivity of the K channels against Na+ ions, resulting in a depolarization of the membrane resting potential. However, TTX and TEA binding effects were unaltered. The kinetics of spontaneous reversal of the electroconformational damage of channel proteins was found to be dependent on the magnitude of imposed membrane potential pulse. These results suggest that muscle and nerve dysfunction after electrical shock may be in part caused by electroconformational damage to voltage-gated ion channels. PMID:7948676

Liquid-liquid extraction of neodymium(III) by dialkylphosphate ionic liquids from acidic medium: the importance of the ionic liquid cation.

PubMed

Rout, Alok; Kotlarska, Justyna; Dehaen, Wim; Binnemans, Koen

2013-10-21

The ionic liquids 1-hexyl-3-methylimidazolium bis(2-ethylhexyl)phosphate, [C6mim][DEHP], 1-hexyl-1-methylpyrrolidinium bis(2-ethylhexyl)phosphate, [C6mpyr][DEHP], and tetrabutylammonium bis(2-ethylhexyl)phosphate, [N4444][DEHP], were prepared and characterized using (1)H and (13)C NMR spectroscopy. The extraction behavior of neodymium(iii) from nitrate medium by these ionic liquids, diluted with the room temperature ionic liquids 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][NTf2], 1-hexyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C6mpyr][NTf2], and tributylmethylammonium bis(trifluoromethylsulfonyl)imide, [N1444][NTf2], was studied. The distribution ratio of neodymium(iii) was measured as a function of various parameters, such as pH, concentration of the ionic liquid extractant, nature of diluents, concentration of ionic liquid cations and nitrate anions in the aqueous phase. The extraction behavior was compared with that obtained for a solution of the molecular extractant bis(2-ethylhexyl)phosphoric acid (DEHPA) in an ionic liquid diluent. The extraction of neodymium(iii) in the ionic liquids [C6mim][DEHP] and [C6mpyr][DEHP] showed markedly different extraction properties in comparison with that of the quaternary ammonium analogue [N4444][DEHP], especially concerning the pH dependence of the extraction process. These results show that the extraction process can be tuned by the selection of the ionic liquid cation. The extraction experiments also included the trivalent rare-earth ions lanthanum(iii), cerium(iii), praseodymium(iii), ytterbium(iii) and yttrium(iii). Studies of the stripping behavior and the reusability of the ionic liquids were carried out, which indicate that the ionic liquids can be reused with no loss in activity.

Ionic liquid molecularly imprinted polymers for application in pipette-tip solid-phase extraction coupled with gas chromatography for rapid screening of dicofol in celery.

PubMed

Yan, Hongyuan; Yang, Chen; Sun, Yunyun; Row, Kyung Ho

2014-09-26

A new type of ionic liquid molecularly imprinted polymers (IL-MIPs) synthesized by precipitation polymerization using 1-allyl-3-methylimidazolium bromide as an auxiliary solvent and α-chloro-dichlorodiphenyltrichloroethane (α-chloro-DDT) as the template was applied as a selective sorbent of minimized pipette tip-solid-phase extraction (PT-SPE) for rapid isolation and extraction of dicofol (DCF) from celery samples. The pretreatment procedure of celery samples involved only 2.0mg of IL-MIPs, 0.8 mL of acetonitrile-water (ACN-H2O; 1:1, v/v) (washing solvent), and 1.0 mL of acetone-10% acetic acid (HOAc) (elution solvent). Compared with molecularly imprinted polymers (MIPs), ionic liquid-non-imprinted polymers (IL-NIPs) and conventional sorbents such as C18, Si, NH2, and Al2O3-N, IL-MIPs showed higher adsorption and purification capacity to DCF in aqueous solution. Good linearity for DCF was observed in the range from 2.3 to 232.5 ng g(-1) (r(2)=0.9995). The average recoveries at three spiking levels ranged from 86.6% to 101.9% with relative standard deviations (RSDs) of ≤ 6.5% (n=3). The presented IL-MIPs-PT-SPE-GC/ECD method combines the advantages of MIPs, IL, and PT-SPE, and can be used in aqueous conditions with high affinity and selectivity to analytes of complex samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon

Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which aremore » anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.« less

Determination of sulfonamides in butter samples by ionic liquid magnetic bar liquid-phase microextraction high-performance liquid chromatography.

PubMed

Wu, Lijie; Song, Ying; Hu, Mingzhu; Xu, Xu; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

2015-01-01

A novel, simple, and environmentally friendly pretreatment method, ionic liquid magnetic bar liquid-phase microextraction, was developed for the determination of sulfonamides in butter samples by high-performance liquid chromatography. The ionic liquid magnetic bar was prepared by inserting a stainless steel wire into the hollow of a hollow fiber and immobilizing ionic liquid in the micropores of the hollow fiber. In the extraction process, the ionic liquid magnetic bars were used to stir the mixture of sample and extraction solvent and enrich the sulfonamides in the mixture. After extraction, the analyte-adsorbed ionic liquid magnetic bars were readily isolated with a magnet from the extraction system. It is notable that the present method was environmentally friendly since water and only several microliters of ionic liquid were used in the whole extraction process. Several parameters affecting the extraction efficiency were investigated and optimized, including the type of ionic liquid, sample-to-extraction solvent ratio, the number of ionic liquid magnetic bars, extraction temperature, extraction time, salt concentration, stirring speed, pH of the extraction solvent, and desorption conditions. The recoveries were in the range of 73.25-103.85 % and the relative standard deviations were lower than 6.84 %. The experiment results indicated that the present method was effective for the extraction of sulfonamides in high-fat content samples.

Diels Alder polyphenylene anion exchange membrane for nonaqueous redox flow batteries

DOE PAGES

Small, Leo J.; Pratt, III, Harry D.; Fujimoto, Cy H.; ...

2015-10-23

Here highly conductive, solvent-resistant anionic Diels Alder polyphenylene (DAPP) membranes were synthesized with three different ionic contents and tested in an ionic liquid-based nonaqueous redox flow battery (RFB). These membranes display 3–10× increase in conductivity in propylene carbonate compared to some commercially available (aqueous) anion exchange membranes. The membrane with an ion content of 1.5 meq/g (DAPP1.5) proved too brittle for operation in a RFB, while the membrane with an ion content of 2.5 meq/g (DAPP2.5) allowed excessive movement of solvent and poor electrochemical yields (capacity fade). Despite having lower voltage efficiencies compared to DAPP2.5, the membrane with an intermediatemore » ion content of 2.0 meq/g (DAPP2.0) exhibited higher coulombic efficiencies (96.4% vs. 89.1%) and electrochemical yields (21.6% vs. 10.9%) after 50 cycles. Crossover of the electroactive species was the primary reason for decreased electrochemical yields. Analysis of the anolyte and catholyte revealed degradation of the electroactive species and formation of a film at the membrane-solution interface. Increases in membrane resistance were attributed to mechanical and thermal aging of the membrane; no chemical change was observed. As a result, improvements in the ionic selectivity and ionic conductivity of the membrane will increase the electrochemical yield and voltage efficiency of future nonaqueous redox flow batteries.« less

syn-Selective crotylation of aldehydes using bismuth-crotyl bromide-(1-butyl-3-methylimidazolium bromide) combination: some synthetic applications.

PubMed

Goswami, Dibakar; Koli, Mrunesh R; Chatterjee, Sucheta; Chattopadhyay, Subrata; Sharma, Anubha

2017-05-03

The Bi-[bmim][Br] combination has been found to offer high syn-selectivity in the crotylation of aldehydes with crotyl bromide using practically stoichiometric amounts of the reagents. The room temperature ionic liquid (RTIL), [bmim][Br], activated Bi metal in the presence of oxygen to produce crotylbismuthdibromide, which reacted with the aldehydes at room temperature. The major anti-syn diastereomeric product obtained from the crotylation of (R)-cyclohexylideneglyceraldehyde was utilized for the synthesis of dictyostatin and cryptophycin segments, and (+)-cis-aerangis lactone, using standard synthetic protocols.

Temperature tunable micellization of polystyrene-block-poly(2-vinylpyridine) at Si-ionic liquid interface.

PubMed

Lu, Haiyun; Lee, Dong Hyun; Russell, Thomas P

2010-11-16

Highly ordered and stable micelles formed from both symmetric and asymmetric block copolymers of polystyrene-block-poly(2-vinylpyridine) (PS-b-P2VP) at the Si-ionic liquid (IL) interface have been investigated by scanning force microscopy (SFM) and transmission electron microscopy (TEM). The 1-butyl-3-methylimidazolium trifluoromethanesulfonate IL, a selective and temperature-tunable solvent for the P2VP block, was used and gave rise to block copolymer micelles having different morphologies that strongly depended on the annealing temperature. The effects of film thickness, molecular weight of block copolymers, and experimental conditions, such as preannealing, rinsing, and substrate properties, on the morphologies of block copolymer micelles were also studied. In addition, spherical micelles consisting of PS core and P2VP shell could also be obtained by core-corona inversion by annealing the as-coated micellar film in the IL at high temperatures. The possible mechanism for micelle formation is discussed.

Absorption degree analysis on biogas separation with ionic liquid systems.

PubMed

Zhang, Xin; Zhang, Suojiang; Bao, Di; Huang, Ying; Zhang, Xiangping

2015-01-01

For biogas upgrading, present work mainly focuses on either thermodynamics or mass transfer properties. A systematical study on these two aspects is important for developing a new biogas separation process. In this work, a new criterion "absorption degree", which combines both thermodynamics and mass transfer properties, was proposed for the first time to comprehensively evaluate the absorption performance. Henry's law constants of CO2 and CH4 in ionic liquids-polyethylene glycol dimethyl ethers mixtures were investigated. The liquid-side mass transfer coefficients (kL) were determined. The results indicate that IL-NHD mixtures exhibit not only a high CO2/CH4 selectivity, but also a fast kL for CO2 absorption. The [bmim][NO3]+NHD mixtures present a high absorption degree value for CO2 but a low value for CH4. For presenting a highest relative absorption degree value, the 50wt% [bmim][NO3]+50wt% NHD mixture is recommended for biogas upgrading. Copyright © 2014 Elsevier Ltd. All rights reserved.

Highly Conductive Ionic-Liquid Gels Prepared with Orthogonal Double Networks of a Low-Molecular-Weight Gelator and Cross-Linked Polymer.

PubMed

Kataoka, Toshikazu; Ishioka, Yumi; Mizuhata, Minoru; Minami, Hideto; Maruyama, Tatsuo

2015-10-21

We prepared a heterogeneous double-network (DN) ionogel containing a low-molecular-weight gelator network and a polymer network that can exhibit high ionic conductivity and high mechanical strength. An imidazolium-based ionic liquid was first gelated by the molecular self-assembly of a low-molecular-weight gelator (benzenetricarboxamide derivative), and methyl methacrylate was polymerized with a cross-linker to form a cross-linked poly(methyl methacrylate) (PMMA) network within the ionogel. Microscopic observation and calorimetric measurement revealed that the fibrous network of the low-molecular-weight gelator was maintained in the DN ionogel. The PMMA network strengthened the ionogel of the low-molecular-weight gelator and allowed us to handle the ionogel using tweezers. The orthogonal DNs produced ionogels with a broad range of storage elastic moduli. DN ionogels with low PMMA concentrations exhibited high ionic conductivity that was comparable to that of a neat ionic liquid. The present study demonstrates that the ionic conductivities of the DN and single-network, low-molecular-weight gelator or polymer ionogels strongly depended on their storage elastic moduli.

Suppressing Shuttle Effect Using Janus Cation Exchange Membrane for High-Performance Lithium-Sulfur Battery Separator.

PubMed

Li, Zhen; Han, Yu; Wei, Junhua; Wang, Wenqiang; Cao, Tiantian; Xu, Shengming; Xu, Zhenghe

2017-12-27

Suppressing the shuttle effect of polysulfide ions to obtain high durability and good electrochemical performance is of great concern in the field of lithium-sulfur batteries. To address this issue, a Janus membrane consisting of an ultrathin dense layer and a robust microporous layer is fabricated using cation exchange resin. Different from the composite membranes made from polyolefin membranes, the multiple layers of the Janus membrane in this study are synchronously generated by one step, getting rid of the additional complex coating processes. Excellent overall performance is obtained by the cooperation of multiple factors. The excellent ionic selectivity of cation exchange resin renders a great suppression of the shuttle effect, endowing the lithium-sulfur battery with high Coulombic efficiency of 92.0-99.0% (LiNO 3 -free electrolyte). The ultrathin property of a dense layer renders a low ionic resistance, resulting in 60% higher discharge capacity over the entire C-rates (versus the control sample with Celgard 2400 membrane). The robust macroporous layer supports the ultrathin layer to achieve a free-standing property, ensuring the usability of the Janus membrane.

Application of ionic liquid in liquid phase microextraction technology.

PubMed

Han, Dandan; Tang, Baokun; Lee, Yu Ri; Row, Kyung Ho

2012-11-01

Ionic liquids (ILs) are novel nonmolecular solvents. Their unique properties, such as high thermal stability, tunable viscosity, negligible vapor pressure, nonflammability, and good solubility for inorganic and organic compounds, make them excellent candidates as extraction media for a range of microextraction techniques. Many physical properties of ILs can be varied, and the structural design can be tuned to impart the desired functionality and enhance the analyte extraction selectivity, efficiency, and sensitivity. This paper provides an overview of the applications of ILs in liquid phase microextraction technology, such as single-drop microextraction, hollow fiber based liquid phase microextraction, and dispersive liquid-liquid microextraction. The sensitivity, linear calibration range, and detection limits for a range of target analytes in the methods were analyzed to determine the advantages of ILs in liquid phase microextraction. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermoelectric Properties of the Ca1- x R x MnO3 Perovskite System (R: Pr, Nd, Sm) for High-Temperature Applications

NASA Astrophysics Data System (ADS)

Choi, Soon-Mok; Lim, Chang-Hyun; Seo, Won-Seon

2011-05-01

Perovskite oxides have attracted considerable attention in the area of thermoelectrics owing to the advantages of their isotropic crystal structure and straightforward control of their electrical properties. Among the many perovskites, different types of polycrystalline Ca1- x R x MnO3 (R: Pr, Nd, Sm) were prepared by solid-state reaction in this study. Three different rare-earth dopants were substituted at the Ca-ion site at various amounts. Considering phase stability, rare-earth ions with nearly the same ionic radius as Ca2+ were selected. To assess thermoelectric performance, the electrical conductivity, Seebeck coefficient, and power factor were measured, and phase analysis was conducted. The effects of ionic radius variation on single phase formation and the effect of doping amount on carrier concentration are discussed.

Molecular origin of high free energy barriers for alkali metal ion transfer through ionic liquid-graphene electrode interfaces.

PubMed

Ivaništšev, Vladislav; Méndez-Morales, Trinidad; Lynden-Bell, Ruth M; Cabeza, Oscar; Gallego, Luis J; Varela, Luis M; Fedorov, Maxim V

2016-01-14

In this work we study mechanisms of solvent-mediated ion interactions with charged surfaces in ionic liquids by molecular dynamics simulations, in an attempt to reveal the main trends that determine ion-electrode interactions in ionic liquids. We compare the interfacial behaviour of Li(+) and K(+) at a charged graphene sheet in a room temperature ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate, and its mixtures with lithium and potassium tetrafluoroborate salts. Our results show that there are dense interfacial solvation structures in these electrolytes that lead to the formation of high free energy barriers for these alkali metal cations between the bulk and direct contact with the negatively charged surface. We show that the stronger solvation of Li(+) in the ionic liquid leads to the formation of significantly higher interfacial free energy barriers for Li(+) than for K(+). The high free energy barriers observed in our simulations can explain the generally high interfacial resistance in electrochemical storage devices that use ionic liquid-based electrolytes. Overcoming these barriers is the rate-limiting step in the interfacial transport of alkali metal ions and, hence, appears to be a major drawback for a generalised application of ionic liquids in electrochemistry. Some plausible strategies for future theoretical and experimental work for tuning them are suggested.

Electroactive nanostructured polymer actuators fabricated using sulfonated styrenic pentablock copolymer/montmorillonite/ionic liquid nanocomposite membranes

NASA Astrophysics Data System (ADS)

Lee, Jang-Woo; Hong, Soon Man; Koo, Chong Min

2014-08-01

High-bendable, air-operable ionic polymer-metal composite (IPMC) actuators composed of electroactive nanostructured middle-block sulfonated styrenic pentablock copolymer (SSPB)/sulfonated montmorillonite (s-MMT) nanocomposite electrolyte membranes with bulky imidazolium ionic liquids (ILs) incorporated were fabricated and their bending actuation performances were evaluated. The SSPB-based IPMC actuators showed larger air-operable bending displacements, higher displacement rates, and higher energy efficiency of actuations without conventional IPMC bottlenecks, including back relaxation and actuation instability during actuation in air, than the Nafion counterpart. Incorporation of s-MMT into the SSPB matrix further enhanced the actuation performance of the IPMC actuators in terms of displacement, displacement rate, and energy efficiency. The remarkably high performance of the SSPB/s-MMT/IL IPMCs was considered to be due to the microphase-separated large ionic domains of the SSPB (the average diameter of the ionic domain: ca. 20 nm) and the role of s-MMT as an ionic bridge between the ionic domains, and the ion pumping effect of the bulky imidazolium cations of the ILs as well. The microphase-separated nanostructure of the composite membranes caused a high dimensional stability upon swelling in the presence of ILs, which effectively preserved the original electrode resistance against swelling, leading to a high actuation performance of IPMC.

Benzyl-Functionalized Room Temperature Ionic Liquids for CO2/N2 Separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mahurin, Shannon Mark; Dai, Thomas N; Yeary, Joshua S

2011-01-01

In this work, three classes of room temperature ionic liquids (RTILs), including imidazolium, pyridinium, and pyrrolidinium ionic liquids with a benzyl group appended to the cation, were synthesized and tested for their performance in separating CO{sub 2} and N{sub 2}. All RTILs contained the bis(trifluoromethylsulfonyl)imide anion, permitting us to distinguish the impact of the benzyl moiety attached to the cation on gas separation performance. In general, the attachment of the benzyl group increased the viscosity of the ionic liquid compared with the unfunctionalized analogs and decreased the CO{sub 2} permeability. However, all of the benzyl-modified ionic liquids exhibited enhanced CO{submore » 2}/N{sub 2} selectivities compared with alkyl-based ionic liquids, with values ranging from 22.0 to 33.1. In addition, CO{sub 2} solubilities in the form of Henry's constants were also measured and compared with unfunctionalized analogs. Results of the membrane performance tests and CO{sub 2} solubility measurements demonstrate that the benzyl-functionalized RTILs have significant potential for use in the separation of carbon dioxide from combustion products.« less

Surface effects on ionic Coulomb blockade in nanometer-size pores

NASA Astrophysics Data System (ADS)

Tanaka, Hiroya; Iizuka, Hideo; Pershin, Yuriy V.; Di Ventra, Massimiliano

2018-01-01

Ionic Coulomb blockade in nanopores is a phenomenon that shares some similarities but also differences with its electronic counterpart. Here, we investigate this phenomenon extensively using all-atom molecular dynamics of ionic transport through nanopores of about one nanometer in diameter and up to several nanometers in length. Our goal is to better understand the role of atomic roughness and structure of the pore walls in the ionic Coulomb blockade. Our numerical results reveal the following general trends. First, the nanopore selectivity changes with its diameter, and the nanopore position in the membrane influences the current strength. Second, the ionic transport through the nanopore takes place in a hopping-like fashion over a set of discretized states caused by local electric fields due to membrane atoms. In some cases, this creates a slow-varying ‘crystal-like’ structure of ions inside the nanopore. Third, while at a given voltage, the resistance of the nanopore depends on its length, the slope of this dependence appears to be independent of the molarity of ions. An effective kinetic model that captures the ionic Coulomb blockade behavior observed in MD simulations is formulated.

Surface effects on ionic Coulomb blockade in nanometer-size pores.

PubMed

Tanaka, Hiroya; Iizuka, Hideo; Pershin, Yuriy V; Ventra, Massimiliano Di

2018-01-12

Ionic Coulomb blockade in nanopores is a phenomenon that shares some similarities but also differences with its electronic counterpart. Here, we investigate this phenomenon extensively using all-atom molecular dynamics of ionic transport through nanopores of about one nanometer in diameter and up to several nanometers in length. Our goal is to better understand the role of atomic roughness and structure of the pore walls in the ionic Coulomb blockade. Our numerical results reveal the following general trends. First, the nanopore selectivity changes with its diameter, and the nanopore position in the membrane influences the current strength. Second, the ionic transport through the nanopore takes place in a hopping-like fashion over a set of discretized states caused by local electric fields due to membrane atoms. In some cases, this creates a slow-varying 'crystal-like' structure of ions inside the nanopore. Third, while at a given voltage, the resistance of the nanopore depends on its length, the slope of this dependence appears to be independent of the molarity of ions. An effective kinetic model that captures the ionic Coulomb blockade behavior observed in MD simulations is formulated.

Correlation between ion diffusional motion and ionic conductivity for different electrolytes based on ionic liquid.

PubMed

Kaur, Dilraj Preet; Yamada, K; Park, Jin-Soo; Sekhon, S S

2009-04-23

Room temperature ionic liquid 2,3-dimethyl-1-hexylimidazolium bis(trifluoromethane sulfonyl)imide (DMHxImTFSI) has been synthesized and used in the preparation of polymer gel electrolytes containing polymethylmethacrylate and propylene carbonate (PC). The onset of ion diffusional motion has been studied by (1)H and (19)F NMR spectroscopy and the results obtained for ionic liquid, liquid electrolytes, and polymer gel electrolytes have been correlated with the ionic conductivity results for these electrolytes in the 100-400 K temperature range. The temperature at which (1)H and (19)F NMR lines show motional narrowing and hence ion diffusional motion starts has been found to be closely related to the temperature at which a large increase in ionic conductivity has been observed for these electrolytes. Polymer gel electrolytes have high ionic conductivity over a wide range of temperatures. Thermogravimetric analysis/differential scanning calorimetry studies show that the ionic liquid (DMHxImTFSI) used in the present study is thermally stable up to 400 degrees C, whereas the addition of PC lowers the thermal stability of polymer gel electrolytes containing the ionic liquid. Different electrolytes have been observed to show high ionic conductivity in different range of temperatures, which can be helpful in the design of polymer gel electrolytes for specific applications.

Microcontact Printing of Thiol-Functionalized Ionic Liquid Microarrays for "Membrane-less" and "Spill-less" Gas Sensors.

PubMed

Gondosiswanto, Richard; Gunawan, Christian A; Hibbert, David B; Harper, Jason B; Zhao, Chuan

2016-11-16

Lab-on-a-chip systems have gained significant interest for both chemical synthesis and assays at the micro-to-nanoscale with a unique set of benefits. However, solvent volatility represents one of the major hurdles to the reliability and reproducibility of the lab-on-a-chip devices for large-scale applications. Here we demonstrate a strategy of combining nonvolatile and functionalized ionic liquids with microcontact printing for fabrication of "wall-less" microreactors and microfluidics with high reproducibility and high throughput. A range of thiol-functionalized ionic liquids have been synthesized and used as inks for microcontact printing of ionic liquid microdroplet arrays onto gold chips. The covalent bonds formed between the thiol-functionalized ionic liquids and the gold substrate offer enhanced stability of the ionic liquid microdroplets, compared to conventional nonfunctionalized ionic liquids, and these microdroplets remain stable in a range of nonpolar and polar solvents, including water. We further demonstrate the use of these open ionic liquid microarrays for fabrication of "membrane-less" and "spill-less" gas sensors with enhanced reproducibility and robustness. Ionic-liquid-based microarray and microfluidics fabricated using the described microcontact printing may provide a versatile platform for a diverse number of applications at scale.

Biological Activity of Ionic Liquids and Their Application in Pharmaceutics and Medicine.

PubMed

Egorova, Ksenia S; Gordeev, Evgeniy G; Ananikov, Valentine P

2017-05-24

Ionic liquids are remarkable chemical compounds, which find applications in many areas of modern science. Because of their highly tunable nature and exceptional properties, ionic liquids have become essential players in the fields of synthesis and catalysis, extraction, electrochemistry, analytics, biotechnology, etc. Apart from physical and chemical features of ionic liquids, their high biological activity has been attracting significant attention from biochemists, ecologists, and medical scientists. This Review is dedicated to biological activities of ionic liquids, with a special emphasis on their potential employment in pharmaceutics and medicine. The accumulated data on the biological activity of ionic liquids, including their antimicrobial and cytotoxic properties, are discussed in view of possible applications in drug synthesis and drug delivery systems. Dedicated attention is given to a novel active pharmaceutical ingredient-ionic liquid (API-IL) concept, which suggests using traditional drugs in the form of ionic liquid species. The main aim of this Review is to attract a broad audience of chemical, biological, and medical scientists to study advantages of ionic liquid pharmaceutics. Overall, the discussed data highlight the importance of the research direction defined as "Ioliomics", studies of ions in liquids in modern chemistry, biology, and medicine.

Lewis Acidic Ionic Liquids.

PubMed

Brown, Lucy C; Hogg, James M; Swadźba-Kwaśny, Małgorzata

2017-08-21

Until very recently, the term Lewis acidic ionic liquids (ILs) was nearly synonymous with halometallate ILs, with a strong focus on chloroaluminate(III) systems. The first part of this review covers the historical context in which these were developed, speciation of a range of halometallate ionic liquids, attempts to quantify their Lewis acidity, and selected recent applications: in industrial alkylation processes, in supported systems (SILPs/SCILLs) and in inorganic synthesis. In the last decade, interesting alternatives to halometallate ILs have emerged, which can be divided into two sub-sections: (1) liquid coordination complexes (LCCs), still based on halometallate species, but less expensive and more diverse than halometallate ionic liquids, and (2) ILs with main-group Lewis acidic cations. The two following sections cover these new liquid Lewis acids, also highlighting speciation studies, Lewis acidity measurements, and applications.

High-performance ionic diode membrane for salinity gradient power generation.

PubMed

Gao, Jun; Guo, Wei; Feng, Dan; Wang, Huanting; Zhao, Dongyuan; Jiang, Lei

2014-09-03

Salinity difference between seawater and river water is a sustainable energy resource that catches eyes of the public and the investors in the background of energy crisis. To capture this energy, interdisciplinary efforts from chemistry, materials science, environmental science, and nanotechnology have been made to create efficient and economically viable energy conversion methods and materials. Beyond conventional membrane-based processes, technological breakthroughs in harvesting salinity gradient power from natural waters are expected to emerge from the novel fluidic transport phenomena on the nanoscale. A major challenge toward real-world applications is to extrapolate existing single-channel devices to macroscopic materials. Here, we report a membrane-scale nanofluidic device with asymmetric structure, chemical composition, and surface charge polarity, termed ionic diode membrane (IDM), for harvesting electric power from salinity gradient. The IDM comprises heterojunctions between mesoporous carbon (pore size ∼7 nm, negatively charged) and macroporous alumina (pore size ∼80 nm, positively charged). The meso-/macroporous membrane rectifies the ionic current with distinctly high ratio of ca. 450 and keeps on rectifying in high-concentration electrolytes, even in saturated solution. The selective and rectified ion transport furthermore sheds light on salinity-gradient power generation. By mixing artificial seawater and river water through the IDM, substantially high power density of up to 3.46 W/m(2) is discovered, which largely outperforms some commercial ion-exchange membranes. A theoretical model based on coupled Poisson and Nernst-Planck equations is established to quantitatively explain the experimental observations and get insights into the underlying mechanism. The macroscopic and asymmetric nanofluidic structure anticipates wide potentials for sustainable power generation, water purification, and desalination.

An optimized procedure for preconcentration, determination and on-line recovery of palladium using highly selective diphenyldiketone-monothiosemicarbazone modified silica gel.

PubMed

Sharma, R K; Pandey, Amit; Gulati, Shikha; Adholeya, Alok

2012-03-30

A novel, highly selective, efficient and reusable chelating resin, diphenyldiketone-monothiosemicarbazone modified silica gel, was prepared and applied for the on-line separation and preconcentration of Pd(II) ions in catalytic converter and spiked tap water samples. Several parameters like effect of pH, sample volume, flow rate, type of eluent, and influence of various ionic interferences, etc. were evaluated for effective adsorption of palladium at trace levels. The resin was found to be highly selective for Pd(II) ions in the pH range 4-5 with a very high sorption capacity of 0.73 mmol/g and preconcentration factor of 335. The present environment friendly procedure has also been applied for large-scale extraction by employing the use of newly designed reactor in which on-line separation and preconcentration of Pd can be carried out easily and efficiently in short duration of time. Copyright © 2012 Elsevier B.V. All rights reserved.

Computational solvation analysis of biomolecules in aqueous ionic liquid mixtures : From large flexible proteins to small rigid drugs.

PubMed

Zeindlhofer, Veronika; Schröder, Christian

2018-06-01

Based on their tunable properties, ionic liquids attracted significant interest to replace conventional, organic solvents in biomolecular applications. Following a Gartner cycle, the expectations on this new class of solvents dropped after the initial hype due to the high viscosity, hydrolysis, and toxicity problems as well as their high cost. Since not all possible combinations of cations and anions can be tested experimentally, fundamental knowledge on the interaction of the ionic liquid ions with water and with biomolecules is mandatory to optimize the solvation behavior, the biodegradability, and the costs of the ionic liquid. Here, we report on current computational approaches to characterize the impact of the ionic liquid ions on the structure and dynamics of the biomolecule and its solvation layer to explore the full potential of ionic liquids.

Enzymes immobilized on amine-terminated ionic liquid-functionalized carbon nanotube for hydrogen peroxide determination.

PubMed

Liu, Xiuhui; Bu, Caihong; Nan, Zhihan; Zheng, Lichun; Qiu, Yu; Lu, Xiaoquan

2013-02-15

We report on a new approach for the electrochemical detection of hydrogen peroxide (H2O2) based on Cytochrome C (Cyt c) immobilized ionic liquid (IL)-functionalized multi-walled carbon nanotubes (MWCNTs) modified glass carbon electrode (GCE). Functionalization of multi-walled carbon nanotube with amine-terminated ionic liquid materials was characterized using fourier transform infrared spectroscopy (FTIR), UV-vis spectra, and electrochemical impedance spectroscopy (EIS), and the results showed that the covalent modification of MWCNTs with ILs exhibited a high surface area for enzyme immobilization and provided a good microenvironment for Cyt c to retain its bioelectrocatalytic activity toward H2O2. Amperometry was used to evaluate the catalytic activity of the cyt c towards H2O2. The proposed biosensor exhibited a wide linear response range nearly 4 orders of magnitude of H2O2 (4.0 × 10(-8)M-1.0 × 10(-4)M) with a good linearity (0.9980) and a low detection limit of 1.3 × 10(-8)M (based on S/N=3). Furthermore, the biosensor also displays some other excellent characteristics such as high selectivity, good reproducibility and long-term stability. Thus, the biosensor constructed in this study has great potential for detecting H2O2 in the complex biosystems. Copyright © 2012 Elsevier B.V. All rights reserved.

High-Speed Lateral Flow Strategy for a Fast Biosensing with an Improved Selectivity and Binding Affinity.

PubMed

Cho, Dong Guk; Yoo, Haneul; Lee, Haein; Choi, Yeol Kyo; Lee, Minju; Ahn, Dong June; Hong, Seunghun

2018-05-10

We report a high-speed lateral flow strategy for a fast biosensing with an improved selectivity and binding affinity even under harsh conditions. In this strategy, biosensors were fixed at a location away from the center of a round shape disk, and the disk was rotated to create the lateral flow of a target solution on the biosensors during the sensing measurements. Experimental results using the strategy showed high reaction speeds, high binding affinity, and low nonspecific adsorptions of target molecules to biosensors. Furthermore, binding affinity between target molecules and sensing molecules was enhanced even in harsh conditions such as low pH and low ionic strength conditions. These results show that the strategy can improve the performance of conventional biosensors by generating high-speed lateral flows on a biosensor surface. Therefore, our strategy can be utilized as a simple but powerful tool for versatile bio and medical applications.

Ionic Liquids as Quasihydrostatic Pressure Media for Diamond Anvil Cell Experiments

NASA Astrophysics Data System (ADS)

Mayorga, Sierra; Moldowan, Kaela; Dan, Ioana; Forster, Paul; Iota, Valentin

2012-02-01

Ionic liquids (ILs) are salts in which the ions are poorly coordinated to the point where the eutectic mixture remains liquid at room temperature. In general, ILs exhibit high chemical and thermal stability, have extended liquid regions in the pressure-temperature domain, and can be easily obtained. Commercial ionic liquids are relatively inexpensive and custom ionic solutions can be easily synthesized by mixing common reactants. These properties make ionic liquids attractive candidates for high-pressure media in Diamond Anvil Cell (DAC) experiments. In this presentation we explore the use of ionic liquids as DAS quasihydrostatic pressure media for pressures up to 50 GPa. As a measure of hydrostaticity we monitor the splitting and peak-widths of the R1 andR 2 fluorescence lines from small ruby chips (Al2O3 :Cr^3+) imbedded in the pressure medium. We present results on a series of commercially available ionic fluids against standard pressure media: methanol-ethanol mixtures, silicone oil, sodium chloride (NaCl) and noble gases (Ar, Ne, He).

A model of ion transport processes along and across the neuronal membrane.

PubMed

Xiang, Z X; Liu, G Z; Tang, C X; Yan, L X

2017-01-01

In this study, we provide a foundational model of ion transport processes in the intracellular and extracellular compartments of neurons at the nanoscale. There are two different kinds of ionic transport processes: (i) ionic transport across the neuronal membrane (trans-membrane), and (ii) ionic transport along both the intracellular and extracellular surfaces of the membrane. Brownian dynamics simulations are used to give a description of ionic trans-membrane transport. Electro-diffusion is used to model ion transport along the membrane surface, and the two transport processes can be linked analytically. In our model, we found that the interactions between ions and ion channels result in high-frequency ionic oscillations during trans-membrane transport. In ion transport along the membrane, high-frequency ionic oscillations may be evoked on both the intracellular and extracellular surfaces of the plasma membrane. The electric field caused by Coulomb interactions between the ions is found to be the most likely origin of those ionic oscillations.

Combination of counterpropagation artificial neural networks and antioxidant activities for comprehensive evaluation of associated-extraction efficiency of various cyclodextrins in the traditional Chinese formula Xue-Zhi-Ning.

PubMed

Sun, Lili; Yang, Jianwen; Wang, Meng; Zhang, Huijie; Liu, Yanan; Ren, Xiaoliang; Qi, Aidi

2015-11-10

Xue-Zhi-Ning (XZN) is a widely used traditional Chinese medicine formula to treat hyperlipidemia. Recently, cyclodextrins (CDs) have been extensively used to minimize problems relative to medicine bioavailability, such as low solubility and poor stability. The objective of this study was to determine the associated-extraction efficiency of various CDs in XZN. Three various type CDs were evaluated, including native CDs (α-CD, β-CD), hydrophilic CD derivatives (HP-β-CD and Me-β-CD), and ionic CD derivatives (SBE-β-CD and CM-β-CD). An ultra high-performance liquid chromatography (UHPLC) fingerprint was applied to determine the components in CD extracts and original aqueous extract (OAE). A counterpropagation artificial neural network (CP-ANN) was used to analyze the components in different extracts and compare the selective extraction of various CDs. Extraction efficiencies of the various CDs in terms of extracted components follow the ranking, ionic CD derivatives>hydrophilic CD derivatives>native CDs>OAE. Besides, different types of CDs have their own selective extraction and ionic CD derivatives present the strongest associated-extraction efficiency. Antioxidant potentials of various extracts were evaluated by determining the inhibition of spontaneous, H2O2-induced, CCl4-induced and Fe(2+)/ascorbic acid-induced lipid peroxidation (LPO) and analyzing the scavenging capacity for DPPH and hydroxyl radicals. The order of extraction efficiencies of the various CDs relative to antioxidant activities is as follows: SBE-β-CD>CM-β-CD>HP-β-CD>Me-β-CD>β-CD>α-CD. It can be demonstrated that all of the CDs studied increase the extraction efficiency and that ionic CD derivatives (SBE-β-CD and CM-β-CD) present the highest extraction capability in terms of amount extracted and antioxidant activities of extracts. Copyright © 2015 Elsevier B.V. All rights reserved.

Synthesis and Properties of Highly Dispersed Ionic Silica–Poly(ethylene oxide) Nanohybrids

PubMed Central

2013-01-01

We report an ionic hybrid based on silica nanoparticles as the anion and amine-terminated poly(ethylene oxide) (PEO) as a cation. The charge on the nanoparticle anion is carried by the surface hydroxyls. SAXS and TEM reveal an exceptional degree of dispersion of the silica in the polymer and high degree of order in both thin film and bulk forms. In addition to better dispersion, the ionic hybrid shows improved flow characteristics compared to silica/PEO mixtures in which the ionic interactions are absent. PMID:23351113

Sulfur tolerant hydrophobic ionic liquid solvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luebke, David; Nulwala, Hunaid; Kail, Brian

Exemplary embodiments relate to methods for removal of CO.sub.2 and other acid gases from gaseous fuels prior to combustion. Exemplary methods may be used for CO.sub.2 capture, H.sub.2 purification and natural gas sweetening. Exemplary methods use at least one ionic liquid that has excellent CO.sub.2 solubility, selectivity over hydrogen, low viscosity, and resistance to H.sub.2S.

Block Copolymers and Ionic Liquids: A New Class of Functional Nanocomposites

NASA Astrophysics Data System (ADS)

Lodge, Timothy

2009-03-01

Block copolymers provide a remarkably versatile platform for achieving desired nanostructures by self-assembly, with lengthscales varying from a few nanometers up to several hundred nanometers. Ionic liquids are an emerging class of solvents, with an appealing set of physical attributes. These include negligible vapor pressure, high chemical and thermal stability, tunable solvation properties, high ionic conductivity, and wide electrochemical windows. For various applications it will be necessary to solidify the ionic liquid into particular spatial arrangements, such as membranes or gels, or to partition the ionic liquid in coexisting phases, such as microemulsions and micelles. One example includes formation of spherical, cylindrical, and vesicular micelles by poly(butadiene-b-ethylene oxide) and poly(styrene-b-methylmethacrylate) in the common hydrophobic ionic liquids [BMI][PF6] and [EMI][TFSI]. This work has been extended to the formation of reversible micelle shuttles between ionic liquids and water, whereby entire micelles transfer from one phase to the other, reversibly, depending on temperature and solvent quality. Formation of ion gels has been achieved by self-assembly of poly(styrene-b-ethylene oxide-b-styrene) triblocks in ionic liquids, and by the thermoreversible system poly(N-isopropylacrylamide-b-ethylene oxide-b-N-isopropylacrylamide), using as little as 4% copolymer. Further, these gels have been shown to be remarkably effective as gate dielectrics in organic thin film transistors. The remarkably high capacitance of the ion gels (> 10 μF/cm^2) supports a very high carrier density in an organic semiconductor such as poly(3-hexylthiophene), leading to milliamp currents for low applied voltages. Furthermore, the rapid mobility of the ions enables switching speeds approaching 10 kHz, orders of magnitude higher than achievable with other polymer-based dielectrics such as PEO/LiClO4. Finally, we have shown that ordered nanostructures of block copolymers plus ionic liquids show the characteristic self-assembly properties of strongly-segregated systems. Prospects for anisotropic ionic conductivity are also being explored.

Stability and ionic mobility in argyrodite-related lithium-ion solid electrolytes.

PubMed

Chen, Hao Min; Maohua, Chen; Adams, Stefan

2015-07-07

In the search for fast lithium-ion conducting solids for the development of safe rechargeable all-solid-state batteries with high energy density, thiophosphates and related compounds have been demonstrated to be particularly promising both because of their record ionic conductivities and their typically low charge transfer resistances. In this work we explore a wide range of known and predicted thiophosphates with a particular focus on the cubic argyrodite phase with a robust three-dimensional network of ion migration pathways. Structural and hydrolysis stability are calculated employing density functional method in combination with a generally applicable method of predicting the relevant critical reaction. The activation energy for ion migration in these argyrodites is then calculated using the empirical bond valence pathway method developed in our group, while bandgaps of selected argyrodites are calculated as a basis for assessing the electrochemical window. Findings for the lithium compounds are also compared to those of previously known copper argyrodites and hypothetical sodium argyrodites. Therefrom, guidelines for experimental work are derived to yield phases with the optimum balance between chemical stability and ionic conductivity in the search for practical lithium and sodium solid electrolyte materials.

Electroactive Ionic Soft Actuators with Monolithically Integrated Gold Nanocomposite Electrodes.

PubMed

Yan, Yunsong; Santaniello, Tommaso; Bettini, Luca Giacomo; Minnai, Chloé; Bellacicca, Andrea; Porotti, Riccardo; Denti, Ilaria; Faraone, Gabriele; Merlini, Marco; Lenardi, Cristina; Milani, Paolo

2017-06-01

Electroactive ionic gel/metal nanocomposites are produced by implanting supersonically accelerated neutral gold nanoparticles into a novel chemically crosslinked ion conductive soft polymer. The ionic gel consists of chemically crosslinked poly(acrylic acid) and polyacrylonitrile networks, blended with halloysite nanoclays and imidazolium-based ionic liquid. The material exhibits mechanical properties similar to that of elastomers (Young's modulus ≈ 0.35 MPa) together with high ionic conductivity. The fabrication of thin (≈100 nm thick) nanostructured compliant electrodes by means of supersonic cluster beam implantation (SCBI) does not significantly alter the mechanical properties of the soft polymer and provides controlled electrical properties and large surface area for ions storage. SCBI is cost effective and suitable for the scaleup manufacturing of electroactive soft actuators. This study reports the high-strain electromechanical actuation performance of the novel ionic gel/metal nanocomposites in a low-voltage regime (from 0.1 to 5 V), with long-term stability up to 76 000 cycles with no electrode delamination or deterioration. The observed behavior is due to both the intrinsic features of the ionic gel (elasticity and ionic transport capability) and the electrical and morphological features of the electrodes, providing low specific resistance (<100 Ω cm -2 ), high electrochemical capacitance (≈mF g -1 ), and minimal mechanical stress at the polymer/metal composite interface upon deformation. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Direct Ionic Regulation of the Activity of Myo-Inositol Biosynthesis Enzymes in Mozambique Tilapia

PubMed Central

Villarreal, Fernando D.; Kültz, Dietmar

2015-01-01

Myo-inositol (Ins) is a major compatible osmolyte in many cells, including those of Mozambique tilapia (Oreochromis mossambicus). Ins biosynthesis is highly up-regulated in tilapia and other euryhaline fish exposed to hyperosmotic stress. In this study, enzymatic regulation of two enzymes of Ins biosynthesis, Ins phosphate synthase (MIPS) and inositol monophosphatase (IMPase), by direct ionic effects is analyzed. Specific MIPS and IMPase isoforms from Mozambique tilapia (MIPS-160 and IMPase 1) were selected based on experimental, phylogenetic, and structural evidence supporting their role for Ins biosynthesis during hyperosmotic stress. Recombinant tilapia IMPase 1 and MIPS-160 activity was assayed in vitro at ionic conditions that mimic changes in the intracellular milieu during hyperosmotic stress. The in vitro activities of MIPS-160 and IMPase 1 are highest at alkaline pH of 8.8. IMPase 1 catalytic efficiency is strongly increased during hyperosmolality (particularly for the substrate D-Ins-3-phosphate, Ins-3P), mainly as a result of [Na+] elevation. Furthermore, the substrate-specificity of IMPase 1 towards D-Ins-1-phosphate (Ins-1P) is lower than towards Ins-3P. Because MIPS catalysis results in Ins-3P this results represents additional evidence for IMPase 1 being the isoform that mediates Ins biosynthesis in tilapia. Our data collectively demonstrate that the Ins biosynthesis enzymes are activated under ionic conditions that cells are exposed to during hypertonicity, resulting in Ins accumulation, which, in turn, results in restoration of intracellular ion homeostasis. We propose that the unique and direct ionic regulation of the activities of Ins biosynthesis enzymes represents an efficient biochemical feedback loop for regulation of intracellular physiological ion homeostasis during hyperosmotic stress. PMID:26066044

Direct Ionic Regulation of the Activity of Myo-Inositol Biosynthesis Enzymes in Mozambique Tilapia.

PubMed

Villarreal, Fernando D; Kültz, Dietmar

2015-01-01

Myo-inositol (Ins) is a major compatible osmolyte in many cells, including those of Mozambique tilapia (Oreochromis mossambicus). Ins biosynthesis is highly up-regulated in tilapia and other euryhaline fish exposed to hyperosmotic stress. In this study, enzymatic regulation of two enzymes of Ins biosynthesis, Ins phosphate synthase (MIPS) and inositol monophosphatase (IMPase), by direct ionic effects is analyzed. Specific MIPS and IMPase isoforms from Mozambique tilapia (MIPS-160 and IMPase 1) were selected based on experimental, phylogenetic, and structural evidence supporting their role for Ins biosynthesis during hyperosmotic stress. Recombinant tilapia IMPase 1 and MIPS-160 activity was assayed in vitro at ionic conditions that mimic changes in the intracellular milieu during hyperosmotic stress. The in vitro activities of MIPS-160 and IMPase 1 are highest at alkaline pH of 8.8. IMPase 1 catalytic efficiency is strongly increased during hyperosmolality (particularly for the substrate D-Ins-3-phosphate, Ins-3P), mainly as a result of [Na+] elevation. Furthermore, the substrate-specificity of IMPase 1 towards D-Ins-1-phosphate (Ins-1P) is lower than towards Ins-3P. Because MIPS catalysis results in Ins-3P this results represents additional evidence for IMPase 1 being the isoform that mediates Ins biosynthesis in tilapia. Our data collectively demonstrate that the Ins biosynthesis enzymes are activated under ionic conditions that cells are exposed to during hypertonicity, resulting in Ins accumulation, which, in turn, results in restoration of intracellular ion homeostasis. We propose that the unique and direct ionic regulation of the activities of Ins biosynthesis enzymes represents an efficient biochemical feedback loop for regulation of intracellular physiological ion homeostasis during hyperosmotic stress.

Dynamic ultrasonic nebulisation extraction coupled with headspace ionic liquid-based single-drop microextraction for the analysis of the essential oil in Forsythia suspensa.

PubMed

Yang, Jinjuan; Wei, Hongmin; Teng, Xiane; Zhang, Hanqi; Shi, Yuhua

2014-01-01

Ionic liquids have attracted much attention as an extraction solvent instead of traditional organic solvent in single-drop microextraction. However, non-volatile ionic liquids are difficult to couple with gas chromatography. Thus, the following injection system for the determination of organic compounds is described. To establish an environmentally friendly, simple, and effective extraction method for preparation and analysis of the essential oil from aromatic plants. The dynamic ultrasonic nebulisation extraction was coupled with headspace ionic liquid-based single-drop microextraction(UNE-HS/IL/SDME)for the extraction of essential oils from Forsythia suspense fruits. After 13 min of extraction for 50 mg sample, the extracts in ionic liquid were evaporated rapidly in the gas chromatography injector through a thermal desorption unit (5 s). The traditional extraction method was carried out for comparative study. The optimum conditions were: 3 μL of 1-methyl-3-octylimidazolium hexafluorophosphate was selected as the extraction solvent, the sample amount was 50 mg, the flow rate of purging gas was 200 mL/min, the extraction time was 13 min, the injection volume was 2 μL, and the thermal desorption temperature and time were 240 °C and 5 s respectively. Comparing with hydrodistillation (HD), the proposed method was environment friendly and efficient. The proposed method is environmentally friendly, time saving, with high efficiency and low consumption. It would extend the application range of the HS/SDME and would be useful especially for aromatic plants analysis. Copyright © 2013 John Wiley & Sons, Ltd.

Hydroxyl-Exchanged Nanoporous Ionic Copolymer toward Low-Temperature Cycloaddition of Atmospheric Carbon Dioxide into Carbonates.

PubMed

Guo, Zengjing; Cai, Xiaochun; Xie, Jingyan; Wang, Xiaochen; Zhou, Yu; Wang, Jun

2016-05-25

An ionic copolymer catalyst with nanopores, large surface area, high ionic density, and superior basicity was prepared via the radical copolymerization of amino-functionalized ionic liquid bromide and divinylbenzene, followed with a hydroxyl exchange for removing bromonium. Evaluated in chemical fixation of CO2 with epoxides into cyclic carbonates in the absence of any solvent and basic additive, the nanoporous copolymer catalyst showed high and stable activity, superior to various control catalysts including the halogen-containing analogue. Further, high yields were obtained over a wide scope of substrates including aliphatic long carbon-chain alkyl epoxides and internal epoxide, even under atmospheric pressure and less than 100 °C for the majority of the substrates. On the basis of in situ Fourier transform infrared (FT-IR) investigation and density functional theory (DFT) calculation for the reaction intermediates, we proposed a possible reaction mechanism accounting for the superior catalytic activity of the ionic copolymer. The specifically prepared ionic copolymer material of this work features highly stable, noncorrosive, and sustainable catalysis and, thus, may be a new possibility for efficient chemical fixation of CO2 since it is an environmentally friendly, metal-free solid catalyst.

Thermal Decomposition Mechanism of 1-ethyl-3-methylimidazolium Bromide Ionic Liquid (Preprint)

DTIC Science & Technology

2011-09-14

TetraethylammoniumTrifluoromentanesulfonate Ionic Liquid and Neutralized Nafion 117 for High-Temperature Fuel Cells J. Am. Chem. Soc. 2010, 132, 2183-2195. (7) Kim, S. Y.; Kim, S...bromide 5b. GRANT NUMBER ionic liquid (Preprint) 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Steven D. Chambreau, Jerry A. Boatz, Ghanshyam L. Vaaghjiani...In order to better understand the volatilization process for ionic liquids , the vapor evolved from heating the ionic liquid 1-ethyl-3

Long-range electrostatic screening in ionic liquids

PubMed Central

Gebbie, Matthew A.; Dobbs, Howard A.; Valtiner, Markus; Israelachvili, Jacob N.

2015-01-01

Electrolyte solutions with high concentrations of ions are prevalent in biological systems and energy storage technologies. Nevertheless, the high interaction free energy and long-range nature of electrostatic interactions makes the development of a general conceptual picture of concentrated electrolytes a significant challenge. In this work, we study ionic liquids, single-component liquids composed solely of ions, in an attempt to provide a novel perspective on electrostatic screening in very high concentration (nonideal) electrolytes. We use temperature-dependent surface force measurements to demonstrate that the long-range, exponentially decaying diffuse double-layer forces observed across ionic liquids exhibit a pronounced temperature dependence: Increasing the temperature decreases the measured exponential (Debye) decay length, implying an increase in the thermally driven effective free-ion concentration in the bulk ionic liquids. We use our quantitative results to propose a general model of long-range electrostatic screening in ionic liquids, where thermally activated charge fluctuations, either free ions or correlated domains (quasiparticles), take on the role of ions in traditional dilute electrolyte solutions. This picture represents a crucial step toward resolving several inconsistencies surrounding electrostatic screening and charge transport in ionic liquids that have impeded progress within the interdisciplinary ionic liquids community. More broadly, our work provides a previously unidentified way of envisioning highly concentrated electrolytes, with implications for diverse areas of inquiry, ranging from designing electrochemical devices to rationalizing electrostatic interactions in biological systems. PMID:26040001

Ultraflexible and tailorable all-solid-state supercapacitors using polyacrylamide-based hydrogel electrolyte with high ionic conductivity.

PubMed

Li, Huili; Lv, Tian; Li, Ning; Yao, Yao; Liu, Kai; Chen, Tao

2017-11-30

Hydrogels with high ionic conductivity consisting of a cross-linked polymer network swollen in water are very promising to be used as an electrolyte for all-solid-state supercapacitors. However, there are rather few flexible supercapacitors using ionic conducting hydrogel electrolytes reported to date. In this work, highly flexible and ionic conducting polyacrylamide hydrogels were synthesized through a simple approach. On using the ionic hydrogels as the electrolyte, the resulting supercapacitors not only exhibited a high specific capacitance but also showed a long self-discharge time (over 10 hours to the half of original open-circuit voltage) and a low leakage current. These newly-developed all-solid-state supercapacitors can be bent, knot, and kneaded for 5000 cycles without performance decay, suggesting excellent flexibility and mechanical stability. These all-solid-state supercapacitors can also be easily tailored into strip-like supercapacitors without a short circuit, which provides an efficient approach to fabricate wearable energy storage devices.

Challenges in Determining Intrinsic Viscosity Under Low Ionic Strength Solution Conditions.

PubMed

Pindrus, Mariya A; Shire, Steven J; Yadav, Sandeep; Kalonia, Devendra S

2017-04-01

To determine the intrinsic viscosity of several monoclonal antibodies (mAbs) under varying pH and ionic strength solution conditions. An online viscosity detector attached to HPLC (Viscotek®) was used to determine the intrinsic viscosity of mAbs. The Ross and Minton equation was used for viscosity prediction at high protein concentrations. Bulk viscosity was determined by a Cambridge viscometer. At 15 mM ionic strength, intrinsic viscosity of the mAbs determined by the single-point approach varied from 5.6 to 6.4 mL/g with changes in pH. High ionic strength did not significantly alter intrinsic viscosity, while a significant increase (up to 24.0 mL/g) was observed near zero mM. No difference in bulk viscosity of mAb3 was observed around pH 6 as a function of ionic strength. Data analysis revealed that near zero mM ionic strength limitations of the single-point technique result in erroneously high intrinsic viscosity. Intrinsic viscosity is a valuable tool that can be used to model baseline viscosity at higher protein concentrations. However, it is not predictive of solution non-ideality at higher protein concentrations. Furthermore, breakdown of numerous assumptions limits the applicability of experimental techniques near zero mM ionic strength conditions. For molecules and conditions studied, the single-point approach produced reliable intrinsic viscosity results at 15 mM. However, this approach must be used with caution near zero mM ionic strength. Data analysis can be used to reveal whether determined intrinsic viscosity is reliable or erroneously high.

Phosphonium-based ionic liquids and their use in the capture of polluting gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Sheng; Wang, Congmin; Luo, Huimin

2017-06-06

An ionic liquid composition having the following chemical structural formula: ##STR00001## wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently selected from hydrocarbon groups containing at least 1 and up to 20 carbon atoms, and X.sup.- is a cyclic anion that possesses a negatively-charged group reactive with a gaseous electrophilic species, particularly carbon dioxide or sulfur dioxide. Methods for capturing a gaseous electrophilic species, such as CO.sub.2 or SO.sub.2, by contacting the gaseous electrophilic species with an ionic liquid according to Formula (1) are also described.

Composites comprising novel RTIL-based polymers, and methods of making and using same

DOEpatents

Gin, Douglas; Carlisle, Trevor; Noble, Richard; Nicodemus, Garret; McDanel, William; Cowan, Matthew

2017-06-27

The invention includes compositions comprising curable imidazolium-functionalized poly(room-temperature ionic liquid) copolymers and homopolymers. The invention further includes methods of preparing and using the compositions of the invention. The invention further includes novel methods of preparing thin, supported, room-temperature ionic liquid-containing polymeric films on a porous support. In certain embodiments, the methods of the invention avoid the use of a gutter layer, which greatly reduces the overall gas permeance and selectivity of the composite membrane. In other embodiments, the films of the invention have increased gas selectivity and permeance over films prepared using methods described in the prior art.

Intermolecular ionic cross-linked sulfonated poly(ether ether ketone) membranes containing diazafluorene for direct methanol fuel cell applications

NASA Astrophysics Data System (ADS)

Liang, Yu; Gong, Chenliang; Qi, Zhigang; Li, Hui; Wu, Zhongying; Zhang, Yakui; Zhang, Shujiang; Li, Yanfeng

2015-06-01

A series of novel ionic cross-linking sulfonated poly(ether ether ketone) (SPEEK) membranes containing the diazafluorene functional group are synthesized to reduce the swelling ratio and methanol permeability for direct methanol fuel cell (DMFC) applications. The ionic cross-linking is realized by the interaction between sulfonic acid groups and pyridyl in diazafluorene. The prepared membranes exhibit good mechanical properties, adequate thermal stability, good oxidative stability, appropriate water uptake and low swelling ratio. Moreover, the ionic cross-linked membranes exhibit lower methanol permeability in the range between 0.56 × 10-7 cm2 s-1 and 1.8 × 10-7 cm2 s-1, which is lower than Nafion 117, and they exhibit higher selectivity than Nafion 117 at 30 °C on the basis of applicable proton conductivity.

Radiation-grafted fluoropolymers soaked with imidazolium-based ionic liquids for high-performance ionic polymer-metal composite actuators.

PubMed

Lee, Jang Yeol; Wang, Hyuck Sik; Yoon, Bye Ri; Han, Man Jae; Jho, Jae Young

2010-11-01

On purpose to develop a polymer actuator with high stability in air-operation as well as large bending displacement, a series of ionic polymer-metal composites (IPMC) was constructed with poly(styrene sulfonate)-grafted fluoropolymers as ionomeric matrix and immidazolium-based ionic liquids (IL) as inner solvent. The prepared IPMC actuators exhibited greatly enhanced bending displacement compared to Nafion-based actuators. The actuators were stable in air-operation, maintaining initial displacement for up to 10(4) cycles or 24 h. Investigating the material parameters and morphology of the IPMCs, high ion exchange capacity of the ionomers resulted in high ion conductivity and robust electrode of IPMC, which synergistically contributed to the high bending performance. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single Nanochannel-Aptamer-Based Biosensor for Ultrasensitive and Selective Cocaine Detection.

PubMed

Wang, Jian; Hou, Jue; Zhang, Huacheng; Tian, Ye; Jiang, Lei

2018-01-17

Ultrasensitive and selective detection of molecules at nano or sub-nanomolar level is very important for many areas such as early diagnosis and drug testing. Herein, we report a high-sensitive cocaine sensor based on a single nanochannel coupled with DNA aptamers. The single nanochannel-aptamer-based biosensor can recognize cocaine molecules with an excellent sensitivity and good selectivity. A linear relationship between target cocaine concentration and output ionic current is obtained in a wide concentration range of cocaine from 1 nM to 10 μM. The cocaine sensor also shows a detection limit down to 1 nM. This study provides a new avenue to develop new nanochannel-aptamer-based biosensors for rapid and ultratrace detection of a variety of illicit drugs.

Effects of phosphonium-based ionic liquids on phospholipid membranes studied by small-angle X-ray scattering.

PubMed

Kontro, Inkeri; Svedström, Kirsi; Duša, Filip; Ahvenainen, Patrik; Ruokonen, Suvi-Katriina; Witos, Joanna; Wiedmer, Susanne K

2016-12-01

The effects of ionic liquids on model phospholipid membranes were studied by small-angle X-ray scattering, dynamic light scattering (DLS) and zeta potential measurements. Multilamellar 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine liposomes and large unilamellar vesicles composed of l-α-phosphatidylcholine (eggPC) and l-α-phosphatidylglycerol (eggPG) (80:20mol%) or eggPC, eggPG, and cholesterol (60:20:20mol%) were used as biomimicking membrane models. The effects of the phosphonium-based ionic liquids: tributylmethylphosphonium acetate, trioctylmethylphosphonium acetate, tributyl(tetradecyl)-phosphonium acetate, and tributyl(tetradecyl)-phosphonium chloride, were compared to those of 1-ethyl-3-methyl-imidazolium acetate. With multilamellar vesicles, the ionic liquids that did not disrupt liposomes decreased the lamellar spacing as a function of concentration. The magnitude of the effect depended on concentration for all studied ionic liquids. Using large unilamellar vesicles, first a slight decrease in the vesicle size, then aggregation of vesicles was observed by DLS for increasing ionic liquid concentrations. At concentrations just below those that caused aggregation of liposomes, large unilamellar vesicles were coated by ionic liquid cations, evidenced by a change in their zeta potential. The ability of phosphonium-based ionic liquids to affect liposomes is related to the length of the hydrocarbon chains in the cation. Generally, the ability of ionic liquids to disrupt liposomes goes hand in hand with inducing disorder in the phospholipid membrane. However, trioctylmethylphosphonium acetate selectively extracted and induced a well-ordered lamellar structure in phospholipids from disrupted cholesterol-containing large unilamellar vesicles. This kind of effect was not seen with any other combination of ionic liquids and liposomes. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Nanoscale Ionic Liquids

DTIC Science & Technology

2006-11-01

Technical Report 11 December 2005 - 30 November 2006 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER Nanoscale Ionic Liquids 5b. GRANT NUMBER FA9550-06-1-0012...Title: Nanoscale Ionic Liquids Principal Investigator: Emmanuel P. Giannelis Address: Materials Science and Engineering, Bard Hall, Cornell University...based fluids exhibit high ionic conductivity. The NFs are typically synthesized by grafting a charged, oligomeric corona onto the nanoparticle cores

Comparison of three different dispersive liquid-liquid microextraction modes performed on their most usual configurations for the extraction of phenolic, neutral aromatic, and amino compounds from waters.

PubMed

Saraji, Mohammad; Ghambari, Hoda

2018-06-21

In this work we seek clues to select the appropriate dispersive liquid-liquid microextraction mode for extracting three categories of compounds. For this purpose, three common dispersive liquid-liquid microextraction modes were compared under optimized conditions. Traditional dispersive liquid-liquid microextraction, in situ ionic liquid dispersive liquid-liquid microextraction and conventional ionic liquid dispersive liquid-liquid microextraction using chloroform, 1-butyl-3-methylimidazolium tetrafluoroborate, and 1-hexyl-3-methylimidazolium hexafluorophosphate as the extraction solvent, respectively, were considered in this work. Phenolic, neutral aromatic and amino compounds (each category included six members) were studied as analytes. The analytes in the extracts were determined by high-performance liquid chromatography with UV detection. For the analytes with polar functionalities, the in situ ionic liquid dispersive liquid-liquid microextraction mode mostly led to better results. In contrast, for neutral hydrocarbons without polar functionalities, traditional dispersive liquid-liquid microextraction using chloroform produced better results. In this case, where dispersion forces were the dominant interactions in the extraction, the refractive index of solvent and analyte predicted the extraction performance better than the octanol-water partition coefficient. It was also revealed that none of the methods were successful in extracting very hydrophilic analytes (compounds with the log octanol-water partition coefficient < 2). The results of this study could be helpful in selecting a dispersive liquid-liquid microextraction mode for the extraction of various groups of compounds. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Electroactive polymers for sensing

PubMed Central

2016-01-01

Electromechanical coupling in electroactive polymers (EAPs) has been widely applied for actuation and is also being increasingly investigated for sensing chemical and mechanical stimuli. EAPs are a unique class of materials, with low-moduli high-strain capabilities and the ability to conform to surfaces of different shapes. These features make them attractive for applications such as wearable sensors and interfacing with soft tissues. Here, we review the major types of EAPs and their sensing mechanisms. These are divided into two classes depending on the main type of charge carrier: ionic EAPs (such as conducting polymers and ionic polymer–metal composites) and electronic EAPs (such as dielectric elastomers, liquid-crystal polymers and piezoelectric polymers). This review is intended to serve as an introduction to the mechanisms of these materials and as a first step in material selection for both researchers and designers of flexible/bendable devices, biocompatible sensors or even robotic tactile sensing units. PMID:27499846

Membrane interactions of ionic liquids and imidazolium salts.

PubMed

Wang, Da; Galla, Hans-Joachim; Drücker, Patrick

2018-06-01

Room-temperature ionic liquids (RTILs) have attracted considerable attention in recent years due to their versatile properties such as negligible volatility, inflammability, high extractive selectivity and thermal stability. In general, RTILs are organic salts with a melting point below ~100 °C determined by the asymmetry of at least one of their ions. Due to their amphiphilic character, strong interactions with biological materials can be expected. However, rising attention has appeared towards their similarity and interaction with biomolecules. By employing structural modifications, the biochemical properties of RTILs can be designed to mimic lipid structures and to tune their hydrophobicity towards a lipophilic behavior. This is evident for the interaction with lipid-membranes where some of these compounds present membrane-disturbing effects or cellular toxicity. Moreover, they can form micelles or lipid-like bilayer structures by themselves. Both aspects, cellular effects and membrane-forming capacities, of a novel class of lipophilic imidazolium salts will be discussed.

Understanding cellulose dissolution: energetics of interactions of ionic liquids and cellobiose revealed by solution microcalorimetry.

PubMed

de Oliveira, Heitor Fernando Nunes; Rinaldi, Roberto

2015-05-11

In this report, the interactions between fifteen selected ionic liquids (ILs) and cellobiose (CB) are examined by high-precision solution microcalorimetry. The heat of mixing (Δmix H) of CB and ILs, or CB and IL/molecular solvent (MS) solutions, provides the first ever-published measure of the affinity of CB with ILs. Most importantly, we found that there is a very good correlation between the nature of the results found for Δmix H(CB) and the solubility behavior of cellulose. This correlation suggests that Δmix H(CB) offers a good estimate of the enthalpy of dissolution of cellulose even in solvents in which cellulose is insoluble. Therefore, the current findings open up new horizons for unravelling the intricacies of the thermodynamic factors accounting for the spontaneity of cellulose dissolution in ILs or IL/MS solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chirality-selected phase behaviour in ionic polypeptide complexes

DOE PAGES

Perry, Sarah L.; Leon, Lorraine; Hoffmann, Kyle Q.; ...

2015-01-14

In this study, polyelectrolyte complexes present new opportunities for self-assembled soft matter. Factors determining whether the phase of the complex is solid or liquid remain unclear. Ionic polypeptides enable examination of the effects of stereochemistry on complex formation. Here we demonstrate that chirality determines the state of polyelectrolyte complexes, formed from mixing dilute solutions of oppositely charged polypeptides, via a combination of electrostatic and hydrogen-bonding interactions. Fluid complexes occur when at least one of the polypeptides in the mixture is racemic, which disrupts backbone hydrogen-bonding networks. Pairs of purely chiral polypeptides, of any sense, form compact, fibrillar solids with amore » β-sheet structure. Analogous behaviour occurs in micelles formed from polypeptide block copolymers with polyethylene oxide, where assembly into aggregates with either solid or fluid cores, and eventually into ordered phases at high concentrations, is possible. Chirality is an exploitable tool for manipulating material properties in polyelectrolyte complexation.« less

Long-chain alkylimidazolium ionic liquids, a new class of cationic surfactants coated on ODS columns for anion-exchange chromatography.

PubMed

Qiu, Hongdeng; Zhang, Qinghua; Chen, Limei; Liu, Xia; Jiang, Shengxiang

2008-08-01

Separations of common inorganic anions were carried out on ODS columns coated with two long-chain alkylimidazolium ionic liquids ([C(12)MIm]Br and [C(14)MIm]Br) as new cationic surfactants for ion chromatography. With phthalate buffer solution as the mobile phases and non-suppressed conductivity detection, high column efficiencies and excellent selectivity were obtained in the separation of inorganic anions. Chromatographic parameters are calculated and the results show that the coated column possesses significant potential for the analysis of some inorganic anions such as CH(3)COO(-), IO(3)(-), Cl(-), BrO(3)(-), NO(2)(-), Br(-), NO(3)(-), SO(4)(2-), I(-), BF(4)(-), and SCN(-). The effect of eluent pH values on the separation of anions has been studied on the column coated with [C(12)MIm]Br. The stability of the coated columns was also examined.

Growth of Ionic Selectivity Prussian Blue Modified Celgard Separator for High Performance Lithium Sulfur Battery.

PubMed

Wu, Xian; Fan, Lishuang; Qiu, Yue; Wang, Maoxu; Cheng, Junhan; Guan, Bin; Guo, Zhikun; Zhang, Naiqing; Sun, Kening

2018-06-26

Lithium sulfur batteries have been restricted on their major technical problem of shuttling soluble polysulfides between electrodes, resulting in serious capacity fading. For purpose of develop a high-performance lithium-sulfur battery, we first time utilize a simple growth method to introduce a Prussian blue modified Celgard separator as an ion selective membrane in lithium sulfur batteries. The unique structure of Prussian blue could effectively suppress the shuttle of polysulfides but scarcely affect the transfer ability of lithium ions, which is beneficial to achieve high sulfur conversion efficiency and capacity retention. The lithium sulfur battery with Prussian blue modified Celgard separator reveals an average capacity decaying of only 0.03% per cycle at 1C after 1000 cycles. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanomechanics of layer-by-layer polyelectrolyte complexes: a manifestation of ionic cross-links and fixed charges.

PubMed

Han, Biao; Chery, Daphney R; Yin, Jie; Lu, X Lucas; Lee, Daeyeon; Han, Lin

2016-01-28

This study investigates the roles of two distinct features of ionically cross-linked polyelectrolyte networks - ionic cross-links and fixed charges - in determining their nanomechanical properties. The layer-by-layer assembled poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) network is used as the model material. The densities of ionic cross-links and fixed charges are modulated through solution pH and ionic strength (IS), and the swelling ratio, elastic and viscoelastic properties are quantified via an array of atomic force microscopy (AFM)-based nanomechanical tools. The roles of ionic cross-links are underscored by the distinctive elastic and viscoelastic nanomechanical characters observed here. First, as ionic cross-links are highly sensitive to solution conditions, the instantaneous modulus, E0, exhibits orders-of-magnitude changes upon pH- and IS-governed swelling, distinctive from the rubber elasticity prediction based on permanent covalent cross-links. Second, ionic cross-links can break and self-re-form, and this mechanism dominates force relaxation of PAH/PAA under a constant indentation depth. In most states, the degree of relaxation is >90%, independent of ionic cross-link density. The importance of fixed charges is highlighted by the unexpectedly more elastic nature of the network despite low ionic cross-link density at pH 2.0, IS 0.01 M. Here, the complex is a net charged, loosely cross-linked, where the degree of relaxation is attenuated to ≈50% due to increased elastic contribution arising from fixed charge-induced Donnan osmotic pressure. In addition, this study develops a new method for quantifying the thickness of highly swollen polymer hydrogel films. It also underscores important technical considerations when performing nanomechanical tests on highly rate-dependent polymer hydrogel networks. These results provide new insights into the nanomechanical characters of ionic polyelectrolyte complexes, and lay the ground for further investigation of their unique time-dependent properties.

Glued Langmuir-Blodgett bilayers from calix[ n]arenes: Influence of calix[ n]arene size on ionic cross-linking, film thickness, and permeation selectivity

DOE PAGES

Wang, Minghui; Janout, Vaclav; Regen, Steven L.

2010-07-12

A homologous series of calix[4]arene-, calix[5]arene- and calix[6]arene-based surfactants, containing pendant trimethylammonium and n-hexadecyl groups, have been compared with respect to their ability (i) to undergo ionic crosslinking at the air/water interface, (ii) to incorporate poly(4-styrenesulfonate) (PSS) in Langmuir-Blodgett (LB) bilayers, and (iii) to act as barriers towards He, N 2 and CO 2 when assembled into crosslinked LB bilayers. As these calix[n]arenes increase in size, their ability to undergo ionic crosslinking has been found to increase, the thickness of corresponding glued LB bilayers has been found to decrease, and their barrier properties and permeation selectivities have been found tomore » increase. In conclusion, the likely origin for these effects and the probable mechanism by which He, N 2 and CO 2 cross these ultrathin films are discussed.« less

Flexible single-layer ionic organic-inorganic frameworks towards precise nano-size separation

NASA Astrophysics Data System (ADS)

Yue, Liang; Wang, Shan; Zhou, Ding; Zhang, Hao; Li, Bao; Wu, Lixin

2016-02-01

Consecutive two-dimensional frameworks comprised of molecular or cluster building blocks in large area represent ideal candidates for membranes sieving molecules and nano-objects, but challenges still remain in methodology and practical preparation. Here we exploit a new strategy to build soft single-layer ionic organic-inorganic frameworks via electrostatic interaction without preferential binding direction in water. Upon consideration of steric effect and additional interaction, polyanionic clusters as connection nodes and cationic pseudorotaxanes acting as bridging monomers connect with each other to form a single-layer ionic self-assembled framework with 1.4 nm layer thickness. Such soft supramolecular polymer frameworks possess uniform and adjustable ortho-tetragonal nanoporous structure in pore size of 3.4-4.1 nm and exhibit greatly convenient solution processability. The stable membranes maintaining uniform porous structure demonstrate precisely size-selective separation of semiconductor quantum dots within 0.1 nm of accuracy and may hold promise for practical applications in selective transport, molecular separation and dialysis systems.

Potential Energy Surfaces and Dynamics of High Energy Species

DTIC Science & Technology

2009-04-13

explored include ionic liquids and a range of high-nitrogen content and nitrogen-oxygen content species. Polyhedral oligomeric silisesquioxanes are...Approved for Public Release 13. SUPPLEMENTARY NOTES 14. ABSTRACT Several papers on ionic liquids have been published or submitted as a result of this...in energetic ionic liquids . These are variously substituted triazolium, tertazolium, and pentazolium cations. The heats of formation of all species

Two-cation competition in ionic-liquid-modified electrolytes for lithium ion batteries.

PubMed

Lee, Sang-Young; Yong, Hyun Hang; Lee, Young Joo; Kim, Seok Koo; Ahn, Soonho

2005-07-21

It is a common observation that when ionic liquids are added to electrolytes the performances of lithium ion cells become poor, while the thermal safeties of the electrolytes might be improved. In this study, this behavior is investigated based on the kinetics of ionic diffusion. As a model ionic liquid, we chose butyldimethylimidazolium hexafluorophosphate (BDMIPF(6)). The common solvent was propylene carbonate (PC), and lithium hexafluorophosphate (LiPF(6)) was selected as the lithium conducting salt. Ionic diffusion coefficients are estimated by using a pulsed field gradient NMR technique. From a basic study on the model electrolytes (BDMIPF(6) in PC, LiPF(6) in PC, and BDMIPF(6) + LiPF(6) in PC), it was found that the BDMI(+) from BDMIPF(6) shows larger diffusion coefficients than the Li(+) from LiPF(6). However, the anionic (PF(6)(-)) diffusion coefficients present little difference between the model electrolytes. The higher diffusion coefficient of BDMI(+) than that of Li(+) suggests that the poor C-rate performance of lithium ion cells containing ionic liquids as an electrolyte component can be attributed to the two-cation competition between Li(+) and BDMI(+).

Microscopic properties of ionic liquid/organic semiconductor interfaces revealed by molecular dynamics simulations.

PubMed

Yokota, Yasuyuki; Miyamoto, Hiroo; Imanishi, Akihito; Takeya, Jun; Inagaki, Kouji; Morikawa, Yoshitada; Fukui, Ken-Ichi

2018-05-09

Electric double-layer transistors based on ionic liquid/organic semiconductor interfaces have been extensively studied during the past decade because of their high carrier densities at low operation voltages. Microscopic structures and the dynamics of ionic liquids likely determine the device performance; however, knowledge of these is limited by a lack of appropriate experimental tools. In this study, we investigated ionic liquid/organic semiconductor interfaces using molecular dynamics to reveal the microscopic properties of ionic liquids. The organic semiconductors include pentacene, rubrene, fullerene, and 7,7,8,8-tetracyanoquinodimethane (TCNQ). While ionic liquids close to the substrate always form the specific layered structures, the surface properties of organic semiconductors drastically alter the ionic dynamics. Ionic liquids at the fullerene interface behave as a two-dimensional ionic crystal because of the energy gain derived from the favorable electrostatic interaction on the corrugated periodic substrate.

Spontaneous Ionic Polarization in Ammonia-Based Ionic Liquid [Spontaneous Ionic Polarization in Ionic Liquid

DOE PAGES

Kim, Ki-jeong; Yuan, Hongtao; Jang, Hoyoung; ...

2018-05-24

Ionic liquids and gels have attracted attention for a variety of energy storage applications, as well as for high performance electrolytes for batteries and super-capacitors. Although the electronic structure of ionic electrolytes in these applications is of practical importance for device design and improved performance, the understanding of the electronic structure of ionic liquids and gels is still at an early stage. Here we report soft x-ray spectroscopic measurements of the surface electronic structure of a representative ammonia-based ionic gel (DEME-TFSI with PSPMMA- PS copolymer). We observe that near the outermost surface, the area of the anion peak (1s Nmore » - core level in TFSI) is relatively larger than that of the cation peak (N + in DEME). This spontaneous ionic polarization of the electrolyte surface, which is absent for the pure ionic liquid without copolymer, can be directly tuned by the copolymer content in the ionic gel, and further results in a modulation in work function. Finally, these results shed new light on the control of surface electronic properties of ionic electrolytes, as well as a difference between their implementation in ionic liquids and gels.« less

Spontaneous Ionic Polarization in Ammonia-Based Ionic Liquid [Spontaneous Ionic Polarization in Ionic Liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Ki-jeong; Yuan, Hongtao; Jang, Hoyoung

Ionic liquids and gels have attracted attention for a variety of energy storage applications, as well as for high performance electrolytes for batteries and super-capacitors. Although the electronic structure of ionic electrolytes in these applications is of practical importance for device design and improved performance, the understanding of the electronic structure of ionic liquids and gels is still at an early stage. Here we report soft x-ray spectroscopic measurements of the surface electronic structure of a representative ammonia-based ionic gel (DEME-TFSI with PSPMMA- PS copolymer). We observe that near the outermost surface, the area of the anion peak (1s Nmore » - core level in TFSI) is relatively larger than that of the cation peak (N + in DEME). This spontaneous ionic polarization of the electrolyte surface, which is absent for the pure ionic liquid without copolymer, can be directly tuned by the copolymer content in the ionic gel, and further results in a modulation in work function. Finally, these results shed new light on the control of surface electronic properties of ionic electrolytes, as well as a difference between their implementation in ionic liquids and gels.« less

Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy.

PubMed

Mousavi, Maral P S; Wilson, Benjamin E; Kashefolgheta, Sadra; Anderson, Evan L; He, Siyao; Bühlmann, Philippe; Stein, Andreas

2016-02-10

Key parameters that influence the specific energy of electrochemical double-layer capacitors (EDLCs) are the double-layer capacitance and the operating potential of the cell. The operating potential of the cell is generally limited by the electrochemical window of the electrolyte solution, that is, the range of applied voltages within which the electrolyte or solvent is not reduced or oxidized. Ionic liquids are of interest as electrolytes for EDLCs because they offer relatively wide potential windows. Here, we provide a systematic study of the influence of the physical properties of ionic liquid electrolytes on the electrochemical stability and electrochemical performance (double-layer capacitance, specific energy) of EDLCs that employ a mesoporous carbon model electrode with uniform, highly interconnected mesopores (3DOm carbon). Several ionic liquids with structurally diverse anions (tetrafluoroborate, trifluoromethanesulfonate, trifluoromethanesulfonimide) and cations (imidazolium, ammonium, pyridinium, piperidinium, and pyrrolidinium) were investigated. We show that the cation size has a significant effect on the electrolyte viscosity and conductivity, as well as the capacitance of EDLCs. Imidazolium- and pyridinium-based ionic liquids provide the highest cell capacitance, and ammonium-based ionic liquids offer potential windows much larger than imidazolium and pyridinium ionic liquids. Increasing the chain length of the alkyl substituents in 1-alkyl-3-methylimidazolium trifluoromethanesulfonimide does not widen the potential window of the ionic liquid. We identified the ionic liquids that maximize the specific energies of EDLCs through the combined effects of their potential windows and the double-layer capacitance. The highest specific energies are obtained with ionic liquid electrolytes that possess moderate electrochemical stability, small ionic volumes, low viscosity, and hence high conductivity, the best performing ionic liquid tested being 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

Next-Generation Electrochemical Energy Materials for Intermediate Temperature Molten Oxide Fuel Cells and Ion Transport Molten Oxide Membranes.

PubMed

Belousov, Valery V

2017-02-21

High temperature electrochemical devices such as solid oxide fuel cells (SOFCs) and oxygen separators based on ceramic materials are used for efficient energy conversion. These devices generally operate in the temperature range of 800-1000 °C. The high operating temperatures lead to accelerated degradation of the SOFC and oxygen separator materials. To solve this problem, the operating temperatures of these electrochemical devices must be lowered. However, lowering the temperature is accompanied by decreasing the ionic conductivity of fuel cell electrolyte and oxygen separator membrane. Therefore, there is a need to search for alternative electrolyte and membrane materials that have high ionic conductivity at lower temperatures. A great many opportunities exist for molten oxides as electrochemical energy materials. Because of their unique electrochemical properties, the molten oxide innovations can offer significant benefits for improving energy efficiency. In particular, the newly developed electrochemical molten oxide materials show high ionic conductivities at intermediate temperatures (600-800 °C) and could be used in molten oxide fuel cells (MOFCs) and molten oxide membranes (MOMs). The molten oxide materials containing both solid grains and liquid channels at the grain boundaries have advantages compared to the ceramic materials. For example, the molten oxide materials are ductile, which solves a problem of thermal incompatibility (difference in coefficient of thermal expansion, CTE). Besides, the outstanding oxygen selectivity of MOM materials allows us to separate ultrahigh purity oxygen from air. For their part, the MOFC electrolytes show the highest ionic conductivity at intermediate temperatures. To evaluate the potential of molten oxide materials for technological applications, the relationship between the microstructure of these materials and their transport and mechanical properties must be revealed. This Account summarizes the latest results on oxygen ion transport in potential MOM materials and MOFC electrolytes. In addition, we consider the rapid oxygen transport in a molten oxide scale formed on a metal surface during catastrophic oxidation and show that the same transport could be used beneficially in MOMs and MOFCs. A polymer model explaining the oxygen transport in molten oxides is also considered. Understanding the oxygen transport mechanisms in oxide melts is important for the development of new generation energy materials, which will contribute to more efficient operation of electrochemical devices at intermediate temperatures. Here we highlight the progress made in developing this understanding. We also show the latest advances made in search of alternative molten oxide materials having high mixed ion electronic and ionic conductivities for use in MOMs and MOFCs, respectively. Prospects for further research are presented.

The Mechanism of Room-Temperature Ionic-Liquid-Based Electrochemical CO₂ Reduction: A Review.

PubMed

Lim, Hyung-Kyu; Kim, Hyungjun

2017-03-28

Electrochemical CO₂ conversion technology is becoming indispensable in the development of a sustainable carbon-based economy. While various types of electrocatalytic systems have been designed, those based on room-temperature ionic liquids (RTILs) have attracted considerable attention because of their high efficiencies and selectivities. Furthermore, it should be possible to develop more advanced electrocatalytic systems for commercial use because target-specific characteristics can be fine-tuned using various combinations of RTIL ions. To achieve this goal, we require a systematic understanding of the role of the RTIL components in electrocatalytic systems, however, their role has not yet been clarified by experiment or theory. Thus, the purpose of this short review is to summarize recent experimental and theoretical mechanistic studies to provide insight into and to develop guidelines for the successful development of new CO₂ conversion systems. The results discussed here can be summarized as follows. Complex physical and chemical interactions between the RTIL components and the reaction intermediates, in particular at the electrode surface, are critical for determining the activity and selectivity of the electrocatalytic system, although no single factor dominates. Therefore, more fundamental research is required to understand the physical, chemical, and thermodynamic characteristics of complex RTIL-based electrocatalytic systems.

Static gas-liquid interfacial direct current discharge plasmas using ionic liquid cathode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaneko, T.; CREST/JST, Tokyo 102-0075; Baba, K.

Due to the unique properties of ionic liquids such as their extremely low vapor pressure and high heat capacity, we have succeeded in creating the static and stable gas (plasmas)-liquid (ionic liquids) interfacial field using a direct current discharge under a low gas pressure condition. It is clarified that the ionic liquid works as a nonmetal liquid electrode, and furthermore, a secondary electron emission coefficient of the ionic liquid is larger than that of conventional metal electrodes. The plasma potential structure of the gas-liquid interfacial region, and resultant interactions between the plasma and the ionic liquid are revealed by changingmore » a polarity of the electrode in the ionic liquid. By utilizing the ionic liquid as a cathode electrode, the positive ions in the plasma region are found to be irradiated to the ionic liquid. This ion irradiation causes physical and chemical reactions at the gas-liquid interfacial region without the vaporization of the ionic liquid.« less

Physics of transduction in ionic liquid-swollen Nafion membranes

NASA Astrophysics Data System (ADS)

Bennett, Matthew; Leo, Donald

2006-03-01

Ionic polymer transducers are a class of electroactive polymers that are able to generate large strains (1-5%) in response to low voltage inputs (1-5 V). Additionally, these materials generate electrical charge in response to mechanical strain and are therefore able to operate as soft, distributed sensors. Traditionally, ionic polymer transducers have been limited in their application by their hydration dependence. This work seeks to overcome this limitation by replacing the water with an ionic liquid. Ionic liquids are molten salts that exhibit very high thermal and electrochemical stability while also possessing high ionic conductivity. Results have shown that an ionic liquid-swollen ionic polymer transducer can operate for more than 250,000 cycles in air as compared to about 2,000 cycles for a water-swollen transducer. The current work examines the mechanisms of transduction in ionic liquid-swollen transducers based on Nafion polymer membranes. Specifically, the morphology and relevant ion associations within these membranes are investigated by the use of small-angle X-ray scattering (SAXS), Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). These results reveal that the ionic liquid interacts with the membrane in much the same way that water does, and that the counterions of the Nafion polymer are the primary charge carriers. The results of these analyses are compared to the macroscopic transduction behavior in order to develop a model of the charge transport mechanism responsible for electromechanical coupling in these membranes.

Ionic skin.

PubMed

Sun, Jeong-Yun; Keplinger, Christoph; Whitesides, George M; Suo, Zhigang

2014-12-03

Electronic skins (i.e., stretchable sheets of distributed sensors) report signals using electrons, whereas natural skins report signals using ions. Here, ionic conductors are used to create a new type of sensory sheet, called "ionic skin". Ionic skins are highly stretchable, transparent, and biocompatible. They readily measure strains from 1% to 500%, and pressures as low as 1 kPa. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient platinum-free counter electrodes for dye-sensitized solar cell applications.

PubMed

Ahmad, Shahzada; Yum, Jun-Ho; Butt, Hans-Jürgen; Nazeeruddin, Mohammad K; Grätzel, Michael

2010-09-10

Nanoporous layers of poly(3,4-propylenedioxythiophene) (PProDOT) were fabricated by electrical-field-assisted growth using hydrophobic ionic liquids as the growing medium. A series of PProDoT layers was prepared with three different ionic liquids to control the microstructure and electrochemical properties of the resulting dye-sensitized solar cells, which were highly efficient and showed a power conversion efficiency of >9% under different sunlight intensities. The current-voltage characteristics of the counter electrodes varied depending on the ionic liquids used in the synthesis of PProDOT. The most hydrophobic ionic liquids exhibited high catalytic properties, thus resulting in high power conversion efficiency and allowing the fabrication of platinum-free, stable, flexible, and cost-effective dye-sensitized solar cells.

Evaluation of four ionic liquids for pretreatment of lignocellulosic biomass.

PubMed

Gräsvik, John; Winestrand, Sandra; Normark, Monica; Jönsson, Leif J; Mikkola, Jyri-Pekka

2014-04-30

Lignocellulosic biomass is highly recalcitrant and various pretreatment techniques are needed to facilitate its effective enzymatic hydrolysis to produce sugars for further conversion to bio-based chemicals. Ionic liquids (ILs) are of interest in pretreatment because of their potential to dissolve lignocellulosic materials including crystalline cellulose. Four imidazolium-based ionic liquids (ILs) ([C=C2C1im][MeCO2], [C4C1im][MeCO2], [C4C1im][Cl], and [C4C1im][HSO4]) well known for their capability to dissolve lignocellulosic species were synthesized and then used for pretreatment of substrates prior to enzymatic hydrolysis. In order to achieve a broad evaluation, seven cellulosic, hemicellulosic and lignocellulosic substrates, crystalline as well as amorphous, were selected. The lignocellulosic substrates included hybrid aspen and Norway spruce. The monosaccharides in the enzymatic hydrolysate were determined using high-performance anion-exchange chromatography. The best results, as judged by the saccharification efficiency, were achieved with [C4C1im][Cl] for cellulosic substrates and with the acetate-based ILs for hybrid aspen and Norway spruce. After pretreatment with acetate-based ILs, the conversion to glucose of glucan in recalcitrant softwood lignocellulose reached similar levels as obtained with pure crystalline and amorphous cellulosic substrates. IL pretreatment of lignocellulose resulted in sugar yields comparable with that obtained with acidic pretreatment. Heterogeneous dissolution with [C4C1im][HSO4] gave promising results with aspen, the less recalcitrant of the two types of lignocellulose included in the investigation. The ability of ILs to dissolve lignocellulosic biomass under gentle conditions and with little or no by-product formation contributes to making them highly interesting alternatives for pretreatment in processes where high product yields are of critical importance.

Evaluation of four ionic liquids for pretreatment of lignocellulosic biomass

PubMed Central

2014-01-01

Background Lignocellulosic biomass is highly recalcitrant and various pretreatment techniques are needed to facilitate its effective enzymatic hydrolysis to produce sugars for further conversion to bio-based chemicals. Ionic liquids (ILs) are of interest in pretreatment because of their potential to dissolve lignocellulosic materials including crystalline cellulose. Results Four imidazolium-based ionic liquids (ILs) ([C=C2C1im][MeCO2], [C4C1im][MeCO2], [C4C1im][Cl], and [C4C1im][HSO4]) well known for their capability to dissolve lignocellulosic species were synthesized and then used for pretreatment of substrates prior to enzymatic hydrolysis. In order to achieve a broad evaluation, seven cellulosic, hemicellulosic and lignocellulosic substrates, crystalline as well as amorphous, were selected. The lignocellulosic substrates included hybrid aspen and Norway spruce. The monosaccharides in the enzymatic hydrolysate were determined using high-performance anion-exchange chromatography. The best results, as judged by the saccharification efficiency, were achieved with [C4C1im][Cl] for cellulosic substrates and with the acetate-based ILs for hybrid aspen and Norway spruce. After pretreatment with acetate-based ILs, the conversion to glucose of glucan in recalcitrant softwood lignocellulose reached similar levels as obtained with pure crystalline and amorphous cellulosic substrates. IL pretreatment of lignocellulose resulted in sugar yields comparable with that obtained with acidic pretreatment. Heterogeneous dissolution with [C4C1im][HSO4] gave promising results with aspen, the less recalcitrant of the two types of lignocellulose included in the investigation. Conclusions The ability of ILs to dissolve lignocellulosic biomass under gentle conditions and with little or no by-product formation contributes to making them highly interesting alternatives for pretreatment in processes where high product yields are of critical importance. PMID:24779378

Frequency-Stable Ionic-Type Hybrid Gate Dielectrics for High Mobility Solution-Processed Metal-Oxide Thin-Film Transistors

PubMed Central

Heo, Jae Sang; Choi, Seungbeom; Jo, Jeong-Wan; Kang, Jingu; Park, Ho-Hyun; Kim, Yong-Hoon; Park, Sung Kyu

2017-01-01

In this paper, we demonstrate high mobility solution-processed metal-oxide thin-film transistors (TFTs) by using a high-frequency-stable ionic-type hybrid gate dielectric (HGD). The HGD gate dielectric, a blend of sol-gel aluminum oxide (AlOx) and poly(4-vinylphenol) (PVP), exhibited high dielectric constant (ε~8.15) and high-frequency-stable characteristics (1 MHz). Using the ionic-type HGD as a gate dielectric layer, an minimal electron-double-layer (EDL) can be formed at the gate dielectric/InOx interface, enhancing the field-effect mobility of the TFTs. Particularly, using the ionic-type HGD gate dielectrics annealed at 350 °C, InOx TFTs having an average field-effect mobility of 16.1 cm2/Vs were achieved (maximum mobility of 24 cm2/Vs). Furthermore, the ionic-type HGD gate dielectrics can be processed at a low temperature of 150 °C, which may enable their applications in low-thermal-budget plastic and elastomeric substrates. In addition, we systematically studied the operational stability of the InOx TFTs using the HGD gate dielectric, and it was observed that the HGD gate dielectric effectively suppressed the negative threshold voltage shift during the negative-illumination-bias stress possibly owing to the recombination of hole carriers injected in the gate dielectric with the negatively charged ionic species in the HGD gate dielectric. PMID:28772972

The electrode/ionic liquid interface: electric double layer and metal electrodeposition.

PubMed

Su, Yu-Zhuan; Fu, Yong-Chun; Wei, Yi-Min; Yan, Jia-Wei; Mao, Bing-Wei

2010-09-10

The last decade has witnessed remarkable advances in interfacial electrochemistry in room-temperature ionic liquids. Although the wide electrochemical window of ionic liquids is of primary concern in this new type of solvent for electrochemistry, the unusual bulk and interfacial properties brought about by the intrinsic strong interactions in the ionic liquid system also substantially influence the structure and processes at electrode/ionic liquid interfaces. Theoretical modeling and experimental characterizations have been indispensable in reaching a microscopic understanding of electrode/ionic liquid interfaces and in elucidating the physics behind new phenomena in ionic liquids. This Minireview describes the status of some aspects of interfacial electrochemistry in ionic liquids. Emphasis is placed on high-resolution and molecular-level characterization by scanning tunneling microscopy and vibrational spectroscopies of interfacial structures, and the initial stage of metal electrodeposition with application in surface nanostructuring.

Synthesis and characterization of low viscosity carbon dioxide binding organic liquids for flue gas clean up

DOE Office of Scientific and Technical Information (OSTI.GOV)

Koech, Phillip K.; Malhotra, Deepika; Heldebrant, David J.

2015-01-01

Climate change is partly attributed to global anthropogenic carbon dioxide (CO2) emission to the atmosphere. These environmental effects can be mitigated by CO2 capture, utilization and storage. Alkanolamine solvents, such as monoethanolamine (MEA), which bind CO2 as carbamates or bicarbonate salts are used for CO2 capture in niche applications. These solvents consist of approximately 30 wt% of MEA in water, exhibiting a low, CO2-rich viscosity, fast kinetics and favorable thermodynamics. However, these solvents have low CO2 capacity and high heat capacity of water, resulting in prohibitively high costs of thermal solvent regeneration. Effective capture of the enormous amounts of CO2more » produced by coal-fired plants requires a material with high CO2 capacity and low regeneration energy requirements. To this end, several water-lean transformational solvents systems have been developed in order to reduce these energy penalties. These technologies include nano-material organic hybrids (NOHMs), task-specific, protic and conventional ionic liquids, phase change solvents. As part of an ongoing program in our group, we have developed new water lean transformational solvents known as CO2 binding organic liquids (CO2BOLs) which have the potential to be energy efficient CO2 capture solvents. These solvents, also known as switchable ionic liquids meaning, are organic solvents that can reversibly transform from non- ionic to ionic form and back. The zwitterionic state in these liquids is formed when low polarity non-ionic alkanolguanidines or alkanolamidines react with CO2 or SO2 to form ionic liquids with high polarity. These polar ionic liquids can be thermally converted to the less polar non-ionic solvent by releasing CO2.« less

Electrokinetic mixing at high zeta potentials: ionic size effects on cross stream diffusion.

PubMed

Ahmadian Yazdi, Alireza; Sadeghi, Arman; Saidi, Mohammad Hassan

2015-03-15

The electrokinetic phenomena at high zeta potentials may show several unique features which are not normally observed. One of these features is the ionic size (steric) effect associated with the solutions of high ionic concentration. In the present work, attention is given to the influences of finite ionic size on the cross stream diffusion process in an electrokinetically actuated Y-shaped micromixer. The method consists of a finite difference based numerical approach for non-uniform grid which is applied to the dimensionless form of the governing equations, including the modified Poisson-Boltzmann equation. The results reveal that, neglecting the ionic size at high zeta potentials gives rise to the overestimation of the mixing length, because the steric effects retard liquid flow, thereby enhancing the mixing efficiency. The importance of steric effects is found to be more intense for channels of smaller width to height ratio. It is also observed that, in sharp contrast to the conditions that the ions are treated as point charges, increasing the zeta potential improves the cross stream diffusion when incorporating the ionic size. Moreover, increasing the EDL thickness decreases the mixing length, whereas the opposite is true for the channel aspect ratio. Copyright © 2014 Elsevier Inc. All rights reserved.

Proteins in Ionic Liquids: Current Status of Experiments and Simulations.

PubMed

Schröder, Christian

2017-04-01

In the last two decades, while searching for interesting applications of ionic liquids as potent solvents, their solvation properties and their general impact on biomolecules, and in particular on proteins, gained interest. It turned out that ionic liquids are excellent solvents for protein refolding and crystallization. Biomolecules showed increased solubilities and stabilities, both operational and thermal, in ionic liquids, which also seem to prevent self-aggregation during solubilization. Biomolecules can be immobilized, e.g. in highly viscous ionic liquids, for particular biochemical processes and can be designed to some extent by the proper choice of the ionic liquid cations and anions, which can be characterized by the Hofmeister series.

Role of claudins in renal calcium handling.

PubMed

Negri, Armando Luis

2015-01-01

Paracellular channels occurring in tight junctions play a major role in transepithelial ionic flows. This pathway includes a high number of proteins, such as claudins. Within renal epithelium, claudins result in an ionic selectivity in tight junctions. Ascending thick limb of loop of Henle (ATLH) is the most important segment for calcium reabsorption in renal tubules. Its cells create a water-proof barrier, actively transport sodium and chlorine through a transcellular pathway, and provide a paracellular pathway for selective calcium reabsorption. Several studies have led to a model of paracellular channel consisting of various claudins, particularly claudin-16 and 19. Claudin-16 mediates cationic paracellular permeability in ATLH, whereas claudin-19 increases cationic selectivity of claudin-16 by blocking anionic permeability. Recent studies have shown that claudin-14 promoting activity is only located in ATLH. When co-expressed with claudin-16, claudin-14 inhibits the permeability of claudin-16 and reduces paracellular permeability to calcium. Calcium reabsorption process in ATLH is closely regulated by calcium sensor receptor (CaSR), which monitors circulating Ca levels and adjusts renal excretion rate accordingly. Two microRNA, miR-9 and miR-374, are directly regulated by CaSR. Thus, miR-9 and miR-374 suppress mRNA translation for claudin-14 and induce claudin-14 decline. Copyright © 2015 The Author. Published by Elsevier España, S.L.U. All rights reserved.

Membranes for Food and Bioproduct Processing

NASA Astrophysics Data System (ADS)

Avram, Alexandru M.

Modified membranes for process intensification in biomass hydrolysis: Production of biofuels and chemicals from lignocellulosic biomass is one of the leading candidates for replacement of petroleum based fuels and chemicals. However, conversion of lignocellulosic biomass into fuels and chemicals is not cost effective compared to the production of fuels and chemicals from crude oil reserves. Some novel and economically feasible approaches involve the use of ionic liquids as solvents or co-solvents, since these show improved solvation capability of cellulose over simple aqueous systems. Membranes offer unique opportunities for process intensification which involves fractionation of the resulting biomass hydrolysate leading to a more efficient and cheaper operation. This research attempts to develop membranes that would usher the economics of the biochemical conversion of lignocellulosic biomass into fuels and chemicals by recycling the expensive ionic liquid. The overall aim of this work is the development of novel membranes with unique surface properties that enable the selective separation of non-reacted cellulose and hydrolysis sugars from ionic liquids. Nanofiltration separation for application in food product engineering: With the advent of the modern, well-informed consumer who has high expectations from the nutritional value of consumed food products, novel approaches are being developed to produce nutrient-enhanced foods and drinks. As a response to the consumer needs, different techniques to recover, concentrate and retain as much as possible of bioactive compounds are being investigated. Membrane technology has the advantage of selective fractionation of food products (e.g. salt removal, removal of bitter-tasting compounds or removal of sugar for sweet taste adjustment), volume reduction, and product recovery at mild conditions. In this work, we use nanofiltration in dead-end and crossflow mode to concentrate polyphenols from blueberry pomace. Blueberry pomace is an overlooked waste product form the juice pressing of blueberries that contains high amounts of health-beneficial antioxidants. We aim at developing a simple, yet efficient membrane process that reduces the amount of water and thus concentrates the amount of polyphenols in the retentate.

Task-specific ionic liquid-assisted extraction and separation of astaxanthin from shrimp waste.

PubMed

Bi, Wentao; Tian, Minglei; Zhou, Jun; Row, Kyung Ho

2010-08-15

Astaxanthin, as an outstanding antioxidant reagent, was successfully extracted from shrimp waste by the ionic liquids based ultrasonic-assisted extraction. Seven kinds of imidazolium ionic liquids with different cations and anions were investigated in this work and one task-specific ionic liquid in ethanol with 0.50molL(-1) was selected as the solvent. At the optimized ultrasonic extraction conditions, the extraction amount of astaxanthin increased 98% (92.7microg g(-1)) compared to the conventional method (46.7microg g(-1)). Furthermore, the extracted solution was isolated through the solid-phase extraction with a molecularly imprinted polymer sorbent. After loading the samples on molecularly imprinted polymer cartridge, the different washing and elution solvents, such as water, methanol, n-hexane, acetone and dichloromethane, were evaluated, and finally, astaxanthin was separated from the shrimp waste extract. Copyright 2010 Elsevier B.V. All rights reserved.

Ultrasound-Assisted Extraction of Carnosic Acid and Rosmarinic Acid Using Ionic Liquid Solution from Rosmarinus officinalis

PubMed Central

Zu, Ge; Zhang, Rongrui; Yang, Lei; Ma, Chunhui; Zu, Yuangang; Wang, Wenjie; Zhao, Chunjian

2012-01-01

Ionic liquid based, ultrasound-assisted extraction was successfully applied to the extraction of phenolcarboxylic acids, carnosic acid and rosmarinic acid, from Rosmarinus officinalis. Eight ionic liquids, with different cations and anions, were investigated in this work and [C8mim]Br was selected as the optimal solvent. Ultrasound extraction parameters, including soaking time, solid–liquid ratio, ultrasound power and time, and the number of extraction cycles, were discussed by single factor experiments and the main influence factors were optimized by response surface methodology. The proposed approach was demonstrated as having higher efficiency, shorter extraction time and as a new alternative for the extraction of carnosic acid and rosmarinic acid from R. officinalis compared with traditional reference extraction methods. Ionic liquids are considered to be green solvents, in the ultrasound-assisted extraction of key chemicals from medicinal plants, and show great potential. PMID:23109836

Charge-tagged ligands: useful tools for immobilising complexes and detecting reaction species during catalysis

PubMed Central

Limberger, Jones; Leal, Bárbara C.; Monteiro, Adriano L.

2015-01-01

In recent years, charge-tagged ligands (CTLs) have become valuable tools in organometallic catalysis. Insertion of an ionic side chain into the molecular skeleton of a known ligand has become a useful protocol for anchoring ligands, and consequently catalysts, in polar and ionic liquid phases. In addition, the insertion of a cationic moiety into a ligand is a powerful tool that can be used to detect reaction intermediates in organometallic catalysis through electrospray ionisation mass spectrometry (ESI-MS) experiments. The insertion of an ionic tag ensures the charge in the intermediates independently of the ESI-MS. For this reason, these ligands have been used as ionic probes in mechanistic studies for several catalytic reactions. Here, we summarise selected examples on the use of CTLs as immobilising agents in organometallic catalysis and as probes for studying mechanisms through ESI-MS. PMID:28553458

Cation effect on small phosphonium based ionic liquid electrolytes with high concentrations of lithium salt

NASA Astrophysics Data System (ADS)

Chen, Fangfang; Kerr, Robert; Forsyth, Maria

2018-05-01

Ionic liquid electrolytes with high alkali salt concentrations have displayed some excellent electrochemical properties, thus opening up the field for further improvements to liquid electrolytes for lithium or sodium batteries. Fundamental computational investigations into these high concentration systems are required in order to gain a better understanding of these systems, yet they remain lacking. Small phosphonium-based ionic liquids with high concentrations of alkali metal ions have recently shown many promising results in experimental studies, thereby prompting us to conduct further theoretical exploration of these materials. Here, we conducted a molecular dynamics simulation on four small phosphonium-based ionic liquids with 50 mol. % LiFSI salt, focusing on the effect of cation structure on local structuring and ion diffusional and rotational dynamics—which are closely related to the electrochemical properties of these materials.

Probing the interactions between ionic liquids and water: experimental and quantum chemical approach.

PubMed

Khan, Imran; Kurnia, Kiki A; Mutelet, Fabrice; Pinho, Simão P; Coutinho, João A P

2014-02-20

For an adequate choice or design of ionic liquids, the knowledge of their interaction with other solutes and solvents is an essential feature for predicting the reactivity and selectivity of systems involving these compounds. In this work, the activity coefficient of water in several imidazolium-based ionic liquids with the common cation 1-butyl-3-methylimidazolium was measured at 298.2 K. To contribute to a deeper insight into the interaction between ionic liquids and water, COSMO-RS was used to predict the activity coefficient of water in the studied ionic liquids along with the excess enthalpies. The results showed good agreement between experimental and predicted activity coefficient of water in ionic liquids and that the interaction of water and ionic liquids was strongly influenced by the hydrogen bonding of the anion with water. Accordingly, the intensity of interaction of the anions with water can be ranked as the following: [CF3SO3](-) < [SCN](-) < [TFA](-) < Br(-) < [TOS](-) < Cl(-) < [CH3SO3](-) [DMP](-) < [Ac](-). In addition, fluorination and aromatization of anions are shown to reduce their interaction with water. The effect of temperature on the activity coefficient of water at infinite dilution was measured by inverse gas chromatography and predicted by COSMO-RS. Further analysis based on COSMO-RS provided information on the nature of hydrogen bonding between water and anion as well as the possibility of anion-water complex formation.

Simultaneous analysis of heparan sulfate, chondroitin/dermatan sulfates, and hyaluronan disaccharides by glycoblotting-assisted sample preparation followed by single-step zwitter-ionic-hydrophilic interaction chromatography.

PubMed

Takegawa, Yasuhiro; Araki, Kayo; Fujitani, Naoki; Furukawa, Jun-ichi; Sugiyama, Hiroaki; Sakai, Hideaki; Shinohara, Yasuro

2011-12-15

Glycosaminoglycans (GAGs) play important roles in cell adhesion and growth, maintenance of extracellular matrix (ECM) integrity, and signal transduction. To fully understand the biological functions of GAGs, there is a growing need for sensitive, rapid, and quantitative analysis of GAGs. The present work describes a novel analytical technique that enables high throughput cellular/tissue glycosaminoglycomics for all three families of uronic acid-containing GAGs, hyaluronan (HA), chondroitin sulfate (CS)/dermatan sulfate (DS), and heparan sulfate (HS). A one-pot purification and labeling procedure for GAG Δ-disaccharides was established by chemo-selective ligation of disaccharides onto high density hydrazide beads (glycoblotting) and subsequent labeling by fluorescence. The 17 most common disaccharides (eight comprising HS, eight CS/DS, and one comprising HA) could be separated with a single chromatography for the first time by employing a zwitter-ionic type of hydrophilic-interaction chromatography column. These novel analytical techniques were able to precisely characterize the glycosaminoglycome in various cell types including embryonal carcinoma cells and ocular epithelial tissues (cornea, conjunctiva, and limbus).

Analysis of phenolic acids by ionic liquid-in-water microemulsion liquid chromatography coupled with ultraviolet and electrochemical detector.

PubMed

Peng, Li-Qing; Cao, Jun; Du, Li-Jing; Zhang, Qi-Dong; Shi, Yu-Tin; Xu, Jing-Jing

2017-05-26

An environmentally friendly ionic liquid-in-water (IL/W) microemulsion was established and applied as mobile phase in microemulsion liquid chromatography (MELC) with ultraviolet (UV) detection or electrochemical detector (ECD) for analysis of phenolic compounds in real samples. The optimal condition of the method was using the best composition of microemulsion (0.2% w/v [HMIM]PF 6 , 1.0% w/v SDS, 3.0% w/v n-butanol, 95.8% v/v water, pH 2.5) with UV detection. The validation results indicated that the method provided high degree of sensitivity, precision and accuracy with the low limit of detections ranged from 17.9-238ng/mL, satisfactory mean recovery values in the range of 80.1-105% and good linearity (r 2 >0.9994). Additionally, this method exhibited high selectivity and resolution for the analytes and was more eco-friendly compared with traditional MELC method. Consequently, the established IL/W MELC method was successfully applied to simultaneously separate and determine target compounds in Danshen sample and its preparation. Copyright © 2017 Elsevier B.V. All rights reserved.

Impact of water dilution and cation tail length on ionic liquid characteristics: Interplay between polar and non-polar interactions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hegde, Govind A.; Bharadwaj, Vivek S.; Kinsinger, Corey L.

2016-08-14

The recalcitrance of lignocellulosic biomass poses a major challenge that hinders the economical utilization of biomass for the production of biofuel, plastics, and chemicals. Ionic liquids have become a promising solvent that addresses many issues in both the pretreatment process and the hydrolysis of the glycosidic bond for the deconstruction of cellulosic materials. However, to make the use of ionic liquids economically viable, either the cost of ionic liquids must be reduced, or a less expensive solvent (e.g., water) may be added to reduce the overall amount of ionic liquid used in addition to reducing the viscosity of the binarymore » liquid mixture. In this work, we employ atomistic molecular dynamics simulations to investigate the impact of water dilution on the overall liquid structure and properties of three imidazolium based ionic liquids. It is found that ionic liquid-water mixtures exhibit characteristics that can be grouped into two distinct regions, which are a function of the ionic liquid concentration. The trends observed in each region are found to correlate with the ordering in the local structure of the ionic liquid that arises from the dynamic interactions between the ion pairs. Simulation results suggest that there is a high level of local ordering in the molecular structure at high concentrations of ionic liquids that is driven by the aggregation of the cationic tails and the anion-water interactions. It is found that as the concentration of ionic liquids in the binary mixture is decreased, there is a point at which the competing self and cross interaction energies between the ionic liquid and water shifts away from a cation-anion dominated regime, which results in a significant change in the mixture properties. This break point, which occurs around 75% w/w ionic liquids, corresponds to the point at which water molecules percolate into the ionic liquid network disrupting the ionic liquids’ nanostructure. It is observed that as the cationic alkyl tail length increases, the changes in the binary mixtures’ properties become more pronounced.« less

Recent developments in biocatalysis in multiphasic ionic liquid reaction systems.

PubMed

Meyer, Lars-Erik; von Langermann, Jan; Kragl, Udo

2018-06-01

Ionic liquids are well known and frequently used 'designer solvents' for biocatalytic reactions. This review highlights recent achievements in the field of multiphasic ionic liquid-based reaction concepts. It covers classical biphasic systems including supported ionic liquid phases, thermo-regulated multi-component solvent systems (TMS) and polymerized ionic liquids. These powerful concepts combine unique reaction conditions with a high potential for future applications on a laboratory and industrial scale. The presence of a multiphasic system simplifies downstream processing due to the distribution of the catalyst and reactants in different phases.

Preparation of High Purity, High Molecular-Weight Chitin from Ionic Liquids for Use as an Adsorbate for the Extraction of Uranium from Seawater

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rogers, Robin

Ensuring a domestic supply of uranium is a key issue facing the wider implementation of nuclear power. Uranium is mostly mined in Kazakhstan, Australia, and Canada, and there are few high-grade uranium reserves left worldwide. Therefore, one of the most appealing potential sources of uranium is the vast quantity dissolved in the oceans (estimated to be 4.4 billion tons worldwide). There have been research efforts centered on finding a means to extract uranium from seawater for decades, but so far none have resulted in an economically viable product, due in part to the fact that the materials that have beenmore » successfully demonstrated to date are too costly (in terms of money and energy) to produce on the necessary scale. Ionic Liquids (salts which melt below 100{degrees}C) can completely dissolve raw crustacean shells, leading to recovery of a high purity, high molecular weight chitin powder and to fibers and films which can be spun directly from the extract solution suggesting that continuous processing might be feasible. The work proposed here will utilize the unprecedented control this makes possible over the chitin fiber a) to prepare electrospun nanofibers of very high surface area and in specific architectures, b) to modify the fiber surfaces chemically with selective extractant capacity, and c) to demonstrate their utility in the direct extraction and recovery of uranium from seawater. This approach will 1) provide direct extraction of chitin from shellfish waste thus saving energy over the current industrial process for obtaining chitin; 2) allow continuous processing of nanofibers for very high surface area fibers in an economical operation; 3) provide a unique high molecular weight chitin not available from the current industrial process, leading to stronger, more durable fibers; and 4) allow easy chemical modification of the large surface areas of the fibers for appending uranyl selective functionality providing selectivity and ease of stripping. The resulting sorbent should prove economically feasible, as well as providing an overall net energy gain.« less

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.

Furfural production in biphasic media using an acidic ionic liquid as a catalyst.

PubMed

Peleteiro, Susana; Santos, Valentín; Parajó, Juan C

2016-11-20

Ionic liquids are valuable tools for biorefineries. This study provides an experimental assessment on the utilization of an acidic ionic liquid (1-butyl-3-methylimidazolium hydrogen sulfate) as a catalyst for furfural production in water/solvent media. The substrates employed in experiments were commercial xylose (employed as a reference compound) or hemicellulosic saccharides obtained by hydrothermal processing of Eucalyptus globulus wood (which were employed as produced, after membrane concentration or after freeze-drying). A variety of reaction conditions (defined by temperature, reaction time and type of organic solvent) were considered. The possibility of recycling the catalyst was assessed in selected experiments. Copyright © 2016 Elsevier Ltd. All rights reserved.

Self-assembled oxide films with tailored nanoscale ionic and electronic channels for controlled resistive switching

NASA Astrophysics Data System (ADS)

Cho, Seungho; Yun, Chao; Tappertzhofen, Stefan; Kursumovic, Ahmed; Lee, Shinbuhm; Lu, Ping; Jia, Quanxi; Fan, Meng; Jian, Jie; Wang, Haiyan; Hofmann, Stephan; MacManus-Driscoll, Judith L.

2016-08-01

Resistive switches are non-volatile memory cells based on nano-ionic redox processes that offer energy efficient device architectures and open pathways to neuromorphics and cognitive computing. However, channel formation typically requires an irreversible, not well controlled electroforming process, giving difficulty to independently control ionic and electronic properties. The device performance is also limited by the incomplete understanding of the underlying mechanisms. Here, we report a novel memristive model material system based on self-assembled Sm-doped CeO2 and SrTiO3 films that allow the separate tailoring of nanoscale ionic and electronic channels at high density (~1012 inch-2). We systematically show that these devices allow precise engineering of the resistance states, thus enabling large on-off ratios and high reproducibility. The tunable structure presents an ideal platform to explore ionic and electronic mechanisms and we expect a wide potential impact also on other nascent technologies, ranging from ionic gating to micro-solid oxide fuel cells and neuromorphics.

Gas chromatography on wall-coated open-tubular columns with ionic liquid stationary phases.

PubMed

Poole, Colin F; Lenca, Nicole

2014-08-29

Ionic liquids have moved from novel to practical stationary phases for gas chromatography with an increasing portfolio of applications. Ionic liquids complement conventional stationary phases because of a combination of thermophysical and solvation properties that only exist for ionic solvents. Their high thermal stability and low vapor pressure makes them suitable as polar stationary phases for separations requiring high temperatures. Ionic liquids are good solvents and can be used to expand the chemical space for separations. They are the only stationary phases with significant hydrogen-bond acidity in common use; they extend the hydrogen-bond basicity of conventional stationary phases; they are as dipolar/polarizable as the most polar conventional stationary phases; and some ionic liquids are significantly less cohesive than conventional polar stationary phases. Problems in column coating techniques and related low column performance, column activity, and stationary phase reactivity require further exploration as the reasons for these features are poorly understood at present. Copyright © 2014 Elsevier B.V. All rights reserved.

Preparation and characterization of nonaqueous proton-conducting membranes with protic ionic liquids.

PubMed

Lu, Fei; Gao, Xinpei; Yan, Xiaojun; Gao, Hejun; Shi, Lijuan; Jia, Han; Zheng, Liqiang

2013-08-14

Hybrid Nafion membranes were successfully fabricated by incorporating with protic imidazolium ionic liquids 1-(2-aminoethyl)-3-methylimidazolium chloride ([MimAE]Cl), 1-(2-hydroxylethyl)-3-methylimidazolium chloride ([MimHE]Cl), and 1-carboxylmethyl-3-methylimidazolium chloride ([MimCM]Cl) for high-temperature fuel cells. The composite membranes were characterized by impedance spectroscopy, small-angle X-ray scattering (SAXS), scanning electronic microscopy (SEM), and thermogravimetric analysis (TGA). The incorporated protic ionic liquids enhance the doping of phosphoric acid (PA) and result in a relatively high ionic conductivity. The Nafion/10 wt % [MimAE]Cl/PA composite membrane exhibits an ionic conductivity of 6.0 mS/cm at 130 °C without humidification. [MimAE]Cl can swell the Nafion matrix more homogeneously than [MimHE]Cl or [MimCM]Cl, which results in a better ionic conductivity. It is notable that the composite Nafion/IL/PA membranes have a better thermal stability than the pristine Nafion membranes.

The Colloidal Stability of Magnetic Nanoparticles in Ionic Liquids

DTIC Science & Technology

2015-08-03

Ionic Liquids 5a. CONTRACT NUMBER FA2386-14-1-4062 5b. GRANT NUMBER Grant 14IOA088 AOARD-144062 5c. PROGRAM ELEMENT NUMBER 61102F 6...NOTES 14. ABSTRACT During the reporting period the development of the ionic liquid ferrofluid (ILFF) based on EMIM-NTf2 was continued. The...ferrofluids based on other high-boiling solvents. 15. SUBJECT TERMS Electric Propulsion, Ionic liquids 16. SECURITY CLASSIFICATION

Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air

PubMed Central

Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

2016-01-01

Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m2/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection. PMID:27070588

Fast Conversion of Ionic Liquids and Poly(Ionic Liquid)s into Porous Nitrogen-Doped Carbons in Air.

PubMed

Men, Yongjun; Ambrogi, Martina; Han, Baohang; Yuan, Jiayin

2016-04-08

Ionic liquids and poly(ionic liquid)s have been successfully converted into nitrogen-doped porous carbons with tunable surface area up to 1200 m²/g at high temperatures in air. Compared to conventional carbonization process conducted under inert gas to produce nitrogen-doped carbons, the new production method was completed in a rather shorter time without noble gas protection.

The Properties of HPMC:PEO Extended Release Hydrophilic Matrices and their Response to Ionic Environments.

PubMed

Hu, Anran; Chen, Chen; Mantle, Michael D; Wolf, Bettina; Gladden, Lynn F; Rajabi-Siahboomi, Ali; Missaghi, Shahrzad; Mason, Laura; Melia, Colin D

2017-05-01

Investigate the extended release behaviour of compacts containing mixtures of hydrophilic HPMC and PEO in hydrating media of differing ionic strengths. The extended release behaviour of various HPMC:PEO compacts was investigated using dissolution testing, confocal microscopy and magnetic resonance imaging, with respect to polymer ratio and ionic strength of the hydrating media. Increasing HPMC content gave longer extended release times, but a greater sensitivity to high ionic dissolution environments. Increasing PEO content reduced this sensitivity. The addition of PEO to a predominantly HPMC matrix reduced release rate sensitivity to high ionic environments. Confocal microscopy of early gel layer development showed the two polymers appeared to contribute independently to gel layer structure whilst together forming a coherent and effective diffusion barrier. There was some evidence that poorly swollen HPMC particles added a tortuosity barrier to the gel layer in high ionic strength environments, resulting in prolonged extended release. MRI provides unique, non-invasive spatially resolved information from within the HPMC:PEO compacts that furthers our understanding of USP 1 and USP 4 dissolution data. Confocal microscopy and MRI data show that combinations of HPMC and PEO have advantageous extended release properties, in comparison with matrices containing a single polymer.

Triggering the Chemical Instability of an Ionic Liquid under High Pressure.

PubMed

Faria, Luiz F O; Nobrega, Marcelo M; Temperini, Marcia L A; Bini, Roberto; Ribeiro, Mauro C C

2016-09-01

Ionic liquids are an interesting class of materials due to their distinguished properties, allowing their use in an impressive range of applications, from catalysis to hypergolic fuels. However, the reactivity triggered by the application of high pressure can give rise to a new class of materials, which is not achieved under normal conditions. Here, we report on the high-pressure chemical instability of the ionic liquid 1-allyl-3-methylimidazolium dicyanamide, [allylC1im][N(CN)2], probed by both Raman and IR techniques and supported by quantum chemical calculations. Our results show a reaction occurring above 8 GPa, involving the terminal double bond of the allyl group, giving rise to an oligomeric product. The results presented herein contribute to our understanding of the stability of ionic liquids, which is of paramount interest for engineering applications. Moreover, gaining insight into this peculiar kind of reactivity could lead to the development of new or alternative synthetic routes to achieve, for example, poly(ionic liquids).

Inorganic nanotubes and electro-fluidic devices fabricated therefrom

DOEpatents

Yang, Peidong [Kensington, CA; Majumdar, Arunava [Orinda, CA; Fan, Rong [Pasadena, CA; Karnik, Rohit [Cambridge, MA

2011-03-01

Nanofluidic devices incorporating inorganic nanotubes fluidly coupled to channels or nanopores for supplying a fluid containing chemical or bio-chemical species are described. In one aspect, two channels are fluidly interconnected with a nanotube. Electrodes on opposing sides of the nanotube establish electrical contact with the fluid therein. A bias current is passed between the electrodes through the fluid, and current changes are detected to ascertain the passage of select molecules, such as DNA, through the nanotube. In another aspect, a gate electrode is located proximal the nanotube between the two electrodes thus forming a nanofluidic transistor. The voltage applied to the gate controls the passage of ionic species through the nanotube selected as either or both ionic polarities. In either of these aspects the nanotube can be modified, or functionalized, to control the selectivity of detection or passage.

Theoretical investigation of the interaction between aromatic sulfur compounds and [BMIM](+)[FeCl4](-) ionic liquid in desulfurization: A novel charge transfer mechanism.

PubMed

Li, Hongping; Zhu, Wenshuai; Chang, Yonghui; Jiang, Wei; Zhang, Ming; Yin, Sheng; Xia, Jiexiang; Li, Huaming

2015-06-01

In this work, interaction nature between a group of aromatic sulfur compounds and [BMIM](+)[FeCl4](-) have been investigated by density functional theory (DFT). A coordination structure is found to be critical to the mechanism of extractive desulfurization. Interaction energy and extractive selectivity follow the order: thiophene (TH)

Ionic-liquid-impregnated resin for the microwave-assisted solid-liquid extraction of triazine herbicides in honey.

PubMed

Wu, Lijie; Song, Ying; Hu, Mingzhu; Yu, Cui; Zhang, Hanqi; Yu, Aimin; Ma, Qiang; Wang, Ziming

2015-09-01

Microwave-assisted ionic-liquid-impregnated resin solid-liquid extraction was developed for the extraction of triazine herbicides, including cyanazine, metribuzin, desmetryn, secbumeton, terbumeton, terbuthylazine, dimethametryn, and dipropetryn in honey samples. The ionic-liquid-impregnated resin was prepared by immobilizing 1-hexyl-3-methylimidazolium hexafluorophosphate in the microspores of resin. The resin was used as the extraction adsorbent. The extraction and enrichment of analytes were performed in a single step. The extraction time can be shortened greatly with the help of microwave. The effects of experimental parameters including type of resin, type of ionic liquid, mass ratio of resin to ionic liquid, extraction time, amount of the impregnated resin, extraction temperature, salt concentration, and desorption conditions on the extraction efficiency, were investigated. A Box-Behnken design was applied to the selection of the experimental parameters. The recoveries were in the range of 80.1 to 103.4% and the relative standard deviations were lower than 6.8%. The present method was applied to the analysis of honey samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Continuous synthesis of peralkylated imidazoles and their transformation into ionic liquids with improved (electro)chemical stabilities.

PubMed

Maton, Cedric; De Vos, Nils; Roman, Bart I; Vanecht, Evert; Brooks, Neil R; Binnemans, Koen; Schaltin, Stijn; Fransaer, Jan; Stevens, Christian V

2012-09-17

A versatile and efficient method to synthesize tetrasubstituted imidazoles via a one-pot modified Debus-Radziszewski reaction and their subsequent transformation into the corresponding imidazolium ionic liquids is reported. The tetrasubstituted imidazoles were also synthesized by means of a continuous flow process. This straightforward synthetic procedure allows for a fast and selective synthesis of tetrasubstituted imidazoles on a large scale. The completely substituted imidazolium dicyanamide and bis(trifluoromethylsulfonyl)imide salts were obtained via a metathesis reaction of the imidazolium iodide salts. The melting points and viscosities are of the same order of magnitude as for their non-substituted analogues. In addition to the superior chemical stability of these novel ionic liquids, which allows them to be applied in strong alkaline media, the improved thermal and electrochemical stabilities of these compounds compared with conventional imidazolium ionic liquids is also demonstrated by thermogravimetrical analysis (TGA) and cyclic voltammetry (CV). Although increased substitution of the ionic liquids does not further increase thermal stability, a definite increase in cathodic stability is observable. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid-salt aqueous two-phase extraction based on salting-out coupled with high-performance liquid chromatography for the determination of sulfonamides in water and food.

PubMed

Han, Juan; Wang, Yun; Liu, Yan; Li, Yanfang; Lu, Yang; Yan, Yongsheng; Ni, Liang

2013-02-01

Ionic liquid-salt aqueous two-phase extraction coupled with high-performance liquid chromatography with ultraviolet detection was developed for the determination of sulfonamides in water and food samples. In the procedure, the analytes were extracted from the aqueous samples into the ionic liquid top phase in one step. Three sulfonamides, sulfamerazine, sulfamethoxazole, and sulfamethizole were selected here as model compounds for developing and evaluating the method. The effects of various experimental parameters in extraction step were studied using two optimization methods, one variable at a time and Box-Behnken design. The results showed that the amount of sulfonamides did not have effect on the extraction efficiency. Therefore, a three-level Box-Behnken experimental design with three factors, which combined the response surface modeling, was used to optimize sulfonamides extraction. Under the most favorable extraction parameters, the detection limits (S/N = 3) and quantification limits (S/N = 10) of the proposed method for the target compounds were achieved within the range of 0.15-0.3 ng/mL and 0.5-1.0 ng/mL from spiked samples, respectively, which are lower than or comparable with other reported approaches applied to the determination of the same compounds. Finally, the proposed method was successfully applied to the determination of sulfonamide compounds in different water and food samples and satisfactory recoveries of spiked target compounds in real samples were obtained.

Experimental Studies of Hydrocarbon Flame Phenomena: Enabling Combustion Control

DTIC Science & Technology

2016-07-30

early discussions on the “ionic or electric wind ’ was a term used to describe a fluid flow driven only from the difference in electric potentials at two...locations, Chattock [2] and Robinson [11]. 4 To produce ionic wind , a high potential combined with a favorable electrode geometry, forms an...the secondary electrode. Beyond the formation of the ionic wind , it has been observed that high potentials in ambient air can produce ozone

Utilization of highly robust and selective crosslinked polymeric ionic liquid-based sorbent coatings in direct-immersion solid-phase microextraction and high-performance liquid chromatography for determining polar organic pollutants in waters.

PubMed

Pacheco-Fernández, Idaira; Najafi, Ali; Pino, Verónica; Anderson, Jared L; Ayala, Juan H; Afonso, Ana M

2016-09-01

Several crosslinked polymeric ionic liquid (PIL)-based sorbent coatings of different nature were prepared by UV polymerization onto nitinol wires. They were evaluated in a direct-immersion solid-phase microextraction (DI-SPME) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD). The studied PIL coatings contained either vinyl alkyl or vinylbenzyl imidazolium-based (ViCnIm- or ViBCnIm-) IL monomers with different anions, as well as different dicationic IL crosslinkers. The analytical performance of these PIL-based SPME coatings was firstly evaluated for the extraction of a group of 10 different model analytes, including hydrocarbons and phenols, while exhaustively comparing the performance with commercial SPME fibers such as polydimethylsyloxane (PDMS), polyacrylate (PA) and polydimethylsiloxane/divinylbenzene (PDMS/DVB), and using all fibers under optimized conditions. Those fibers exhibiting a high selectivity for polar compounds were selected to carry out an analytical method for a group of 5 alkylphenols, including bisphenol-A (BPA) and nonylphenol (n-NP). Under optimum conditions, average relative recoveries of 108% and inter-day precision values (3 non-consecutive days) lower than 19% were obtained for a spiked level of 10µgL(-1). Correlations coefficients for the overall method ranged between 0.990 and 0.999, and limits of detection were down to 1µgL(-1). Tap water, river water, and bottled water were analyzed to evaluate matrix effects. Comparison with the PA fiber was also performed in terms of analytical performance. Partition coefficients (logKfs) of the alkylphenols to the SPME coating varied from 1.69 to 2.45 for the most efficient PIL-based fiber, and from 1.58 to 2.30 for the PA fiber. These results agree with those obtained by the normalized calibration slopes, pointing out the affinity of these PILs-based coatings. Copyright © 2016 Elsevier B.V. All rights reserved.

Recent progress of task-specific ionic liquids in chiral resolution and extraction of biological samples and metal ions.

PubMed

Wu, Datong; Cai, Pengfei; Zhao, Xiaoyong; Kong, Yong; Pan, Yuanjiang

2018-01-01

Ionic liquids have been functionalized for modern applications. The functional ionic liquids are also called task-specific ionic liquids. Various task-specific ionic liquids with certain groups have been constructed and exploited widely in the field of separation. To take advantage of their properties in separation science, task-specific ionic liquids are generally used in techniques such as liquid-liquid extraction, solid-phase extraction, gas chromatography, high-performance liquid chromatography, and capillary electrophoresis. This review mainly covers original research papers published in the last five years, and we will focus on task-specific ionic liquids as the chiral selectors in chiral resolution and as extractant or sensor for biological samples and metal ion purification. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic Liquid-Based Optical and Electrochemical Carbon Dioxide Sensors.

PubMed

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

2015-12-04

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.

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

Ionic Blocks

ERIC Educational Resources Information Center

Sevcik, Richard S.; Gamble, Rex; Martinez, Elizabet; Schultz, Linda D.; Alexander, Susan V.

2008-01-01

"Ionic Blocks" is a teaching tool designed to help middle school students visualize the concepts of ions, ionic compounds, and stoichiometry. It can also assist high school students in reviewing their subject mastery. Three dimensional blocks are used to represent cations and anions, with color indicating charge (positive or negative) and size…

Extraction of domoic acid from seawater and urine using a resin based on 2-(trifluoromethyl)acrylic acid.

PubMed

Piletska, Elena V; Villoslada, Fernando Navarro; Chianella, Iva; Bossi, Alessandra; Karim, Kal; Whitcombe, Michael J; Piletsky, Sergey A; Doucette, Gregory J; Ramsdell, John S

2008-03-03

A new solid-phase extraction (SPE) matrix with high affinity for the neurotoxin domoic acid (DA) was designed and tested. A computational modelling study led to the selection of 2-(trifluoromethyl)acrylic acid (TFMAA) as a functional monomer capable of imparting affinity towards domoic acid. Polymeric adsorbents containing TFMAA were synthesised and tested in high ionic strength solutions such as urine and seawater. The TFMAA-based polymers demonstrated excellent performance in solid-phase extraction of domoic acid, retaining the toxin while salts and other interfering compounds such as aspartic and glutamic acids were removed by washing and selective elution. It was shown that the TFMAA-based polymer provided the level of purification of domoic acid from urine and seawater acceptable for its quantification by high performance liquid chromatography-mass spectrometry (HPLC-MS) and enzyme-linked immunosorbent assay (ELISA) without any additional pre-concentration and purification steps.

A novel polythiophene - ionic liquid modified clay composite solid phase microextraction fiber: Preparation, characterization and application to pesticide analysis.

PubMed

Pelit, Füsun Okçu; Pelit, Levent; Dizdaş, Tuğberk Nail; Aftafa, Can; Ertaş, Hasan; Yalçınkaya, E E; Türkmen, Hayati; Ertaş, F N

2015-02-15

This report comprises the novel usage of polythiophene - ionic liquid modified clay surfaces for solid phase microextraction (SPME) fiber production to improve the analysis of pesticides in fruit juice samples. Montmorillonite (Mmt) clay intercalated with ionic liquids (IL) was co-deposited with polythiophene (PTh) polymer coated electrochemically on an SPME fiber. The surface of the fibers were characterized by using scanning electron microscopy (SEM). Operational parameters effecting the extraction efficiency namely; the sample volume and pH, adsorption temperature and time, desorption temperature and time, stirring rate and salt amount were optimized. In order to reveal the major effects, these eight factors were selected and Plackett-Burman Design was constructed. The significant parameters detected; adsorption and temperature along with the stirring rate, were further investigated by Box-Behnken design. Under optimized conditions, calibration graphs were plotted and detection limits were calculated in the range of 0.002-0.667ng mL(-1). Relative standard deviations were no higher than 18%. Overall results have indicated that this novel PTh-IL-Mmt SPME surface developed by the aid of electrochemical deposition could offer a selective and sensitive head space analysis for the selected pesticide residues. Copyright © 2014 Elsevier B.V. All rights reserved.

Effects of Block Length and Membrane Processing Conditions on the Morphology and Properties of Perfluorosulfonated Poly(arylene ether sulfone) Multiblock Copolymer Membranes for PEMFC.

PubMed

Assumma, Luca; Nguyen, Huu-Dat; Iojoiu, Cristina; Lyonnard, Sandrine; Mercier, Régis; Espuche, Eliane

2015-07-01

Perfluorosulfonated poly(arylene ether sulfone) multiblock copolymers have been shown to be promising as proton exchange membranes. The commonly used approach for preparation of the membrane is solvent casting; the properties of the resulting membranes are very dependent on the membrane processing conditions. In this paper, we study the effects of block length, selectivity of the solvent, and thermal treatment on the membrane properties such as morphology, water uptake, and ionic conductivity. DiMethylSulfOxide (DMSO), and DiMethylAcetamide (DMAc) were selected as casting solvents based on the Flory-Huggins parameter calculated by inversion gas chromatography (IGC). It was found that the solvent selectivity has a mild impact on the mean size of the ionic domains and the expansion upon swelling, while it dramatically affects the supramolecular ordering of the blocks. The membranes cast from DMSO exhibit more interconnected ionic clusters yielding higher conductivities and water uptake as compared to membranes cast from DMAc. A 10-fold increase in proton conductivity was achieved after thermal annealing of membranes at 150 °C, and the ionomers with longer block lengths show conductivities similar to Nafion at 80 °C and low relative humidity (30%).

Assessing the influence of media composition and ionic strength on drug release from commercial immediate-release and enteric-coated aspirin tablets.

PubMed

Karkossa, Frank; Klein, Sandra

2017-10-01

The objective of this test series was to elucidate the importance of selecting the right media composition for a biopredictive in-vitro dissolution screening of enteric-coated dosage forms. Drug release from immediate-release (IR) and enteric-coated (EC) aspirin formulations was assessed in phosphate-based and bicarbonate-based media with different pH, electrolyte composition and ionic strength. Drug release from aspirin IR tablets was unaffected by media composition. In contrast, drug release from EC aspirin formulations was affected by buffer species and ionic strength. In all media, drug release increased with increasing ionic strength, but in bicarbonate-based buffers was delayed when compared with that in phosphate-based buffers. Interestingly, the cation species in the dissolution medium had also a clear impact on drug release. Drug release profiles obtained in Blank CarbSIF, a new medium simulating pH and average ionic composition of small intestinal fluid, were different from those obtained in all other buffer compositions studied. Results from this study in which the impact of various media parameters on drug release of EC aspirin formulations was systematically screened clearly show that when developing predictive dissolution tests, it is important to simulate the ionic composition of intraluminal fluids as closely as possible. © 2017 Royal Pharmaceutical Society.

Fundamental Insights into the Dissolution and Precipitation of Cellulosic Biomass from Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Minnick, David L.

Lignocellulose is the most abundant biopolymer on earth making it a promising feedstock for the production of renewable chemicals and fuels. However, utilization of biomass remains a challenge as recalcitrance of cellulose and hemicellulose hinder separation and conversion of these carbohydrates. For instance, the complex inter- and intra- molecular hydrogen bonding network of cellulose renders it insoluble in nearly all aqueous and organic solvents. Alternatively, select ionic liquids (ILs) dissolve significant quantities. Through an ionic liquid mediated dissolution and precipitation process cellulose crystallinity is significantly reduced consequently enhancing subsequent chemical and biochemical reaction processes. Therefore, understanding the thermodynamics of ionic liquid - cellulose mixtures is imperative to developing an IL based biomass processing system. This dissertation illustrates solid-liquid phase equilibrium results for the dissolution and precipitation of cellulose in various IL/cosolvent, IL/antisolvent, and IL/mixed solvent systems with the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]). Molecular interactions between the ionic liquid, organic solvents, and cellulose are assessed by spectroscopic techniques including Kamlet-Taft solvatochromic analysis, FTIR, and NMR. Additionally, this dissertation discusses how preferential solvation of the IL cation and anion by co- and anti-solvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of the various IL-solvent mixtures.

Facile green synthesis of silver doped fluor-hydroxyapatite/β-cyclodextrin nanocomposite in the dual acting fluorine-containing ionic liquid medium for bone substitute applications

NASA Astrophysics Data System (ADS)

Jegatheeswaran, S.; Selvam, S.; Sri Ramkumar, V.; Sundrarajan, M.

2016-05-01

A novel green route has approached for the synthesis of silver doped fluor-hydroxyapatite/β-cyclodextrin composite by the assistance of fluorine-based ionic liquid. The selected [BMIM]BF4 ionic liquid for this work plays a dual role as fluoride source and templating agent. It helps to improve the crystalline structures and the shape of the composites. The crystallinity, surface morphology, topographical studies of the synthesized composite were validated. The XRD results of the composite show typical Ag reflection peaks at 38.1°, 44.2° and 63.4°. The ionic liquid assisted composite displayed the hexagonal shaped HA particles, which are surrounded by spherical nano-Ag particles and these particles are uniformly dispersed in the β-cyclodextrin matrix in both horizontal and cross sections from surface morphology observations. The Ionic liquid assisted silver doped fluor-hydroxyapatite/β-cyclodextrin composite exhibited very good antibacterial activities against Escherichia coli, Salmonella typhi, Klebsiella pneumonia and Serratia liquefaciens pathogens. The antibacterial proficiencies were established using Confocal Laser Scanning Microscopic developed biofilms images and bacterial growth curve analysis. The cytotoxicity results of the ionic liquid assisted composite analyzed by cell proliferation in vitro studies using human osteosarcoma cell line (MG-63) and this study has shown excellent biocompatibility.

Synthesis and characterizations of novel polymer electrolytes

NASA Astrophysics Data System (ADS)

Chanthad, Chalathorn

Polymer electrolytes are an important component of many electrochemical devices. The ability to control the structures, properties, and functions of polymer electrolytes remains a key subject for the development of next generation functional polymers. Taking advantage of synthetic strategies is a promising approach to achieve the desired chemical structures, morphologies, thermal, mechanical, and electrochemical properties. Therefore, the major goal of this thesis is to develop synthetic methods for of novel proton exchange membranes and ion conductive membranes. In Chapter 2, new classes of fluorinated polymer- polysilsesquioxane nanocomposites have been designed and synthesized. The synthetic method employed includes radical polymerization using the functional benzoyl peroxide initiator for the telechelic fluorinated polymers with perfluorosulfonic acids in the side chains and a subsequent in-situ sol-gel condensation of the prepared triethoxylsilane-terminated fluorinated polymers with alkoxide precursors. The properties of the composite membranes have been studied as a function of the content and structure of the fillers. The proton conductivity of the prepared membranes increases steadily with the addition of small amounts of the polysilsesquioxane fillers. In particular, the sulfopropylated polysilsesquioxane based nanocomposites display proton conductivities greater than Nafion. This is attributed to the presence of pendant sulfonic acids in the fillers, which increases ion-exchange capacity and offers continuous proton transport channels between the fillers and the polymer matrix. The methanol permeability of the prepared membranes has also been examined. Lower methanol permeability and higher electrochemical selectivity than those of Nafion have been demonstrated in the polysilsesquioxane based nanocomposites. In Chapter 3, the synthesis of a new class of ionic liquid-containing triblock copolymers with fluoropolymer mid-block and imidazolium methacrylate end-blocks is described for the first time. The synthetic strategy involves the preparation of the telechelic fluoropolymers using a functional benzoyl peroxide initiator as the macro-chain transfer agent for subsequent RAFT polymerization of the imidazolium methacrylate monomer. As revealed in DSC, SAXS and dielectric relaxation spectroscopy (DRS) measurements, there was no microphase separation in the triblock copolymers, likely due to solubility of ionic liquid moieties in the fluoropolymer matrix. The anionic counterion has direct impact on the thermal properties, ionic conductivity and segmental dynamics of the polymers. The temperature dependence of the ionic conductivity is well described by the Vogel-Tamman-Fulcher model, suggesting that ion motion is closely coupled to segmental motion. In Chapter 4 and 5, new solid electrolytes for lithium cations have been synthesized by catalyzed hydrosilylation reaction involving hydrogen atoms of polysiloxane and polyhedral oligomeric silsesquioxane (POSS) and double bonds of vinyl tris17-bromo-3,6,9,12,15- pentaoxaheptadecan-1-ol silane. The obtained structures are based on branched or dendritic with ionic liquid-ethylene oxide oligomer. High room temperature ionic conductivities have been obtained in the range of 10-4-10-5 can be regarded as solid electrolytes. This is attributed to the high concentration of ions from ionic liquid moieties in the tripodand molecule, high segmental mobility, and high ion dissociation from ethylene oxide spacers. The influence of anion structures and lithium salts and concentration has been investigated.

The clinical application of radiopharmaceuticals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leeds, N.E.

1990-11-01

This article highlights the choices and the arguments in the selection of appropriate contrast materials in radiological examinations--nonionic versus ionic contrast material--and aims to assist the physician in decision-making. Various authors have raised questions concerning the proposed advantages of nonionic contrast material. However, studies in low risk patients have shown more complications with the use of ionic contrast than nonionic contrast materials; this is the important group of patients since in high risk patients nonionics are used almost exclusively. The important factor that increases the controversy is cost, which is significant since nonionic agents cost 10 to 15 times moremore » than ionic agents in the USA. Thus, cost-benefit considerations are important because price sensitivity and cost may determine fund availability for equipment or materials that also may be necessary or important in improving patient care. In magnetic resonance imaging (MRI), as in computed tomography (CT), the use of contrast material has improved diagnostic accuracy and the ability to reveal lesions not otherwise easily detected in brain and spinal cord imaging. These include separating scan from disc, meningitis, meningeal spread of tumour, tumour seeding, small metastases, intracanalicular tumours, separating major mass from oedema, determining bulk tumour size and ability to demonstrate blood vessels so dynamic circulatory changes may be revealed. 33 refs.« less

High Ionic Conductivity of Composite Solid Polymer Electrolyte via In Situ Synthesis of Monodispersed SiO2 Nanospheres in Poly(ethylene oxide).

PubMed

Lin, Dingchang; Liu, Wei; Liu, Yayuan; Lee, Hye Ryoung; Hsu, Po-Chun; Liu, Kai; Cui, Yi

2016-01-13

High ionic conductivity solid polymer electrolyte (SPE) has long been desired for the next generation high energy and safe rechargeable lithium batteries. Among all of the SPEs, composite polymer electrolyte (CPE) with ceramic fillers has garnered great interest due to the enhancement of ionic conductivity. However, the high degree of polymer crystallinity, agglomeration of ceramic fillers, and weak polymer-ceramic interaction limit the further improvement of ionic conductivity. Different from the existing methods of blending preformed ceramic particles with polymers, here we introduce an in situ synthesis of ceramic filler particles in polymer electrolyte. Much stronger chemical/mechanical interactions between monodispersed 12 nm diameter SiO2 nanospheres and poly(ethylene oxide) (PEO) chains were produced by in situ hydrolysis, which significantly suppresses the crystallization of PEO and thus facilitates polymer segmental motion for ionic conduction. In addition, an improved degree of LiClO4 dissociation can also be achieved. All of these lead to good ionic conductivity (1.2 × 10(-3) S cm(-1) at 60 °C, 4.4 × 10(-5) S cm(-1) at 30 °C). At the same time, largely extended electrochemical stability window up to 5.5 V can be observed. We further demonstrated all-solid-state lithium batteries showing excellent rate capability as well as good cycling performance.

Ionic Liquids in HPLC and CE: A Hope for Future.

PubMed

Ali, Imran; Suhail, Mohd; Sanagi, Mohd Marsin; Aboul-Enein, Hassan Y

2017-07-04

The ionic liquids (ILs) are salts with melting points below 100°C. These are called as ionic fluids, ionic melts, liquid electrolytes, fused salts, liquid salts, ionic glasses, designer solvents, green solvents and solvents of the future. These have a wide range of applications, including medical, pharmaceutical and chemical sciences. Nowadays, their use is increasing greatly in separation science, especially in chromatography and capillary electrophoresis due to their remarkable properties. The present article describes the importance of ILs in high-performance liquid chromatography and capillary electrophoresis. Efforts were also made to highlight the future expectations of ILs.

Catalytic conversion of cellulose to fuels and chemicals using boronic acids

DOEpatents

Raines, Ronald; Caes, Benjamin; Palte, Michael

2015-10-20

Methods and catalyst compositions for formation of furans from carbohydrates. A carbohydrate substrate is heating in the presence of a 2-substituted phenylboronic acid (or salt or hydrate thereof) and optionally a magnesium or calcium halide salt. The reaction is carried out in a polar aprotic solvent other than an ionic liquid, an ionic liquid or a mixture thereof. Additional of a selected amount of water to the reaction can enhance the yield of furans.

Improving on aquaporins

DOE PAGES

Siwy, Zuzanna; Fornasiero, Francesco

2017-08-25

Biological nanopores can selectively and rapidly transport ions and molecules through membranes. For example, many biological ion channels conduct only one type of ion across the cell membrane, and they do so in response to external stimuli. Aquaporins transport water at astonishingly high rates and are efficient desalination units, in that they have excellent rejection of all ions, including protons. In conclusion, on page 792 of this issue, Tunuguntla et al. present an artificial nanopore system that sustains water fluxes exceeding those of aquaporins, exhibits ionic selectivities comparable to those of biological ion channels, and consists of carbon nanotubes (CNTs)more » that are 10 nm long and merely 0.8 nm in diameter embedded in a lipid bilayer.« less

Ordered mesoporous ternary mixed oxide materials as potential adsorbent of biomolecules

NASA Astrophysics Data System (ADS)

Pal, Nabanita; Bhaumik, Asim

2012-05-01

Designing a suitable mesoporous framework material for the selective adsorption or immobilization of biomolecules is a very challenging area of research. Mesoporous ternary Co-Si-Al oxide materials with large mesopore and their nanoscale ordering have been reported. The synthesis of these ternary oxides are accomplished through evaporation induced self-assembly (EISA) method using Pluronic non-ionic surfactant F127 under non-aqueous sol-gel route. N2 sorption study revealed high BET surface areas for these materials. These materials exhibited very efficient and selective adsorption for the essential biomolecules like vitamin C (ascorbic acid), vitamin B6 (pyridoxine) and vitamin B3 (nicotinic acid) from their respective aqueous solutions.

Highly efficient and selective adsorption of In{sup 3+} on pristine Zn/Al layered double hydroxide (Zn/Al-LDH) from aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnabas, Mary Jenisha; Parambadath, Surendran; Mathew, Aneesh

2016-01-15

A pristine Zn/Al-layered double hydroxide (Zn/Al-LDH) showed excellent adsorption ability and selectivity towards In{sup 3+} ions from aqueous solutions. The adsorption behaviour as a function of the contact time, solution pH, ionic strength, and amount of adsorbent under ambient conditions revealed a strong dependency on the pH and ionic strength over In{sup 3+} intake. The structure and properties of Zn/Al-LDH and In{sup 3+} adsorbed Zn/Al-LDH (In–Zn/Al-LDH) were examined carefully by X-ray diffraction, Fourier transform infrared spectroscopy, N{sub 2}-sorption/desorption, UV–vis spectroscopy, and X-ray photoelectron spectroscopy. The adsorbent had a sufficient number of active sites that were responsible for the In{sup 3+}more » adsorption and quite stable even after the adsorption process. The selective adsorption of In{sup 3+} on Zn/Al-LDH was also observed even from a mixture containing competing ions, such as Mn{sup 2+}, Co{sup 2+}, Ni{sup 2+}, Cd{sup 2+}, Pb{sup 2+}, and Cu{sup 2+}. The adsorption experiments showed that Zn/Al-LDH is a promising material for the pre-concentration and selective removal of In{sup 3+} from large volumes of aqueous solutions. - Highlights: • A pristine Zn/Al-layered double hydroxide showed good selectivity for In{sup 3+} ions. • The material exhibited a maximum In{sup 3+} intake of 205 mg g{sup −1} at pH 6. • The materials showed good affinity of In{sup 3+} over Cu{sup 2+} and Pb{sup 2+} from ion mixtures.« less

Ionic liquids. Combination of combustion calorimetry with high-level quantum chemical calculations for deriving vaporization enthalpies.

PubMed

Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas; Schick, Christoph

2008-07-10

In this work, the molar enthalpies of formation of the ionic liquids [C2MIM][NO3] and [C4MIM][NO3] were measured by means of combustion calorimetry. The molar enthalpy of fusion of [C2MIM][NO3] was measured using differential scanning calorimetry. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for the ionic species using the G3MP2 theory. We have used a combination of traditional combustion calorimetry with modern high-level ab initio calculations in order to obtain the molar enthalpies of vaporization of a series of the ionic liquids under study.

Solid-phase extraction of chlorophenols in seawater using a magnetic ionic liquid molecularly imprinted polymer with incorporated silicon dioxide as a sorbent.

PubMed

Ma, Wanwan; Row, Kyung Ho

2018-07-20

A type of magnetic ionic liquid based molecularly imprinted polymer coated on SiO 2 (Fe 3 O 4 @SiO 2 @IL-MIPs) was prepared with 1-vinyl-3-ethylimidazole ionic liquid as functional monomer, and 1,4-butane-3,3'-bis-1-ethylimidazole ionic liquid as cross linker, 4-Chlorophenol as template was successfully applied as a selective adsorbent for selective extraction of 5 chlorophenols in seawater samples by using the magnetic solid-phase extraction (MSPE) method. 11 types of Fe 3 O 4 @SiO 2 @IL-MIPs were synthesized and investigated for their different compositions of functional monomer (such as [C 2 min][Br], [C 2 min][BF 4 ], [C 2 min][PF 6 ], acrylamide, methacrylic acid and 4-vinyl pyridine) and cross-linker (such as [C 4 min 2 ][Br], [C 4 min 2 ][BF 4 ], [C 4 min 2 ][PF 6 ], divinylbenzene, and ethylene glycol dimethacrylate), respectively. The [C 2 min][BF 4 ] and [C 4 min 2 ][PF 6 ] based Fe 3 O 4 @SiO 2 @IL-MIP with the highest extraction efficiencies was applied to the optimization experiment of MSPE process (including extraction time, adsorbent mass and desorption solvents). Good linearity was obtained with correlation coefficients (R 2 ) over 0.9990 and the relative standard deviations for the intra-day and inter-day determination were less than 3.10% with the extraction recoveries ranged from 85.0% to 98.4%. The results indicated that the proposed Fe 3 O 4 @SiO 2 @IL-MIPs possesses great identification and adsorption properties, and could be used as a good sorbent for selective extraction of CPs in environment waters. Copyright © 2018 Elsevier B.V. All rights reserved.

Ionic liquids and ionic liquid acids with high temperature stability for fuel cell and other high temperature applications, method of making and cell employing same

DOEpatents

Angell, C Austen [Mesa, AZ; Xu, Wu [Broadview Heights, OH; Belieres, Jean-Philippe [Chandler, AZ; Yoshizawa, Masahiro [Tokyo, JP

2011-01-11

Disclosed are developments in high temperature fuel cells including ionic liquids with high temperature stability and the storage of inorganic acids as di-anion salts of low volatility. The formation of ionically conducting liquids of this type having conductivities of unprecedented magnitude for non-aqueous systems is described. The stability of the di-anion configuration is shown to play a role in the high performance of the non-corrosive proton-transfer ionic liquids as high temperature fuel cell electrolytes. Performance of simple H.sub.2(g) electrolyte/O.sub.2(g) fuel cells with the new electrolytes is described. Superior performance both at ambient temperature and temperatures up to and above 200.degree. C. are achieved. Both neutral proton transfer salts and the acid salts with HSO.sup.-.sub.4 anions, give good results, the bisulphate case being particularly good at low temperatures and very high temperatures. The performance of all electrolytes is improved by the addition of a small amount of involatile base of pK.sub.a value intermediate between those of the acid and base that make the bulk electrolyte. The preferred case is the imidazole-doped ethylammonium hydrogensulfate which yields behavior superior in all respects to that of the industry standard phosphoric acid electrolyte.

Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

1996-01-01

A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.

Atmospheric Pressure Method and Apparatus for Removal of Organic Matter with Atomic and Ionic Oxygen

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor); Rutledge, Sharon K. (Inventor)

1997-01-01

A gas stream containing ionic and atomic oxygen in inert gas is used to remove organic matter from a substrate. The gas stream is formed by flowing a mixture of gaseous oxygen in an inert gas such as helium at atmospheric pressure past a high voltage, current limited, direct current arc which contacts the gas mixture and forms the ionic and atomic oxygen. The arc is curved at the cathode end and the ionic oxygen formed by the arc nearer to the anode end of the arc is accelerated in a direction towards the cathode by virtue of its charge. The relatively high mass to charge ratio of the ionic oxygen enables at least some of it to escape the arc before contacting the cathode and it is directed onto the substrate. This is useful for cleaning delicate substrates such as fine and historically important paintings and delicate equipment and the like.

[Atomic/ionic fluorescence in microwave plasma torch discharge with excitation of high current and microsecond pulsed hollow cathode lamp: Ca atomic/ionic fluorescence spectrometry].

PubMed

Gong, Zhen-bin; Liang, Feng; Yang, Peng-yuan; Jin, Qin-han; Huang, Ben-li

2002-02-01

A system of atomic and ionic fluorescence spectrometry in microwave plasma torch (MPT) discharge excited by high current microsecond pulsed hollow cathode lamp (HCMP HCL) has been developed. The operation conditions for Ca atomic and ionic fluorescence spectrometry have been optimized. Compared with atomic fluorescence spectrometry (AFS) in argon microwave induced plasma (MIP) and MPT with the excitation of direct current and conventional pulsed HCL, the system with HCMP HCL excitation can improve AFS and ionic fluorescence spectrometry (IFS) detection limits in MPT atomizer and ionizer. Detection limits (3 sigma) with HCMP HCL-MPT-AFS/IFS are 10.1 ng.mL-1 for Ca I 422.7 nm, 14.6 ng.mL-1 for Ca II 393.4 nm, and 37.4 ng.mL-1 for Ca II 396.8 nm, respectively.

Robust and versatile ionic liquid microarrays achieved by microcontact printing

NASA Astrophysics Data System (ADS)

Gunawan, Christian A.; Ge, Mengchen; Zhao, Chuan

2014-04-01

Lab-on-a-chip and miniaturized systems have gained significant popularity motivated by marked differences in material performance at the micro-to-nano-scale realm. However, to fully exploit micro-to-nano-scale chemistry, solvent volatility and lack of reproducibility need to be overcome. Here, we combine the non-volatile and versatile nature of ionic liquids with microcontact printing in an attempt to establish a facile protocol for high throughput fabrication of open microreactors and microfluidics. The micropatterned ionic liquid droplets have been demonstrated as electrochemical cells and reactors for microfabrication of metals and charge transfer complexes, substrates for immobilization of proteins and as membrane-free high-performance amperometric gas sensor arrays. The results suggest that miniaturized ionic liquid systems can be used to solve the problems of solvent volatility and slow mass transport in viscous ionic liquids in lab-on-a-chip devices, thus providing a versatile platform for a diverse number of applications.

Preparation and Characterization of Facilitated Transport Membranes Composed of Chitosan-Styrene and Chitosan-Acrylonitrile Copolymers Modified by Methylimidazolium Based Ionic Liquids for CO2 Separation from CH4 and N2

PubMed Central

Otvagina, Ksenia V.; Mochalova, Alla E.; Sazanova, Tatyana S.; Petukhov, Anton N.; Moskvichev, Alexandr A.; Vorotyntsev, Andrey V.; Afonso, Carlos A. M.; Vorotyntsev, Ilya V.

2016-01-01

CO2 separation was found to be facilitated by transport membranes based on novel chitosan (CS)–poly(styrene) (PS) and chitosan (CS)–poly(acrylonitrile) (PAN) copolymer matrices doped with methylimidazolium based ionic liquids: [bmim][BF4], [bmim][PF6], and [bmim][Tf2N] (IL). CS plays the role of biodegradable film former and selectivity promoter. Copolymers were prepared implementing the latest achievements in radical copolymerization with chosen monomers, which enabled the achievement of outstanding mechanical strength values for the CS-based membranes (75–104 MPa for CS-PAN and 69–75 MPa for CS-PS). Ionic liquid (IL) doping affected the surface and mechanical properties of the membranes as well as the gas separation properties. The highest CO2 permeability 400 Barrers belongs to CS-b-PS/[bmim][BF4]. The highest selectivity α (CO2/N2) = 15.5 was achieved for CS-b-PAN/[bmim][BF4]. The operational temperature of the membranes is under 220 °C. PMID:27294964

Thermal Decomposition Mechanisms of Alkylimidazolium Ionic Liquids with CN-containing Anions

DTIC Science & Technology

2014-11-01

anion calculated at the M06/6-31+G(d,p) level of theory and using the generic ionic liquid (GIL) model to simulate the condensed phase methyl...decomposition mechanisms of alkylimidazolium ionic liquids with CN-containing anions 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d...perform, display, or disclose the work. 14. ABSTRACT Due to the unusually high heats of vaporization of room-temperature ionic liquids (RTILs

Simultaneous determination of brazilin and protosappanin B in Caesalpinia sappan by ionic-liquid dispersive liquid-phase microextraction method combined with HPLC.

PubMed

Xia, Zhaoyang; Li, Dongdong; Li, Qing; Zhang, Yan; Kang, Wenyi

2017-11-13

The conditions of heating, ionic liquid-based ultrasonic-assisted extraction combined with reverse-phase high performance liquid chromatography were optimized to simultaneously isolate and determinate brazilin and protosappanin B in Caesalpinia sappan. Ionic liquids, including [BMIM]Br, [BMIM]BF 4 , [BMIM]PF 6 and [HMIM]PF 6 , were selected as extraction solvents while methanol, acetone, acetonitrile, ethanol and water were selected as dispersants. The chromatographic column was Purospher star RP-C 18 (250 mm × 4.6 mm, 5 μm), a mixture of methanol and 0.2% phosphoric acid-water was used as mobile phase at a flow rate 0.65 mL/min. The result displayed that the extraction yields of brazilin and protosappanin B were highest when the concentration of [BMIM]Br methanol solution as extraction solvent was 0.5 mol/L and the solid-liquid ratio was 1:50 (g/mL). Under the optimal extraction conditions, the contents of brazilin showed a good linearity (r = 1.0000) within the range of 1.25-7.50 μg with the average recovery of 99.33%, the contents of protosappanin B also showed a good linearity (r = 0.9999) within the range of 0.50-3.00 μg with the average recovery of 98.31%. This experiment, which adopted environmentally friendly reagent as extraction solvent, not only improved the extraction efficiency, but also avoided the environmental pollution caused by organic solvent. Moreover, it was simple and reliable, and can be of important significance in the study of Traditional Chinese Medicine active ingredient extraction methods. The antibacterial activities of the ionic liquids and methanol extracts were determined using the paper disc diffusion method. The ionic liquid extract was found to possess antibacterial activity against Staphylococcus aureus and methicillin-resistant S. aureus (MIC value of 37.5 mg crude drug/mL), β-Lactamase producing S. aureus (MIC values of 18.8 mg crude drug/mL), but not against E. coli, Extended spectrum β-Lactamases E. coli and P. aeruginosa. Compared with the ionic liquid extract, the methanol extract was found to have antibacterial activity against S. aureus and methicillin-resistant S. aureus (MIC value of 75.0 mg crude drug/mL), β-Lactamase producing S. aureus (MIC values of 150.0 mg crude drug/mL). However, the same, the methanol extract did not have antibacterial activity against E. coli, Extended spectrum β-Lactamases E. coli and P. aeruginosa.

High H⁻ ionic conductivity in barium hydride.

PubMed

Verbraeken, Maarten C; Cheung, Chaksum; Suard, Emmanuelle; Irvine, John T S

2015-01-01

With hydrogen being seen as a key renewable energy vector, the search for materials exhibiting fast hydrogen transport becomes ever more important. Not only do hydrogen storage materials require high mobility of hydrogen in the solid state, but the efficiency of electrochemical devices is also largely determined by fast ionic transport. Although the heavy alkaline-earth hydrides are of limited interest for their hydrogen storage potential, owing to low gravimetric densities, their ionic nature may prove useful in new electrochemical applications, especially as an ionically conducting electrolyte material. Here we show that barium hydride shows fast pure ionic transport of hydride ions (H(-)) in the high-temperature, high-symmetry phase. Although some conductivity studies have been reported on related materials previously, the nature of the charge carriers has not been determined. BaH2 gives rise to hydride ion conductivity of 0.2 S cm(-1) at 630 °C. This is an order of magnitude larger than that of state-of-the-art proton-conducting perovskites or oxide ion conductors at this temperature. These results suggest that the alkaline-earth hydrides form an important new family of materials, with potential use in a number of applications, such as separation membranes, electrochemical reactors and so on.

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%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

PubMed

Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

2017-09-04

Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water dynamics in rigid ionomer networks.

PubMed

Osti, N C; Etampawala, T N; Shrestha, U M; Aryal, D; Tyagi, M; Diallo, S O; Mamontov, E; Cornelius, C J; Perahia, D

2016-12-14

The dynamics of water within ionic polymer networks formed by sulfonated poly(phenylene) (SPP), as revealed by quasi-elastic neutron scattering (QENS), is presented. These polymers are distinguished from other ionic macromolecules by their rigidity and therefore in their network structure. QENS measurements as a function of temperature as the fraction of ionic groups and humidity were varied have shown that the polymer molecules are immobile while absorbed water molecules remain dynamic. The water molecules occupy multiple sites, either bound or loosely constrained, and bounce between the two. With increasing temperature and hydration levels, the system becomes more dynamic. Water molecules remain mobile even at subzero temperatures, illustrating the applicability of the SPP membrane for selective transport over a broad temperature range.

Iodinated contrast media and contrast-induced nephropathy: is there a preferred cost-effective agent?

PubMed

Sharma, Samin K

2008-05-01

Over 20 years have passed since the introduction of the tri-iodinated low-osmolar nonionic contrast agents such as iopamidol, iohexol, ioversol and iopromide. During this time, most cardiology practices have switched to these nonionic agents to avoid the nuisance side effects and cardiac adverse events associated with the older ionic contrast agents. Although the improved tolerability of the nonionic agents is generally attributed to their decreased osmolality (approximately half that of the older ionic contrast agents), in fact, these contrast agents also differ from the older agents in their ionicity, viscosity and direct chemotoxicity. The impact of these properties on safety, together with cost differences, should be considered when selecting a contrast agent.

Solid-contact pH-selective electrode using multi-walled carbon nanotubes.

PubMed

Crespo, Gastón A; Gugsa, Derese; Macho, Santiago; Rius, F Xavier

2009-12-01

Multi-walled carbon nanotubes (MWCNT) are shown to be efficient transducers of the ionic-to-electronic current. This enables the development of a new solid-contact pH-selective electrode that is based on the deposition of a 35-microm thick layer of MWCNT between the acrylic ion-selective membrane and the glassy carbon rod used as the electrical conductor. The ion-selective membrane was prepared by incorporating tridodecylamine as the ionophore, potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate as the lipophilic additive in a polymerized methylmethacrylate and an n-butyl acrylate matrix. The potentiometric response shows Nernstian behaviour and a linear dynamic range between 2.89 and 9.90 pH values. The response time for this electrode was less than 10 s throughout the whole working range. The electrode shows a high selectivity towards interfering ions. Electrochemical impedance spectroscopy and chronopotentiometry techniques were used to characterise the electrochemical behaviour and the stability of the carbon-nanotube-based ion-selective electrodes.

Na⁺ and K⁺ ion selectivity by size-controlled biomimetic graphene nanopores.

PubMed

Kang, Yu; Zhang, Zhisen; Shi, Hui; Zhang, Junqiao; Liang, Lijun; Wang, Qi; Ågren, Hans; Tu, Yaoquan

2014-09-21

Because biological ionic channels play a key role in cellular transport phenomena, they have attracted extensive research interest for the design of biomimetic nanopores with high permeability and selectivity in a variety of technical applications. Inspired by the structure of K(+) channel proteins, we designed a series of oxygen doped graphene nanopores of different sizes by molecular dynamics simulations to discriminate between K(+) and Na(+) channel transport. The results from free energy calculations indicate that the ion selectivity of such biomimetic graphene nanopores can be simply controlled by the size of the nanopore; compared to K(+), the smaller radius of Na(+) leads to a significantly higher free energy barrier in the nanopore of a certain size. Our results suggest that graphene nanopores with a distance of about 3.9 Å between two neighboring oxygen atoms could constitute a promising candidate to obtain excellent ion selectivity for Na(+) and K(+) ions.

Ion-mediated enhancement of xylem hydraulic conductivity in four Acer species: relationships with ecological and anatomical features.

PubMed

Nardini, Andrea; Dimasi, Federica; Klepsch, Matthias; Jansen, Steven

2012-12-01

The 'ionic effect', i.e., changes in xylem hydraulic conductivity (k(xyl)) due to variation of the ionic sap composition in vessels, was studied in four Acer species growing in contrasting environments differing in water availability. Hydraulic measurements of the ionic effect were performed together with measurements on the sap electrical conductivity, leaf water potential and vessel anatomy. The low ionic effect recorded in Acer pseudoplatanus L. and Acer campestre L. (15.8 and 14.7%, respectively), which represented two species from shady and humid habitats, was associated with a low vessel grouping index, high sap electrical conductivity and least negative leaf water potential. Opposite traits were found for Acer monspessulanum L. and Acer platanoides L., which showed an ionic effect of 23.6 and 23.1%, respectively, and represent species adapted to higher irradiance and/or lower water availability. These findings from closely related species provide additional support that the ionic effect could function as a compensation mechanism for embolism-induced loss of k(xyl), either as a result of high evaporative demand or increased risk of hydraulic failure.

Self-assembled oxide films with tailored nanoscale ionic and electronic channels for controlled resistive switching

DOE PAGES

Cho, Seungho; Yun, Chao; Tappertzhofen, Stefan; ...

2016-08-05

Resistive switches are non-volatile memory cells based on nano-ionic redox processes that offer energy efficient device architectures and open pathways to neuromorphics and cognitive computing. However, channel formation typically requires an irreversible, not well controlled electroforming process, giving difficulty to independently control ionic and electronic properties. The device performance is also limited by the incomplete understanding of the underlying mechanisms. Here, we report a novel memristive model material system based on self-assembled Sm-doped CeO 2 and SrTiO 3 films that allow the separate tailoring of nanoscale ionic and electronic channels at high density (~10 12 inch –2). Here, we systematicallymore » show that these devices allow precise engineering of the resistance states, thus enabling large on–off ratios and high reproducibility. The tunable structure presents an ideal platform to explore ionic and electronic mechanisms and we expect a wide potential impact also on other nascent technologies, ranging from ionic gating to micro-solid oxide fuel cells and neuromorphics.« less

Nanoporous array anodic titanium-supported co-polymeric ionic liquids as high performance solid-phase microextraction sorbents for hydrogen bonding compounds.

PubMed

Jia, Jing; Liang, Xiaojing; Wang, Licheng; Guo, Yong; Liu, Xia; Jiang, Shengxiang

2013-12-13

A nanoporous array anodic titanium-supported co-polymeric ionic liquids (NAAT/PILs) solid-phase microextraction (SPME) fiber was prepared in situ on the titanium wire. NAAT was selected as the substrate, in view of its high surface-to-volume ratio, easy preparation, mechanical stability, and rich titanol groups on its surface which can anchor silica coupling agent containing vinyl and then introduce ionic liquid copolymers as sorbents. In this work, 1-vinyl-3-nonanol imidazolium bromide ([C9OHVIm]Br) and 1,4-di(3-vinylimidazolium) butane dibromide ([(VIM)2C4]2[Br]) were synthesized and used as monomer and crosslinker, respectively. Extraction properties of the NAAT/PILs fiber for polar alcohols and volatile fatty acids (VFAs) in aqueous matrix were examined using gaseous sampling-SPME (GS-SPME) and headspace SPME (HS-SPME) mode, respectively. Combining the superior properties of NAAT substrate and the strong hydrogen bond interaction of PILs to polar compounds, the NAAT/PILs SPME fiber showed much higher adsorption affinity to aliphatic alcohols than bare NAAT and pure PILs fibers. The detection limits (LOD) of established GS-SPME-GC-FID method are in the range of 0.35-17.30ngL(-1) with a linear range from 0.01 to 500ngmL(-1). Also, it showed high extraction performance toward volatile fatty acids (VFAs) compounds from aqueous matrix. Under the optimized SPME conditions, wide linear ranges were obtained with correlation coefficients (R(2)) greater than 0.99 and limits of detection were in the range of 0.85-8.74ngL(-1). Moreover, real-world samples were analyzed and good results were obtained. Copyright © 2013. Published by Elsevier B.V.

Conjunctival mucin mRNA expression in contact lens wear.

PubMed

Corrales, Rosa M; Galarreta, David; Herreras, Jose M; Saez, Victoria; Arranz, Isabel; González, Maria J; Mayo, Agustin; Calonge, Margarita; Chaves, Felipe J

2009-09-01

To investigate the influence of the water content in non-ionic hydrogel contact lenses (HCL) on the mRNA levels of human conjunctival mucin genes (MUCs). Sixteen healthy subjects with no history of contact lenses wear were selected and randomized into two equal groups. Group 1 subjects wore low water content (38%, Soflens 38) non-ionic HCLs. Group 2 wore high water content (66%, Soflens 66) non-ionic HCLs. Conjunctival impression cytology was applied to the superior bulbar conjunctiva of both eyes before, 6 months, and 1 year after HCL fitting, and 15 days after discontinuation of wearing. Total RNA was isolated, retrotranscribed, and amplified by conventional polymerase chain reaction (PCR) and by quantitative real time PCR to study the mRNA levels of MUCs and to analyze variations during the study period. Time- and HCL-dependent variations in mRNA expression were analyzed using Student's test. From the known MUCs, transcripts from MUC1, MUC2, MUC4, MUC5AC, MUC7, MUC13, MUC15, MUC16, and MUC17 genes were detected in all subjects before HCL fitting. Except for MUC2, the expression of some MUC genes significantly increased whereas others significantly decreased at either the 6- and 12-month period. Statistically significant differences between both HCL groups (p < 0.001) were found in the MUC4, MUC13, and MUC15 mRNA expression after 1 year of wear and after the 15 days without HCL wear. However, these differences were not clearly related to the water content of the lenses. Low and high water content non-ionic HCLs induced different changes in the mRNA levels of several MUCs, but the water content was not related to the changes. Recovery to basal levels of conjunctival MUC mRNA expression after wearing HCL lenses for a year takes longer than 15 days for some MUCs.

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 major advance exploited by these techniques.

Improving Cellulose Dissolution in Ionic Liquids by Tuning the Size of the Ions: Impact of the Length of the Alkyl Chains in Tetraalkylammonium Carboxylate.

PubMed

Meng, Xiangqian; Devemy, Julien; Verney, Vincent; Gautier, Arnaud; Husson, Pascale; Andanson, Jean-Michel

2017-04-22

Twenty ionic liquids based on tetraalkylammonium cations and carboxylate anions have been synthesized, characterized, and tested for cellulose dissolution. The amount of cellulose dissolved in these ionic liquids depends strongly on the size of the ions: from 0 to 22 wt % cellulose can be dissolved at 90 °C. The best ionic liquids are less viscous and ammonium carboxylate based ionic liquids can dissolve as much as imidazolium-based ones. The viscosity of an ionic liquid can be decreased by the addition of DMSO as a cosolvent. After the addition of cosolvent, similar amounts of cellulose per ions are reached for most ionic liquids. As observed by rheology, ionic liquids with the longest alkyl chains form a gel when a high amount of cellulose is dissolved; this drastically limits their potential. Molecular simulations and IR spectroscopy have also been used with the aim of understanding how molecular interactions differ between efficient and inefficient ionic liquids. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A hybrid nanosensor for TNT vapor detection.

PubMed

Díaz Aguilar, Alvaro; Forzani, Erica S; Leright, Mathew; Tsow, Francis; Cagan, Avi; Iglesias, Rodrigo A; Nagahara, Larry A; Amlani, Islamshah; Tsui, Raymond; Tao, N J

2010-02-10

Real-time detection of trace chemicals, such as explosives, in a complex environment containing various interferents has been a difficult challenge. We describe here a hybrid nanosensor based on the electrochemical reduction of TNT and the interaction of the reduction products with conducting polymer nanojunctions in an ionic liquid. The sensor simultaneously measures the electrochemical current from the reduction of TNT and the conductance change of the polymer nanojunction caused from the reduction product. The hybrid detection mechanism, together with the unique selective preconcentration capability of the ionic liquid, provides a selective, fast, and sensitive detection of TNT. The sensor, in its current form, is capable of detecting parts-per-trillion level TNT in the presence of various interferents within a few minutes.

Guar gum as biosourced building block to generate highly conductive and elastic ionogels with poly(ionic liquid) and ionic liquid.

PubMed

Zhang, Biao; Sudre, Guillaume; Quintard, Guilhem; Serghei, Anatoli; David, Laurent; Bernard, Julien; Fleury, Etienne; Charlot, Aurélia

2017-02-10

In this study, we report on the simple and straightforward preparation of ionogels arising from the addition of guar gum (a plant-based polysaccharide) in a solution of precisely-defined poly(ionic liquid) chains (PIL) in imidazolium-based ionic liquid (IL). The development of intermolecular polar interactions (mainly hydrogen bonds) and topologic chain entanglements induces the formation of physical biohybrid ionogels, whose elastic properties can be easily tuned by varying the composition (up to 30000Pa). The combined presence of guar gum and PIL confers excellent dimensional stability to the ionogels with no IL exudation combined with high thermal properties (up to 310°C). The resulting materials are shown to exhibit gel scattering profiles and high conductivities (> 10 -4 S/cm at 30°C). The benefit linked to the formation of guar/PIL associations in IL medium enables to find a good compromise between the mechanical cohesion and the mobility ensuring the ionic transport. Copyright © 2016 Elsevier Ltd. All rights reserved.

Specific binding of (/sup 3/H-Tyr8)physalaemin to rat submaxillary gland substance P receptor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bahouth, S.W.; Lazaro, D.M.; Brundish, D.E.

1985-01-01

(/sup 3/H)Physalaemin ((/sup 3/H)PHY) binds to a single class of noninteracting sites on rat submaxillary gland membranes suspended in high ionic strength media with a KD of 2.7 nM, a Bmax of 240 fmol/mg of protein, and low nonspecific binding. The relative potencies of substance P (SP) and its fragments in competing with (/sup 3/H)PHY correlate with their relative salivation potencies. This indicates that (/sup 3/H)PHY interacts with a physiologically relevant SP receptor. In low ionic strength media, the KD of (/sup 3/H)PHY does not change, but SP and some of its fragments are more potent than PHY in competingmore » with (/sup 3/H) PHY. Computer-assisted analysis of (/sup 3/H)PHY and (/sup 3/H)SP binding in high and low ionic strength media demonstrated that both peptides are equipotent in high ionic strength but that the affinity of SP increases by 70-fold in low ionic strength. The SP fragments that contain a basic residue in positions 1 and/or 3 also display an increased affinity in low ionic strength. These findings document that (/sup 3/H)PHY binding in high ionic strength (mu . 0.6) accurately reflects the pharmacological potencies of agonists on the SP-P receptor. The binding of (/sup 3/H)PHY, like that of (/sup 3/H)SP, increases by the addition of divalent cations (Mg2+ greater than Ca2+ greater than Mn2+). Guanine nucleotides decrease (/sup 3/H)PHY binding by decreasing the Bmax to the same level (160 fmol/mg of protein), in the presence or absence of Mg2+.« less

Femtosecond Raman-Induced Kerr Effect Study of Temperature-Dependent Intermolecular Dynamics in Molten Bis(trifluoromethylsulfonyl)amide Salts: Effects of Cation Species.

PubMed

Kakinuma, Shohei; Shirota, Hideaki

2018-05-25

In this study, we have investigated the effects of cation structures on the temperature dependence of the intermolecular vibrational dynamics of ionic liquids using femtosecond Raman-induced Kerr effect spectroscopy. The ionic liquids used in this study are bis(trifluoromethylsulfonyl)amide [NTf 2 ] - salts of the cations 1-butyl-3-methylimidazolium [C 4 MIm] + , 1-butyl-1-methylpyrrolidinium [Pyrr 14 ] + , 1-butylpyridinium [C 4 Py] + , butyldiethylmethylammonium [N 1224 ] + , triethyloctylammonium [N 2228 ] + , and triethyloctylphosphonium [P 2228 ] + . All of the ionic liquids show temperature-dependent low-frequency spectra. A difference in the temperature dependence between the spectra of the aromatic and nonaromatic cation based ionic liquids is especially significant. In the case of the aromatic cation based ionic liquids [C 4 MIm][NTf 2 ] and [C 4 Py][NTf 2 ], the spectral intensities in the low-frequency region below ca. 50 cm -1 increase and the high-frequency components at ca. 80 cm -1 shift to lower frequencies with rising temperature. In contrast, the ionic liquids based on nonaromatic cations only exhibit an increase in the low-frequency region below ca. 50 cm -1 with increasing temperature, while the high-frequency region of the spectra above ca. 50 cm -1 shows little change with variation of the temperature. These results suggest that the presence or absence of aromatic rings is the main factor in determining the temperature-dependent spectral features, particularly in the high-frequency region. We also found that the alkyl chain length and central atoms of the nonaromatic quaternary cations do not have much influence on the temperature-dependent spectral features. The first moments of the aromatic cation based ionic liquids are a little more sensitive to temperature than those of the nonaromatic cation based ionic liquids. The temperature-dependent viscosities and fragilities of the ionic liquids have also been examined.

Neptunium(V) Adsorption to Bacteria at Low and High Ionic Strength

NASA Astrophysics Data System (ADS)

Ams, D.; Swanson, J. S.; Reed, D. T.

2010-12-01

Np(V) is expected to be the predominant oxidation state of neptunium in aerobic natural waters. Np(V), as the NpO2+ aquo and associated complexed species, is readily soluble, interacts weakly with geologic media, and has a high redox stability under a relatively wide range of subsurface conditions. These chemical properties, along with a long half-life make it a primary element of concern regarding long-term nuclear waste storage and subsurface containment. The fate and transport of neptunium in the environment may be influenced by adsorption onto bacterial surfaces. The adsorption of neptunium to bacterial surfaces ties the mobility of the contaminant to the mobility of the bacterium. In this study, the adsorption of the neptunyl (NpO2+) ion was evaluated at low ionic strength on a common soil bacterium and at high ionic strength on a halophilic bacterium isolated from a briny groundwater near the Waste Isolation Pilot Plant (WIPP) in southeast New Mexico. Adsorption experiments were performed in batch reactors as a function of pH, ionic strength, and bacteria/Np mass ratio. Np(V) adsorption was modeled using a surface complexation approach with the mathematical program FITEQL to determine functional group specific binding constants. The data from acid and base titrations of the bacteria used were also modeled to estimate the concentrations and deprotonation constants of discrete bacterial surface functional groups. Bacterial functional group characteristics and Np(V) adsorption behavior between the soil bacterium and the halophilic bacterium were compared. These results highlight key similarities and differences in actinide adsorption behavior in environments of significantly different ionic strength. The observed adsorption behavior may be linked to similarities and differences in the characteristics of the moieties between the cell walls of common gram-negative soil and halophilic bacteria. Moreover, differences in adsorption behavior may also reflect ionic strength effects as the electronic double layer is compressed with increasing ionic strength. These results further highlight the importance of electrostatic interactions in the adsorption process between dissolved metals and bacterial surfaces. This work expands the understanding of actinide-bacteria adsorption phenomena to high ionic strength environmental conditions that are relevant as an aid to predicting Np(V) fate and transport behavior in areas such as the vicinity of salt-based nuclear waste repositories and high ionic-strength groundwaters at DOE sites.

Ionic strength and DOC determinations from various freshwater sources to the San Francisco Bay

USGS Publications Warehouse

Hunter, Y.R.; Kuwabara, J.S.

1994-01-01

An exact estimation of dissolved organic carbon (DOC) within the salinity gradient of zinc and copper metals is significant in understanding the limit to which DOC could influence metal speciation. A low-temperature persulfate/oxygen/ultraviolet wet oxidation procedure was utilized for analyzing DOC samples adapted for ionic strength from major freshwater sources of the northern and southern regions of San Francisco Bay. The ionic strength of samples was modified with a chemically defined seawater medium up to 0.7M. Based on the results, a minimum effect of ionic strength on oxidation proficiency for DOC sources to the Bay over an ionic strength gradient of 0.0 to 0.7 M was observed. There was no major impacts of ionic strength on two Suwanee River fulvic acids. In general, the noted effects associated with ionic strength were smaller than the variances seen in the aquatic environment between high- and low-temperature methods.

Hybrid Encapsulated Ionic Liquids for Post-Combustion Carbon Dioxide (CO 2) Capture

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brennecke, Joan F; Degnan, Jr, Thomas Francis; McCready, Mark J.

Ionic liquids (ILs) and Phase Change Ionic Liquids (PCILs) are excellent materials for selective removal of carbon dioxide from dilute post-combustion streams. However, they are typically characterized as having high viscosities, which impairs their effectiveness due to mass transfer limitations, caused by the high viscosities. In this project, we are examining the benefits of encapsulating ILs and PCILs in thin polymeric shells to produce particles of approximately 100 to 600 µm in diameter that can be used in a fluidized bed absorber. The particles are produced by microencapsulation of the ILs and PCILs in CO 2-permeable polymer shells. Here wemore » report on the encapsulation of the IL and PCIL materials, thermodynamic testing of the encapsulated materials, mass transfer measurements in both a fluidized bed and a packed bed, determination of the effect of impurities (SO 2, NO x and water) on the free and encapsulated IL and PCIL, recyclability of the CO 2 uptake, selection and synthesis of kg quantities of the IL and PCIL, identification of scale-up methods for encapsulation and production of a kg quantity of the PCIL, construction and shakedown of the laboratory scale unit to test the encapsulated particles for CO 2 capture ability and efficiency, use of our mass transfer model to predict mass transfer and identify optimal properties of the encapsulated particles, and initial testing of the encapsulated particles in the laboratory scale unit. We also show our attempts at developing shell materials that are resistant to water permeation. Overall, we have shown that the selected IL and PCIL can be successfully encapsulated in polymer shells and the methods scaled up to production levels. The IL/PCIL and encapsulated IL/PCIL react irreversibly with SO 2 and NO x so the CO 2 capture unit would need to be placed after the flue gas desulfurization and NO x reduction units. However, the reaction with CO 2 in the presence of water is completely reversible. Therefore, it is not necessary to exclude water from the capsules. Mass transfer in the fluidized and packed beds confirm that the fluidized bed arrangement is preferred and that the mass transfer can be predicted accurately by the rate based model that we have developed. Absorption and desorption experiments in the laboratory scale unit show good uptake and recyclability.« less

High performance photolithographically-patterned polymer thin-film transistors gated with an ionic liquid/poly(ionic liquid) blend ion gel

NASA Astrophysics Data System (ADS)

Thiburce, Q.; Porcarelli, L.; Mecerreyes, D.; Campbell, A. J.

2017-06-01

We demonstrate the fabrication of polymer thin-film transistors gated with an ion gel electrolyte made of the blend of an ionic liquid and a polymerised ionic liquid. The ion gel exhibits a high stability and ionic conductivity, combined with facile processing by simple drop-casting from solution. In order to avoid parasitic effects such as high hysteresis, high off-currents, and slow switching, a fluorinated photoresist is employed in order to enable high-resolution orthogonal patterning of the polymer semiconductor over an area that precisely defines the transistor channel. The resulting devices exhibit excellent characteristics, with an on/off ratio of 106, low hysteresis, and a very large transconductance of 3 mS. We show that this high transconductance value is mostly the result of ions penetrating the polymer film and doping the entire volume of the semiconductor, yielding an effective capacitance per unit area of about 200 μF cm-2, one order of magnitude higher than the double layer capacitance of the ion gel. This results in channel currents larger than 1 mA at an applied gate bias of only -1 V. We also investigate the dynamic performance of the devices and obtain a switching time of 20 ms, which is mostly limited by the overlap capacitance between the ion gel and the source and drain contacts.

Symmetric supercapacitor: Sulphurized graphene and ionic liquid.

PubMed

Shaikh, Jasmin S; Shaikh, Navajsharif S; Kharade, Rohini; Beknalkar, Sonali A; Patil, Jyoti V; Suryawanshi, Mahesh P; Kanjanaboos, Pongsakorn; Hong, Chang Kook; Kim, Jin Hyeok; Patil, Pramod S

2018-10-01

Symmetric supercapacitor is advanced over simple supercapacitor device due to their stability over a large potential window and high energy density. Graphene is a desired candidate for supercapacitor application since it has a high surface area, good electronic conductivity and high electro chemical stability. There is a pragmatic use of ionic liquid electrolyte for supercapacitor due to its stability over a large potential window, good ionic conductivity and eco-friendly nature. For high performance supercapacitor, the interaction between ionic liquid electrolyte and graphene are crucial for better charge transportation. In respect of this, a three-dimensional (3D) nanoporous honeycomb shaped sulfur embedded graphene (S-graphene) has been synthesized by simple chemical method. Here, the fabrication of high performance symmetric supercapacitor is done by using S-graphene as an electrode and [BMIM-PF 6 ] as an electrolyte. The particular architecture of S-graphene benefited to reduce the ion diffusion resistance, providing the large surface area for charge transportation and efficient charge storage. The S-graphene and ionic liquid-based symmetric supercapacitor device showed the large potential window of 3.2 V with high energy density 124 Wh kg -1 at 0.2 A g -1 constant applied current density. Furthermore, this device shows good cycling performance (stability) with a capacitive retention of 95% over 20,000 cycles at a higher current density of 2 A g -1 . Copyright © 2018 Elsevier Inc. All rights reserved.

Method for isotope enrichment by photoinduced chemiionization

DOEpatents

Dubrin, James W.

1985-01-01

Isotope enrichment, particularly .sup.235 U enrichment, is achieved by irradiating an isotopically mixed vapor feed with radiant energy at a wavelength or wavelengths chosen to selectively excite the species containing a desired isotope to a predetermined energy level. The vapor feed if simultaneously reacted with an atomic or molecular reactant species capable of preferentially transforming the excited species into an ionic product by a chemiionization reaction. The ionic product, enriched in the desired isotope, is electrostatically or electromagnetically extracted from the reaction system.

Reactions of Ions with Ionic Liquid Vapors by Selected-Ion Flow Tube Mass Spectrometry

DTIC Science & Technology

2011-03-04

Internet at http://pubs.acs.org. References (1) Emel’yanenko, V. N.; Verevkin, S. P.; Heintz, A.; Corfield, J.-A.; Deyko, A.; Lovelock , K. R. J...Spectrometry, and ab Initio Calculations J. Phys. Chem. B 2008, 112, 11734-11742. (2) Lovelock , K. R. J.; Deyko, A.; Licence, P.; Jones, R. G. Vaporisation of...Licence, P.; Lovelock , K. R. J.; Satterly, C. J.; Villar-Garcia, I. J. Vapourisation of ionic liquids PCCP 2007, 9, 982-990. (14) Chiu, Y.-H

Application of an immobilized ionic liquid for the passive sampling of perfluorinated substances in water.

PubMed

Wang, Lei; Gong, Xinying; Wang, Ruonan; Gan, Zhiwei; Lu, Yuan; Sun, Hongwen

2017-09-15

Ionic liquids have been used to efficiently extract a wide range of polar and nonpolar organic contaminants from water. In this study, imidazole ionic liquids immobilized on silica gel were synthesized through a chemical bonding method, and the immobilized dodecylimidazolium ionic liquid was selected as the receiving phase material in a POCIS (polar organic chemical integrative sampler) like passive sampler to monitor five perfluoroalkyl substances (PFASs) in water. Twenty-one days of integrative accumulation was conducted in laboratory scale experiments, and the accumulated PFASs in the samplers were eluted and analyzed by high performance liquid chromatography coupled with tandem mass spectrometry (HPLC-MS/MS). The partitioning coefficients of most PFASs between sampler sorbents and water in the immobilized ionic liquid (IIL)-sampler were higher than those in the HLB-sampler, especially for compounds with shorter alkyl chains. The effects of flow velocity, temperature, dissolved organic matter (DOM) and pH on the uptake of these analytes were also evaluated. Under the experimental conditions, the uptake of PFASs in the IIL-sampler slightly increased with the flow velocity and temperature, while different influences of DOM and pH on the uptake of PFAS homologues with short or long chains were observed. The designed IIL-samplers were applied in the influent and effluent of a wastewater treatment plant. All five PFASs could be accumulated in the samplers, with concentrations ranging from 6.5×10 -3 -3.6×10 -1 nmol/L in the influent and from 1.3×10 -2 -2.2×10 -1 nmol/L in the effluent. The calculated time-weighted average concentrations of most PFASs fit well with the detected concentrations of the active sampling, indicating the applicability of the IIL-sampler in monitoring these compounds in water. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular Simulation of Ionic Polyimides and Composites with Ionic Liquids as Gas-Separation Membranes.

PubMed

Abedini, Asghar; Crabtree, Ellis; Bara, Jason E; Turner, C Heath

2017-10-24

Polyimides are at the forefront of advanced membrane materials for CO 2 capture and gas-purification processes. Recently, ionic polyimides (i-PIs) have been reported as a new class of condensation polymers that combine structural components of both ionic liquids (ILs) and polyimides through covalent linkages. In this study, we report CO 2 and CH 4 adsorption and structural analyses of an i-PI and an i-PI + IL composite containing [C 4 mim][Tf 2 N]. The combination of molecular dynamics (MD) and grand canonical Monte Carlo (GCMC) simulations is used to compute the gas solubility and the adsorption performance with respect to the density, fractional free volume (FFV), and surface area of the materials. Our results highlight the polymer relaxation process and its correlation to the gas solubility. In particular, the surface area can provide meaningful guidance with respect to the gas solubility, and it tends to be a more sensitive indicator of the adsorption behavior versus only considering the system density and FFV. For instance, as the polymer continues to relax, the density, FFV, and pore-size distribution remain constant while the surface area can continue to increase, enabling more adsorption. Structural analyses are also conducted to identify the nature of the gas adsorption once the ionic liquid is added to the polymer. The presence of the IL significantly displaces the CO 2 molecules from the ligand nitrogen sites in the neat i-PI to the imidazolium rings in the i-PI + IL composite. However, the CH 4 molecules move from the imidazolium ring sites in the neat i-PI to the ligand nitrogen atoms in the i-PI + IL composite. These molecular details can provide critical information for the experimental design of highly selective i-PI materials as well as provide additional guidance for the interpretation of the simulated adsorption systems.

Engineering the electrochemical capacitive properties of graphene sheets in ionic-liquid electrolytes by correct selection of anions.

PubMed

Shi, Minjie; Kou, Shengzhong; Yan, Xingbin

2014-11-01

Graphene sheet (GS)-ionic liquid (IL) supercapacitors are receiving intense interest because their specific energy density far exceeds that of GS-aqueous electrolytes supercapacitors. The electrochemical properties of ILs mainly depend on their diverse ions, especially anions. Therefore, identifying suitable IL electrolytes for GSs is currently one of the most important tasks. The electrochemical behavior of GSs in a series of ILs composed of 1-ethyl-3-methylimidazolium cation (EMIM(+)) with different anions is systematically studied. Combined with the formula derivation and building models, it is shown that the viscosity, ion size, and molecular weight of ILs affect the electrical conductivity of ILs, and thus, determine the electrochemical performances of GSs. Because the EMIM-dicyanamide IL has the lowest viscosity, ion size, and molecular weight, GSs in it exhibit the highest specific capacitance, smallest resistance, and best rate capability. In addition, because the tetrafluoroborate anion (BF4(-)) has the best electrochemical stability, the GS-[EMIM][BF4] supercapacitor has the widest potential window, and thus, displays the largest energy density. These results may provide valuable information for selecting appropriate ILs and designing high-performance GS-IL supercapacitors to meet different needs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Toxicity prediction of ionic liquids based on Daphnia magna by using density functional theory

NASA Astrophysics Data System (ADS)

Nu’aim, M. N.; Bustam, M. A.

2018-04-01

By using a model called density functional theory, the toxicity of ionic liquids can be predicted and forecast. It is a theory that allowing the researcher to have a substantial tool for computation of the quantum state of atoms, molecules and solids, and molecular dynamics which also known as computer simulation method. It can be done by using structural feature based quantum chemical reactivity descriptor. The identification of ionic liquids and its Log[EC50] data are from literature data that available in Ismail Hossain thesis entitled “Synthesis, Characterization and Quantitative Structure Toxicity Relationship of Imidazolium, Pyridinium and Ammonium Based Ionic Liquids”. Each cation and anion of the ionic liquids were optimized and calculated. The geometry optimization and calculation from the software, produce the value of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). From the value of HOMO and LUMO, the value for other toxicity descriptors were obtained according to their formulas. The toxicity descriptor that involves are electrophilicity index, HOMO, LUMO, energy gap, chemical potential, hardness and electronegativity. The interrelation between the descriptors are being determined by using a multiple linear regression (MLR). From this MLR, all descriptors being analyzed and the descriptors that are significant were chosen. In order to develop the finest model equation for toxicity prediction of ionic liquids, the selected descriptors that are significant were used. The validation of model equation was performed with the Log[EC50] data from the literature and the final model equation was developed. A bigger range of ionic liquids which nearly 108 of ionic liquids can be predicted from this model equation.

Influences of porous reservoir Laplace pressure on emissions from passively fed ionic liquid electrospray sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Courtney, Daniel G., E-mail: dcourtney@alum.mit.edu; Shea, Herbert

2015-09-07

Passively fed ionic liquid electrospray sources are capable of efficiently emitting a variety of ion beams with promising applications to spacecraft propulsion and as focused ion beams. Practical devices will require integrated or coupled ionic liquid reservoirs; the effects of which have not been explored in detail. Porous reservoirs are a simple, scalable solution. However, we have shown that their pore size can dramatically alter the beam composition. Emitting the ionic liquid 1-ethyl-3-methylimidazolium bis(triflouromethylsulfonyl)amide, the same device was shown to yield either an ion or droplet dominated beam when using reservoirs of small or large pore size, respectively; with themore » latter having a mass flow in excess of 15 times larger than the former at negative polarity. Another source, emitting nearly purely ionic beams of 1-ethyl-3-methylimidazolium tetrafluoroborate, was similarly shown to emit a significant droplet population when coupled to reservoirs of large (>100 μm) pores; constituting a reduction in propulsive efficiency from greater than 70% to less than 30%. Furthermore, we show that reservoir selection can alter the voltage required to obtain and sustain emission, increasing with smaller pore size.« less

Application of Ionic Liquids in the Microwave-Assisted Extraction of Proanthocyanidins from Larix gmelini Bark

PubMed Central

Yang, Lei; Sun, Xiaowei; Yang, Fengjian; Zhao, Chunjian; Zhang, Lin; Zu, Yuangang

2012-01-01

Ionic liquid based, microwave-assisted extraction (ILMAE) was successfully applied to the extraction of proanthocyanidins from Larix gmelini bark. In this work, in order to evaluate the performance of ionic liquids in the microwave-assisted extraction process, a series of 1-alkyl-3-methylimidazolium ionic liquids with different cations and anions were evaluated for extraction yield, and 1-butyl-3-methylimidazolium bromide was selected as the optimal solvent. In addition, the ILMAE procedure for the proanthocyanidins was optimized and compared with other conventional extraction techniques. Under the optimized conditions, satisfactory extraction yield of the proanthocyanidins was obtained. Relative to other methods, the proposed approach provided higher extraction yield and lower energy consumption. The Larix gmelini bark samples before and after extraction were analyzed by Thermal gravimetric analysis, Fourier-transform infrared spectroscopy and characterized by scanning electron microscopy. The results showed that the ILMAE method is a simple and efficient technique for sample preparation. PMID:22606036

Development of an automated experimental setup for the study of ionic-exchange kinetics. Application to the ionic adsorption, equilibrium attainment and dissolution of apatite compounds.

PubMed

Thomann, J M; Gasser, P; Bres, E F; Voegel, J C; Gramain, P

1990-02-01

An ion-selective electrode and microcomputer-based experimental setup for the study of ionic-exchange kinetics between a powdered solid and the solution is described. The equipment is composed of easily available commercial devices and a data acquisition and regularization computer program is presented. The system, especially developed to investigate the ionic adsorption, equilibrium attainment and dissolution of hard mineralized tissues, provides good reliable results by taking into account the volume changes of the reacting solution and the electrode behaviour under different experimental conditions, and by avoiding carbonation of the solution. A second computer program, using the regularized data and the experimental parameters, calculates the quantities of protons consumed and calcium released in the case of equilibrium attainment and dissolution of apatite-like compounds. Finally, typical examples of ion-exchange and dissolution kinetics under constant pH of enamel and synthetic hydroxyapatite are examined.

Ionic liquids as lubricants or lubrication additives: an ecotoxicity and biodegradability assessment.

PubMed

Stolte, Stefan; Steudte, Stephanie; Areitioaurtena, Olatz; Pagano, Francesco; Thöming, Jorg; Stepnowski, Piotr; Igartua, Amaya

2012-11-01

This paper reports on the (eco)toxicity and biodegradability of ionic liquids considered for application as lubricants or lubrication additives. Ammonium- and pyrrolidinium-based cations combined with methylsulphate, methylsulphonate and/or (CF(3)SO(2))(2)N(-) anions were investigated in tests to determine their aquatic toxicity using water fleas Daphnia magna, green algae Selenastrum capricornutum and marine bacteria (Vibrio fischeri). Additional test systems with an isolated enzyme (acetylcholinesterase) and isolated leukaemia cells from rats (IPC-81) were used to assess the biological activity of the ionic liquids. These compounds generally exhibit low acute toxicity and biological activity. Their biodegradability was screened according to OECD test procedures 301 B and 301 F. For choline and methoxy-choline ionic liquids ready biodegradability was observed within 5 or 10 d, respectively. Some of the compounds selected have a considerable potential to contribute to the development of more sustainable products and processes. Copyright © 2012 Elsevier Ltd. All rights reserved.

Non-conventional solvents in liquid phase microextraction and aqueous biphasic systems.

PubMed

An, Jiwoo; Trujillo-Rodríguez, María J; Pino, Verónica; Anderson, Jared L

2017-06-02

The development of rapid, convenient, and high throughput sample preparation approaches such as liquid phase microextraction techniques have been continuously developed over the last decade. More recently, significant attention has been given to the replacement of conventional organic solvents used in liquid phase microextraction techniques in order to reduce toxic waste and to improve selectivity and/or extraction efficiency. With these objectives, non-conventional solvents have been explored in liquid phase microextraction and aqueous biphasic systems. The utilized non-conventional solvents include ionic liquids, magnetic ionic liquids, and deep eutectic solvents. They have been widely used as extraction solvents or additives in various liquid phase microextraction modes including dispersive liquid-liquid microextraction, single-drop microextraction, hollow fiber-liquid phase microextraction, as well as in aqueous biphasic systems. This review provides an overview into the use of non-conventional solvents in these microextraction techniques in the past 5 years (2012-2016). Analytical applications of the techniques are also discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Water-Borne Endovascular Embolics Inspired by the Undersea Adhesive of Marine Sandcastle Worms.

PubMed

Jones, Joshua P; Sima, Monika; O'Hara, Ryan G; Stewart, Russell J

2016-04-06

Transcatheter embolization is used to treat vascular malformations and defects, to control bleeding, and to selectively block blood supply to tissues. Liquid embolics are used for small vessel embolization that require distal penetration. Current liquid embolic agents have serious drawbacks, mostly centered around poor handling characteristics and toxicity. In this work, a water-borne in situ setting liquid embolic agent is described that is based on electrostatically condensed, oppositely charged polyelectrolytes-complex coacervates. At high ionic strengths, the embolic coacervates are injectable fluids that can be delivered through long narrow microcatheters. At physiological ionic strength, the embolic coacervates transition into a nonflowing solid morphology. Transcatheter embolization of rabbit renal arteries demonstrated capillary level penetration, homogeneous occlusion, and 100% devascularization of the kidney, without the embolic crossing into venous circulation. The benign water-borne composition and setting mechanism avoids many of the problems of current liquid embolics, and provides precise temporal and spatial control during endovascular embolization. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The hydrophilicity vs. ion interaction selectivity plot revisited: The effect of mobile phase pH and buffer concentration on hydrophilic interaction liquid chromatography selectivity behavior.

PubMed

Iverson, Chad D; Gu, Xinyun; Lucy, Charles A

2016-08-05

This work systematically investigates the selectivity changes on many HILIC phases from w(w)pH 3.7-6.8, at 5 and 25mM buffer concentrations. Hydrophilicity (kcytosine/kuracil) vs. ion interaction (kBTMA/kuracil) selectivity plots developed by Ibrahim et al. (J. Chromatogr. A 1260 (2012) 126-131) are used to investigate the effect of mobile phase changes on the selectivity of 18 HILIC columns from various classes. "Selectivity change plots" focus on the change in hydrophilicity and ion interaction that the columns exhibit upon changing mobile phase conditions. In general, the selectivity behavior of most HILIC columns is dominated by silanol activity. Minimal changes in selectivity are observed upon changing pH between w(w)pH 5 and 6.8. However, a reduction in ionic interaction is observed when the buffer concentration is increased at w(w)pH≥5.0 due to ionic shielding. Reduction of the w(w)pH to<5.0 results in decreasing cation exchange activity due to silanol protonation. Under all eluent conditions, the majority of phases show little change in their hydrophilicity. Copyright © 2016 Elsevier B.V. All rights reserved.

MicroRNA Detection by DNA-Mediated Liposome Fusion.

PubMed

Jumeaux, Coline; Wahlsten, Olov; Block, Stephan; Kim, Eunjung; Chandrawati, Rona; Howes, Philip D; Höök, Fredrik; Stevens, Molly M

2018-03-02

Membrane fusion is a process of fundamental importance in biological systems that involves highly selective recognition mechanisms for the trafficking of molecular and ionic cargos. Mimicking natural membrane fusion mechanisms for the purpose of biosensor development holds great potential for amplified detection because relatively few highly discriminating targets lead to fusion and an accompanied engagement of a large payload of signal-generating molecules. In this work, sequence-specific DNA-mediated liposome fusion is used for the highly selective detection of microRNA. The detection of miR-29a, a known flu biomarker, is demonstrated down to 18 nm within 30 min with high specificity by using a standard laboratory microplate reader. Furthermore, one order of magnitude improvement in the limit of detection is demonstrated by using a novel imaging technique combined with an intensity fluctuation analysis, which is coined two-color fluorescence correlation microscopy. © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Ionic supramolecular networks fully based on chemicals coming from renewable sources.

PubMed

Aboudzadeh, Ali; Fernandez, Mercedes; Muñoz, Maria Eugenia; Santamaría, Antxon; Mecerreyes, David

2014-02-01

New supramolecular ionic networks are synthesized by proton transfer reaction between a bio-based fatty diamine molecule (Priamine 1074) and a series of naturally occurring carboxylic acids such as malonic acid, citric acid, tartaric acid, and 2,5-furandicarboxylic acid. The resulting solid soft material exhibits a thermoreversible transition becoming a viscoelastic liquid at high temperatures. All the networks show an elastic behavior at low temperatures/high frequencies, with elastic modulus values ranging from 4.5 × 10(6) to 4.5 × 10(7) Pa and soft network to liquid transitions T(nl) between -10 and 60 °C. The supramolecular ionic network based on cationic Priamine 1074 and anionic citrate shows promising self-healing properties at room temperature as well as relatively high ionic conductivity values close to 10(-6) S cm(-1). © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A highly aromatic and sulfonated ionomer for high elastic modulus ionic polymer membrane micro-actuators

NASA Astrophysics Data System (ADS)

Hatipoglu, Gokhan; Liu, Yang; Zhao, Ran; Yoonessi, Mitra; Tigelaar, Dean M.; Tadigadapa, Srinivas; Zhang, Q. M.

2012-05-01

A high modulus, sulfonated ionomer synthesized from 4,6-bis(4-hydroxyphenyl)-N,N-diphenyl-1,3,5-triazin-2-amine and 4,4‧-biphenol with bis(4-fluorophenyl)sulfone (DPA-PS:BP) is investigated for ionic polymer actuators. The uniqueness of DPA-PS:BP is that it can have a high ionic liquid (IL) uptake and consequently generates a high intrinsic strain response, which is >1.1% under 1.6 V while maintaining a high elastic modulus (i.e. 600 MPa for 65 vol% IL uptake). Moreover, such a high modulus of the active ionomer, originating from the highly aromatic backbone and side-chain-free structure, allows for the fabrication of free-standing thin film micro-actuators (down to 5 µm thickness) via the solution cast method and focused-ion-beam milling, which exhibits a much higher bending actuation, i.e. 43 µm tip displacement and 180 kPa blocking stress for a 200 µm long and 5 µm thick cantilever actuator, compared with the ionic actuators based on traditional ionomers such as Nafion, which has a much lower elastic modulus (50 MPa) and actuation strain.

Exceptionally High Electric Double Layer Capacitances of Oligomeric Ionic Liquids.

PubMed

Matsumoto, Michio; Shimizu, Sunao; Sotoike, Rina; Watanabe, Masayoshi; Iwasa, Yoshihiro; Itoh, Yoshimitsu; Aida, Takuzo

2017-11-15

Electric double layer (EDL) capacitors are promising as next-generation energy accumulators if their capacitances and operation voltages are both high. However, only few electrolytes can simultaneously fulfill these two requisites. Here we report that an oligomeric ionic liquid such as IL4 TFSI with four imidazolium ion units in its structure provides a wide electrochemical window of ∼5.0 V, similar to monomeric ionic liquids. Furthermore, electrochemical impedance measurements using Au working electrodes demonstrated that IL4 TFSI exhibits an exceptionally high EDL capacitance of ∼66 μF/cm 2 , which is ∼6 times as high as those of monomeric ionic liquids so far reported. We also found that an EDL-based field effect transistor (FET) using IL4 TFSI as a gate dielectric material and SrTiO 3 as a channel material displays a very sharp transfer curve with an enhanced carrier accumulation capability of ∼64 μF/cm 2 , as determined by Hall-effect measurements.

Determination of chlorophenols in honey samples using in-situ ionic liquid-dispersive liquid-liquid microextraction as a pretreatment method followed by high-performance liquid chromatography.

PubMed

Fan, Chen; Li, Nai; Cao, Xueli

2015-05-01

In-situ ionic liquid-dispersive liquid-liquid microextraction (IL-DLLME) method was developed as a pretreatment method for the detection of six chlorophenols (CPs) in honey samples. The hydrophobic ionic liquid [C4MIM][NTf2], formed in-situ by the hydrophilic ionic liquid [C4MIM][BF4] and the ion exchange reagent LiNTf2 was used as the microextractant solvent of CPs from honey sample. Then the enriched analytes were back-extracted into 40 μL of 0.14 M NaOH solution and finally subjected to analysis by high-performance liquid chromatography. The method showed low limit of detection of CPs, 0.8-3.2 μg/L and high enrichment factor, 34-65 with the recoveries range from 91.60% to 114.33%. The method is simple, rapid, environmentally friendly and with high extraction efficiency. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

Graphitic carbon nitride nanosheet electrode-based high-performance ionic actuator

PubMed Central

Wu, Guan; Hu, Ying; Liu, Yang; Zhao, Jingjing; Chen, Xueli; Whoehling, Vincent; Plesse, Cédric; Nguyen, Giao T. M.; Vidal, Frédéric; Chen, Wei

2015-01-01

Ionic actuators have attracted attention due to their remarkably large strain under low-voltage stimulation. Because actuation performance is mainly dominated by the electrochemical and electromechanical processes of the electrode layer, the electrode material and structure are crucial. Here, we report a graphitic carbon nitride nanosheet electrode-based ionic actuator that displays high electrochemical activity and electromechanical conversion abilities, including large specific capacitance (259.4 F g−1) with ionic liquid as the electrolyte, fast actuation response (0.5±0.03% in 300 ms), large electromechanical strain (0.93±0.03%) and high actuation stability (100,000 cycles) under 3 V. The key to the high performance lies in the hierarchical pore structure with dominant size <2 nm, optimal pyridinic nitrogen active sites (6.78%) and effective conductivity (382 S m−1) of the electrode. Our study represents an important step towards artificial muscle technology in which heteroatom modulation in electrodes plays an important role in promoting electrochemical actuation performance. PMID:26028354

Highly Efficient Plastic Crystal Ionic Conductors for Solid-state Dye-sensitized Solar Cells

PubMed Central

Hwang, Daesub; Kim, Dong Young; Jo, Seong Mu; Armel, Vanessa; MacFarlane, Douglas R.; Kim, Dongho; Jang, Sung-Yeon

2013-01-01

We have developed highly efficient, ambient temperature, solid-state ionic conductors (SSICs) for dye-sensitized solar cells (DSSCs) by doping a molecular plastic crystal, succinonitrile (SN), with trialkyl-substituted imidazolium iodide salts. High performance SSICs with enhanced ionic conductivity (2–4 mScm−1) were obtained. High performance solid-state DSSCs with power conversion efficiency of 7.8% were fabricated using our SSICs combined with unique hierarchically nanostructured TiO2 sphere (TiO2-SP) photoelectrodes; these electrodes have significant macroporosity, which assists penetration of the solid electrolyte into the electrode. The performance of our solid-state DSSCs is, to the best of our knowledge, the highest reported thus far for cells using plastic crystal-based SSICs, and is comparable to that of the state-of-the-art DSSCs which use ionic liquid type electrolytes. This report provides a logical strategy for the development of efficient plastic crystal-based SSICs for DSSCs and other electrochemical devices. PMID:24343425

Response surface method (RSM) for optimization of ionic conductivity of membranes polymer electrolyte poly (vinylidene fluoride) (PVDF) with polyvinyl pyrrolidone (PVP) as pore forming agent

NASA Astrophysics Data System (ADS)

Dyartanti, E. R.; Susanto, H.; Widiasa, I. N.; Purwanto, A.

2017-06-01

The Membranes Polymer Gel Electrolyte (MPGEs) based poly (vinylidene fluoride) (PVDF) was prepared by a phase inversion method using polyvinyl pyrrolidone (PVP) as a pore-forming agent and N, N-dimethyl acetamide (DMAc) as a solvent and water as non solvet. The membranes were then soaked in 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC) / dimethyl carbonate (DMC) / Diethyl carbonate (DEC) (4:2:4 %vol) solution in order to prepare polymer electrolyte membranes. The MPEGs PVDF/PVP/Nanoclay was applied using central composite design (CCD) experimental design to obtain a quantitative relationship between selected membranes prepared parameters namely (PVDF, PVP as pore forming agent and nanoclay filler concentration) and Ionic conductivity MPEGs. The model was used to find the optimum ionic conductivity from polymer electrolyte membranes. The polymer electrolyte membranes show good ionic conductivity on the order of 6.3 - 8.7 x 10-3 S cm-1 at the ambient temperatures. The ionic conductivity tended to increase with PVP and nanoclay concentration and decrease with PVDF composition. The model predicted the maximum ionic conductivity of 8.47 x 10-3 S cm-1 when the PVDF, PVP and nanoclay concentration were set at 8.01 %, 8.04 % and 10.12%, respectively. The first section in your paper.

Facile ionothermal synthesis of microporous and mesoporous carbons from task specific ionic liquids.

PubMed

Lee, Je Seung; Wang, Xiqing; Luo, Huimin; Baker, Gary A; Dai, Sheng

2009-04-08

An expedient, template-free, high-yield, and solventless route to nitrogen-rich micro- and mesoporous carbons is reported based on direct, atmospheric-pressure carbonization of task-specific ionic liquids bearing one or more nitrile side chains. The resulting textural properties (pore regime, surface area) are highly dependent upon the structural motifs of the ions comprising the corresponding parent ionic liquid, and uniform carbon films are routinely deposited with this novel methodology, highlighting excited new opportunities in the development of advanced functional carbon composites.

Solid electrolytes for fluoride ion batteries: ionic conductivity in polycrystalline tysonite-type fluorides.

PubMed

Rongeat, Carine; Reddy, M Anji; Witter, Raiker; Fichtner, Maximilian

2014-02-12

Batteries based on a fluoride shuttle (fluoride ion battery, FIB) can theoretically provide high energy densities and can thus be considered as an interesting alternative to Li-ion batteries. Large improvements are still needed regarding their actual performance, in particular for the ionic conductivity of the solid electrolyte. At the current state of the art, two types of fluoride families can be considered for electrolyte applications: alkaline-earth fluorides having a fluorite-type structure and rare-earth fluorides having a tysonite-type structure. As regard to the latter, high ionic conductivities have been reported for doped LaF3 single crystals. However, polycrystalline materials would be easier to implement in a FIB due to practical reasons in the cell manufacturing. Hence, we have analyzed in detail the ionic conductivity of La(1-y)Ba(y)F(3-y) (0 ≤ y ≤ 0.15) solid solutions prepared by ball milling. The combination of DC and AC conductivity analyses provides a better understanding of the conduction mechanism in tysonite-type fluorides with a blocking effect of the grain boundaries. Heat treatment of the electrolyte material was performed and leads to an improvement of the ionic conductivity. This confirms the detrimental effect of grain boundaries and opens new route for the development of solid electrolytes for FIB with high ionic conductivities.

Pair distribution function analysis of sulfide glassy electrolytes for all-solid-state batteries: Understanding the improvement of ionic conductivity under annealing condition.

PubMed

Shiotani, Shinya; Ohara, Koji; Tsukasaki, Hirofumi; Mori, Shigeo; Kanno, Ryoji

2017-08-01

In general, the ionic conductivity of sulfide glasses decreases with their crystallization, although it increases for a few sulphide glasses owing to the crystallization of a highly conductive new phase (e.g., Li 7 P 3 S 11 : 70Li 2 S-30P 2 S 5 ). We found that the ionic conductivity of 75Li 2 S-25P 2 S 5 sulfide glass, which consists of glassy and crystalline phases, is improved by optimizing the conditions of the heat treatment, i.e., annealing. A different mechanism of high ionic conductivity from the conventional mechanism is expected in the glassy phase. Here, we report the glassy structure of 75Li 2 S-25P 2 S 5 immediately before the crystallization by using the differential pair distribution function (d-PDF) analysis of high-energy X-ray diffraction. Even though the ionic conductivity increases during the optimum annealing, the d-PDF analysis indicated that the glassy structure undergoes no structural change in the sulfide glass-ceramic electrolyte at a crystallinity of 33.1%. We observed the formation of a nanocrystalline phase in the X-ray and electron diffraction patterns before the crystallization, which means that Bragg peaks were deformed. Thus, the ionic conductivity in the mixture of glassy and crystalline phases is improved by the coexistence of the nanocrystalline phase.

Soft but Powerful Artificial Muscles Based on 3D Graphene-CNT-Ni Heteronanostructures.

PubMed

Kim, Jaehwan; Bae, Seok-Hu; Kotal, Moumita; Stalbaum, Tyler; Kim, Kwang J; Oh, Il-Kwon

2017-08-01

Bioinspired soft ionic actuators, which exhibit large strain and high durability under low input voltages, are regarded as prospective candidates for future soft electronics. However, due to the intrinsic drawback of weak blocking force, the feasible applications of soft ionic actuators are limited until now. An electroactive artificial muscle electro-chemomechanically reinforced with 3D graphene-carbon nanotube-nickel heteronanostructures (G-CNT-Ni) to improve blocking force and bending deformation of the ionic actuators is demonstrated. The G-CNT-Ni heteronanostructure, which provides an electrically conductive 3D network and sufficient contact area with mobile ions in the polymer electrolyte, is embedded as a nanofiller in both ionic polymer and conductive electrodes of the ionic actuators. An ionic exchangeable composite membrane consisting of Nafion, G-CNT-Ni and ionic liquid (IL) shows improved tensile modulus and strength of up to 166% and 98%, respectively, and increased ionic conductivity of 0.254 S m -1 . The ionic actuator exhibits enhanced actuation performances including three times larger bending deformation, 2.37 times higher blocking force, and 4 h durability. The electroactive artificial muscle electro-chemomechanically reinforced with 3D G-CNT-Ni heteronanostructures offers improvements over current soft ionic actuator technologies and can advance the practical engineering applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel double-confined polymeric ionic liquids as sorbents for solid-phase microextraction with enhanced stability and durability in high-ionic-strength solution.

PubMed

Feng, Juanjuan; Sun, Min; Xu, Lili; Wang, Shuai; Liu, Xia; Jiang, Shengxiang

2012-12-14

Because of the occurrence of ion exchange between high-ionic-strength solution and anions of polymeric ionic liquids (PILs), PILs based solid-phase microextraction (SPME) fibers were rarely used in direct immersion mode to high-salt-added samples. In this work, a novel double-confined PIL sorbent was prepared by co-polymerization of cation and anion of 1-vinyl-3-octylimidzaolium p-styrenesulfonate (VOIm(+)SS(-)). The poly(VOIm(+)-SS(-)) was chemically bonded onto functionalized stainless steel wire via surface radical chain-transfer reaction. Stability of poly(VOIm(+)-SS(-)) in high-ionic-strength solution was investigated and compared with that of poly(1-vinyl-3-octylimidzaolium benzenesulfonate) (poly(VOIm(+)BS(-))) by elemental analysis of sulfur element, and results turned out that the poly(VOIm(+)-SS(-)) was more stable. Coupled to gas chromatography (GC), the poly(VOIm(+)-SS(-)) fiber was used to extract three sorts of compounds including anilines, phenols and phthalate esters in aqueous solution. The as-established method showed good linearity, low detection limits, and acceptable repeatability. The direct immersion SPME-GC method was applied to determine the model phthalate esters in bottled mineral water. The determination results were satisfactory. Copyright © 2012 Elsevier B.V. All rights reserved.

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

PubMed

Ding, Xueqin; Li, Li; Wang, Yuzhi; Chen, Jing; Huang, Yanhua; Xu, Kaijia

2014-12-01

A series of novel tetramethylguanidinium ionic liquids and hexaalkylguanidinium ionic liquids have been synthesized based on 1,1,3,3-tetramethylguanidine. The structures of the ionic liquids were confirmed by (1)H NMR spectroscopy and mass spectrometry. A green guanidinium ionic liquid based microwave-assisted extraction method has been developed with these guanidinium ionic liquids for the effective extraction of Praeruptorin A from Radix peucedani. After extraction, reversed-phase high-performance liquid chromatography with UV detection was employed for the analysis of Praeruptorin A. Several significant operating parameters were systematically optimized by single-factor and L9 (3(4)) orthogonal array experiments. The amount of Praeruptorin A extracted by [1,1,3,3-tetramethylguanidine]CH2CH(OH)COOH is the highest, reaching 11.05 ± 0.13 mg/g. Guanidinium ionic liquid based microwave-assisted extraction presents unique advantages in Praeruptorin A extraction compared with guanidinium ionic liquid based maceration extraction, guanidinium ionic liquid based heat reflux extraction and guanidinium ionic liquid based ultrasound-assisted extraction. The precision, stability, and repeatability of the process were investigated. The mechanisms of guanidinium ionic liquid based microwave-assisted extraction were researched by scanning electron microscopy and IR spectroscopy. All the results show that guanidinium ionic liquid based microwave-assisted extraction has a huge potential in the extraction of bioactive compounds from complex samples. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Super ionic conductive glass

DOEpatents

Susman, Sherman; Volin, Kenneth J.

1984-01-01

An ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A.sub.1+x D.sub.2-x/3 Si.sub.x P.sub.3-x O.sub.12-2x/3, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

Ionic liquids for separation of olefin-paraffin mixtures

DOEpatents

Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

2013-09-17

The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

Ionic liquids for separation of olefin-paraffin mixtures

DOEpatents

Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

2014-07-15

The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

Selective extraction and separation of oxymatrine from Sophora flavescens Ait. extract by silica-confined ionic liquid.

PubMed

Bi, Wentao; Tian, Minglei; Row, Kyung Ho

2012-01-01

This study highlighted the application of a two-stepped extraction method for extraction and separation of oxymatrine from Sophora flavescens Ait. extract by utilizing silica-confined ionic liquids as sorbent. The optimized silica-confined ionic liquid was firstly mixed with plant extract to adsorb oxymatrine. Simultaneously, some interference, such as matrine, was removed. The obtained suspension was then added to a cartridge for solid phase extraction. Through these two steps, target compound was adequately separated from interferences with 93.4% recovery. In comparison with traditional solid phase extraction, this method accelerates loading and reduces the use of organic solvents during washing. Moreover, the optimization of loading volume was simplified as optimization of solid/liquid ratio. Copyright © 2011 Elsevier B.V. All rights reserved.

Developing ionic liquid forms of picloram with reduced negative effects on the aquatic environment.

PubMed

Tang, Gang; Wang, Baitao; Ding, Guanglong; Zhang, Wenbing; Liang, You; Fan, Chen; Dong, Hongqiang; Yang, Jiale; Kong, Dandan; Cao, Yongsong

2018-03-01

As a widely used herbicide, picloram has been frequently detected in the aquatic environment due to its high leaching potential and low adsorption by soil. To reduce aquatic environmental risk of this herbicide caused by leaching and runoff, five herbicidal ionic liquids (HILs) based on picloram were prepared by pairing isopropylamine, octylamine, octadecylamine, 1-methylimidazole, 4-methylmorpholine respectively. Their physicochemical properties including water solubility, octanol-water partition coefficient, surface activity, leaching, as well as soil adsorption were compared. The results showed that these properties could be adjusted by appropriate selection of counter cations. The HILs with long alkyl chains in cations had low water solubility and leaching characteristics, good surface tension and lipophilicity, as well as high soil adsorption. Compared with currently used picloram in the forms of potassium salts, HIL3 had more excellent herbicidal activity against broadleaf weeds and may offer a lower use dosage. The HILs based on picloram can reduce its negative effects on the aquatic environment and can be used as a desirable alternative to commercial herbicidal formulations of picloram in future. Copyright © 2017 Elsevier B.V. All rights reserved.

Aqueous two-phase based on ionic liquid liquid-liquid microextraction for simultaneous determination of five synthetic food colourants in different food samples by high-performance liquid chromatography.

PubMed

Sha, Ou; Zhu, Xiashi; Feng, Yanli; Ma, Weixing

2015-05-01

A rapid and effective method of aqueous two-phase systems based on ionic liquid microextraction for the simultaneous determination of five synthetic food colourants (tartrazine, sunset yellow, amaranth, ponceau 4R and brilliant blue) in food samples was established. High-performance liquid chromatography coupled with an ultraviolet detector of variable wavelength was used for the determinations. 1-alkyl-3-methylimidazolium bromide was selected as the extraction reagent. The extraction efficiency of the five colourants in the proposed system is influenced by the types of salts, concentrations of salt and [CnMIM]Br, as well as the extracting time. Under the optimal conditions, the extraction efficiencies for these five colourants were above 95%. The phase behaviours of aqueous two-phase system and extraction mechanism were investigated by UV-vis spectroscopy. This method was applied to the analysis of the five colourants in real food samples with the detection limit of 0.051-0.074 ng/mL. Good spiked recoveries from 93.2% to 98.9% were obtained. Copyright © 2014 Elsevier Ltd. All rights reserved.

Studies of ciprofloxacin encapsulation on alginate/pectin matrixes and its relationship with biodisponibility.

PubMed

Islan, Germán A; de Verti, Ignacio Pérez; Marchetti, Sergio G; Castro, Guillermo R

2012-07-01

Screening of ciprofloxacin (Cip) with selected biopolymers brings about 90% antibiotic interactions with a coacervate composed of alginate/high metoxylated pectin in 2:1 ratio. Fourier transform infrared spectroscopy analysis provides information about the nature of this interaction, revealing ionic and hydrophobic patterns among the molecules. Alginate/high methoxylated pectin gel microspheres developed by ionic gelation encapsulates 46.8 ± 5.0% Cip. The gel matrix can release Cip in a sustained manner, releasing 42.7 ± 0.2% in 2 h under simulated stomach pH conditions, and 83.3 ± 1.1% Cip release in 80 mM phosphate at pH = 7.40 (intestinal). The increase of sodium chloride from 50 to 200 mM implies a Cip release from 69.0 ± 1.5% to 95.1 ± 3.6% respectively in 2 h. Scanning electron microscopy revealed the cohesive effect of HM pectin over alginate molecules on the microsphere surface. Those results guarantee all Cip contained in the alginate/HM pectin microspheres could be released in an established kinetic profile along the gastrointestinal tract, avoiding the Cip undesirable side effects during absorption.

Quantitative and qualitative optimization of allergen extraction from peanut and selected tree nuts. Part 1. Screening of optimal extraction conditions using a D-optimal experimental design.

PubMed

L'Hocine, Lamia; Pitre, Mélanie

2016-03-01

A D-optimal design was constructed to optimize allergen extraction efficiency simultaneously from roasted, non-roasted, defatted, and non-defatted almond, hazelnut, peanut, and pistachio flours using three non-denaturing aqueous (phosphate, borate, and carbonate) buffers at various conditions of ionic strength, buffer-to-protein ratio, extraction temperature, and extraction duration. Statistical analysis showed that roasting and non-defatting significantly lowered protein recovery for all nuts. Increasing the temperature and the buffer-to-protein ratio during extraction significantly increased protein recovery, whereas increasing the extraction time had no significant impact. The impact of the three buffers on protein recovery varied significantly among the nuts. Depending on the extraction conditions, protein recovery varied from 19% to 95% for peanut, 31% to 73% for almond, 17% to 64% for pistachio, and 27% to 88% for hazelnut. A modulation by the buffer type and ionic strength of protein and immunoglobuline E binding profiles of extracts was evidenced, where high protein recovery levels did not always correlate with high immunoreactivity. Crown Copyright © 2015. Published by Elsevier Ltd. All rights reserved.

Methane–oxygen electrochemical coupling in an ionic liquid: a robust sensor for simultaneous quantification†

PubMed Central

Wang, Zhe; Guo, Min; Baker, Gary A.; Stetter, Joseph R.; Lin, Lu; Mason, Andrew J.

2017-01-01

Current sensor devices for the detection of methane or natural gas emission are either expensive and have high power requirements or fail to provide a rapid response. This report describes an electrochemical methane sensor utilizing a non-volatile and conductive pyrrolidinium-based ionic liquid (IL) electrolyte and an innovative internal standard method for methane and oxygen dual-gas detection with high sensitivity, selectivity, and stability. At a platinum electrode in bis(trifluoromethylsulfonyl)imide (NTf2)-based ILs, methane is electro-oxidized to produce CO2 and water when an oxygen reduction process is included. The in situ generated CO2 arising from methane oxidation was shown to provide an excellent internal standard for quantification of the electrochemical oxygen sensor signal. The simultaneous quantification of both methane and oxygen in real time strengthens the reliability of the measurements by cross-validation of two ambient gases occurring within a single sample matrix and allows for the elimination of several types of random and systematic errors in the detection. We have also validated this IL-based methane sensor employing both conventional solid macroelectrodes and flexible microfabricated electrodes using single- and double-potential step chronoamperometry. PMID:25093213

High performance preconcentration of inorganic Se species by dispersive micro-solid phase extraction with a nanosilica-ionic liquid hybrid material

NASA Astrophysics Data System (ADS)

Llaver, Mauricio; Coronado, Eduardo A.; Wuilloud, Rodolfo G.

2017-12-01

A highly sensitive and efficient dispersive micro-solid phase extraction (D-μ-SPE) method was developed for inorganic Se speciation analysis. A novel ionic liquid (IL)-nanomaterial hybrid consisting of 1-dodecyl-3-methylimidazolium bromide-functionalized nanosilica was used for the efficient retention of Se(IV) complexed with ammonium pyrrolidine dithiocarbamate, followed by elution with an ethyl acetate/Triton X-114 mixture and determination by electrothermal atomic absorption spectroscopy. The Se(VI) species was selectively determined by difference between total inorganic Se and Se(IV) after pre-reduction. The IL-nanomaterial hybrid was characterized by Fourier transform infrared spectroscopy and transmission electronic microscopy. Likewise, Se(IV) sorption capacity of the retention material and maximum amount of IL loaded on its surface were determined. Several factors concerning the functionalization, extraction and elution steps were optimized, yielding a 100% extraction efficiency for Se(IV) under optimal conditions. A limit of detection of 1.1 ng L- 1, a relative standard deviation of 5.7% and a 110-fold enhancement factor were obtained. The D-μ-SPE method was successfully applied to several water samples from different origins and compositions, including rain, tap, underground, river and sea.

Renewable bio ionic liquids-water mixtures-mediated selective removal of lignin from rice straw: visualization of changes in composition and cell wall structure.

PubMed

Hou, Xue-Dan; Li, Ning; Zong, Min-Hua

2013-07-01

Pretreatment of rice straw by using renewable cholinium amino acids ionic liquids ([Ch][AA] ILs)-water mixtures and the subsequent enzymatic hydrolysis of the residues were conducted in the present work. Of the eight mixtures composed of ILs and water, most were found to be effective for rice straw pretreatment. After pretreatment with 50% ILs-water mixtures, the enzymatic digestion of the lignocellulosic biomass was enhanced significantly, thus leading to satisfactory sugar yields of >80% for glucose and approximately 50% for xylose. To better understand the ILs pretreatment mechanism, confocal laser scanning microscopy combined with immunolabeling and transmission electron microscopy were used to visualize changes in the contents and distribution of two major components--lignin and xylan. The results coupled with changes in chemical structures (infrared spectra) of the substrates indicated occurrence of extensive delignification, especially in cell corner and compound middle lumen of cell walls, which made polysaccharides more accessible to enzymes. This pretreatment process is promising for large-scale application because of the high sugar yields, easy handling, being environmentally benign and highly tolerant to moisture, and significantly reduced cost and energy consumption. Copyright © 2013 Wiley Periodicals, Inc.

Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([Cnmim][PF6], n=4, 6, and 8)

NASA Astrophysics Data System (ADS)

Hardacre, Christopher; Holbrey, John D.; Mullan, Claire L.; Youngs, Tristan G. A.; Bowron, Daniel T.

2010-08-01

The presence of local anisotropy in the bulk, isotropic, and ionic liquid phases—leading to local mesoscopic inhomogeneity—with nanoscale segregation and expanding nonpolar domains on increasing the length of the cation alkyl-substituents has been proposed on the basis of molecular dynamics (MD) simulations. However, there has been little conclusive experimental evidence for the existence of intermediate mesoscopic structure between the first/second shell correlations shown by neutron scattering on short chain length based materials and the mesophase structure of the long chain length ionic liquid crystals. Herein, small angle neutron scattering measurements have been performed on selectively H/D-isotopically substituted 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids with butyl, hexyl, and octyl substituents. The data show the unambiguous existence of a diffraction peak in the low-Q region for all three liquids which moves to longer distances (lower Q), sharpens, and increases in intensity with increasing length of the alkyl substituent. It is notable, however, that this peak occurs at lower values of Q (longer length scale) than predicted in any of the previously published MD simulations of ionic liquids, and that the magnitude of the scattering from this peak is comparable with that from the remainder of the amorphous ionic liquid. This strongly suggests that the peak arises from the second coordination shells of the ions along the vector of alkyl-chain substituents as a consequence of increasing the anisotropy of the cation, and that there is little or no long-range correlated nanostructure in these ionic liquids.

Direct synthesis of sorbitol and glycerol from cellulose over ionic Ru/magnetite nanoparticles in the absence of external hydrogen.

PubMed

Negoi, Alina; Trotus, Ioan Teodor; Mamula Steiner, Olimpia; Tudorache, Madalina; Kuncser, Victor; Macovei, Dan; Parvulescu, Vasile I; Coman, Simona M

2013-11-01

A sweet catalyst: A catalyst formed of Ru/functionalized silica-coated magnetite nanoparticles is highly efficient in the one-pot production of sorbitol and glycerol, starting from cellulose and in the absence of an external hydrogen source. The ease of recoverability of the catalyst from the solid residues, and its reuse without loss of activity or selectivity for several runs, is an important green element of the process. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vertically Aligned and Continuous Nanoscale Ceramic-Polymer Interfaces in Composite Solid Polymer Electrolytes for Enhanced Ionic Conductivity.

PubMed

Zhang, Xiaokun; Xie, Jin; Shi, Feifei; Lin, Dingchang; Liu, Yayuan; Liu, Wei; Pei, Allen; Gong, Yongji; Wang, Hongxia; Liu, Kai; Xiang, Yong; Cui, Yi

2018-06-13

Among all solid electrolytes, composite solid polymer electrolytes, comprised of polymer matrix and ceramic fillers, garner great interest due to the enhancement of ionic conductivity and mechanical properties derived from ceramic-polymer interactions. Here, we report a composite electrolyte with densely packed, vertically aligned, and continuous nanoscale ceramic-polymer interfaces, using surface-modified anodized aluminum oxide as the ceramic scaffold and poly(ethylene oxide) as the polymer matrix. The fast Li + transport along the ceramic-polymer interfaces was proven experimentally for the first time, and an interfacial ionic conductivity higher than 10 -3 S/cm at 0 °C was predicted. The presented composite solid electrolyte achieved an ionic conductivity as high as 5.82 × 10 -4 S/cm at the electrode level. The vertically aligned interfacial structure in the composite electrolytes enables the viable application of the composite solid electrolyte with superior ionic conductivity and high hardness, allowing Li-Li cells to be cycled at a small polarization without Li dendrite penetration.

Electrostatic Interactions Influence Protein Adsorption (but Not Desorption) at the Silica-Aqueous Interface.

PubMed

McUmber, Aaron C; Randolph, Theodore W; Schwartz, Daniel K

2015-07-02

High-throughput single-molecule total internal reflection fluorescence microscopy was used to investigate the effects of pH and ionic strength on bovine serum albumin (BSA) adsorption, desorption, and interfacial diffusion at the aqueous-fused silica interface. At high pH and low ionic strength, negatively charged BSA adsorbed slowly to the negatively charged fused silica surface. At low pH and low ionic strength, where BSA was positively charged, or in solutions at higher ionic strength, adsorption was approximately 1000 times faster. Interestingly, neither surface residence times nor the interfacial diffusion coefficients of BSA were influenced by pH or ionic strength. These findings suggested that adsorption kinetics were dominated by energy barriers associated with electrostatic interactions, but once adsorbed, protein-surface interactions were dominated by short-range nonelectrostatic interactions. These results highlight the ability of single-molecule techniques to isolate elementary processes (e.g., adsorption and desorption) under steady-state conditions, which would be impossible to measure using ensemble-averaging methods.

Colloidal nickel/gallium nanoalloys obtained from organometallic precursors in conventional organic solvents and in ionic liquids: noble-metal-free alkyne semihydrogenation catalysts

NASA Astrophysics Data System (ADS)

Schütte, Kai; Doddi, Adinarayana; Kroll, Clarissa; Meyer, Hajo; Wiktor, Christian; Gemel, Christian; van Tendeloo, Gustaaf; Fischer, Roland A.; Janiak, Christoph

2014-04-01

Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)2] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)3] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)4]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions.Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)2] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)3] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)4]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions. Electronic supplementary information (ESI) available: Ni-Ga phase diagrams, EDX (XPS) of NP1-NP8, table of Ni : Ga ratios, TG of Ni-Ga SSPs, analysis of NP4, dec. of [Ni(GaCp*)3(PCy3)] with characterization, local resolution EDX of NP3-IL, Ni-NP characterization from Ni(COD)2 and details of (semi-)hydrogenation catalysis. See DOI: 10.1039/c4nr00111g

Rare earth metal-containing ionic liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prodius, Denis; Mudring, Anja-Verena

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Rare earth metal-containing ionic liquids

DOE PAGES

Prodius, Denis; Mudring, Anja-Verena

2018-03-07

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Novel applications of ionic liquids in materials processing

NASA Astrophysics Data System (ADS)

Reddy, Ramana G.

2009-05-01

Ionic liquids are mixtures of organic and inorganic salts which are liquids at room temperature. Several potential applications of ionic liquids in the field of materials processing are electrowinning and electrodeposition of metals and alloys, electrolysis of active metals at low temperature, liquid-liquid extraction of metals. Results using 1-butyl-3-methylimidazolium chloride with AlCl3 at low temperatures yielded high purity aluminium deposits (>99.9% pure) and current efficiencies >98%. Titanium and aluminium were co-deposited with/without the addition of TiCl4 with up to 27 wt% Ti in the deposit with current efficiencies in the range of 78-85 %. Certain ionic liquids are potential replacements for thermal oils and molten salts as heat transfer fluids in solar energy applications due to high thermal stability, very low corrosivity and substantial sensible heat retentivity. The calculated storage densities for several chloride and fluoride ionic liquids are in the range of 160-210 MJ/m3. A 3-D mathematical model was developed to simulate the large scale electrowinning of aluminium. Since ionic liquids processing results in their low energy consumption, low pollutant emissions many more materials processing applications are expected in future.

Durable and water-floatable ionic polymer actuator with hydrophobic and asymmetrically laser-scribed reduced graphene oxide paper electrodes.

PubMed

Kim, Jaehwan; Jeon, Jin-Han; Kim, Hyun-Jun; Lim, Hyuneui; Oh, Il-Kwon

2014-03-25

Ionic polymer actuators driven by electrical stimuli have been widely investigated for use in practical applications such as bioinspired robots, sensors, and biomedical devices. However, conventional ionic polymer-metal composite actuators have a serious drawback of poor durability under long-term actuation in open air, mainly because of the leakage of the inner electrolyte and hydrated cations through cracks in the metallic electrodes. Here, we developed a highly durable and water-floatable ionic polymer artificial muscle by employing hydrophobic and asymmetrically laser-scribed reduced graphene oxide paper electrodes (HLrGOP). The highly conductive, flexible, and cost-effective HLrGOP electrodes have asymmetrically smooth hydrophobic outer and rough inner surfaces, resulting in liquid-impermeable and water-floatable functionalities and strong bonding between an ionic polymer and the electrodes. More interestingly, the HLrGOP electrode, which has a unique functionality to prevent the leakage of the vaporized or liquid electrolyte and mobile ions during electrical stimuli, greatly contributes to an exceptionally durable ionic polymer-graphene composite actuator that is a prerequisite for practical applications in active biomedical devices, biomimetic robots, touch-feedback haptic systems, and flexible soft electronics.

Microwave-Assisted Resolution of α-Lipoic Acid Catalyzed by an Ionic Liquid Co-Lyophilized Lipase.

PubMed

Liu, Ning; Wang, Lei; Wang, Zhi; Jiang, Liyan; Wu, Zhuofu; Yue, Hong; Xie, Xiaona

2015-05-29

The combination of the ionic liquid co-lyophilized lipase and microwave irradiation was used to improve enzyme performance in enantioselective esterification of α-lipoic acid. Effects of various reaction conditions on enzyme activity and enantioselectivity were investigated. Under optimal condition, the highest enantioselectivity (E = 41.2) was observed with a high enzyme activity (178.1 μmol/h/mg) when using the ionic liquid co-lyophilized lipase with microwave assistance. Furthermore, the ionic liquid co-lyophilized lipase exhibited excellent reusability under low power microwave.

Disorder from the Bulk Ionic Liquid in Electric Double Layer Transistors

DOE PAGES

Petach, Trevor A.; Reich, Konstantin V.; Zhang, Xiao; ...

2017-07-28

Ionic liquid gating has a number of advantages over solid-state gating, especially for flexible or transparent devices and for applications requiring high carrier densities. But, the large number of charged ions near the channel inevitably results in Coulomb scattering, which limits the carrier mobility in otherwise clean systems. We develop a model for this Coulomb scattering. We then validate our model experimentally using ionic liquid gating of graphene across varying thicknesses of hexagonal boron nitride, demonstrating that disorder in the bulk ionic liquid often dominates the scattering.

Cobalt-Bridged Ionic Liquid Polymer on a Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity.

PubMed

Ding, Yuxiao; Klyushin, Alexander; Huang, Xing; Jones, Travis; Teschner, Detre; Girgsdies, Frank; Rodenas, Tania; Schlögl, Robert; Heumann, Saskia

2018-03-19

By taking inspiration from the catalytic properties of single-site catalysts and the enhancement of performance through ionic liquids on metal catalysts, we exploited a scalable way to place single cobalt ions on a carbon-nanotube surface bridged by polymerized ionic liquid. Single dispersed cobalt ions coordinated by ionic liquid are used as heterogeneous catalysts for the oxygen evolution reaction (OER). Performance data reveals high activity and stable operation without chemical instability. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Industrial uses and applications of ionic liquids

NASA Astrophysics Data System (ADS)

Gutowski, Keith E.

2018-02-01

Ionic liquids are salts that melt at low temperatures (usually defined as less than 100 °C) and have a number of interesting properties that make them useful for industrial applications. Typical ionic liquid properties include high thermal stabilities, negligible vapor pressures, wide liquidus ranges, broad electrochemical windows, and unique solvation properties. Furthermore, the potential combinations of cations and anions provide nearly unlimited chemical tunability. This article will describe the diverse industrial uses of ionic liquids and how their unique properties are leveraged, with examples ranging from chemical processing to consumer packaged goods.

Formation of p-n-p junction with ionic liquid gate in graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Xin; Tang, Ning, E-mail: ntang@pku.edu.cn, E-mail: geweikun@mail.tsinghua.edu.cn, E-mail: bshen@pku.edu.cn; Duan, Junxi

2014-04-07

Ionic liquid gating is a technique which is much more efficient than solid gating to tune carrier density. To observe the electronic properties of such a highly doped graphene device, a top gate made of ionic liquid has been used. By sweeping both the top and back gate voltage, a p-n-p junction has been created. The mechanism of forming the p-n-p junction has been discussed. Tuning the carrier density by ionic liquid gate can be an efficient method to be used in flexible electronics.

Spectacular Rate Enhancement of the Diels-Alder Reaction at the Ionic Liquid/n-Hexane Interface.

PubMed

Beniwal, Vijay; Manna, Arpan; Kumar, Anil

2016-07-04

The use of the ionic liquid/n-hexane interface as a new class of reaction medium for the Diels-Alder reaction gives large rate enhancements of the order of 10(6) to 10(8) times and high stereoselectivity, as compared to homogeneous media. The rate enhancement is attributed to the H-bonding abilities and polarities of the ionic liquids, whereas the hydrophobicity of ionic liquids was considered to be the factor in controlling stereoselectivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface-active ionic liquids for palladium-catalysed cross coupling in water: effect of ionic liquid concentration on the catalytically active species† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7ra07757b

PubMed Central

Taskin, Meltem; Cognigni, Alice; Zirbs, Ronald; Reimhult, Erik

2017-01-01

We report the design and synthesis of surface-active ionic liquids for application in palladium-catalyzed cross coupling reactions. A series of dodecylimidazolium-based ionic liquids were applied as additives in the Heck reaction of ethyl acrylate and iodobenzene, and high yields of >90% could be obtained in water without the addition of further ligands. Our results indicate that the ionic liquid concentration in water is the key factor affecting the formation of the catalytically active species and hence the yield. Moreover, imidazolium-based ionic liquids that are able to form a carbene species differ significantly from conventional cationic surfactants, as a concentration dependent formation of the N-heterocyclic carbene complex was observed. PMID:29308189

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

2015-12-16

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.

Advanced Supported Liquid Membranes for Carbon Dioxide Control in Extravehicular Activity Applications

NASA Technical Reports Server (NTRS)

Gleason, Kevin J. (Inventor); Cowley, Scott W. (Inventor); Wickham, David T. (Inventor)

2015-01-01

There is disclosed a portable life support system with a component for removal of at least one selected gas. In an embodiment, the system includes a supported liquid membrane having a first side and a second side in opposition to one another, the first side configured for disposition toward an astronaut and the second side configured for disposition toward a vacuum atmosphere. The system further includes an ionic liquid disposed between the first side and the second side of the supported liquid membrane, the ionic liquid configured for removal of at least one selected gas from a region housing the astronaut adjacent the first side of the supported liquid membrane to the vacuum atmosphere adjacent the second side of the supported liquid membrane. Other embodiments are also disclosed.

Microwave-assisted synthesis of gold, silver, platinum and palladium nanostructures and their use in electrocatalytic applications.

PubMed

Safavi, Afsaneh; Tohidi, Maryam

2014-09-01

Microwave-assisted ionic liquid method was used for synthesis of various noble metals, such as gold, silver, platinum and palladium nanomaterials. This route does not employ any template agent, surface capping agents or reducing agents. The process is fast, simple and of high yield. Different metal precursors in various ionic liquids media (1-butyl-3-methylimidazolium tetrafluoroborate, octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate) were applied to produce metal nanomaterials. Silver, platinium and palladium nanoparticles exhibit spherical morphology while nanosheets with high aspect ratio were obtained for gold. These metal nanostructures were incorporated into a carbon ionic liquid electrode to investigate their electrocatalytic properties. It was found that synthesis in different ionic liquids result in different activity. Excellent electrocatalytic effects toward adenine, hydrazine, formaldehyde and ethanol were observed for the modified electrodes with different nanoparticles synthesized in 1-butyl-3-methylimidazolium tetrafluoroborate. The high conductivity, large surface-to-volume ratio and active sites of nanosized metal particles are responsible for their electrocatalytic activity. In contrast, the carbon ionic liquid electrode modified with synthesized metal nanoparticles in octyl pyridinium hexaflurophosphate and 1-octyl-3-methylimidazolium hexaflurophosphate showed negligible activity for detection of these probes.

Salting-out homogenous extraction followed by ionic liquid/ionic liquid liquid-liquid micro-extraction for determination of sulfonamides in blood by high performance liquid chromatography.

PubMed

Liu, Zhongling; Yu, Wei; Zhang, Hanqi; Gu, Fanbin; Jin, Xiangqun

2016-12-01

Salting-out homogenous extraction followed by ionic liquid/ionic liquid dispersive liquid-liquid micro-extraction system was developed and applied to the extraction of sulfonamides in blood. High-performance liquid chromatography was applied to the determination of the analytes. The blood sample was centrifuged to obtain the serum. After the proteins in the serum were removed in the presence of acetonitrile, ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, dipotassium hydrogen phosphate, ionic liquid 1-Hexyl-3-methylimidazolium hexafluorophosphate were added into the resulting solution. After the resulting mixture was ultrasonically shaken and centrifuged, the precipitate was separated. The acetonitrile was added in the precipitate and the analytes were extracted into the acetonitrile phase. The parameters affecting the extraction efficiency, such as volume of ionic liquid, amount of dipotassium hydrogen phosphate, volume of dispersant, extraction time and temperature were investigated. The limits of detection of sulfamethizole (STZ), sulfachlorpyridazine (SCP), sulfamethoxazole (SMX) and Sulfisoxazole (SSZ) were 4.78, 3.99, 5.21 and 3.77μgL -1 , respectively. When the present method was applied to the analysis of real blood samples, the recoveries of analytes ranged from 90.0% to 113.0% and relative standard deviations were lower than 7.2%. Copyright © 2016 Elsevier B.V. All rights reserved.

Ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction for the separation and determination of estrogens in water samples by high-performance liquid chromatography with fluorescence detection.

PubMed

Zhang, Rui; Wang, Chuanliu; Yue, Qiaohong; Zhou, Tiecheng; Li, Na; Zhang, Hanqi; Hao, Xiaoke

2014-11-01

An ionic liquid foam floatation coupled with ionic liquid dispersive liquid-liquid microextraction method was proposed for the extraction and concentration of 17-α-estradiol, 17-β-estradiol-benzoate, and quinestrol in environmental water samples by high-performance liquid chromatography with fluorescence detection. 1-Hexyl-3-methylimidazolium tetrafluoroborate was applied as foaming agent in the foam flotation process and dispersive solvent in microextraction. The introduction of the ion-pairing and salting-out agent NH4 PF6 was beneficial to the improvement of recoveries for the hydrophobic ionic liquid phase and analytes. Parameters of the proposed method including concentration of 1-hexyl-3-methylimidazolium tetrafluoroborate, flow rate of carrier gas, floatation time, types and concentration of ionic liquids, salt concentration in samples, extraction time, and centrifugation time were evaluated. The recoveries were between 98 and 105% with relative standard deviations lower than 7% for lake water and well water samples. The isolation of the target compounds from the water was found to be efficient, and the enrichment factors ranged from 4445 to 4632. This developing method is free of volatile organic solvents compared with regular extraction. Based on the unique properties of ionic liquids, the application of foam floatation, and dispersive liquid-liquid microextraction was widened. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tunable Molecular-Scale Materials for Catalyzing the Low-Overpotential Electrochemical Conversion of CO2.

PubMed

Rosen, Brian A; Hod, Idan

2018-04-25

Electrochemical CO 2 reduction provides a clean and viable alternative for mitigating the environmental aspects of global greenhouse gas emissions. To date, the simultaneous goals of CO 2 reduction at high selectivity and activity have yet to be achieved. Here, the importance of engineering both sides of the electrode-electrolyte interface as a rational strategy for achieving this milestone is highlighted. An emphasis is placed on researchers contributing to the design of solid electrodes based on metal-organic frameworks (MOFs) and electrolytes based on room-temperature ionic liquids (RTILs). Future research geared toward optimizing the electrode-electrolyte interface for efficient and selective CO 2 reduction can be achieved by understanding the structure of newly designed RTILs at the electrified interface, as well as structure-activity relationships in highly tunable MOF platforms. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic thermal barrier coatings

DOEpatents

Kulkarni, Anand A.; Campbell, Christian X.; Subramanian, Ramesh

2009-06-02

A catalyst element (30) for high temperature applications such as a gas turbine engine. The catalyst element includes a metal substrate such as a tube (32) having a layer of ceramic thermal barrier coating material (34) disposed on the substrate for thermally insulating the metal substrate from a high temperature fuel/air mixture. The ceramic thermal barrier coating material is formed of a crystal structure populated with base elements but with selected sites of the crystal structure being populated by substitute ions selected to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a higher rate than would the base compound without the ionic substitutions. Precious metal crystallites may be disposed within the crystal structure to allow the ceramic thermal barrier coating material to catalytically react the fuel-air mixture at a lower light-off temperature than would the ceramic thermal barrier coating material without the precious metal crystallites.

Multiple environmental factors regulate the expression of the carbohydrate-selective OprB porin of Pseudomonas aeruginosa.

PubMed

Adewoye, L O; Worobec, E A

1999-12-01

In response to low extracellular glucose concentration, Pseudomonas aeruginosa induces the expression of the outer membrane carbohydrate-selective OprB porin. The promoter region of the oprB gene was cloned into a lacZ transcriptional fusion vector, and the construct was mobilized into P. aeruginosa OprB-deficient strain, WW100, to evaluate additional environmental factors that influence OprB porin gene expression. Growth temperature, pH of the growth medium, salicylate concentration, and carbohydrate source were found to differentially influence porin expression. This expression pattern was compared to those of whole-cell [14C]glucose uptake under conditions of high osmolarity, ionicity, variable pH, growth temperatures, and carbohydrate source. These studies revealed that the high-affinity glucose transport genes are down-regulated by salicylic acid, differentially regulated by pH and temperature, and are specifically responsive to exogenous glucose induction.

Electric Field-Controlled Ion Transport In TiO2 Nanochannel.

PubMed

Li, Dan; Jing, Wenheng; Li, Shuaiqiang; Shen, Hao; Xing, Weihong

2015-06-03

On the basis of biological ion channels, we constructed TiO2 membranes with rigid channels of 2.3 nm to mimic biomembranes with flexible channels; an external electric field was employed to regulate ion transport in the confined channels at a high ionic strength in the absence of electrical double layer overlap. Results show that transport rates for both Na+ and Mg2+ were decreased irrespective of the direction of the electric field. Furthermore, a voltage-gated selective ion channel was formed, the Mg2+ channel closed at -2 V, and a reversed relative electric field gradient was at the same order of the concentration gradient, whereas the Na+ with smaller Stokes radius and lower valence was less sensitive to the electric field and thus preferentially occupied and passed the channel. Thus, when an external electric field is applied, membranes with larger nanochannels have promising applications in selective separation of mixture salts at a high concentration.

Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pilar, Kartik; Rua, Armando; Suarez, Sophia N.

A comprehensive variable temperature, pressure and frequency multinuclear ( 1H, 2H, and 19F) magnetic resonance study was undertaken on selectively deuterated 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMIM TFSA) ionic liquid isotopologues. This study builds on our earlier investigation of the effects of increasing alkyl chain length on diffusion and dynamics in imidazolium-based TFSA ionic liquids. Fast field cycling 1H T 1 data revealed multiple modes of motion. Through calculation of diffusion coefficient (D) values and activation energies, the low- and high-field regimes were assigned to the translational and reorientation dynamics respectively. Variable-pressure 2H T 1 measurements reveal site-dependent interactions in the cation withmore » strengths in the order MD 3 > CD 3 > CD 2, indicating dissimilarities in the electric field gradients along the alkyl chain, with the CD 2 sites having the largest gradient. Additionally, the α saturation effect in T 1 vs. P was observed for all three sites, suggesting significant reduction of the short-range rapid reorientational dynamics. This reduction was also deduced from the variable pressure 1H T 1 data, which showed an approach to saturation for both the methyl and butyl group terminal methyl sites. Pressure-dependent D measurements show independent motions for both cations and anions, with the cations having greater D values over the entire pressure range.« less

Investigation of Dynamics in BMIM TFSA Ionic Liquid through Variable Temperature and Pressure NMR Relaxometry and Diffusometry

DOE PAGES

Pilar, Kartik; Rua, Armando; Suarez, Sophia N.; ...

2017-05-11

A comprehensive variable temperature, pressure and frequency multinuclear ( 1H, 2H, and 19F) magnetic resonance study was undertaken on selectively deuterated 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide (BMIM TFSA) ionic liquid isotopologues. This study builds on our earlier investigation of the effects of increasing alkyl chain length on diffusion and dynamics in imidazolium-based TFSA ionic liquids. Fast field cycling 1H T 1 data revealed multiple modes of motion. Through calculation of diffusion coefficient (D) values and activation energies, the low- and high-field regimes were assigned to the translational and reorientation dynamics respectively. Variable-pressure 2H T 1 measurements reveal site-dependent interactions in the cation withmore » strengths in the order MD 3 > CD 3 > CD 2, indicating dissimilarities in the electric field gradients along the alkyl chain, with the CD 2 sites having the largest gradient. Additionally, the α saturation effect in T 1 vs. P was observed for all three sites, suggesting significant reduction of the short-range rapid reorientational dynamics. This reduction was also deduced from the variable pressure 1H T 1 data, which showed an approach to saturation for both the methyl and butyl group terminal methyl sites. Pressure-dependent D measurements show independent motions for both cations and anions, with the cations having greater D values over the entire pressure range.« less

Electroviscous Effects in Ceramic Nanofiltration Membranes.

PubMed

Farsi, Ali; Boffa, Vittorio; Christensen, Morten Lykkegaard

2015-11-16

Membrane permeability and salt rejection of a γ-alumina nanofiltration membrane were studied and modeled for different salt solutions. Salt rejection was predicted by using the Donnan-steric pore model, in which the extended Nernst-Planck equation was applied to predict ion transport through the pores. The solvent flux was modeled by using the Hagen-Poiseuille equation by introducing electroviscosity instead of bulk viscosity. γ-Alumina particles were used for ζ-potential measurements. The ζ-potential measurements show that monovalent ions did not adsorb on the γ-alumina surface, whereas divalent ions were highly adsorbed. Thus, for divalent ions, the model was modified, owing to pore shrinkage caused by ion adsorption. The ζ-potential lowered the membrane permeability, especially for membranes with a pore radius lower than 3 nm, a ζ-potential higher than 20 mV, and an ionic strength lower than 0.01 m. The rejection model showed that, for a pore radius lower than 3 nm and for solutions with ionic strengths lower than 0.01 m, there is an optimum ζ-potential for rejection, because of the concurrent effects of electromigration and convection. Hence, the model can be used as a prediction tool to optimize membrane perm-selectivity by designing a specific pore size and surface charge for application at specific ionic strengths and pH levels. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hg⁰ removal from flue gas by ionic liquid/H₂O₂.

PubMed

Cheng, Guangwen; Bai, Bofeng; Zhang, Qiang; Cai, Ming

2014-09-15

1-Alkyl-3-methylimidazolium chloride ionic liquids ([Cnmim] Cl, n=4, 6, 8) were prepared. The ionic liquid was then mixed with hydrogen peroxide (H2O2) to form an absorbent. The Hg(0) removal performance of the absorbent was investigated in a gas/liquid scrubber using simulated flue gas. It was found that the ionic liquid/H2O2 mixture was an excellent absorbent and could be used to remove Hg(0) from flue gas. When the mass ratio of H2O2 to ionic liquid was 0.5, the absorbent showed high Hg(0) removal efficiency (up to 98%). The Hg(0) removal efficiency usually increased with the absorption temperature, while decreased with the increase of alkyl chain length in ionic liquid molecule. The Hg(0) removal mechanism involved with Hg(0) oxidation by H2O2 and Hg(2+) transfer from aqueous phase to ionic liquid phase. Copyright © 2014 Elsevier B.V. All rights reserved.

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Ionic liquid-mediated molecularly imprinted solid-phase extraction coupled with gas chromatography-electron capture detector for rapid screening of dicofol in vegetables.

PubMed

Yan, Hongyuan; Sun, Ning; Han, Yehong; Yang, Chen; Wang, Mingyu; Wu, Ruijun

2013-09-13

New ionic liquid-mediated molecularly imprinted polymers (IL-MIPs) were prepared by precipitation polymerization using 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM(+)PF6(-)) as the auxiliary solvent, α-chloro-DDT as the dummy template, and they were successfully applied as the sorbents of solid-phase extraction (SPE) for rapid screening of dicofol from cabbage, tomato, and carrot samples. The IL-MIPs were characterized by FTIR, FE-SEM, static adsorption and chromatographic evaluation, and the results revealed that the IL-MIPs had higher adsorption capacity and selectivity to dicofol in aqueous solution than that of ionic liquid-mediated non-imprinted polymers (IL-NIPs) and non-imprinted polymers (NIPs). Under the optimized conditions, the IL-MIPs-SPE-GC method offered good linearity (0.4-40.0ngg(-1), r(2)=0.9995) and the average recoveries of dicofol at three spiked levels were in a range of 84.6-104.1% (n=3) with RSD≤7.6%. The proposed method obviously improved the selectivity and purification effect, and eliminated the effect of template leakage on dicofol quantitative analysis. Copyright © 2013 Elsevier B.V. All rights reserved.

Determination of triazine herbicides in juice samples by microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography.

PubMed

Su, Rui; Li, Dan; Wu, Lijie; Han, Jing; Lian, Wenhui; Wang, Keren; Yang, Hongmei

2017-07-01

A novel microextraction method, termed microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction, has been developed for the rapid enrichment and analysis of triazine herbicides in fruit juice samples by high-performance liquid chromatography. Instead of using hazardous organic solvents, two kinds of ionic liquids, a hydrophobic ionic liquid (1-hexyl-3-methylimidazolium hexafluorophosphate) and a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate), were used as the extraction solvent and dispersion agent, respectively, in this method. The extraction procedure was induced by the formation of cloudy solution, which was composed of fine drops of 1-hexyl-3-methylimidazolium hexafluorophosphate dispersed entirely into sample solution with the help of 1-butyl-3-methylimidazolium tetrafluoroborate. In addition, an ion-pairing agent (NH 4 PF 6 ) was introduced to improve recoveries of the ionic liquid phase. Several experimental parameters that might affect the extraction efficiency were investigated. Under the optimum experimental conditions, the linearity for determining the analytes was in the range of 5.00-250.00 μg/L, with the correlation coefficients of 0.9982-0.9997. The practical application of this effective and green method is demonstrated by the successful analysis of triazine herbicides in four juice samples, with satisfactory recoveries (76.7-105.7%) and relative standard deviations (lower than 6.6%). In general, this method is fast, effective, and robust to determine triazine herbicides in juice samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Catalytic Ignition of Ionic Liquid Fuels by Ionic Liquids

DTIC Science & Technology

2014-07-01

catalytically decompose hydrogen peroxide. Catalytic approach for H2O2 decomposition Distribution NOT APPROVED through STINFO process Distribution...Charts 3. DATES COVERED (From - To) July 2014- August 2014 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER In-House Catalytic Ignition of Ionic...are highly hazardous. To gain a true advantage, a more environmentally friendly oxidizer must be considered. Hydrogen peroxide might be an attractive

Extraction of benzene and cyclohexane using [BMIM][N(CN)2] and their equilibrium modeling

NASA Astrophysics Data System (ADS)

Ismail, Marhaina; Bustam, M. Azmi; Man, Zakaria

2017-12-01

The separation of aromatic compound from aliphatic mixture is one of the essential industrial processes for an economically green process. In order to determine the separation efficiency of ionic liquid (IL) as a solvent in the separation, the ternary diagram of liquid-liquid extraction (LLE) 1-butyl-3-methylimidazolium dicyanamide [BMIM][N(CN)2] with benzene and cyclohexane was studied at T=298.15 K and atmospheric pressure. The solute distribution coefficient and solvent selectivity derived from the equilibrium data were used to evaluate if the selected ionic liquid can be considered as potential solvent for the separation of benzene from cyclohexane. The experimental tie line data was correlated using non-random two liquid model (NRTL) and Margules model. It was found that the solute distribution coefficient is (0.4430-0.0776) and selectivity of [BMIM][N(CN)2] for benzene is (53.6-13.9). The ternary diagram showed that the selected IL can perform the separation of benzene and cyclohexane as it has extractive capacity and selectivity. Therefore, [BMIM][N(CN)2] can be considered as a potential extracting solvent for the LLE of benzene and cyclohexane.

Ionic Liquids Can Selectively Change the Conformational Free-Energy Landscape of Sugar Rings.

PubMed

Jarin, Zack; Pfaendtner, Jim

2014-02-11

We investigated the conformational free energy landscape of glucose solvated in water and in the ionic liquids (ILs) 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) and 1-butyl-3-methylimidazoulim boron tetrafluoride ([Bmim][BF4]). To quantify equilibrium thermodynamic solvent effects, molecular dynamics simulations in conjunction with enhanced sampling based on the metadynamics framework were used. The results show that the solvent choice induces significant differences in the equilibrium ring structures, which may help further resolve the molecular mechanism governing IL-mediated cellulose dissolution.

Improved Activity of a Thermophilic Cellulase, Cel5A, from Thermotoga maritima on Ionic Liquid Pretreated Switchgrass

PubMed Central

Chen, Zhiwei; Pereira, Jose H.; Liu, Hanbin; Tran, Huu M.; Hsu, Nathan S. Y.; Dibble, Dean; Singh, Seema; Adams, Paul D.; Sapra, Rajat; Hadi, Masood Z.; Simmons, Blake A.; Sale, Kenneth L.

2013-01-01

Ionic liquid pretreatment of biomass has been shown to greatly reduce the recalcitrance of lignocellulosic biomass, resulting in improved sugar yields after enzymatic saccharification. However, even under these improved saccharification conditions the cost of enzymes still represents a significant proportion of the total cost of producing sugars and ultimately fuels from lignocellulosic biomass. Much of the high cost of enzymes is due to the low catalytic efficiency and stability of lignocellulolytic enzymes, especially cellulases, under conditions that include high temperatures and the presence of residual pretreatment chemicals, such as acids, organic solvents, bases, or ionic liquids. Improving the efficiency of the saccharification process on ionic liquid pretreated biomass will facilitate reduced enzyme loading and cost. Thermophilic cellulases have been shown to be stable and active in ionic liquids but their activity is typically at lower levels. Cel5A_Tma, a thermophilic endoglucanase from Thermotoga maritima, is highly active on cellulosic substrates and is stable in ionic liquid environments. Here, our motivation was to engineer mutants of Cel5A_Tma with higher activity on 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) pretreated biomass. We developed a robotic platform to screen a random mutagenesis library of Cel5A_Tma. Twelve mutants with 25–42% improvement in specific activity on carboxymethyl cellulose and up to 30% improvement on ionic-liquid pretreated switchgrass were successfully isolated and characterized from a library of twenty thousand variants. Interestingly, most of the mutations in the improved variants are located distally to the active site on the protein surface and are not directly involved with substrate binding. PMID:24244549

Improved activity of a thermophilic cellulase, Cel5A, from Thermotoga maritima on ionic liquid pretreated switchgrass.

PubMed

Chen, Zhiwei; Pereira, Jose H; Liu, Hanbin; Tran, Huu M; Hsu, Nathan S Y; Dibble, Dean; Singh, Seema; Adams, Paul D; Sapra, Rajat; Hadi, Masood Z; Simmons, Blake A; Sale, Kenneth L

2013-01-01

Ionic liquid pretreatment of biomass has been shown to greatly reduce the recalcitrance of lignocellulosic biomass, resulting in improved sugar yields after enzymatic saccharification. However, even under these improved saccharification conditions the cost of enzymes still represents a significant proportion of the total cost of producing sugars and ultimately fuels from lignocellulosic biomass. Much of the high cost of enzymes is due to the low catalytic efficiency and stability of lignocellulolytic enzymes, especially cellulases, under conditions that include high temperatures and the presence of residual pretreatment chemicals, such as acids, organic solvents, bases, or ionic liquids. Improving the efficiency of the saccharification process on ionic liquid pretreated biomass will facilitate reduced enzyme loading and cost. Thermophilic cellulases have been shown to be stable and active in ionic liquids but their activity is typically at lower levels. Cel5A_Tma, a thermophilic endoglucanase from Thermotoga maritima, is highly active on cellulosic substrates and is stable in ionic liquid environments. Here, our motivation was to engineer mutants of Cel5A_Tma with higher activity on 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) pretreated biomass. We developed a robotic platform to screen a random mutagenesis library of Cel5A_Tma. Twelve mutants with 25-42% improvement in specific activity on carboxymethyl cellulose and up to 30% improvement on ionic-liquid pretreated switchgrass were successfully isolated and characterized from a library of twenty thousand variants. Interestingly, most of the mutations in the improved variants are located distally to the active site on the protein surface and are not directly involved with substrate binding.

Ionic liquids and their solid-state analogues as materials for energy generation and storage

NASA Astrophysics Data System (ADS)

Macfarlane, Douglas R.; Forsyth, Maria; Howlett, Patrick C.; Kar, Mega; Passerini, Stefano; Pringle, Jennifer M.; Ohno, Hiroyuki; Watanabe, Masayoshi; Yan, Feng; Zheng, Wenjun; Zhang, Shiguo; Zhang, Jie

2016-02-01

Salts that are liquid at room temperature, now commonly called ionic liquids, have been known for more than 100 years; however, their unique properties have only come to light in the past two decades. In this Review, we examine recent work in which the properties of ionic liquids have enabled important advances to be made in sustainable energy generation and storage. We discuss the use of ionic liquids as media for synthesis of electromaterials, for example, in the preparation of doped carbons, conducting polymers and intercalation electrode materials. Focusing on their intrinsic ionic conductivity, we examine recent reports of ionic liquids used as electrolytes in emerging high-energy-density and low-cost batteries, including Li-ion, Li-O2, Li-S, Na-ion and Al-ion batteries. Similar developments in electrolyte applications in dye-sensitized solar cells, thermo-electrochemical cells, double-layer capacitors and CO2 reduction are also discussed.

Cytotoxic Activity of Salicylic Acid-Containing Drug Models with Ionic and Covalent Binding

PubMed Central

2015-01-01

Three different types of drug delivery platforms based on imidazolium ionic liquids (ILs) were synthesized in high preparative yields, namely, the models involving (i) ionic binding of drug and IL; (ii) covalent binding of drug and IL; and (iii) dual binding using both ionic and covalent approaches. Seven ionic liquids containing salicylic acid (SA-ILs) in the cation or/and in the anion were prepared, and their cytotoxicity toward the human cell lines CaCo-2 (colorectal adenocarcinoma) and 3215 LS (normal fibroblasts) was evaluated. Cytotoxicity of SA-ILs was significantly higher than that of conventional imidazolium-based ILs and was comparable to the pure salicylic acid. It is important to note that the obtained SA-ILs dissolved in water more readily than salicylic acid, suggesting benefits of possible usage of traditional nonsoluble active pharmaceutical ingredients in an ionic liquid form. PMID:26617961

Ionic liquid as an electrolyte additive for high performance lead-acid batteries

NASA Astrophysics Data System (ADS)

Deyab, M. A.

2018-06-01

The performance of lead-acid battery is improved in this work by inhibiting the corrosion of negative battery electrode (lead) and hydrogen gas evolution using ionic liquid (1-ethyl-3-methylimidazolium diethyl phosphate). The results display that the addition of ionic liquid to battery electrolyte (5.0 M H2SO4 solution) suppresses the hydrogen gas evolution to very low rate 0.049 ml min-1 cm-2 at 80 ppm. Electrochemical studies show that the adsorption of ionic liquid molecules on the lead electrode surface leads to the increase in the charge transfer resistance and the decrease in the double layer capacitance. I also notice a noteworthy improvement of battery capacity from 45 mAh g-1 to 83 mAh g-1 in the presence of ionic liquid compound. Scanning electron microscopy and energy dispersive X-ray analysis confirm the adsorption of ionic liquid molecules on the battery electrode surface.

Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography.

PubMed

Liu, Yong-Qiang; Yu, Hong

2017-04-01

A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg 2+ , Ca 2+ , and Sr 2+ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV-absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg 2+ , Ca 2+ , and Sr 2+ were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg 2+ , Ca 2+ , and Sr 2+ within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Bunch-Like Tertiary Amine Grafted Polysulfone Membrane for VRFBs with Simultaneously High Proton Conductivity and Low Vanadium Ion Permeability.

PubMed

Tan, Qinglong; Lu, Shanfu; Si, Jiangju; Wang, Haining; Wu, Chunxiao; Li, Xianfeng; Xiang, Yan

2017-04-01

Novel polysulfone membranes with bunch-like tertiary amine groups are synthesized with high ion selectivity and outstanding chemical stability for vanadium redox flow batteries (VRFBs). The bunch-like tertiary amine groups simultaneously act as an ionic conductor for proton hopping and vanadium ion transport obstacles. The performance of the membrane is tuned via controlling the grafting degree of the chloromethylated polysulfone. The results show that membranes show increasing proton over vanadium ion (σ/p) selectivity with increasing functional tertiary groups. VRFBs assembled with the prepared membranes demonstrate an impressive Coulombic efficiency of 98.9% and energy efficiency of 90.9% at a current density of 50 mA cm -2 . Furthermore, the prepared membrane reported in this work shows excellent stability in 1 m VO 2 + solution at 35 °C over 240 h. Overall, the synthesized polymers provide a new insight into the design of high-performance membranes toward VRFB applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon Dioxide Transformation in Imidazolium Salts: Hydroaminomethylation Catalyzed by Ru-Complexes.

PubMed

Ali, Meher; Gual, Aitor; Ebeling, Gunter; Dupont, Jairton

2016-08-23

The catalytic species generated by dissolving Ru3 (CO)12 in the ionic liquids 1-n-butyl-3-methyl-imidazolium chloride or 1-n-butyl-2,3-dimethyl-imidazolium chloride are efficient multifunctional catalysts for: (a) reverse water-gas shift, (b) hydroformylation of alkenes, and (c) reductive amination of aldehydes. Thus the reaction of alkenes with primary or secondary amines (alkene/amine, 1:1) under CO2 /H2 (1:1) affords the hydroaminomethylations products in high alkene conversions (up to 99 %) and selectivities (up to 96 %). The reaction proceeds under relatively mild reaction conditions (120 °C, 60 bar=6 MPa) and affords selectively secondary and tertiary amines. The presence of amine strongly reduces the alkene hydrogenation competitive pathway usually observed in the hydroformylation of terminal alkenes by Ru complexes. The catalytic system is also highly active for the reductive amination of aldehydes and ketones yielding amines in high yields (>90 %). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of poly(N-isopropylacrylamide) particles for metal affinity binding of peptides

PubMed Central

Tsai, Hsin-Yi; Lee, Alexander; Peng, Wei; Yates, Matthew Z.

2013-01-01

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPAM) microgel particles with metal affinity ligands were prepared for selective binding of peptides containing the His6-tag (six consecutive histidine residues). The PNIPAM particles were copolymerized with the functional ligand vinylbenzyl iminodiacetic acid (VBIDA) through a two-stage dispersion polymerization using poly(N-vinyl pyrrolidone) (PVP) as a steric stabilizer. The resulting particles were monodisperse in size and colloidally stable over a wide range of temperature and ionic strength due to chemically grafted PVP chains. The particle size was also found to be sensitive to ionic strength and pH of the aqueous environment, likely due to the electrostatic repulsion between ionized VBIDA groups. Divalent nickel ions were chelated to the VBIDA groups, allowing selective metal affinity attachment of a His6-Cys peptide. The peptide was released upon the addition of the competitive ligand imidazole, demonstrating that the peptide attachment to the particles is reversible and selective. PMID:24176889

Ideal gas solubilities and solubility selectivities in a binary mixture of room-temperature ionic liquids.

PubMed

Finotello, Alexia; Bara, Jason E; Narayan, Suguna; Camper, Dean; Noble, Richard D

2008-02-28

This study focuses on the solubility behaviors of CO2, CH4, and N2 gases in binary mixtures of imidazolium-based room-temperature ionic liquids (RTILs) using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N]) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim][BF4]) at 40 degrees C and low pressures (approximately 1 atm). The mixtures tested were 0, 25, 50, 75, 90, 95, and 100 mol % [C2mim][BF4] in [C2mim][Tf2N]. Results show that regular solution theory (RST) can be used to describe the gas solubility and selectivity behaviors in RTIL mixtures using an average mixture solubility parameter or an average measured mixture molar volume. Interestingly, the solubility selectivity, defined as the ratio of gas mole fractions in the RTIL mixture, of CO2 with N2 or CH4 in pure [C2mim][BF4] can be enhanced by adding 5 mol % [C2mim][Tf2N].

Aligned Carbon Nanotubes for Highly Efficient Energy Generation and Storage Devices

DTIC Science & Technology

2012-01-24

solution processing methods, including filtration, solution-casting, electrophoretic deposition, and Langmuir - Blodgett deposition. However, most...supercapacitors with environmentally friendly ionic liquid electrolytes. These new nanocomposite electrodes consist of the high-surface-area activated...carbons, carbon nanotubes, and ionic liquids as the integrated constituent components. The resultant composites show significantly improved charge

CHLORIDEDETERMINATION IN HIGH IONIC STRENGTH SOLUTION OF AMMONIUM ACETATE USING NEGATIVE ION ELECTRON SPRAY IONIZATION (HPLC/MS)

EPA Science Inventory

A precise ion chromatography method has been developed for the determination of chloride in high ionic strength ammonium acetate solutions (10-5 M-5 M) using sodium carbonate/sodium bicarbonate as eluent. Negative ion electrospray ionization (ESI) mass spectrometry was used for q...

Functionalized graphene sheets with poly(ionic liquid)s and high adsorption capacity of anionic dyes

NASA Astrophysics Data System (ADS)

Zhao, Weifeng; Tang, Yusheng; Xi, Jia; Kong, Jie

2015-01-01

Graphene sheets were covalently functionalized with poly(1-vinylimidazole) (PVI) type poly(ionic liquid), by utilizing a diazonium addition reaction and the subsequent grafting of PVI polymers onto the graphene sheet surface by a quaternarization reaction. The resultant modified graphene sheets showed improved dispersion property when being dissolved in DMF and ethanol. FTIR, XPS, XRD and TEM observations confirmed the success of the covalent functionalization, and thermogravimetric analysis revealed that the grafting ratio of PVI was ∼12 wt%. The obtained PVI-functionalized graphene showed a high capability for removing anionic dyes such as methyl blue (MB) from water solution. The experimental data of isotherm fitted well with the Langmuir adsorption model. The adsorption capacity of 1910 mg g-1 for methyl blue (MB) dye was observed for functionalized graphene sheets with poly(ionic liquid)s, which was higher than that of unmodified graphene. The high adsorption capacity observed in this study emphasizes that poly(ionic liquid)s-modified graphene materials have a great potential for water purification as they are highly efficient and stable adsorbents for sustainability.

High ionic conductivity P(VDF-TrFE)/PEO blended polymer electrolytes for solid electrochromic devices.

PubMed

Nguyen, Chien A; Xiong, Shanxin; Ma, Jan; Lu, Xuehong; Lee, Pooi See

2011-08-07

Solid polymer electrolytes with excellent ionic conductivity (above 10(-4) S cm(-1)), which result in high optical modulation for solid electrochromic (EC) devices are presented. The combination of a polar host matrix poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) and a solid plasticized of a low molecular weight poly(ethylene oxide) (PEO) (M(w)≤ 20,000) blended polymer electrolyte serves to enhance both the dissolution of lithium salt and the ionic transport. Calorimetric measurement shows a reduced crystallization due to a better intermixing of the polymers with small molecular weight PEO. Vibrational spectroscopy identifies the presence of free ions and ion pairs in the electrolytes with PEO of M(w)≤ 8000. The ionic dissolution is improved using PEO as a plasticizer when compared to liquid propylene carbonate, evidently shown in the transference number analysis. Ionic transport follows the Arrhenius equation with a low activation energy (0.16-0.2 eV), leading to high ionic conductivities. Solid electrochromic devices fabricated with the blended P(VDF-TrFE)/PEO electrolytes and polyaniline show good spectroelectrochemical performance in the visible (300-800 nm) and near-infrared (0.9-2.4 μm) regions with a modulation up to 60% and fast switching speed of below 20 seconds. The successful introduction of the solid polymer electrolytes with its best harnessed qualities helps to expedite the application of various electrochemical devices. This journal is © the Owner Societies 2011

Surface-bonded ionic liquid stationary phases in high-performance liquid chromatography--a review.

PubMed

Pino, Verónica; Afonso, Ana M

2012-02-10

Ionic liquids (ILs) are a class of ionic, nonmolecular solvents which remain in liquid state at temperatures below 100°C. ILs possess a variety of properties including low to negligible vapor pressure, high thermal stability, miscibility with water or a variety of organic solvents, and variable viscosity. IL-modified silica as novel high-performance liquid chromatography (HPLC) stationary phases have attracted considerable attention for their differential behavior and low free-silanol activity. Indeed, around 21 surface-confined ionic liquids (SCIL) stationary phases have been developed in the last six years. Their chromatographic behavior has been studied, and, despite the presence of a positive charge on the stationary phase, they showed considerable promise for the separation of neutral solutes (not only basic analytes), when operated in reversed phase mode. This aspect points to the potential for truly multimodal stationary phases. This review attempts to summarize the state-of-the-art about SCIL phases including their preparation, chromatographic behavior, and analytical performance. Copyright © 2011 Elsevier B.V. All rights reserved.

Super ionic conductive glass

DOEpatents

Susman, S.; Volin, K.J.

Described is an ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A/sub 1 + x/D/sub 2-x/3/Si/sub x/P/sub 3 - x/O/sub 12 - 2x/3/, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

Strongly correlated perovskite fuel cells

NASA Astrophysics Data System (ADS)

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

2016-06-01

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Strongly correlated perovskite fuel cells

DOE PAGES

Zhou, You; Guan, Xiaofei; Zhou, Hua; ...

2016-05-16

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes.more » Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.« less

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.

Strongly correlated perovskite fuel cells.

PubMed

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

2016-06-09

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Selective removal of cesium by ammonium molybdophosphate - polyacrylonitrile bead and membrane.

PubMed

Ding, Dahu; Zhang, Zhenya; Chen, Rongzhi; Cai, Tianming

2017-02-15

The selective removal of radionuclides with extremely low concentrations from environmental medium remains a big challenge. Ammonium molybdophosphate possess considerable selectivity towards cesium ion (Cs + ) due to the specific ion exchange between Cs + and NH 4 + . Ammonium molybdophosphate - polyacrylonitrile (AMP-PAN) membrane was successfully prepared for the first time in this study. Efficient removal of Cs + (95.7%, 94.1% and 91.3% of 1mgL -1 ) from solutions with high ionic strength (400mgL -1 of Na + , Ca 2+ or K + ) was achieved by AMP-PAN composite. Multilayer chemical adsorption process was testified through kinetic and isotherm studies. The estimated maximum adsorption capacities even reached 138.9±21.3mgg -1 . Specifically, the liquid film diffusion was identified as the rate-limiting step throughout the removal process. Finally, AMP-PAN membrane could eliminate Cs + from water effectively through the filtration adsorption process. Copyright © 2016 Elsevier B.V. All rights reserved.

Surface stability and the selection rules of substrate orientation for optimal growth of epitaxial II-VI semiconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yin, Wan-Jian; Department of Physics & Astronomy, and Wright Center for Photovoltaics Innovation and Commercialization, The University of Toledo, Toledo, Ohio 43606; Yang, Ji-Hui

2015-10-05

The surface structures of ionic zinc-blende CdTe (001), (110), (111), and (211) surfaces are systematically studied by first-principles density functional calculations. Based on the surface structures and surface energies, we identify the detrimental twinning appearing in molecular beam epitaxy (MBE) growth of II-VI compounds as the (111) lamellar twin boundaries. To avoid the appearance of twinning in MBE growth, we propose the following selection rules for choosing optimal substrate orientations: (1) the surface should be nonpolar so that there is no large surface reconstructions that could act as a nucleation center and promote the formation of twins; (2) the surfacemore » structure should have low symmetry so that there are no multiple equivalent directions for growth. These straightforward rules, in consistent with experimental observations, provide guidelines for selecting proper substrates for high-quality MBE growth of II-VI compounds.« less

Exploring the role of ionic liquids to tune the polymorphic outcome of organic compounds.

PubMed

Zeng, Qingying; Mukherjee, Arijit; Müller, Peter; Rogers, Robin D; Myerson, Allan S

2018-02-14

While molecular solvents are commonly used in the screening of polymorphs, the choices are often restricted. Ionic liquids (ILs) - also referred as designer solvents - have immense possibility in this regard because of their wide flexibility of tunability. More importantly, the interactions among the IL components are completely unique compared to those present in the molecular solvents. In this context, we have chosen tetrolic acid (TA) and isonicotinamide (INA), which showed solution-structure link in molecular solvents in the past, as probes to investigate the role of imidazolium based ionic liquids in the polymorphism of these two systems and whether the different solute-solvent interactions in ILs affect the polymorphic outcome. It is observed that the selected imidazolium-based ILs, with varying anion basicity have influenced the crystallization outcome by the interaction between ILs and model compounds. Later, we have utilized the concept of double salt ionic liquids (DSIL) for INA, a penta-morphic system, to investigate the variation in the polymorphic outcome. This approach helped to obtain the forms that were otherwise inaccessible in ILs.

Static and dynamic wetting behaviour of ionic liquids.

PubMed

Delcheva, Iliana; Ralston, John; Beattie, David A; Krasowska, Marta

2015-08-01

Ionic liquids (ILs) are a unique family of molecular liquids ('molten salts') that consist of a combination of bulky organic cations coupled to inorganic or organic anions. The net result of steric hindrance and strong hydrogen bonding between components results in a material that is liquid at room temperature. One can alter the properties of ionic liquids through chemical modification of anion and cation, thus tailoring the IL for a given application. One such property that can be controlled or selected is the wettability of an IL on a particular solid substrate. However, the study of wetting of ionic liquids is complicated by the care required for accurate and reproducible measurement, due to both the susceptibility of the IL properties to water content, as well as to the sensitivity of wettability measurements to the state of the solid surface. This review deals with wetting studies of ILs to date, including both static and dynamic wetting, as well as issues concerning line tension and the formation of precursor and wetting films. Copyright © 2014 Elsevier B.V. All rights reserved.

Amino acid anions in organic ionic compounds. An ab initio study of selected ion pairs.

PubMed

Benedetto, A; Bodo, E; Gontrani, L; Ballone, P; Caminiti, R

2014-03-06

The combination of amino acids in their deprotonated and thus anionic form with a choline cation gives origin to a new and potentially important class of organic ionic compounds. A series of such neutral ion pairs has been investigated by first principle methods. The results reveal intriguing structural motives as well as regular patterns in the charge distribution and predict a number of vibrational and optical properties that could guide the experimental investigation of these compounds. The replacement of choline with its phosphocholine analogue causes the spontaneous reciprocal neutralization of cations and anions, taking place through the transfer of a proton between the two ions. Systems of this kind, therefore, provide a wide and easily accessible playground to probe the ionic/polar transition in organic systems, while the easy transfer of H(+) among neutral and ionic species points to their potential application as proton conductors. The analysis of the ab initio data highlights similarities as well as discrepancies from the rigid-ions force-field picture and suggests directions for the improvement of empirical models.

Determination of the solubility parameter of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate by inverse gas chromatography.

PubMed

Ma, Xiaohong; Wang, Qiang; Li, Xiaoping; Tang, Jun; Zhang, Zhengfang

2015-11-01

Thermodynamic properties of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM] BF4) were determined via inverse gas chromatography (IGC). Two groups of solvents with different chemical natures and polarities were used to obtain information about [BMIM] BF4-solvent interactions. The specific retention volume, molar heat of sorption, weight fraction activity coefficient, Flory-Huggins interaction parameter as well as solubility parameter were also determined in a temperature range of 333 - 373 K. The results showed that the selected solvents n-C10 to n-C12, carbon tetrachloride, cyclohexane and toluene were poor solvents for [BMIM] BF4, while dichloromethane, acetone, chloroform, methyl acetate, ethanol and methanol were favorite solvents for [BMIM] BF4. In addition, the solubility parameter of [ BMIM] BF4 was determined as 23.39 (J/cm3)0.5 by the extrapolation at 298 K. The experiment proved that IGC was a simple and accurate method to obtain the thermodynamic properties of ionic liquids. This study could be used as a reference to the application and research of the ionic liquids.

Targeting adequate thermal stability and fire safety in selecting ionic liquid-based electrolytes for energy storage.

PubMed

Chancelier, L; Diallo, A O; Santini, C C; Marlair, G; Gutel, T; Mailley, S; Len, C

2014-02-07

The energy storage market relating to lithium based systems regularly grows in size and expands in terms of a portfolio of energy and power demanding applications. Thus safety focused research must more than ever accompany related technological breakthroughs regarding performance of cells, resulting in intensive research on the chemistry and materials science to design more reliable batteries. Formulating electrolyte solutions with nonvolatile and hardly flammable ionic liquids instead of actual carbonate mixtures could be safer. However, few definitions of thermal stability of electrolytes based on ionic liquids have been reported in the case of abuse conditions (fire, shortcut, overcharge or overdischarge). This work investigates thermal stability up to combustion of 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C1C4Im][NTf2]) and 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide ([PYR14][NTf2]) ionic liquids, and their corresponding electrolytes containing lithium bis(trifluoromethanesulfonyl)imide LiNTf2. Their possible routes of degradation during thermal abuse testings were investigated by thermodynamic studies under several experimental conditions. Their behaviours under fire were also tested, including the analysis of emitted compounds.

Binder-free three-dimensional high energy density electrodes for ionic-liquid supercapacitors.

PubMed

Tran, Chau; Lawrence, Daniel; Richey, Francis W; Dillard, Caitlin; Elabd, Yossef A; Kalra, Vibha

2015-09-18

We demonstrate a facile methodology to fabricate binder-free porous carbon nanofiber electrodes for room temperature ionic-liquid supercapacitors. The device provides an energy density of 80 W h kg(-1) based on the mass of two electrodes while retaining the high rate capability of supercapacitors with near-ideal CV curves at a high scan rate of 200 mV s(-1).

Evaluation of Vapor Pressure and Ultra-High Vacuum Tribological Properties of Ionic Liquids (2) Mixtures and Additives

NASA Technical Reports Server (NTRS)

Morales, Wilfredo; Koch, Victor R.; Street, Kenneth W., Jr.; Richard, Ryan M.

2008-01-01

Ionic liquids are salts, many of which are typically viscous fluids at room temperature. The fluids are characterized by negligible vapor pressures under ambient conditions. These properties have led us to study the effectiveness of ionic liquids containing both organic cations and anions for use as space lubricants. In the previous paper we have measured the vapor pressure and some tribological properties of two distinct ionic liquids under simulated space conditions. In this paper we will present vapor pressure measurements for two new ionic liquids and friction coefficient data for boundary lubrication conditions in a spiral orbit tribometer using stainless steel tribocouples. In addition we present the first tribological data on mixed ionic liquids and an ionic liquid additive. Post mortem infrared and Raman analysis of the balls and races indicates the major degradation pathway for these two organic ionic liquids is similar to those of other carbon based lubricants, i.e. deterioration of the organic structure into amorphous graphitic carbon. The coefficients of friction and lifetimes of these lubricants are comparable to or exceed these properties for several commonly used space oils.

Electropolymerized polyazulene as active material in flexible supercapacitors

NASA Astrophysics Data System (ADS)

Suominen, Milla; Lehtimäki, Suvi; Yewale, Rahul; Damlin, Pia; Tuukkanen, Sampo; Kvarnström, Carita

2017-07-01

We report the capacitive behavior of electrochemically polymerized polyazulene films in different ionic liquids. The ionic liquids in this study represent conventional imidazolium based ionic liquids with tetrafluoroborate and bis(trifluoromethylsulfonyl)imide anions as well as an unconventional choline based ionic liquid. The effect of different ionic liquids on the polymerization and capacitive performance of polyazulene films is demonstrated by cyclic voltammetry and electrochemical impedance spectroscopy in a 3-electrode cell configuration. The films exhibit the highest capacitances in the lowest viscosity ionic liquid (92 mF cm-2), while synthesis in high viscosity ionic liquid shortens the conjugation length and results in lower electroactivity (25 mF cm-2). The obtained films also show good cycling stabilities retaining over 90% of their initial capacitance over 1200 p-doping cycles. We also demonstrate, for the first time, flexible polyazulene supercapacitors of symmetric and asymmetric configurations using the choline based ionic liquid as electrolyte. In asymmetric configuration, capacitance of 55 mF (27 mF cm-2) with an equivalent series resistance of 19 Ω is obtained at operating voltage of 1.5 V. Upon increasing the operating voltage up to 2.4 V, the capacitance increases to 72 mF (36 mF cm-2).

Multi-Scale Simulation of High Energy Density Ionic Liquids

DTIC Science & Technology

2007-06-19

and simulation of ionic liquids (ILs). A polarizable model was developed to simulate ILs more accurately at the atomistic level. A multiscale coarse...propellant, 1- hydroxyethyl-4-amino-1, 2, 4-triazolium nitrate (HEATN), were studied with the all-atom polarizable model. The mechanism suggested for HEATN...with this AFOSR-supported project, a polarizable forcefield for the ionic liquids such as 1-ethyl-3-methylimidazolium nitrate (EMIM*/NO3-) was

Molecular simulations and experimental studies of solubility and diffusivity for pure and mixed gases of H2, CO2, and Ar absorbed in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]).

PubMed

Shi, Wei; Sorescu, Dan C; Luebke, David R; Keller, Murphy J; Wickramanayake, Shan

2010-05-20

Classical molecular dynamics and Monte Carlo simulations are used to calculate the self-diffusivity and solubility of pure and mixed CO(2), H(2), and Ar gases absorbed in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf(2)N]). Overall, the computed absorption isotherms, Henry's law constants, and partial molar enthalpies for pure H(2) agree well with the experimental data obtained by Maurer et al. [J. Chem. Eng. Data 2006, 51, 1364] and the experimental values determined in this work. However, the agreement is poor between the simulations and the experimental data by Noble et al. [Ind. Eng. Chem. Res. 2008, 47, 3453] and Costa Gomes [J. Chem. Eng. Data 2007, 52, 472] at high temperatures. The computed H(2) permeability values are in good agreement with the experimental data at 313 K obtained by Luebke et al. [J. Membr. Sci. 2007, 298, 41; ibid, 2008, 322, 28], but about three times larger than the experimental value at 573 K from the same group. Our computed H(2) solubilities using different H(2) potential models have similar values and solute polarizations were found to have a negligible effect on the predicted gas solubilities for both the H(2) and Ar. The interaction between H(2) and the ionic liquid is weak, about three times smaller than between the ionic liquid and Ar and six times smaller than that of CO(2) with the ionic liquid, results that are consistent with a decreasing solubility from CO(2) to Ar and to H(2). The molar volume of the ionic liquid was found to be the determining factor for the H(2) solubility. For mixed H(2) and Ar gases, the solubilities for both solutes decrease compared to the respective pure gas solubilities. For mixed gases of CO(2) and H(2), the solubility selectivity of CO(2) over H(2) decreases from about 30 at 313 K to about 3 at 573 K. For the permeability, the simulated values for CO(2) in [hmim][Tf(2)N] are about 20-60% different than the experimental data by Luebke et al. [J. Membr. Sci. 2008, 322, 28].

On the origin of high ionic conductivity in Na-doped SrSiO 3

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chien, Po-Hsiu; Jee, Youngseok; Huang, Chen

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na xSr 1-xSiO 3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation ofmore » an amorphous phase β-Na 2Si 2O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2Si 2O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.« less

On the origin of high ionic conductivity in Na-doped SrSiO 3

DOE PAGES

Chien, Po-Hsiu; Jee, Youngseok; Huang, Chen; ...

2016-02-17

Understanding the local structure and ion dynamics is at the heart of ion conductor research. This paper reports on high-resolution solid-state 29Si, 23Na, and 17O NMR investigation of the structure, chemical composition, and ion dynamics of a newly discovered fast ion conductor, Na-doped SrSiO 3, which exhibited a much higher ionic conductivity than most of current oxide ion conductors. Quantitative analyses reveal that with a small dose (<10 mol%) of Na, the doped Na integrates into the SrSiO 3 structure to form Na xSr 1-xSiO 3-0.5x, and with >10 mol% Na doping, phase separation occurs, leading to the formation ofmore » an amorphous phase β-Na 2Si 2O 5 and a crystalline Sr-rich phase. Variable-temperature 23Na and 17O magic-angle-spinning NMR up to 618 °C have shown significant changes in Na ion dynamics at high temperatures but little oxide ion motion, suggesting that Na ions are responsible for the observed high ionic conductivity. In addition, β-Na 2Si 2O 5 starts to crystallize at temperatures higher than 480 °C with prolonged heating, resulting in reduction in Na+ motion, and thus degradation of ionic conductivity. This study has contributed critical evidence to the understanding of ionic conduction in Na-doped SrSiO 3 and demonstrated that multinuclear high-resolution and high-temperature solid-state NMR is a uniquely useful tool for investigating ion conductors at their operating conditions.« less

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.

Cloud point extraction: an alternative to traditional liquid-liquid extraction for lanthanides(III) separation.

PubMed

Favre-Réguillon, Alain; Draye, Micheline; Lebuzit, Gérard; Thomas, Sylvie; Foos, Jacques; Cote, Gérard; Guy, Alain

2004-06-17

Cloud point extraction (CPE) was used to extract and separate lanthanum(III) and gadolinium(III) nitrate from an aqueous solution. The methodology used is based on the formation of lanthanide(III)-8-hydroxyquinoline (8-HQ) complexes soluble in a micellar phase of non-ionic surfactant. The lanthanide(III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud point temperature (CPT). The structure of the non-ionic surfactant, and the chelating agent-metal molar ratio are identified as factors determining the extraction efficiency and selectivity. In an aqueous solution containing equimolar concentrations of La(III) and Gd(III), extraction efficiency for Gd(III) can reach 96% with a Gd(III)/La(III) selectivity higher than 30 using Triton X-114. Under those conditions, a Gd(III) decontamination factor of 50 is obtained.

Controlling Ionic Transport for Device Design in Synthetic Nanopores

NASA Astrophysics Data System (ADS)

Kalman, Eric Boyd

Polymer nanopores present a number of behaviors not seen in microscale systems, such as ion current rectification, ionic selectivity, size exclusion and potential dependent ion concentrations in and near the pore. The existence of these effects stems from the small size of nanopores with respect to the characteristic length scales of surface interactions at the interface between the nanopore surface and the solution within it. The large surface-to-volume ratio due to the nanoscale geometry of a nanopore, as well as similarity in scale between geometry and interaction demands the solution interact with the nanopore walls. As surfaces in solution almost always carry residual charge, these surface forces are primarily the electrostatic interactions between the charge groups on the pore surface and the ions in solution. These interactions may be used by the experimentalist to control ionic transport through synthetic nanopores, and use them as a template for the construction of devices. In this research, we present our work on creating a number of ionic analogs to seminal electronic devices, specifically diodes, and transistors, by controlling ionic transport through the electrostatic interactions between a single synthetic nanopore and ions. Control is achieved by "doping" the effective charge carrier concentration in specific regions of the nanopore through manipulation of the pore's surface charge. This manipulation occurs through two mechanisms: chemical modification of the surface charge and electrostatic manipulation of the local internal nanopore potential using a gate electrode. Additionally, the innate selectivity of the charged nanopores walls allows for the separation of charges in solution. This well-known effect, which spawns measureable quantities, the streaming potential and current, has been used to create nanoscale water desalination membranes. We attempt to create a device using membranes with large nanopore densities for the desalination of water which should theoretically outperform currently available devices, as through our previous work we have developed techniques allowing for transport manipulation not current accessible in traditional membrane motifs.

Predicting the partitioning of biological compounds between room-temperature ionic liquids and water by means of the solvation-parameter model.

PubMed

Padró, Juan M; Ponzinibbio, Agustín; Mesa, Leidy B Agudelo; Reta, Mario

2011-03-01

The partition coefficients, P(IL/w), for different probe molecules as well as for compounds of biological interest between the room-temperature ionic liquids (RTILs) 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF(6)], 1-hexyl-3-methylimidazolium hexafluorophosphate, [HMIM][PF(6)], 1-octyl-3-methylimidazolium tetrafluoroborate, [OMIM][BF(4)] and water were accurately measured. [BMIM][PF(6)] and [OMIM][BF(4)] were synthesized by adapting a procedure from the literature to a simpler, single-vessel and faster methodology, with a much lesser consumption of organic solvent. We employed the solvation-parameter model to elucidate the general chemical interactions involved in RTIL/water partitioning. With this purpose, we have selected different solute descriptor parameters that measure polarity, polarizability, hydrogen-bond-donor and hydrogen-bond-acceptor interactions, and cavity formation for a set of specifically selected probe molecules (the training set). The obtained multiparametric equations were used to predict the partition coefficients for compounds not present in the training set (the test set), most being of biological interest. Partial solubility of the ionic liquid in water (and water into the ionic liquid) was taken into account to explain the obtained results. This fact has not been deeply considered up to date. Solute descriptors were obtained from the literature, when available, or else calculated through commercial software. An excellent agreement between calculated and experimental log P(IL/w) values was obtained, which demonstrated that the resulting multiparametric equations are robust and allow predicting partitioning for any organic molecule in the biphasic systems studied.

Enhancing Adsorption Capacity while Maintaining Specific Recognition Performance of Mesoporous Silica: A Novel Imprinting Strategy with Amphiphilic Ionic Liquid as Surfactant.

PubMed

Ding, Shichao; Li, Zhiling; Cheng, Yuan; Du, Chunbao; Gao, Junfeng; Zhang, Yong-Wei; Zhang, Nan; Li, Zhaotong; Chang, Ninghui; Hu, Xiaoling

2018-06-21

In order to facilitate the broad applications of molecular recognition materials in biomedical areas, it is critical to enhance their adsorption capacity while maintaining their excellent recognition performance. In this work, we designed and synthesized well-defined peptide-imprinted mesoporous silica (PIMS) for specific recognition of an immunostimulating hexapeptide from human casein (IHHC) by using amphiphilic ionic liquid as the surfactant to anchor IHHC via a combination of one step sol-gel method and docking oriented imprinting approach. Thereinto, theoretical calculation was employed to reveal the multiple binding interactions and dual-template configuration between amphiphilic ionic liquid and IHHC. The fabricated PIMS was characterized and an in-depth analysis of specific recognition mechanism was conducted. Results revealed that both adsorption and recognition capabilities of PIMS far exceeded that of the NIMS's. More significantly, the PIMS exhibited a superior binding capacity (60.5 mg g-1), which could increase 18.9% than the previous work. The corresponding imprinting factor and selectivity coefficient could reach up to 4.51 and 3.30, respectively. The PIMS also possessed lickety-split kinetic binding for IHHC, which the equilibrium time was only 10 min. All of these merits were due to the high surface area and the synergistic effect of multiple interactions (including hydrogen bonding, π-π stacking, ion-ion electrostatic interactions and van der Waals interactions, etc.) between PIMS and IHHC in imprinted sites. The present work suggests the potential application of PIMS for large-scale and high-effective separation of IHHC, which may lead to their broad applications in drug/gene deliver, biosensors, catalyst and so on. © 2018 IOP Publishing Ltd.

Highly Efficient Extraction of Phenolic Compounds by Use of Magnetic Room Temperature Ionic Liquids for Environmental Remediation

PubMed Central

Deng, Ning; Li, Min; Zhao, Lijie; Lu, Chengfei; de Rooy, Sergio L.; Warner, Isiah M.

2011-01-01

A hydrophobic magnetic room temperature ionic liquid (MRTIL), trihexyltetradecylphosphonium tetrachloroferrate(III) ([3C6PC14][FeCl4]), was synthesized from trihexyltetradecylphosphonium chloride and FeCl3·6H2O. This MRTIL was investigated as a possible separation agent for solvent extraction of phenolic compounds from aqueous solution. Due to its strong paramagnetism, [3C6PC14][FeCl4] responds to an external neodymium magnet, which was employed in the design of a novel magnetic extraction technique. The conditions for extraction, including extraction time, volume ratio between MRTIL and aqueous phase, pH of aqueous solution, and structures of phenolic compounds were investigated and optimized. The magnetic extraction of phenols achieved equilibrium in 20 min and the phenolic compounds were found to have higher distribution ratios under acidic conditions. In addition, it was observed that phenols containing a greater number of chlorine or nitro substitutents exhibited higher distribution ratios. For example, the distribution ratio of phenol (DPh) was 107. In contrast, 3,5-dichlorophenol distribution ratio (D3,5-DCP) had a much higher value of 6372 under identical extraction conditions. When compared with four selected traditional non-magnetic room temperature ionic liquids, our [3C6PC14][FeCl4] exhibited significantly higher extraction efficiency under the same experimental conditions used in this work. Pentachlorophenol, a major component in the contaminated soil sample obtained from a superfund site, was successfully extracted and removed by use of [3C6PC14][FeCl4] with high extraction efficiency. Pentachlorophenol concentration was dramatically reduced from 7.8 μg.mL−1 to 0.2 μg.mL−1 after the magnetic extraction by use of [3C6PC14][FeCl4]. PMID:21783320

Reversible and strong immobilization of proteins by ionic exchange on supports coated with sulfate-dextran.

PubMed

Fuentes, Manuel; Pessela, Benevides C C; Maquiese, Jorgette V; Ortiz, Claudia; Segura, Rosa L; Palomo, Jose M; Abian, Olga; Torres, Rodrigo; Mateo, Cesar; Fernández-Lafuente, Roberto; Guisán, J M

2004-01-01

New and strong ionic exchange resins have been prepared by the simple and rapid ionic adsorption of anionic polymers (sulfate-dextran) on porous supports activated with the opposite ionic group (DEAE/MANAE). Ionic exchange properties of such composites were strongly dependent on the size of the ionic polymers as well as on the conditions of the ionic coating of the solids with the ionic polymers (optimal conditions were 400 mg of sulfate-dextran 5000 kDa per gram of support). Around 80% of the proteins contained in crude extracts from Escherichia coli and Acetobacter turbidans could be adsorbed on these porous composites even at pH 7. This interaction was stronger than that using conventional carboxymethyl cellulose (CMC) and even others such as supports coated with aspartic-dextran polymer. By means of the sequential use of the new supports and supports coated with polyethyleneimine (PEI), all proteins from crude extracts could be immobilized. In fact, a large percentage (over 50%) could be immobilized on both supports. Finally, some industrially relevant enzymes (beta-galactosidases from Aspergillus oryzae, Kluyveromyces lactis, and Thermussp. strain T2, lipases from Candida antarctica A and B, Candida rugosa, Rhizomucor miehei, and Rhyzopus oryzae and bovine pancreas trypsin and chymotrypsin) have been immobilized on these supports with very high activity recoveries and immobilization rates. After enzyme inactivation, the protein could be fully desorbed from the support, and then the support could be reused for several cycles. Moreover, in some instances the enzyme stability was significantly improved, mainly in the presence of organic solvents, perhaps as a consequence of the highly hydrophilic microenvironment of the support.

Can the scaling behavior of electric conductivity be used to probe the self-organizational changes in solution with respect to the ionic liquid structure? The case of [C8MIM][NTf2].

PubMed

Paluch, Marian; Wojnarowska, Zaneta; Goodrich, Peter; Jacquemin, Johan; Pionteck, Jürgen; Hensel-Bielowka, Stella

2015-08-28

Electrical conductivity of the supercooled ionic liquid [C8MIM][NTf2], determined as a function of temperature and pressure, highlights strong differences in its ionic transport behavior between low and high temperature regions. To date, the crossover effect which is very well known for low molecular van der Waals liquids has been rarely described for classical ionic liquids. This finding highlights that the thermal fluctuations could be dominant mechanisms driving the dramatic slowing down of ion motions near Tg. An alternative way to analyze separately low and high temperature dc-conductivity data using a density scaling approach was then proposed. Based on which a common value of the scaling exponent γ = 2.4 was obtained, indicating that the applied density scaling is insensitive to the crossover effect. By comparing the scaling exponent γ reported herein along with literature data for other ionic liquids, it appears that γ decreases by increasing the alkyl chain length on the 1-alkyl-3-methylimidazolium-based ionic liquids. This observation may be related to changes in the interaction between ions in solution driven by an increase in the van der Waals type interaction by increasing the alkyl chain length on the cation. This effect may be related to changes in the ionic liquid nanostructural organization with the alkyl chain length on the cation as previously reported in the literature based on molecular dynamic simulations. In other words, the calculated scaling exponent γ may be then used as a key parameter to probe the interaction and/or self-organizational changes in solution with respect to the ionic liquid structure.

Evaluation of effects of pH and ionic strength on colloidal stability of IgG solutions by PEG-induced liquid-liquid phase separation.

PubMed

Thompson, Ronald W; Latypov, Ramil F; Wang, Ying; Lomakin, Aleksey; Meyer, Julie A; Vunnum, Suresh; Benedek, George B

2016-11-14

Colloidal stability of IgG antibody solutions is important for pharmaceutical and medicinal applications. Solution pH and ionic strength are two key factors that affect the colloidal stability of protein solutions. In this work, we use a method based on the PEG-induced liquid-liquid phase separation to examine the effects of pH and ionic strength on the colloidal stability of IgG solutions. We found that at high ionic strength (≥0.25M), the colloidal stability of most of our IgGs is insensitive to pH, and at low ionic strength (≤0.15M), all IgG solutions are much more stable at pH 5 than at pH 7. In addition, the PEG-induced depletion force is less efficient in causing phase separation at pH 5 than at pH 7. In contrast to the native inter-protein interaction of IgGs, the effect of depletion force on phase separation of the antibody solutions is insensitive to ionic strength. Our results suggest that the long-range electrostatic inter-protein repulsion at low ionic strength stabilizes the IgG solutions at low pH. At high ionic strength, the short-range electrostatic interactions do not make a significant contribution to the colloidal stability for most IgGs with a few exceptions. The weaker effect of depletion force at lower pH indicates a reduction of protein concentration in the condensed phase. This work advances our basic understanding of the colloidal stability of IgG solutions and also introduces a practical approach to measuring protein colloidal stability under various solution conditions.

Highly selective isolation and purification of heme proteins in biological samples using multifunctional magnetic nanospheres.

PubMed

Liu, Yating; Li, Yan; Wei, Yun

2014-12-01

Magnetic particles with suitable surface modification are capable of binding proteins selectively, and magnetic separations have advantages of rapidity, convenience, and high selectivity. In this paper, new magnetic nanoparticles modified with imidazolium ionic liquid (Fe3O4 @SiO2 @ILs) were successfully fabricated. N-Methylimidazolium was immobilized onto silica-coated magnetic nanoparticles via γ-chloropropyl modification as a magnetic nanoadsorbent for heme protein separation. The particle size was about 90 nm without significant aggregation during the preparation process. Hemoglobin as one of heme proteins used in this experiment was compared with other nonheme proteins. It has been found that the magnetic nanoparticles can be used for more rapid, efficient, and specific adsorption of hemoglobin with a binding capacity as high as 5.78 mg/mg. In comparison with other adsorption materials of proteins in the previous reports, Fe3 O4 @SiO2 @ILs magnetic nanoparticles exhibit the excellent performance in isolation of heme proteins with higher binding capacity and selectivity. In addition, a short separation time makes the functionalized nanoparticles suitable for purifying unstable proteins, as well as having other potential applications in a variety of biomedical fields. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Strong Stretching of Poly(ethylene glycol) Brushes Mediated by Ionic Liquid Solvation.

PubMed

Han, Mengwei; Espinosa-Marzal, Rosa M

2017-09-07

We have measured forces between mica surfaces coated with a poly(ethylene glycol) (PEG) brush solvated by a vacuum-dry ionic liquid, 1-ethyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)imide, with a surface forces apparatus. At high grafting density, the solvation mediated by the ionic liquid causes the brush to stretch twice as much as in water. Modeling of the steric repulsion indicates that PEG behaves as a polyelectrolyte; the hydrogen bonding between ethylene glycol and the imidazolium cation seems to effectively charge the polymer brush, which justifies the strong stretching. Importantly, under strong polymer compression, solvation layers are squeezed out at a higher rate than for the neat ionic liquid. We propose that the thermal fluctuations of the PEG chains, larger in the brush than in the mushroom configuration, maintain the fluidity of the ionic liquid under strong compression, in contrast to the solid-like squeezing-out behavior of the neat ionic liquid. This is the first experimental study of the behavior of a polymer brush solvated by an ionic liquid under nanoconfinement.

Sensitivities of ionic explosives

NASA Astrophysics Data System (ADS)

Politzer, Peter; Lane, Pat; Murray, Jane S.

2017-03-01

We have investigated the relevance for ionic explosive sensitivity of three factors that have been demonstrated to be related to the sensitivities of molecular explosives. These are (1) the maximum available heat of detonation, (2) the amount of free space per molecule (or per formula unit) in the crystal lattice and (3) specific features of the electrostatic potential on the molecular or ionic surface. We find that for ionic explosives, just as for molecular ones, there is an overall tendency for impact sensitivity to increase as the maximum detonation heat release is greater. This means that the usual emphasis upon designing explosives with large heats of detonation needs to be tempered somewhat. We also show that a moderate detonation heat release does not preclude a high level of detonation performance for ionic explosives, as was already demonstrated for molecular ones. Relating the free space per formula unit to sensitivity may require a modified procedure for ionic explosives; this will continue to be investigated. Finally, an encouraging start has been made in linking impact sensitivities to the electrostatic potentials on ionic surfaces, although limited so far to ammonium salts.

Influence of Polar Organic Solvents in an Ionic Liquid Containing Lithium Bis(fluorosulfonyl)amide: Effect on the Cation-Anion Interaction, Lithium Ion Battery Performance, and Solid Electrolyte Interphase.

PubMed

Lahiri, Abhishek; Li, Guozhu; Olschewski, Mark; Endres, Frank

2016-12-14

Ionic liquid-organic solvent mixtures have recently been investigated as potential battery electrolytes. However, contradictory results with these mixtures have been shown for battery performance. In this manuscript, we studied the influence of the addition of polar organic solvents into the ionic liquid electrolyte 1 M lithium bis(fluorosulfonyl)amide (LiFSI)-1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)amide ([Py 1,4 ]FSI) and tested it for lithium ion battery applications. From infrared and Raman spectroscopy, clear changes in the lithium solvation and cation-anion interactions in the ionic liquid were observed on addition of organic solvents. From the lithiation/delithiation studies on electrodeposited Ge, the storage capacity for the ionic liquid-highly polar organic solvent (acetonitrile) mixture was found to be the highest at low C-rates (0.425 C) compared to using an ionic liquid alone and ionic liquid-less polar solvent (dimethyl carbonate) mixtures. Furthermore, XPS and AFM were used to evaluate the solid electrolyte interphase (SEI) and to correlate its stability with Li storage capacity.

Selectivity of substrate binding and ionization of 2-methyl-3-hydroxypyridine-5-carboxylic acid oxygenase.

PubMed

Luanloet, Thikumporn; Sucharitakul, Jeerus; Chaiyen, Pimchai

2015-08-01

2-Methyl-3-hydroxypyridine-5-carboxylic acid (MHPC) oxygenase (EC 1.14.12.4) from Pseudomonas sp. MA-1 is a flavin-dependent monooxygenase that catalyzes a hydroxylation and aromatic ring cleavage reaction. The functional roles of two residues, Tyr223 and Tyr82, located ~ 5 Å away from MHPC, were characterized using site-directed mutagenesis, along with ligand binding, product analysis and transient kinetic experiments. Mutation of Tyr223 resulted in enzyme variants that were impaired in their hydroxylation activity and had Kd values for substrate binding 5-10-fold greater than the wild-type enzyme. Because this residue is adjacent to the water molecule that is located next to the 3-hydroxy group of MHPC, the results indicate that the interaction between Tyr223, H2 O and the 3-hydroxyl group of MHPC are important for substrate binding and hydroxylation. By contrast, the Kd for substrate binding of Tyr82His and Tyr82Phe variants were similar to that of the wild-type enzyme. However, only ~ 40-50% of the substrate was hydroxylated in the reactions of both variants, whereas most of the substrate was hydroxylated in the wild-type enzyme reaction. In free solution, MHPC or 5-hydroxynicotinic acid exists in a mixture of monoanionic and tripolar ionic forms, whereas only the tripolar ionic form binds to the wild-type enzyme. The binding of tripolar ionic MHPC would allow efficient hydroxylation through an electrophilic aromatic substitution mechanism. For the Tyr82His and Tyr82Phe variants, both forms of substrates can bind to the enzymes, indicating that the mutation at Tyr82 abolished the selectivity of the enzyme towards the tripolar ionic form. Transient kinetic studies indicated that the hydroxylation rate constants of both Tyr82 variants are approximately two- to 2.5-fold higher than that of the wild-type enzyme. Altogether, our findings suggest that Tyr82 is important for the binding selectivity of MHPC oxygenase towards the tripolar ionic species, whereas the interaction between Tyr223 and the substrate is important for ensuring hydroxylation. These results highlight how the active site of a flavoenzyme is able to deal with the presence of multiple forms of a substrate in solution and ensure efficient hydroxylation. © 2015 FEBS.

Antifungal activity of ionic liquids based on (-)-menthol: a mechanism study.

PubMed

Suchodolski, Jakub; Feder-Kubis, Joanna; Krasowska, Anna

2017-04-01

The mechanism of toxicity of chiral ionic liquids with (1R,2S,5R)-(-)-menthol [C n -Am-Men][Cl] (n=10, 11 or 12) in the fungus Candida albicans is reported here. Ionic liquids were more toxic towards Candida strain lacking all identified multidrug resistance efflux pumps. Moreover, the compounds tested inhibited C. albicans filamentation at the concentration at which detached fungal cells also adhered to the plastic surface. Our results showed the high activity of all the tested chiral ionic liquids in the permeabilization of C. albicans' membranes and in the digestion and interruption of the cell wall. The investigated ionic liquids thus have potential as disinfectants because besides their antifungal and antiadhesive action these compounds do not cause hemolysis. Copyright © 2017 Elsevier GmbH. All rights reserved.

Dissolution of cellulose in ionic liquid: A review

NASA Astrophysics Data System (ADS)

Mohd, N.; Draman, S. F. S.; Salleh, M. S. N.; Yusof, N. B.

2017-02-01

Dissolution of cellulose with ionic liquids (IL) and deep eutectic solvent (DES) lets the comprehensive dissolution of cellulose. Basically, cellulose can be dissolved, in some hydrophilic ionic liquids, such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-allyl-3-methylimidazolium chloride (AMIMCl). Chloride based ionic liquids are suitable solvents for cellulose dissolution. Although the ILs is very useful in fine chemical industry, its application in the pharmaceutical and food industry have been very limited due to issues with toxicity, purity, and high cost. Seeing to these limitations, new green alternative solvent which is DES was used. This green solvents, may be definitely treated as the next-generation reagents for more sustainable industrial development. Thus, this review aims to discuss the dissolution of cellulose either with ionic liquids or DES and its application.

Ionic liquids as solvents for Čerenkov counting and the effect of a wavelength shifter.

PubMed

Mirenda, M; Rodrigues, D; Ferreyra, C; Arenillas, P; Sarmiento, G P; Krimer, N; Japas, M L

2018-04-01

We study the wavelength shift of the Čerenkov light - generated in the ionic liquid (BMIMCl) - caused by the addition of the highly fluorescent ionic liquid (BMIMHPTS). 18 F and 32 P efficiencies increases up to 124% and 14%, respectively, compared with the values obtained with pure BMIMCl. With this improvement, ionic liquid mixtures become a good alternative - when using the TDCR-Cherenkov technique - to standardize radionuclides having electron emissions energies close to the threshold energy in water (∼ 260keV). As an advantage compared with other solvents, the Ionic liquid mixture can be reused, in the case of short-lived radionuclides, by simply removing all water content in a vacuum oven. Copyright © 2017 Elsevier Ltd. All rights reserved.

Acceptor-type hydroxide graphite intercalation compounds electrochemically formed in high ionic strength solutions.

PubMed

Miyazaki, Kohei; Iizuka, Asuka; Mikata, Koji; Fukutsuka, Tomokazu; Abe, Takeshi

2017-09-05

The intercalation of hydroxide ions (OH - ) into graphite formed graphite intercalation compounds (GICs) in high ionic strength solutions. GICs of solvated OH - anions with two water molecules (OH - ·2H 2 O) in alkaline aqueous solutions and GICs of only OH - anions in a molten NaOH-KOH salt solution were electrochemically synthesized.

Sequestration of U(VI) from Acidic, Alkaline, and High Ionic-Strength Aqueous Media by Functionalized Magnetic Mesoporous Silica Nanoparticles: Capacity and Binding Mechanisms

EPA Science Inventory

Uranium (VI) exhibits little adsorption onto sediment minerals in acidic, alkaline or high ionic-strength aqueous media that often occur in U mining or contaminated sites, which makes U(VI) very mobile and difficult to sequester. In this work, magnetic mesoporous silica nanoparti...