Diffuse-charge dynamics of ionic liquids in electrochemical systems.

PubMed

Zhao, Hui

2011-11-01

We employ a continuum theory of solvent-free ionic liquids accounting for both short-range electrostatic correlations and steric effects (finite ion size) [Bazant et al., Phys. Rev. Lett. 106, 046102 (2011)] to study the response of a model microelectrochemical cell to a step voltage. The model problem consists of a 1-1 symmetric ionic liquid between two parallel blocking electrodes, neglecting any transverse transport phenomena. Matched asymptotic expansions in the limit of thin double layers are applied to analyze the resulting one-dimensional equations and study the overall charge-time relation in the weakly nonlinear regime. One important conclusion is that our simple scaling analysis suggests that the length scale √(λ*(D)l*(c)) accurately characterizes the double-layer structure of ionic liquids with strong electrostatic correlations where l*(c) is the electrostatic correlation length (in contrast, the Debye screening length λ*(D) is the primary double-layer length for electrolytes) and the response time of λ(D)(*3/2)L*/(D*l(c)(1/2)) (not λ*(D)L*/D* that is the primary charging time of electrolytes) is the correct charging time scale of ionic liquids with strong electrostatic correlations where D* is the diffusivity and L* is the separation length of the cell. With these two new scales, data of both electric potential versus distance from the electrode and the total diffuse charge versus time collapse onto each individual master curve in the presence of strong electrostatic correlations. In addition, the dependance of the total diffuse charge on steric effects, short-range correlations, and driving voltages is thoroughly examined. The results from the asymptotic analysis are compared favorably with those from full numerical simulations. Finally, the absorption of excess salt by the double layer creates a depletion region outside the double layer. Such salt depletion may bring a correction to the leading order terms and break down the weakly nonlinear analysis. A criterion which justifies the weakly nonlinear analysis is verified with numerical simulations.

Microwave absorption in substances that form hydration layers with water

NASA Astrophysics Data System (ADS)

Garner, H. R.; Ohkawa, T.; Tuason, O.; Lee, R. L.

1990-12-01

The microwave absorption of certain water soluble polymers (polyethylene glycol, polyvinyl pyrrolidone, proteins, and DNA) in solution is composed of three parts: absorption in the free water, absorption in the substance, and absorption in the hydration layer. Ethanol, sucrose, glycerol, and sodium acetate, which form weak hydrogen bonds or have an ionic nature in aqueous solutions, also have microwave absorption signatures similar to polymers that form hydration layers. The frequency-dependent absorption of the free water and of the hydration layer water is described by a simple Debye relaxation model. The absorption per unit sample volume attributable to the hydration layer is solute concentration dependent, and a simple model is used to describe the dependence. The hydration-layer relaxation time was found to vary from substance to substance and with solute concentration. The relaxation time was also found to be independent of solute length.

Interpretation with a Donnan-based concept of the influence of simple salt concentration on the apparent binding of divalent ions to the polyelectrolytes polystyrenesulfonate and dextran sulfate

USGS Publications Warehouse

Marinsky, J.A.; Baldwin, Robert F.; Reddy, M.M.

1985-01-01

It has been shown that the apparent enhancement of divalent metal ion binding to polyions such as polystyrenesulfonate (PSS) and dextran sulfate (DS) by decreasing the ionic strength of these mixed counterion systems (M2+, M+, X-, polyion) can be anticipated with the Donnan-based model developed by one of us (J.A.M.). Ion-exchange distribution methods have been employed to measure the removal by the polyion of trace divalent metal ion from simple salt (NaClO4)-polyion (NaPSS) mixtures. These data and polyion interaction data published earlier by Mattai and Kwak for the mixed counterion systems MgCl2-LiCl-DS and MgCl2-CsCl-DS have been shown to be amenable to rather precise analysis by this model. ?? 1985 American Chemical Society.

Effect of electrostatic interactions on the ultrafiltration behavior of charged bacterial capsular polysaccharides.

PubMed

Hadidi, Mahsa; Buckley, John J; Zydney, Andrew L

2016-11-01

Charged polysaccharides are used in the food industry, as cosmetics, and as vaccines. The viscosity, thermodynamics, and hydrodynamic properties of these charged polysaccharides are known to be strongly dependent on the solution ionic strength because of both inter- and intramolecular electrostatic interactions. The goal of this work was to quantitatively describe the effect of these electrostatic interactions on the ultrafiltration behavior of several charged capsular polysaccharides obtained from Streptococcus pneumoniae and used in the production of Pneumococcus vaccines. Ultrafiltration data were obtained using various Biomax™ polyethersulfone membranes with different nominal molecular weight cutoffs. Polysaccharide transmission decreased with decreasing ionic strength primarily because of the expansion of the charged polysaccharide associated with intramolecular electrostatic repulsion. Data were in good agreement with a simple theoretical model based on solute partitioning in porous membranes, with the effective size of the different polysaccharide serotypes evaluated using size exclusion chromatography at the same ionic conditions. These results provide fundamental insights and practical guidelines for exploiting the effects of electrostatic interactions during the ultrafiltration of charged polysaccharides. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:1531-1538, 2016. © 2016 American Institute of Chemical Engineers.

Insight on the formation of chitosan nanoparticles through ionotropic gelation with tripolyphosphate.

PubMed

Koukaras, Emmanuel N; Papadimitriou, Sofia A; Bikiaris, Dimitrios N; Froudakis, George E

2012-10-01

This work reports details pertaining to the formation of chitosan nanoparticles that we prepare by the ionic gelation method. The molecular interactions of the ionic cross-linking of chitosan with tripolyphosphate have been investigated and elucidated by means of all-electron density functional theory. Solvent effects have been taken into account using implicit models. We have identified primary-interaction ionic cross-linking configurations that we define as H-link, T-link, and M-link, and we have quantified the corresponding interaction energies. H-links, which display high interaction energies and are also spatially broadly accessible, are the most probable cross-linking configurations. At close range, proton transfer has been identified, with maximum interaction energies ranging from 12.3 up to 68.3 kcal/mol depending on the protonation of the tripolyphosphate polyanion and the relative coordination of chitosan with tripolyphosphate. On the basis of our results for the linking types (interaction energies and torsion bias), we propose a simple mechanism for their impact on the chitosan/TPP nanoparticle formation process. We introduce the β ratio, which is derived from the commonly used α ratio but is more fundamental since it additionally takes into account structural details of the oligomers.

Determination of the distribution constants of aromatic compounds and steroids in biphasic micellar phosphonium ionic liquid/aqueous buffer systems by capillary electrokinetic chromatography.

PubMed

Lokajová, Jana; Railila, Annika; King, Alistair W T; Wiedmer, Susanne K

2013-09-20

The distribution constants of some analytes, closely connected to the petrochemical industry, between an aqueous phase and a phosphonium ionic liquid phase, were determined by ionic liquid micellar electrokinetic chromatography (MEKC). The phosphonium ionic liquids studied were the water-soluble tributyl(tetradecyl)phosphonium with chloride or acetate as the counter ion. The retention factors were calculated and used for determination of the distribution constants. For calculating the retention factors the electrophoretic mobilities of the ionic liquids were required, thus, we adopted the iterative process, based on a homologous series of alkyl benzoates. Calculation of the distribution constants required information on the phase-ratio of the systems. For this the critical micelle concentrations (CMC) of the ionic liquids were needed. The CMCs were calculated using a method based on PeakMaster simulations, using the electrophoretic mobilities of system peaks. The resulting distribution constants for the neutral analytes between the ionic liquid and the aqueous (buffer) phase were compared with octanol-water partitioning coefficients. The results indicate that there are other factors affecting the distribution of analytes between phases, than just simple hydrophobic interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

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

PubMed

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

2016-09-01

With the advent of ionic liquids, much was expected concerning their applicability as an alternative to organic solvents in the chemical technology and biotechnology fields. However, the most studied and commonly used ionic liquids based on imidazolium and pyridinium were found not to be as environmentally friendly as it was first expected. Therefore, a new generation of alternative solvents named natural ionic liquids and deep eutectic solvents, composed of natural and/or renewable compounds, have come into focus in recent years. Since the number of newly synthesized chemicals increases yearly, simple and reliable methods for their ecotoxicological assessment are necessary. Permanent fish cell lines can serve as a test system for the evaluation of a chemical's cytotoxicity. This paper presents research results on the cytotoxic effects on Channel Catfish Ovary (CCO) cell line induced by fifteen cholinium-based ionic liquids and deep eutectic solvents. Based on the decrease in cell viability, the most obvious toxic effect on CCO cells was caused by ionic liquid choline oxalate, while other solvents tested exhibited low cytotoxicity. Therefore, we can conclude that cholinium-based ionic liquids and deep eutectic solvents are comparatively less toxic to CCO cells than conventional ionic liquids. Copyright © 2016 Elsevier Inc. All rights reserved.

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.

DNA Sequence-Dependent Ionic Currents in Ultra-Small Solid-State Nanopores†

PubMed Central

Comer, Jeffrey

2016-01-01

Measurements of ionic currents through nanopores partially blocked by DNA have emerged as a powerful method for characterization of the DNA nucleotide sequence. Although the effect of the nucleotide sequence on the nanopore blockade current has been experimentally demonstrated, prediction and interpretation of such measurements remain a formidable challenge. Using atomic resolution computational approaches, here we show how the sequence, molecular conformation, and pore geometry affect the blockade ionic current in model solid-state nanopores. We demonstrate that the blockade current from a DNA molecule is determined by the chemical identities and conformations of at least three consecutive nucleotides. We find the blockade currents produced by the nucleotide triplets to vary considerably with their nucleotide sequence despite having nearly identical molecular conformations. Encouragingly, we find blockade current differences as large as 25% for single-base substitutions in ultra small (1.6 nm × 1.1 nm cross section; 2 nm length) solid-state nanopores. Despite the complex dependence of the blockade current on the sequence and conformation of the DNA triplets, we find that, under many conditions, the number of thymine bases is positively correlated with the current, whereas the number of purine bases and the presence of both purine and pyrimidines in the triplet are negatively correlated with the current. Based on these observations, we construct a simple theoretical model that relates the ion current to the base content of a solid-state nanopore. Furthermore, we show that compact conformations of DNA in narrow pores provide the greatest signal-to-noise ratio for single base detection, whereas reduction of the nanopore length increases the ionic current noise. Thus, the sequence dependence of nanopore blockade current can be theoretically rationalized, although the predictions will likely need to be customized for each nanopore type. PMID:27103233

Applications of statistical and atomic physics to the spectral line broadening and stock markets

NASA Astrophysics Data System (ADS)

Volodko, Dmitriy

The purpose of this investigation is the application of time correlation function methodology on the theoretical research of the shift of hydrogen and hydrogen-like spectral lines due to electrons and ions interaction with the spectral line emitters-dipole ionic-electronic shift (DIES) and the describing a behavior of stock-market in terms of a simple physical model simulation which obeys Levy statistical distribution---the same as that of the real stock-market index. Using Generalized Theory of Stark broadening of electrons in plasma we discovered a new source of the shift of hydrogen and hydrogen-like spectral lines that we called a dipole ionic-electronic shift (DIES). This shift results from the indirect coupling of electron and ion microfields in plasmas which is facilitated by the radiating atom/ion. We have shown that the DIES, unlike all previously known shifts, is highly nonlinear and has a different sign for different ranges of plasma parameters. The most favorable conditions for observing the DIES correspond to plasmas of high densities, but of relatively low temperature. For the Balmer-alpha line of hydrogen with the most favorable observational conditions Ne > 1018 cm-3, T < 2 eV, the DIES has been already confirmed experimentally. Based on the study of the time correlations and of the probability distribution of fluctuations in the stock market, we developed a relatively simple physical model, which simulates the Dow Jones Industrials index and makes short-term (a couple of days) predictions of its trend.

A simple recovery process for biodegradable plastics accumulated in cyanobacteria treated with ionic liquids.

PubMed

Kobayashi, Daigo; Fujita, Kyoko; Nakamura, Nobuhumi; Ohno, Hiroyuki

2015-02-01

Here, we proposed a simple recovery process for poly(3-hydroxybutyrate) (PHB) accumulated in cyanobacteria by using ionic liquids (ILs), which dissolve cyanobacteria but not PHB. First, we investigated the effects of IL polarity on hydrogen-bonding receipt ability (β value) and hydrogen-bonding donating ability (α value) and evaluated the subsequent dissolution of cyanobacteria. We found that ILs having α values higher than approximately 0.4 and β values of approximately 0.9 were suitable for dissolution of cyanobacteria. In particular, 1-ethyl-3-methylimidazolium methylphosphonate ([C2mim][MeO(H)PO2]) was found to dissolve cyanobacteria components, but not PHB. Thus, we verified that PHB produced in cyanobacteria could be separated and recovered by simple filtering after dissolution of cyanobacteria in [C2mim][MeO(H)PO2]. Using this technique, more than 98 % of PHB was obtained on the filter as residues separated from cyanobacteria. Furthermore, [C2mim][MeO(H)PO2] maintained the ability to dissolve cyanobacteria after a simple recycling procedure.

Nucleation and growth of microdroplets of ionic liquids deposited by physical vapor method onto different surfaces

NASA Astrophysics Data System (ADS)

Costa, José C. S.; Coelho, Ana F. S. M. G.; Mendes, Adélio; Santos, Luís M. N. B. F.

2018-01-01

Nanoscience and technology has generated an important area of research in the field of properties and functionality of ionic liquids (ILs) based materials and their thin films. This work explores the deposition process of ILs droplets as precursors for the fabrication of thin films, by means of physical vapor deposition (PVD). It was found that the deposition (by PVD on glass, indium tin oxide, graphene/nickel and gold-coated quartz crystal surfaces) of imidazolium [C4mim][NTf2] and pyrrolidinium [C4C1Pyrr][NTf2] based ILs generates micro/nanodroplets with a shape, size distribution and surface coverage that could be controlled by the evaporation flow rate and deposition time. No indication of the formation of a wetting-layer prior to the island growth was found. Based on the time-dependent morphological analysis of the micro/nanodroplets, a simple model for the description of the nucleation process and growth of ILs droplets is presented. The proposed model is based on three main steps: minimum free area to promote nucleation; first order coalescence; second order coalescence.

Uranium vacancy mobility at the Σ5 symmetric tilt and Σ5 twist grain boundaries in UO₂

DOE PAGES

Uberuaga, Blas Pedro; Andersson, David A.

2015-10-01

Ionic transport at grain boundaries in oxides dictates a number of important phenomena, from ionic conductivity to sintering to creep. For nuclear fuels, it also influences fission gas bubble nucleation and growth. Here, using a combination of atomistic calculations and object kinetic Monte Carlo (okMC) simulations, we examine the kinetic pathways associated with uranium vacancies at two model grain boundaries in UO 2. The barriers for vacancy motion were calculated using the nudged elastic band method at all uranium sites at each grain boundary and were used as the basis of the okMC simulations. For both boundaries considered – amore » simple tilt and a simple twist boundary – the mobility of uranium vacancies is significantly higher than in the bulk. For the tilt boundary, there is clearly preferred migration along the tilt axis as opposed to in the perpendicular direction while, for the twist boundary, migration is essentially isotropic within the boundary plane. These results show that cation defect mobility in fluorite-structured materials is enhanced at certain types of grain boundaries and is dependent on the boundary structure with the tilt boundary exhibiting higher rates of migration than the twist boundary.« less

Separation of Lignin from Corn Stover Hydrolysate with Quantitative Recovery of Ionic Liquid

PubMed Central

Underkofler, Kaylee A.; Teixeira, Rodrigo E.; Pietsch, Stephen A.; Knapp, Kurtis G.; Raines, Ronald T.

2015-01-01

Abundant lignocellulosic biomass could become a source of sugars and lignin, potential feedstocks for the now emergent bio-renewable economy. The production and conversion of sugars from biomass have been well-studied, but far less is known about the production of lignin that is amenable to valorization. Here we report the isolation of lignin generated from the hydrolysis of biomass dissolved in the ionic liquid 1-butyl-3-methylimidazolium chloride. We show that lignin can be isolated from the hydrolysate slurry by simple filtration or centrifugation, and that the ionic liquid can be recovered quantitatively by a straightforward wash with water. The isolated lignin is not only free from ionic liquid, but also lacks cellulosic residues and is substantially depolymerized, making it a promising feedstock for valorization by conversion into fuels and chemicals. PMID:25866701

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

Newton Output Blocking Force under Low-Voltage Stimulation for Carbon Nanotube-Electroactive Polymer Composite Artificial Muscles.

PubMed

Chen, I-Wen Peter; Yang, Ming-Chia; Yang, Chia-Hui; Zhong, Dai-Xuan; Hsu, Ming-Chun; Chen, YiWen

2017-02-15

This is a study on the development of carbon nanotube-based composite actuators using a new ionic liquid-doped electroactive ionic polymer. For scalable production purposes, a simple hot-pressing method was used. Carbon nanotube/ionic liquid-Nafion/carbon nanotube composite films were fabricated that exhibited a large output blocking force and a stable cycling life with low alternating voltage stimuli in air. Of particular interest and importance, a blocking force of 1.5 N was achieved at an applied voltage of 6 V. Operational durability was confirmed by testing in air for over 30 000 cycles (or 43 h). The superior actuation performance of the carbon nanotube/ionic liquid-Nafion/carbon nanotube composite, coupled with easy manufacturability, low driving voltage, and reliable operation, promises great potential for artificial muscle and biomimetic applications.

Ionic Liquids Beyond Simple Solvents: Glimpses at the State of the Art in Organic Chemistry.

PubMed

Kuchenbuch, Andrea; Giernoth, Ralf

2015-12-01

Within the last 25 years ionic liquids have written a tremendous success story, which is documented in a nearly uncountable amount of original research papers, reviews, and numerous applications in research and industry. These days, ionic liquids can be considered as a mature class of compounds for many different applications. Frequently, they are used as neoteric solvents for chemical tansformations, and the number of reviews on this field of research is huge. In this focused review, though, we are trying to evaluate the state of the art of ionic liquid chemistry beyond using them simply as solvents for chemical transformations. It is not meant to be a comprehensive overview on the topic; the choice of emphasis and examples rather refects the authors' personal view on the field. We are especially highlighting fields in which we believe the most fundamental developments within the next five years will take place: biomass processing, (chiral) ionic liquids from natural sources, biotransformations, and organic synthesis.

Determination of trihalomethanes in waters by ionic liquid-based single drop microextraction/gas chromatographic/mass spectrometry.

PubMed

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

2008-10-31

A simple, rapid, solventless method for the determination of trihalomethanes (THMs) (chloroform, bromodichloromethane, dibromochloromethane and bromoform) in water samples is presented. The analytes are extracted from the headspace of the aqueous matrix into a 2 microL drop of the ionic liquid 1-octyl-3-methyl-imidazolium hexafluorophosphate working at 30 degrees C for 30 min. The separation and detection of the target compounds is accomplished by gas chromatography/mass spectrometry owing to the use of an interface that efficiently transfers the analytes extracted in the ionic liquid drop to the gas chromatograph while preventing the ionic liquid from entering the column. The detection limits obtained are below the values compelled by the legislation, ranging from 0.5 microg L(-1) for chloroform and bromodichloromethane to 0.9 microg L(-1) for dibromochloromethane. The use of ionic liquid in the extraction procedure avoids the use of organic solvents and leads to relative standard deviations that range from 3.1% to 4.8%.

Engineering polyelectrolyte multilayer structure at the nanometer length scale by tuning polymer solution conformation.

NASA Astrophysics Data System (ADS)

Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

2008-03-01

Chitosan (a weak polycation) and heparin (a strong polyanion) are used to make polyelectrolyte multilayers (PEM). PEM thickness and composition are determined as a function of solution pH (4.6 to 5.8) and ionic strength (0.1 to 0.5 M). Over this range, increasing pH increases the PEM thickness; however, the sensitivity to changes in pH is a strong function of ionic strength. The PEM thickness data are correlated to the polymer conformation in solution. Polyelectrolyte conformation in solution is characterized by gel permeation chromatography (GPC). The highest sensitivity of PEM structure to pH is obtained at intermediate ionic strength. Different interactions govern the conformation and adsorption phenomena at low and high ionic strength, leading to reduced sensitivity to solution pH at extreme ionic strengths. The correspondence between PEM thickness and polymer solution conformation offers opportunities to tune polymer thin film structure at the nanometer length scale by controlling simple, reproducible processing conditions.

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.

Anionic membrane and ionomer based on poly(2,6-dimethyl-1,4-phenylene oxide) for alkaline membrane fuel cells

NASA Astrophysics Data System (ADS)

Ong, Ai Lien; Saad, Saeed; Lan, Rong; Goodfellow, Robert J.; Tao, Shanwen

2011-10-01

Hydroxyl-ion conductive poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) membranes with different characteristics were prepared via relatively simple bromination/amination serial reactions with reduced number of involved chemicals and shorter reaction time. The effects of reactants ratio, reaction atmosphere, polymer concentration, casting solvent, and hydroxylation treatment on reaction were investigated in details. The microstructure, water uptake, swelling ratio, ion-exchange capacity and ionic conductivity of the membranes were also studied. The obtained results demonstrate that, the ionic conductivity of the membrane is dependent on casting solvent. The N-methyl-2-pyrrolidonecast membrane exhibits the highest conductivity with the thinnest film. Although the membrane was prepared via a relatively simple preparation route with least toxic chemicals, a competitive ionic conductivity value of 1.64 × 10-2 S cm-1 was achieved at 60 °C. A power density of 19.5 mW cm-2 has been demonstrated from the alkaline membrane fuel cell operated at 70 °C, assembled from the entirely homemade membrane electrode assembly without any hot-pressing.

Numerical modeling of ultrasonic cavitation in ionic liquids

NASA Astrophysics Data System (ADS)

Calvisi, Michael L.; Elder, Ross M.

2017-11-01

Ionic liquids have favorable properties for sonochemistry applications in which the high temperatures and pressures achieved by cavitation bubbles are important drivers of chemical processes. Two different numerical models are presented to simulate ultrasonic cavitation in ionic liquids, each with different capabilities and physical assumptions. A model based on a compressible form of the Rayleigh-Plesset equation (RPE) simulates ultrasonic cavitation of a spherical bubble with a homogeneous interior, incorporating evaporation and condensation at the bubble surface, and temperature-varying thermodynamic properties in the interior. A second, more computationally intensive model of a spherical bubble uses the finite element method (FEM) and accounts for spatial variations in pressure and temperature throughout the flow domain. This model provides insight into heat transfer across the bubble surface and throughout the bubble interior and exterior. Parametric studies are presented for sonochemistry applications involving ionic liquids as a solvent, examining a range of realistic ionic liquid properties and initial conditions to determine their effect on temperature and pressure. Results from the two models are presented for parametric variations including viscosity, thermal conductivity, water content of the ionic liquid solvent, acoustic frequency, and initial bubble pressure. An additional study performed with the FEM model examines thermal penetration into the surrounding ionic liquid during bubble oscillation. The results suggest the prospect of tuning ionic liquid properties for specific applications.

Meta-analysis of pesticide sorption in subsoils

NASA Astrophysics Data System (ADS)

Jarvis, Nicholas

2017-04-01

It has been known for several decades that sorption koc values tend to be larger in soils that are low in organic carbon (i.e. subsoils). Nevertheless, in a regulatory context, the models used to assess leaching of pesticides to groundwater still rely on a constant koc value, which is usually measured on topsoil samples. This is mainly because the general applicability of any improved model approach that is also simple enough to use for regulatory purposes has not been demonstrated. The objective of this study was therefore first to summarize and generalize available literature data in order to assess the magnitude of any systematic increase of koc values in subsoil and to test an alternative model of subsoil sorption that could be useful in pesticide risk assessment and management. To this end, a database containing the results of batch sorption experiments for pesticides was compiled from published studies in the literature, which placed at least as much emphasis on measurements in subsoil horizons as in topsoil. The database includes 967 data entries from 46 studies and for 34 different active substances (15 non-ionic compounds, 13 weak acids, 6 weak bases). In order to minimize pH effects on sorption, data for weak acids and bases were only included if the soil pH was more than two units larger than the compound pKa. A simple empirical model, whereby the sorption constant is given as a power law function of the soil organic carbon content, gave good fits to most data sets. Overall, the apparent koc value, koc(app), for non-ionic compounds and weak bases roughly doubled as the soil organic carbon content decreased by a factor of ten. The typical increase in koc(app) was even larger for weak acids: on average koc(app) increased by a factor of six as soil organic carbon content decreased by a factor of ten. These results suggest the koc concept currently used in leaching models should be replaced by an alternative approach that gives a more realistic representation of pesticide sorption in subsoil. The model tested in this study appears to be widely applicable and simple enough to parameterize for risk assessment purposes. However, more data on subsoil sorption should first be included in the analysis to enable reliable estimation of worst-case percentile values of the power law exponent in the model.

Comparative study of bending characteristics of ionic polymer actuators containing ionic liquids for modeling actuation

NASA Astrophysics Data System (ADS)

Kikuchi, Kunitomo; Sakamoto, Takumi; Tsuchitani, Shigeki; Asaka, Kinji

2011-04-01

Ionic polymer metal composites (IPMCs) that can operate in air have recently been developed by incorporating an ionic liquid in ionic polymers. To understand transduction in these composites, it is important to determine the role of the ionic liquid in the ionic polymer (Nafion®), to identify the counter cation, and to investigate the interaction of IPMCs with water vapor in the air. We used Fourier-transform infrared spectroscopy to analyze three Nafion® membranes, which were soaked in mixtures of water and an ionic liquid (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIBF4), 1-buthyl-3-methyl-imidazolium tetrafluoroborate (BMIBF4), and 1-buthyl-3-methyl-imidazolium hexafluorophosphate (BMIPF6)). The results demonstrate that only cations (EMI+ and BMI+) in the ionic liquids are taken into the Nafion® membranes as counter ions and that the water content of the membranes in air is less than ˜4% that of Nafion® swollen with water. Based on the experimental results, a transduction model is proposed for an IPMC with an ionic liquid. In this model, bending is caused by local swelling due to the volume effect of the bulky counter cations. This model can explain 30-50% of the experimentally observed bending curvature.

An Alternative to the Ionic Model

ERIC Educational Resources Information Center

Sanderson, R. T.

1975-01-01

Describes the "coordinated polymeric model," which yields more accurate energy calculations than the "ionic model" for compounds which exhibit considerable covalency. The dichotomy between ionic and covalent bonding is thus largely broken down for solids which are nonmolecular in the crystalline state. (MLH)

Chemical association in simple models of molecular and ionic fluids. III. The cavity function

NASA Astrophysics Data System (ADS)

Zhou, Yaoqi; Stell, George

1992-01-01

Exact equations which relate the cavity function to excess solvation free energies and equilibrium association constants are rederived by using a thermodynamic cycle. A zeroth-order approximation, derived previously by us as a simple interpolation scheme, is found to be very accurate if the associative bonding occurs on or near the surface of the repulsive core of the interaction potential. If the bonding radius is substantially less than the core radius, the approximation overestimates the association degree and the association constant. For binary association, the zeroth-order approximation is equivalent to the first-order thermodynamic perturbation theory (TPT) of Wertheim. For n-particle association, the combination of the zeroth-order approximation with a ``linear'' approximation (for n-particle distribution functions in terms of the two-particle function) yields the first-order TPT result. Using our exact equations to go beyond TPT, near-exact analytic results for binary hard-sphere association are obtained. Solvent effects on binary hard-sphere association and ionic association are also investigated. A new rule which generalizes Le Chatelier's principle is used to describe the three distinct forms of behaviors involving solvent effects that we find. The replacement of the dielectric-continuum solvent model by a dipolar hard-sphere model leads to improved agreement with an experimental observation. Finally, equation of state for an n-particle flexible linear-chain fluid is derived on the basis of a one-parameter approximation that interpolates between the generalized Kirkwood superposition approximation and the linear approximation. A value of the parameter that appears to be near optimal in the context of this application is obtained from comparison with computer-simulation data.

Separation of lignin from corn stover hydrolysate with quantitative recovery of ionic liquid

DOE PAGES

Underkofler, Kaylee A.; Teixeira, Rodrigo E.; Pietsch, Stephen A.; ...

2015-02-20

Abundant lignocellulosic biomass could become a source of sugars and lignin, potential feedstocks for the now emergent biorenewable economy. The production and conversion of sugars from biomass have been well-studied, but far less is known about the production of lignin that is amenable to valorization. In this paper, we report the isolation of lignin generated from the hydrolysis of biomass dissolved in the ionic liquid 1-butyl-3-methylimidazolium chloride. We show that lignin can be isolated from the hydrolysate slurry by simple filtration or centrifugation, and that the ionic liquid can be recovered quantitatively by a straightforward wash with water. Finally, themore » isolated lignin is not only free from ionic liquid but also lacks cellulosic residues and is substantially depolymerized, making it a promising feedstock for valorization by conversion into fuels and chemicals.« less

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.

A mean-density model of ionic surfactants for the dispersion of carbon nanotubes in aqueous solutions

NASA Astrophysics Data System (ADS)

Joung, Young Soo

2018-05-01

We propose a new analytical model of ionic surfactants used for the dispersion of carbon nanotubes (CNTs) in aqueous solutions. Although ionic surfactants are commonly used to facilitate the dispersion of CNTs in aqueous solutions, understanding the dispersion process is challenging and time-consuming owing to its complexity and nonlinearity. In this work, we develop a mean-density model of ionic surfactants to simplify the calculation of interaction forces between CNTs stabilized by ionic surfactants. Using this model, we can evaluate various interaction forces between the CNTs and ionic surfactants under different conditions. The dispersion mechanism is investigated by estimating the potential of mean force (PMF) as a function of van der Waals forces, electrostatic forces, interfacial tension, and osmotic pressure. To verify the proposed model, we compare the PMFs derived using our method with those derived from molecular dynamics simulations using comparable CNTs and ionic surfactants. Notably, for stable dispersions, the osmotic pressure and interfacial energy are important for long-range and short-range interactions, respectively, in comparison with the effect of electrostatic forces. Our model effectively prescribes specific surfactants and their concentrations to achieve stable aqueous suspensions of CNTs.

Direct pore-scale reactive transport modelling of dynamic wettability changes induced by surface complexation

NASA Astrophysics Data System (ADS)

Maes, Julien; Geiger, Sebastian

2018-01-01

Laboratory experiments have shown that oil production from sandstone and carbonate reservoirs by waterflooding could be significantly increased by manipulating the composition of the injected water (e.g. by lowering the ionic strength). Recent studies suggest that a change of wettability induced by a change in surface charge is likely to be one of the driving mechanism of the so-called low-salinity effect. In this case, the potential increase of oil recovery during waterflooding at low ionic strength would be strongly impacted by the inter-relations between flow, transport and chemical reaction at the pore-scale. Hence, a new numerical model that includes two-phase flow, solute reactive transport and wettability alteration is implemented based on the Direct Numerical Simulation of the Navier-Stokes equations and surface complexation modelling. Our model is first used to match experimental results of oil droplet detachment from clay patches. We then study the effect of wettability change on the pore-scale displacement for simple 2D calcite micro-models and evaluate the impact of several parameters such as water composition and injected velocity. Finally, we repeat the simulation experiments on a larger and more complex pore geometry representing a carbonate rock. Our simulations highlight two different effects of low-salinity on oil production from carbonate rocks: a smaller number of oil clusters left in the pores after invasion, and a greater number of pores invaded.

Minimal models of electric potential oscillations in non-excitable membranes.

PubMed

Perdomo, Guillermo; Hernández, Julio A

2010-01-01

Sustained oscillations in the membrane potential have been observed in a variety of cellular and subcellular systems, including several types of non-excitable cells and mitochondria. For the plasma membrane, these electrical oscillations have frequently been related to oscillations in intracellular calcium. For the inner mitochondrial membrane, in several cases the electrical oscillations have been attributed to modifications in calcium dynamics. As an alternative, some authors have suggested that the sustained oscillations in the mitochondrial membrane potential induced by some metabolic intermediates depends on the direct effect of internal protons on proton conductance. Most theoretical models developed to interpret oscillations in the membrane potential integrate several transport and biochemical processes. Here we evaluate whether three simple dynamic models may constitute plausible representations of electric oscillations in non-excitable membranes. The basic mechanism considered in the derivation of the models is based upon evidence obtained by Hattori et al. for mitochondria and assumes that an ionic species (i.e., the proton) is transported via passive and active transport systems between an external and an internal compartment and that the ion affects the kinetic properties of transport by feedback regulation. The membrane potential is incorporated via its effects on kinetic properties. The dynamic properties of two of the models enable us to conclude that they may represent alternatives enabling description of the generation of electrical oscillations in membranes that depend on the transport of a single ionic species.

Direct Preparation of Few Layer Graphene Epoxy Nanocomposites from Untreated Flake Graphite.

PubMed

Throckmorton, James; Palmese, Giuseppe

2015-07-15

The natural availability of flake graphite and the exceptional properties of graphene and graphene-polymer composites create a demand for simple, cost-effective, and scalable methods for top-down graphite exfoliation. This work presents a novel method of few layer graphite nanocomposite preparation directly from untreated flake graphite using a room temperature ionic liquid and laminar shear processing regimen. The ionic liquid serves both as a solvent and initiator for epoxy polymerization and is incorporated chemically into the matrix. This nanocomposite shows low electrical percolation (0.005 v/v) and low thickness (1-3 layers) graphite/graphene flakes by TEM. Additionally, the effect of processing conditions by rheometry and comparison with solvent-free conditions reveal the interactions between processing and matrix properties and provide insight into the theory of the chemical and physical exfoliation of graphite crystals and the resulting polymer matrix dispersion. An interaction model that correlates the interlayer shear physics of graphite flakes and processing parameters is proposed and tested.

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.

Introducing biobased ionic liquids as the nonaqueous media for enzymatic synthesis of phosphatidylserine.

PubMed

Bi, Yan-Hong; Duan, Zhang-Qun; Li, Xiang-Qian; Wang, Zhao-Yu; Zhao, Xi-Rong

2015-02-11

Biobased ionic liquids with cholinium as the cation and amino acids as the anions, which could be prepared from renewable biomaterials by simple neutralization reactions, have recently been described as promising and green solvents. Herein, they were successfully used as the reaction media for enzyme-mediated transphosphatidylation of phosphatidylcholine with l-serine for phosphatidylserine synthesis for the first time. Our results indicated that the highest phosphatidylserine yield of 86.5% was achieved. Moreover, 75% original activity of the enzyme was maintained after being used for 10 batches. The present work could be considered an alternative enzymatic strategy for preparing phosphatidylserine. Additionally, the excellent results make the biobased ionic liquids more promising candidates for use as environmentally friendly solvents in biocatalysis fields.

Simple Ion Channels: From Structure to Electrophysiology and Back

NASA Technical Reports Server (NTRS)

Pohorille, Andrzej

2018-01-01

A reliable way to establish whether our understanding of a channel is satisfactory is to reproduce its measured ionic conductance over a broad range of applied voltages in computer simulations. In molecular dynamics (MD), this can be done by way of applying an external electric field to the system and counting the number of ions that traverse the channel per unit time. Since this approach is computationally very expensive, we have developed a markedly more efficient alternative in which MD is combined with the electrodiffusion (ED) equation. In this approach, the assumptions of the ED equation can be rigorously tested, and the precision and consistency of the calculated conductance can be determined. We have demonstrated that the full current/voltage dependence and the underlying free energy profile for a simple channel can be reliably calculated from equilibrium or non-equilibrium MD simulations at a single voltage. To carry out MD simulations, a structural model of a channel has to be assumed, which is an important constraint, considering that high-resolution structures are available for only very few simple channels. If the comparison of calculated ionic conductance with electrophysiological data is satisfactory, it greatly increases our confidence that the structure and the function are described sufficiently accurately. We examined the validity of the ED for several channels embedded in phospholipid membranes - four naturally occurring channels: trichotoxin, alamethicin, p7 from hepatitis C virus (HCV) and Vpu from the HIV-1 virus, and a synthetic, hexameric channel, formed by a 21-residue peptide that contains only leucine and serine. All these channels mediate transport of potassium and chloride ions. It was found that the ED equation is satisfactory for these systems. In some of them experimental and calculated electrophysiological properties are in good agreement, whereas in others there are strong indications that the structural models are incorrect.

Molecular mobility, morphology, and ion conduction in ionomers for electroactive devices

NASA Astrophysics Data System (ADS)

Tudryn, Gregory J.

A sequential study of ion-containing polymers capable of ion solvation with varied ion content, dielectric constant, and counterions is presented in this dissertation in order to compare ion transport properties in ionomers with various ionic interactions. Structure-property relationships in these ion containing polymers are defined using x-ray scattering, rheology and dielectric spectroscopy, enabling the quantification of ion transport dynamics. Poly(ethylene oxide), (PEO) based ionomers are investigated in order to probe the relation between ion conduction and segmental relaxation, and copolymers of PEO and Poly(tetramethylene oxide), (PTMO) further develop an understanding of the trade-off between ion solvation and segmental dynamics. Ionomers with ionic liquid counterions probe diffuse charge interactions and steric effects on ion transport, and incorporation of ionic liquids into ionomer membranes such as Nafion provides desirable thermal and ion conducting properties which extend the use of such membranes for electroactive devices. PEO ionomers exhibit a strong relation between ionic conductivity and segmental dynamics, providing insight that the glass transition temperature, Tg, dominates the ion conduction mechanism. Increasing temperature induces aggregation of ionic groups as evidenced by the static dielectric constant and X-ray scattering as a function of temperature, revealing the contribution of ionic dipoles in the measured dielectric constant. The trade-off between ion solvation and fast polymer segmental dynamics are quantified in copolymer ionomers of PEO and lower Tg PTMO. While conducting ion content remains nearly unchanged, conductivity is lowered upon incorporation of PTMO, because the vast majority of the PTMO microphase separates from the PEO-rich microdomain that remains continuous and contributes most of the ion conduction. Dielectric constants and X-ray scattering show consistent changes with temperature that suggest a cascading aggregation process in Na ionomers as ionic dipoles thermally randomize and lower the measured dielectric constant of the medium, leading to further aggregation. We observe amplified microphase-separation through ionic groups preferentially solvated by PEO chains, as seen in block copolymers with added salt. Even at 25%PEO / 75%PTMO the ionomers have VFT temperature dependence of conducting ion mobility, meaning that the 25% PEO/ion microphase is still continuous A model is developed to describe the frequency dependent storage and loss modulus and the delay in Rouse motion due to ion association lifetime, as functions of ion content and molecular weight for our low molecular weight ionomers. The ion rearrangement relaxation in dielectric spectroscopy is clearly the ion association lifetime that controls terminal dynamics in linear viscoelasticity, allowing a simple sticky Rouse model, using the most-probable distribution based on NMR Mn, to fully describe master curves of the frequency dependent storage and loss modulus. Using insight from ionic interaction strength, ionic liquids are used as counterions, effectively plasticizing the ionomers without added solvent. Ionic interactions were weakened with increasing counterion size, and with modification of cations using ether-oxygen, promoting self-solvation, which increases conducting ion density by an order of magnitude. Room temperature ionic liquids were subsequently used in combination with NafionRTM membranes as electroactive substrates to correlate ion transport to morphology as a function of volume fraction of ionic liquid. This study illuminated the critical volume uptake of ionic liquid in Nafion, identifying percolation of ionic pathways and a significant increase in dielectric constant at low frequencies, indicating an increase in the number density of ions capable of polarizing at the electrode surface. Consequently, the fundamental information obtained about the structure-property relations of ionomers can be used to predict and design advanced ion-containing polymers to be used in battery membranes and a variety of electroactive devices, including actuators and electromechanical sensors.

Aggregation work at polydisperse micellization: ideal solution and "dressed micelle" models comparing to molecular dynamics simulations.

PubMed

Burov, S V; Shchekin, A K

2010-12-28

General thermodynamic relations for the work of polydisperse micelle formation in the model of ideal solution of molecular aggregates in nonionic surfactant solution and the model of "dressed micelles" in ionic solution have been considered. In particular, the dependence of the aggregation work on the total concentration of nonionic surfactant has been analyzed. The analogous dependence for the work of formation of ionic aggregates has been examined with regard to existence of two variables of a state of an ionic aggregate, the aggregation numbers of surface active ions and counterions. To verify the thermodynamic models, the molecular dynamics simulations of micellization in nonionic and ionic surfactant solutions at two total surfactant concentrations have been performed. It was shown that for nonionic surfactants, even at relatively high total surfactant concentrations, the shape and behavior of the work of polydisperse micelle formation found within the model of the ideal solution at different total surfactant concentrations agrees fairly well with the numerical experiment. For ionic surfactant solutions, the numerical results indicate a strong screening of ionic aggregates by the bound counterions. This fact as well as independence of the coefficient in the law of mass action for ionic aggregates on total surfactant concentration and predictable behavior of the "waterfall" lines of surfaces of the aggregation work upholds the model of "dressed" ionic aggregates.

Binding in alkali and alkaline-earth tetrahydroborates: Special position of magnesium tetrahydroborate

NASA Astrophysics Data System (ADS)

Łodziana, Zbigniew; van Setten, Michiel J.

2010-01-01

Compounds of light elements and hydrogen are currently extensively studied due to their potential application in the field of hydrogen or energy storage. A number of new interesting tetrahydroborates that are especially promising due to their very high gravimetric hydrogen content were recently reported. However, the determination and understanding of their complex crystalline structures has created considerable debate. Metal tetrahydroborates, in general, form a large variety of structures ranging from simple for NaBH4 to very complex for Mg(BH4)2 . Despite the extensive discussion in the literature no clear explanation has been offered for this variety so far. In this paper we analyze the structural and electronic properties of a broad range of metal tetrahydroborates and reveal the factors that determine their structure: ionic bonding, the orientation of the BH4 groups, and the coordination number of the metal cation. We show, in a simple way, that the charge transfer in the metal tetrahydroborates rationally explains the structural diversity of these compounds. Being ionic systems, the metal tetrahydroborates fall into the classification of Linus Pauling. By using the ionic radius for the BH4 group as determined in this paper, this allows for structural predictions for new and mixed compounds.

Simple modification of basic dyes with bulky &symmetric WCAs for improving their solubilities in organic solvents without color change.

PubMed

Kim, Jeong Yun; Hwang, Tae Gyu; Woo, Sung Wun; Lee, Jae Moon; Namgoong, Jin Woong; Yuk, Sim Bum; Chung, Sei-Won; Kim, Jae Pil

2017-04-06

A simple and easy solubility enhancement of basic dyes was performed with bulky and symmetric weakly coordinating anions (WCAs). The WCAs decreased the ionic character of the dyes by broadening the partial charge distribution and causing a screening effect on the ionic bonding. This new modification with WCAs has advantages in that it has no influence on the optical properties of the dyes. The solubilities of unmodified and modified dyes were tested in several organic solvents. X-ray powder diffraction patterns of the dyes were measured. Color films were prepared with the dyes and their color loci were analyzed to evaluate the optical properties. By the modification with WCAs, commercial basic dyes showed sufficient solubilities for be applied to various applications while preserving their superior optical properties.

Improving the light-emitting properties of single-layered polyfluorene light-emitting devices by simple ionic liquid blending

NASA Astrophysics Data System (ADS)

Horike, Shohei; Nagaki, Hiroto; Misaki, Masahiro; Koshiba, Yasuko; Morimoto, Masahiro; Fukushima, Tatsuya; Ishida, Kenji

2018-03-01

This paper describes an evaluation of ionic liquids (ILs) as potential electrolytes for single-layered light-emitting devices with good emission performance. As optoelectronic devices continue to grow in abundance, high-performance light-emitting devices with a single emission layer are becoming increasingly important for low-cost production. We show that a simple technique of osmosing IL into the polymer layer can result in high luminous efficiency and good response times of single-layered light-emitting polymers, even without the additional stacking of charge carrier injection and transport layers. The IL contributions to the light-emission of the polymer are discussed from the perspectives of energy diagrams and of the electric double layers on the electrodes. Our findings enable a faster, cheaper, and lower-in-waste production of light-emitting devices.

Parylene-coated ionic liquid-carbon nanotube actuators for user-safe haptic devices.

PubMed

Bubak, Grzegorz; Gendron, David; Ceseracciu, Luca; Ansaldo, Alberto; Ricci, Davide

2015-07-22

Simple fabrication, high power-to-weight and power-to-volume ratios, and the ability to operate in open air at low voltage make the ionic electroactive polymer actuators highly attractive for haptic applications. Whenever a direct tactile stimulation of the skin is involved, electrical and chemical insulation as well as a long-term stability of the actuator are required. Because of its inherent physicochemical properties such as high dielectric strength, resistance to solvents, and biological inactivity, Parylene C meets the requirements for making biocompatible actuators. We have studied the displacement and the generated force of Parylene-coated carbon nanotube actuators as well as the encapsulation quality. A 2 μm coating creates an effective electrical insulation of the actuators without altering the blocking force at frequencies from 50 mHz to 1 Hz. Moreover, the generated strain is preserved at higher frequencies (from 0.5 to 5 Hz). We employed a simple mechanical model to explain the relation between the key parameters-flexural stiffness, displacement, and force-for uncoated and coated actuators. In addition, we demonstrated that our Parylene-coated actuators are not damaged by rinsing in liquid media such as 2-propanol or water. In conclusion, our results indicate that Parylene C encapsulated actuators are safe to touch and can be used in contact with human skin and in biomedical applications in direct contact with tissues and physiological fluids.

Structure of electric double layers in capacitive systems and to what extent (classical) density functional theory describes it

NASA Astrophysics Data System (ADS)

Härtel, Andreas

2017-10-01

Ongoing scientific interest is aimed at the properties and structure of electric double layers (EDLs), which are crucial for capacitive energy storage, water treatment, and energy harvesting technologies like supercapacitors, desalination devices, blue engines, and thermocapacitive heat-to-current converters. A promising tool to describe their physics on a microscopic level is (classical) density functional theory (DFT), which can be applied in order to analyze pair correlations and charge ordering in the primitive model of charged hard spheres. This simple model captures the main properties of ionic liquids and solutions and it predicts many of the phenomena that occur in EDLs. The latter often lead to anomalous response in the differential capacitance of EDLs. This work constructively reviews the powerful theoretical framework of DFT and its recent developments regarding the description of EDLs. It explains to what extent current approaches in DFT describe structural ordering and in-plane transitions in EDLs, which occur when the corresponding electrodes are charged. Further, the review briefly summarizes the history of modeling EDLs, presents applications, and points out limitations and strengths in present theoretical approaches. It concludes that DFT as a sophisticated microscopic theory for ionic systems is expecting a challenging but promising future in both fundamental research and applications in supercapacitive technologies.

Ionically cross-linked poly(allylamine) as a stimulus-responsive underwater adhesive: ionic strength and pH effects.

PubMed

Lawrence, Patrick G; Lapitsky, Yakov

2015-02-03

Gel-like coacervates that adhere to both hydrophilic and hydrophobic substrates under water have recently been prepared by ionically cross-linking poly(allylamine) (PAH) with pyrophosphate (PPi) and tripolyphosphate (TPP). Among the many advantages of these underwater adhesives (which include their simple preparation and low cost) is their ability to dissolve on demand when exposed to high or low pH. To further analyze their stimulus-responsive properties, we have investigated the pH and ionic strength effects on the formation, rheology and adhesion of PAH/PPi and PAH/TPP complexes. The ionic cross-linker concentrations needed to form these adhesives decreased with increasing pH and ionic strength (although the complexes ceased to form when the parent solution pH exceeded ca. 8.5; i.e., the effective pKa of PAH). Once formed, their ionic cross-links were most stable (as inferred from their relaxation times) at near-neutral or slightly alkaline pH values (of roughly 6.5-9) and at low ionic strengths. The decrease in ionic cross-link stability within complexes prepared at other pH values and at elevated (150-300 mM) NaCl concentrations diminished both the strength and longevity of adhesion (although, under most conditions tested, the short-term tensile adhesion strengths remained above 10(5) Pa). Additionally, the sensitivity of PAH/PPi and PAH/TPP complexes to ionic strength was demonstrated as a potential route to injectable adhesive design (where spontaneous adhesive formation was triggered via injection of low-viscosity, colloidal PAH/TPP dispersions into phosphate buffered saline). Thus, while the sensitivity of ionically cross-linked PAH networks to pH and ionic strength can weaken their adhesion, it can also impart them with additional functionality, such as minimally invasive, injectable delivery, and ability to form and dissolve their bonds on demand.

Prediction of pH-Dependent Hydrophobic Profiles of Small Molecules from Miertus-Scrocco-Tomasi Continuum Solvation Calculations.

PubMed

Zamora, William J; Curutchet, Carles; Campanera, Josep M; Luque, F Javier

2017-10-26

Hydrophobicity is a key physicochemical descriptor used to understand the biological profile of (bio)organic compounds as well as a broad variety of biochemical, pharmacological, and toxicological processes. This property is estimated from the partition coefficient between aqueous and nonaqueous environments for neutral compounds (P N ) and corrected for the pH-dependence of ionizable compounds as the distribution coefficient (D). Here, we have extended the parametrization of the Miertus-Scrocco-Tomasi continuum solvation model in n-octanol to nitrogen-containing heterocyclic compounds, as they are present in many biologically relevant molecules (e.g., purines and pyrimidines bases, amino acids, and drugs), to obtain accurate log P N values for these molecules. This refinement also includes solvation calculations for ionic species in n-octanol with the aim of reproducing the experimental partition of ionic compounds (P I ). Finally, the suitability of different formalisms to estimate the distribution coefficient for a wide range of pH values has been examined for a set of small acidic and basic compounds. The results indicate that in general the simple pH-dependence model of the ionizable compound in water suffices to predict the partitioning at or around physiological pH. However, at extreme pH values, where ionic species are predominant, more elaborate models provide a better prediction of the n-octanol/water distribution coefficient, especially for amino acid analogues. Finally, the results also show that these formalisms are better suited to reproduce the experimental pH-dependent distribution curves of log D for both acidic and basic compounds as well as for amino acid analogues.

Discrimination of ionic species from broad-beam ion sources

NASA Technical Reports Server (NTRS)

Anderson, J. R.

1993-01-01

The performance of a broad-beam, three-grid, ion extraction system incorporating radio frequency (RF) mass discrimination was investigated experimentally. This testing demonstrated that the system, based on a modified single-stage Bennett mass spectrometer, can discriminate between ionic species having about a 2-to-1 mass ratio while producing a broad-beam of ions with low kinetic energy (less than 15 eV). Testing was conducted using either argon and krypton ions or atomic and diatomic oxygen ions. A simple one-dimensional model, which ignores magnetic field and space-charge effects, was developed to predict the species separation capabilities as well as the kinetic energies of the extracted ions. The experimental results correlated well with the model predictions. This RF mass discrimination system can be used in applications where both atomic and diatomic ions are produced, but a beam of only one of the species is desired. An example of such an application is a 5 eV atomic oxygen source. This source would produce a beam of atomic oxygen with 5 eV kinetic energy, which would be directed onto a material specimen, to simulate the interaction between the surface of a satellite and the rarefied atmosphere encountered in low-Earth orbit.

Heuristics for the Hodgkin-Huxley system.

PubMed

Hoppensteadt, Frank

2013-09-01

Hodgkin and Huxley (HH) discovered that voltages control ionic currents in nerve membranes. This led them to describe electrical activity in a neuronal membrane patch in terms of an electronic circuit whose characteristics were determined using empirical data. Due to the complexity of this model, a variety of heuristics, including relaxation oscillator circuits and integrate-and-fire models, have been used to investigate activity in neurons, and these simpler models have been successful in suggesting experiments and explaining observations. Connections between most of the simpler models had not been made clear until recently. Shown here are connections between these heuristics and the full HH model. In particular, we study a new model (Type III circuit): It includes the van der Pol-based models; it can be approximated by a simple integrate-and-fire model; and it creates voltages and currents that correspond, respectively, to the h and V components of the HH system. Copyright © 2012 Elsevier Inc. All rights reserved.

Dynamic dielectrophoresis model of multi-phase ionic fluids.

PubMed

Yan, Ying; Luo, Jing; Guo, Dan; Wen, Shizhu

2015-01-01

Ionic-based dielectrophoretic microchips have attracted significant attention due to their wide-ranging applications in electro kinetic and biological experiments. In this work, a numerical method is used to simulate the dynamic behaviors of ionic droplets in a microchannel under the effect of dielectrophoresis. When a discrete liquid dielectric is encompassed within a continuous fluid dielectric placed in an electric field, an electric force is produced due to the dielectrophoresis effect. If either or both of the fluids are ionic liquids, the magnitude and even the direction of the force will be changed because the net ionic charge induced by an electric field can affect the polarization degree of the dielectrics. However, using a dielectrophoresis model, assuming ideal dielectrics, results in significant errors. To avoid the inaccuracy caused by the model, this work incorporates the electrode kinetic equation and defines a relationship between the polarization charge and the net ionic charge. According to the simulation conditions presented herein, the electric force obtained in this work has an error exceeding 70% of the actual value if the false effect of net ionic charge is not accounted for, which would result in significant issues in the design and optimization of experimental parameters. Therefore, there is a clear motivation for developing a model adapted to ionic liquids to provide precise control for the dielectrophoresis of multi-phase ionic liquids.

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

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.

Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating

PubMed Central

Shi, Wu; Ye, Jianting; Zhang, Yijin; Suzuki, Ryuji; Yoshida, Masaro; Miyazaki, Jun; Inoue, Naoko; Saito, Yu; Iwasa, Yoshihiro

2015-01-01

Functionalities of two-dimensional (2D) crystals based on semiconducting transition metal dichalcogenides (TMDs) have now stemmed from simple field effect transistors (FETs) to a variety of electronic and opto-valleytronic devices, and even to superconductivity. Among them, superconductivity is the least studied property in TMDs due to methodological difficulty accessing it in different TMD species. Here, we report the systematic study of superconductivity in MoSe2, MoTe2 and WS2 by ionic gating in different regimes. Electrostatic gating using ionic liquid was able to induce superconductivity in MoSe2 but not in MoTe2 because of inefficient electron accumulation limited by electronic band alignment. Alternative gating using KClO4/polyethylene glycol enabled a crossover from surface doping to bulk doping, which induced superconductivities in MoTe2 and WS2 electrochemically. These new varieties greatly enriched the TMD superconductor families and unveiled critical methodology to expand the capability of ionic gating to other materials. PMID:26235962

Superconductivity Series in Transition Metal Dichalcogenides by Ionic Gating.

PubMed

Shi, Wu; Ye, Jianting; Zhang, Yijin; Suzuki, Ryuji; Yoshida, Masaro; Miyazaki, Jun; Inoue, Naoko; Saito, Yu; Iwasa, Yoshihiro

2015-08-03

Functionalities of two-dimensional (2D) crystals based on semiconducting transition metal dichalcogenides (TMDs) have now stemmed from simple field effect transistors (FETs) to a variety of electronic and opto-valleytronic devices, and even to superconductivity. Among them, superconductivity is the least studied property in TMDs due to methodological difficulty accessing it in different TMD species. Here, we report the systematic study of superconductivity in MoSe2, MoTe2 and WS2 by ionic gating in different regimes. Electrostatic gating using ionic liquid was able to induce superconductivity in MoSe2 but not in MoTe2 because of inefficient electron accumulation limited by electronic band alignment. Alternative gating using KClO4/polyethylene glycol enabled a crossover from surface doping to bulk doping, which induced superconductivities in MoTe2 and WS2 electrochemically. These new varieties greatly enriched the TMD superconductor families and unveiled critical methodology to expand the capability of ionic gating to other materials.

Relationships between lattice energies of inorganic ionic solids

NASA Astrophysics Data System (ADS)

Kaya, Savaş

2018-06-01

Lattice energy, which is a measure of the stabilities of inorganic ionic solids, is the energy required to decompose a solid into its constituent independent gaseous ions. In the present work, the relationships between lattice energies of many diatomic and triatomic inorganic ionic solids are revealed and a simple rule that can be used for the prediction of the lattice energies of inorganic ionic solids is introduced. According to this rule, the lattice energy of an AB molecule can be predicted with the help of the lattice energies of AX, BY and XY molecules in agreement with the experimental data. This rule is valid for not only diatomic molecules but also triatomic molecules. The lattice energy equations proposed in this rule provides compatible results with previously published lattice energy equations by Jenkins, Kaya, Born-Lande, Born-Mayer, Kapustinskii and Reddy. For a large set of tested molecules, calculated percent standard deviation values considering experimental data and the results of the equations proposed in this work are in general between %1-2%.

A precision structured smart hydrogel for sensing applications

NASA Astrophysics Data System (ADS)

Menges, J.; Kleinschmidt, P.; Bart, H.-J.; Oesterschulze, E.

2017-10-01

We report on a macroinitiator based smart hydrogel film applied on a microcantilever for sensing applications. The studied hydrogel features a comparatively wide dynamic range for changes in the electrolyte's ionic strength. Furthermore, it offers a simple spin coating process for thin film deposition as well as the capability to obtain high aspect ratio microstructures by reactive ion etching. This makes the hydrogel compatible to microelectromechanical system integration. As a proof of concept, we study the response of hydrogel functionalized cantilevers in aqueous sodium chloride solutions of varying ionic strength. In contrast to the majority of hydrogel materials reported in the literature, we found that our hydrogel still responds in high ionic strength environments. This may be of future interest for sensing e.g., in sea water or physiological environments like urine.

Mean-Field Description of Ionic Size Effects with Non-Uniform Ionic Sizes: A Numerical Approach

PubMed Central

Zhou, Shenggao; Wang, Zhongming; Li, Bo

2013-01-01

Ionic size effects are significant in many biological systems. Mean-field descriptions of such effects can be efficient but also challenging. When ionic sizes are different, explicit formulas in such descriptions are not available for the dependence of the ionic concentrations on the electrostatic potential, i.e., there is no explicit, Boltzmann type distributions. This work begins with a variational formulation of the continuum electrostatics of an ionic solution with such non-uniform ionic sizes as well as multiple ionic valences. An augmented Lagrange multiplier method is then developed and implemented to numerically solve the underlying constrained optimization problem. The method is shown to be accurate and efficient, and is applied to ionic systems with non-uniform ionic sizes such as the sodium chloride solution. Extensive numerical tests demonstrate that the mean-field model and numerical method capture qualitatively some significant ionic size effects, particularly those for multivalent ionic solutions, such as the stratification of multivalent counterions near a charged surface. The ionic valence-to-volume ratio is found to be the key physical parameter in the stratification of concentrations. All these are not well described by the classical Poisson–Boltzmann theory, or the generalized Poisson–Boltzmann theory that treats uniform ionic sizes. Finally, various issues such as the close packing, limitation of the continuum model, and generalization of this work to molecular solvation are discussed. PMID:21929014

Synthesis of flower-like Boehmite (γ-AlOOH) via a one-step ionic liquid-assisted hydrothermal route

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

Tang, Zhe, E-mail: tangzhe1983@163.com; Liang, Jilei, E-mail: liangjilei_httplan@126.com; Li, Xuehui, E-mail: lxhhmx@163.com

A simple and novel synthesis process, one-step ionic liquid-assisted hydrothermal synthesis route, has been developed in the work to synthesize Bohemithe (γ-AlOOH) with flower-like structure. The samples were characterized by X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscope (SEM). Ionic liquid [Omim]{sup +}Cl{sup −}, as a template, plays an important role in the morphology and pore structure of the products due to its strong interactions with reaction particles. With the increase in the dosage of ionic liquid [Omim]{sup +}Cl{sup −}, the morphology of the γ-AlOOH was changed from initial bundles of nanosheets (without ionic liquid) intomore » final well-developed monodispersed 3D flower-like architectures ([Omim]{sup +}Cl{sup −}=72 mmol). The pore structure was also altered gradually from initial disordered slit-like pore into final relatively ordered ink-bottle pore. Furthermore, the proposed formation mechanism and other influencing factors such as reaction temperature and urea on formation and morphology of the γ-AlOOH have also been investigated. - Graphical abstract: The flower-like γ-AlOOH architectures composed by nanosheets with narrow size distribution (1.6–2.2 μm) and uniform pore size (6.92 nm) have been synthesized via a one-step ionic liquid-assisted hydrothermal route. - Highlights: • The γ-AlOOH microflowers were synthesized via an ionic liquid-assisted hydrothermal route. • Ionic liquid plays an important role on the morphology and porous structure of the products. • Ionic liquid can be easily removed from the products and reused in recycling experiments. • A “aggregation–recrystallization–Ostwald Ripening“formation mechanism may occur.« less

Nonlocal electrostatics in ionic liquids: The key to an understanding of the screening decay length and screened interactions.

PubMed

Kjellander, Roland

2016-09-28

Screened electrostatic interactions in ionic liquids are investigated by means of exact statistical mechanical analysis combined with physical arguments that enhance the transparency and conceptual accessibility of the analysis and results. The constituent ions and immersed particles in the liquid can have arbitrary shapes and any internal charge distributions. The decay of the screened electrostatic potential and the free energy of interaction in ionic liquids can be exponentially damped oscillatory (like in molten simple salts) as well as plain exponential and long-ranged (like in dilute electrolyte solutions). Both behaviors are in agreement with the exact statistical mechanical analysis and reasons for their appearances are investigated. Exact but surprisingly simple expressions for the decay parameter κ of the screened electrostatics are obtained, which replace the classical expression for the Debye-Hückel parameter κ DH (the reciprocal Debye length). The expressions are applicable both for cases with plain exponential and oscillatory behaviors. The key importance of nonlocal electrostatics is thereby demonstrated explicitly. Dielectric properties of ionic liquids and other electrolytes are investigated, in particular the static dielectric function ϵ̃(k) and some effective relative permittivities (E r eff and E r ∗ ), which take roles that the dielectric constant ε r has for polar liquids consisting of electroneutral molecules. The dielectric constant in the latter case, which is the limit of ϵ̃(k) when the wave number k → 0, can be expressed solely in terms of dipolar features of the molecules. In contrast to this, the effective dielectric permittivities of ionic liquids have contributions also from quadrupolar, octupolar, and higher multipolar features of the constituent ions. The "dielectric constant" of electrolytes does not exist since ϵ̃(k)→∞ when k → 0, a well-known effect of perfect screening. The effective relative permittivities, E r eff , and E r ∗ of ionic liquids are obtained from the non-diverging part of ϵ̃(k), but not as a k → 0 limit. Influences of ion associations, especially pairing, are investigated for screened electrostatics and these permittivities. A general, multipolar expansion of ϵ̃(k) is derived and used to analyze dielectric properties of ionic liquids and other electrolytes.

Nonlocal electrostatics in ionic liquids: The key to an understanding of the screening decay length and screened interactions

NASA Astrophysics Data System (ADS)

Kjellander, Roland

2016-09-01

Screened electrostatic interactions in ionic liquids are investigated by means of exact statistical mechanical analysis combined with physical arguments that enhance the transparency and conceptual accessibility of the analysis and results. The constituent ions and immersed particles in the liquid can have arbitrary shapes and any internal charge distributions. The decay of the screened electrostatic potential and the free energy of interaction in ionic liquids can be exponentially damped oscillatory (like in molten simple salts) as well as plain exponential and long-ranged (like in dilute electrolyte solutions). Both behaviors are in agreement with the exact statistical mechanical analysis and reasons for their appearances are investigated. Exact but surprisingly simple expressions for the decay parameter κ of the screened electrostatics are obtained, which replace the classical expression for the Debye-Hückel parameter κDH (the reciprocal Debye length). The expressions are applicable both for cases with plain exponential and oscillatory behaviors. The key importance of nonlocal electrostatics is thereby demonstrated explicitly. Dielectric properties of ionic liquids and other electrolytes are investigated, in particular the static dielectric function ɛ ˜ ( k ) and some effective relative permittivities ( Er eff and Er ∗ ), which take roles that the dielectric constant ɛr has for polar liquids consisting of electroneutral molecules. The dielectric constant in the latter case, which is the limit of ɛ ˜ ( k ) when the wave number k → 0, can be expressed solely in terms of dipolar features of the molecules. In contrast to this, the effective dielectric permittivities of ionic liquids have contributions also from quadrupolar, octupolar, and higher multipolar features of the constituent ions. The "dielectric constant" of electrolytes does not exist since ɛ ˜ ( k ) → ∞ when k → 0, a well-known effect of perfect screening. The effective relative permittivities, Er eff , and Er ∗ of ionic liquids are obtained from the non-diverging part of ɛ ˜ ( k ) , but not as a k → 0 limit. Influences of ion associations, especially pairing, are investigated for screened electrostatics and these permittivities. A general, multipolar expansion of ɛ ˜ ( k ) is derived and used to analyze dielectric properties of ionic liquids and other electrolytes.

A novel conductance glucose biosensor in ultra-low ionic strength solution triggered by the oxidation of Ag nanoparticles.

PubMed

Song, Yonghai; Chen, Jingyi; Liu, Hongyu; Li, Ping; Li, Hongbo; Wang, Li

2015-09-03

A simple, sensitive and effective method to detect glucose in ultra-low ionic strength solution containing citrate-capped silver nanoparticles (CCAgNPs) was developed by monitoring the change of solution conductance. Glucose was catalyzed into gluconic acid firstly by glucose oxidase in an O2-saturated solution accompanied by the reduction of O2 into hydrogen peroxide (H2O2). Then, CCAgNPs was oxidized by H2O2 into Ag(+) and the capping regent of citrate was released at the same time. All these resulted Ag(+), gluconic acid and the released citrate would contribute to the increase of solution ionic strength together, leading to a detectable increase of solution conductance. And a novel conductance glucose biosensor was developed with a routine linear range of 0.06-4.0 mM and a suitable detection limit of 18.0 μM. The novel glucose biosensor was further applied in energy drink sample and proven to be suitable for practical system with low ionic strength. The proposed conductance biosensor achieved a significant breakthrough of glucose detection in ultra-low ionic strength media. Copyright © 2015 Elsevier B.V. All rights reserved.

Bis(trifluoromethylsulfonyl)imide-based frozen ionic liquid for the hollow-fiber solid-phase microextraction of dichlorodiphenyltrichloroethane and its main metabolites.

PubMed

Pang, Long; Yang, Peijie; Pang, Rong; Li, Shunyi

2017-08-01

1-Hexadecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide is a solid-phase ionic organic material under ambient temperature and is considered as a kind of "frozen" ionic liquid. Because of their solid-state and ultra-hydrophobicity, "frozen" ionic liquids are able to be confined in the pores of hollow fiber, based on which a simple method was developed for the hollow-fiber solid-phase microextraction of dichlorodiphenyltrichloroethane and its main metabolites. Under optimized conditions, the proposed method results in good linearity (R 2 > 0.9965) over the range of 0.5-50 μg/L, with low limits of detection and quantification in the range of 0.33-0.38 and 1.00-1.25 μg/L, respectively. Intra- and interday precisions evaluated by relative standard deviation were 3-6 and 1-6%, respectively. The spiked recoveries of dichlorodiphenyltrichloroethane and its main metabolites from real water samples were in the range of 64-113 and 79-112%, respectively, at two different concentration levels. The results suggest that "frozen" ionic liquids are promising for use as a class of novel sorbents. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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

Oxidative desulfurization of dibenzothiophene from model oil using ionic liquids as extracting agent

NASA Astrophysics Data System (ADS)

Taha, Mohd F.; Atikah, N.; Chong, F. K.; Shaharun, Maizatul S.

2012-09-01

The oxidative desulfurization of dibenzothiophene (DBT) from model oil (in n-dodecane) was carried out using ionic liquid as the extractant and catalyst, and hydrogen peroxide (H2O2) in combination with acetic acid (CH3COOH) and sulphuric acid (H2SO4) as the oxidant. The ionic liquids used were 1-butyl-3-methylimidazolium octyl sulphate ([Bmim][OcSO4]) and 1-butyl-3-methylimidazolium acetate ([Bmim][Ac]). The effect of the amounts of H2O2 on oxidative desulphurization of model oil was first investigated without the usage of ionic liquids at room temperature. The results indicate that greater amount of H2O2 give higher desulfurization and the maximum desulfurization in this study, i.e. 34 %, was occurred when the molar ratio of H2O2 to sulfur was 5:1. With the usage of ionic liquid and the molar ratio of 5:1 (H2O2:sulfur), the efficiency of DBT removal from model oil was increased significantly in terms of percent removal and removal time. Ionic liquid of [Bmim][OcSO4] performed better than [Bmim][Ac] with 72 % DBT removal. When molar ratio of H2O2 to sulphur was 5:1, volume ratio of ionic liquid to model oil was 1:1 and mixing time was 60 min at room temperature. The results indicate the potential of ionic liquids as the extractant and catalyst for oxidative desulfurization of hydrocarbon fuels.

Extraction of S- and N-compounds from the mixture of hydrocarbons by ionic liquids as selective solvents.

PubMed

Gabrić, Beata; Sander, Aleksandra; Cvjetko Bubalo, Marina; Macut, Dejan

2013-01-01

Liquid-liquid extraction is an alternative method that can be used for desulfurization and denitrification of gasoline and diesel fuels. Recent approaches employ different ionic liquids as selective solvents, due to their general immiscibility with gasoline and diesel, negligible vapor pressure, and high selectivity to sulfur- and nitrogen-containing compounds. For that reason, five imidazolium-based ionic liquids and one pyridinium-based ionic liquid were selected for extraction of thiophene, dibenzothiophene, and pyridine from two model solutions. The influences of hydrodynamic conditions, mass ratio, and number of stages were investigated. Increasing the mass ratio of ionic liquid/model fuel and multistage extraction promotes the desulfurization and denitrification abilities of the examined ionic liquids. All selected ionic liquids can be reused and regenerated by means of vacuum evaporation.

Extraction of S- and N-Compounds from the Mixture of Hydrocarbons by Ionic Liquids as Selective Solvents

PubMed Central

Gabrić, Beata; Sander, Aleksandra; Cvjetko Bubalo, Marina; Macut, Dejan

2013-01-01

Liquid-liquid extraction is an alternative method that can be used for desulfurization and denitrification of gasoline and diesel fuels. Recent approaches employ different ionic liquids as selective solvents, due to their general immiscibility with gasoline and diesel, negligible vapor pressure, and high selectivity to sulfur- and nitrogen-containing compounds. For that reason, five imidazolium-based ionic liquids and one pyridinium-based ionic liquid were selected for extraction of thiophene, dibenzothiophene, and pyridine from two model solutions. The influences of hydrodynamic conditions, mass ratio, and number of stages were investigated. Increasing the mass ratio of ionic liquid/model fuel and multistage extraction promotes the desulfurization and denitrification abilities of the examined ionic liquids. All selected ionic liquids can be reused and regenerated by means of vacuum evaporation. PMID:23843736

Ultrasound-assisted magnetic solid-phase extraction based ionic liquid-coated Fe3O4@graphene for the determination of nitrobenzene compounds in environmental water samples.

PubMed

Cao, Xiaoji; Shen, Lingxiao; Ye, Xuemin; Zhang, Feifei; Chen, Jiaoyu; Mo, Weimin

2014-04-21

An ultrasound-assisted magnetic solid-phase extraction procedure with the [C7MIM][PF6] ionic liquid-coated Fe3O4-grafted graphene nanocomposite as the magnetic adsorbent has been developed for the determination of five nitrobenzene compounds (NBs) in environmental water samples, in combination with high performance liquid chromatography-photodiode array detector (HPLC-PDA). Several significant factors that affect the extraction efficiency, such as the types of magnetic nanoparticle and ionic liquid, the volume of ionic liquid and the amount of magnetic nanoparticles, extraction time, ionic strength, and solution pH, were investigated. With the assistance of ultrasound, adsorbing nitrobenzene compounds by ionic liquid and self-aggregating ionic liquid onto the surface of the Fe3O4-grafted graphene proceeded synchronously, which made the extraction achieved the maximum within 20 min using only 144 μL [C7MIM][PF6] and 3 mg Fe3O4-grafted graphene. Under the optimized conditions, satisfactory linearities were obtained for all NBs with correlation coefficients larger than 0.9990. The mean recoveries at two spiked levels ranged from 80.35 to 102.77%. Attributed to the convenient magnetic separation, the Fe3O4-grafted graphene could be recycled many times. The proposed method was demonstrated to be feasible, simple, solvent-saving and easy to operate for the trace analysis of NBs in environmental water samples.

Tested Demonstrations.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.

1979-01-01

Presents two demonstrations for classroom use related to precipitation of ferrous hydroxide and to variation of vapor pressure with temperature. The former demonstration is simple and useful when discussing solubility of ionic compounds electrode potential of transition elements, and mixed valence compounds. (Author/SA)

Transparent conducting oxide induced by liquid electrolyte gating

NASA Astrophysics Data System (ADS)

ViolBarbosa, Carlos; Karel, Julie; Kiss, Janos; Gordan, Ovidiu-dorin; Altendorf, Simone G.; Utsumi, Yuki; Samant, Mahesh G.; Wu, Yu-Han; Tsuei, Ku-Ding; Felser, Claudia; Parkin, Stuart S. P.

2016-10-01

Optically transparent conducting materials are essential in modern technology. These materials are used as electrodes in displays, photovoltaic cells, and touchscreens; they are also used in energy-conserving windows to reflect the infrared spectrum. The most ubiquitous transparent conducting material is tin-doped indium oxide (ITO), a wide-gap oxide whose conductivity is ascribed to n-type chemical doping. Recently, it has been shown that ionic liquid gating can induce a reversible, nonvolatile metallic phase in initially insulating films of WO3. Here, we use hard X-ray photoelectron spectroscopy and spectroscopic ellipsometry to show that the metallic phase produced by the electrolyte gating does not result from a significant change in the bandgap but rather originates from new in-gap states. These states produce strong absorption below ˜1 eV, outside the visible spectrum, consistent with the formation of a narrow electronic conduction band. Thus WO3 is metallic but remains colorless, unlike other methods to realize tunable electrical conductivity in this material. Core-level photoemission spectra show that the gating reversibly modifies the atomic coordination of W and O atoms without a substantial change of the stoichiometry; we propose a simple model relating these structural changes to the modifications in the electronic structure. Thus we show that ionic liquid gating can tune the conductivity over orders of magnitude while maintaining transparency in the visible range, suggesting the use of ionic liquid gating for many applications.

Solid phase extraction of copper(II) by fixed bed procedure on cation exchange complexing resins.

PubMed

Pesavento, Maria; Sturini, Michela; D'Agostino, Girolamo; Biesuz, Raffaela

2010-02-19

The efficiency of the metal ion recovery by solid phase extraction (SPE) in complexing resins columns is predicted by a simple model based on two parameters reflecting the sorption equilibria and kinetics of the metal ion on the considered resin. The parameter related to the adsorption equilibria was evaluated by the Gibbs-Donnan model, and that related to the kinetics by assuming that the ion exchange is the adsorption rate determining step. The predicted parameters make it possible to evaluate the breakthrough volume of the considered metal ion, Cu(II), from different kinds of complexing resins, and at different conditions, such as acidity and ionic composition. Copyright 2009. Published by Elsevier B.V.

Phytoremediation of Ionic and Methyl Mercury Pollution

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

Meagher, Richard B.

Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species. Several of these genes have already been shown to enhance mercury phytoremediation. Mercury pollution is a serious, world-wide problem affecting the health of humanmore » and wildlife populations. Environmentally, the most serious mercury threat is the production of methylmercury (CH3Hg+) by native bacteria at mercury contaminated wetland sites. Methylmercury is inherently more toxic than metallic (Hg(0)) or ionic (Hg(II)) mercury, and because methylmercury is prolifically biomagnified up the food chain, it poses the most immediate danger to animal populations. We have successfully engineered two model plants, Arabidopsis and tobacco, to use the bacterial merB gene to convert methylmercury to less toxic ionic mercury and to use the bacterial merA gene to further detoxify ionic mercury to the least toxic form of mercury, metallic mercury. Plants expressing both MerA and MerB proteins detoxify methylmercury in two steps to the metallic form. These plants germinate, grow, and set seed at normal growth rates on levels of methylmercury or ionic mercury that are lethal to normal plants. Our newest efforts involve engineering plants with several additional bacterial and plant genes that allow for higher levels of mercury resistance and mercury hyperaccumulation. The potential for these plants to hyperaccumulate mercury was further advanced by developing constitutive, aboveground, and root-specific gene expression systems. Our current strategy is to engineer plants to control the chemical speciation, electrochemical state, transport, and aboveground binding of mercury in order to manage this toxicant. To advance this mercury phytoremediation strategy, our planned research focuses on the following Specific Aims: (1) to increase the transport of mercury to aboveground tissue; (2) to identify small mercury binding peptides that enhance hyperaccumulation aboveground; (3) to test the ability of multiple genes acting together to enhance resistance and hyperaccumulation; (4) to construct a simple molecular system for creating male/female sterility, allowing engineered grass, shrub, and tree species to be released indefinitely at contaminated sites; (5) to test the ability of transgenic cottonwood and rice plants to detoxify ionic mercury and prevent methylmercury release from contaminated sediment; and (6) to initiate field testing with transgenic cottonwood and rice for the remediation of methylmercury and ionic mercury. The results of these experiments will enable the phytoremediation of methyl- and ionic mercury by a wide spectrum of deep-rooted, fast-growing plants adapted to diverse environments. We have made significant progress on all six of these specific aims as summarized below.« less

Ionic structures and transport properties of hot dense W and U plasmas

NASA Astrophysics Data System (ADS)

Hou, Yong; Yuan, Jianmin

2016-10-01

We have combined the average-atom model with the hyper-netted chain approximation (AAHNC) to describe the electronic and ionic structure of uranium and tungsten in the hot dense matter regime. When the electronic structure is described within the average-atom model, the effects of others ions on the electronic structure are considered by the correlation functions. And the ionic structure is calculated though using the hyper-netted chain (HNC) approximation. The ion-ion pair potential is calculated using the modified Gordon-Kim model based on the electronic density distribution in the temperature-depended density functional theory. And electronic and ionic structures are determined self-consistently. On the basis of the ion-ion pair potential, we perform the classical (CMD) and Langevin (LMD) molecular dynamics to simulate the ionic transport properties, such as ionic self-diffusion and shear viscosity coefficients, through the ionic velocity correlation functions. Due that the free electrons become more and more with increasing the plasma temperature, the influence of the electron-ion collisions on the transport properties become more and more important.

Database and new models based on a group contribution method to predict the refractive index of ionic liquids.

PubMed

Wang, Xinxin; Lu, Xingmei; Zhou, Qing; Zhao, Yongsheng; Li, Xiaoqian; Zhang, Suojiang

2017-08-02

Refractive index is one of the important physical properties, which is widely used in separation and purification. In this study, the refractive index data of ILs were collected to establish a comprehensive database, which included about 2138 pieces of data from 1996 to 2014. The Group Contribution-Artificial Neural Network (GC-ANN) model and Group Contribution (GC) method were employed to predict the refractive index of ILs at different temperatures from 283.15 K to 368.15 K. Average absolute relative deviations (AARD) of the GC-ANN model and the GC method were 0.179% and 0.628%, respectively. The results showed that a GC-ANN model provided an effective way to estimate the refractive index of ILs, whereas the GC method was simple and extensive. In summary, both of the models were accurate and efficient approaches for estimating refractive indices of ILs.

Ionic liquid-based ultrasonic/microwave-assisted extraction combined with UPLC-MS-MS for the determination of tannins in Galla chinensis.

PubMed

Lu, Chunxia; Wang, Hongxin; Lv, Wenping; Ma, Chaoyang; Lou, Zaixiang; Xie, Jun; Liu, Bo

2012-01-01

Ionic liquid was used as extraction solvents and applied to the extraction of tannins from Galla chinensis in the simultaneous ultrasonic- and microwave-assisted extraction (UMAE) technique. Several parameters of UMAE were optimised, and the results were compared with of the conventional extraction techniques. Under optimal conditions, the content of tannins was 630.2 ± 12.1 mg g⁻¹. Compared with the conventional heat-reflux extraction, maceration extraction, regular ultrasound- and microwave-assisted extraction, the proposed approach exhibited higher efficiency (11.7-22.0% enhanced) and shorter extraction time (from 6 h to 1 min). The tannins were then identified by ultraperformance liquid chromatography tandem mass spectrometry. This study suggests that ionic liquid-based UMAE is an efficient, rapid, simple and green sample preparation technique.

High-throughput approach for the identification of anilinium-based ionic liquids that are suitable for electropolymerisation.

PubMed

Abdelhamid, Muhammad E; Murdoch, Timothy; Greaves, Tamar L; O'Mullane, Anthony P; Snook, Graeme A

2015-07-21

We report the synthesis of new protic ionic liquids (PILs) based on aniline derivatives and the use of high-throughput (HT) techniques to screen possible candidates. In this work, a simple HT method was applied to rapidly screen different aniline derivatives against different acids in order to identify possible combinations that produce PILs. This was followed by repeating the HT process with a Chemspeed robotic synthesis platform for more accurate results. One of the successful combinations were then chosen to be synthesised on a larger scale for further analysis. The new PILs are of interest to the fields of ionic liquids, energy storage and especially, conducting polymers as they serve as solvents, electrolytes and monomers at the same time for possible electropolymerisation (i.e. a self-contained polymer precursor).

Investigation of Secondary School, Undergraduate, and Graduate Learners' Mental Models of Ionic Bonding.

ERIC Educational Resources Information Center

Coll, Richard K.; Treagust, David F.

2003-01-01

Explores secondary school, undergraduate, and graduate level learners' mental models of bonding with ionic substances through an interview protocol involving the use of physical substances and a focus card containing depictions of ionic bonding and structure. Suggests that teachers and university faculty need to provide stronger links between the…

Diffusion of aqueous solutions of ionic, zwitterionic, and polar solutes

NASA Astrophysics Data System (ADS)

Teng, Xiaojing; Huang, Qi; Dharmawardhana, Chamila Chathuranga; Ichiye, Toshiko

2018-06-01

The properties of aqueous solutions of ionic, zwitterionic, and polar solutes are of interest to many fields. For instance, one of the many anomalous properties of aqueous solutions is the behavior of water diffusion in different monovalent salt solutions. In addition, solutes can affect the stabilities of macromolecules such as proteins in aqueous solution. Here, the diffusivities of aqueous solutions of sodium chloride, potassium chloride, tri-methylamine oxide (TMAO), urea, and TMAO-urea are examined in molecular dynamics simulations. The decrease in the diffusivity of water with the concentration of simple ions and urea can be described by a simple model in which the water molecules hydrogen bonded to the solutes are considered to diffuse at the same rate as the solutes, while the remainder of the water molecules are considered to be bulk and diffuse at almost the same rate as pure water. On the other hand, the decrease in the diffusivity of water with the concentration of TMAO is apparently affected by a decrease in the diffusion rate of the bulk water molecules in addition to the decrease due to the water molecules hydrogen bonded to TMAO. In other words, TMAO enhances the viscosity of water, while urea barely affects it. Overall, this separation of water molecules into those that are hydrogen bonded to solute and those that are bulk can provide a useful means of understanding the short- and long-range effects of solutes on water.

Polymer-induced phase separation and crystallization in immunoglobulin G solutions.

PubMed

Li, Jianguo; Rajagopalan, Raj; Jiang, Jianwen

2008-05-28

We study the effects of the size of polymer additives and ionic strength on the phase behavior of a nonglobular protein-immunoglobulin G (IgG)-by using a simple four-site model to mimic the shape of IgG. The interaction potential between the protein molecules consists of a Derjaguin-Landau-Verwey-Overbeek-type colloidal potential and an Asakura-Oosawa depletion potential arising from the addition of polymer. Liquid-liquid equilibria and fluid-solid equilibria are calculated by using the Gibbs ensemble Monte Carlo technique and the Gibbs-Duhem integration (GDI) method, respectively. Absolute Helmholtz energy is also calculated to get an initial coexisting point as required by GDI. The results reveal a nonmonotonic dependence of the critical polymer concentration rho(PEG) (*) (i.e., the minimum polymer concentration needed to induce liquid-liquid phase separation) on the polymer-to-protein size ratio q (equivalently, the range of the polymer-induced depletion interaction potential). We have developed a simple equation for estimating the minimum amount of polymer needed to induce the liquid-liquid phase separation and show that rho(PEG) (*) approximately [q(1+q)(3)]. The results also show that the liquid-liquid phase separation is metastable for low-molecular weight polymers (q=0.2) but stable at large molecular weights (q=1.0), thereby indicating that small sizes of polymer are required for protein crystallization. The simulation results provide practical guidelines for the selection of polymer size and ionic strength for protein phase separation and crystallization.

Regioselctive Thiocyanation of Aromatic and Heteroaromatic Compounds Using a Novel Bronsted Acidic Ionic Liquid.

PubMed

Rezayati, Sobhan; Sheikholeslami-Farahani, Fatemeh; Hossaini, Zinatossadat; Hajinasiri, Rahimeh; Abad, Saeid Afshari Sharif

2016-01-01

A convenient procedure for the preparation of 1-(1-Propylsulfonic)-3- methylimidazolium thiocyanate as a novel Brønsted acidic ionic liquid thiocyanation agent and highly efficient heterogeneous catalytic is described. This catalyst is used in regioselective thiocyanation of indoles, anilines, pyrroles and their derivatives (aromatic and heteroaromatic organic compounds) in the presence of H2O2 as a mild and oxidant in EtOH:H2O (1:1 v/v). These reactions are performed under mild and simple conditions and give regioselective products in high yields and short reaction time.

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.

Changes in the Molar Ellipticities of HEWL Observed by Circular Dichroism and Quantitated by Time Resolved Fluorescence Anisotropy Under Crystallizing Conditions

NASA Technical Reports Server (NTRS)

Sumida, John

2002-01-01

Fluid models for simple colloids predict that as the protein concentration is increased, crystallization should occur at some sufficiently high concentration regardless of the strength of attraction. However, empirical measurements do not fully support this assertion. Measurements of the second virial coefficient (B22) indicate that protein crystallization occurs only over a discrete range of solution parameters. Furthermore, observations of a strong correlation between protein solubility and B22, has led to an ongoing debate regarding the relationship between the two. Experimental work in our lab, using Hen Egg White Lysozyme (HEWL), previously revealed that the rotational anisotropy of the protein under crystallizing conditions changes systematically with pH, ionic strength and temperature. These observations are now supported by recent work revealing that small changes in the molar ellipticity also occur systematically with changes in ionic strength and temperature. This work demonstrates that under crystallization conditions, the protein native state is characterized by a conformational heterogeneity that may prove fundamental to the relationship between protein crystallization and protein solubility.

Lattice model of ionic liquid confined by metal electrodes

NASA Astrophysics Data System (ADS)

Girotto, Matheus; Malossi, Rodrigo M.; dos Santos, Alexandre P.; Levin, Yan

2018-05-01

We study, using Monte Carlo simulations, the density profiles and differential capacitance of ionic liquids confined by metal electrodes. To compute the electrostatic energy, we use the recently developed approach based on periodic Green's functions. The method also allows us to easily calculate the induced charge on the electrodes permitting an efficient implementation of simulations in a constant electrostatic potential ensemble. To speed up the simulations further, we model the ionic liquid as a lattice Coulomb gas and precalculate the interaction potential between the ions. We show that the lattice model captures the transition between camel-shaped and bell-shaped capacitance curves—the latter characteristic of ionic liquids (strong coupling limit) and the former of electrolytes (weak coupling). We observe the appearance of a second peak in the differential capacitance at ≈0.5 V for 2:1 ionic liquids, as the packing fraction is increased. Finally, we show that ionic size asymmetry decreases substantially the capacitance maximum, when all other parameters are kept fixed.

Solvent induced temperature dependencies of NMR parameters of hydrogen bonded anionic clusters

NASA Astrophysics Data System (ADS)

Golubev, Nikolai S.; Shenderovich, Ilja G.; Tolstoy, Peter M.; Shchepkin, Dmitry N.

2004-07-01

The solvent induced temperature dependence of NMR parameters (proton and fluorine chemical shifts, the two-bond scalar spin coupling constant across the hydrogen bridge, 2hJFF) for dihydrogen trifluoride anion, (FH) 2F -, in a polar aprotic solvent, CDF 3/CDF 2Cl, is reported and discussed. The results are interpreted in terms of a simple electrostatic model, accounting a decrease of electrostatic repulsion of two negatively charged fluorine atoms on placing into a dielectric medium. The conclusion is drawn that polar medium causes some contraction of hydrogen bonds in ionic clusters combined with a decrease of hydrogen bond asymmetry.

Gas-liquid phase coexistence and crossover behavior of binary ionic fluids with screened Coulomb interactions.

PubMed

Patsahan, O

2014-06-01

We study the effects of an interaction range on the gas-liquid phase diagram and the crossover behavior of a simple model of ionic fluids: an equimolar binary mixture of equisized hard spheres interacting through screened Coulomb potentials which are repulsive between particles of the same species and attractive between particles of different species. Using the collective variables theory, we find explicit expressions for the relevant coefficients of the effective φ{4} Ginzburg-Landau Hamiltonian in a one-loop approximation. Within the framework of this approximation, we calculate the critical parameters and gas-liquid phase diagrams for varying inverse screening length z. Both the critical temperature scaled by the Yukawa potential contact value and the critical density rapidly decrease with an increase of the interaction range (a decrease of z) and then for z<0.05 they slowly approach the values found for a restricted primitive model (RPM). We find that gas-liquid coexistence region reduces with an increase of z and completely vanishes at z≃2.78. Our results clearly show that an increase in the interaction range leads to a decrease of the crossover temperature. For z≃0.01, the crossover temperature is the same as for the RPM.

Structure-property relationships in semicrystalline copolymers and ionomers

NASA Astrophysics Data System (ADS)

Wakabayashi, Katsuyuki

Many outstanding physical properties of ethylene/(meth)acrylic acid (E/(M)AA) copolymers and ionomers are associated with their nanometer-scale morphology, which consists of ethylene crystallites, amorphous segments, and acid/ionic functional groups. The goal of this dissertation is a fundamental understanding of the interplay between these structural motifs and the consequent effects on the material properties. We identify small-strain modulus as a key mechanical property and investigate its dependence upon material structure through X-ray scattering, calorimetry, and mechanical property measurements. We first treat E/(M)AA copolymers as composites of polyethylene crystallites and amorphous regions, and establish a quantitative combining rule to describe the copolymer modulus. At temperatures above the Tg of the copolymers, a monotonic increase in modulus with crystallinity is quantitatively described by the Davies equation for two-phase composites, which serves as the basis for separating the effects of amorphous and crystalline phases throughout this dissertation. The room-temperature modulus of E/(M)AA copolymers is concurrently affected by ethylene crystallinity and proximity to the amorphous phase Tg, which rises through room temperature with increasing comonomer content. In E/(M)AA ionomers, phase separation and aggregation of ionic groups provide additional stiffness and toughness. Ionomers are modeled as composites of crystallites and ionically crosslinked rubber, whose amorphous phase modulus far above the ionomer Tg is satisfactorily described by simple rubber elasticity theory. Thermomechanical analyses probe the multi-step relaxation behavior of E/(M)AA ionomers and lead to the development of a new semicrystalline ionomer morphological model, wherein secondary crystallites and ionic aggregates together form rigid percolated pathways throughout the amorphous phase. Metal soaps are oligomeric analogs of E/(M)AA ionomers, which can be blended into ionomers to achieve high ion content and in turn desirable physical properties. We assess the compatibility of various types of metal soaps with E/(M)AA ionomers, and investigate how the soap modifies the ionomers' structure and properties. The mechanical properties and phase behavior of these hybrids, which are found to differ significantly depending on the neutralizing cation type and crystallinizability of the metal soap, are traced back to various levels of molecular coassembly involving the hydrocarbon chains and/or the ionic groups of both entities.

A simulation assessment of the thermodynamics of dense ion-dipole mixtures with polarization

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

Bastea, Sorin, E-mail: sbastea@llnl.gov

Molecular dynamics (MD) simulations are employed to ascertain the relative importance of various electrostatic interaction contributions, including induction interactions, to the thermodynamics of dense, hot ion-dipole mixtures. In the absence of polarization, we find that an MD-constrained free energy term accounting for the ion-dipole interactions, combined with well tested ionic and dipolar contributions, yields a simple, fairly accurate free energy form that may be a better option for describing the thermodynamics of such mixtures than the mean spherical approximation (MSA). Polarization contributions induced by the presence of permanent dipoles and ions are found to be additive to a good approximation,more » simplifying the thermodynamic modeling. We suggest simple free energy corrections that account for these two effects, based in part on standard perturbative treatments and partly on comparisons with MD simulation. Even though the proposed approximations likely need further study, they provide a first quantitative assessment of polarization contributions at high densities and temperatures and may serve as a guide for future modeling efforts.« less

Remarkable enhancement of charge carrier mobility of conjugated polymer field-effect transistors upon incorporating an ionic additive

PubMed Central

Luo, Hewei; Yu, Chenmin; Liu, Zitong; Zhang, Guanxin; Geng, Hua; Yi, Yuanping; Broch, Katharina; Hu, Yuanyuan; Sadhanala, Aditya; Jiang, Lang; Qi, Penglin; Cai, Zhengxu; Sirringhaus, Henning; Zhang, Deqing

2016-01-01

Organic semiconductors with high charge carrier mobilities are crucial for flexible electronic applications. Apart from designing new conjugated frameworks, different strategies have been explored to increase charge carrier mobilities. We report a new and simple approach to enhancing the charge carrier mobility of DPP-thieno[3,2-b]thiophene–conjugated polymer by incorporating an ionic additive, tetramethylammonium iodide, without extra treatments into the polymer. The resulting thin films exhibit a very high hole mobility, which is higher by a factor of 24 than that of thin films without the ionic additive under the same conditions. On the basis of spectroscopic grazing incidence wide-angle x-ray scattering and atomic force microscopy studies as well as theoretical calculations, the remarkable enhancement of charge mobility upon addition of tetramethylammonium iodide is attributed primarily to an inhibition of the torsion of the alkyl side chains by the presence of the ionic species, facilitating a more ordered lamellar packing of the alkyl side chains and interchain π-π interactions. PMID:27386541

Modifying Mechanical, Optical Properties and Thermal Processability of Iridescent Cellulose Nanocrystal Films Using Ionic Liquid.

PubMed

Liu, Ping; Guo, Xin; Nan, Fuchun; Duan, Yongxin; Zhang, Jianming

2017-01-25

Iridescent films formed from the self-assembly of cellulose nanocrystals (CNCs) are brittle and difficult to handle or integrate within an industrial process. Here we present a simple approach to prepare iridescent CNC films with tunable pliability and coloration through the addition of ionic liquids (ILs) of 1-allyl-3-methylimidazolium chloride (AmimCl) as plasticizers. By using the undried CNC film as a filter membrane and ILs solution as a leaching liquid, it was found that the filtration process made ILs uniformly interpenetrate into CNC film due to the strong ionic interaction between CNC and AmimCl. Unexpectedly, the filtration process also gave rise to partial desulfurization of CNC film, which is conducive to the improvement of thermal stability. Benefiting from the improved thermal stability and the dissolving capacity of AmimCl for cellulose at high temperature, the incorporated ILs enable the cholesteric CNC film to be further toughened via a hot-pressing treatment. This study demonstrates that ionic liquids have great potential to modify the mechanical, optical properties as well as the thermal stability of iridescent CNC films.

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.

Chromatin ionic atmosphere analyzed by a mesoscale electrostatic approach.

PubMed

Gan, Hin Hark; Schlick, Tamar

2010-10-20

Characterizing the ionic distribution around chromatin is important for understanding the electrostatic forces governing chromatin structure and function. Here we develop an electrostatic model to handle multivalent ions and compute the ionic distribution around a mesoscale chromatin model as a function of conformation, number of nucleosome cores, and ionic strength and species using Poisson-Boltzmann theory. This approach enables us to visualize and measure the complex patterns of counterion condensation around chromatin by examining ionic densities, free energies, shielding charges, and correlations of shielding charges around the nucleosome core and various oligonucleosome conformations. We show that: counterions, especially divalent cations, predominantly condense around the nucleosomal and linker DNA, unburied regions of histone tails, and exposed chromatin surfaces; ionic screening is sensitively influenced by local and global conformations, with a wide ranging net nucleosome core screening charge (56-100e); and screening charge correlations reveal conformational flexibility and interactions among chromatin subunits, especially between the histone tails and parental nucleosome cores. These results provide complementary and detailed views of ionic effects on chromatin structure for modest computational resources. The electrostatic model developed here is applicable to other coarse-grained macromolecular complexes. Copyright © 2010 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Molecular modeling of field-driven ion emission from ionic liquids

NASA Astrophysics Data System (ADS)

Zhang, Fei; He, Yadong; Qiao, Rui

2017-11-01

Traditionally, operating electrosprays in the purely ionic mode is challenging, but recent experiments confirmed that such operation can be achieved using room-temperature ionic liquids as working electrolytes. Such electrosprays have shown promise in applications including chemical analysis, nanomanufacturing, and space propulsion. The mechanistic and quantitative understanding of such electrosprays at the molecular level, however, remain limited at present. In this work, we simulated ion emission from EMIM-PF6 ionic liquid films using the molecular dynamics method. We show that, when the surface electric field is smaller than 1.5V/nm, the ion emission current predicted using coarse-grained ionic liquid model observes the classical scaling law by J. V. Iribarne and B. A. Thomson, i.e., ln(Je/ σ) En1/2. These simulations, however, cannot capture the co-emission of cations and anions from ionic liquid surface observed in some experiments. Such co-emission was successfully captured when united-atom models were adopted for the ionic liquids. By examining the co-emission events with picosecond, sub-angstrom resolution, we clarified the origins of the co-emission phenomenon and delineate the molecular events leading to ion emission.

Effects of novel triple-stage antimalarial ionic liquids on lipid membrane models.

PubMed

Ferraz, Ricardo; Pinheiro, Marina; Gomes, Ana; Teixeira, Cátia; Prudêncio, Cristina; Reis, Salette; Gomes, Paula

2017-09-01

Primaquine-based ionic liquids, obtained by acid-base reaction between parent primaquine and cinnamic acids, were recently found as triple-stage antimalarial hits. These ionic compounds displayed significant activity against both liver- and blood-stage Plasmodium parasites, as well as against stage V P. falciparum parasites. Remarkably, blood-stage activity of the ionic liquids against both chloroquine-sensitive (3D7) and resistant (Dd2) P. falciparum strains was clearly superior to those of the respective covalent (amide) analogues and of parent primaquine. Having hypothesized that such behaviour might be ascribed to an enhanced ability of the ionic compounds to permeate into Plasmodium-infected erythrocytes, we have carried out a differential scanning calorimetry-based study of the interactions between the ionic liquids and membrane models. Results provide evidence, at the molecular level, that the primaquine-derived ionic liquids may contribute to an increased permeation of the parent drug into malaria-infected erythrocytes, which has relevant implications towards novel antimalarial approaches based on ionic liquids. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

Ionic conduction and self-diffusion near infinitesimal concentration in lithium salt-organic solvent electrolytes

NASA Astrophysics Data System (ADS)

Aihara, Yuichi; Sugimoto, Kyoko; Price, William S.; Hayamizu, Kikuko

2000-08-01

The Debye-Hückel-Onsager and Nernst-Einstein equations, which are based on two different conceptual approaches, constitute the most widely used equations for relating ionic conduction to ionic mobility. However, both of these classical (simple) equations are predictive of ionic conductivity only at very low salt concentrations. In the present work the ionic conductivity of four organic solvent-lithium salt-based electrolytes were measured. These experimental conductivity values were then contrasted with theoretical values calculated using the translational diffusion (also known as self-diffusion or intradiffusion) coefficients of all of the species present obtained using pulsed-gradient spin-echo (1H, 19F and 7Li) nuclear magnetic resonance self-diffusion measurements. The experimental results verified the applicability of both theoretical approaches at very low salt concentrations for these particular systems as well as helping to clarify the reasons for the divergence between theory and experiment. In particular, it was found that the correspondence between the Debye-Hückel-Onsager equation and experimental values could be improved by using the measured solvent self-diffusion values to correct for salt-induced changes in the solution viscosity. The concentration dependence of the self-diffusion coefficients is discussed in terms of the Jones-Dole equation.

Direct extraction of genomic DNA from maize with aqueous ionic liquid buffer systems for applications in genetically modified organisms analysis.

PubMed

Gonzalez García, Eric; Ressmann, Anna K; Gaertner, Peter; Zirbs, Ronald; Mach, Robert L; Krska, Rudolf; Bica, Katharina; Brunner, Kurt

2014-12-01

To date, the extraction of genomic DNA is considered a bottleneck in the process of genetically modified organisms (GMOs) detection. Conventional DNA isolation methods are associated with long extraction times and multiple pipetting and centrifugation steps, which makes the entire procedure not only tedious and complicated but also prone to sample cross-contamination. In recent times, ionic liquids have emerged as innovative solvents for biomass processing, due to their outstanding properties for dissolution of biomass and biopolymers. In this study, a novel, easily applicable, and time-efficient method for the direct extraction of genomic DNA from biomass based on aqueous-ionic liquid solutions was developed. The straightforward protocol relies on extraction of maize in a 10 % solution of ionic liquids in aqueous phosphate buffer for 5 min at room temperature, followed by a denaturation step at 95 °C for 10 min and a simple filtration to remove residual biopolymers. A set of 22 ionic liquids was tested in a buffer system and 1-ethyl-3-methylimidazolium dimethylphosphate, as well as the environmentally benign choline formate, were identified as ideal candidates. With this strategy, the quality of the genomic DNA extracted was significantly improved and the extraction protocol was notably simplified compared with a well-established method.

Comparison of micellar extraction combined with ionic liquid based vortex-assisted liquid-liquid microextraction and modified quick, easy, cheap, effective, rugged, and safe method for the determination of difenoconazole in cowpea.

PubMed

Chen, Xiaochu; Bian, Yanli; Liu, Fengmao; Teng, Peipei; Sun, Pan

2017-10-06

Two simple sample pretreatment for the determination of difenoconazole in cowpea was developed including micellar extraction combined with ionic liquid based vortex-assisted liquid-liquid microextraction (ME-IL-VALLME) prior to high performance liquid chromatography (HPLC), and modified quick, easy, cheap, effective, rugged, and safe method (QuEChERS) coupled with HPLC-MS/MS. In ME-IL-VALLME method, the target analyte was extracted by surfactant Tween 20 micellar solution, then the supernatant was diluted with 3mL water to decrease the solubility of micellar solution. Subsequently, the vortex-assisted liquid-liquid microextraction (VALLME) procedure was performed in the diluted extraction solution by using the ionic liquid of 1-hexyl-3-methylimidazolium hexafluorophosphate ([HMIM]PF 6 ) as the extraction solvent and Tween 20 as an emulsifier to enhance the dispersion of the water-immiscible ionic liquid into the aqueous phase. Parameters that affect the extraction have been investigated in both methods Under the optimum conditions, the limits of quantitation were 0.10 and 0.05mgkg -1 , respectively. And good linearity was achieved with the correlation coefficient higher than 0.9941. The relative recoveries ranged from 78.6 to 94.8% and 92.0 to 118.0% with the relative standard deviations (RSD) of 7.9-9.6% and 1.2-3.2%, respectively. Both methods were quick, simple and inexpensive. However, the ME-IL-VALLME method provides higher enrichment factor compared with conventional QuEChERS method. The ME-IL-VALLME method has a strong potential for the determination of difenoconazole in complex vegetable matrices with HPLC. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Surface Adsorption in Nonpolarizable Atomic Models.

PubMed

Whitmer, Jonathan K; Joshi, Abhijeet A; Carlton, Rebecca J; Abbott, Nicholas L; de Pablo, Juan J

2014-12-09

Many ionic solutions exhibit species-dependent properties, including surface tension and the salting-out of proteins. These effects may be loosely quantified in terms of the Hofmeister series, first identified in the context of protein solubility. Here, our interest is to develop atomistic models capable of capturing Hofmeister effects rigorously. Importantly, we aim to capture this dependence in computationally cheap "hard" ionic models, which do not exhibit dynamic polarization. To do this, we have performed an investigation detailing the effects of the water model on these properties. Though incredibly important, the role of water models in simulation of ionic solutions and biological systems is essentially unexplored. We quantify this via the ion-dependent surface attraction of the halide series (Cl, Br, I) and, in so doing, determine the relative importance of various hypothesized contributions to ionic surface free energies. Importantly, we demonstrate surface adsorption can result in hard ionic models combined with a thermodynamically accurate representation of the water molecule (TIP4Q). The effect observed in simulations of iodide is commensurate with previous calculations of the surface potential of mean force in rigid molecular dynamics and polarizable density-functional models. Our calculations are direct simulation evidence of the subtle but sensitive role of water thermodynamics in atomistic simulations.

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

Dicationic ionic liquid mediated fabrication of Au@Pt nanoparticles supported on reduced graphene oxide with highly catalytic activity for oxygen reduction and hydrogen evolution

NASA Astrophysics Data System (ADS)

Shi, Ya-Cheng; Chen, Sai-Sai; Feng, Jiu-Ju; Lin, Xiao-Xiao; Wang, Weiping; Wang, Ai-Jun

2018-05-01

Ionic liquids as templates or directing agents have attracted great attention for shaping-modulated synthesis of advanced nanomaterials. In this work, reduced graphene oxide supported uniform core-shell Au@Pt nanoparticles (Au@Pt NPs/rGO) were fabricated by a simple one-pot aqueous approach, using N-methylimidazolium-based dicationic ionic liquid (1,1-bis(3-methylimadazoilum-1-yl)butylene bromide, [C4(Mim)2]2Br) as the shape-directing agent. The morphology evolution, structural information and formation mechanism of Au@Pt NPs anchored on rGO were investigated by a series of characterization techniques. The obtained nanocomposites displayed superior electrocatalytic features toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) compared with commercial Pt/C catalyst. This approach provides a novel route for facile synthesis of nanocatalysts in fuel cells.

Ultralow percolation threshold of single walled carbon nanotube-epoxy composites synthesized via an ionic liquid dispersant/initiator

NASA Astrophysics Data System (ADS)

Watters, Arianna L.; Palmese, Giuseppe R.

2014-09-01

Uniform dispersion of single walled carbon nanotubes (SWNTs) in an epoxy was achieved by a streamlined mechano-chemical processing method. SWNT-epoxy composites were synthesized using a room temperature ionic liquid (IL) with an imidazolium cation and dicyanamide anion. The novel approach of using ionic liquid that behaves as a dispersant for SWNTs and initiator for epoxy polymerization greatly simplifies nanocomposite synthesis. The material was processed using simple and scalable three roll milling. The SWNT dispersion of the resultant composite was evaluated by electron microscopy and electrical conductivity measurements in conjunction with percolation theory. Processing conditions were optimized to achieve the lowest possible percolation threshold, 4.29 × 10-5 volume fraction SWNTs. This percolation threshold is among the best reported in literature yet it was obtained using a streamlined method that greatly simplifies processing.

Free Energies of Formation Measurements on Solid-State Electrochemical Cells

ERIC Educational Resources Information Center

Rollino, J. A.; Aronson, S.

1972-01-01

A simple experiment is proposed that can provide the student with some insight into the chemical properties of solids. It also demonstrates the relationship between the Gibbs free energy of formation of an ionic solid and the emf of an electrochemical cell. (DF)

Ionic structure in liquids confined by dielectric interfaces

NASA Astrophysics Data System (ADS)

Jing, Yufei; Jadhao, Vikram; Zwanikken, Jos W.; Olvera de la Cruz, Monica

2015-11-01

The behavior of ions in liquids confined between macromolecules determines the outcome of many nanoscale assembly processes in synthetic and biological materials such as colloidal dispersions, emulsions, hydrogels, DNA, cell membranes, and proteins. Theoretically, the macromolecule-liquid boundary is often modeled as a dielectric interface and an important quantity of interest is the ionic structure in a liquid confined between two such interfaces. The knowledge gleaned from the study of ionic structure in such models can be useful in several industrial applications, such as in the design of double-layer supercapacitors for energy storage and in the extraction of metal ions from wastewater. In this article, we compute the ionic structure in a model system of electrolyte confined by two planar dielectric interfaces using molecular dynamics simulations and liquid state theory. We explore the effects of high electrolyte concentrations, multivalent ions, dielectric contrasts, and external electric field on the ionic distributions. We observe the presence of non-monotonic ionic density profiles leading to a layered structure in the fluid which is attributed to the competition between electrostatic and steric (entropic) interactions. We find that thermal forces that arise from symmetry breaking at the interfaces can have a profound effect on the ionic structure and can oftentimes overwhelm the influence of the dielectric discontinuity. The combined effect of ionic correlations and inhomogeneous dielectric permittivity significantly changes the character of the effective interaction between the two interfaces.

Modeling an Excitable Biosynthetic Tissue with Inherent Variability for Paired Computational-Experimental Studies.

PubMed

Gokhale, Tanmay A; Kim, Jong M; Kirkton, Robert D; Bursac, Nenad; Henriquez, Craig S

2017-01-01

To understand how excitable tissues give rise to arrhythmias, it is crucially necessary to understand the electrical dynamics of cells in the context of their environment. Multicellular monolayer cultures have proven useful for investigating arrhythmias and other conduction anomalies, and because of their relatively simple structure, these constructs lend themselves to paired computational studies that often help elucidate mechanisms of the observed behavior. However, tissue cultures of cardiomyocyte monolayers currently require the use of neonatal cells with ionic properties that change rapidly during development and have thus been poorly characterized and modeled to date. Recently, Kirkton and Bursac demonstrated the ability to create biosynthetic excitable tissues from genetically engineered and immortalized HEK293 cells with well-characterized electrical properties and the ability to propagate action potentials. In this study, we developed and validated a computational model of these excitable HEK293 cells (called "Ex293" cells) using existing electrophysiological data and a genetic search algorithm. In order to reproduce not only the mean but also the variability of experimental observations, we examined what sources of variation were required in the computational model. Random cell-to-cell and inter-monolayer variation in both ionic conductances and tissue conductivity was necessary to explain the experimentally observed variability in action potential shape and macroscopic conduction, and the spatial organization of cell-to-cell conductance variation was found to not impact macroscopic behavior; the resulting model accurately reproduces both normal and drug-modified conduction behavior. The development of a computational Ex293 cell and tissue model provides a novel framework to perform paired computational-experimental studies to study normal and abnormal conduction in multidimensional excitable tissue, and the methodology of modeling variation can be applied to models of any excitable cell.

Nonlocal Poisson-Fermi double-layer models: Effects of nonuniform ion sizes on double-layer structure

NASA Astrophysics Data System (ADS)

Xie, Dexuan; Jiang, Yi

2018-05-01

This paper reports a nonuniform ionic size nonlocal Poisson-Fermi double-layer model (nuNPF) and a uniform ionic size nonlocal Poisson-Fermi double-layer model (uNPF) for an electrolyte mixture of multiple ionic species, variable voltages on electrodes, and variable induced charges on boundary segments. The finite element solvers of nuNPF and uNPF are developed and applied to typical double-layer tests defined on a rectangular box, a hollow sphere, and a hollow rectangle with a charged post. Numerical results show that nuNPF can significantly improve the quality of the ionic concentrations and electric fields generated from uNPF, implying that the effect of nonuniform ion sizes is a key consideration in modeling the double-layer structure.

Transferable atomistic model to describe the energetics of zirconia

NASA Astrophysics Data System (ADS)

Wilson, Mark; Schönberger, Uwe; Finnis, Michael W.

1996-10-01

We have investigated the energies of a number of phases of ZrO2 using models of an increasing degree of sophistication: the simple ionic model, the polarizable ion model, the compressible ion model, and finally a model including quadrupole polarizability of the oxygen ions. The three structures which are observed with increasing temperatures are monoclinic, tetragonal, and cubic (fluorite). Besides these we have studied some hypothetical structures which certain potentials erroneously predict or which occur in other oxides with this stoichiometry, e.g., the α-PbO2 structure and rutile. We have also performed ab initio density functional calculations with the full-potential linear combination of muffin-tin orbitals method to investigate the cubic-tetragonal distortion. A detailed comparison is made between the results using classical potentials, the experimental data, and our own and other ab initio results. The factors which stabilize the various structure are analyzed. We find the only genuinely transferable model is the one including compressible ions and anion polarizability to the quadrupole level.

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

A spectroscopic and thermodynamic study of porphyrin/DNA supramolecular assemblies.

PubMed Central

Pasternack, R F; Goldsmith, J I; Szép, S; Gibbs, E J

1998-01-01

Assemblies of trans-bis(N-methylpyridinium-4-yl)diphenylporphine ions on the surface of calf thymus DNA have been studied using several spectroscopic techniques: absorbance, circular dichroism, and resonance light scattering. The aggregation equilibrium can be treated as a two-state system-monomer and assembly-each bound to the nucleic acid template. The aggregate absorption spectrum in the Soret region is resolved into two bands of Lorentzian line shape, while the DNA-bound monomer spectrum in this region is composed of two Gaussian bands. The Beer-Lambert law is obeyed by both porphyrin forms. The assembly is also characterized by an extremely large, bisignate induced circular dichroism (CD) profile and by enhanced resonance light scattering (RLS). Both the CD and RLS intensities depend linearly on aggregate concentration. The RLS result is consistent with a model for the aggregates as being either of a characteristic size or of a fixed distribution of sizes, independent of total porphyrin concentration or ionic strength. Above threshold values of concentration and ionic strength, the mass action expression for the equilibrium has a particularly simple form: K' = cac-1; where cac is defined as the "critical assembly concentration."offe dependence of the cac upon temperature and ionic strength (NaCl) has been investigated at a fixed DNA concentration. The value of the cac scales as the inverse square of the sodium chloride concentration and, from temperature dependence studies, the aggregation process is shown to be exothermic. PMID:9675203

High-resolution mapping of molecules in an ionic liquid via scanning transmission electron microscopy.

PubMed

Miyata, Tomohiro; Mizoguchi, Teruyasu

2018-03-01

Understanding structures and spatial distributions of molecules in liquid phases is crucial for the control of liquid properties and to develop efficient liquid-phase processes. Here, real-space mapping of molecular distributions in a liquid was performed. Specifically, the ionic liquid 1-Ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (C2mimTFSI) was imaged using atomic-resolution scanning transmission electron microscopy. Simulations revealed network-like bright regions in the images that were attributed to the TFSI- anion, with minimal contributions from the C2mim+ cation. Simple visualization of the TFSI- distribution in the liquid sample was achieved by binarizing the experimental image.

Preoptimised VB: a fast method for the ground and excited states of ionic clusters I. Localised preoptimisation for (ArCO) +, (ArN 2) + and N 4+

NASA Astrophysics Data System (ADS)

Langenberg, J. H.; Bucur, I. B.; Archirel, P.

1997-09-01

We show that in the simple case of van der Waals ionic clusters, the optimisation of orbitals within VB can be easily simulated with the help of pseudopotentials. The procedure yields the ground and the first excited states of the cluster simultaneously. This makes the calculation of potential energy surfaces for tri- and tetraatomic clusters possible, with very acceptable computation times. We give potential curves for (ArCO) +, (ArN 2) + and N 4+. An application to the simulation of the SCF method is shown for Na +H 2O.

Ionic Liquids for Advanced Materials

DTIC Science & Technology

2008-12-01

optical clarity to completely opacity with increased amounts of ionic liquid . This transition was not previously observed in Nafion ® membranes swollen...1 IONIC LIQUIDS FOR ADVANCED MATERIALS Timothy E. Long, Sean M. Ramirez, Randy Heflin, Harry W. Gibson, Louis A. Madsen, Donald J. Leo, Nakhiah...is to develop a micromechanical model for the electrochemomechanical transduction mechanisms in newly synthesized ionic liquid polymers in order to

Impurity effects on ionic-liquid-based supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Kun; Lian, Cheng; Henderson, Douglas; Wu, Jianzhong

2017-02-01

Small amounts of an impurity may affect the key properties of an ionic liquid and such effects can be dramatically amplified when the electrolyte is under confinement. Here the classical density functional theory is employed to investigate the impurity effects on the microscopic structure and the performance of ionic-liquid-based electrical double-layer capacitors, also known as supercapacitors. Using a primitive model for ionic species, we study the effects of an impurity on the double layer structure and the integral capacitance of a room temperature ionic liquid in model electrode pores and find that an impurity strongly binding to the surface of a porous electrode can significantly alter the electric double layer structure and dampen the oscillatory dependence of the capacitance with the pore size of the electrode. Meanwhile, a strong affinity of the impurity with the ionic species affects the dependence of the integral capacitance on the pore size. Up to 30% increase in the integral capacitance can be achieved even at a very low impurity bulk concentration. By comparing with an ionic liquid mixture containing modified ionic species, we find that the cooperative effect of the bounded impurities is mainly responsible for the significant enhancement of the supercapacitor performance.

Viscoelastic Properties, Ionic Conductivity, and Materials Design Considerations for Poly(styrene-b-ethylene oxide-b-styrene)-Based Ion Gel Electrolytes

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

Zhang, Sipei; Lee, Keun Hyung; Sun, Jingru

2013-03-07

The viscoelastic properties and ionic conductivity of ion gels based on the self-assembly of a poly(styrene-b-ethylene oxide-b-styrene) (SOS) triblock copolymer (M{sub n,S} = 3 kDa, M{sub n,O} = 35 kDa) in the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMI][TFSA]) were investigated over the composition range of 10-50 wt % SOS and the temperature range of 25-160 C. The poly(styrene) (PS) end-blocks associate into micelles, whereas the poly(ethylene oxide) (PEO) midblocks are well-solvated by this ionic liquid. The ion gel with 10 wt % SOS melts at 54 C, with the longest relaxation time exhibiting a similar temperature dependence to that of themore » viscosity of bulk PS. However, the actual values of the gel relaxation time are more than 4 orders of magnitude larger than the relaxation time of bulk PS. This is attributed to the thermodynamic penalty of pulling PS end-blocks through the PEO/[EMI][TFSA] matrix. Ion gels with 20-50 wt % SOS do not melt and show two plateaus in the storage modulus over the temperature and frequency ranges measured. The one at higher frequencies is that of an entangled network of PEO strands with PS cross-links; the modulus displays a quadratic dependence on polymer weight fraction and agrees with the prediction of linear viscoelastic theory assuming half of the PEO chains are elastically effective. The frequency that separates the two plateaus, {omega}{sub c}, reflects the time scale of PS end-block pull-out. The other plateau at lower frequencies is that of a congested micelle solution with PS cores and PEO coronas, which has a power law dependence on domain spacing similar to diblock melts. The ionic conductivity of the ion gels is compared to PEO homopolymer solutions at similar polymer concentrations; the conductivity is reduced by a factor of 2.1 or less, decreases with increasing PS volume fraction, and follows predictions based on a simple obstruction model. Our collective results allow the formulation of basic design considerations for optimizing the mechanical properties, thermal stability, and ionic conductivity of these gels.« less

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

Mean ionic activity coefficients in aqueous NaCl solutions from molecular dynamics simulations

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

Mester, Zoltan; Panagiotopoulos, Athanassios Z., E-mail: azp@princeton.edu

The mean ionic activity coefficients of aqueous NaCl solutions of varying concentrations at 298.15 K and 1 bar have been obtained from molecular dynamics simulations by gradually turning on the interactions of an ion pair inserted into the solution. Several common non-polarizable water and ion models have been used in the simulations. Gibbs-Duhem equation calculations of the thermodynamic activity of water are used to confirm the thermodynamic consistency of the mean ionic activity coefficients. While the majority of model combinations predict the correct trends in mean ionic activity coefficients, they overestimate their values at high salt concentrations. The solubility predictionsmore » also suffer from inaccuracies, with all models underpredicting the experimental values, some by large factors. These results point to the need for further ion and water model development.« less

A STUDY OF BROADBAND FARADAY ROTATION AND POLARIZATION BEHAVIOR OVER 1.3–10 GHz IN 36 DISCRETE RADIO SOURCES

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

Anderson, C. S.; Gaensler, B. M.; Feain, I. J., E-mail: craiga@physics.usyd.edu.au

We present a broadband polarization analysis of 36 discrete polarized radio sources over a very broad, densely sampled frequency band. Our sample was selected on the basis of polarization behavior apparent in narrowband archival data at 1.4 GHz: half the sample shows complicated frequency-dependent polarization behavior (i.e., Faraday complexity) at these frequencies, while half shows comparatively simple behavior (i.e., they appear Faraday simple ). We re-observed the sample using the Australia Telescope Compact Array in full polarization, with 6 GHz of densely sampled frequency coverage spanning 1.3–10 GHz. We have devised a general polarization modeling technique that allows us tomore » identify multiple polarized emission components in a source, and to characterize their properties. We detect Faraday complex behavior in almost every source in our sample. Several sources exhibit particularly remarkable polarization behavior. By comparing our new and archival data, we have identified temporal variability in the broadband integrated polarization spectra of some sources. In a number of cases, the characteristics of the polarized emission components, including the range of Faraday depths over which they emit, their temporal variability, spectral index, and the linear extent of the source, allow us to argue that the spectropolarimetric data encode information about the magneto-ionic environment of active galactic nuclei themselves. Furthermore, the data place direct constraints on the geometry and magneto-ionic structure of this material. We discuss the consequences of restricted frequency bands on the detection and interpretation of polarization structures, and the implications for upcoming spectropolarimetric surveys.« less

Renormalized charge in a two-dimensional model of colloidal suspension from hypernetted chain approach.

PubMed

Camargo, Manuel; Téllez, Gabriel

2008-04-07

The renormalized charge of a simple two-dimensional model of colloidal suspension was determined by solving the hypernetted chain approximation and Ornstein-Zernike equations. At the infinite dilution limit, the asymptotic behavior of the correlation functions is used to define the effective interactions between the components of the system and these effective interactions were compared to those derived from the Poisson-Boltzmann theory. The results we obtained show that, in contrast to the mean-field theory, the renormalized charge does not saturate, but exhibits a maximum value and then decays monotonically as the bare charge increases. The results also suggest that beyond the counterion layer near to the macroion surface, the ionic cloud is not a diffuse layer which can be handled by means of the linearized theory, as the two-state model claims, but a more complex structure is settled by the correlations between microions.

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

Nonlocal Poisson-Fermi model for ionic solvent.

PubMed

Xie, Dexuan; Liu, Jinn-Liang; Eisenberg, Bob

2016-07-01

We propose a nonlocal Poisson-Fermi model for ionic solvent that includes ion size effects and polarization correlations among water molecules in the calculation of electrostatic potential. It includes the previous Poisson-Fermi models as special cases, and its solution is the convolution of a solution of the corresponding nonlocal Poisson dielectric model with a Yukawa-like kernel function. The Fermi distribution is shown to be a set of optimal ionic concentration functions in the sense of minimizing an electrostatic potential free energy. Numerical results are reported to show the difference between a Poisson-Fermi solution and a corresponding Poisson solution.

Understanding the effect models of ionic liquids in the synthesis of NH4-Dw and γ-AlOOH nanostructures and their conversion into porous γ-Al2O3.

PubMed

Duan, Xiaochuan; Kim, Tongil; Li, Di; Ma, Jianmin; Zheng, Wenjun

2013-05-03

Well-dispersed ammonium aluminum carbonate hydroxide (NH4-Dw) and γ-AlOOH nanostructures with controlled morphologies have been synthesized by employing an ionic-liquid-assisted hydrothermal process. The basic strategies that were used in this work were: 1) A controllable phase transition from NH4-Dw to γ-AlOOH could be realized by increasing the reaction temperature and 2) the morphological evolution of NH4-Dw and γ-AlOOH nanostructures could be influenced by the concentration of the ionic liquid. Based on these experimental results, the main objective of this work was to clarify the effect models of the ionic liquids on the synthesis of NH4-Dw and γ-AlOOH nanostructures, which could be divided into cationic- or anionic-dominant effect models, as determined by the different surface structures of the targets. Specifically, under the cationic-dominant regime, the ionic liquids mainly showed dispersion effects for the NH4-Dw nanostructures, whereas the anionic-dominant model could induce the self-assembly of the γ-AlOOH particles to form hierarchical structures. Under the guidance of the proposed models, the effect of the ionic liquids would be optimized by an appropriate choice of cations or anions, as well as by considering the different effect models with the substrate surface. We expect that such effect models between ionic liquids and the target products will be helpful for understanding and designing rational ionic liquids that contain specific functional groups, thus open up new opportunities for the synthesis of inorganic nanomaterials with new morphologies and improved properties. In addition, these as-prepared NH4-Dw and γ-AlOOH nanostructures were converted into porous γ-Al2O3 nanostructures by thermal decomposition, whilst preserving the same morphology. By using HRTEM and nitrogen-adsorption analysis, the obtained γ-Al2O3 samples were found to have excellent porous properties and, hence, may have applications in catalysis and adsorption. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystal at imperfect metals

PubMed Central

Kaiser, V.; Comtet, J.; Niguès, A.; Siria, A.; Coasne, B.; Bocquet, L.

2017-01-01

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon the approach by [Kornyshev et al. Zh. Eksp. Teor. Fiz., 78(3):1008–1019, 1980] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allow for an estimate of interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. A counterintuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length ℓTF, profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement. PMID:28436506

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.

Microfludic Device for Creating Ionic Strength Gradients over DNA Microarrays for Efficient DNA Melting Studies and Assay Development

PubMed Central

Petersen, Jesper; Poulsen, Lena; Birgens, Henrik; Dufva, Martin

2009-01-01

The development of DNA microarray assays is hampered by two important aspects: processing of the microarrays is done under a single stringency condition, and characteristics such as melting temperature are difficult to predict for immobilized probes. A technical solution to these limitations is to use a thermal gradient and information from melting curves, for instance to score genotypes. However, application of temperature gradients normally requires complicated equipment, and the size of the arrays that can be investigated is restricted due to heat dissipation. Here we present a simple microfluidic device that creates a gradient comprising zones of defined ionic strength over a glass slide, in which each zone corresponds to a subarray. Using this device, we demonstrated that ionic strength gradients function in a similar fashion as corresponding thermal gradients in assay development. More specifically, we noted that (i) the two stringency modulators generated melting curves that could be compared, (ii) both led to increased assay robustness, and (iii) both were associated with difficulties in genotyping the same mutation. These findings demonstrate that ionic strength stringency buffers can be used instead of thermal gradients. Given the flexibility of design of ionic gradients, these can be created over all types of arrays, and encompass an attractive alternative to temperature gradients, avoiding curtailment of the size or spacing of subarrays on slides associated with temperature gradients. PMID:19277213

Microfludic device for creating ionic strength gradients over DNA microarrays for efficient DNA melting studies and assay development.

PubMed

Petersen, Jesper; Poulsen, Lena; Birgens, Henrik; Dufva, Martin

2009-01-01

The development of DNA microarray assays is hampered by two important aspects: processing of the microarrays is done under a single stringency condition, and characteristics such as melting temperature are difficult to predict for immobilized probes. A technical solution to these limitations is to use a thermal gradient and information from melting curves, for instance to score genotypes. However, application of temperature gradients normally requires complicated equipment, and the size of the arrays that can be investigated is restricted due to heat dissipation. Here we present a simple microfluidic device that creates a gradient comprising zones of defined ionic strength over a glass slide, in which each zone corresponds to a subarray. Using this device, we demonstrated that ionic strength gradients function in a similar fashion as corresponding thermal gradients in assay development. More specifically, we noted that (i) the two stringency modulators generated melting curves that could be compared, (ii) both led to increased assay robustness, and (iii) both were associated with difficulties in genotyping the same mutation. These findings demonstrate that ionic strength stringency buffers can be used instead of thermal gradients. Given the flexibility of design of ionic gradients, these can be created over all types of arrays, and encompass an attractive alternative to temperature gradients, avoiding curtailment of the size or spacing of subarrays on slides associated with temperature gradients.

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.

A green ionic liquid-based vortex-forced MSPD method for the simultaneous determination of 5-HMF and iridoid glycosides from Fructus Corni by ultra-high performance liquid chromatography.

PubMed

Du, Kunze; Li, Jin; Bai, Yun; An, Mingrui; Gao, Xiu-Mei; Chang, Yan-Xu

2018-04-01

A simple and green ionic liquid-based vortex-forced matrix solid phase dispersion (IL-VFMSPD) method was presented to simultaneously extract 5-hydroxymethyl furfurol (5-HMF) and iridoid glycosides in Fructus Corni by ultra-high performance liquid chromatography. Ionic liquid was used as a green elution reagent in vortex-forced MSPD process. A few parameters such as the type of ionic liquid, the type of sorbent, ratio of sample to sorbent, the concentration and volume of ionic liquid, grinding time and vortex time, were investigated in detail and an orthogonal design experiment was introduced to confirm the best conditions in this procedure. With the final optimized method, the recoveries of the target compounds in Fructus Corni were in the range of 95.2-103% (RSD<5.0%) and the method displayed a good linearity within the range of 0.8-200 μg mL -1 for morroniside, sweroside, loganin, cornuside and 1.2-300 μg mL -1 for 5-HMF. The limits of detection ranged from 0.02 to 0.08 μg mL -1 for all compounds. The results showed that the newly established method was efficiently applied to extract and determine iridoid glycosides and 5-HMF for quality control of Fructus Corni. Copyright © 2017 Elsevier Ltd. All rights reserved.

Facile synthesis of poly(ionic liquid)-bonded magnetic nanospheres as a high-performance sorbent for the pretreatment and determination of phenolic compounds in water samples.

PubMed

Bi, Wentao; Wang, Man; Yang, Xiaodi; Row, Kyung Ho

2014-07-01

Poly(ionic liquid)-bonded magnetic nanospheres were easily synthesized and applied to the pretreatment and determination of phenolic compounds in water samples, which have detrimental effects on water quality and the health of living beings. The high affinity of poly(ionic liquid)s toward the target compounds as well as the magnetic behavior of Fe3 O4 were combined in this material to provide an efficient and simple magnetic solid-phase extraction approach. The adsorption behavior of the poly(ionic liquid)-bonded magnetic nanospheres was examined to optimize the synthesis. Different parameters affecting the magnetic solid-phase extraction of phenolic compounds were assessed in terms of adsorption and recovery. Under the optimal conditions, the proposed method showed excellent detection sensitivity with limits of detection in the range of 0.3-0.8 ng/mL and precision in the range of 1.2-3.3%. This method was also applied successfully to the analysis of real water samples; good spiked recoveries over the range of 82.5-99.2% were obtained. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Healing Natural Rubber with Tailorable Mechanical Properties Based on Ionic Supramolecular Hybrid Network.

PubMed

Xu, Chuanhui; Cao, Liming; Huang, Xunhui; Chen, Yukun; Lin, Baofeng; Fu, Lihua

2017-08-30

In most cases, the strength of self-healing supramolecular rubber based on noncovalent bonds is in the order of KPa, which is a challenge for their further applications. Incorporation of conventional fillers can effectively enhance the strength of rubbers, but usually accompanied by a sacrifice of self-healing capability due to that the filler system is independent of the reversible supramolecular network. In the present work, in situ reaction of methacrylic acid (MAA) and excess zinc oxide (ZnO) was realized in natural rubber (NR). Ionic cross-links in NR matrix were obtained by limiting the covalent cross-linking of NR molecules and allowing the in situ polymerization of MAA/ZnO. Because of the natural affinity between Zn 2+ ion-rich domains and ZnO, the residual nano ZnO participated in formation of a reversible ionic supramolecular hybrid network, thus having little obstructions on the reconstruction of ionic cross-links. Meanwhile, the well dispersed residual ZnO could tailor the mechanical properties of NR by changing the MAA/ZnO molar ratios. The present study thus provides a simple method to fabricate a new self-healing NR with tailorable mechanical properties that may have more potential applications.

Instrumentation for low noise nanopore-based ionic current recording under laser illumination

NASA Astrophysics Data System (ADS)

Roelen, Zachary; Bustamante, José A.; Carlsen, Autumn; Baker-Murray, Aidan; Tabard-Cossa, Vincent

2018-01-01

We describe a nanopore-based optofluidic instrument capable of performing low-noise ionic current recordings of individual biomolecules under laser illumination. In such systems, simultaneous optical measurements generally introduce significant parasitic noise in the electrical signal, which can severely reduce the instrument sensitivity, critically hindering the monitoring of single-molecule events in the ionic current traces. Here, we present design rules and describe simple adjustments to the experimental setup to mitigate the different noise sources encountered when integrating optical components to an electrical nanopore system. In particular, we address the contributions to the electrical noise spectra from illuminating the nanopore during ionic current recording and mitigate those effects through control of the illumination source and the use of a PDMS layer on the SiNx membrane. We demonstrate the effectiveness of our noise minimization strategies by showing the detection of DNA translocation events during membrane illumination with a signal-to-noise ratio of ˜10 at 10 kHz bandwidth. The instrumental guidelines for noise minimization that we report are applicable to a wide range of nanopore-based optofluidic systems and offer the possibility of enhancing the quality of synchronous optical and electrical signals obtained during single-molecule nanopore-based analysis.

Chiral separation of phenylalanine and tryptophan by capillary electrophoresis using a mixture of β-CD and chiral ionic liquid ([TBA] [L-ASP]) as selectors.

PubMed

Yujiao, Wu; Guoyan, Wang; Wenyan, Zhao; Hongfen, Zhang; Huanwang, Jing; Anjia, Chen

2014-05-01

In this paper, a simple, effective and green capillary electrophoresis separation and detection method was developed for the quantification of underivatized amino acids (dl-phenylalanine; dl-tryptophan) using β-Cyclodextrin and chiral ionic liquid ([TBA] [l-ASP]) as selectors. Separation parameters such as buffer concentrations, pH, β-CD and chiral ionic liquid concentrations and separation voltage were investigated for the enantioseparation in order to achieve the maximum possible resolution. A good separation was achieved in a background electrolyte composed of 15 mm sodium tetraborate, 5 mm β-CD and 4 mm chiral ionic liquid at pH 9.5, and an applied voltage of 10 kV. Under optimum conditions, linearity was achieved within concentration ranges from 0.08 to 10 µg/mL for the analytes with correlation coefficients from 0.9956 to 0.9998, and the analytes were separated in less than 6 min with efficiencies up to 970,000 plates/m. The proposed method was successfully applied to the determination of amino acid enantiomers in compound amino acids injections, such as 18AA-I, 18AA-II and 3AA.

An interatomic pair potential for cadmium selenide

NASA Astrophysics Data System (ADS)

Rabani, Eran

2002-01-01

We have developed a set of interatomic pair potentials for cadmium selenide based on a form similar to the Born-Mayer model. We show that this simple form of the pair potential, which has been used to describe the properties of alkali halides in the sixfold-coordinate structure, provides a realistic description of the properties of cadmium selenide in all three crystal structures: wurtzite, zinc blende, and rocksalt. Using the new pair potential we have studied the pressure-induced phase transition from the fourfold-coordinate wurtzite structure to the sixfold-coordinate rocksalt structure. The pressure transformation and the equation of state are in good agreement with experimental observations. Using the dispersion term in our pair potential we have also calculated the Hamaker constant for cadmium selenide within the framework of the original microscopic approach due to Hamaker. The results indicate that for ionic materials many-body terms that are included in the Lifshitz theory are well captured by the simple pair potential.

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(+).

Accurate and self-consistent procedure for determining pH in seawater desalination brines and its manifestation in reverse osmosis modeling.

PubMed

Nir, Oded; Marvin, Esra; Lahav, Ori

2014-11-01

Measuring and modeling pH in concentrated aqueous solutions in an accurate and consistent manner is of paramount importance to many R&D and industrial applications, including RO desalination. Nevertheless, unified definitions and standard procedures have yet to be developed for solutions with ionic strength higher than ∼0.7 M, while implementation of conventional pH determination approaches may lead to significant errors. In this work a systematic yet simple methodology for measuring pH in concentrated solutions (dominated by Na(+)/Cl(-)) was developed and evaluated, with the aim of achieving consistency with the Pitzer ion-interaction approach. Results indicate that the addition of 0.75 M of NaCl to NIST buffers, followed by assigning a new standard pH (calculated based on the Pitzer approach), enabled reducing measured errors to below 0.03 pH units in seawater RO brines (ionic strength up to 2 M). To facilitate its use, the method was developed to be both conceptually and practically analogous to the conventional pH measurement procedure. The method was used to measure the pH of seawater RO retentates obtained at varying recovery ratios. The results matched better the pH values predicted by an accurate RO transport model. Calibrating the model by the measured pH values enabled better boron transport prediction. A Donnan-induced phenomenon, affecting pH in both retentate and permeate streams, was identified and quantified. Copyright © 2014 Elsevier Ltd. All rights reserved.

Ionomer Design, Synthesis and Characterization for Ion-Conducting Energy Materials

NASA Astrophysics Data System (ADS)

Colby, Ralph H.

2013-03-01

For ionic actuators and battery separators, it is vital to utilize single-ion conductors that avoid the detrimental polarization of other ions; the commonly studied dual-ion conductors simply will not be used in the next generation of materials for these applications. Ab initio quantum chemistry calculations at 0 K in vacuum characterize ion interactions and ion solvation by various functional groups, allowing identification of constituents with weak interactions to be incorporated in ionomers for facile ion transport. Simple ideas for estimating the ion interactions and solvation at practical temperatures and dielectric constants are presented that indicate the rank ordering observed at 0 K in vacuum should be preserved. Hence, such ab initio calculations are useful for screening the plethora of combinations of polymer-ion, counterion and polar functional groups, to decide which are worthy of synthesis for new ionomers. Single-ion conducting ionomers are synthesized based on these calculations, with low glass transition temperatures (facile dynamics) to prepare ion-conducting membranes for ionic actuators and battery separators. Characterization by X-ray scattering, dielectric spectroscopy, NMR and linear viscoelasticity collectively develop a coherent picture of ionic aggregation and both counterion and polymer dynamics. Examples are shown of how ab initio calculations can be used to understand experimental observations of dielectric constant, glass transition temperature and conductivity of polymerized ionic liquids with counterions being either lithium, sodium, fluoride, hydroxide (for batteries) or bulky ionic liquids (for ionic actuators). This work was supported by the Department of Energy under Grant BES-DE-FG02-07ER46409.

Optimization of ionic conductivity in doped ceria

PubMed Central

Andersson, David A.; Simak, Sergei I.; Skorodumova, Natalia V.; Abrikosov, Igor A.; Johansson, Börje

2006-01-01

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy–dopant interactions, represented by association (binding) energies of vacancy–dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately. PMID:16478802

Optimization of ionic conductivity in doped ceria.

PubMed

Andersson, David A; Simak, Sergei I; Skorodumova, Natalia V; Abrikosov, Igor A; Johansson, Börje

2006-03-07

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy-dopant interactions, represented by association (binding) energies of vacancy-dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately.

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.

Mathematical modeling of electrical activity of uterine muscle cells.

PubMed

Rihana, Sandy; Terrien, Jeremy; Germain, Guy; Marque, Catherine

2009-06-01

The uterine electrical activity is an efficient parameter to study the uterine contractility. In order to understand the ionic mechanisms responsible for its generation, we aimed at building a mathematical model of the uterine cell electrical activity based upon the physiological mechanisms. First, based on the voltage clamp experiments found in the literature, we focus on the principal ionic channels and their cognate currents involved in the generation of this electrical activity. Second, we provide the methodology of formulations of uterine ionic currents derived from a wide range of electrophysiological data. The model is validated step by step by comparing simulated voltage-clamp results with the experimental ones. The model reproduces successfully the generation of single spikes or trains of action potentials that fit with the experimental data. It allows analyzing ionic channels implications. Likewise, the calcium-dependent conductance influences significantly the cellular oscillatory behavior.

Theoretical Thermodynamics of Mixtures at High Pressures

NASA Technical Reports Server (NTRS)

Hubbard, W. B.

1985-01-01

The development of an understanding of the chemistry of mixtures of metallic hydrogen and abundant, higher-z material such as oxygen, carbon, etc., is important for understanding of fundamental processes of energy release, differentiation, and development of atmospheric abundances in the Jovian planets. It provides a significant theoretical base for the interpretation of atmospheric elemental abundances to be provided by atmospheric entry probes in coming years. Significant differences are found when non-perturbative approaches such as Thomas-Fermi-Dirac (TFD) theory are used. Mapping of the phase diagrams of such binary mixtures in the pressure range from approx. 10 Mbar to approx. 1000 Mbar, using results from three-dimensional TFD calculations is undertaken. Derivation of a general and flexible thermodynamic model for such binary mixtures in the relevant pressure range was facilitated by the following breakthrough: there exists an accurate nd fairly simple thermodynamic representation of a liquid two-component plasma (TCP) in which the Helmholtz free energy is represented as a suitable linear combination of terms dependent only on density and terms which depend only on the ion coupling parameter. It is found that the crystal energies of mixtures of H-He, H-C, and H-O can be satisfactorily reproduced by the same type of model, except that an effective, density-dependent ionic charge must be used in place of the actual total ionic charge.

Single-coil properties and concentration effects for polyelectrolyte-like wormlike micelles: a Monte Carlo study

NASA Astrophysics Data System (ADS)

Cannavacciuolo, Luigi; Skov Pedersen, Jan; Schurtenberger, Peter

2002-03-01

Results of an extensive Monte Carlo (MC) study on both single and many semiflexible charged chains with excluded volume (EV) are summarized. The model employed has been tailored to mimic wormlike micelles in solution. Simulations have been performed at different ionic strengths of added salt, charge densities, chain lengths and volume fractions Φ, covering the dilute to concentrated regime. At infinite dilution the scattering functions can be fitted by the same fitting functions as for uncharged semiflexible chains with EV, provided that an electrostatic contribution bel is added to the bare Kuhn length. The scaling of bel is found to be more complex than the Odijk-Skolnick-Fixman predictions, and qualitatively compatible with more recent variational calculations. Universality in the scaling of the radius of gyration is found if all lengths are rescaled by the total Kuhn length. At finite concentrations, the simple model used is able to reproduce the structural peak in the scattering function S(q) observed in many experiments, as well as other properties of polyelectrolytes (PELs) in solution. Universal behaviour of the forward scattering S(0) is established after a rescaling of Φ. MC data are found to be in very good agreement with experimental scattering measurements with equilibrium PELs, which are giant wormlike micelles formed in mixtures of nonionic and ionic surfactants in dilute aqueous solution, with added salt.

Hydrogen bonding in a mixture of protic ionic liquids: a molecular dynamics simulation study.

PubMed

Paschek, Dietmar; Golub, Benjamin; Ludwig, Ralf

2015-04-07

We report results of molecular dynamics (MD) simulations characterising the hydrogen bonding in mixtures of two different protic ionic liquids sharing the same cation: triethylammonium-methylsulfonate (TEAMS) and triethylammonium-triflate (TEATF). The triethylammonium-cation acts as a hydrogen-bond donor, being able to donate a single hydrogen-bond. Both, the methylsulfonate- and the triflate-anions can act as hydrogen-bond acceptors, which can accept multiple hydrogen bonds via their respective SO3-groups. In addition, replacing a methyl-group in the methylsulfonate by a trifluoromethyl-group in the triflate significantly weakens the strength of a hydrogen bond from an adjacent triethylammonium cation to the oxygen-site in the SO3-group of the anion. Our MD simulations show that these subtle differences in hydrogen bond strength significantly affect the formation of differently-sized hydrogen-bonded aggregates in these mixtures as a function of the mixture-composition. Moreover, the reported hydrogen-bonded cluster sizes can be predicted and explained by a simple combinatorial lattice model, based on the approximate coordination number of the ions, and using statistical weights that mostly account for the fact that each anion can only accept three hydrogen bonds.

Impurity effects on ionic-liquid-based supercapacitors

DOE PAGES

Liu, Kun; Lian, Cheng; Henderson, Douglas; ...

2016-12-27

Small amounts of an impurity may affect the key properties of an ionic liquid and such effects can be dramatically amplified when the electrolyte is under confinement. Here the classical density functional theory is employed to investigate the impurity effects on the microscopic structure and the performance of ionic-liquid-based electrical double-layer capacitors, also known as supercapacitors. Using a primitive model for ionic species, we study the effects of an impurity on the double layer structure and the integral capacitance of a room temperature ionic liquid in model electrode pores and find that an impurity strongly binding to the surface ofmore » a porous electrode can significantly alter the electric double layer structure and dampen the oscillatory dependence of the capacitance with the pore size of the electrode. Meanwhile, a strong affinity of the impurity with the ionic species affects the dependence of the integral capacitance on the pore size. Up to 30% increase in the integral capacitance can be achieved even at a very low impurity bulk concentration. As a result, by comparing with an ionic liquid mixture containing modified ionic species, we find that the cooperative effect of the bounded impurities is mainly responsible for the significant enhancement of the supercapacitor performance.« less

Deposition and reentrainment of Brownian particles in porous media under unfavorable chemical conditions: some concepts and applications.

PubMed

Hahn, Melinda W; O'Meliae, Charles R

2004-01-01

The deposition and reentrainment of particles in porous media have been examined theoretically and experimentally. A Brownian Dynamics/Monte Carlo (MC/BD) model has been developed that simulates the movement of Brownian particles near a collector under "unfavorable" chemical conditions and allows deposition in primary and secondary minima. A simple Maxwell approach has been used to estimate particle attachment efficiency by assuming deposition in the secondary minimum and calculating the probability of reentrainment. The MC/BD simulations and the Maxwell calculations support an alternative view of the deposition and reentrainment of Brownian particles under unfavorable chemical conditions. These calculations indicate that deposition into and subsequent release from secondary minima can explain reported discrepancies between classic model predictions that assume irreversible deposition in a primary well and experimentally determined deposition efficiencies that are orders of magnitude larger than Interaction Force Boundary Layer (IFBL) predictions. The commonly used IFBL model, for example, is based on the notion of transport over an energy barrier into the primary well and does not address contributions of secondary minimum deposition. A simple Maxwell model based on deposition into and reentrainment from secondary minima is much more accurate in predicting deposition rates for column experiments at low ionic strengths. It also greatly reduces the substantial particle size effects inherent in IFBL models, wherein particle attachment rates are predicted to decrease significantly with increasing particle size. This view is consistent with recent work by others addressing the composition and structure of the first few nanometers at solid-water interfaces including research on modeling water at solid-liquid interfaces, surface speciation, interfacial force measurements, and the rheological properties of concentrated suspensions. It follows that deposition under these conditions will depend on the depth of the secondary minimum and that some transition between secondary and primary depositions should occur when the height of the energy barrier is on the order of several kT. When deposition in secondary minima predominates, observed deposition should increase with increasing ionic strength, particle size, and Hamaker constant. Since an equilibrium can develop between bound and bulk particles, the collision efficiency [alpha] can no longer be considered a constant for a given physical and chemical system. Rather, in many cases it can decrease over time until it eventually reaches zero as equilibrium is established.

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

Average-atom model for two-temperature states and ionic transport properties of aluminum in the warm dense matter regime

NASA Astrophysics Data System (ADS)

Hou, Yong; Fu, Yongsheng; Bredow, Richard; Kang, Dongdong; Redmer, Ronald; Yuan, Jianmin

2017-03-01

The average-atom model combined with the hyper-netted chain approximation is an efficient tool for electronic and ionic structure calculations for warm dense matter. Here we generalize this method in order to describe non-equilibrium states with different electron and ion temperature as produced in laser-matter interactions on ultra-short time scales. In particular, the electron-ion and ion-ion correlation effects are considered when calculating the electron structure. We derive an effective ion-ion pair-potential using the electron densities in the framework of temperature-depended density functional theory. Using this ion-ion potential we perform molecular dynamics simulations in order to determine the ionic transport properties such as the ionic diffusion coefficient and the shear viscosity through the ionic velocity autocorrelation functions.

Enhanced ionic conductivity of AgI nanowires/AAO composites fabricated by a simple approach.

PubMed

Liu, Li-Feng; Lee, Seung-Woo; Li, Jing-Bo; Alexe, Marin; Rao, Guang-Hui; Zhou, Wei-Ya; Lee, Jae-Jong; Lee, Woo; Gösele, Ulrich

2008-12-10

AgI nanowires/anodic aluminum oxide (AgI NWs/AAO) composites have been fabricated by a simple approach, which involves the thermal melting of AgI powders on the surface of the AAO membrane, followed by the infiltration of the molten AgI inside the nanochannels. As-prepared AgI nanowires have corrugated outer surfaces and are polycrystalline according to scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. X-ray diffraction (XRD) shows that a considerable amount of 7H polytype AgI exists in the composites, which is supposed to arise from the interfacial interactions between the embedded AgI and the alumina. AC conductivity measurements for the AgI nanowires/AAO composites exhibit a notable conductivity enhancement by three orders of magnitude at room temperature compared with that of pristine bulk AgI. Furthermore, a large conductivity hysteresis and abnormal conductivity transitions were observed in the temperature-dependent conductivity measurements, from which an ionic conductivity as high as 8.0 × 10(2) Ω(-1) cm(-1) was obtained at around 70 °C upon cooling. The differential scanning calorimetry (DSC) result demonstrates a similar phase transition behavior as that found in the AC conductivity measurements. The enhanced ionic conductivity, as well as the abnormal phase transitions, can be explained in terms of the existence of the highly conducting 7H polytype AgI and the formation of well-defined conduction paths in the composites.

Ionic liquid catalyzed one-pot multi-component synthesis, characterization and antibacterial activity of novel chromeno[2,3-d]pyrimidin-8-amine derivatives

NASA Astrophysics Data System (ADS)

Kanakaraju, Sankari; Prasanna, Bethanamudi; Basavoju, Srinivas; Chandramouli, G. V. P.

2012-06-01

An efficient, simple and convenient method for the one-pot multi-component synthesis of novel chromeno[2,3-d]pyrimidin-8-amine derivatives has been accomplished by starting from α-naphthol, aryl aldehydes, malononitrile and NH4Cl. The reaction has been catalyzed by 1-butyl-3-methylimidazolium tetrafluoroborate [bmim]BF4 ionic liquid. The newly synthesized compounds were characterized by IR, 1H NMR, 13C NMR, mass spectra, and elemental analysis. The structure of compound 4a was confirmed by single-crystal X-ray diffraction. All the synthesized compounds were evaluated for their in vitro antibacterial activity.

Coulomb interactions in charged fluids.

PubMed

Vernizzi, Graziano; Guerrero-García, Guillermo Iván; de la Cruz, Monica Olvera

2011-07-01

The use of Ewald summation schemes for calculating long-range Coulomb interactions, originally applied to ionic crystalline solids, is a very common practice in molecular simulations of charged fluids at present. Such a choice imposes an artificial periodicity which is generally absent in the liquid state. In this paper we propose a simple analytical O(N(2)) method which is based on Gauss's law for computing exactly the Coulomb interaction between charged particles in a simulation box, when it is averaged over all possible orientations of a surrounding infinite lattice. This method mitigates the periodicity typical of crystalline systems and it is suitable for numerical studies of ionic liquids, charged molecular fluids, and colloidal systems with Monte Carlo and molecular dynamics simulations.

Steric effects in the dynamics of electrolytes at large applied voltages. II. Modified Poisson-Nernst-Planck equations.

PubMed

Kilic, Mustafa Sabri; Bazant, Martin Z; Ajdari, Armand

2007-02-01

In situations involving large potentials or surface charges, the Poisson-Boltzman (PB) equation has shortcomings because it neglects ion-ion interactions and steric effects. This has been widely recognized by the electrochemistry community, leading to the development of various alternative models resulting in different sets "modified PB equations," which have had at least qualitative success in predicting equilibrium ion distributions. On the other hand, the literature is scarce in terms of descriptions of concentration dynamics in these regimes. Here, adapting strategies developed to modify the PB equation, we propose a simple modification of the widely used Poisson-Nernst-Planck (PNP) equations for ionic transport, which at least qualitatively accounts for steric effects. We analyze numerical solutions of these modified PNP equations on the model problem of the charging of a simple electrolyte cell, and compare the outcome to that of the standard PNP equations. Finally, we repeat the asymptotic analysis of Bazant, Thornton, and Ajdari [Phys. Rev. E 70, 021506 (2004)] for this new system of equations to further document the interest and limits of validity of the simpler equivalent electrical circuit models introduced in Part I [Kilic, Bazant, and Ajdari, Phys. Rev. E 75, 021502 (2007)] for such problems.

Two-Term Asymptotic Approximation of a Cardiac Restitution Curve*

PubMed Central

Cain, John W.; Schaeffer, David G.

2007-01-01

If spatial extent is neglected, ionic models of cardiac cells consist of systems of ordinary differential equations (ODEs) which have the property of excitability, i.e., a brief stimulus produces a prolonged evolution (called an action potential in the cardiac context) before the eventual return to equilibrium. Under repeated stimulation, or pacing, cardiac tissue exhibits electrical restitution: the steady-state action potential duration (APD) at a given pacing period B shortens as B is decreased. Independent of ionic models, restitution is often modeled phenomenologically by a one-dimensional mapping of the form APDnext = f(B – APDprevious). Under some circumstances, a restitution function f can be derived as an asymptotic approximation to the behavior of an ionic model. In this paper, extending previous work, we derive the next term in such an asymptotic approximation for a particular ionic model consisting of two ODEs. The two-term approximation exhibits excellent quantitative agreement with the actual restitution curve, whereas the leading-order approximation significantly underestimates actual APD values. PMID:18080006

Going full circle: phase-transition thermodynamics of ionic liquids.

PubMed

Preiss, Ulrich; Verevkin, Sergey P; Koslowski, Thorsten; Krossing, Ingo

2011-05-27

We present the full enthalpic phase transition cycle for ionic liquids (ILs) as examples of non-classical salts. The cycle was closed for the lattice, solvation, dissociation, and vaporization enthalpies of 30 different ILs, relying on as much experimental data as was available. High-quality dissociation enthalpies were calculated at the G3 MP2 level. From the cycle, we could establish, for the first time, the lattice and solvation enthalpies of ILs with imidazolium ions. For vaporization, lattice, and dissociation enthalpies, we also developed new prediction methods in the course of our investigations. Here, as only single-ion values need to be calculated and the tedious optimization of an ion pair can be circumvented, the computational time is short. For the vaporization enthalpy, a very simple approach was found, using a surface term and the calculated enthalpic correction to the total gas-phase energy. For the lattice enthalpy, the most important constituent proved to be the calculated conductor-like screening model (COSMO) solvation enthalpy in the ideal electric conductor. A similar model was developed for the dissociation enthalpy. According to our assessment, the typical error of the lattice enthalpy would be 9.4 kJ mol(-1), which is less than half the deviation we get when using the (optimized) Kapustinskii equation or the recent volume-based thermodynamics (VBT) theory. In contrast, the non-optimized VBT formula gives lattice enthalpies 20 to 140 kJ mol(-1) lower than the ones we assessed in the cycle, because of the insufficient description of dispersive interactions. Our findings show that quantum-chemical calculations can greatly improve the VBT approaches, which were parameterized for simple, inorganic salts with ideally point-shaped charges. In conclusion, we suggest the term "augmented VBT", or "aVBT", to describe this kind of theoretical approach. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Validity of the Electrodiffusion Model for Calculating Conductance of Simple Ion Channels.

PubMed

Pohorille, Andrew; Wilson, Michael A; Wei, Chenyu

2017-04-20

We examine the validity and utility of the electrodiffusion (ED) equation, i.e., the generalized Nernst-Planck equation, to characterize, in combination with molecular dynamics, the electrophysiological behavior of simple ion channels. As models, we consider three systems-two naturally occurring channels formed by α-helical bundles of peptaibols, trichotoxin, and alamethicin, and a synthetic, hexameric channel, formed by a peptide that contains only leucine and serine. All these channels mediate transport of potassium and chloride ions. Starting with equilibrium properties, such as the potential of mean force experienced by an ion traversing the channel and diffusivity, obtained from molecular dynamics simulations, the ED equation can be used to determine the full current-voltage dependence with modest or no additional effort. The potential of mean force can be obtained not only from equilibrium simulations, but also, with comparable accuracy, from nonequilibrium simulations at a single voltage. The main assumptions underlying the ED equation appear to hold well for the channels and voltages studied here. To expand the utility of the ED equation, we examine what are the necessary and sufficient conditions for Ohmic and nonrectifying behavior and relate deviations from this behavior to the shape of the ionic potential of mean force.

Developing a multipoint titration method with a variable dose implementation for anaerobic digestion monitoring.

PubMed

Salonen, K; Leisola, M; Eerikäinen, T

2009-01-01

Determination of metabolites from an anaerobic digester with an acid base titration is considered as superior method for many reasons. This paper describes a practical at line compatible multipoint titration method. The titration procedure was improved by speed and data quality. A simple and novel control algorithm for estimating a variable titrant dose was derived for this purpose. This non-linear PI-controller like algorithm does not require any preliminary information from sample. Performance of this controller is superior compared to traditional linear PI-controllers. In addition, simplification for presenting polyprotic acids as a sum of multiple monoprotic acids is introduced along with a mathematical error examination. A method for inclusion of the ionic strength effect with stepwise iteration is shown. The titration model is presented with matrix notations enabling simple computation of all concentration estimates. All methods and algorithms are illustrated in the experimental part. A linear correlation better than 0.999 was obtained for both acetate and phosphate used as model compounds with slopes of 0.98 and 1.00 and average standard deviations of 0.6% and 0.8%, respectively. Furthermore, insensitivity of the presented method for overlapping buffer capacity curves was shown.

Solubility of KF and NaCl in water by molecular simulation.

PubMed

Sanz, E; Vega, C

2007-01-07

The solubility of two ionic salts, namely, KF and NaCl, in water has been calculated by Monte Carlo molecular simulation. Water has been modeled with the extended simple point charge model (SPC/E), ions with the Tosi-Fumi model and the interaction between water and ions with the Smith-Dang model. The chemical potential of the solute in the solution has been computed as the derivative of the total free energy with respect to the number of solute particles. The chemical potential of the solute in the solid phase has been calculated by thermodynamic integration to an Einstein crystal. The solubility of the salt has been calculated as the concentration at which the chemical potential of the salt in the solution becomes identical to that of the pure solid. The methodology used in this work has been tested by reproducing the results for the solubility of KF determined previously by Ferrario et al. [J. Chem. Phys. 117, 4947 (2002)]. For KF, it was found that the solubility of the model is only in qualitative agreement with experiment. The variation of the solubility with temperature for KF has also been studied. For NaCl, the potential model used predicts a solubility in good agreement with the experimental value. The same is true for the hydration chemical potential at infinite dilution. Given the practical importance of solutions of NaCl in water the model used in this work, whereas simple, can be of interest for future studies.

Stabilizing lithium metal using ionic liquids for long-lived batteries

PubMed Central

Basile, A.; Bhatt, A. I.; O'Mullane, A. P.

2016-01-01

Suppressing dendrite formation at lithium metal anodes during cycling is critical for the implementation of future lithium metal-based battery technology. Here we report that it can be achieved via the facile process of immersing the electrodes in ionic liquid electrolytes for a period of time before battery assembly. This creates a durable and lithium ion-permeable solid–electrolyte interphase that allows safe charge–discharge cycling of commercially applicable Li|electrolyte|LiFePO4 batteries for 1,000 cycles with Coulombic efficiencies >99.5%. The tailored solid–electrolyte interphase is prepared using a variety of electrolytes based on the N-propyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide room temperature ionic liquid containing lithium salts. The formation is both time- and lithium salt-dependant, showing dynamic morphology changes, which when optimized prevent dendrite formation and consumption of electrolyte during cycling. This work illustrates that a simple, effective and industrially applicable lithium metal pretreatment process results in a commercially viable cycle life for a lithium metal battery. PMID:27292652

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).

Trace detection of oxygen--ionic liquids in gas sensor design.

PubMed

Baltes, N; Beyle, F; Freiner, S; Geier, F; Joos, M; Pinkwart, K; Rabenecker, P

2013-11-15

This paper presents a novel electrochemical membrane sensor on basis of ionic liquids for trace analysis of oxygen in gaseous atmospheres. The faradaic response currents for the reduction of oxygen which were obtained by multiple-potential-step-chronoamperometry could be used for real time detection of oxygen down to concentrations of 30 ppm. The theoretical limit of detection was 5 ppm. The simple, non-expensive sensors varied in electrolyte composition and demonstrated a high sensitivity, a rapid response time and an excellent reproducibility at room temperature. Some of them were continuously used for at least one week and first results promise good long term stability. Voltammetric, impedance and oxygen detection studies at temperatures up to 200 °C (in the presence and absence of humidity and CO2) revealed also the limitations of certain ionic liquids for some electrochemical high temperature applications. Application areas of the developed sensors are control and analysis processes of non oxidative and oxygen free atmospheres. Copyright © 2013 Elsevier B.V. All rights reserved.

Comparison of Dilute Acid and Ionic Liquid Pretreatment of Switchgrass: Biomass Recalcitrance, Delignification and Enzymatic Saccharification

USDA-ARS?s Scientific Manuscript database

The efficiency of two biomass pretreatment technologies, dilute acid hydrolysis and dissolution in an ionic liquid, are compared in terms of delignification, saccharification efficiency and saccharide yields with switchgrass serving as a model bioenergy crop. When subject to ionic liquid pretreatme...

Ionic interactions in biological and physical systems: a variational treatment.

PubMed

Eisenberg, Bob

2013-01-01

Chemistry is about chemical reactions. Chemistry is about electrons changing their configurations as atoms and molecules react. Chemistry has for more than a century studied reactions as if they occurred in ideal conditions of infinitely dilute solutions. But most reactions occur in salt solutions that are not ideal. In those solutions everything (charged) interacts with everything else (charged) through the electric field, which is short and long range extending to the boundaries of the system. Mathematics has recently been developed to deal with interacting systems of this sort. The variational theory of complex fluids has spawned the theory of liquid crystals (or vice versa). In my view, ionic solutions should be viewed as complex fluids, particularly in the biological and engineering context. In both biology and electrochemistry ionic solutions are mixtures highly concentrated (to approximately 10 M) where they are most important, near electrodes, nucleic ids, proteins, active sites of enzymes, and ionic channels. Ca2+ is always involved in biological solutions because the concentration (really free energy per mole) of Ca2+ in a particular location is the signal that controls many biological functions. Such interacting systems are not simple fluids, and it is no wonder that analysis of interactions, such as the Hofmeister series, rooted in that tradition has not succeeded as one would hope. Here, we present a variational treatment of ard spheres in a frictional dielectric with the hope that such a treatment of an lectrolyte as a complex fluid will be productive. The theory automatically extends to spatially nonuniform boundary conditions and the nonequilibrium systems and flows they produce. The theory is unavoidably self-consistent since differential equations are derived (not assumed) from models of (Helmholtz free) nergy and dissipation of the electrolyte. The origin of the Hofmeister series is (in my view) an inverse problem that becomes well posed when enough data from disjoint experimental traditions are interpreted with a self-consistent theory.

Measurements and theoretical interpretation of points of zero charge/potential of BSA protein.

PubMed

Salis, Andrea; Boström, Mathias; Medda, Luca; Cugia, Francesca; Barse, Brajesh; Parsons, Drew F; Ninham, Barry W; Monduzzi, Maura

2011-09-20

The points of zero charge/potential of proteins depend not only on pH but also on how they are measured. They depend also on background salt solution type and concentration. The protein isoelectric point (IEP) is determined by electrokinetical measurements, whereas the isoionic point (IIP) is determined by potentiometric titrations. Here we use potentiometric titration and zeta potential (ζ) measurements at different NaCl concentrations to study systematically the effect of ionic strength on the IEP and IIP of bovine serum albumin (BSA) aqueous solutions. It is found that high ionic strengths produce a shift of both points toward lower (IEP) and higher (IIP) pH values. This result was already reported more than 60 years ago. At that time, the only available theory was the purely electrostatic Debye-Hückel theory. It was not able to predict the opposite trends of IIP and IEP with ionic strength increase. Here, we extend that theory to admit both electrostatic and nonelectrostatic (NES) dispersion interactions. The use of a modified Poisson-Boltzmann equation for a simple model system (a charge regulated spherical colloidal particle in NaCl salt solutions), that includes these ion specific interactions, allows us to explain the opposite trends observed for isoelectric point (zero zeta potential) and isoionic point (zero protein charge) of BSA. At higher concentrations, an excess of the anion (with stronger NES interactions than the cation) is adsorbed at the surface due to an attractive ionic NES potential. This makes the potential relatively more negative. Consequently, the IEP is pushed toward lower pH. But the charge regulation condition means that the surface charge becomes relatively more positive as the surface potential becomes more negative. Consequently, the IIP (measuring charge) shifts toward higher pH as concentration increases, in the opposite direction from the IEP (measuring potential). © 2011 American Chemical Society

A simple and green pathway toward nitrogen and sulfur dual doped hierarchically porous carbons from ionic liquids for oxygen reduction

NASA Astrophysics Data System (ADS)

Cui, Zhentao; Wang, Shuguang; Zhang, Yihe; Cao, Minhua

2014-08-01

We for the first time demonstrate a simple and green approach to heteroatom (N and S) co-doped hierarchically porous carbons (N-S-HC) with high surface area by using one organic ionic liquid as nitrogen, sulfur and carbon sources and the eutectic salt as templating. The resultant dual-doped N-S-HC catalysts exhibit significantly enhanced electrocatalytic activity, long-term operation stability, and tolerance to crossover effect compared to commercial Pt/C for oxygen reduction reactions (ORR) in alkaline environment. The excellent electrocatalytic performance may be attributed to the synergistic effects, which includes more catalytic sites for ORR provided by N-S heteroatom doping and high electron transfer rate provided by hierarchically porous structure. The DFT calculations reveal that the dual doping of S and N atoms lead to the redistribution of spin and charge densities, which may be responsible for the formation of a large number of carbon atom active sites. This newly developed approach may supply an efficient platform for the synthesis of a series of heteroatom doped carbon materials for fuel cells and other applications.

Exact Analytic Result of Contact Value for the Density in a Modified Poisson-Boltzmann Theory of an Electrical Double Layer.

PubMed

Lou, Ping; Lee, Jin Yong

2009-04-14

For a simple modified Poisson-Boltzmann (SMPB) theory, taking into account the finite ionic size, we have derived the exact analytic expression for the contact values of the difference profile of the counterion and co-ion, as well as of the sum (density) and product profiles, near a charged planar electrode that is immersed in a binary symmetric electrolyte. In the zero ionic size or dilute limit, these contact values reduce to the contact values of the Poisson-Boltzmann (PB) theory. The analytic results of the SMPB theory, for the difference, sum, and product profiles were compared with the results of the Monte-Carlo (MC) simulations [ Bhuiyan, L. B.; Outhwaite, C. W.; Henderson, D. J. Electroanal. Chem. 2007, 607, 54 ; Bhuiyan, L. B.; Henderson, D. J. Chem. Phys. 2008, 128, 117101 ], as well as of the PB theory. In general, the analytic expression of the SMPB theory gives better agreement with the MC data than the PB theory does. For the difference profile, as the electrode charge increases, the result of the PB theory departs from the MC data, but the SMPB theory still reproduces the MC data quite well, which indicates the importance of including steric effects in modeling diffuse layer properties. As for the product profile, (i) it drops to zero as the electrode charge approaches infinity; (ii) the speed of the drop increases with the ionic size, and these behaviors are in contrast with the predictions of the PB theory, where the product is identically 1.

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

Petach, Trevor A.; Reich, Konstantin V.; Zhang, Xiao

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.

Generation Mechanism of Alternans in Luo-Rudy Model

NASA Astrophysics Data System (ADS)

Kitajima, Hiroyuki; Ioka, Eri; Yazawa, Toru

Electrical alternans is the alternating amplitude from beat to beat in the action potential of the cardiac cell. It has been associated with ventricular arrhythmias in many clinical studies; however, its dynamical mechanisms remain unknown. The reason is that we do not have realistic network models of the heart system. Recently, Yazawa clarified the network structure of the heart and the central nerve system in the crustacean heart. In this study, we construct a simple model of the heart system based on Yazawa’s experimental data. Using this model, we clarify that two parameters (the conductance of sodium ions and free concentration of potassium ions in the extracellular compartment) play the key roles of generating alternans. In particular, we clarify that the inactivation gate of the time-independent potassium channel is the most important parameter. Moreover, interaction between the membrane potential and potassium ionic currents is significant for generating alternate rhythms. This result indicates that if the muscle cell has problems such as channelopathies, there is great risk of generating alternans.

Effect of surface bilayer charges on the magnetic field around ionic channels

NASA Astrophysics Data System (ADS)

Gomes Soares, Marília Amável; Cortez, Celia Martins; Oliveira Cruz, Frederico Alan de; Silva, Dilson

2017-01-01

In this work, we present a physic-mathematical model for representing the ion transport through membrane channels, in special Na+ and K+-channels, and discuss the influence of surface bilayer charges on the magnetic field behavior around the ionic current. The model was composed of a set of equations, including: a nonlinear differential Poisson-Boltzmann equation which usually allows to estimate the surface potentials and electric potential profile across membrane; equations for the ionic flux through channel and the ionic current density based on Armstrong's model for Na+ and K+ permeability and other Physics concepts; and a magnetic field expression derived from the classical Ampère equation. Results from computational simulations using the finite element method suggest that the ionic permeability is strongly dependent of surface bilayer charges, the current density through a K+-channel is very less sensible to temperature changes than the current density through a Na+- channel, active Na+-channels do not directly interfere with the K+-channels around, and vice-versa, since the magnetic perturbation generated by an active channel is of short-range.

A Spectral-SAR Model for the Anionic-Cationic Interaction in Ionic Liquids: Application to Vibrio fischeri Ecotoxicity

PubMed Central

Lacrămă, Ana-Maria; Putz, Mihai V.; Ostafe, Vasile

2007-01-01

Within the recently launched the spectral-structure activity relationship (S-SAR) analysis, the vectorial anionic-cationic model of a generic ionic liquid is proposed, along with the associated algebraic correlation factor in terms of the measured and predicted activity norms. The reliability of the present scheme is tested by assessing the Hansch factors, i.e. lipophylicity, polarizability and total energy, to predict the ecotoxicity endpoints of wide types of ionic liquids with ammonium, pyridinium, phosphonium, choline and imidazolium cations on the aquatic bacteria Vibrio fischeri. The results, while confirming the cationic dominant influence when only lipophylicity is considered, demonstrate that the anionic effect dominates all other more specific interactions. It was also proved that the S-SAR vectorial model predicts considerably higher activity for the ionic liquids than for its anionic and cationic subsystems separately, in all considered cases. Moreover, through applying the least norm-correlation path principle, the complete toxicological hierarchies are presented, unfolding the ecological rules of combined cationic and anionic influences in ionic liquid toxicity.

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

PubMed

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

2015-04-21

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

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.

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

Contributions of the Model of Modelling Diagram to the Learning of Ionic Bonding: Analysis of a Case Study

ERIC Educational Resources Information Center

Mendonca, Paula Cristina Cardoso; Justi, Rosaria

2011-01-01

Current proposals for science education recognise the importance of students' involvement in activities aimed at favouring the understanding of science as a human, dynamic and non-linear construct. Modelling-based teaching is one of the alternatives through which to address such issues. Modelling-based teaching activities for ionic bonding were…

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

PubMed

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

2016-09-01

Predictive QSAR models for the inhibitors of B. subtilis and Ps. aeruginosa among imidazolium-based ionic liquids were developed using literary data. The regression QSAR models were created through Artificial Neural Network and k-nearest neighbor procedures. The classification QSAR models were constructed using WEKA-RF (random forest) method. The predictive ability of the models was tested by fivefold cross-validation; giving q(2) = 0.77-0.92 for regression models and accuracy 83-88% for classification models. Twenty synthesized samples of 1,3-dialkylimidazolium ionic liquids with predictive value of activity level of antimicrobial potential were evaluated. For all asymmetric 1,3-dialkylimidazolium ionic liquids, only compounds containing at least one radical with alkyl chain length of 12 carbon atoms showed high antibacterial activity. However, the activity of symmetric 1,3-dialkylimidazolium salts was found to have opposite relationship with the length of aliphatic radical being maximum for compounds based on 1,3-dioctylimidazolium cation. The obtained experimental results suggested that the application of classification QSAR models is more accurate for the prediction of activity of new imidazolium-based ILs as potential antibacterials. © 2016 John Wiley & Sons A/S.

Boundary control of bidomain equations with state-dependent switching source functions in the ionic model

NASA Astrophysics Data System (ADS)

Chamakuri, Nagaiah; Engwer, Christian; Kunisch, Karl

2014-09-01

Optimal control for cardiac electrophysiology based on the bidomain equations in conjunction with the Fenton-Karma ionic model is considered. This generic ventricular model approximates well the restitution properties and spiral wave behavior of more complex ionic models of cardiac action potentials. However, it is challenging due to the appearance of state-dependent discontinuities in the source terms. A computational framework for the numerical realization of optimal control problems is presented. Essential ingredients are a shape calculus based treatment of the sensitivities of the discontinuous source terms and a marching cubes algorithm to track iso-surface of excitation wavefronts. Numerical results exhibit successful defibrillation by applying an optimally controlled extracellular stimulus.

Electrostatic interactions between ions near Thomas-Fermi substrates and the surface energy of ionic crystals at imperfect metals.

PubMed

Kaiser, V; Comtet, J; Niguès, A; Siria, A; Coasne, B; Bocquet, L

2017-07-01

The electrostatic interaction between two charged particles is strongly modified in the vicinity of a metal. This situation is usually accounted for by the celebrated image charges approach, which was further extended to account for the electronic screening properties of the metal at the level of the Thomas-Fermi description. In this paper we build upon a previous approach [M. A. Vorotyntsev and A. A. Kornyshev, Zh. Eksp. Teor. Fiz., 1980, 78(3), 1008-1019] and successive works to calculate the 1-body and 2-body electrostatic energy of ions near a metal in terms of the Thomas-Fermi screening length. We propose workable approximations suitable for molecular simulations of ionic systems close to metallic walls. Furthermore, we use this framework to calculate analytically the electrostatic contribution to the surface energy of a one dimensional crystal at a metallic wall and its dependence on the Thomas-Fermi screening length. These calculations provide a simple interpretation for the surface energy in terms of image charges, which allows for an estimation of the interfacial properties in more complex situations of a disordered ionic liquid close to a metal surface. The counter-intuitive outcome is that electronic screening, as characterized by a molecular Thomas-Fermi length l TF , profoundly affects the wetting of ionic systems close to a metal, in line with the recent experimental observation of capillary freezing of ionic liquids in metallic confinement.

Determination of three estrogens and bisphenol A by functional ionic liquid dispersive liquid-phase microextraction coupled with ultra-high performance liquid chromatography and ultraviolet detection.

PubMed

Jiang, Yuehuang; Tang, Tingting; Cao, Zhen; Shi, Guoyue; Zhou, Tianshu

2015-06-01

A hydroxyl-functionalized ionic liquid, 1-hydroxyethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, was employed in an improved dispersive liquid-phase microextraction method coupled with ultra high performance liquid chromatography for the enrichment and determination of three estrogens and bisphenol A in environmental water samples. The introduced hydroxyl group acted as the H-bond acceptor that dispersed the ionic liquid effectively in the aqueous phase without dispersive solvent or external force. Fourier transform infrared spectroscopy indicated that the hydroxyl group of the cation of the ionic liquid enhanced the combination of extractant and analytes through the formation of hydrogen bonds. The improvement of the extraction efficiency compared with that with the use of alkyl ionic liquid was proved by a comparison study. The main parameters including volume of extractant, temperature, pH, and extraction time were investigated. The calibration curves were linear in the range of 5.0-1000 μg/L for estrone, estradiol, and bisphenol A, and 10.0-1000 μg/L for estriol. The detection limits were in the range of 1.7-3.4 μg/L. The extraction efficiency was evaluated by enrichment factor that were between 85 and 129. The proposed method was proved to be simple, low cost, and environmentally friendly for the determination of the four endocrine disruptors in environmental water samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A scaled-ionic-charge simulation model that reproduces enhanced and suppressed water diffusion in aqueous salt solutions.

PubMed

Kann, Z R; Skinner, J L

2014-09-14

Non-polarizable models for ions and water quantitatively and qualitatively misrepresent the salt concentration dependence of water diffusion in electrolyte solutions. In particular, experiment shows that the water diffusion coefficient increases in the presence of salts of low charge density (e.g., CsI), whereas the results of simulations with non-polarizable models show a decrease of the water diffusion coefficient in all alkali halide solutions. We present a simple charge-scaling method based on the ratio of the solvent dielectric constants from simulation and experiment. Using an ion model that was developed independently of a solvent, i.e., in the crystalline solid, this method improves the water diffusion trends across a range of water models. When used with a good-quality water model, e.g., TIP4P/2005 or E3B, this method recovers the qualitative behaviour of the water diffusion trends. The model and method used were also shown to give good results for other structural and dynamic properties including solution density, radial distribution functions, and ion diffusion coefficients.

AIE-doped poly(ionic liquid) photonic spheres: a single sphere-based customizable sensing platform for the discrimination of multi-analytes† †Electronic supplementary information (ESI) available: Synthesis and characterization of the AIE luminogen, experimental details, response profiles and results of the multivariate analysis. See DOI: 10.1039/c7sc02409f Click here for additional data file.

PubMed Central

Zhang, Wanlin; Gao, Ning; Cui, Jiecheng; Wang, Chen; Wang, Shiqiang; Zhang, Guanxin; Dong, Xiaobiao

2017-01-01

By simultaneously exploiting the unique properties of ionic liquids and aggregation-induced emission (AIE) luminogens, as well as photonic structures, a novel customizable sensing system for multi-analytes was developed based on a single AIE-doped poly(ionic liquid) photonic sphere. It was found that due to the extraordinary multiple intermolecular interactions involved in the ionic liquid units, one single sphere could differentially interact with broader classes of analytes, thus generating response patterns with remarkable diversity. Moreover, the optical properties of both the AIE luminogen and photonic structure integrated in the poly(ionic liquid) sphere provide multidimensional signal channels for transducing the involved recognition process in a complementary manner and the acquisition of abundant and sufficient sensing information could be easily achieved on only one sphere sensor element. More importantly, the sensing performance of our poly(ionic liquid) photonic sphere is designable and customizable through a simple ion-exchange reaction and target-oriented multi-analyte sensing can be conveniently realized using a selective receptor species, such as counterions, showing great flexibility and extendibility. The power of our single sphere-based customizable sensing system was exemplified by the successful on-demand detection and discrimination of four multi-analyte challenge systems: all 20 natural amino acids, nine important phosphate derivatives, ten metal ions and three pairs of enantiomers. To further demonstrate the potential of our spheres for real-life application, 20 amino acids in human urine and their 26 unprecedented complex mixtures were also discriminated between by the single sphere-based array. PMID:28989662

Electrostatic interactions in soft particle systems: mesoscale simulations of ionic liquids.

PubMed

Wang, Yong-Lei; Zhu, You-Liang; Lu, Zhong-Yuan; Laaksonen, Aatto

2018-05-21

Computer simulations provide a unique insight into the microscopic details, molecular interactions and dynamic behavior responsible for many distinct physicochemical properties of ionic liquids. Due to the sluggish and heterogeneous dynamics and the long-ranged nanostructured nature of ionic liquids, coarse-grained meso-scale simulations provide an indispensable complement to detailed first-principles calculations and atomistic simulations allowing studies over extended length and time scales with a modest computational cost. Here, we present extensive coarse-grained simulations on a series of ionic liquids of the 1-alkyl-3-methylimidazolium (alkyl = butyl, heptyl-, and decyl-) family with Cl, [BF4], and [PF6] counterions. Liquid densities, microstructures, translational diffusion coefficients, and re-orientational motion of these model ionic liquid systems have been systematically studied over a wide temperature range. The addition of neutral beads in cationic models leads to a transition of liquid morphologies from dispersed apolar beads in a polar framework to that characterized by bi-continuous sponge-like interpenetrating networks in liquid matrices. Translational diffusion coefficients of both cations and anions decrease upon lengthening of the neutral chains in the cationic models and by enlarging molecular sizes of the anionic groups. Similar features are observed in re-orientational motion and time scales of different cationic models within the studied temperature range. The comparison of the liquid properties of the ionic systems with their neutral counterparts indicates that the distinctive microstructures and dynamical quantities of the model ionic liquid systems are intrinsically related to Coulombic interactions. Finally, we compared the computational efficiencies of three linearly scaling O(N log N) Ewald summation methods, the particle-particle particle-mesh method, the particle-mesh Ewald summation method, and the Ewald summation method based on a non-uniform fast Fourier transform technique, to calculate electrostatic interactions. Coarse-grained simulations were performed using the GALAMOST and the GROMACS packages and hardware efficiently utilizing graphics processing units on a set of extended [1-decyl-3-methylimidazolium][BF4] ionic liquid systems of up to 131 072 ion pairs.

Time scale of dynamic heterogeneity in model ionic liquids and its relation to static length scale and charge distribution.

PubMed

Park, Sang-Won; Kim, Soree; Jung, YounJoon

2015-11-21

We study how dynamic heterogeneity in ionic liquids is affected by the length scale of structural relaxation and the ionic charge distribution by the molecular dynamics simulations performed on two differently charged models of ionic liquid and their uncharged counterpart. In one model of ionic liquid, the charge distribution in the cation is asymmetric, and in the other it is symmetric, while their neutral counterpart has no charge with the ions. It is found that all the models display heterogeneous dynamics, exhibiting subdiffusive dynamics and a nonexponential decay of structural relaxation. We investigate the lifetime of dynamic heterogeneity, τ(dh), in these systems by calculating the three-time correlation functions to find that τ(dh) has in general a power-law behavior with respect to the structural relaxation time, τ(α), i.e., τ(dh) ∝ τ(α)(ζ(dh)). Although the dynamics of the asymmetric-charge model is seemingly more heterogeneous than that of the symmetric-charge model, the exponent is found to be similar, ζ(dh) ≈ 1.2, for all the models studied in this work. The same scaling relation is found regardless of interactions, i.e., with or without Coulomb interaction, and it holds even when the length scale of structural relaxation is long enough to become the Fickian diffusion. This fact indicates that τ(dh) is a distinctive time scale from τ(α), and the dynamic heterogeneity is mainly affected by the short-range interaction and the molecular structure.

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.

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.

Screen-printed electrode-based electrochemical detector coupled with in-situ ionic-liquid-assisted dispersive liquid-liquid microextraction for determination of 2,4,6-trinitrotoluene.

PubMed

Fernández, Elena; Vidal, Lorena; Iniesta, Jesús; Metters, Jonathan P; Banks, Craig E; Canals, Antonio

2014-03-01

A novel method is reported, whereby screen-printed electrodes (SPELs) are combined with dispersive liquid-liquid microextraction. In-situ ionic liquid (IL) formation was used as an extractant phase in the microextraction technique and proved to be a simple, fast and inexpensive analytical method. This approach uses miniaturized systems both in sample preparation and in the detection stage, helping to develop environmentally friendly analytical methods and portable devices to enable rapid and onsite measurement. The microextraction method is based on a simple metathesis reaction, in which a water-immiscible IL (1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, [Hmim][NTf2]) is formed from a water-miscible IL (1-hexyl-3-methylimidazolium chloride, [Hmim][Cl]) and an ion-exchange reagent (lithium bis[(trifluoromethyl)sulfonyl]imide, LiNTf2) in sample solutions. The explosive 2,4,6-trinitrotoluene (TNT) was used as a model analyte to develop the method. The electrochemical behavior of TNT in [Hmim][NTf2] has been studied in SPELs. The extraction method was first optimized by use of a two-step multivariate optimization strategy, using Plackett-Burman and central composite designs. The method was then evaluated under optimum conditions and a good level of linearity was obtained, with a correlation coefficient of 0.9990. Limits of detection and quantification were 7 μg L(-1) and 9 μg L(-1), respectively. The repeatability of the proposed method was evaluated at two different spiking levels (20 and 50 μg L(-1)), and coefficients of variation of 7 % and 5 % (n = 5) were obtained. Tap water and industrial wastewater were selected as real-world water samples to assess the applicability of the method.

The Relation between Vaporization Enthalpies and Viscosities: Eyring's Theory Applied to Selected Ionic Liquids.

PubMed

Bonsa, Anne-Marie; Paschek, Dietmar; Zaitsau, Dzmitry H; Emel'yanenko, Vladimir N; Verevkin, Sergey P; Ludwig, Ralf

2017-05-19

Key properties for the use of ionic liquids as electrolytes in batteries are low viscosities, low vapor pressure and high vaporization enthalpies. Whereas the measurement of transport properties is well established, the determination of vaporization enthalpies of these extremely low volatile compounds is still a challenge. At a first glance both properties seem to describe different thermophysical phenomena. However, eighty years ago Eyring suggested a theory which related viscosities and vaporization enthalpies to each other. The model is based on Eyring's theory of absolute reaction rates. Recent attempts to apply Eyring's theory to ionic liquids failed. The motivation of our study is to show that Eyring's theory works, if the assumptions specific for ionic liquids are fulfilled. For that purpose we measured the viscosities of three well selected protic ionic liquids (PILs) at different temperatures. The temperature dependences of viscosities were approximated by the Vogel-Fulcher-Tamann (VFT) relation and extrapolated to the high-temperature regime up to 600 K. Then the VFT-data could be fitted to the Eyring-model. The values of vaporization enthalpies for the three selected PILs predicted by the Eyring model have been very close to the experimental values measured by well-established techniques. We conclude that the Eyring theory can be successfully applied to the chosen set of PILs, if the assumption that ionic pairs of the viscous flow in the liquid and the ionic pairs in the gas phase are similar is fulfilled. It was also noticed that proper transfer of energies can be only derived if the viscosities and the vaporization energies are known for temperatures close to the liquid-gas transition temperature. The idea to correlate easy measurable viscosities of ionic liquids with their vaporization enthalpies opens a new way for a reliable assessment of these thermodynamic properties for a broad range of ionic liquids. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Transport Properties of Complex Oxides: New Ideas and Insights from Theory and Simulation

NASA Astrophysics Data System (ADS)

Benedek, Nicole

Complex oxides are one of the largest and most technologically important materials families. The ABO3 perovskite oxides in particular display an unparalleled variety of physical properties. The microscopic origin of these properties (how they arise from the structure of the material) is often complicated, but in many systems previous research has identified simple guidelines or `rules of thumb' that link structure and chemistry to the physics of interest. For example, the tolerance factor is a simple empirical measure that relates the composition of a perovskite to its tendency to adopt a distorted structure. First-principles calculations have shown that the tendency towards ferroelectricity increases systematically as the tolerance factor of the perovskite decreases. Can we uncover a similar set of simple guidelines to yield new insights into the ionic and thermal transport properties of perovskites? I will discuss recent research from my group on the link between crystal structure and chemistry, soft phonons and ionic transport in a family of layered perovskite oxides, the Ln2NiO4+δ Ruddlesden-Popper phases. In particular, we show how the lattice dynamical properties of these materials (their tendency to undergo certain structural distortions) can be correlated with oxide ion transport properties. Ultimately, we seek new ways to understand the microscopic origins of complex transport processes and to develop first-principles-based design rules for new materials based on our understanding.

Insight into the grain boundary effect on the ionic transport of yttria-stabilized zirconia at elevated temperatures from a molecular modeling perspective

NASA Astrophysics Data System (ADS)

Chang, Kai-Shiun; Lin, Yi-Feng; Tung, Kuo-Lun

A molecular dynamics (MD) simulation is used to reveal the grain boundary effect on the ionic transport of yttria-stabilized zirconia (YSZ). The oxygen ion displacements and diffusivities of the ideal and grain boundary-inserted YSZ models are analyzed at elevated temperatures. An optimized Y 2O 3 concentration within YSZ for the best ionic conductivity is achieved by balancing the trade-off between the increased vacancies and the decreased accessible free space. The mass transfer resistance of the grain boundary in YSZ can be more easily found at higher temperatures by observing the oxygen ion diffusivities or traveling trajectories. At lower temperatures, the grain interior and the grain boundary control the ionic transport. In contrast, the grain boundary effect on the diffusion barrier is gradually eliminated at elevated temperatures. The modeled results in this work agree well with previous experimental data.

Ionic solubility and solutal advection governed augmented evaporation kinetics of salt solution pendant droplets

NASA Astrophysics Data System (ADS)

Jaiswal, Vivek; Harikrishnan, A. R.; Khurana, Gargi; Dhar, Purbarun

2018-01-01

The presence of dispersed inclusions is known to modify the interfacial characteristics in liquids by adsorption-desorption of the ions at interfaces. The present article reports the influencing role of dissolved ions in a polar fluid on its evaporation dynamics. The evaporation dynamics of pendant droplets of aqueous solutions of variant simple salts and concentrations have been experimentally studied. The presence of salts is observed to enhance the evaporation rate (obeying the classical D2 law), and the enhancement has been found to hold a direct proportionality to the concentration of the dissolved salt. Furthermore, it is observed that the degree of enhancement in the evaporation rate is also directly proportional to the solubility of the salt in question. The phenomenon is explained based on the chemical kinetics and thermodynamics of hydration of the ionic species in the polar fluid. The classical evaporation rate constant formulation is found to be inadequate in modeling the enhanced species transport. Additional probing via particle image velocimetry reveals augmented internal circulation within the evaporating salt based drops compared to pure water. Mapping the dynamic surface tension reveals that a salt concentration gradient is generated between the bulk and periphery of the droplet and it could be responsible for the internal advection cells visualized. A thermo-solutal Marangoni and Rayleigh convection based mathematical formulation has been put forward, and it is shown that the enhanced solute-thermal convection could play a major role in enhanced evaporation. The internal circulation mapped from experiments is found to be in good quantitative agreement with the model predictions. Scaling analysis further reveals that the stability of the solutal Marangoni convection surpasses the thermal counterpart with higher salt concentration and solubility. The present article sheds insight into the possible domineering role of conjugate thermohydraulic and mass transport phenomena on the evaporation kinetics aqueous droplets with ionic inclusions.

Development of Monopole Interaction Models for Ionic Compounds. Part I: Estimation of Aqueous Henry’s Law Constants for Ions and Gas Phase pKa Values for Acidic Compounds

EPA Science Inventory

The SPARC (SPARC Performs Automated Reasoning in Chemistry) physicochemical mechanistic models for neutral compounds have been extended to estimate Henry’s Law Constant (HLC) for charged species by incorporating ionic electrostatic interaction models. Combinations of absolute aq...

Charge Transport and Phase Behavior of Imidazolium-Based Ionic Liquid Crystals from Fully Atomistic Simulations.

PubMed

Quevillon, Michael J; Whitmer, Jonathan K

2018-01-02

Ionic liquid crystals occupy an intriguing middle ground between room-temperature ionic liquids and mesostructured liquid crystals. Here, we examine a non-polarizable, fully atomistic model of the 1-alkyl-3-methylimidazolium nitrate family using molecular dynamics in the constant pressure-constant temperature ensemble. These materials exhibit a distinct "smectic" liquid phase, characterized by layers formed by the molecules, which separate the ionic and aliphatic moieties. In particular, we discuss the implications this layering may have for electrolyte applications.

Innovative Poly(Ionic Liquid)s by the Polymerization of Deep Eutectic Monomers.

PubMed

Isik, Mehmet; Ruiperez, Fernando; Sardon, Haritz; Gonzalez, Alba; Zulfiqar, Sonia; Mecerreyes, David

2016-07-01

The incorporation of ionic liquid (IL) chemistry into functional polymers has extended the properties and applications of polyelectrolytes. However, ILs are expensive due to the presence of fluorinated anions or complicated synthetic steps which limit their technological viability. Here, we show a new family of poly(ionic liquid)s (PILs) which are based in cheap and renewable chemicals and involves facile synthetic approaches. Thus, deep eutectic monomers (DEMs) are prepared for the first time by using quaternary ammonium compounds and various hydrogen bond donors such as citric acid, terephthalic acid or an amidoxime. The deep eutectic formation is made through a simple mixing of the ingredients. Differential scanning calorimetry, nuclear magnetic resonance (NMR) and computational studies reveal the formation of the DEMs due to the ionic interactions. The resulting DEMs are liquid which facilitates their polymerization using mild photopolymerization or polycondensation strategies. Spectroscopic characterizations reveal the successful formation of the polymers. By this way, a new family of PILs can be synthesized which can be used for different applications. As an example, the polymers show promising performance as solid CO2 sorbents. Altogether the deep eutectic monomer route can lead to non-toxic, cheap and easy-to-prepare alternatives to current PILs for different applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microbundles of zinc oxide nanorods: Assembly in ionic liquid [EMIM]{sup +}[BF{sub 4}]{sup -}, photoluminescence and photocatalytic properties

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

Wang Li; Xu Shenzhi; Li Huijun

2011-03-15

A simple, efficient and low-temperature approach for the assembly of hierarchical Zinc oxide (ZnO) microstructures in ionic liquid [EMIM]{sup +}[BF{sub 4}]{sup -} is reported. The as-obtained ZnO superstructures are composed of microbundles of nanorods from the center points, with the diameter and length in the range of 100-150 nm and 2-4 {mu}m, which have been characterized by X-ray diffraction, scanning and transmission electron microscopy, and photoluminescence spectroscopy. The ZnO microstructures exhibit significant defect-related green-yellow emission and high photodegradation of dye Methyl Orange (5x10{sup -5} mol/L) under UV excitation within 80 min. -- Graphical abstract: Easy formation of microbundles of ZnOmore » nanorods were accomplished in low temperature with [EMIM]{sup +}[BF{sub 4}]{sup -} (1-ethyl-3-methylimidazolium tetrafluoroborate) ionic liquid, which exhibit significant green-yellow photoluminescence property and high photodegradation of Methyl Orange dye. Display Omitted Research highlights: {yields} Ionic liquid assisted solid-state route was introduced into synthesis of ZnO nanorods. {yields} The distinctive microbundles ZnO nanorod assembles was evidenced by SEM and TEM. {yields} ZnO nano-material exhibited high efficiency in photodegradation of Methyl Orange.« less

Highly efficient micellar extraction of toxic picric acid into novel ionic liquid: Effect of parameters, solubilization isotherm, evaluation of thermodynamics and design parameters.

PubMed

Bhatt, Darshak R; Maheria, Kalpana C; Parikh, Jigisha K

2015-12-30

A simple and new approach in cloud point extraction (CPE) method was developed for removal of picric acid (PA) by the addition of N,N,N,N',N',N'-hexaethyl-ethane-1,2-diammonium dibromide ionic liquid (IL) in non-ionic surfactant Triton X-114 (TX-114). A significant increase in extraction efficiency was found upon the addition of dicationic ionic liquid (DIL) at both nearly neutral and high acidic pH. The effects of different operating parameters such as pH, temperature, time, concentration of surfactant, PA and DIL on extraction of PA were investigated and optimum conditions were established. The extraction mechanism was also proposed. A developed Langmuir isotherm was used to compute the feed surfactant concentration required for the removal of PA up to an extraction efficiency of 90%. The effects of temperature and concentration of surfactant on various thermodynamic parameters were examined. It was found that the values of ΔG° increased with temperature and decreased with surfactant concentration. The values of ΔH° and ΔS° increased with surfactant concentration. The developed approach for DIL mediated CPE has proved to be an efficient and green route for extraction of PA from water sample. Copyright © 2015 Elsevier B.V. All rights reserved.

Acid-base titrations of functional groups on the surface of the thermophilic bacterium Anoxybacillus flavithermus: comparing a chemical equilibrium model with ATR-IR spectroscopic data.

PubMed

Heinrich, Hannah T M; Bremer, Phil J; Daughney, Christopher J; McQuillan, A James

2007-02-27

Acid-base functional groups at the surface of Anoxybacillus flavithermus (AF) were assigned from the modeling of batch titration data of bacterial suspensions and compared with those determined from in situ infrared spectroscopic titration analysis. The computer program FITMOD was used to generate a two-site Donnan model (site 1: pKa = 3.26, wet concn = 2.46 x 10(-4) mol g(-1); site 2: pKa = 6.12, wet concn = 6.55 x 10(-5) mol g(-1)), which was able to describe data for whole exponential phase cells from both batch acid-base titrations at 0.01 M ionic strength and electrophoretic mobility measurements over a range of different pH values and ionic strengths. In agreement with information on the composition of bacterial cell walls and a considerable body of modeling literature, site 1 of the model was assigned to carboxyl groups, and site 2 was assigned to amino groups. pH difference IR spectra acquired by in situ attenuated total reflection infrared (ATR-IR) spectroscopy confirmed the presence of carboxyl groups. The spectra appear to show a carboxyl pKa in the 3.3-4.0 range. Further peaks were assigned to phosphodiester groups, which deprotonated at slightly lower pH. The presence of amino groups could not be confirmed or discounted by IR spectroscopy, but a positively charged group corresponding to site 2 was implicated by electrophoretic mobility data. Carboxyl group speciation over a pH range of 2.3-10.3 at two different ionic strengths was further compared to modeling predictions. While model predictions were strongly influenced by the ionic strength change, pH difference IR data showed no significant change. This meant that modeling predictions agreed reasonably well with the IR data for 0.5 M ionic strength but not for 0.01 M ionic strength.

Coupled ion redistribution and electronic breakdown in low-alkali boroaluminosilicate glass

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

Choi, Doo Hyun, E-mail: cooldoo@add.re.kr; Randall, Clive, E-mail: car4@psu.edu; Furman, Eugene, E-mail: euf1@psu.edu

2015-08-28

Dielectrics with high electrostatic energy storage must have exceptionally high dielectric breakdown strength at elevated temperatures. Another important consideration in designing a high performance dielectric is understanding the thickness and temperature dependence of breakdown strengths. Here, we develop a numerical model which assumes a coupled ionic redistribution and electronic breakdown is applied to predict the breakdown strength of low-alkali glass. The ionic charge transport of three likely charge carriers (Na{sup +}, H{sup +}/H{sub 3}O{sup +}, Ba{sup 2+}) was used to calculate the ionic depletion width in low-alkali boroaluminosilicate which can further be used for the breakdown modeling. This model predictsmore » the breakdown strengths in the 10{sup 8}–10{sup 9 }V/m range and also accounts for the experimentally observed two distinct thickness dependent regions for breakdown. Moreover, the model successfully predicts the temperature dependent breakdown strength for low-alkali glass from room temperature up to 150 °C. This model showed that breakdown strengths were governed by minority charge carriers in the form of ionic transport (mostly sodium) in these glasses.« less

Underscreening in ionic liquids: a first principles analysis.

PubMed

Rotenberg, Benjamin; Bernard, Olivier; Hansen, Jean-Pierre

2018-02-07

An attempt is made to understand the underscreening effect, observed in concentrated electrolyte solutions or melts, on the basis of simple, admittedly crude models involving charged (for the ions) and neutral (for the solvent molecules) hard spheres. The thermodynamic and structural properties of these 'primitive' and 'semi-primitive' models are calculated within mean spherical approximation, which provides the basic input required to determine the partial density response functions. The screening length [Formula: see text], which is unambiguously defined in terms of the wave-number-dependent response functions, exhibits a cross-over from a low density, Debye-like regime, to a regime where [Formula: see text] increases with density beyond a critical density at which the Debye length [Formula: see text] becomes comparable to the ion diameter. In this high density regime the ratio [Formula: see text] increases according to a power law, in qualitative agreement with experimental measurements, albeit at a much slower rate.

Underscreening in ionic liquids: a first principles analysis

NASA Astrophysics Data System (ADS)

Rotenberg, Benjamin; Bernard, Olivier; Hansen, Jean-Pierre

2018-02-01

An attempt is made to understand the underscreening effect, observed in concentrated electrolyte solutions or melts, on the basis of simple, admittedly crude models involving charged (for the ions) and neutral (for the solvent molecules) hard spheres. The thermodynamic and structural properties of these ‘primitive’ and ‘semi-primitive’ models are calculated within mean spherical approximation, which provides the basic input required to determine the partial density response functions. The screening length λS , which is unambiguously defined in terms of the wave-number-dependent response functions, exhibits a cross-over from a low density, Debye-like regime, to a regime where λS increases with density beyond a critical density at which the Debye length λD becomes comparable to the ion diameter. In this high density regime the ratio λ_S/λD increases according to a power law, in qualitative agreement with experimental measurements, albeit at a much slower rate.

The Octet Rules: A Dating Game for Atoms

ERIC Educational Resources Information Center

Welborn, Jennifer

2004-01-01

To develop student interest in the periodic table, the author developed a simple, but fun, role-playing activity. This play is used after students have learned the basic structure of atoms and the general layout of the periodic table. It also comes after students have learned the basics of ionic and covalent bonding. The basic idea of bonding is…

Determination of ionic species formed during growth of Escherichia coli by capillary isotachophoresis.

PubMed

Futschik, K; Ammann, M; Bachmayer, S; Kenndler, E

1993-08-06

The ionic species that are formed during the microbial growth of Escherichia coli were determined by capillary isotachophoresis as a function of the time of cultivation. This formation was indicated by the change in a sum parameter, the impedance of the nutrient broth, measured by a special electrode system. Based on the determination of the individual ions formed under the given conditions (identified as acetate, lactate, alpha-ketoglutarate, fumarate, ammonium and probably a simple amine), the change in conductivity was calculated and compared with that obtained by the impedance measurement of the bulk medium. From the results it can be concluded that the change in the sum parameter as a function of time is originated by the ions determined.

Simulation of mechano-electrical transduction in the cochlea considering basilar membrane vibration and the ionic current of the inner hair cells

NASA Astrophysics Data System (ADS)

Lee, Sinyoung; Koike, Takuji

2018-05-01

The inner hair cells (IHCs) in the cochlea transduce mechanical vibration of the basilar membrane (BM), caused by sound pressure, to electrical signals that are transported along the acoustic nerve to the brain. The mechanical vibration of the BM and the ionic behaviors of the IHCs have been investigated. However, consideration of the ionic behavior of the IHCs related to mechanical vibration is necessary to investigate the mechano-electrical transduction of the cochlea. In this study, a finite-element model of the BM, which takes into account the non-linear activities of the outer hair cells (OHCs), and an ionic current model of IHC were combined. The amplitudes and phases of the vibration at several points on the BM were obtained from the finite-element model by applying sound pressure. These values were fed into the ionic current model, and changes in membrane potential and calcium ion concentration of the IHCs were calculated. The membrane potential of the IHC at the maximum amplitude point (CF point) was higher than that at the non-CF points. The calcium ion concentration at the CF point was also higher than that at the non-CF points. These results suggest that the cochlea achieves its good frequency discrimination ability through mechano-electrical transduction.

Electrochemical-mechanical coupled modeling and parameterization of swelling and ionic transport in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Sauerteig, Daniel; Hanselmann, Nina; Arzberger, Arno; Reinshagen, Holger; Ivanov, Svetlozar; Bund, Andreas

2018-02-01

The intercalation and aging induced volume changes of lithium-ion battery electrodes lead to significant mechanical pressure or volume changes on cell and module level. As the correlation between electrochemical and mechanical performance of lithium ion batteries at nano and macro scale requires a comprehensive and multidisciplinary approach, physical modeling accounting for chemical and mechanical phenomena during operation is very useful for the battery design. Since the introduced fully-coupled physical model requires proper parameterization, this work also focuses on identifying appropriate mathematical representation of compressibility as well as the ionic transport in the porous electrodes and the separator. The ionic transport is characterized by electrochemical impedance spectroscopy (EIS) using symmetric pouch cells comprising LiNi1/3Mn1/3Co1/3O2 (NMC) cathode, graphite anode and polyethylene separator. The EIS measurements are carried out at various mechanical loads. The observed decrease of the ionic conductivity reveals a significant transport limitation at high pressures. The experimentally obtained data are applied as input to the electrochemical-mechanical model of a prismatic 10 Ah cell. Our computational approach accounts intercalation induced electrode expansion, stress generation caused by mechanical boundaries, compression of the electrodes and the separator, outer expansion of the cell and finally the influence of the ionic transport within the electrolyte.

Pressure and temperature dependences of the ionic conductivities of the thallous halidesTlCl, TlBr, and TlI

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

Samara, G.A.

1981-01-15

Detailed studies of the pressure and temperature dependences of the ionic conductivities of TlCl and TlBr have allowed determination of the lattice volume relaxations and energies associated with the formation and motion of Schottky defects in these crystals. The volume relaxations deduced from the conductivity are found to be comparable in magnitude with values calculated from the strain energy model and a dynamical model. The association energy of Tl/sup +/ vacancies and divalent impurities was also determined for TlBr. A particularly important result is the finding that for these CsCl-type crystals the relaxation of the lattice associated with vacancy formationmore » is outward. Earlier studies on ionic crystals having the NaCl structure have yielded a similar result. This outward relaxation thus appears to be a general result for ionic crystals of both the NaCl and CsCl types (and possibly other ionic lattice types), in disagreement with earlier theoretical calculations which show that the relaxation should be inward for all models of ionic vacancies investigated. The conductivity of TlI was studied in both the (low temperature and pressure) orthorhombic phase as well as in the cubic CsCl-type phase. There is a large electronic contribution to the conductivity in the orthorhombic phase. An interesting result for all three materials is the observation in the cubic phase of a pressure-induced transition from ionic to electronic conduction. This is in qualitative agreement with what is known about the pressure dependences of the electronic structure of these materials.« less

Modelling the influence of ionic and fluid transport on rebars corrosion in unsaturated cement systems

NASA Astrophysics Data System (ADS)

Dridi, W.; Dangla, P.; Foct, F.; Petre-Lazar, I.

2006-11-01

This paper deals with numerical modelling of rebar corrosion kinetics in unsaturated concrete structures. The corrosion kinetics is investigated in terms of mechanistic coupling between reaction rates at the steel surface and the ionic transport processes in the concrete pore system. The ionic and mass transport model consists of time-dependent equations for the concentration of dissolved species, the liquid pressure and the electrical potential. The complete set of nonlinear equations is solved using the finite-volume method. The nonlinear boundary conditions dealing with corrosion are introduced at the steel-concrete interface where they are implicitly coupled with the mass transport model in the concrete structure. Both the case of free corrosion and potentiostatic polarisation are discussed in a one dimensional model.

Counterion-induced swelling of ionic microgels

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Tang, Qiyun

2016-10-01

Ionic microgel particles, when dispersed in a solvent, swell to equilibrium sizes that are governed by a balance between electrostatic and elastic forces. Tuning of particle size by varying external stimuli, such as pH, salt concentration, and temperature, has relevance for drug delivery, microfluidics, and filtration. To model swelling of ionic microgels, we derive a statistical mechanical theorem, which proves exact within the cell model, for the electrostatic contribution to the osmotic pressure inside a permeable colloidal macroion. Applying the theorem, we demonstrate how the distribution of counterions within an ionic microgel determines the internal osmotic pressure. By combining the electrostatic pressure, which we compute via both Poisson-Boltzmann theory and molecular dynamics simulation, with the elastic pressure, modeled via the Flory-Rehner theory of swollen polymer networks, we show how deswelling of ionic microgels with increasing concentration of particles can result from a redistribution of counterions that reduces electrostatic pressure. A linearized approximation for the electrostatic pressure, which proves remarkably accurate, provides physical insight and greatly eases numerical calculations for practical applications. Comparing with experiments, we explain why soft particles in deionized suspensions deswell upon increasing concentration and why this effect may be suppressed at higher ionic strength. The failure of the uniform ideal-gas approximation to adequately account for counterion-induced deswelling below close packing of microgels is attributed to neglect of spatial variation of the counterion density profile and the electrostatic pressure of incompletely neutralized macroions.

ERRORS IN APPLYING LOW IONIC-STRENGTH ACTIVITY COEFFICIENT ALGORITHMS TO HIGHER IONIC-STRENGTH AQUATIC MEDIA

EPA Science Inventory

The toxicological and regulatory communities are currently exploring the use of the free-ion-activity (FIA) model both alone and in conjunction with the biotic ligand model (BLM) as a means of reducing uncertainties in current methods for assessing metals bioavailability from aqu...

Separating a Mixture

ERIC Educational Resources Information Center

Lotter, Christine; Taylor, Laurie

2016-01-01

In the 2 day lesson presented in this article, students explain how ionic substances interact in solutions by developing and revising their own explanatory models. The lesson engaged students in three-dimensional learning through creating and revising their own models to explain the interaction of ionic substances and polar molecules in a closed…

Integral equation model for warm and hot dense mixtures.

PubMed

Starrett, C E; Saumon, D; Daligault, J; Hamel, S

2014-09-01

In a previous work [C. E. Starrett and D. Saumon, Phys. Rev. E 87, 013104 (2013)] a model for the calculation of electronic and ionic structures of warm and hot dense matter was described and validated. In that model the electronic structure of one atom in a plasma is determined using a density-functional-theory-based average-atom (AA) model and the ionic structure is determined by coupling the AA model to integral equations governing the fluid structure. That model was for plasmas with one nuclear species only. Here we extend it to treat plasmas with many nuclear species, i.e., mixtures, and apply it to a carbon-hydrogen mixture relevant to inertial confinement fusion experiments. Comparison of the predicted electronic and ionic structures with orbital-free and Kohn-Sham molecular dynamics simulations reveals excellent agreement wherever chemical bonding is not significant.

Improving accuracy of electrochemical capacitance and solvation energetics in first-principles calculations

NASA Astrophysics Data System (ADS)

Sundararaman, Ravishankar; Letchworth-Weaver, Kendra; Schwarz, Kathleen A.

2018-04-01

Reliable first-principles calculations of electrochemical processes require accurate prediction of the interfacial capacitance, a challenge for current computationally efficient continuum solvation methodologies. We develop a model for the double layer of a metallic electrode that reproduces the features of the experimental capacitance of Ag(100) in a non-adsorbing, aqueous electrolyte, including a broad hump in the capacitance near the potential of zero charge and a dip in the capacitance under conditions of low ionic strength. Using this model, we identify the necessary characteristics of a solvation model suitable for first-principles electrochemistry of metal surfaces in non-adsorbing, aqueous electrolytes: dielectric and ionic nonlinearity, and a dielectric-only region at the interface. The dielectric nonlinearity, caused by the saturation of dipole rotational response in water, creates the capacitance hump, while ionic nonlinearity, caused by the compactness of the diffuse layer, generates the capacitance dip seen at low ionic strength. We show that none of the previously developed solvation models simultaneously meet all these criteria. We design the nonlinear electrochemical soft-sphere solvation model which both captures the capacitance features observed experimentally and serves as a general-purpose continuum solvation model.

The Role of Repulsion in Colloidal Crystal Engineering with DNA

DOE PAGES

Seo, Soyoung E.; Li, Tao; Senesi, Andrew J.; ...

2017-10-24

Hybridization interactions between DNA-functionalized nanoparticles (DNA-NPs) can be used to program the crystallization behavior of superlattices, yielding access to complex three-dimensional structures with more than 30 different lattice symmetries. The first superlattice structures using DNA-NPs as building blocks were identified almost a decade ago, yet the role of repulsive interactions in guiding structure formation is still largely unexplored. In this paper, a comprehensive approach is taken to study the role of repulsion in the assembly behavior of DNA-NPs, enabling the calculation of interparticle interaction potentials based on experimental results. In this work, we used two different means to assemble DNA-NPs—Watson–Crickmore » base-pairing interactions and depletion interactions—and systematically varied the salt concentration to study the effective interactions in DNA-NP superlattices. A comparison between the two systems allows us to decouple the repulsive forces from the attractive hybridization interactions that are sensitive to the ionic environment. We find that the gap distance between adjacent DNA-NPs follows a simple power law dependence on solution ionic strength regardless of the type of attractive forces present. This result suggests that the observed trend is driven by repulsive interactions. To better understand such behavior, we propose a mean-field model that provides a mathematical description for the observed trend. Finally, this model shows that the trend is due to the variation in the effective cross-sectional diameter of DNA duplex and the thickness of DNA shell.« less

The Role of Repulsion in Colloidal Crystal Engineering with DNA

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

Seo, Soyoung E.; Li, Tao; Senesi, Andrew J.

Hybridization interactions between DNA-functionalized nanoparticles (DNA-NPs) can be used to program the crystallization behavior of superlattices, yielding access to complex three-dimensional structures with more than 30 different lattice symmetries. The first superlattice structures using DNA-NPs as building blocks were identified almost a decade ago, yet the role of repulsive interactions in guiding structure formation is still largely unexplored. In this paper, a comprehensive approach is taken to study the role of repulsion in the assembly behavior of DNA-NPs, enabling the calculation of interparticle interaction potentials based on experimental results. In this work, we used two different means to assemble DNA-NPs—Watson–Crickmore » base-pairing interactions and depletion interactions—and systematically varied the salt concentration to study the effective interactions in DNA-NP superlattices. A comparison between the two systems allows us to decouple the repulsive forces from the attractive hybridization interactions that are sensitive to the ionic environment. We find that the gap distance between adjacent DNA-NPs follows a simple power law dependence on solution ionic strength regardless of the type of attractive forces present. This result suggests that the observed trend is driven by repulsive interactions. To better understand such behavior, we propose a mean-field model that provides a mathematical description for the observed trend. Finally, this model shows that the trend is due to the variation in the effective cross-sectional diameter of DNA duplex and the thickness of DNA shell.« less

The Role of Repulsion in Colloidal Crystal Engineering with DNA

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

Seo, Soyoung E.; Li, Tao; Senesi, Andrew J.

Hybridization interactions between DNA-functionalized nanoparticles (DNA-NPs) can be used to program the crystallization behavior of superlattices, yielding access to complex three-dimensional structures with more than 30 different lattice symmetries. The first superlattice structures using DNA-NPs as building blocks were identified almost two decades ago, yet the role of repulsive interactions in guiding structure formation is still largely unexplored. Here, a com-prehensive approach is taken to study the role of repulsion in the assembly behavior of DNA-NPs, enabling the calculation of interparticle interaction potentials based on experimental results. In this work, we used two different means to assemble DNA-NPs—Watson-Crick base pairingmore » interactions and depletion interactions—and systematically varied the salt concen-tration to study the effective interactions in DNA-NP superlattices. A comparison between the two systems allows us to decouple the repulsive forces from the attractive hybridization interactions that are sensitive to the ionic environment. We find that the gap distance between adjacent DNA-NPs follows a simple power law dependence on solution ionic strength regardless of the type of attractive forces present. This result suggests that the observed trend is driven by repulsive inter-actions. To better understand such behavior, we propose a mean-field model that provides a mathematical description for the observed trend. This model shows that the trend is due to the variation in the effective cross-sectional diameter of DNA duplex and the thickness of DNA shell.« less

Chromatographic and spectroscopic methods for the determination of solvent properties of room temperature ionic liquids.

PubMed

Poole, Colin F

2004-05-28

Room temperature ionic liquids are novel solvents with favorable environmental and technical features. Synthetic routes to over 200 room temperature ionic liquids are known but for most ionic liquids physicochemical data are generally lacking or incomplete. Chromatographic and spectroscopic methods afford suitable tools for the study of solvation properties under conditions that approximate infinite dilution. Gas-liquid chromatography is suitable for the determination of gas-liquid partition coefficients and activity coefficients as well as thermodynamic constants derived from either of these parameters and their variation with temperature. The solvation parameter model can be used to define the contribution from individual intermolecular interactions to the gas-liquid partition coefficient. Application of chemometric procedures to a large database of system constants for ionic liquids indicates their unique solvent properties: low cohesion for ionic liquids with weakly associated ions compared with non-ionic liquids of similar polarity; greater hydrogen-bond basicity than typical polar non-ionic solvents; and a range of dipolarity/polarizability that encompasses the same range as occupied by the most polar non-ionic liquids. These properties can be crudely related to ion structures but further work is required to develop a comprehensive approach for the design of ionic liquids for specific applications. Data for liquid-liquid partition coefficients is scarce by comparison with gas-liquid partition coefficients. Preliminary studies indicate the possibility of using the solvation parameter model for interpretation of liquid-liquid partition coefficients determined by shake-flask procedures as well as the feasibility of using liquid-liquid chromatography for the convenient and rapid determination of liquid-liquid partition coefficients. Spectroscopic measurements of solvatochromic and fluorescent probe molecules in room temperature ionic liquids provide insights into solvent intermolecular interactions although interpretation of the different and generally uncorrelated "polarity" scales is sometimes ambiguous. All evidence points to the ionic liquids as a unique class of polar solvents suitable for technical development. In terms of designer solvents, however, further work is needed to fill the gaps in our knowledge of the relationship between ion structures and physicochemical properties.

Charge Transport and Phase Behavior of Imidazolium-Based Ionic Liquid Crystals from Fully Atomistic Simulations

PubMed Central

2018-01-01

Ionic liquid crystals occupy an intriguing middle ground between room-temperature ionic liquids and mesostructured liquid crystals. Here, we examine a non-polarizable, fully atomistic model of the 1-alkyl-3-methylimidazolium nitrate family using molecular dynamics in the constant pressure–constant temperature ensemble. These materials exhibit a distinct “smectic” liquid phase, characterized by layers formed by the molecules, which separate the ionic and aliphatic moieties. In particular, we discuss the implications this layering may have for electrolyte applications. PMID:29301305

Sustained release of antibiotic complexed by multivalent ion: in vitro and in vivo study for the treatment of peritonitis.

PubMed

Na, Seung Yeon; Oh, Se Heang; Kim, Tae Ho; Yoon, Jin A; Lee, In Soo; Lee, Jin Ho

2014-12-10

The main aims of this study are (i) the development of an antibiotic complexed with multivalent ion, which can allow sustained release of the antibiotic without any additional matrix or difficult process and (ii) the feasibility study of the ion-complexed antibiotic as a therapeutic technique for peritonitis treatment. An ion-complexed antibiotic is prepared by simple mixing of two aqueous solutions containing an ionized (water-soluble) drug (tetracycline) and a multivalent counter ionic compound. The ion-complexed antibiotic shows a continuous release of the antibiotic up to 21 days, and thus prolonged anti-bacterial effect by gradual ionic exchange between the multivalent ions in the complex and same-charged monovalent ions in surrounding medium. From the in vivo animal study using a cecum perforated peritonitis mouse model, the ion-complexed antibiotic group shows sufficient anti-bacterial effect and thus effectively treat the peritonitis because of the extermination of the contaminated enteric bacteria in the peritoneum during wound healing of injury cecum (by the sustained release of antibiotic from the ion complex). These results suggest that the ion-complexed antibiotic system may be promising for the effective treatment of the peritonitis caused by frequent gastrointestinal defect in clinical fields. Copyright © 2014 Elsevier B.V. All rights reserved.

Ionic Liquid Droplet Microreactor for Catalysis Reactions Not at Equilibrium.

PubMed

Zhang, Ming; Ettelaie, Rammile; Yan, Tao; Zhang, Suojiang; Cheng, Fangqin; Binks, Bernard P; Yang, Hengquan

2017-12-06

We develop a novel strategy to more effectively and controllably process continuous enzymatic or homogeneous catalysis reactions based on nonaqueous Pickering emulsions. A key element of this strategy is "bottom-up" construction of a macroscale continuous flow reaction system through packing catalyst-containing micron-sized ionic liquid (IL) droplet in oil in a column reactor. Due to the continuous influx of reactants into the droplet microreactors and the continuous release of products from the droplet microreactors, catalysis reactions in such a system can take place without limitations arising from establishment of the reaction equilibrium and catalyst separation, inherent in conventional batch reactions. As proof of the concept, enzymatic enantioselective trans-esterification and CuI-catalyzed cycloaddition reactions using this IL droplet-based flow system both exhibit 8 to 25-fold enhancement in catalysis efficiency compared to their batch counterparts, and a durability of at least 4000 h for the enantioselective trans-esterification of 1-phenylethyl alcohol, otherwise unattainable in their batch counterparts. We further establish a theoretical model for such a catalysis system working under nonequilibrium conditions, which not only supports the experimental results but also helps to predict reaction progress at a microscale level. Being operationally simple, efficient, and adaptive, this strategy provides an unprecedented platform for practical applications of enzymes and homogeneous catalysts even at a controllable level.

Surface structure evolution in a homologous series of ionic liquids.

PubMed

Haddad, Julia; Pontoni, Diego; Murphy, Bridget M; Festersen, Sven; Runge, Benjamin; Magnussen, Olaf M; Steinrück, Hans-Georg; Reichert, Harald; Ocko, Benjamin M; Deutsch, Moshe

2018-02-06

Interfaces of room temperature ionic liquids (RTILs) are important for both applications and basic science and are therefore intensely studied. However, the evolution of their interface structure with the cation's alkyl chain length [Formula: see text] from Coulomb to van der Waals interaction domination has not yet been studied for even a single broad homologous RTIL series. We present here such a study of the liquid-air interface for [Formula: see text], using angstrom-resolution X-ray methods. For [Formula: see text], a typical "simple liquid" monotonic surface-normal electron density profile [Formula: see text] is obtained, like those of water and organic solvents. For [Formula: see text], increasingly more pronounced nanoscale self-segregation of the molecules' charged moieties and apolar chains yields surface layering with alternating regions of headgroups and chains. The layering decays into the bulk over a few, to a few tens, of nanometers. The layering periods and decay lengths, their linear [Formula: see text] dependence, and slopes are discussed within two models, one with partial-chain interdigitation and the other with liquid-like chains. No surface-parallel long-range order is found within the surface layer. For [Formula: see text], a different surface phase is observed above melting. Our results also impact general liquid-phase issues like supramolecular self-aggregation and bulk-surface structure relations.

Multiscale modeling of electroosmotic flow: Effects of discrete ion, enhanced viscosity, and surface friction

NASA Astrophysics Data System (ADS)

Bhadauria, Ravi; Aluru, N. R.

2017-05-01

We propose an isothermal, one-dimensional, electroosmotic flow model for slit-shaped nanochannels. Nanoscale confinement effects are embedded into the transport model by incorporating the spatially varying solvent and ion concentration profiles that correspond to the electrochemical potential of mean force. The local viscosity is dependent on the solvent local density and is modeled using the local average density method. Excess contributions to the local viscosity are included using the Onsager-Fuoss expression that is dependent on the local ionic strength. A Dirichlet-type boundary condition is provided in the form of the slip velocity that is dependent on the macroscopic interfacial friction. This solvent-surface specific interfacial friction is estimated using a dynamical generalized Langevin equation based framework. The electroosmotic flow of Na+ and Cl- as single counterions and NaCl salt solvated in Extended Simple Point Charge (SPC/E) water confined between graphene and silicon slit-shaped nanochannels are considered as examples. The proposed model yields a good quantitative agreement with the solvent velocity profiles obtained from the non-equilibrium molecular dynamics simulations.

Charge-screening role of c -axis atomic displacements in YBa 2 Cu 3 O 6 + x and related superconductors

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

Božin, E. S.; Huq, A.; Shen, Bing

2016-02-01

The importance of charge reservoir layers for supplying holes to the CuO2 planes of cuprate superconductors has long been recognized. Less attention has been paid to the screening of the charge transfer by the intervening ionic layers.We address this issue in the case of YBa2Cu3O6+x , where CuO chains supply the holes for the planes. We present a simple dielectric-screening model that gives a linear correlation between the relative displacements of ions along the c axis, determined by neutron powder diffraction, and the hole density of the planes. Applying this model to the temperature-dependent shifts of ions along the cmore » axis, we infer a charge transfer of 5–10% of the hole density from the planes to the chains on warming from the superconducting transition to room temperature. Given the significant coupling of c-axis displacements to the average charge density, we point out the relevance of local displacements for screening charge modulations and note recent evidence for dynamic screening of in-plane quasiparticles. This line of argument leads us to a simple model for atomic displacements and charge modulation that is consistent with images from scanning-tunneling microscopy for underdoped Bi2Sr2CaCu2O8+δ .« less

Charge-screening role of c-axis atomic displacements in YBa 2Cu 3O 6+x and related superconductors

DOE PAGES

E. S. Bozin; Huq, A.; Shen, Bing; ...

2016-02-29

The importance of charge reservoir layers for supplying holes to the CuO 2 planes of cuprate superconductors has long been recognized. Less attention has been paid to the screening of the charge transfer by the intervening ionic layers. We address this issue in the case of YBa 2Cu 3O 6+x, where CuO chains supply the holes for the planes. We present a simple dielectric-screening model that gives a linear correlation between the relative displacements of ions along the c axis, determined by neutron powder diffraction, and the hole density of the planes. Applying this model to the temperature-dependent shifts ofmore » ions along the c axis, we infer a charge transfer of 5-10% of the hole density from the planes to the chains on warming from the superconducting transition to room temperature. Given the significant coupling of c-axis displacements to the average charge density, we point out the relevance of local displacements for screening charge modulations and note recent evidence for dynamic screening of in-plane quasiparticles. Furthermore, this line of argument leads us to a simple model for atomic displacements and charge modulation that is consistent with images from scanning-tunneling microscopy for underdoped Bi 2Sr 2CaCu 2O 8+δ.« less

Communication: Stiff and soft nano-environments and the "Octopus Effect" are the crux of ionic liquid structural and dynamical heterogeneity

NASA Astrophysics Data System (ADS)

Daly, Ryan P.; Araque, Juan C.; Margulis, Claudio J.

2017-08-01

In a recent set of articles [J. C. Araque et al., J. Phys. Chem. B 119(23), 7015-7029 (2015) and J. C. Araque et al., J. Chem. Phys. 144, 204504 (2016)], we proposed the idea that for small neutral and charged solutes dissolved in ionic liquids, deviation from simple hydrodynamic predictions in translational and rotational dynamics can be explained in terms of diffusion through nano-environments that are stiff (high electrostriction, charge density, and number density) and others that are soft (charge depleted). The current article takes a purely solvent-centric approach in trying to provide molecular detail and intuitive visual understanding of time-dependent local mobility focusing on the most common case of an ionic liquid with well defined polar and apolar nano-domains. We find that at intermediate time scales, apolar regions are fluid, whereas the charge network is much less mobile. Because apolar domains and cationic heads must diffuse as single species, at long time the difference in mobility also necessarily dissipates.

Catalytic Conversion of Carbohydrates to Levulinate Ester over Heteropolyanion-Based Ionic Liquids.

PubMed

Song, Changhua; Liu, Sijie; Peng, Xinwen; Long, Jinxing; Lou, Wenyong; Li, Xuehui

2016-12-08

An efficient one-pot approach for the production of levulinate ester from renewable carbohydrates is demonstrated over heteropolyanion-based ionic liquid (IL-POM) catalysts with alcohols as the promoters and solvents. The relationships between the structure, acidic strength, and solubility of the IL-POM in methanol and the catalytic performance were studied intensively. A cellulose conversion of 100 % could be achieved with a 71.4 % yield of methyl levulinate over the catalyst [PyPS] 3 PW 12 O 40 [PyPS=1-(3-sulfopropyl)pyridinium] at 150 °C for 5 h. This high efficiency is ascribed to the reasonably high activity of the ionic liquid (IL) catalyst and reaction coupling with rapid in situ esterification of the generated levulinic acid with the alcohol promoter, which allows the insolubility of cellulose encountered in biomass conversion to be overcome. Furthermore, the present process exhibits high feedstock adaptability for typical carbohydrates and handy catalyst recovery by a simple self-separation procedure through temperature control. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquid-based air-assisted liquid-liquid microextraction followed by high performance liquid chromatography for the determination of five fungicides in juice samples.

PubMed

You, Xiangwei; Chen, Xiaochu; Liu, Fengmao; Hou, Fan; Li, Yiqiang

2018-01-15

A novel and simple ionic liquid-based air-assisted liquid-liquid microextraction technique combined with high performance liquid chromatography was developed to analyze five fungicides in juice samples. In this method, ionic liquid was used instead of a volatile organic solvent as the extraction solvent. The emulsion was formed by pulling in and pushing out the mixture of aqueous sample solution and extraction solvent repeatedly using a 10mL glass syringe. No organic dispersive solvent was required. Under the optimized conditions, the limits of detection (LODs) were 0.4-1.8μgL -1 at a signal-to-noise ratio of 3. The limits of quantification (LOQs) set as the lowest spiking levels with acceptable recovery in juices were 10μgL -1 , except for fludioxonil whose LOQ was 20μgL -1 . The proposed method was applied to determine the target fungicides in juice samples, and acceptable recoveries ranging from 74.9% to 115.4% were achieved. Copyright © 2017. Published by Elsevier Ltd.

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.

Ionic liquids as electrolytes for the development of a robust amperometric oxygen sensor.

PubMed

Wang, Zhe; Lin, Peiling; Baker, Gary A; Stetter, Joseph; Zeng, Xiangqun

2011-09-15

A simple Clark-type online electrochemical cell design, consisting of a platinum gauze working electrode and incorporating ionic liquids (IL) as electrolytes, has been successfully applied for the amperometric sensing of oxygen. Studying ILs comprising the bis(trifluoromethylsulfonyl)imide anion, the obtained analytical parameters were found to be strongly dependent on the choice of cation. Compared with a conventional Clark cell design based on an aqueous supporting electrolyte, the modified oxygen sensor achieves substantial improvements in performance and stability. A limit of detection for oxygen as low as 0.05 vol %, linearity over an oxygen partial pressure between 0% and 20%, and a steady-state response time of 2 min was demonstrated, with a stable analytical response shown over the examined period of 90 days with no obvious fouling of the electrode surface. Based on the attractive physical attributes of ionic liquids (e.g., thermal stability beyond 150 °C), one can envision intriguing utility in nonstandard conditions and long-term online applications, as well as extension to the determination of other gases, such as methane and nitric oxide.

Effect of pressure on decoupling of ionic conductivity from structural relaxation in hydrated protic ionic liquid, lidocaine HCl.

PubMed

Swiety-Pospiech, A; Wojnarowska, Z; Hensel-Bielowka, S; Pionteck, J; Paluch, M

2013-05-28

Broadband dielectric spectroscopy and pressure-temperature-volume methods are employed to investigate the effect of hydrostatic pressure on the conductivity relaxation time (τσ), both in the supercooled and glassy states of protic ionic liquid lidocaine hydrochloride monohydrate. Due to the decoupling between the ion conductivity and structural dynamics, the characteristic change in behavior of τσ(T) dependence, i.e., from Vogel-Fulcher-Tammann-like to Arrhenius-like behavior, is observed. This crossover is a manifestation of the liquid-glass transition of lidocaine HCl. The similar pattern of behavior was also found for pressure dependent isothermal measurements. However, in this case the transition from one simple volume activated law to another was noticed. Additionally, by analyzing the changes of conductivity relaxation times during isothermal densification of the sample, it was found that compression enhances the decoupling of electrical conductivity from the structural relaxation. Herein, we propose a new parameter, dlogRτ∕dP, to quantify the pressure sensitivity of the decoupling phenomenon. Finally, the temperature and volume dependence of τσ is discussed in terms of thermodynamic scaling concept.

Micropatterned Pyramidal Ionic Gels for Sensing Broad-Range Pressures with High Sensitivity.

PubMed

Cho, Sung Hwan; Lee, Seung Won; Yu, Seunggun; Kim, Hyeohn; Chang, Sooho; Kang, Donyoung; Hwang, Ihn; Kang, Han Sol; Jeong, Beomjin; Kim, Eui Hyuk; Cho, Suk Man; Kim, Kang Lib; Lee, Hyungsuk; Shim, Wooyoung; Park, Cheolmin

2017-03-22

The development of pressure sensors that are effective over a broad range of pressures is crucial for the future development of electronic skin applicable to the detection of a wide pressure range from acoustic wave to dynamic human motion. Here, we present flexible capacitive pressure sensors that incorporate micropatterned pyramidal ionic gels to enable ultrasensitive pressure detection. Our devices show superior pressure-sensing performance, with a broad sensing range from a few pascals up to 50 kPa, with fast response times of <20 ms and a low operating voltage of 0.25 V. Since high-dielectric-constant ionic gels were employed as constituent sensing materials, an unprecedented sensitivity of 41 kPa -1 in the low-pressure regime of <400 Pa could be realized in the context of a metal-insulator-metal platform. This broad-range capacitive pressure sensor allows for the efficient detection of pressure from a variety of sources, including sound waves, a lightweight object, jugular venous pulses, radial artery pulses, and human finger touch. This platform offers a simple, robust approach to low-cost, scalable device design, enabling practical applications of electronic skin.

Ionic Liquid Activation of Amorphous Metal-Oxide Semiconductors for Flexible Transparent Electronic Devices

DOE PAGES

Pudasaini, Pushpa Raj; Noh, Joo Hyon; Wong, Anthony T.; ...

2016-02-09

To begin this abstract, amorphous metal-oxide semiconductors offer the high carrier mobilities and excellent large-area uniformity required for high performance, transparent, flexible electronic devices; however, a critical bottleneck to their widespread implementation is the need to activate these materials at high temperatures which are not compatible with flexible polymer substrates. The highly controllable activation of amorphous indium gallium zinc oxide semiconductor channels using ionic liquid gating at room temperature is reported. Activation is controlled by electric field-induced oxygen migration across the ionic liquid-semiconductor interface. In addition to activation of unannealed devices, it is shown that threshold voltages of a transistormore » can be linearly tuned between the enhancement and depletion modes. Finally, the first ever example of transparent flexible thin film metal oxide transistor on a polyamide substrate created using this simple technique is demonstrated. Finally, this study demonstrates the potential of field-induced activation as a promising alternative to traditional postdeposition thermal annealing which opens the door to wide scale implementation into flexible electronic applications.« less

Growth of self-textured Ga3+-substituted Li7La3Zr2O12 ceramics by solid state reaction and their significant enhancement in ionic conductivity

NASA Astrophysics Data System (ADS)

Qin, Shiying; Zhu, Xiaohong; Jiang, Yue; Ling, Ming'en; Hu, Zhiwei; Zhu, Jiliang

2018-03-01

A highly self-textured Ga2O3-substituted Li7La3Zr2O12 (LLZO-Ga) solid electrolyte with a nominal composition of Li6.55Ga0.15La3Zr2O12 is obtained by a simple and low-cost solid-state reaction technique, requiring no seed crystals to achieve grain orientation. The as-prepared self-textured LLZO-Ga shows a strong (420) preferred orientation with a high Lotgering factor of 0.91. Coherently, a terrace-shaped microstructure consisting of many parallel layers, indicating a two-dimensional-like growth mode, is clearly observed in the self-textured sample. As a result, the highly self-textured garnet-type lithium-ion conducting solid electrolyte of LLZO-Ga exhibits an extremely high ionic conductivity, reaching a state-of-the-art level of 2.06 × 10-3 S cm-1 at room temperature (25 °C) and thus shedding light on an important strategy for improving the structure and ionic conductivity of solid electrolytes.

Characterization and structural study of the complex of Al(III) with 2,4-dihydroxy-benzophenone. Ionic strength and solvent effects.

PubMed

Castro, G T; Blanco, S E; Arce, S L; Ferretti, F H

2003-10-01

The complexation reaction between AlCl(3) and 2,4-dihydroxy-benzophenone with varying permittivity and ionic strength of the reaction medium was investigated by theoretical and experimental procedures, namely, density functional (DFT) and UV-vis spectroscopic methods, respectively. The stoichiometric composition of the complex formed, which was determined by means of the molar ratio method, is 1:1. The molar absorptivity and stability constant of the complex were determined using a method designed by the authors. It was observed that the stoichiometric composition of the complex does not change with the used solvents and that the stability constant in methanol is higher than ethanol. Kinetic experiments in solutions with different ionic strength were also performed. The results obtained permit to conclude that the complex is formed through of a mechanism whose rate-determining step is a reaction between two ions with opposite unitary charges. In the theoretical study performed at the B3LYP/6-31G(d) level of theory using Tomasi's model, it was proposed that the formation of the complex involves one simple covalent bond between the aluminum atom and the oxygen atom of o-hydroxyl group of the ligand and a stronger coulombic attraction (or a second covalent bond) between the central atom and the carbonyl oxygen atom of 2,4-dihydroxy-benzophenone. Using the calculated magnitudes, it was predicted that the complex formed has higher thermodynamic stability in methanol than ethanol. It was also concluded that the planarity of the chelate ring favors a greater planarity of 4-hydroxy-benzoyl group of the complex with respect to the ligand, which agrees with the observed batochromic shifts. The formulated theoretical conclusions satisfactorily match the experimental determinations performed.

Determination of triazine herbicides in fresh vegetables by dynamic microwave-assisted extraction coupled with homogeneous ionic liquid microextraction high performance liquid chromatography.

PubMed

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

2015-02-01

A novel extraction method, dynamic microwave-assisted extraction coupled with homogeneous ionic liquid microextraction, was developed for the determination of triazine herbicides, including desmetryn, terbumeton, propazine, terbuthylazine, dimethametryn, and dipropetryn in fresh vegetable samples by high performance liquid chromatography (HPLC). In the developed method, 120 μL of 1-butyl-3-methylimidazolium tetrafluoroborate ([C4MIM][BF4]) was added to 10 mL of aqueous solution containing 0.3 g of NaCl to obtained the extraction solvent. Six triazines could be extracted completely within 4 min by the present method. Then, [NH4][PF6] was added into the extract to form a water-insoluble ionic liquid [C4MIM][PF6] via a simple metathesis reaction, and the analytes were enriched into the ionic liquid phase. After centrifugation and dilution with acetonitrile, the resulting solution was analyzed directly by HPLC. The effects of some experimental parameters, including type and volume of ionic liquid, volume of extraction solvent, amount of ion-pairing agent [NH4][PF6], salt concentration, microwave power, and flow rate of extraction solvent on the extraction efficiency were investigated and optimized. Under the optimum experimental conditions, the linearity for determining the analytes was in the range of 2.50-250.00 μg kg(-1), with the correlation coefficients ranging from 0.9989 to 0.9999. When the present method was applied to the analysis of vegetable samples, satisfactory recoveries were obtained in the range of 76.8%-106.9%, and relative standard deviations were lower than 9.8%.

Electrohydrodynamic ionic wind, force field, and ionic mobility in a positive dc wire-to-cylinders corona discharge in air

NASA Astrophysics Data System (ADS)

Monrolin, Nicolas; Praud, Olivier; Plouraboué, Franck

2018-06-01

Ionic wind refers to the acceleration of partially ionized air between two high-voltage electrodes. We study the momentum transfer from ions to air, resulting from ionic wind created by two asymmetric electrodes and producing a net thrust. This electrohydrodynamic (EHD) thrust, has already been measured in previous studies with digital scales. In this study, we provide more insights into the electrohydrodynamic momentum transfer for a wire-to-cylinder(s) positive dc corona discharge. We provide a simple and general theoretical derivation for EHD thrust, which is proportional to the current/mobility ratio and also to an effective distance integrated on the surface of the electrodes. By considering various electrode configurations, our investigation brings out the physical origin of previously obtained optimal configurations, associated with a better tradeoff between Coulomb forcing, friction occurring at the collector, and wake interactions. By measuring two-dimensional velocity fields using particle image velocimetry (PIV), we are able to evaluate the resulting local net force, including the pressure gradient. It is shown that the contribution of velocity fluctuations in the wake of the collecting electrode(s) must be taken into account to recover the net thrust. We confirm the proportionality between the EHD force and the current/mobility ratio experimentally, and evaluate the ion mobility from PIV measurements. A spectral analysis of the velocity fluctuations indicates a dominant frequency corresponding to a Strouhal number of 0.3 based on the ionic wind velocity and the collector size. Finally, the effective mobility of charge carriers is estimated by a PIV based method inside the drift region.

Transferable Coarse-Grained Models for Ionic Liquids.

PubMed

Wang, Yanting; Feng, Shulu; Voth, Gregory A

2009-04-14

The effective force coarse-graining (EF-CG) method was applied to the imidazolium-based nitrate ionic liquids with various alkyl side-chain lengths. The nonbonded EF-CG forces for the ionic liquid with a short side chain were extended to generate the nonbonded forces for the ionic liquids with longer side chains. The EF-CG force fields for the ionic liquids exhibit very good transferability between different systems at various temperatures and are suitable for investigating the mesoscopic structural properties of this class of ionic liquids. The good additivity and ease of manipulation of the EF-CG force fields can allow for an inverse design methodology of ionic liquids at the coarse-grained level. With the EF-CG force field, the molecular dynamics (MD) simulation at a very large scale has been performed to check the significance of finite size effects on the structural properties. From these MD simulation results, it can be concluded that the finite size effect on the phenomenon of ionic liquid spatial heterogeneity (Wang, Y.; Voth, G. A. J. Am. Chem. Soc. 2005, 127, 12192) is small and that this phenomenon is indeed a nanostructural behavior which leads to the experimentally observed mesoscopic heterogeneous structure of ionic liquids.

Generation of a mesoporous silica MSU shell onto solid core silica nanoparticles using a simple two-step sol-gel process.

PubMed

Allouche, Joachim; Dupin, Jean-Charles; Gonbeau, Danielle

2011-07-14

Silica core-shell nanoparticles with a MSU shell have been synthesized using several non-ionic poly(ethylene oxide) based surfactants via a two step sol-gel method. The materials exhibit a typical worm-hole pore structure and tunable pore diameters between 2.4 nm and 5.8 nm.

The Synthesis and Characterization of Rouaite, a Copper Hydroxy Nitrate: An Integrated First-Year Laboratory Project

ERIC Educational Resources Information Center

Bushong, Elizabeth J.; Yoder, Claude H.

2009-01-01

The synthesis and analysis of a copper hydroxy nitrate provides an exposure to a simple ionic synthesis, qualitative analysis of copper and nitrate, two gravimetric analyses (copper and nitrate), one volumetric analysis (hydroxide), and a colorimetric analysis (copper). The results allow the student to determine the identity of the double salt and…

Effects of molecular model, ionic strength, divalent ions, and hydrophobic interaction on human neurofilament conformation

NASA Astrophysics Data System (ADS)

Lee, Joonseong; Kim, Seonghoon; Chang, Rakwoo; Jayanthi, Lakshmi; Gebremichael, Yeshitila

2013-01-01

The present study examines the effects of the model dependence, ionic strength, divalent ions, and hydrophobic interaction on the structural organization of the human neurofilament (NF) brush, using canonical ensemble Monte Carlo (MC) simulations of a coarse-grained model with the amino-acid resolution. The model simplifies the interactions between the NF core and the sidearm or between the sidearms by the sum of excluded volume, electrostatic, and hydrophobic interactions, where both monovalent salt ions and solvents are implicitly incorporated into the electrostatic interaction potential. Several important observations are made from the MC simulations of the coarse-grained model NF systems. First, the mean-field type description of monovalent salt ions works reasonably well in the NF system. Second, the manner by which the NF sidearms are arranged on the surface of the NF backbone core has little influence on the lateral extension of NF sidearms. Third, the lateral extension of the NF sidearms is highly affected by the ionic strength of the system: at low ionic strength, NF-M is most extended but at high ionic strength, NF-H is more stretched out because of the effective screening of the electrostatic interaction. Fourth, the presence of Ca2 + ions induces the attraction between negatively charged residues, which leads to the contraction of the overall NF extension. Finally, the introduction of hydrophobic interaction does not change the general structural organization of the NF sidearms except that the overall extension is contracted.

Osmotic Pressure of Aqueous Chondroitin Sulfate Solution: A Molecular Modeling Investigation

PubMed Central

Bathe, Mark; Rutledge, Gregory C.; Grodzinsky, Alan J.; Tidor, Bruce

2005-01-01

The osmotic pressure of chondroitin sulfate (CS) solution in contact with an aqueous 1:1 salt reservoir of fixed ionic strength is studied using a recently developed coarse-grained molecular model. The effects of sulfation type (4- vs. 6-sulfation), sulfation pattern (statistical distribution of sulfate groups along a chain), ionic strength, CS intrinsic stiffness, and steric interactions on CS osmotic pressure are investigated. At physiological ionic strength (0.15 M NaCl), the sulfation type and pattern, as measured by a standard statistical description of copolymerization, are found to have a negligible influence on CS osmotic pressure, which depends principally on the mean volumetric fixed charge density. The intrinsic backbone stiffness characteristic of polysaccharides such as CS, however, is demonstrated to contribute significantly to its osmotic pressure behavior, which is similar to that of a solution of charged rods for the 20-disaccharide chains considered. Steric excluded volume is found to play a negligible role in determining CS osmotic pressure at physiological ionic strength due to the dominance of repulsive intermolecular electrostatic interactions that maintain chains maximally spaced in that regime, whereas at high ionic-strength steric interactions become dominant due to electrostatic screening. Osmotic pressure predictions are compared to experimental data and to well-established theoretical models including the Donnan theory and the Poisson-Boltzmann cylindrical cell model. PMID:16055525

Improved thermodynamic model for interaction of EDTA with trivalent actinides and lanthanide to ionic strength of 6.60 m

NASA Astrophysics Data System (ADS)

Thakur, Punam; Xiong, Yongliang; Borkowski, Marian; Choppin, Gregory R.

2014-05-01

The dissociation constants of ethylenediaminetetraacetic acid (H4EDTA), and the stability constants of Am3+, Cm3+and Eu3+ with EDTA4- have been determined at 25 °C, over a range of concentration varying from 0.1 to 6.60 m NaClO4 using potentiometric titration and an extraction technique, respectively. The formation of only 1:1 complex, M(EDTA)-, where (M = Am3+, Cm3+ and Eu3+), was observed under the experimental conditions. The observed ionic strength dependencies of the dissociation constants and the stability constants have been described successfully over the entire ionic strength range using the Pitzer model. The thermodynamic stability constant: logβ1010=20.55±0.18 for Am3+, logβ1010=20.43±0.20 for Cm3+ and logβ1010=20.65±0.19 for Eu3+ were calculated by extrapolation of data to zero ionic strength in an NaClO4 medium. In addition, logβ1010 of 20.05 ± 0.40 for Am3+ was obtained by simultaneously modeling data both in NaCl and NaClO4 media. For all stability constants, the Pitzer model gives an excellent representation of the data using interaction parameters β(0), β(1), and Cϕ determined in this work. The improved model presented in this work would enable researchers to model accurately the potential mobility of actinides (III) and light rare earth elements to ionic strength of 6.60 m in low temperature environments in the presence of EDTA.

Determination of heat capacity of ionic liquid based nanofluids using group method of data handling technique

NASA Astrophysics Data System (ADS)

Sadi, Maryam

2018-01-01

In this study a group method of data handling model has been successfully developed to predict heat capacity of ionic liquid based nanofluids by considering reduced temperature, acentric factor and molecular weight of ionic liquids, and nanoparticle concentration as input parameters. In order to accomplish modeling, 528 experimental data points extracted from the literature have been divided into training and testing subsets. The training set has been used to predict model coefficients and the testing set has been applied for model validation. The ability and accuracy of developed model, has been evaluated by comparison of model predictions with experimental values using different statistical parameters such as coefficient of determination, mean square error and mean absolute percentage error. The mean absolute percentage error of developed model for training and testing sets are 1.38% and 1.66%, respectively, which indicate excellent agreement between model predictions and experimental data. Also, the results estimated by the developed GMDH model exhibit a higher accuracy when compared to the available theoretical correlations.

Charge ordering in ionic fluids mediate repulsive surface interactions

NASA Astrophysics Data System (ADS)

Dasbiswas, Kinjal; Ludwig, Nicholas B.; Zhang, Hao; Talapin, Dmitri; Vaikuntanathan, Suri

Recent experiments on ionic fluids, such as surface force measurements in organic ionic liquids and the observation of colloidal stability in inorganic molten salts, suggest the presence of long-ranged repulsive forces. These cannot be explained within the classical Debye-Hückel theory for dilute electrolytes. We argue that such repulsive interactions can arise from long-range (several nm) charge density oscillations induced by a surface that preferentially binds one of the ionic species in an ionic fluid. We present a continuum theory that accounts for such charge layering based on a frustrated Ising model that incorporates both long-range Coulombic and short-range steric interactions. The mean-field analytic treatment qualitatively matches results from molecular simulations. A careful analysis of the ionic correlation functions arising from such charge ordering may also explain the long electrostatic screening lengths observed in various ionic fluids and their non-monotonic dependence on the electrolyte concentration. We acknowledge the University of Chicago for support.

Studies of ionic current rectification using polyethyleneimines coated glass nanopipettes.

PubMed

Liu, Shujuan; Dong, Yitong; Zhao, Wenbo; Xie, Xiang; Ji, Tianrong; Yin, Xiaohong; Liu, Yun; Liang, Zhongwei; Momotenko, Dmitry; Liang, Dehai; Girault, Hubert H; Shao, Yuanhua

2012-07-03

The modification of glass nanopipettes with polyethyleneimines (PEIs) has been successfully achieved by a relatively simple method, and the smallest tip opening is around 3 nm. Thus, in a much wider range of glass pipettes with radii from several nanometers to a few micrometers, the ion current rectification (ICR) phenomenon has been observed. The influences of different KCl concentrations, pH values, and tip radii on the ICR are investigated in detail. The sizes of PEIs have been determined by dynamic light scattering, and the effect of the sizes of PEIs for the modification, especially for a few nanometer-pipettes in radii, is also discussed. These findings systemically confirm and complement the theoretical model and provide a platform for possible selectively molecular detection and mimic biological ion channels.

Conductivity of an inverse lyotropic lamellar phase under shear flow

NASA Astrophysics Data System (ADS)

Panizza, P.; Soubiran, L.; Coulon, C.; Roux, D.

2001-08-01

We report conductivity measurements on solutions of closed compact monodisperse multilamellar vesicles (the so-called ``onion texture'') formed by shearing an inverse lyotropic lamellar Lα phase. The conductivity measured in different directions as a function of the applied shear rate reveals a small anisotropy of the onion structure due to the existence of free oriented membranes. The results are analyzed in terms of a simple model that allows one to deduce the conductivity tensor of the Lα phase itself and the proportion of free oriented membranes. The variation of these two parameters is measured along a dilution line and discussed. The high value of the conductivity perpendicular to the layers with respect to that of solvent suggests the existence of a mechanism of ionic transport through the insulating solvent.

Shaking stack model of ion conduction through the Ca(2+)-activated K+ channel.

PubMed Central

Schumaker, M F

1992-01-01

Motivated by the results of Neyton and Miller (1988. J. Gen. Physiol. 92:549-586), suggesting that the Ca(2+)-activated K+ channel has four high affinity ion binding sites, we propose a physically attractive variant of the single-vacancy conduction mechanism for this channel. Simple analytical expressions for conductance, current, flux ratio exponent, and reversal potential under bi-ionic conditions are found. A set of conductance data are analyzed to determine a realistic range of parameter values. Using these, we find qualitative agreement with a variety of experimental results previously reported in the literature. The exquisite selectivity of the Ca(2+)-activated K+ channel may be explained as a consequence of the concerted motion of the "stack" in the proposed mechanism. PMID:1420923

Electron Impact K-shell Ionization Cross Sections at high energies

NASA Astrophysics Data System (ADS)

Haque, A. K. F.; Sarker, M. S. I.; Patoary, M. A. R.; Shahjahan, M.; Ismail Hossain, M.; Alfaz Uddin, M.; Basak, A. K.; Saha, Bidhan

2008-10-01

A simple modification of the empirical model of Deutsh et. al. [1] by incorporating both the ionic [2] and relativistic corrections [3] is proposed for evaluating the electron impact K -shell ionization cross sections of neutral atomic targets. Present results for 30 atomic targets with atomic number Z=1 -- 92 for incident energies up to E=2 GeV, agree well with available experimental cross sections. Comparisons with other theoretical findings will also be presented at the conference. [1] H. Deutsh, K. Becker, T. D. Mark, Int. J. Mass Spect. 177, 47 (1998). [2] M. A. Uddin, A. K. F. Haque, M. M. Billah, A. K. Basak, K. R. Karim, B. C. Saha, Phys. Rev. A 71, 032715 (2005).; Phys. Rev. A 73, 012708 (2006). [3] M. Gryzinski, Phys. Rev 138, 336 (1965).

Complete description of all self-similar models driven by Lévy stable noise

NASA Astrophysics Data System (ADS)

Weron, Aleksander; Burnecki, Krzysztof; Mercik, Szymon; Weron, Karina

2005-01-01

A canonical decomposition of H -self-similar Lévy symmetric α -stable processes is presented. The resulting components completely described by both deterministic kernels and the corresponding stochastic integral with respect to the Lévy symmetric α -stable motion are shown to be related to the dissipative and conservative parts of the dynamics. This result provides stochastic analysis tools for study the anomalous diffusion phenomena in the Langevin equation framework. For example, a simple computer test for testing the origins of self-similarity is implemented for four real empirical time series recorded from different physical systems: an ionic current flow through a single channel in a biological membrane, an energy of solar flares, a seismic electric signal recorded during seismic Earth activity, and foreign exchange rate daily returns.

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.

Selective complexation of K+ and Na+ in simple polarizable ion-ligating systems.

PubMed

Bostick, David L; Brooks, Charles L

2010-09-29

An influx of experimental and theoretical studies of ion transport protein structure has inspired efforts to understand underlying determinants of ionic selectivity. Design principles for selective ion binding can be effectively isolated and interrogated using simplified models composed of a single ion surrounded by a set of ion-ligating molecular species. While quantum mechanical treatments of such systems naturally incorporate electronic degrees of freedom, their computational overhead typically prohibits thorough dynamic sampling of configurational space and, thus, requires approximations when determining ion-selective free energy. As an alternative, we employ dynamical simulations with a polarizable force field to probe the structure and K(+)/Na(+) selectivity in simple models composed of one central K(+)/Na(+) ion surrounded by 0-8 identical model compounds: N-methylacetamide, formamide, or water. In the absence of external restraints, these models represent gas-phase clusters displaying relaxed coordination structures with low coordination number. Such systems display Na(+) selectivity when composed of more than ∼3 organic carbonyl-containing compounds and always display K(+) selectivity when composed of water molecules. Upon imposing restraints that solely enforce specific coordination numbers, we find all models are K(+)-selective when ∼7-8-fold ion coordination is achieved. However, when models composed of the organic compounds provide ∼4-6-fold coordination, they retain their Na(+) selectivity. From these trends, design principles emerge that are of basic importance in the behavior of K(+) channel selectivity filters and suggest a basis not only for K(+) selectivity but also for modulation of block and closure by smaller ions.

Ginzburg criterion for ionic fluids: the effect of Coulomb interactions.

PubMed

Patsahan, O

2013-08-01

The effect of the Coulomb interactions on the crossover between mean-field and Ising critical behavior in ionic fluids is studied using the Ginzburg criterion. We consider the charge-asymmetric primitive model supplemented by short-range attractive interactions in the vicinity of the gas-liquid critical point. The model without Coulomb interactions exhibiting typical Ising critical behavior is used to calibrate the Ginzburg temperature of the systems comprising electrostatic interactions. Using the collective variables method, we derive a microscopic-based effective Hamiltonian for the full model. We obtain explicit expressions for all the relevant Hamiltonian coefficients within the framework of the same approximation, i.e., the one-loop approximation. Then we consistently calculate the reduced Ginzburg temperature t(G) for both the purely Coulombic model (a restricted primitive model) and the purely nonionic model (a hard-sphere square-well model) as well as for the model parameters ranging between these two limiting cases. Contrary to the previous theoretical estimates, we obtain the reduced Ginzburg temperature for the purely Coulombic model to be about 20 times smaller than for the nonionic model. For the full model including both short-range and long-range interactions, we show that t(G) approaches the value found for the purely Coulombic model when the strength of the Coulomb interactions becomes sufficiently large. Our results suggest a key role of Coulomb interactions in the crossover behavior observed experimentally in ionic fluids as well as confirm the Ising-like criticality in the Coulomb-dominated ionic systems.

Fluids of the lower crust and upper mantle: deep is different

NASA Astrophysics Data System (ADS)

Manning, C. E.

2017-12-01

Deep fluids are important for the evolution and properties of the lower crust and upper mantle in tectonically active settings. Uncertainty about their chemistry has led past workers to use upper crustal fluids as analogues. However, recent results show that fluids at >15 km differ fundamentally from shallow fluids and help explain high-pressure metasomatism and resistivity patterns. Deep fluids are comprised of four components: H2O, non-polar gases (chiefly CO2), salts (mostly alkali chlorides), and rock-derived solutes (dominated by aluminosilicates and related components). The first three generally define the solvent properties of the fluid, and models must account for observations that H2O activity may be quite low. The contrasting behavior of H2O-gas and H2O-salt mixtures yields immiscibility in the ternary system, which can lead to separation of two phases with fundamentally different chemical and transport properties. Thermodynamic modeling of equilibrium between rocks and H2O using simple ionic species known from shallow-crustal systems yields solutions possessing total dissolved solids and ionic strength that are too low to be consistent with experiments and resistivity surveys. Addition of CO2 further lowers bulk solubility and conductivity. Therefore, additional species must be present in H2O, and H2O-salt solutions likely explain much of the evidence for fluid action in high-P settings. At low salinity, H2O-rich fluids are powerful solvents for aluminosilicate rock components that are dissolved as previously unrecognized polymerized clusters. Experiments show that, near H2O-saturated melting, Al-Si polymers comprise >80% of solutes. The stability of these species facilitates critical critical mixing in rock-H2O systems. Addition of salt (e.g., NaCl) changes solubility patterns, but aluminosilicate contents remain high. Thermodynamic models indicate that the ionic strength of fluids with Xsalt = 0.05 to 0.4 and equilibrated with model crustal rocks have predicted bulk conductivities of 10-1.5 to 100 S/m at porosity of 0.001. Such fluids are thus consistent with conductivity anomalies commonly observed in the lower crust (e.g., the "G" anomaly), and are capable of the mass transfer commonly seen in metamorphic rocks exhumed from the lower crust and subduction zones.

Ionic liquid phase microextraction combined with fluorescence spectrometry for preconcentration and quantitation of carvedilol in pharmaceutical preparations and biological media.

PubMed

Zeeb, Mohsen; Mirza, Behrooz

2015-04-30

Carvedilol belongs to a group of medicines termed non-selective beta-adrenergic blocking agents. In the presented approach, a practical and environmentally friendly microextraction method based on the application of ionic liquids (ILs) was followed by fluorescence spectrometry for trace determination of carvedilol in pharmaceutical and biological media. A rapid and simple ionic liquid phase microextraction was utilized for preconcentration and extraction of carvedilol. A hydrophobic ionic liquid (IL) was applied as a microextraction solvent. In order to disperse the IL through the aqueous media and extract the analyte of interest, IL was injected into the sample solution and a proper temperature was applied and then for aggregating the IL-phase, the sample was cooled in an ice water-bath. The aqueous media was centrifuged and IL-phase collected at the bottom of the test tube was introduced to the micro-cell of spectrofluorimeter, in order to determine the concentration of the enriched analyte. Main parameters affecting the accuracy and precision of the proposed approach were investigated and optimized values were obtained. A linear response range of 10-250 μg I(-1) and a limit of detection (LOD) of 1.7 μg I(-1) were obtained. Finally, the presented method was utilized for trace determination of carvedilol in commercial pharmaceutical preparations and biological media.

Ionic Liquid Dispersive Liquid-Liquid Microextraction Method for the Determination of Irinotecan, an Anticancer Drug, in Water and Urine Samples Using UV-Vis Spectrophotometry.

PubMed

Uysal, Deniz; Karadaş, Cennet; Kara, Derya

2017-05-01

A new, simple, efficient, and environmentally friendly ionic liquid dispersive liquid-liquid microextraction method was developed for the determination of irinotecan, an anticancer drug, in water and urine samples using UV-Vis spectrophotometry. The ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate was used as the extraction solvent, and ethanol was used as the disperser solvent. The main parameters affecting the extraction efficiency, including sample pH, volume of the ionic liquid, choice of the dispersive solvent and its volume, concentration of NaCl, and extraction and centrifugation times, were investigated and optimized. The effect of interfering species on the recovery of irinotecan was also examined. Under optimal conditions, the LOD (3σ) was 48.7 μg/L without any preconcentration. Because the urine sample was diluted 10-fold, the LOD for urine would be 487 μg/L. However, this could be improved 16-fold if preconcentration using a 40 mL aliquot of the sample is used. The proposed method was successfully applied to the determination of irinotecan in tap water, river water, and urine samples spiked with 10.20 mg/L for the water samples and 8.32 mg/L for the urine sample. The average recovery values of irinotecan determined were 99.1% for tap water, 109.4% for river water, and 96.1% for urine.

Ionic liquid-assisted photochemical synthesis of ZnO/Ag2O heterostructures with enhanced visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Zhao, Shuo; Zhang, Yiwei; Zhou, Yuming; Zhang, Chao; Fang, Jiasheng; Sheng, Xiaoli

2017-07-01

ZnO/Ag2O heterostructures have been successfully fabricated using ionic liquids (ILs) as templates by a simple photochemical route. The influence of the type of ionic liquid and synthetic method on the morphology of ZnO, as well as the photocatalytic activity for the degradation of Rhodamine B (RhB), tetracycline (TC) and ciprofloxacin (CIP) under ultraviolet and visible light irradiation was studied. The samples were characterized by XRD, SEM, TEM, PL and UV-vis DRS. The results established that the type of ionic liquid and synthetic method played an important role in the growth of ZnO nanoparticles. And as-fabricated ZnO/Ag2O materials exhibited self-assembled flower-like architecture whose size was about 3 μm. Moreover, as-prepared ZnO/Ag2O exhibited the enhanced photocatalytic activity than ZnO sample, which may be due to the special structure, heterojunction, enhanced adsorption capability of dye, the improved separation rate of photogenerated electron-hole pairs. According to the results of radical trapping experiments, it can be found that •OH and h+ were the main active species for the photocatalytic degradation of RhB. It is valuable to develop this facile route preparing the highly dispersive flower-like ZnO/Ag2O materials, which can be beneficial for environmental protection.

Ionic complexation as a non-covalent approach for the design of folate anchored rifampicin Gantrez nanoparticles.

PubMed

Date, Praveen V; Patel, Mitesh D; Majee, Sharmila B; Samad, Abdul; Devarajan, Padma V

2013-05-01

The present study discloses the design of folate anchored Rifampicin-Poly methylvinylether maleic anhydride copolymer (Gantrez AN-119, Gantrez) nanoparticles (RFMGzFa) by ionic complexation. Folic acid was anchored to the preformed drug loaded nanoparticles. Folic acid was anchored in different concentration by simply varying the amount of folic acid added during preparation. RFMGzFa nanoparticles were prepared by emulsion solvent diffusion method. Gantrez AN-119 rapidly hydrolyzes in aqueous medium releasing carboxylic acid groups, to create an acidic environment. This facilitates protonation and subsequent ionic complexation of folic acid with the carboxylic groups, to enable anchoring. FTIR spectra confirmed this interaction. Infrared imaging revealed distribution of folic acid across the nanoparticle surface. Nanoparticles were obtained in the size range 350-450 nm with RFM loading of 12-14% w/w. Zeta potential confirmed colloidal stability. TEM/SEM revealed spherical morphology. RFMGzFa nanoparticles exhibited sustained release of RFM and folic acid. Folic acid showed sustained release upto 12 h, which was ion exchange mediated. A 480% enhancement in RFM uptake with RFMGzFa nanoparticles compared to 300% with RFMGz nanoparticles in-vitro, in human macrophage cell line U-937, suggested the role of folic acid in folate receptor mediated uptake. Ionic complexation represents a simple non-covalent approach for anchoring folic acid on polymeric nanoparticles of Gantrez.

Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent.

PubMed

Liu, Yong-Qiang; Yu, Hong

2016-08-01

Indirect ultraviolet detection was conducted in ultraviolet-absorption-agent-added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li(+) , Na(+) , K(+) , and NH4 (+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography-indirect ultraviolet detection. The successful separation and detection of Li(+) , Na(+) , K(+) , and NH4 (+) within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new theoretical model for transmembrane potential and ion currents induced in a spherical cell under low frequency electromagnetic field.

PubMed

Zheng, Yu; Gao, Yang; Chen, Ruijuan; Wang, Huiquan; Dong, Lei; Dou, Junrong

2016-10-01

Time-varying electromagnetic fields (EMF) can induce some physiological effects in neuronal tissues, which have been explored in many applications such as transcranial magnetic stimulation. Although transmembrane potentials and induced currents have already been the subjects of many theoretical studies, most previous works about this topic are mainly completed by utilizing Maxwell's equations, often by solving a Laplace equation. In previous studies, cells were often considered to be three-compartment models with different electroconductivities in different regions (three compartments are often intracellular regions, membrane, and extracellular regions). However, models like that did not take dynamic ion channels into consideration. Therefore, one cannot obtain concrete ionic current changes such as potassium current change or sodium current change by these models. The aim of the present work is to present a new and more detailed model for calculating transmembrane potentials and ionic currents induced by time-varying EMF. Equations used in the present paper originate from Nernst-Plank equations, which are ionic current-related equations. The main work is to calculate ionic current changes induced by EMF exposure, and then transmembrane potential changes are calculated with Hodgkin-Huxley model. Bioelectromagnetics. 37:481-492, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

A potential model for sodium chloride solutions based on the TIP4P/2005 water model

NASA Astrophysics Data System (ADS)

Benavides, A. L.; Portillo, M. A.; Chamorro, V. C.; Espinosa, J. R.; Abascal, J. L. F.; Vega, C.

2017-09-01

Despite considerable efforts over more than two decades, our knowledge of the interactions in electrolyte solutions is not yet satisfactory. Not even one of the most simple and important aqueous solutions, NaCl(aq), escapes this assertion. A requisite for the development of a force field for any water solution is the availability of a good model for water. Despite the fact that TIP4P/2005 seems to fulfill the requirement, little work has been devoted to build a force field based on TIP4P/2005. In this work, we try to fill this gap for NaCl(aq). After unsuccessful attempts to produce accurate predictions for a wide range of properties using unity ionic charges, we decided to follow recent suggestions indicating that the charges should be scaled in the ionic solution. In this way, we have been able to develop a satisfactory non-polarizable force field for NaCl(aq). We evaluate a number of thermodynamic properties of the solution (equation of state, maximum in density, enthalpies of solution, activity coefficients, radial distribution functions, solubility, surface tension, diffusion coefficients, and viscosity). Overall the results for the solution are very good. An important achievement of our model is that it also accounts for the dynamical properties of the solution, a test for which the force fields so far proposed failed. The same is true for the solubility and for the maximum in density where the model describes the experimental results almost quantitatively. The price to pay is that the model is not so good at describing NaCl in the solid phase, although the results for several properties (density and melting temperature) are still acceptable. We conclude that the scaling of the charges improves the overall description of NaCl aqueous solutions when the polarization is not included.

Ionics of nanoheterogeneous materials

NASA Astrophysics Data System (ADS)

Uvarov, Nikolay F.

2007-05-01

The results of studies of composite ionic conductors are considered. The relationship between their properties and the ionic salt disordering and the interfacial interaction between the components of the material is analysed. Special attention is paid to models that describe the surface disordering and the mechanism of defect formation. The methods of calculation of physicochemical characteristics of composites, the thermodynamic stability and peculiarities of the genesis of the nanocomposite morphology are discussed.

Ionocovalency and Applications 1. Ionocovalency Model and Orbital Hybrid Scales

PubMed Central

Zhang, Yonghe

2010-01-01

Ionocovalency (IC), a quantitative dual nature of the atom, is defined and correlated with quantum-mechanical potential to describe quantitatively the dual properties of the bond. Orbiotal hybrid IC model scale, IC, and IC electronegativity scale, XIC, are proposed, wherein the ionicity and the covalent radius are determined by spectroscopy. Being composed of the ionic function I and the covalent function C, the model describes quantitatively the dual properties of bond strengths, charge density and ionic potential. Based on the atomic electron configuration and the various quantum-mechanical built-up dual parameters, the model formed a Dual Method of the multiple-functional prediction, which has much more versatile and exceptional applications than traditional electronegativity scales and molecular properties. Hydrogen has unconventional values of IC and XIC, lower than that of boron. The IC model can agree fairly well with the data of bond properties and satisfactorily explain chemical observations of elements throughout the Periodic Table. PMID:21151444

Mathematical modeling of the integrated process of mercury bioremediation in the industrial bioreactor.

PubMed

Głuszcz, Paweł; Petera, Jerzy; Ledakowicz, Stanisław

2011-03-01

The mathematical model of the integrated process of mercury contaminated wastewater bioremediation in a fixed-bed industrial bioreactor is presented. An activated carbon packing in the bioreactor plays the role of an adsorbent for ionic mercury and at the same time of a carrier material for immobilization of mercury-reducing bacteria. The model includes three basic stages of the bioremediation process: mass transfer in the liquid phase, adsorption of mercury onto activated carbon and ionic mercury bioreduction to Hg(0) by immobilized microorganisms. Model calculations were verified using experimental data obtained during the process of industrial wastewater bioremediation in the bioreactor of 1 m³ volume. It was found that the presented model reflects the properties of the real system quite well. Numerical simulation of the bioremediation process confirmed the experimentally observed positive effect of the integration of ionic mercury adsorption and bioreduction in one apparatus.

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.

New reversed phase-high performance liquid chromatographic method for selective separation of yttrium from all rare earth elements employing nitrilotriacetate complexes in anion exchange mode.

PubMed

Dybczyński, Rajmund S; Kulisa, Krzysztof; Pyszynska, Marta; Bojanowska-Czajka, Anna

2015-03-20

Separation of Y from other rare earth elements (REE) is difficult because of similarity of its ionic radius to ionic radii of Tb, Dy and Ho. In the new RP-HPLC system with C18 column, tetra-n-butyl ammonium hydroxide (TBAOH) as an ion interaction reagent (IIR), nitrilotriacetic acid (NTA) as a complexing agent at pH=2.8-3.5, and post column derivatization with Arsenazo III, yttrium is eluted in the region of light REE, between Nd and Sm and is base line separated from Nd and Sm and even from promethium. Simple model employing literature data on complex formation of REE with NTA and based on anion exchange mechanism was developed to foresee the order of elution of individual REE. The model correctly predicted that lanthanides up to Tb will be eluted in the order of increasing Atomic Number (At.No.) but all heavier REE will show smaller retention factors than Tb. Concurrent UV/VIS detection at 658nm and the use of radioactive tracers together with γ-ray spectrometric measurements made possible to establish an unique elution order of elution of REE: La, Ce, Pr, Nd, Pm, Y, Sm, Er, Ho, Tm, Yb, Eu, Lu, Dy+Gd, Tb, Sc. The real place of Y however, in this elution series differs from that predicted by the model (Y between Sm and Eu). The method described in this work enables selective separation of Y from La, Ce, Pr, Nd, Pm, Sm and all heavier REE treated as a group. Copyright © 2015 Elsevier B.V. All rights reserved.

Ionic micelles and aromatic additives: a closer look at the molecular packing parameter.

PubMed

Lutz-Bueno, Viviane; Isabettini, Stéphane; Walker, Franziska; Kuster, Simon; Liebi, Marianne; Fischer, Peter

2017-08-16

Wormlike micellar aggregates formed from the mixture of ionic surfactants with aromatic additives result in solutions with impressive viscoelastic properties. These properties are of high interest for numerous industrial applications and are often used as model systems for soft matter physics. However, robust and simple models for tailoring the viscoelastic response of the solution based on the molecular structure of the employed additive are required to fully exploit the potential of these systems. We address this shortcoming with a modified packing parameter based model, considering the additive-surfactant pair. The role of charge neutralization on anisotropic micellar growth was investigated with derivatives of sodium salicylate. The impact of the additives on the morphology of the micellar aggregates is explained from the molecular level to the macroscopic viscoelasticity. Changes in the micelle's volume, headgroup area and additive structure are explored to redefine the packing parameter. Uncharged additives penetrated deeper into the hydrophobic region of the micelle, whilst charged additives remained trapped in the polar region, as revealed by a combination of 1 H-NMR, SAXS and rheological measurements. A deeper penetration of the additives densified the hydrophobic core of the micelle and induced anisotropic growth by increasing the effective volume of the additive-surfactant pair. This phenomenon largely influenced the viscosity of the solutions. Partially penetrating additives reduced the electrostatic repulsions between surfactant headgroups and neighboring micelles. The resulting increased network density governed the elasticity of the solutions. Considering a packing parameter composed of the additive-surfactant pair proved to be a facile means of engineering the viscoelastic response of surfactant solutions. The self-assembly of the wormlike micellar aggregates could be tailored to desired morphologies resulting in a specific and predictable rheological response.

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.

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

Optoelectronics of organic nanofibers formed by co-assembly of porphyrin and perylenediimide.

PubMed

Li, Yuangang; Wang, Weina; Leow, Wan Ru; Zhu, Bowen; Meng, Fanben; Zheng, Liyan; Zhu, Jia; Chen, Xiaodong

2014-07-23

Organic nanofibers are formed by simple ionic co-assembly of positively charged porphyrin (electron donor) and negatively charged perylenediimide (electron acceptor) derivatives in aqueous solution. Two kinds of electron transfer routes between electron donor and electron acceptor under light excitation in nanofibers are confirmed by DFT calculations and experimental data. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling of charge transport in ion bipolar junction transistors.

PubMed

Volkov, Anton V; Tybrandt, Klas; Berggren, Magnus; Zozoulenko, Igor V

2014-06-17

Spatiotemporal control of the complex chemical microenvironment is of great importance to many fields within life science. One way to facilitate such control is to construct delivery circuits, comprising arrays of dispensing outlets, for ions and charged biomolecules based on ionic transistors. This allows for addressability of ionic signals, which opens up for spatiotemporally controlled delivery in a highly complex manner. One class of ionic transistors, the ion bipolar junction transistors (IBJTs), is especially attractive for these applications because these transistors are functional at physiological conditions and have been employed to modulate the delivery of neurotransmitters to regulate signaling in neuronal cells. Further, the first integrated complementary ionic circuits were recently developed on the basis of these ionic transistors. However, a detailed understanding of the device physics of these transistors is still lacking and hampers further development of components and circuits. Here, we report on the modeling of IBJTs using Poisson's and Nernst-Planck equations and the finite element method. A two-dimensional model of the device is employed that successfully reproduces the main characteristics of the measurement data. On the basis of the detailed concentration and potential profiles provided by the model, the different modes of operation of the transistor are analyzed as well as the transitions between the different modes. The model correctly predicts the measured threshold voltage, which is explained in terms of membrane potentials. All in all, the results provide the basis for a detailed understanding of IBJT operation. This new knowledge is employed to discuss potential improvements of ion bipolar junction transistors in terms of miniaturization and device parameters.

Effect of porosity and tortuosity of electrodes on carbon polymer soft actuators

NASA Astrophysics Data System (ADS)

S, Sunjai Nakshatharan; Punning, Andres; Johanson, Urmas; Aabloo, Alvo

2018-01-01

This work presents an electro-mechanical model and simulation of ionic electroactive polymer soft actuators with a porous carbon electrode, polymer membrane, and ionic liquid electrolyte. An attempt is made to understand the effects of specific properties of the porous electrodes such as porosity and tortuosity on the charge dynamics and mechanical performance of the actuator. The model uses porous electrode theory to study the electrochemical response of the system. The mechanical response of the whole laminate is attributed to the evolution of local stresses caused by diffusion of ions (diffusion-induced stresses or chemical stresses). The model indicates that in actuators with porous electrode, the diffusion coefficient of ions, conductivity of the electrodes, and ionic conductivity in both electrodes and separator are altered significantly. In addition, the model leads to an obvious deduction that the ions that are highly active in terms of mobility will dominate the whole system in terms of resulting mechanical deformation direction and rate of deformation. Finally, to validate the model, simulations are conducted using the finite element method, and the outcomes are compared with the experimental data. Significant effort has been put forward to experimentally measure the key parameters essential for the validation of the model. The results show that the model developed is able to well predict the behavior of the actuator, providing a comprehensive understanding of charge dynamics in ionic polymer actuator with porous electrodes.

WtF‐Nano: One‐Pot Dewatering and Water‐Free Topochemical Modification of Nanocellulose in Ionic Liquids or γ‐Valerolactone

PubMed Central

Laaksonen, Tiina; Helminen, Jussi K. J.; Lemetti, Laura; Långbacka, Jesper; Rico del Cerro, Daniel; Hummel, Michael; Rantamäki, Antti H.; Kakko, Tia; Kemell, Marianna L.; Wiedmer, Susanne K.; Heikkinen, Sami; Kilpeläinen, Ilkka

2017-01-01

Abstract Ionic liquids are used to dewater a suspension of birch Kraft pulp cellulose nanofibrils (CNF) and as a medium for water‐free topochemical modification of the nanocellulose (a process denoted as “WtF‐Nano”). Acetylation was applied as a model reaction to investigate the degree of modification and scope of effective ionic liquid structures. Little difference in reactivity was observed when water was removed, after introduction of an ionic liquid or molecular co‐solvent. However, the viscoelastic properties of the CNF suspended in two ionic liquids show that the more basic, but non‐dissolving ionic liquid, allows for better solvation of the CNF. Vibrio fischeri bacterial tests show that all ionic liquids in this study were harmless. Scanning electron microscopy and wide‐angle X‐ray scattering on regenerated samples show that the acetylated CNF is still in a fibrillar form. 1 D and 2 D NMR analyses, after direct dissolution in a novel ionic liquid electrolyte solution, indicate that both cellulose and residual xylan on the surface of the nanofibrils reacts to give acetate esters. PMID:29112334

Class of cooperative stochastic models: Exact and approximate solutions, simulations, and experiments using ionic self-assembly of nanoparticles.

PubMed

Mazilu, I; Mazilu, D A; Melkerson, R E; Hall-Mejia, E; Beck, G J; Nshimyumukiza, S; da Fonseca, Carlos M

2016-03-01

We present exact and approximate results for a class of cooperative sequential adsorption models using matrix theory, mean-field theory, and computer simulations. We validate our models with two customized experiments using ionically self-assembled nanoparticles on glass slides. We also address the limitations of our models and their range of applicability. The exact results obtained using matrix theory can be applied to a variety of two-state systems with cooperative effects.

Reactive Force Fields via Explicit Valency

NASA Astrophysics Data System (ADS)

Kale, Seyit

Computational simulations are invaluable in elucidating the dynamics of biological macromolecules. Unfortunately, reactions present a fundamental challenge. Calculations based on quantum mechanics can predict bond formation and rupture; however they suffer from severe length- and time-limitations. At the other extreme, classical approaches provide orders of magnitude faster simulations; however they regard chemical bonds as immutable entities. A few exceptions exist, but these are not always trivial to adopt for routine use. We bridge this gap by providing a novel, pseudo-classical approach, based on explicit valency. We unpack molecules into valence electron pairs and atomic cores. Particles bear ionic charges and interact via pairwise-only potentials. The potentials are informed of quantum effects in the short-range and obey dissociation limits in the long-range. They are trained against a small set of isolated species, including geometries and thermodynamics of small hydrides and of dimers formed by them. The resulting force field captures the essentials of reactivity, polarizability and flexibility in a simple, seamless setting. We call this model LEWIS, after the chemical theory that inspired the use of valence pairs. Following the introduction in Chapter 1, we initially focus on the properties of water. Chapter 2 considers gas phase clusters. To transition to the liquid phase, Chapter 3 describes a novel pairwise long-range compensation that performs comparably to infinite lattice summations. The approach is suited to ionic solutions in general. In Chapters 4 and 5, LEWIS is shown to correctly predict the dipolar and quadrupolar response in bulk liquid, and can accommodate proton transfers in both acid and base. Efficiency permits the study of proton defects at dilutions not accessible to experiment or quantum mechanics. Chapter 6 discusses explicit valency approaches in other hydrides, forming the basis of a reactive organic force field. Examples of simple proton transfer and more complex reactions are discussed. Chapter 7 provides a framework for variable electron spread. This addition resolves some of the inherent limitations of the former model which implicitly assumed that electron spread was not affected by the environment. A brief summary is provided in Chapter 8.

Preparation of stir cake sorptive extraction based on polymeric ionic liquid for the enrichment of benzimidazole anthelmintics in water, honey and milk samples.

PubMed

Wang, Yulei; Zhang, Jie; Huang, Xiaojia; Yuan, Dongxing

2014-08-20

In this work, a new stir cake sorptive extraction (SCSE) using polymeric ionic liquid monolith as sorbent was prepared. The sorbent was obtained by in situ copolymerization of an ionic liquid, 1-allyl-3-methylimidazolium bis[(trifluoro methyl)sulfonyl]imide (AMII) and divinylbenzene (DB) in the presence of N,N-dimethylformamide. The influence of the content of ionic liquid and the porogen in the polymerization mixture on extraction performance was studied thoroughly. The physicochemical properties of the polymeric ionic liquid were characterized by infrared spectroscopy, elemental analysis, scanning electron microscopy and mercury intrusion porosimetry. The usefulness of SCSE-AMIIDB was demonstrated by the enrichment of trace benzimidazole anthelmintics. Several parameters affecting the extraction efficiency were investigated, and under the optimized conditions, a simple and effective method for the determination of trace benzimidazoles residues in water, milk and honey samples was established by coupling SCSE-AMIIDB with high performance liquid chromatography/diode array detection (SCSE-AMIIDB-HPLC/DAD). Results indicated that the limits of detection (S/N=3) for target compounds were 0.020-0.072 μg L(-1), 0.035-0.10 μg L(-1) and 0.026-0.076 μg L(-1) in water, milk and honey samples, respectively. In addition, an acceptable reproducibility was achieved by evaluating the repeatability and intermediate precision with relative standard deviations (RSD) of less than 9% and 11%, respectively. Finally, the established AMII-SCSE-HPLC/DAD method was successfully applied for the determination of benzimidazoles residues in milk, honey and environmental water samples. Recoveries obtained for the determination of benzimidazole anthelmintics in spiking samples ranged from 70.2% to 117.6%, with RSD below 12% in all cases. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Probing the Bond Order Wave Phase Transitions of the Ionic Hubbard Model by Superlattice Modulation Spectroscopy

NASA Astrophysics Data System (ADS)

Loida, Karla; Bernier, Jean-Sébastien; Citro, Roberta; Orignac, Edmond; Kollath, Corinna

2017-12-01

An exotic phase, the bond order wave, characterized by the spontaneous dimerization of the hopping, has been predicted to exist sandwiched between the band and Mott insulators in systems described by the ionic Hubbard model. Despite growing theoretical evidence, this phase still evades experimental detection. Given the recent realization of the ionic Hubbard model in ultracold atomic gases, we propose here to detect the bond order wave using superlattice modulation spectroscopy. We demonstrate, with the help of time-dependent density-matrix renormalization group and bosonization, that this spectroscopic approach reveals characteristics of both the Ising and Kosterlitz-Thouless transitions signaling the presence of the bond order wave phase. This scheme also provides insights into the excitation spectra of both the band and Mott insulators.

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.

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.

Osmotic Pressure in Ionic Microgel Dispersions

NASA Astrophysics Data System (ADS)

Denton, Alan R.; Tang, Qiyun

2015-03-01

Microgels are microscopic gel particles, typically 10-1000 nm in size, that are swollen by a solvent. Hollow microgels (microcapsules) can encapsulate cargo, such as dye molecules or drugs, in their solvent-filled cavities. Their sensitive response to environmental conditions (e.g., temperature, pH) and influence on flow properties suit microgels to widespread applications in the chemical, pharmaceutical, food, and consumer care industries. When dispersed in water, polyelectrolyte gels become charged through dissociation of counterions. The electrostatic contribution to the osmotic pressure inside and outside of ionic microgels influences particle swelling and bulk materials properties, including thermodynamic, structural, optical, and rheological properties. Within the primitive and cell models of polyelectrolyte solutions, we derive an exact statistical mechanical formula for the contribution of mobile microions to the osmotic pressure within ionic microgels. Using Poisson-Boltzmann theory, we validate this result by explicitly calculating ion distributions across the surface of an ionic microgel and the electrostatic contribution to the osmotic pressure. Within a coarse-grained one-component model, we further chart the limits of the cell model for salty dispersions. This work was supported by the National Science Foundation under Grant No. DMR-1106331.

Executive summary - Assessing the response of Emerald Lake, an alpine watershed in Sequoia National Park, California, to acidification during snowmelt using a simple hydrochemical model

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

Hooper, R.P.; West, C.T.; Peters, N.E.

1990-01-01

A simple process-oriented model, called the Alpine Lake Forecaster (ALF), was constructed using data collected from the Integrated Watershed Study of Emerald Lake, Sequoia National Park, California. ALF is able to capture the basic solute patterns during snowmelt in this alpine catchment where groundwater is a minor contributor to streamflow. It includes an empirical representation of primary mineral weathering as the only alkalinity generating mechanism. During a heavy snow year, such as the one used for calibrating the model, the model accurately simulated the surface water chemical change in response to the initial ionic pulse from the snowpack and tomore » the dilution that occurs at peak snowmelt. Because the model does not consider cation exchange, it over-predicts the acidification during the initial period of snowmelt, and therefore is a conservative predictor. However, the minimum alkalinity observed in the main inflows to Emerald Lake and in the lake outflow is accurately simulated by the model. The representation of the lake as simply a missing volume with no additional chemical reactions is supported by the observation. The model predicts a change of 2 to 5 microequiv/L in the minimum alkalinity of the lake outflow during snowmelt if the deposition would have to increase between two and 18 times the current load-alkalinity of the lake; the precise increase depends on hydrologic conditions and on the pattern of solute release from the snowpack. An acidic rainstorm that exhausted the alkalinity of the lake was observed during summer 1984 after the lake had stratified, and is the likely cause of the acidification of Emerald Lake.« less

Mesoscale studies of ionic closed membranes with polyhedral geometries

DOE PAGES

Olvera de la Cruz, Monica

2016-06-01

Large crystalline molecular shells buckle spontaneously into icosahedra while multicomponent shells buckle into various polyhedra. Continuum elastic theory explains the buckling of closed shells with one elastic component into icosahedra. A generalized elastic model, on the other hand, describes the spontaneous buckling of inhomogeneous shells into regular and irregular polyhedra. By coassembling water-insoluble anionic (–1) amphiphiles with cationic (3+) amphiphiles, we realized ionic vesicles. Results revealed that surface crystalline domains and the unusual shell shapes observed arise from the competition of ionic correlations with charge-regulation. We explain here the mechanism by which these ionic membranes generate a mechanically heterogeneous vesicle.

Model for diffuse interstellar clouds: improvements to the theory of molecular hydrogen photodestruction and to the gas phase chemistry of carbon monoxide

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

Federman, S.R.

1979-01-01

A theoretical model has been developed to determine physical processes in conjunction with astrophysical observation. The calculations are based on isobaric, steady-state, plane-parallel conditions. In the model, the cloud is illuminated by ultraviolet radiation from one side. The density and temperature of the gas are derived by invoking energy conservation in terms of thermal balance. The derived values for density and temperature then are used to determine the abundances of approximately fifty atomic and molecular species, including important ionic species and simple carbon and oxygen bearing molecules. Except for molecular hydrogen formation on dust grains, binary gas phase reactions aremore » used to develop the chemistry of the model cloud. The theoretical model has been found to be appropriate for a particular range of physical parameters. The results of the steady-state calculations have been compared to ultraviolet observations, predominantly those made with the Copernicus satellite. The theory of molecular hydrogen photodestruction has been reexamined so that improvements to the model can be made. By analyzing the region where the atomic to molecuar hydrogen transition occurs, several processes have been found to contribute to dissociation.« 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.

Ionically Cross-Linked Polymer Networks for the Multiple-Month Release of Small Molecules

PubMed Central

2016-01-01

Long-term (multiple-week or -month) release of small, water-soluble molecules from hydrogels remains a significant pharmaceutical challenge, which is typically overcome at the expense of more-complicated drug carrier designs. Such approaches are payload-specific and include covalent conjugation of drugs to base materials or incorporation of micro- and nanoparticles. As a simpler alternative, here we report a mild and simple method for achieving multiple-month release of small molecules from gel-like polymer networks. Densely cross-linked matrices were prepared through ionotropic gelation of poly(allylamine hydrochloride) (PAH) with either pyrophosphate (PPi) or tripolyphosphate (TPP), all of which are commonly available commercial molecules. The loading of model small molecules (Fast Green FCF and Rhodamine B dyes) within these polymer networks increases with the payload/network binding strength and with the PAH and payload concentrations used during encapsulation. Once loaded into the PAH/PPi and PAH/TPP ionic networks, only a few percent of the payload is released over multiple months. This extended release is achieved regardless of the payload/network binding strength and likely reflects the small hydrodynamic mesh size within the gel-like matrices. Furthermore, the PAH/TPP networks show promising in vitro cytocompatibility with model cells (human dermal fibroblasts), though slight cytotoxic effects were exhibited by the PAH/PPi networks. Taken together, the above findings suggest that PAH/PPi and (especially) PAH/TPP networks might be attractive materials for the multiple-month delivery of drugs and other active molecules (e.g., fragrances or disinfectants). PMID:26811936

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

Potentiometric chip-based multipumping flow system for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples.

PubMed

Chango, Gabriela; Palacio, Edwin; Cerdà, Víctor

2018-08-15

A simple potentiometric chip-based multipumping flow system (MPFS) has been developed for the simultaneous determination of fluoride, chloride, pH, and redox potential in water samples. The proposed system was developed by using a poly(methyl methacrylate) chip microfluidic-conductor using the advantages of flow techniques with potentiometric detection. For this purpose, an automatic system has been designed and built by optimizing the variables involved in the process, such as: pH, ionic strength, stirring and sample volume. This system was applied successfully to water samples getting a versatile system with an analysis frequency of 12 samples per hour. Good correlation between chloride and fluoride concentration measured with ISE and ionic chromatography technique suggests satisfactory reliability of the system. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

NASA Astrophysics Data System (ADS)

Davidson, Jacob D.; Goulbourne, N. C.

2011-01-01

Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an optimal electromechanical conversion efficiency for bending actuation is achieved by using an ionic liquid where only a relatively small fraction of the ionic liquid ions exist as free ions. Conversely, if it is desired to increase the overall amount of charge transferred, an ionic liquid with a large fraction of free ions should be used. These theoretical considerations are found to be in good qualitative agreement with recent experimental results.

Hydrodynamic model of temperature change in open ionic channels.

PubMed Central

Chen, D P; Eisenberg, R S; Jerome, J W; Shu, C W

1995-01-01

Most theories of open ionic channels ignore heat generated by current flow, but that heat is known to be significant when analogous currents flow in semiconductors, so a generalization of the Poisson-Nernst-Planck theory of channels, called the hydrodynamic model, is needed. The hydrodynamic theory is a combination of the Poisson and Euler field equations of electrostatics and fluid dynamics, conservation laws that describe diffusive and convective flow of mass, heat, and charge (i.e., current), and their coupling. That is to say, it is a kinetic theory of solute and solvent flow, allowing heat and current flow as well, taking into account density changes, temperature changes, and electrical potential gradients. We integrate the equations with an essentially nonoscillatory shock-capturing numerical scheme previously shown to be stable and accurate. Our calculations show that 1) a significant amount of electrical energy is exchanged with the permeating ions; 2) the local temperature of the ions rises some tens of degrees, and this temperature rise significantly alters for ionic flux in a channel 25 A long, such as gramicidin-A; and 3) a critical parameter, called the saturation velocity, determines whether ionic motion is overdamped (Poisson-Nernst-Planck theory), is an intermediate regime (called the adiabatic approximation in semiconductor theory), or is altogether unrestricted (requiring the full hydrodynamic model). It seems that significant temperature changes are likely to accompany current flow in the open ionic channel. PMID:8599638

Trace element partitioning between ionic crystal and liquid

NASA Technical Reports Server (NTRS)

Tsang, T.; Philpotts, J. A.; Yin, L.

1978-01-01

The partitioning of trace elements between ionic crystals and the melt has been correlated with lattice energy of the host. The solid-liquid partition coefficient has been expressed in terms of the difference in relative ionic radius of the trace element and the homogeneous and heterogeneous strain of the host lattice. Predictions based on this model appear to be in general agreement with data for alkali nitrates and for rare-earth elements in natural garnet phenocrysts.

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.

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

Simulation of polymer translocation through protein channels

PubMed Central

Muthukumar, M.; Kong, C. Y.

2006-01-01

A modeling algorithm is presented to compute simultaneously polymer conformations and ionic current, as single polymer molecules undergo translocation through protein channels. The method is based on a combination of Langevin dynamics for coarse-grained models of polymers and the Poisson–Nernst–Planck formalism for ionic current. For the illustrative example of ssDNA passing through the α-hemolysin pore, vivid details of conformational fluctuations of the polymer inside the vestibule and β-barrel compartments of the protein pore, and their consequent effects on the translocation time and extent of blocked ionic current are presented. In addition to yielding insights into several experimentally reported puzzles, our simulations offer experimental strategies to sequence polymers more efficiently. PMID:16567657

Structure and Binding of Ionic Clusters in Th and Zr Chloride Melts

NASA Astrophysics Data System (ADS)

Akdeniz, Z.; Tosi, M. P.

2001-11-01

We discuss microscopic ionic models for the structure and the binding of small clusters which may exist as structural units in molten ThCl4 and ZrCl4 and in their mixtures with alkali halides according to Raman scattering studies of Photiadis and Papatheodorou. The models are adjusted to the two isolated tetrahedral molecules. Appreciably higher ionicity is found for ThCl4 than for ZrCl4, and this fact underlies the strikingly different behaviour of the two systems in the dense liquid state -in particular, a molecular-type structure for molten ZrCl4 against a structure including charged oligomers in molten ThCl4.

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.

Determination of antimony and tin in beverages using inductively coupled plasma-optical emission spectrometry after ultrasound-assisted ionic liquid dispersive liquid-liquid phase microextraction.

PubMed

Biata, N Raphael; Nyaba, Luthando; Ramontja, James; Mketo, Nomvano; Nomngongo, Philiswa N

2017-12-15

The aim of this study was to develop a simple and fast ultrasound-assisted ionic liquid dispersive liquid-liquid phase microextraction (UA-IL-DLLME) method for preconcetration of trace antimony and tin in beverage samples. The novelty of this study was based on the application of ligandless UA-IL-DLLME using low-density ionic liquid and organic solvents for preconcentration of Sb and Sn. The concentration of Sb and Sn were quantified using ICP-OES. Under the optimum conditions, the calibration graph was found to be LOQ-250µgL -1 (r 2 =0.9987) for Sb and LOQ-350µgL -1 for Sn. The LOD and LOQ of Sb and Sn ranged from 1.2to 2.5ngL -1 and 4.0 to 8.3ngL -1 , respectively, with high preconcentration factors. The precisions (%RSD) of the proposed method ranged from 2.1% to 2.5% and 3.9% to 4.7% for Sb and Sn, respectively. The proposed method was successfully applied for determination of Sb and Sn in beverages. Copyright © 2017 Elsevier Ltd. All rights reserved.

Detection of Organophosphorus Pesticides in Wheat by Ionic Liquid-Based Dispersive Liquid-Liquid Microextraction Combined with HPLC

PubMed Central

Quan, Ji; Hu, Zeshu

2018-01-01

Food safety issues closely related to human health have always received widespread attention from the world society. As a basic food source, wheat is the fundamental support of human survival; therefore, the detection of pesticide residues in wheat is very necessary. In this work, the ultrasonic-assisted ionic liquid-dispersive liquid-liquid microextraction (DLLME) method was firstly proposed, and the extraction and analysis of three organophosphorus pesticides were carried out by combining high-performance liquid chromatography (HPLC). The extraction efficiencies of three ionic liquids with bis(trifluoromethylsulfonyl)imide (Tf2N) anion were compared by extracting organophosphorus in wheat samples. It was found that the use of 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([OMIM][Tf2N]) had both high enrichment efficiency and appropriate extraction recovery. Finally, the method was used for the determination of three wheat samples, and the recoveries of them were 74.8–112.5%, 71.8–104.5%, and 83.8–115.5%, respectively. The results show that the method proposed is simple, fast, and efficient, which can be applied to the extraction of organic matters in wheat samples. PMID:29854562

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.

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.

Theoretical and experimental studies on ionic currents in nanopore-based biosensors.

PubMed

Liu, Lei; Li, Chu; Ma, Jian; Wu, Yingdong; Ni, Zhonghua; Chen, Yunfei

2014-12-01

Novel generation of analytical technology based on nanopores has provided possibilities to fabricate nanofluidic devices for low-cost DNA sequencing or rapid biosensing. In this paper, a simplified model was suggested to describe DNA molecule's translocation through a nanopore, and the internal potential, ion concentration, ionic flowing speed and ionic current in nanopores with different sizes were theoretically calculated and discussed on the basis of Poisson-Boltzmann equation, Navier-Stokes equation and Nernst-Planck equation by considering several important parameters, such as the applied voltage, the thickness and the electric potential distributions in nanopores. In this way, the basic ionic currents, the modulated ionic currents and the current drops induced by translocation were obtained, and the size effects of the nanopores were carefully compared and discussed based on the calculated results and experimental data, which indicated that nanopores with a size of 10 nm or so are more advantageous to achieve high quality ionic current signals in DNA sensing.

On the influence of hydrated ionic liquids on the dynamical structure of model proteins: a computational study.

PubMed

Haberler, Michael; Steinhauser, Othmar

2011-10-28

The solvation of the protein ubiquitin (PDB entry "1UBQ") in hydrated molecular ionic liquids was studied for varying water content or, equivalently, a diversity of ionic strengths. The cations and anions were 1-ethyl-3-methylimidazolium and trifluoromethanesulfonate, respectively. The protein's shape and stability as well as the solvation structure, the shell dynamics and the shell resolved dielectric properties were investigated by means of molecular dynamics simulations. The respective simulation trajectories covered 200 nanoseconds. Besides the characteristic point already found for the zinc finger motif at the transition from the pure aqueous environment to the ionic solution an even more pronounced state is found where several properties show extremal behaviour (maximum or minimum). This second characteristic point occurs at the transition from the ionic solution to the hydrated ionic melt where water changes its role from a solvent to a co-solvent. Most of the data analysis presented here is based on the Voronoi decomposition of space. This journal is © the Owner Societies 2011

Structure and dynamics of mica-confined films of [C10C1Pyrr][NTf2] ionic liquid

NASA Astrophysics Data System (ADS)

Freitas, Adilson Alves de; Shimizu, Karina; Smith, Alexander M.; Perkin, Susan; Canongia Lopes, José Nuno

2018-05-01

The structure of the ionic liquid 1-decyl-1-methylpyrrolidinium bis[(trifluoromethane)sulfonyl]imide, [C10C1Pyrr][NTf2], has been probed using Molecular Dynamics (MD) simulations. The simulations endeavour to model the behaviour of the ionic liquid in bulk isotropic conditions and also at interfaces and in confinement. The MD results have been confronted and validated with scattering and surface force experiments reported in the literature. The calculated structure factors, distribution functions, and density profiles were able to provide molecular and mechanistic insights into the properties of these long chain ionic liquids under different conditions, in particular those that lead to the formation of multi-layered ionic liquid films in confinement. Other properties inaccessible to experiment such as in-plane structures and relaxation rates within the films have also been analysed. Overall the work contributes structural and dynamic information relevant to many applications of ionic liquids with long alkyl chains, ranging from nanoparticle synthesis to lubrication.

Electroosmotic Flow Reversal Outside Glass Nanopores

PubMed Central

2015-01-01

We report observations of a striking reversal in the direction of electroosmotic flow (EOF) outside a conical glass nanopore as a function of salt concentration. At high ionic strengths (>100 mM), we observe EOF in the expected direction as predicted by classical electrokinetic theory, while at low salt concentrations (<1 mM) the direction of the flow is reversed. The critical crossover salt concentration depends on the pore diameter. Finite-element simulations indicate a competition between the EOF generated from the inner and outer walls of the pore, which drives flows in opposite directions. We have developed a simple analytical model which reveals that, as the salt concentration is reduced, the flow rates inside the pore are geometrically constrained, whereas there is no such limit for flows outside the pore. This model captures all of the essential physics of the system and explains the observed data, highlighting the key role the external environment plays in determining the overall electroosmotic behavior. PMID:25490120

From Ion Current to Electroosmotic Flow Rectification in Asymmetric Nanopore Membranes

PubMed Central

Wu, Xiaojian

2017-01-01

Asymmetrically shaped nanopores have been shown to rectify the ionic current flowing through pores in a fashion similar to a p-n junction in a solid-state diode. Such asymmetric nanopores include conical pores in polymeric membranes and pyramidal pores in mica membranes. We review here both theoretical and experimental aspects of this ion current rectification phenomenon. A simple intuitive model for rectification, stemming from previously published more quantitative models, is discussed. We also review experimental results on controlling the extent and sign of rectification. It was shown that ion current rectification produces a related rectification of electroosmotic flow (EOF) through asymmetric pore membranes. We review results that show how to measure and modulate this EOF rectification phenomenon. Finally, EOF rectification led to the development of an electroosmotic pump that works under alternating current (AC), as opposed to the currently available direct current EOF pumps. Experimental results on AC EOF rectification are reviewed, and advantages of using AC to drive EOF are discussed. PMID:29240676

From Ion Current to Electroosmotic Flow Rectification in Asymmetric Nanopore Membranes.

PubMed

Experton, Juliette; Wu, Xiaojian; Martin, Charles R

2017-12-14

Asymmetrically shaped nanopores have been shown to rectify the ionic current flowing through pores in a fashion similar to a p-n junction in a solid-state diode. Such asymmetric nanopores include conical pores in polymeric membranes and pyramidal pores in mica membranes. We review here both theoretical and experimental aspects of this ion current rectification phenomenon. A simple intuitive model for rectification, stemming from previously published more quantitative models, is discussed. We also review experimental results on controlling the extent and sign of rectification. It was shown that ion current rectification produces a related rectification of electroosmotic flow (EOF) through asymmetric pore membranes. We review results that show how to measure and modulate this EOF rectification phenomenon. Finally, EOF rectification led to the development of an electroosmotic pump that works under alternating current (AC), as opposed to the currently available direct current EOF pumps. Experimental results on AC EOF rectification are reviewed, and advantages of using AC to drive EOF are discussed.

Reverse osmosis filtration for space mission wastewater: membrane properties and operating conditions

NASA Technical Reports Server (NTRS)

Lee, S.; Lueptow, R. M.

2001-01-01

Reverse osmosis (RO) is a compact process that has potential for the removal of ionic and organic pollutants for recycling space mission wastewater. Seven candidate RO membranes were compared using a batch stirred cell to determine the membrane flux and the solute rejection for synthetic space mission wastewaters. Even though the urea molecule is larger than ions such as Na+, Cl-, and NH4+, the rejection of urea is lower. This indicates that the chemical interaction between solutes and the membrane is more important than the size exclusion effect. Low pressure reverse osmosis (LPRO) membranes appear to be most desirable because of their high permeate flux and rejection. Solute rejection is dependent on the shear rate, indicating the importance of concentration polarization. A simple transport model based on the solution-diffusion model incorporating concentration polarization is used to interpret the experimental results and predict rejection over a range of operating conditions. Grant numbers: NAG 9-1053.

Polyelectrolyte-coated carbons used in the generation of blue energy from salinity differences.

PubMed

Ahualli, S; Jiménez, M L; Fernández, M M; Iglesias, G; Brogioli, D; Delgado, A V

2014-12-14

In this work we present a method for the production of clean, renewable electrical energy from the exchange of solutions with different salinities. Activated carbon films are coated with negatively or positively charged polyelectrolytes using well-established adsorption methods. When two oppositely charged coated films are placed in contact with an ionic solution, the potential difference between them will be equal to the difference between their Donnan potentials, and hence, energy can be extracted by building an electrochemical cell with such electrodes. A model is elaborated on the operation of the cell, based on the electrokinetic theory of soft particles. All the features of the model are experimentally reproduced, although a small quantitative difference concerning the maximum open-circuit voltage is found, suggesting that the coating is the key point to improve the efficiency. In the experimental conditions used, we obtain a power of 12.1 mW m(-2). Overall, the method proves to be a fruitful and simple approach to salinity-gradient energy production.

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

PubMed

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

2014-12-01

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

Physics and Chemistry of Earth Materials

NASA Astrophysics Data System (ADS)

Navrotsky, Alexandra

1994-11-01

Stressing the fundamental solid state behavior of minerals, and emphasizing both theory and experiment, this text surveys the physics and chemistry of earth materials. The author begins with a systematic tour of crystal chemistry of both simple and complex structures (with completely new structural drawings) and discusses how to obtain structural and thermodynamic information experimentally. Dr. Navrotsky also reviews the quantitative concepts of chemical bonding--band theory, molecular orbit and ionic models. She then covers physical properties and relates microscopic features to macroscopic thermodynamic behavior and treats high pressure phase transitions, amorphous materials and solid state reactions. The author concludes with a look at the interface between mineral physics and materials science. Highly illustrated throughout, this book fills the gap between undergraduate texts and specialized review volumes and is appropriate for students and researchers in earth science and materials science.

Enhanced super-hydrophobic and switching behavior of ZnO nanostructured surfaces prepared by simple solution--immersion successive ionic layer adsorption and reaction process.

PubMed

Suresh Kumar, P; Sundaramurthy, J; Mangalaraj, D; Nataraj, D; Rajarathnam, D; Srinivasan, M P

2011-11-01

A simple and cost-effective successive ionic layer adsorption and reaction (SILAR) method was adopted to fabricate hydrophobic ZnO nanostructured surfaces on transparent indium-tin oxide (ITO), glass and polyethylene terephthalate (PET) substrates. ZnO films deposited on different substrates show hierarchical structures like spindle, flower and spherical shape with diameters ranging from 30 to 300 nm. The photo-induced switching behaviors of ZnO film surfaces between hydrophobic and hydrophilic states were examined by water contact angle and X-ray photoelectron spectroscopy (XPS) analysis. ZnO nanostructured films had contact angles of ~140° and 160°±2 on glass and PET substrates, respectively, exhibiting hydrophobic behavior without any surface modification or treatment. Upon exposure to ultraviolet (UV) illumination, the films showed hydrophilic behavior (contact angle: 15°±2), which upon low thermal stimuli revert back to its original hydrophobic nature. Such reversible and repeatable switching behaviors were observed upon cyclical exposure to ultraviolet radiation. These biomimetic ZnO surfaces exhibit good anti-reflective properties with lower reflectance of 9% for PET substrates. Thus, the present work is significant in terms of its potential application in switching devices, solar coatings and self-cleaning smart windows. Copyright © 2011 Elsevier Inc. All rights reserved.

Concentration Dependent Ion-Protein Interaction Patterns Underlying Protein Oligomerization Behaviours

NASA Astrophysics Data System (ADS)

Batoulis, Helena; Schmidt, Thomas H.; Weber, Pascal; Schloetel, Jan-Gero; Kandt, Christian; Lang, Thorsten

2016-04-01

Salts and proteins comprise two of the basic molecular components of biological materials. Kosmotropic/chaotropic co-solvation and matching ion water affinities explain basic ionic effects on protein aggregation observed in simple solutions. However, it is unclear how these theories apply to proteins in complex biological environments and what the underlying ionic binding patterns are. Using the positive ion Ca2+ and the negatively charged membrane protein SNAP25, we studied ion effects on protein oligomerization in solution, in native membranes and in molecular dynamics (MD) simulations. We find that concentration-dependent ion-induced protein oligomerization is a fundamental chemico-physical principle applying not only to soluble but also to membrane-anchored proteins in their native environment. Oligomerization is driven by the interaction of Ca2+ ions with the carboxylate groups of aspartate and glutamate. From low up to middle concentrations, salt bridges between Ca2+ ions and two or more protein residues lead to increasingly larger oligomers, while at high concentrations oligomers disperse due to overcharging effects. The insights provide a conceptual framework at the interface of physics, chemistry and biology to explain binding of ions to charged protein surfaces on an atomistic scale, as occurring during protein solubilisation, aggregation and oligomerization both in simple solutions and membrane systems.

In-house-made capillary electrophoresis instruments coupled with contactless conductivity detection as a simple and inexpensive solution for water analysis: a case study in Vietnam.

PubMed

Duong, Hong Anh; Le, Minh Duc; Nguyen, Kim Diem Mai; Hauser, Peter C; Pham, Hung Viet; Mai, Thanh Duc

2015-11-01

A simple and inexpensive method for the determination of various ionic species in different water matrices is discussed in this study. The approach is based on the employment of in-house-made capillary electrophoresis (CE) instruments with capacitively coupled contactless conductivity detection (C(4)D), which can be realized even when only a modest financial budget and limited expertise are available. Advantageous features and considerations of these instruments are detailed following their pilot deployment in Vietnam. Different categories of ionic species, namely major inorganic cations (K(+), Na(+), Ca(2+), Mg(2+), and NH4(+)) and major inorganic anions (Cl(-), NO3(-), NO2(-), SO4(2-), and phosphate), in different water matrices in Vietnam were determined using these in-house fabricated instruments. Inorganic trivalent arsenic (As(iii)), which is the most abundant form of arsenic in reducing groundwater, was determined by CE-C(4)D. The effect of some interfering ions in groundwater on the analytical performance was investigated and is highlighted. The results from in-house-made CE-C(4)D-instruments were cross-checked with those obtained using the standard methods (AAS, AES, UV and IC), with correlation coefficients r(2) ≥ 0.9 and deviations from the referenced results less than 15%.

Surface structure evolution in a homologous series of ionic liquids

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

Haddad, Julia; Pontoni, Diego; Murphy, Bridget M.

Interfaces of room temperature ionic liquids (RTILs) are important for both applications and basic science and are therefore intensely studied. However, the evolution of their interface structure with the cation’s alkyl chain length n from Coulomb to van der Waals interaction domination has not yet been studied for even a single broad homologous RTIL series. We present in this paper such a study of the liquid–air interface for n = 2 to 22, using angstrom-resolution X-ray methods. For n < 6, a typical “simple liquid” monotonic surface-normal electron density profile ρ e more » ( z ) is obtained, like those of water and organic solvents. For n > 6, increasingly more pronounced nanoscale self-segregation of the molecules’ charged moieties and apolar chains yields surface layering with alternating regions of headgroups and chains. The layering decays into the bulk over a few, to a few tens, of nanometers. The layering periods and decay lengths, their linear n dependence, and slopes are discussed within two models, one with partial-chain interdigitation and the other with liquid-like chains. No surface-parallel long-range order is found within the surface layer. For n = 22, a different surface phase is observed above melting. Finally, our results also impact general liquid-phase issues like supramolecular self-aggregation and bulk–surface structure relations.« less

Solutions to a reduced Poisson–Nernst–Planck system and determination of reaction rates

PubMed Central

Li, Bo; Lu, Benzhuo; Wang, Zhongming; McCammon, J. Andrew

2010-01-01

We study a reduced Poisson–Nernst–Planck (PNP) system for a charged spherical solute immersed in a solvent with multiple ionic or molecular species that are electrostatically neutralized in the far field. Some of these species are assumed to be in equilibrium. The concentrations of such species are described by the Boltzmann distributions that are further linearized. Others are assumed to be reactive, meaning that their concentrations vanish when in contact with the charged solute. We present both semi-analytical solutions and numerical iterative solutions to the underlying reduced PNP system, and calculate the reaction rate for the reactive species. We give a rigorous analysis on the convergence of our simple iteration algorithm. Our numerical results show the strong dependence of the reaction rates of the reactive species on the magnitude of its far field concentration as well as on the ionic strength of all the chemical species. We also find non-monotonicity of electrostatic potential in certain parameter regimes. The results for the reactive system and those for the non-reactive system are compared to show the significant differences between the two cases. Our approach provides a means of solving a PNP system which in general does not have a closed-form solution even with a special geometrical symmetry. Our findings can also be used to test other numerical methods in large-scale computational modeling of electro-diffusion in biological systems. PMID:20228879

Theory of the formation of the electric double layer at the ion exchange membrane-solution interface.

PubMed

Moya, A A

2015-02-21

This work aims to extend the study of the formation of the electric double layer at the interface defined by a solution and an ion-exchange membrane on the basis of the Nernst-Planck and Poisson equations, including different values of the counter-ion diffusion coefficient and the dielectric constant in the solution and membrane phases. The network simulation method is used to obtain the time evolution of the electric potential, the displacement electric vector, the electric charge density and the ionic concentrations at the interface between a binary electrolyte solution and a cation-exchange membrane with total co-ion exclusion. The numerical results for the temporal evolution of the interfacial electric potential and the surface electric charge are compared with analytical solutions derived in the limit of the shortest times by considering the Poisson equation for a simple cationic diffusion process. The steady-state results are justified from the Gouy-Chapman theory for the diffuse double layer in the limits of similar and high bathing ionic concentrations with respect to the fixed-charge concentration inside the membrane. Interesting new physical insights arise from the interpretation of the process of the formation of the electric double layer at the ion exchange membrane-solution interface on the basis of a membrane model with total co-ion exclusion.

Surface structure evolution in a homologous series of ionic liquids

DOE PAGES

Haddad, Julia; Pontoni, Diego; Murphy, Bridget M.; ...

2018-01-22

Interfaces of room temperature ionic liquids (RTILs) are important for both applications and basic science and are therefore intensely studied. However, the evolution of their interface structure with the cation’s alkyl chain length n from Coulomb to van der Waals interaction domination has not yet been studied for even a single broad homologous RTIL series. We present in this paper such a study of the liquid–air interface for n = 2 to 22, using angstrom-resolution X-ray methods. For n < 6, a typical “simple liquid” monotonic surface-normal electron density profile ρ e more » ( z ) is obtained, like those of water and organic solvents. For n > 6, increasingly more pronounced nanoscale self-segregation of the molecules’ charged moieties and apolar chains yields surface layering with alternating regions of headgroups and chains. The layering decays into the bulk over a few, to a few tens, of nanometers. The layering periods and decay lengths, their linear n dependence, and slopes are discussed within two models, one with partial-chain interdigitation and the other with liquid-like chains. No surface-parallel long-range order is found within the surface layer. For n = 22, a different surface phase is observed above melting. Finally, our results also impact general liquid-phase issues like supramolecular self-aggregation and bulk–surface structure relations.« less

Micelle-induced depletion interaction and resultant structure in charged colloidal nanoparticle system

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

Ray, D.; Aswal, V. K., E-mail: vkaswal@barc.gov.in; Kohlbrecher, J.

2015-04-28

The evolution of the interaction and the resultant structure in the mixed system of anionic silica nanoparticles (Ludox LS30) and non-ionic surfactant decaethylene glycol monododecylether (C12E10), undergoing phase separation, have been studied using small-angle neutron scattering and dynamic light scattering. The measurements have been carried out for a fixed concentration of nanoparticle (1 wt. %) with varying concentration of surfactant (0 to 1 wt. %), in the absence and presence of an electrolyte. It is found that the micelles of non-ionic surfactant adsorb on the nanoparticle in the absence of electrolyte (form stable system), whereas these micelles become non-adsorbing in the presence of electrolytemore » (show phase separation). The phase separation arises because of C12E10 micelles, causing depletion interaction between nanoparticles and leading to their aggregation. The interaction is modeled by double Yukawa potential accounting for attractive depletion as well as repulsive electrostatic forces. Both the interactions (attraction and repulsion) are found to be of long-range. The nanoparticle aggregation (phase separation) is governed by the increase in the magnitude and the range of the depletion attraction with the increase in the surfactant concentration. The nanoparticle aggregates formed are quite large in size (order of micron) and are characterized by the surface fractal having simple cubic packing of nanoparticles within the aggregates.« less

Fitting membrane resistance along with action potential shape in cardiac myocytes improves convergence: application of a multi-objective parallel genetic algorithm.

PubMed

Kaur, Jaspreet; Nygren, Anders; Vigmond, Edward J

2014-01-01

Fitting parameter sets of non-linear equations in cardiac single cell ionic models to reproduce experimental behavior is a time consuming process. The standard procedure is to adjust maximum channel conductances in ionic models to reproduce action potentials (APs) recorded in isolated cells. However, vastly different sets of parameters can produce similar APs. Furthermore, even with an excellent AP match in case of single cell, tissue behaviour may be very different. We hypothesize that this uncertainty can be reduced by additionally fitting membrane resistance (Rm). To investigate the importance of Rm, we developed a genetic algorithm approach which incorporated Rm data calculated at a few points in the cycle, in addition to AP morphology. Performance was compared to a genetic algorithm using only AP morphology data. The optimal parameter sets and goodness of fit as computed by the different methods were compared. First, we fit an ionic model to itself, starting from a random parameter set. Next, we fit the AP of one ionic model to that of another. Finally, we fit an ionic model to experimentally recorded rabbit action potentials. Adding the extra objective (Rm, at a few voltages) to the AP fit, lead to much better convergence. Typically, a smaller MSE (mean square error, defined as the average of the squared error between the target AP and AP that is to be fitted) was achieved in one fifth of the number of generations compared to using only AP data. Importantly, the variability in fit parameters was also greatly reduced, with many parameters showing an order of magnitude decrease in variability. Adding Rm to the objective function improves the robustness of fitting, better preserving tissue level behavior, and should be incorporated.

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

A rapid and simple pretreatment method for benzoylurea insecticides in honey samples using in-syringe dispersive liquid-liquid microextraction based on the direct solidification of ionic liquids.

PubMed

Wang, Huazi; Hu, Lu; Li, Wanzhen; Lu, Runhua; Zhang, Sanbing; Zhou, Wenfeng; Gao, Haixiang

2016-11-04

A pretreatment method using in-syringe dispersive liquid-liquid microextraction based on the direct solidification of ionic liquids before high performance liquid chromatography analysis was developed for the determination of benzoylurea insecticides (BUs) in honey samples. The hydrophobic ionic liquid [N 4444 ][PF 6 ], formed in situ by the hydrophilic ionic liquid [N 4444 ]Cl and the ion exchange reagent KPF 6 , was used to extract the target analytes. The entire extraction procedure was performed in a syringe. The extractant was solidified at room temperature and collected using a nylon membrane filter. This technique did not require a dispersive solvent, vortex mixer, ultrasound bath, or centrifugation. The parameters affecting the extraction efficiency were investigated through an experimental design. Under the optimal conditions, the limits of detection for the four BUs varied from 0.21 to 0.42μgL -1 in solution (2.1-4.2μgkg -1 in honey). Good linearities were obtained in the range of 2-300μgL -1 , with coefficients of determination greater than 0.999. The recoveries of the four BUs ranged from 80.94% to 84.59%. The intra-day (n=3) and inter-day (n=3) relative standard deviations were less than 5.08%. Finally, the proposed method was applied to the determination of BUs in commercial honey samples with satisfactory results. Copyright © 2016 Elsevier B.V. All rights reserved.

Application of ionic liquids in vacuum microwave-assisted extraction followed by macroporous resin isolation of three flavonoids rutin, hyperoside and hesperidin from Sorbus tianschanica leaves.

PubMed

Gu, Huiyan; Chen, Fengli; Zhang, Qiang; Zang, Jing

2016-03-01

Rutin, hyperoside and hesperidin were effectively extracted from Sorbus tianschanica leaves by an ionic liquid vacuum microwave-assisted method. A series of ionic liquids with various anions and alkyl chain length of the cations were studied and the extraction was performed in [C6mim][BF4] aqueous solution. After optimization by a factorial design and response surface methodology, total extraction yield of 2.37mg/g with an error of 0.12mg/g (0.71±0.04mg/g, 1.18±0.06mg/g and 0.48±0.02 for rutin, hyperoside and hesperidin, respectively) was achieved under -0.08MPa for vacuum, 19min and 420W for microwave irradiation time and power, and 15mL/g for liquid-solid ratio. The proposed method here is more efficient and needs a shorter extraction time for rutin, hyperoside and hesperidin from S. tianschanica leaves than reference extraction techniques. In stability studies performed with standard rutin, hyperoside and hesperidin, the target analytes were stable under the optimum conditions. The proposed method had a high reproducibility and precision. In addition, separation of rutin, hyperoside and hesperidin from [C6mim][BF4] extraction solution was completed effectively by AB-8 macroporous resin adsorption and desorption process. Ionic liquid vacuum microwave-assisted extraction is a simple, rapid and efficient sample extraction technique. Copyright © 2016 Elsevier B.V. All rights reserved.

Toward practical all-solid-state lithium-ion batteries with high energy density and safety: Comparative study for electrodes fabricated by dry- and slurry-mixing processes

NASA Astrophysics Data System (ADS)

Nam, Young Jin; Oh, Dae Yang; Jung, Sung Hoo; Jung, Yoon Seok

2018-01-01

Owing to their potential for greater safety, higher energy density, and scalable fabrication, bulk-type all-solid-state lithium-ion batteries (ASLBs) employing deformable sulfide superionic conductors are considered highly promising for applications in battery electric vehicles. While fabrication of sheet-type electrodes is imperative from the practical point of view, reports on relevant research are scarce. This might be attributable to issues that complicate the slurry-based fabrication process and/or issues with ionic contacts and percolation. In this work, we systematically investigate the electrochemical performance of conventional dry-mixed electrodes and wet-slurry fabricated electrodes for ASLBs, by varying the different fractions of solid electrolytes and the mass loading. This information calls for a need to develop well-designed electrodes with better ionic contacts and to improve the ionic conductivity of solid electrolytes. As a scalable proof-of-concept to achieve better ionic contacts, a premixing process for active materials and solid electrolytes is demonstrated to significantly improve electrochemical performance. Pouch-type 80 × 60 mm2 all-solid-state LiNi0·6Co0·2Mn0·2O2/graphite full-cells fabricated by the slurry process show high cell-based energy density (184 W h kg-1 and 432 W h L-1). For the first time, their excellent safety is also demonstrated by simple tests (cutting with scissors and heating at 110 °C).

Biologically Inspired Electronic, Photovoltaic and Microfluidic Devices Based on Aqueous Soft Matter

NASA Astrophysics Data System (ADS)

Koo, Hyung Jun

Hydrogels are a water-based soft material where three dimensional networks of hydrophilic polymer retain large amounts of water. We developed hydrogel based devices with new functionalities inspired by materials, structures and processes in nature. The advantages, such as softness, biocompatibility and high ionic conductivity, could enable hydrogels to be novel materials for biomimetic devices operated by ionic current. Moreover, microfluidic patterns are easily embedded in moldable hydrogels and allow for unique convective/diffusive transport mechanism in porous gel to be used for uniform delivery of reagent solution. We first developed and characterized a device with unidirectional ionic current flow across a SiO2/Gel junction, which showed highly efficient rectification of the ionic current by non-linear conductivity of SiO2 films. Addition of polyelectrolytes and salt to the gel layer significantly improved the performance of the new diode device because of the enhanced gel conductance. A soft matter based diode composed of hydrogel and liquid metal (eutectic gallium indium, EGaIn) was also presented. The ability to control the thickness, and thus resistivity, of an insulating oxide skin on the metal enables the current rectification. The effect of ionic conductivity and pH on the formation of the insulating oxide was investigated in a simple model system with liquid metal/electrolyte solution or hydrogel/Pt interfaces. Finally, we present a diode composed entirely of soft materials by replacing the platinum electrode with a second liquid metal electrode. A new type of hydrogel-based photovoltaic systems (HGPVs) was constructed. Two photosensitive ionized molecules embedded in aqueous gel served as photoactive species. The HGPVs showed performance comparable with or higher than those of some other biomimetic or ionic photovoltaic systems reported recently. We suggest a provisional mechanism of the device operation, based on a synergetic effect of the two dye molecules. To reduce the fabrication cost without efficiency loss, we found an inexpensive replacement of the expensive Pt counter-electrode with copper coated with carbon materials. Biologically derived photoactive molecules, such as Chlorophyll and Photosystem II, were successfully operated in the aqueous gel of such HGPVs. As a proof of demonstration of biomimetic structures, a light driven biomimetic reactor was developed by using hydrogel media with embedded photocatalytic TiO2 nanoparticles. Uniform supply of the reactants and extraction of the products was accomplished via a microfluidic channel network, broadly similar to the vein structure of live leaves. The dyes were transported in the gel between the microchannels and degraded by photocatalytic oxidation by the illuminated TiO2 particles. Quantitative analysis of the photocatalytic degradation rate of the injected dyes revealed that the microvascular reactor has high quantum efficiency per catalyst mass. Numerical modeling was performed to explore how a soluble reagent could be supplied rapidly and efficiently through microfluidic channel networks embedded in hydrogels. The computational model takes into account the fluid transport in porous media and the solute convection and diffusion, to simulate the solute distribution and outflux with time in microfluidic hydrogel media. The effect of the channel dimensions and shapes on mass transport rapidity and efficiency was quantitatively evaluated. Experimental data proved the validity of the time dependent concentration profile calculated by the simulation. Lastly, a microfluidic hydrogel solar cell with biomimetic regeneration functionality was demonstrated as a result of the above experimental and modeling studies. A new concept of open and replenishable photovoltaics was constructed on the basis of dye-sensitized solar cells. Photovoltaic reagents, dyes and redox electrolytes, were uniformly delivered via microfluidic networks embedded in a hydrogel, resulting in increase of photocurrent generation. The regeneration process was established, based on the pH dependence of adsorption/desorption kinetics of the dye molecules on a TiO2 photoanode. Complete and reliable recovery of the photocurrent after an accelerated photodegradation in the biomimetic photovoltaics was demonstrated.

Interaction of slow highly charged ions with a metal surface covered with a thin dielectric film. The role of the neutralization energy in the nanostructures formation

NASA Astrophysics Data System (ADS)

Majkić, M. D.; Nedeljković, N. N.; Dojčilović, R. J.

2017-09-01

We consider the slow highly charged ions impinging upon a metal surface covered with a thin dielectric film, and formation of the surface nanostructures (craters) from the standpoint of the required energy. For the moderate ionic velocities, the size of the surface features depends on the deposited kinetic energy of the projectile and the ionic neutralization energy. The neutralization energy is calculated by employing the recently developed quasi-resonant two-state vector model for the intermediate Rydberg state population and the micro-staircase model for the cascade neutralization. The electron interactions with the ionic core, polarized dielectric and charge induced on the metal surface are modelled by the appropriate asymptotic expressions and the method for calculation of the effective ionic charges in the dielectric is proposed. The results are presented for the interaction of \\text{X}{{\\text{e}}Z+} ions (velocity v=0.25 a.u.; 25) with the metal surface (Co) covered with a thin dielectric film, for model values of dielectric constant inside the interaction region. In the absence of dielectric film, the neutralization energy is lower than the potential (ionization) energy due to the incomplete neutralization. The presence of dielectric film additionally decreases the neutralization energy. We calculate the projectile neutralization energy in the perturbed dielectric (perturbation is caused by the ionic motion and the surface structure formation). We correlate the neutralization energy added to the deposited kinetic energy with the experimentally obtained energy necessary for the formation of the nano-crater of a given depth.

Modeling the [NTf2] pyridinium ionic liquids family and their mixtures with the soft statistical associating fluid theory equation of state.

PubMed

Oliveira, M B; Llovell, F; Coutinho, J A P; Vega, L F

2012-08-02

In this work, the soft statistical associating fluid theory (soft-SAFT) equation of state (EoS) has been used to provide an accurate thermodynamic characterization of the pyridinium-based family of ionic liquids (ILs) with the bis(trifluoromethylsulfonyl)imide anion [NTf(2)](-). On the basis of recent molecular simulation studies for this family, a simple molecular model was proposed within the soft-SAFT EoS framework. The chain length value was transferred from the equivalent imidazolium-based ILs family, while the dispersive energy and the molecular parameters describing the cation-anion interactions were set to constant values for all of the compounds. With these assumptions, an appropriate set of molecular parameters was found for each compound fitting to experimental temperature-density data at atmospheric pressure. Correlations for the nonconstant parameters (describing the volume of the IL) with the molecular weight were established, allowing the prediction of the parameters for other pyridiniums not included in the fitting. Then, the suitability of the proposed model and its optimized parameters were tested by predicting high-pressure densities and second-order thermodynamic derivative properties such as isothermal compressibilities of selected [NTf(2)] pyridinium ILs, in a large range of thermodynamic conditions. The surface tension was also provided using the density gradient theory coupled to the soft-SAFT equation. Finally, the soft-SAFT EoS was applied to describe the phase behavior of several binary mixtures of [NTf(2)] pyridinium ILs with carbon dioxide, sulfur dioxide, and water. In all cases, a temperature-independent binary parameter was enough to reach quantitative agreement with the experimental data. The description of the solubility of CO(2) in these ILs also allowed identification of a relation between the binary parameter and the molecular weight of the ionic liquid, allowing the prediction of the CO(2) + C(12)py[NTf(2)] mixture. The good agreement with the experimental data shows the excellent ability of the soft-SAFT EoS to describe the thermophysical properties of ILs as well as their phase behavior. Results prove that this equation of state can be a valuable tool to assist the design of ILs (in what concerns cation and anion selection) in order to obtain ILs with the desired properties and, consequently, enhancing their potential industrial applications.

Light scattering measurements supporting helical structures for chromatin in solution.

PubMed

Campbell, A M; Cotter, R I; Pardon, J F

1978-05-01

Laser light scattering measurements have been made on a series of polynucleosomes containing from 50 to 150 nucleosomes. Radii of gyration have been determined as a function of polynucleosome length for different ionic strength solutions. The results suggest that at low ionic strength the chromatin adopts a loosely helical structure rather than a random coil. The helix becomes more regular on increasing the ionic strength, the dimension resembling those proposed by Finch and Klug for their solenoid model.

First Principles Modeling of Structure and Transport in Solid Polymer Electrolytes, Ionic Liquids, and Methanol/Water Mixtures

DTIC Science & Technology

2016-02-10

potential in making high- performance solid state lithium ion batteries [1,2]. Among them, the polyethylene oxide-alkali salts systems PEO6:XPF6 (X = H...electrolytes for magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group...magnesium batteries incorporating chloro- or iodo- ionic liquids. Much of this work was done in collaboration with the experimental group of Prof. Vito Di

Modeling of robotic fish propelled by an ionic polymer-metal composite caudal fin

NASA Astrophysics Data System (ADS)

Chen, Zheng; Shatara, Stephan; Tan, Xiaobo

2009-03-01

In this paper, a model is proposed for a biomimetic robotic fish propelled by an ionic polymer metal composite (IPMC) actuator with a rigid passive fin at the end. The model incorporates both IPMC actuation dynamics and the hydrodynamics, and predicts the steady-state speed of the robot under a periodic actuation voltage. Experimental results have shown that the proposed model can predict the fish motion for different tail dimensions. Since its parameters are expressed in terms of physical properties and geometric dimensions, the model is expected to be instrumental in optimal design of the robotic fish.

Synthesis and Characterization of Ionically Crosslinked Elastomers

DTIC Science & Technology

2015-05-12

SECURITY CLASSIFICATION OF: In this research poly(n-butyl acrylate) (PBA) elastomers were investigated as model systems to study the thermomechanical...subject to any oenalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO...Ionically Crosslinked Elastomers Report Title In this research poly(n-butyl acrylate) (PBA) elastomers were investigated as model systems to study the

Flow-induced immobilization of glucose oxidase in nonionic micellar nanogels for glucose sensing.

PubMed

Cardiel, Joshua J; Zhao, Ya; Tonggu, Lige; Wang, Liguo; Chung, Jae-Hyun; Shen, Amy Q

2014-10-21

A simple microfluidic platform was utilized to immobilize glucose oxidase (GOx) in a nonionic micellar scaffold. The immobilization of GOx was verified by using a combination of cryogenic electron microscopy (cryo-EM), scanning electron microscopy (SEM), and ultraviolet spectroscopy (UV) techniques. Chronoamperometric measurements were conducted on nanogel-GOx scaffolds under different glucose concentrations, exhibiting linear amperometric responses. Without impacting the lifetime and denaturation of GOx, the nonionic nanogel provides a favorable microenvironment for GOx in biological media. This flow-induced immobilization method in a nonionic nanogel host matrix opens up new pathways for designing a simple, fast, biocompatible, and cost-effective process to immobilize biomolecules that are averse to ionic environments.

Charge-screening role of c -axis atomic displacements in YBa 2 Cu 3 O 6 + x and related superconductors

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

Božin, E. S.; Huq, A.; Shen, Bing

2016-02-01

The importance of charge reservoir layers for supplying holes to the CuO 2 planes of cuprate superconductors has long been recognized. Less attention has been paid to the screening of the charge transfer by the intervening ionic layers. We address this issue in the case of YBa 2 Cu 3 O 6 + x , where CuO chains supply the holes for the planes. We present a simple dielectric-screening model that gives a linear correlation between the relative displacements of ions along the c axis, determined by neutron powder diffraction, and the hole density of the planes. Applying this modelmore » to the temperature-dependent shifts of ions along the c axis, we infer a charge transfer of 5–10% of the hole density from the planes to the chains on warming from the superconducting transition to room temperature. Given the significant coupling of c -axis displacements to the average charge density, we point out the relevance of local displacements for screening charge modulations and note recent evidence for dynamic screening of in-plane quasiparticles. This line of argument leads us to a simple model for atomic displacements and charge modulation that is consistent with images from scanning-tunneling microscopy for underdoped Bi 2 Sr 2 CaCu 2 O 8 + δ .« less

Development of a carbon-nanoparticle-coated stirrer for stir bar sorptive extraction by a simple carbon deposition in flame.

PubMed

Feng, Juanjuan; Sun, Min; Bu, Yanan; Luo, Chuannan

2016-03-01

Stir bar sorptive extraction is an environmentally friendly microextraction technique based on a stir bar with various sorbents. A commercial stirrer is a good support, but it has not been used in stir bar sorptive extraction due to difficult modification. A stirrer was modified with carbon nanoparticles by a simple carbon deposition process in flame and characterized by scanning electron microscopy and energy-dispersive X-ray spectrometry. A three-dimensional porous coating was formed with carbon nanoparticles. In combination with high-performance liquid chromatography, the stir bar was evaluated using five polycyclic aromatic hydrocarbons as model analytes. Conditions including extraction time and temperature, ionic strength, and desorption solvent were investigated by a factor-by-factor optimization method. The established method exhibited good linearity (0.01-10 μg/L) and low limits of quantification (0.01 μg/L). It was applied to detect model analytes in environmental water samples. No analyte was detected in river water, and five analytes were quantified in rain water. The recoveries of five analytes in two samples with spiked at 2 μg/L were in the range of 92.2-106% and 93.4-108%, respectively. The results indicated that the carbon nanoparticle-coated stirrer was an efficient stir bar for extraction analysis of some polycyclic aromatic hydrocarbons. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multilevel Molecular Modeling Approach for a Rational Design of Ionic Current Sensors for Nanofluidics.

PubMed

Kirch, Alexsandro; de Almeida, James M; Miranda, Caetano R

2018-05-10

The complexity displayed by nanofluidic-based systems involves electronic and dynamic aspects occurring across different size and time scales. To properly model such kind of system, we introduced a top-down multilevel approach, combining molecular dynamics simulations (MD) with first-principles electronic transport calculations. The potential of this technique was demonstrated by investigating how the water and ionic flow through a (6,6) carbon nanotube (CNT) influences its electronic transport properties. We showed that the confinement on the CNT favors the partially hydrated Na, Cl, and Li ions to exchange charge with the nanotube. This leads to a change in the electronic transmittance, allowing for the distinguishing of cations from anions. Such an ionic trace may handle an indirect measurement of the ionic current that is recorded as a sensing output. With this case study, we are able to show the potential of this top-down multilevel approach, to be applied on the design of novel nanofluidic devices.

Surface science and model catalysis with ionic liquid-modified materials.

PubMed

Steinrück, H-P; Libuda, J; Wasserscheid, P; Cremer, T; Kolbeck, C; Laurin, M; Maier, F; Sobota, M; Schulz, P S; Stark, M

2011-06-17

Materials making use of thin ionic liquid (IL) films as support-modifying functional layer open up a variety of new possibilities in heterogeneous catalysis, which range from the tailoring of gas-surface interactions to the immobilization of molecularly defined reactive sites. The present report reviews recent progress towards an understanding of "supported ionic liquid phase (SILP)" and "solid catalysts with ionic liquid layer (SCILL)" materials at the microscopic level, using a surface science and model catalysis type of approach. Thin film IL systems can be prepared not only ex-situ, but also in-situ under ultrahigh vacuum (UHV) conditions using atomically well-defined surfaces as substrates, for example by physical vapor deposition (PVD). Due to their low vapor pressure, these systems can be studied in UHV using the full spectrum of surface science techniques. We discuss general strategies and considerations of this approach and exemplify the information available from complementary methods, specifically photoelectron spectroscopy and surface vibrational spectroscopy. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interactions of lysozyme in concentrated electrolyte solutions from dynamic light-scattering measurements.

PubMed Central

Kuehner, D E; Heyer, C; Rämsch, C; Fornefeld, U M; Blanch, H W; Prausnitz, J M

1997-01-01

The diffusion of hen egg-white lysozyme has been studied by dynamic light scattering in aqueous solutions of ammonium sulfate as a function of protein concentration to 30 g/liter. Experiments were conducted under the following conditions: pH 4-7 and ionic strength 0.05-5.0 M. Diffusivity data for ionic strengths up to 0.5 M were interpreted in the context of a two-body interaction model for monomers. From this analysis, two potential-of-mean-force parameters, the effective monomer charge, and the Hamaker constant were obtained. At higher ionic strength, the data were analyzed using a model that describes the diffusion coefficient of a polydisperse system of interacting protein aggregates in terms of an isodesmic, indefinite aggregation equilibrium constant. Data analysis incorporated multicomponent virial and hydrodynamic effects. The resulting equilibrium constants indicate that lysozyme does not aggregate significantly as ionic strength increases, even at salt concentrations near the point of salting-out precipitation. PMID:9414232

Development of Monopole Interaction Models for Ionic Compounds. Part I: Estimation of Aqueous Henry's Law Constants for Ions and Gas Phase pKa Values for Acidic Compounds.

PubMed

Hilal, S H; Saravanaraj, A N; Carreira, L A

2014-02-01

The SPARC (SPARC Performs Automated Reasoning in Chemistry) physicochemical mechanistic models for neutral compounds have been extended to estimate Henry's Law Constant (HLC) for charged species by incorporating ionic electrostatic interaction models. Combinations of absolute aqueous pKa values, relative pKa values in the gas phase, and aqueous HLC for neutral compounds have been used to develop monopole interaction models that quantify the energy differences upon moving an ionic solute molecule from the gas phase to the liquid phase. Inter-molecular interaction energies were factored into mechanistic contributions of monopoles with polarizability, dipole, H-bonding, and resonance. The monopole ionic models were validated by a wide range of measured gas phase pKa data for 450 acidic compounds. The RMS deviation error and R(2) for the OH, SH, CO2 H, CH3 and NR2 acidic reaction centers (C) were 16.9 kcal/mol and 0.87, respectively. The calculated HLCs of ions were compared to the HLCs of 142 ions calculated by quantum mechanics. Effects of inter-molecular interaction of the monopoles with polarizability, dipole, H-bonding, and resonance on acidity of the solutes in the gas phase are discussed. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of the ionic liquid 1-butyl-3-methylimidazolium bromide on amyloid fibrillogenesis in lysozyme: Evidence from photophysical and imaging studies.

PubMed

Basu, Anirban; Bhattacharya, Subhash Chandra; Kumar, Gopinatha Suresh

2018-02-01

Many proteins can abnormally fold to form pathological amyloid deposits/aggregates that are responsible for various degenerative disorders called amyloidosis. Here we have examined the anti-amyloidogenic potency of an ionic liquid, 1-butyl-3-methylimidazolium bromide, using lysozyme as a model system. Thioflavin T fluorescence assay demonstrated that the ionic liquid suppressed the formation of lysozyme fibrils significantly. This observation was further confirmed by the Congo red assay. Fluorescence microscopy, intrinsic fluorescence studies, nile red fluorescence assay, ANS binding assay and circular dichroism studies also testified diminishing of the fibrillogenesis in the presence of ionic liquid. Formation of amyloid fibrils was also characterized by α to β conformational transition. From far-UV circular dichroism studies it was observed that the β-sheet content of the lysozyme samples decreased in the presence of the ionic liquid which in turn implied that fibrillogenesis was supressed by the ionic liquid. Atomic force microscopy imaging unequivocally established that the ionic liquid attenuated fibrillogenesis in lysozyme. These results may be useful for the development of more effective therapeutics for amyloidosis. Copyright © 2017 Elsevier B.V. All rights reserved.

Removal of natural organic matter by titanium tetrachloride: The effect of total hardness and ionic strength.

PubMed

Zhao, Y X; Shon, H K; Phuntsho, S; Gao, B Y

2014-02-15

This study is the first attempt to investigate the effect of total hardness and ionic strength on coagulation performance and the floc characteristics of titanium tetrachloride (TiCl4). Membrane fouling under different total hardness and ionic strength conditions was also evaluated during a coagulation-ultrafiltration (C-UF) hybrid process. Coagulation experiments were performed with two simulated waters, using humic acid (HA, high molecular weight) and fulvic acid (FA, relatively low molecular weight), respectively, as model natural organic matter (NOM). Results show that both particle and organic matter removal can be enhanced by increasing total hardness and ionic strength. Floc characteristics were significantly influenced by total hardness and ionic strength and were improved in terms of floc size, growth rate, strength, recoverability and compactness. The results of the UF tests show that the pre-coagulation with TiCl4 significantly improves the membrane permeate fluxes. Under different total hardness and ionic strength conditions, the membrane permeate flux varied according to both NOM and floc characteristics. The increase in total hardness and ionic strength improved the membrane permeate flux in the case of HA simulated water treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Molecular dynamics simulation of the ionic liquid N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide.

PubMed

Siqueira, Leonardo J A; Ribeiro, Mauro C C

2007-10-11

Thermodynamics, structure, and dynamics of an ionic liquid based on a quaternary ammonium salt with ether side chain, namely, N-ethyl-N,N-dimethyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide, MOENM2E TFSI, are investigated by molecular dynamics (MD) simulations. Average density and configurational energy of simulated MOENM2E TFSI are interpreted with models that take into account empirical ionic volumes. A throughout comparison of the equilibrium structure of MOENM2E TFSI with previous results for the more common ionic liquids based on imidazolium cations is provided. Several time correlation functions are used to reveal the microscopic dynamics of MOENM2E TFSI. Structural relaxation is discussed by the calculation of simultaneous space-time correlation functions. Temperature effects on transport coefficients (diffusion, conductivity, and viscosity) are investigated. The ratio between the actual conductivity and the estimate from ionic diffusion by the Nernst-Einstein equation indicates that correlated motion of neighboring ions in MOENM2E TFSI is similar to imidazolium ionic liquids. In line with experiment, Walden plot of conductivity and viscosity indicates that simulated MOENM2E TFSI should be classified as a poor ionic liquid.

Analysis of the statistical thermodynamic model for nonlinear binary protein adsorption equilibria.

PubMed

Zhou, Xiao-Peng; Su, Xue-Li; Sun, Yan

2007-01-01

The statistical thermodynamic (ST) model was used to study nonlinear binary protein adsorption equilibria on an anion exchanger. Single-component and binary protein adsorption isotherms of bovine hemoglobin (Hb) and bovine serum albumin (BSA) on DEAE Spherodex M were determined by batch adsorption experiments in 10 mM Tris-HCl buffer containing a specific NaCl concentration (0.05, 0.10, and 0.15 M) at pH 7.40. The ST model was found to depict the effect of ionic strength on the single-component equilibria well, with model parameters depending on ionic strength. Moreover, the ST model gave acceptable fitting to the binary adsorption data with the fitted single-component model parameters, leading to the estimation of the binary ST model parameter. The effects of ionic strength on the model parameters are reasonably interpreted by the electrostatic and thermodynamic theories. The effective charge of protein in adsorption phase can be separately calculated from the two categories of the model parameters, and the values obtained from the two methods are consistent. The results demonstrate the utility of the ST model for describing nonlinear binary protein adsorption equilibria.

Equations of state and transport properties of mixtures in the warm dense regime

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

Hou, Yong; Dai, Jiayu; Kang, Dongdong

2015-02-15

We have performed average-atom molecular dynamics to simulate the CH and LiH mixtures in the warm dense regime, and obtained equations of state and the ionic transport properties. The electronic structures are calculated by using the modified average-atom model, which have included the broadening of energy levels, and the ion-ion pair potentials of mixtures are constructed based on the temperature-dependent density functional theory. The ionic transport properties, such as ionic diffusion and shear viscosity, are obtained through the ionic velocity correlation functions. The equations of state and transport properties for carbon, hydrogen and lithium, hydrogen mixtures in a wide regionmore » of density and temperature are calculated. Through our computing the average ionization degree, average ion-sphere diameter and transition properties in the mixture, it is shown that transport properties depend not only on the ionic mass but also on the average ionization degree.« less

Electrical charging effects on the sliding friction of a model nano-confined ionic liquid

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

Capozza, R.; Vanossi, A.; CNR-IOM Democritos National Simulation Center, Via Bonomea 265, 34136 Trieste

2015-10-14

Recent measurements suggest the possibility to exploit ionic liquids (ILs) as smart lubricants for nano-contacts, tuning their tribological and rheological properties by charging the sliding interfaces. Following our earlier theoretical study of charging effects on nanoscale confinement and squeezout of a model IL, we present here molecular dynamics simulations of the frictional and lubrication properties of that model under charging conditions. First, we describe the case when two equally charged plates slide while being held together to a confinement distance of a few molecular layers. The shear sliding stress is found to rise strongly and discontinuously as the number ofmore » IL layers decreases stepwise. However, the shear stress shows, within each given number of layers, only a weak dependence upon the precise value of the normal load, a result in agreement with data extracted from recent experiments. We subsequently describe the case of opposite charging of the sliding plates and follow the shear stress when the charging is slowly and adiabatically reversed in the course of time, under fixed load. Despite the fixed load, the number and structure of the confined IL layers change with changing charge, and that in turn drives strong friction variations. The latter involves first of all charging-induced freezing of the IL film, followed by a discharging-induced melting, both made possible by the nanoscale confinement. Another mechanism for charging-induced frictional changes is a shift of the plane of maximum shear from mid-film to the plate-film interface, and vice versa. While these occurrences and results invariably depend upon the parameters of the model IL and upon its specific interaction with the plates, the present study helps identifying a variety of possible behavior, obtained under very simple assumptions, while connecting it to an underlying equilibrium thermodynamics picture.« less

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'.

Temperature- and pressure-dependent infrared spectroscopy of 1-butyl-3-methylimidazolium trifluoromethanesulfonate: A dipolar coupling theory analysis

NASA Astrophysics Data System (ADS)

Burba, Christopher M.; Chang, Hai-Chou

2018-03-01

Continued growth and development of ionic liquids requires a thorough understanding of how cation and anion molecular structure defines the liquid structure of the materials as well as the various properties that make them technologically useful. Infrared spectroscopy is frequently used to assess molecular-level interactions among the cations and anions of ionic liquids because the intramolecular vibrational modes of the ions are sensitive to the local potential energy environments in which they reside. Thus, different interaction modes among the ions may lead to different spectroscopic signatures in the vibrational spectra. Charge organization present in ionic liquids, such as 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4mim]CF3SO3), is frequently modeled in terms of a quasicrystalline structure. Highly structured quasilattices enable the dynamic coupling of vibrationally-induced dipole moments to produce optical dispersion and transverse optical-longitudinal optical (TO-LO) splitting of vibrational modes of the ionic liquid. According to dipolar coupling theory, the degree of TO-LO splitting is predicted to have a linear dependence on the number density of the ionic liquid. Both temperature and pressure will affect the number density of the ionic liquid and, therefore, the amount of TO-LO splitting for this mode. Therefore, we test these relationships through temperature- and pressure-dependent FT-IR spectroscopic studies of [C4mim]CF3SO3, focusing on the totally symmetric Ssbnd O stretching mode for the anion, νs(SO3). Increased temperature decreases the amount of TO-LO splitting for νs(SO3), whereas elevated pressure is found to increase the amount of band splitting. In both cases, the experimental observations follow the general predictions of dipolar coupling theory, thereby supporting the quasilattice model for this ionic liquid.

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.

Write-Read 3D Patterning with a Dual-Channel Nanopipette.

PubMed

Momotenko, Dmitry; Page, Ashley; Adobes-Vidal, Maria; Unwin, Patrick R

2016-09-27

Nanopipettes are becoming extremely versatile and powerful tools in nanoscience for a wide variety of applications from imaging to nanoscale sensing. Herein, the capabilities of nanopipettes to build complex free-standing three-dimensional (3D) nanostructures are demonstrated using a simple double-barrel nanopipette device. Electrochemical control of ionic fluxes enables highly localized delivery of precursor species from one channel and simultaneous (dynamic and responsive) ion conductance probe-to-substrate distance feedback with the other for reliable high-quality patterning. Nanopipettes with 30-50 nm tip opening dimensions of each channel allowed confinement of ionic fluxes for the fabrication of high aspect ratio copper pillar, zigzag, and Γ-like structures, as well as permitted the subsequent topographical mapping of the patterned features with the same nanopipette probe as used for nanostructure engineering. This approach offers versatility and robustness for high-resolution 3D "printing" (writing) and read-out at the nanoscale.

Determination of acrylamide in brewed coffee and coffee powder using polymeric ionic liquid-based sorbent coatings in solid-phase microextraction coupled to gas chromatography-mass spectrometry.

PubMed

Cagliero, Cecilia; Ho, Tien D; Zhang, Cheng; Bicchi, Carlo; Anderson, Jared L

2016-06-03

This study describes a simple and rapid sampling method employing a polymeric ionic liquid (PIL) sorbent coating in direct immersion solid-phase microextraction (SPME) for the trace-level analysis of acrylamide in brewed coffee and coffee powder. The crosslinked PIL sorbent coating demonstrated superior sensitivity in the extraction of acrylamide compared to all commercially available SPME coatings. A spin coating method was developed to evenly distribute the PIL coating on the SPME support and reproducibly produce fibers with a large film thickness. Ninhydrin was employed as a quenching reagent during extraction to inhibit the production of interfering acrylamide. The PIL fiber produced a limit of quantitation for acrylamide of 10μgL(-1) and achieved comparable results to the ISO method in the analysis of six coffee powder samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericity

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

Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun

We report the discovery of an ionic small molecule surfactant that undergoes water-drive self- assembly into quasispherical micelles, which pack into the first lyotropic liquid crystalline Frank–Kasper σ phase. Small-angle X-ray scattering studies indicate that this unexpected, low-symmetry phase is characterized by a tetragonal unit cell, in which 30 sub-2 nm micelles of five discrete types are arranged into a tetrahedral close packing with exceptional translational order. Varying the relative amounts of surfactant and water in these lyotropic phases enables formation of a Frank–Kasper A15 sphere packing and a more common body-centered cubic structure. MD simulations reveal that the symmetrymore » breaking that drives the selection of the σ and A15 phases arises from a delicate interplay between the drive to maintain local spherical particle symmetry and the maximization of electrostatic cohesion between the soft micellar particles.« less

Bulk and Thin film Properties of Nanoparticle-based Ionic Materials

NASA Astrophysics Data System (ADS)

Fang, Jason

2008-03-01

Nanoparticle-based ionic materials (NIMS) offer exciting opportunities for research at the forefront of science and engineering. NIMS are hybrid particles comprised of a charged oligomeric corona attached to hard, inorganic nanoparticle cores. Because of their hybrid nature, physical properties --rheological, optical, electrical, thermal - of NIMS can be tailored over an unusually wide range by varying geometric and chemical characteristics of the core and canopy and thermodynamic variables such as temperature and volume fraction. On one end of the spectrum are materials with a high core content, which display properties similar to crystalline solids, stiff waxes, and gels. At the opposite extreme are systems that spontaneously form particle-based fluids characterized by transport properties remarkably similar to simple liquids. In this poster I will present our efforts to synthesize NIMS and discuss their bulk and surface properties. In particular I will discuss our work on preparing smart surfaces using NIMS.

Enhanced Born Charge and Proximity to Ferroelectricity in Thallium Halides

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

Du, Mao-Hua; Singh, David J

2010-01-01

Electronic structure and lattice dynamics calculations on thallium halides show that the Born effective charges in these compounds are more than twice larger than the nominal ionic charges. This is a result of cross-band-gap hybridization between Tl-p and halogen-p states. The large Born charges cause giant splitting between longitudinal and transverse optic phonon modes, bringing the lattice close to ferroelectric instability. Our calculations indeed show spontaneous lattice polarization upon lattice expansion starting at 2%. It is remarkable that the apparently ionic thallium halides with a simple cubic CsCl structure and large differences in electronegativity between cations and anions can bemore » very close to ferroelectricity. This can lead to effective screening of defects and impurities that would otherwise be strong carrier traps and may therefore contribute to the relatively good carrier transport properties in TlBr radiation detectors.« less

Enhanced Born charge and proximity to ferroelectricity in thallium halides

NASA Astrophysics Data System (ADS)

Du, Mao-Hua; Singh, David J.

2010-04-01

Electronic-structure and lattice-dynamics calculations on thallium halides show that the Born effective charges in these compounds are more than twice larger than the nominal ionic charges. This is a result of cross-band-gap hybridization between Tlp and halogen- p states. The large Born charges cause giant splitting between longitudinal and transverse-optic phonon modes, bringing the lattice close to ferroelectric instability. Our calculations indeed show that cubic TlBr develops ferroelectric instabilities upon lattice expansion starting at 2%. It is remarkable that the apparently ionic thallium halides with a simple cubic CsCl structure and large differences in electronegativity between cations and anions can be very close to ferroelectricity. This can lead to effective screening of defects and impurities that would otherwise be strong carrier traps and may therefore contribute to the relatively good carrier transport properties in TlBr radiation detectors.

Auto-Tandem Catalysis in Ionic Liquids: Synthesis of 2-Oxazolidinones by Palladium-Catalyzed Oxidative Carbonylation of Propargylic Amines in EmimEtSO₄.

PubMed

Mancuso, Raffaella; Maner, Asif; Ziccarelli, Ida; Pomelli, Christian; Chiappe, Cinzia; Della Ca', Nicola; Veltri, Lucia; Gabriele, Bartolo

2016-07-08

A convenient carbonylative approach to 2-oxazolidinone derivatives carried out using an ionic liquid (1-ethyl-3-methylimidazolium ethyl sulfate, EmimEtSO₄) as the solvent is presented. It is based on the sequential concatenation of two catalytic cycles, both catalyzed by the same metal species (auto-tandem catalysis): the first cycle corresponds to the oxidative monoaminocarbonylation of the triple bond of propargylic amines to give the corresponding 2-ynamide intermediates, while the second one involves the cyclocarbonylation of the latter to yield 2-(2-oxooxazolidin-5-ylidene)-acetamides. Reactions are carried out using a simple catalytic system consisting of PdI₂ in conjunction with an excess of KI, and the catalyst/solvent system could be recycled several times without appreciable loss of activity after extraction of the organic product with Et₂O.

VUV Dissociative Photoionization of Quinoline in the 7-26 eV Photon Energy Range

NASA Astrophysics Data System (ADS)

Leach, Sydney; Jochims, Hans-Werner; Baumgärtel, Helmut; Champion, Norbert

2018-05-01

The dissociative photoionization of quinoline was studied by photoionization mass spectrometry and ion yield measurements over a synchrotron photon excitation energy range 7-26 eV. The ionic and neutral products were identified with the aid of thermochemical calculations that, in some cases, led to deeper understanding of photodissociation pathways and the determination of upper limits of heats of formation of ionic and neutral dissociation products. A detailed comparison between the 20 eV photon excitation and 70 eV electron impact mass spectra, coupled with estimation of thermochemical appearance energies, leads to assignment of the dissociative ionization cation and neutral products for each detected ion. Reaction schemes for formation of these products are proposed in a number of cases. Ion intensities in the photon and electron impact mass spectra were used to consider extending a rule of charge retention in simple bond cleavage to more complex cases of dissociative ionization.

Low-symmetry sphere packings of simple surfactant micelles induced by ionic sphericity

DOE PAGES

Kim, Sung A.; Jeong, Kyeong-Jun; Yethiraj, Arun; ...

2017-04-03

We report the discovery of an ionic small molecule surfactant that undergoes water-drive self- assembly into quasispherical micelles, which pack into the first lyotropic liquid crystalline Frank–Kasper σ phase. Small-angle X-ray scattering studies indicate that this unexpected, low-symmetry phase is characterized by a tetragonal unit cell, in which 30 sub-2 nm micelles of five discrete types are arranged into a tetrahedral close packing with exceptional translational order. Varying the relative amounts of surfactant and water in these lyotropic phases enables formation of a Frank–Kasper A15 sphere packing and a more common body-centered cubic structure. MD simulations reveal that the symmetrymore » breaking that drives the selection of the σ and A15 phases arises from a delicate interplay between the drive to maintain local spherical particle symmetry and the maximization of electrostatic cohesion between the soft micellar particles.« less

Electrochemical study of the anticancer drug daunorubicin at a water/oil interface: drug lipophilicity and quantification.

PubMed

Ribeiro, José A; Silva, F; Pereira, Carlos M

2013-02-05

In this work, the ion transfer mechanism of the anticancer drug daunorubicin (DNR) at a liquid/liquid interface has been studied for the first time. This study was carried out using electrochemical techniques, namely cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The lipophilicity of DNR was investigated at the water/1,6-dichlorohexane (DCH) interface, and the results obtained were presented in the form of an ionic partition diagram. The partition coefficients of both neutral and ionic forms of the drug were determined. The analytical parameter for the detection of DNR was also investigated in this work. An electrochemical DNR sensor is proposed by means of simple ion transfer at the water/DCH interface, using DPV as the quantification technique. Experimental conditions for the analytical determination of DNR were established, and a detection limit of 0.80 μM was obtained.

Analysis and experiment on a self-sensing ionic polymer-metal composite actuator

NASA Astrophysics Data System (ADS)

Nam, Doan Ngoc Chi; Ahn, Kyoung Kwan

2014-07-01

An ionic polymer-metal composite (IPMC) actuator is an electro-active polymer (EAP) that bends in response to a small applied electrical field as a result of the mobility of cations in the polymer network. This paper aims to develop a self-sensing actuator for practical use, since current sensing methods generally face limitations due to the compact size and mobility of the IPMC actuator. Firstly, the variation of surface resistance during bending operations is investigated. Then, the behavior of IPMC corresponding to the variation of surface resistance is mathematically analyzed. Based on the analysis results, a simple configuration to realize the self-sensing behavior is introduced. In this technique, the bending curvature of an IPMC can be obtained accurately by employing several feedback voltage signals along with the IPMC length. Finally, experimental evaluations proved the ability of the proposed scheme to estimate the bending behavior of IPMC actuators.

Bionanocomposites of regenerated cellulose/zeolite prepared using environmentally benign ionic liquid solvent.

PubMed

Soheilmoghaddam, Mohammad; Wahit, Mat Uzir; Tuck Whye, Wong; Ibrahim Akos, Noel; Heidar Pour, Raheleh; Ali Yussuf, Abdirahman

2014-06-15

Bionanocomposite films based on regenerated cellulose (RC) and incorporated with zeolite at different concentrations were fabricated by dissolving cellulose in 1-ethyl-3-methylimidazolium chloride (EMIMCl) ionic liquid using a simple green method. The interactions between the zeolite and the cellulose matrix were confirmed by Fourier transform infrared spectra. Mechanical properties of the nanocomposite films significantly improved as compared with the pure regenerated cellulose film, without the loss of extensibility. Zeolite incorporation enhanced the thermal stability and char yield of the nanocomposites. The scanning electron microscopy and transmission electron microscopy showed that zeolite was uniformly dispersed in the regenerated cellulose matrix. In vitro cytotoxicity test demonstrated that both RC and RC/zeolite nanocomposite films are cytocompatible. These results indicate that the prepared nanocomposites have potential applications in biodegradable packaging, membranes and biomedical areas. Copyright © 2014 Elsevier Ltd. All rights reserved.

An electrochemical fungicide pyrimethanil sensor based on carbon nanotubes/ionic-liquid construction modified electrode.

PubMed

Yang, Jichun; Wang, Qiong; Zhang, Minhui; Zhang, Shuming; Zhang, Lei

2015-11-15

In this study, a simple, rapid, sensitive and environmentally friendly electroanalytical detection method for pyrimethanil (PMT) was developed, which was based on multi-walled carbon nanotubes (MWCNTs) and ionic liquids (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]) modified glassy carbon electrode (GCE). MWCNTs-IL modified electrode significantly enhanced the oxidation peak current of PMT by combining the excellent electrochemical properties of MWCNTs and IL, suggesting that the modified electrode can remarkably improve the sensitivity of PMT detection. Under the optimum conditions, this electrochemical sensor exhibited a linear concentration range for PMT of 1.0 × 10(-7)-1.0 × 10(-4) mol L(-1) and the detection limit was 1.6 × 10(-8) mol L(-1) (S/N = 3). The fabricated electrode showed good reproducibility, stability and anti-interference, and also it was successfully employed to detect PMT in real samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

Isothermogravimetric determination of the enthalpies of vaporization of 1-alkyl-3-methylimidazolium ionic liquids.

PubMed

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

2008-08-21

Vaporization enthalpies for two series of ionic liquids (ILs) composed of 1- n-alkyl-3-methylimidazolium cations, [Imm1+] (m=2, 3, 4, 6, 8, or 10), paired with either the bis(trifluoromethanesulfonyl)amide, [Tf2N-], or the bis(perfluoroethylsulfonyl)amide anion, [beti-], were determined using a simple, convenient, and highly reproducible thermogravimetric approach, and from these values, Hildebrand solubility parameters were estimated. Our results reveal two interesting and unanticipated outcomes: (i) methylation at the C2 position of [Imm1+] affords a significantly higher vaporization enthalpy; (ii) in all cases, the [beti-] anion served to lower the enthalpy of vaporization relative to [Tf2N-]. The widespread availability of the apparatus required for these measurements coupled with the ease of automation suggests the broad potential of this methodology for determining this critical parameter in a multitude of ILs.

Notre Dame Geothermal Ionic Liquids Research: Ionic Liquids for Utilization of Geothermal Energy

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

Brennecke, Joan F.

The goal of this project was to develop ionic liquids for two geothermal energy related applications. The first goal was to design ionic liquids as high temperature heat transfer fluids. We identified appropriate compounds based on both experiments and molecular simulations. We synthesized the new ILs, and measured their thermal stability, measured storage density, viscosity, and thermal conductivity. We found that the most promising compounds for this application are aminopyridinium bis(trifluoromethylsulfonyl)imide based ILs. We also performed some measurements of thermal stability of IL mixtures and used molecular simulations to better understand the thermal conductivity of nanofluids (i.e., mixtures of ILsmore » and nanoparticles). We found that the mixtures do not follow ideal mixture theories and that the addition of nanoparticles to ILs may well have a beneficial influence on the thermal and transport properties of IL-based heat transfer fluids. The second goal was to use ionic liquids in geothermally driven absorption refrigeration systems. We performed copious thermodynamic measurements and modeling of ionic liquid/water systems, including modeling of the absorption refrigeration systems and the resulting coefficients of performance. We explored some IL/organic solvent mixtures as candidates for this application, both with experimentation and molecular simulations. We found that the COPs of all of the IL/water systems were higher than the conventional system – LiBr/H2O. Thus, IL/water systems appear very attractive for absorption refrigeration applications.« less

Nanoparticle transport in water-unsaturated porous media: effects of solution ionic strength and flow rate

NASA Astrophysics Data System (ADS)

Prédélus, Dieuseul; Lassabatere, Laurent; Louis, Cédric; Gehan, Hélène; Brichart, Thomas; Winiarski, Thierry; Angulo-Jaramillo, Rafael

2017-03-01

This paper presents the influence of ionic strength and flow on nanoparticle (NP) retention rate in an unsaturated calcareous medium, originating from a heterogeneous glaciofluvial deposit of the region of Lyon (France). Laboratory columns 10 cm in diameter and 30 cm in length were used. Silica nanoparticles (Au-SiO2-FluoNPs), with hydrodynamic diameter ranging from 50 to 60 nm and labeled with fluorescein derivatives, were used to simulate particle transport, and bromide was used to characterize flow. Three flow rates and five different ionic strengths were tested. The transfer model based on fractionation of water into mobile and immobile fractions was coupled with the attachment/detachment model to fit NPs breakthrough curves. The results show that increasing flow velocity induces a decrease in nanoparticle retention, probably as the result of several physical but also geochemical factors. The results show that NPs retention increases with ionic strength. However, an inversion of retention occurs for ionic strength >5.10-2 M, which has been scarcely observed in previous studies. The measure of zeta potential and DLVO calculations show that NPs may sorb on both solid-water and air-water interfaces. NPs size distribution shows the potential for nanoparticle agglomeration mostly at low pH, leading to entrapment in the soil pores. These mechanisms are highly sensitive to both hydrodynamic and geochemical conditions, which explains their high sensitivity to flow rates and ionic strength.

Effects of polarizability on the structural and thermodynamics properties of [C{sub n}mim][Gly] ionic liquids (n = 1–4) using EEM/MM molecular dynamic simulations

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

Wu, Yang; Hu, Na; Yue, Lili

2015-02-14

An extended electronegativity equalization method/molecular mechanics (EEM/MM) model for ionic liquids is used to investigate the structures and properties of 1-alkyl-3-methylimidazolium glycine ionic liquids [C{sub n}mim][Gly] (n = 1–4) with alkyl substituents of different lengths. The EEM/MM model describes the electrostatic interactions of atoms and their changes in different ambient environments. This property is the most outstanding characteristic of the model. EEM parameters (i.e., valence electronegativities and valence hardness parameters) are calibrated using linear regression and least-squares methods, which can accurately predict the gas-phase properties of [C{sub n}mim]{sup +}, [Gly]{sup −}, and [C{sub n}mim][Gly] ion pairs. We utilize the EEM/MMmore » force field to systematically investigate the effects of polarizability on the accuracy of [C{sub n}mim][Gly] properties predicted through the molecular dynamic simulations. EEM/MM explicitly describes the atom-based polarizability of [C{sub n}mim][Gly]; thus, the densities, enthalpies of vaporization, self-diffusion coefficients, and conductivities of the [C{sub n}mim][Gly] are consistent with the experimental values. The calculated radial distribution functions provide a mechanistic understanding of the effects of polarizability on ionic aggregations in amino acid ionic liquids. The effects of alkyl chain length on the diffusion coefficient and conductivity are also discussed.« less

Polarizability effects on the structure and dynamics of ionic liquids

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

Cavalcante, Ary de Oliveira, E-mail: arycavalcante@ufam.edu.br; Departamento de Química, Universidade Federal do Amazonas, Av. Rodrigo Octávio, 6200, Coroado, Manaus, AM; Ribeiro, Mauro C. C.

2014-04-14

Polarization effects on the structure and dynamics of ionic liquids are investigated using molecular dynamics simulations. Four different ionic liquids were simulated, formed by the anions Cl{sup −} and PF{sub 6}{sup −}, treated as single fixed charge sites, and the 1-n-alkyl-3-methylimidazolium cations (1-ethyl and 1-butyl-), which are polarizable. The partial charge fluctuation of the cations is provided by the electronegativity equalization model (EEM) and a complete parameter set for the cations electronegativity (χ) and hardness (J) is presented. Results obtained from a non-polarizable model for the cations are also reported for comparison. Relative to the fixed charged model, the equilibriummore » structure of the first solvation shell around the imidazolium cations shows that inclusion of EEM polarization forces brings cations closer to each other and that anions are preferentially distributed above and below the plane of the imidazolium ring. The polarizable model yields faster translational and reorientational dynamics than the fixed charges model in the rotational-diffusion regime. In this sense, the polarizable model dynamics is in better agreement with the experimental data.« less

PULSE: A numerical model for the simulation of snowpack solute dynamics to capture runoff ionic pulses during snowmelt

NASA Astrophysics Data System (ADS)

Costa, D.; Pomeroy, J. W.; Wheater, H. S.

2017-12-01

Early ionic pulses in spring snowmelt can cause the temporary acidification of streams and account for a significant portion of the total annual nutrient export, particularly in seasonally snow-covered areas where the frozen ground may limit runoff-soil contact and cause the rapid delivery of these ions to streams. Ionic pulses are a consequence of snow ion exclusion, a process induced by snow metamorphism where ions are segregated from the snow grains losing mass to the surface of the grains gaining mass. While numerous studies have been successful in providing quantitative evidence of this process, few mechanistic mathematical models have been proposed for diagnostic and prediction. A few early modelling attempts have been successful in capturing this process assuming transport through porous media with variable porosity, however their implementation is difficult because they require complex models of snow physics to resolve the evolution of in-snow properties and processes during snowmelt, such as heat conduction, metamorphism, melt and water flow. Furthermore, initial snowpack to snow-surface ion concentration ratios are difficult to measure but are required to initiate these models and ion exclusion processes are not represented in a physically-based transparent fashion. In this research, a standalone numerical model has been developed to capture ionic pulses in snowmelt by emulating solute leaching from snow grains during melt and its subsequent transport by the percolating meltwater. Estimating snow porosity and water content dynamics is shown to be a viable alternative to deployment of complex snow physics models for this purpose. The model was applied to four study sites located in the Arctic and in Sierra Nevada to test for different climatic and hydrological conditions. The model compares very well with observations and could capture both the timing and magnitude of early melt ionic pulses accurately. This study demonstrates how physically based approaches can provide successful simulations of the spatial and temporal fluxes of snowmelt ions, which can be used to improve the prediction of nutrient export in cold regions for the spring freshet.

PULSE: A numerical model for the simulation of snowpack solute dynamics to capture runoff ionic pulses during snowmelt

NASA Astrophysics Data System (ADS)

Clark, M. P.; Nijssen, B.; Lundquist, J. D.; Luce, C. H.; Musselman, K. N.; Wayand, N. E.; Ou, M.; Lapo, K. E.

2016-12-01

Early ionic pulses in spring snowmelt can cause the temporary acidification of streams and account for a significant portion of the total annual nutrient export, particularly in seasonally snow-covered areas where the frozen ground may limit runoff-soil contact and cause the rapid delivery of these ions to streams. Ionic pulses are a consequence of snow ion exclusion, a process induced by snow metamorphism where ions are segregated from the snow grains losing mass to the surface of the grains gaining mass. While numerous studies have been successful in providing quantitative evidence of this process, few mechanistic mathematical models have been proposed for diagnostic and prediction. A few early modelling attempts have been successful in capturing this process assuming transport through porous media with variable porosity, however their implementation is difficult because they require complex models of snow physics to resolve the evolution of in-snow properties and processes during snowmelt, such as heat conduction, metamorphism, melt and water flow. Furthermore, initial snowpack to snow-surface ion concentration ratios are difficult to measure but are required to initiate these models and ion exclusion processes are not represented in a physically-based transparent fashion. In this research, a standalone numerical model has been developed to capture ionic pulses in snowmelt by emulating solute leaching from snow grains during melt and its subsequent transport by the percolating meltwater. Estimating snow porosity and water content dynamics is shown to be a viable alternative to deployment of complex snow physics models for this purpose. The model was applied to four study sites located in the Arctic and in Sierra Nevada to test for different climatic and hydrological conditions. The model compares very well with observations and could capture both the timing and magnitude of early melt ionic pulses accurately. This study demonstrates how physically based approaches can provide successful simulations of the spatial and temporal fluxes of snowmelt ions, which can be used to improve the prediction of nutrient export in cold regions for the spring freshet.

Linear finite-difference bond graph model of an ionic polymer actuator

NASA Astrophysics Data System (ADS)

Bentefrit, M.; Grondel, S.; Soyer, C.; Fannir, A.; Cattan, E.; Madden, J. D.; Nguyen, T. M. G.; Plesse, C.; Vidal, F.

2017-09-01

With the recent growing interest for soft actuation, many new types of ionic polymers working in air have been developed. Due to the interrelated mechanical, electrical, and chemical properties which greatly influence the characteristics of such actuators, their behavior is complex and difficult to understand, predict and optimize. In light of this challenge, an original linear multiphysics finite difference bond graph model was derived to characterize this ionic actuation. This finite difference scheme was divided into two coupled subparts, each related to a specific physical, electrochemical or mechanical domain, and then converted into a bond graph model as this language is particularly suited for systems from multiple energy domains. Simulations were then conducted and a good agreement with the experimental results was obtained. Furthermore, an analysis of the power efficiency of such actuators as a function of space and time was proposed and allowed to evaluate their performance.

Thermodynamics of interaction of ionic liquids with lipid monolayer.

PubMed

Bhattacharya, G; Mitra, S; Mandal, P; Dutta, S; Giri, R P; Ghosh, S K

2018-06-01

Understanding the interaction of ionic liquids with cellular membrane becomes utterly important to comprehend the activities of these liquids in living organisms. Lipid monolayer formed at the air-water interface is employed as a model system to follow this interaction by investigating important thermodynamic parameters. The penetration kinetics of the imidazolium-based ionic liquid 1-decyl-3-methylimidazolium tetrafluoroborate ([DMIM][BF4]) into the zwitterionic 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) lipid layer is found to follow the Boltzmann-like equation that reveals the characteristic time constant which is observed to be the function of initial surface pressure. The enthalpy and entropy calculated from temperature-dependent pressure-area isotherms of the monolayer show that the added ionic liquids bring about a disordering effect in the lipid film. The change in Gibbs free energy indicates that an ionic liquid with longer chain has a far greater disordering effect compared to an ionic liquid with shorter chain. The differential scanning calorimetric measurement on a multilamellar vesicle system shows the main phase transition temperature to shift to a lower value, which, again, indicates the disordering effect of the ionic liquid on lipid membrane. All these studies fundamentally point out that, when ionic liquids interact with lipid molecules, the self-assembled structure of a cellular membrane gets perturbed, which may be the mechanism of these molecules having adverse effects on living organisms.

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.

Response surface optimization of pH and ionic strength for emulsion characteristics of egg yolk.

PubMed

Kurt, S; Zorba, O

2009-11-01

Effects of pH (3.5, 4.5, 6.0, 7.5, and 8.5) and ionic strength (0.05, 0.15, 0.30, 0.45, and 0.55 M NaCl) on emulsion capacity, emulsion stability (ES), apparent yield stress of emulsion (AYS), and emulsion density (ED) of egg yolk were studied by using a model system. Ionic strength and pH had significant (P < 0.01) effects on the emulsion characteristics of egg yolk. Their interaction effects also have been found significant on ES, AYS, and ED. Predicted solutions of ES, emulsion capacity, and ED were minimum. The critical point of ES was determined to be at pH 6.08 and an ionic strength of 0.49 (M NaCl). Predicted solution for AYS was a maximum, which was determined to be at pH 6.04 and an ionic strength of 0.29 (M NaCl). Optimum values of pH and ionic strenght were 4.61 to 7.43 and 0.10 to 0.47, respectively.

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

NASA Astrophysics Data System (ADS)

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

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

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.

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

A novel hydroxyapatite film coated with ionic silver via inositol hexaphosphate chelation prevents implant-associated infection

NASA Astrophysics Data System (ADS)

Funao, Haruki; Nagai, Shigenori; Sasaki, Aya; Hoshikawa, Tomoyuki; Tsuji, Takashi; Okada, Yasunori; Koyasu, Shigeo; Toyama, Yoshiaki; Nakamura, Masaya; Aizawa, Mamoru; Matsumoto, Morio; Ishii, Ken

2016-03-01

Various silver-coated implants have been developed to prevent implant-associated infections, and have shown dramatic effects in vitro. However, the in vivo results have been inconsistent. Recent in vitro studies showed that silver exerts antibacterial activity by mediating the generation of reactive oxygen species in the presence of oxygen. To maintain its antibacterial activity in vivo, the silver should remain in an ionic state and be stably bound to the implant surface. Here, we developed a novel bacteria-resistant hydroxyapatite film in which ionic silver is immobilized via inositol hexaphosphate chelation using a low-heat immersion process. This bacteria-resistant coating demonstrated significant antibacterial activity both in vitro and in vivo. In a murine bioluminescent osteomyelitis model, no bacteria were detectable 21 days after inoculation with S. aureus and placement of this implant. Serum interleukin-6 was elevated in the acute phase in this model, but it was significantly lower in the ionic-silver group than the control group on day 2. Serum C-reactive protein remained significantly higher in the control group than the ionic-silver group on day 14. Because this coating is produced by a low-heat immersion process, it can be applied to complex structures of various materials, to provide significant protection against implant-associated infections.

Self-consistent field theory of polymer-ionic molecule complexation.

PubMed

Nakamura, Issei; Shi, An-Chang

2010-05-21

A self-consistent field theory is developed for polymers that are capable of binding small ionic molecules (adsorbates). The polymer-ionic molecule association is described by Ising-like binding variables, C(i) ((a))(kDelta)(=0 or 1), whose average determines the number of adsorbed molecules, n(BI). Polymer gelation can occur through polymer-ionic molecule complexation in our model. For polymer-polymer cross-links through the ionic molecules, three types of solutions for n(BI) are obtained, depending on the equilibrium constant of single-ion binding. Spinodal lines calculated from the mean-field free energy exhibit closed-loop regions where the homogeneous phase becomes unstable. This phase instability is driven by the excluded-volume interaction due to the single occupancy of ion-binding sites on the polymers. Moreover, sol-gel transitions are examined using a critical degree of conversion. A gel phase is induced when the concentration of adsorbates is increased. At a higher concentration of the adsorbates, however, a re-entrance from a gel phase into a sol phase arises from the correlation between unoccupied and occupied ion-binding sites. The theory is applied to a model system, poly(vinyl alcohol) and borate ion in aqueous solution with sodium chloride. Good agreement between theory and experiment is obtained.

A Rayleighian approach for modeling kinetics of ionic transport in polymeric media

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

Kumar, Rajeev

2017-02-14

Here, we report a theoretical approach for analyzing impedance of ionic liquids (ILs) and charged polymers such as polymerized ionic liquids (PolyILs) within linear response. The approach is based on the Rayleigh dissipation function formalism, which provides a computational framework for a systematic study of various factors, including polymer dynamics, in affecting the impedance. We present an analytical expression for the impedance within linear response by constructing a one-dimensional model for ionic transport in ILs/PolyILs. This expression is used to extract mutual diffusion constants, the length scale of mutual diffusion, and thicknesses of a low-dielectric layer on the electrodes frommore » the broadband dielectric spectroscopy (BDS) measurements done for an IL and three PolyILs. Also, static dielectric permittivities of the IL and the PolyILs are determined. The extracted mutual diffusion constants are compared with the self diffusion constants of ions measured using pulse field gradient (PFG) fluorine nuclear magnetic resonance (NMR). For the first time, excellent agreements between the diffusivities extracted from the Electrode Polarization spectra (EPS) of IL/PolyILs and those measured using the PFG-NMR are found, which allows the use of the EPS and the PFG-NMR techniques in a complimentary manner for a general understanding of the ionic transport.« less

Interaction between 2',4-dihydroxychalcone and the N, f, e conformers of bovine serum albumin: influence of temperature and ionic strength.

PubMed

Curvale, Rolando A; Debattista, Nora B; Pappano, Nora B

2012-04-01

UV-Vis spectroscopy was used to study the interaction between the 2',4- dihydroxychalcone, flavonoid which is known to have anti-tumor activity in vitro, and others biological properties, and the N, F and E conformers of bovine serum albumin at different ionic strengths and temperatures. The Klotz model was found to be adequate to determine the constants and number of binding sites. The reaction was found to be exothermic and spontaneous. The number of binding sites decreases and the reaction is more exergonic along with the increase in ionic strength and the conformational change of N to E. The reactions were necessarily hydrophobic and followed by a process of ionic character.

A molecular model of proteoglycan-associated electrostatic forces in cartilage mechanics.

PubMed

Buschmann, M D; Grodzinsky, A J

1995-05-01

Measured values of the swelling pressure of charged proteoglycans (PG) in solution (Williams RPW, and Comper WD; Biophysical Chemistry 36:223, 1990) and the ionic strength dependence of the equilibrium modulus of PG-rich articular cartilage (Eisenberg SR, and Grodzinsky AJ; J Orthop Res 3: 148, 1985) are compared to the predictions of two models. Each model is a representation of electrostatic forces arising from charge present on spatially fixed macromolecules and spatially mobile micro-ions. The first is a macroscopic continuum model based on Donnan equilibrium that includes no molecular-level structure and assumes that the electrical potential is spatially invariant within the polyelectrolyte medium (i.e. zero electric field). The second model is based on a microstructural, molecular-level solution of the Poisson-Boltzmann (PB) equation within a unit cell containing a charged glycosaminoglycan (GAG) molecule and its surrounding atmosphere of mobile ions. This latter approach accounts for the space-varying electrical potential and electrical field between the GAG constituents of the PG. In computations involving no adjustable parameters, the PB-cell model agrees with the measured pressure of PG solutions to within experimental error (10%), whereas the ideal Donnan model overestimates the pressure by up to 3-fold. In computations involving one adjustable parameter for each model, the PB-cell model predicts the ionic strength dependence of the equilibrium modulus of articular cartilage. Near physiological ionic strength, the Donnan model overpredicts the modulus data by 2-fold, but the two models coincide for low ionic strengths (C0 < 0.025M) where the spatially invariant Donnan potential is a closer approximation to the PB potential distribution. The PB-cell model result indicates that electrostatic forces between adjacent GAGs predominate in determining the swelling pressure of PG in the concentration range found in articular cartilage (20-80 mg/ml). The PB-cell model is also consistent with data (Eisenberg and Grodzinsky, 1985, Lai WM, Hou JS, and Mow VC; J Biomech Eng 113: 245, 1991) showing that these electrostatic forces account for approximately 1/2 (290kPa) the equilibrium modulus of cartilage at physiological ionic strength while absolute swelling pressures may be as low as approximately 25-100kPa. This important property of electrostatic repulsion between GAGs that are highly charged but spaced a few Debye lengths apart allows cartilage to resist compression (high modulus) without generating excessive intratissue swelling pressures.

Density-functional theory study of ionic inhomogeneity in metal clusters using SC-ISJM

NASA Astrophysics Data System (ADS)

Payami, Mahmoud; Mahmoodi, Tahereh

2017-12-01

In this work we have applied the recently formulated self-compressed inhomogeneous stabilized jellium model [51] to describe the equilibrium electronic and geometric properties of atomic-closed-shell simple metal clusters of AlN (N = 13, 19, 43, 55, 79, 87, 135, 141), NaN, and CsN (N = 9, 15, 27, 51, 59, 65, 89, 113). To validate the results, we have also performed first-principles pseudo-potential calculations and used them as our reference. In the model, we have considered two regions consisting of ;surface; and ;inner; ones, the border separating them being sharp. This generalization makes possible to decouple the relaxations of different parts of the system. The results show that the present model correctly predicts the size reductions seen in most of the clusters. It also predicts increase in size of some clusters, as observed from first-principles results. Moreover, the changes in inter-layer distances, being as contractions or expansions, are in good agreement with the atomic simulation results. For a more realistic description of the properties, it is possible to improve the method of choosing the surface thicknesses or generalize the model to include more regions than just two.

Development of multilayer conducting polymer actuator for power application

NASA Astrophysics Data System (ADS)

Ikushima, Kimiya; Kudoh, Yuji; Hiraoka, Maki; Yokoyama, Kazuo; Nagamitsu, Sachio

2009-03-01

In late years many kinds of home-use robot have been developed to assist elderly care and housework. Most of these robots are designed with conventional electromagnetic motors. For safety it is desirable to replace these electromagnetic motors with artificial muscle. However, an actuator for such a robot is required to have simple structure, low driving voltage, high stress generation, high durability, and operability in the air. No polymer actuator satisfying all these requirements has been realized yet. To meet these we took following two approaches focusing on conducting polymer actuators which can output high power in the air. (Approach 1) We have newly developed an actuator by multiply laminating ionic liquid infiltrated separators and polypyrrole films. Compared with conventional actuator that is driven in a bath of ionic liquid, the new actuator can greatly increase generated stress since the total sectional area is tremendously small. In our experiment, the new actuator consists of minimum unit with thickness of 128um and has work/weight ratio of 0.92J/kg by laminating 9 units in 0.5Hz driving condition. In addition, the driving experiment has shown a stable driving characteristic even for 10,000 cycles durability test. Furthermore, from our design consideration, it has been found that the work/weight ratio can be improved up to 8J/kg (1/8 of mammalian muscle of 64J/kg) in 0.1Hz by reducing the thickness of each unit to 30um. (Approach 2) In order to realize a simplified actuator structure in the air without sealing, we propose the use of ionic liquid gel. The actuation characteristic of suggested multilayered actuator using ionic liquid gel is simulated by computer. The result shows that performance degradation due to the use of ionic liquid gel is negligible small when ionic liquid gel with the elasticity of 3kPa or less is used. From above two results it is concluded that the proposed multilayerd actuator is promising for the future robotic applications because it has advantages of high work/weight ratio and in-the-air operation, in addition to advantages of conventional polymer actuators.

Method for Reduction of Silver Biocide Plating on Metal Surfaces

NASA Technical Reports Server (NTRS)

Steele, John; Nalette, Timothy; Beringer, Durwood

2013-01-01

Silver ions in aqueous solutions (0.05 to 1 ppm) are used for microbial control in water systems. The silver ions remain in solution when stored in plastic containers, but the concentration rapidly decreases to non-biocidal levels when stored in metal containers. The silver deposits onto the surface and is reduced to non-biocidal silver metal when it contacts less noble metal surfaces, including stainless steel, titanium, and nickel-based alloys. Five methods of treatment of contact metal surfaces to deter silver deposition and reduction are proposed: (1) High-temperature oxidation of the metal surface; (2) High-concentration silver solution pre-treatment; (3) Silver plating; (4) Teflon coat by vapor deposition (titanium only); and (5) A combination of methods (1) and (2), which proved to be the best method for the nickel-based alloy application. The mechanism associated with surface treatments (1), (2), and (5) is thought to be the development of a less active oxide layer that deters ionic silver deposition. Mechanism (3) is an attempt to develop an equilibrium ionic silver concentration via dissolution of metallic silver. Mechanism (4) provides a non-reactive barrier to deter ionic silver plating. Development testing has shown that ionic silver in aqueous solution was maintained at essentially the same level of addition (0.4 ppm) for up to 15 months with method (5) (a combination of methods (1) and (2)), before the test was discontinued for nickel-based alloys. Method (1) resulted in the maintenance of a biocidal level (approximately 0.05 ppm) for up to 10 months before that test was discontinued for nickel-based alloys. Methods (1) and (2) used separately were able to maintain ionic silver in aqueous solution at essentially the same level of addition (0.4 ppm) for up to 10 months before the test was discontinued for stainless steel alloys. Method (3) was only utilized for titanium alloys, and was successful at maintaining ionic silver in aqueous solution at essentially the same level of addition (0.4 ppm) for up to 10 months before the test was discontinued for simple flat geometries, but not for geometries that are difficult to Teflon coat.

Computational Studies of [Bmim][PF6]/n-Alcohol Interfaces with Many-Body Potentials

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

Chang, Tsun-Mei; Dang, Liem X.

2014-09-04

In this paper, we present the results from molecular-dynamics simulations of the equilibrium properties of liquid/liquid interfaces of room temperature ionic liquid [bmim][PF6] and simple alcohols (i.e., methanol, 1-butanol, and 1-hexanol) at room temperature. Polarizable potential models are employed to describe the interactions among species. Results from our simulations show stable interfaces between the ionic liquid and n-alcohols, and we found that the interfacial widths decrease from methanol to 1-butanol systems, and then increase for 1-hexanol interfaces. Angular distribution analysis reveals that the interface induces a strong orientational order of [bmim] and n-alcohol molecules near the interface, with [bmim] extendingmore » its butyl group into the alcohol phase while the alcohol has the OH group pointing into the ion liquid region, which is consistent with the recent sum-frequency-generation experiments. We found the interface to have a significant influence on the dynamics of ionic liquids and n-alcohols. The orientational autocorrelation functions illustrate that [bmim] rotate more freely near the interface than in the bulk, while the rotation of n-alcohol is hindered at the interface. Additionally, the time scale associated with the diffusion along the interfacial direction is found to be faster for [bmim] but slowed down for n-alcohols approaching the interface. We also calculate the dipole moment of n-alcohols as a function of the distance normal to the interface. We found that, even though methanol and 1-butanol have different dipole moments in bulk phase, they reach a similar value at the interface. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is a multiprogram national laboratory operated for the Department of Energy by Battelle. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.« less

Theoretical analysis of aqueous solutions of mixed strong electrolytes by a smaller-ion shell electrostatic model

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

Fraenkel, Dan, E-mail: dfraenkel@eltronresearch.com

2014-02-07

In spite of the great importance of mixed electrolytes in science and technology, no compelling theoretical explanation has been offered yet for the thermodynamic behavior of such systems, such as their deviation from ideality and the variation of their excess functions with ionic composition and concentration. Using the newly introduced Smaller-ion Shell treatment – an extension of the Debye–Hückel theory to ions of dissimilar size (hence DH–SiS) – simple analytic mathematical expressions can be derived for the mean and single-ion activity coefficients of binary electrolyte components of ternary ionic systems. Such expressions are based on modifying the parallel DH–SiS equationsmore » for pure binary ionic systems, by adding to the three ion-size parameters – a (of counterions), b{sub +} (of positive coions), and b{sub −} (of negative coions) – a fourth parameter. For the (+ + −) system, this is “b{sub ++},” the contact distance between non-coion cations. b{sub ++} is derived from fits with experiment and, like the other b’s, is constant at varying ion concentration and combination. Four case studies are presented: (1) HCl–NaCl–H{sub 2}O, (2) HCl–NH{sub 4}Cl–H{sub 2}O, (3) (0.01 M HX)–MX–H{sub 2}O with X = Cl, Br, and with M = Li, Na, K, Cs, and (4) HCl–MCl{sub n}–H{sub 2}O with n = 2, M = Sr, Ba; and n = 3, M = Al, Ce. In all cases, theory is fully consistent with experiment when using a of the measured binary electrolyte as the sole fitting parameter. DH–SiS is thus shown to explain known “mysteries” in the behavior of ternary electrolytes, including Harned rule, and to adequately predict the pH of acid solutions in which ionized salts are present at different concentrations.« less

The electrical response of turtle cones to flashes and steps of light.

PubMed

Baylor, D A; Hodgkin, A L; Lamb, T D

1974-11-01

1. The linear response of turtle cones to weak flashes or steps of light was usually well fitted by equations based on a chain of six or seven reactions with time constants varying over about a 6-fold range.2. The temperature coefficient (Q(10)) of the reciprocal of the time to peak of the response to a flash was 1.8 (15-25 degrees C), corresponding to an activation energy of 10 kcal/mole.3. Electrical measurements with one internal electrode and a balancing circuit gave the following results on red-sensitive cones of high resistance: resistance across cell surface in dark 50-170 MOmega; time constant in dark 4-6.5 msec. The effect of a bright light was to increase the resistance and time constant by 10-30%.4. If the cell time constant, resting potential and maximum hyperpolarization are known, the fraction of ionic channels blocked by light at any instant can be calculated from the hyperpolarization and its rate of change. At times less than 50 msec the shape of this relation is consistent with the idea that the concentration of a blocking molecule which varies linearly with light intensity is in equilibrium with the fraction of ionic channels blocked.5. The rising phase of the response to flashes and steps of light covering a 10(5)-fold range of intensities is well fitted by a theory in which the essential assumptions are that (i) light starts a linear chain of reactions leading to the production of a substance which blocks ionic channels in the outer segment, (ii) an equilibrium between the blocking molecules and unblocked channels is established rapidly, and (iii) the electrical properties of the cell can be represented by a simple circuit with a time constant in the dark of about 6 msec.6. Deviations from the simple theory which occur after 50 msec are attributed partly to a time-dependent desensitization mechanism and partly to a change in saturation potential resulting from a voltage-dependent change in conductance.7. The existence of several components in the relaxation of the potential to its resting level can be explained by supposing that the ;substance' which blocks light sensitive ionic channels is inactivated in a series of steps.

Influence of dissolved organic carbon content on modelling natural organic matter acid-base properties.

PubMed

Garnier, Cédric; Mounier, Stéphane; Benaïm, Jean Yves

2004-10-01

Natural organic matter (NOM) behaviour towards proton is an important parameter to understand NOM fate in the environment. Moreover, it is necessary to determine NOM acid-base properties before investigating trace metals complexation by natural organic matter. This work focuses on the possibility to determine these acid-base properties by accurate and simple titrations, even at low organic matter concentrations. So, the experiments were conducted on concentrated and diluted solutions of extracted humic and fulvic acid from Laurentian River, on concentrated and diluted model solutions of well-known simple molecules (acetic and phenolic acids), and on natural samples from the Seine river (France) which are not pre-concentrated. Titration experiments were modelled by a 6 acidic-sites discrete model, except for the model solutions. The modelling software used, called PROSECE (Programme d'Optimisation et de SpEciation Chimique dans l'Environnement), has been developed in our laboratory, is based on the mass balance equilibrium resolution. The results obtained on extracted organic matter and model solutions point out a threshold value for a confident determination of the studied organic matter acid-base properties. They also show an aberrant decreasing carboxylic/phenolic ratio with increasing sample dilution. This shift is neither due to any conformational effect, since it is also observed on model solutions, nor to ionic strength variations which is controlled during all experiments. On the other hand, it could be the result of an electrode troubleshooting occurring at basic pH values, which effect is amplified at low total concentration of acidic sites. So, in our conditions, the limit for a correct modelling of NOM acid-base properties is defined as 0.04 meq of total analysed acidic sites concentration. As for the analysed natural samples, due to their high acidic sites content, it is possible to model their behaviour despite the low organic carbon concentration.

Reliable, responsive pacemaking and pattern generation with minimal cell numbers: the crustacean cardiac ganglion.

PubMed

Cooke, Ian M

2002-04-01

Investigations of the electrophysiology of crustacean cardiac ganglia over the last half-century are reviewed for their contributions to elucidating the cellular mechanisms and interactions by which a small (as few as nine cells) neuronal network accomplishes extremely reliable, rhythmical, patterned activation of muscular activity-in this case, beating of the neurogenic heart. This ganglion is thus a model for pacemaking and central pattern generation. Favorable anatomy has permitted voltage- and space-clamp analyses of voltage-dependent ionic currents that endow each neuron with the intrinsic ability to respond with rhythmical, patterned impulse activity to nonpatterned stimulation. The crustacean soma and initial axon segment do not support impulse generation but integrate input from stretch-sensitive dendrites and electrotonic and chemically mediated synapses on axonal processes in neuropils. The soma and initial axon produce a depolarization-activated, calcium-mediated, sustained potential, the "driver potential," so-called because it drives a train of impulses at the "trigger zone" of the axon. Extreme reliability results from redundancy and the electrotonic coupling and synaptic interaction among all the neurons. Complex modulation by central nervous system inputs and by neurohormones to adjust heart pumping to physiological demands has long been demonstrated, but much remains to be learned about the cellular and molecular mechanisms of action. The continuing relevance of the crustacean cardiac ganglion as a relatively simple model for pacemaking and central pattern generation is confirmed by the rapidly widening documentation of intrinsic potentials such as plateau potentials in neurons of all major animal groups. The suite of ionic currents (a slowly inactivating calcium current and various potassium currents, with variations) observed for the crustacean cardiac ganglion have been implicated in or proven to underlie a majority of the intrinsic potentials of neurons involved in pattern generation.

The What and Where of Adding Channel Noise to the Hodgkin-Huxley Equations

PubMed Central

Goldwyn, Joshua H.; Shea-Brown, Eric

2011-01-01

Conductance-based equations for electrically active cells form one of the most widely studied mathematical frameworks in computational biology. This framework, as expressed through a set of differential equations by Hodgkin and Huxley, synthesizes the impact of ionic currents on a cell's voltage—and the highly nonlinear impact of that voltage back on the currents themselves—into the rapid push and pull of the action potential. Later studies confirmed that these cellular dynamics are orchestrated by individual ion channels, whose conformational changes regulate the conductance of each ionic current. Thus, kinetic equations familiar from physical chemistry are the natural setting for describing conductances; for small-to-moderate numbers of channels, these will predict fluctuations in conductances and stochasticity in the resulting action potentials. At first glance, the kinetic equations provide a far more complex (and higher-dimensional) description than the original Hodgkin-Huxley equations or their counterparts. This has prompted more than a decade of efforts to capture channel fluctuations with noise terms added to the equations of Hodgkin-Huxley type. Many of these approaches, while intuitively appealing, produce quantitative errors when compared to kinetic equations; others, as only very recently demonstrated, are both accurate and relatively simple. We review what works, what doesn't, and why, seeking to build a bridge to well-established results for the deterministic equations of Hodgkin-Huxley type as well as to more modern models of ion channel dynamics. As such, we hope that this review will speed emerging studies of how channel noise modulates electrophysiological dynamics and function. We supply user-friendly MATLAB simulation code of these stochastic versions of the Hodgkin-Huxley equations on the ModelDB website (accession number 138950) and http://www.amath.washington.edu/~etsb/tutorials.html. PMID:22125479

Short-time vibrational dynamics of metaphosphate glasses

NASA Astrophysics Data System (ADS)

Kalampounias, Angelos G.

2012-02-01

In this paper we present the picosecond vibrational dynamics of a series of binary metaphosphate glasses, namely Na2O-P2O5, MO-P2O5 (M=Ba, Sr, Ca, Mg) and Al2O3-3P2O5 by means of Raman spectroscopy. We studied the vibrational dephasing and vibrational frequency modulation by calculating time correlation functions of vibrational relaxation by fits in the frequency domain. The fitting method used enables one to model the real line profiles intermediate between Lorentzian and Gaussian by an analytical function, which has an analytical counterpart in the time domain. The symmetric stretching modes νs(PO2-) and νs(P-O-P) of the PO2- entity of PØ2O2- units and of P-O-P bridges in metaphosphate arrangements have been investigated by Raman spectroscopy and we used them as probes of the dynamics of these glasses. The vibrational time correlation functions of both modes studied are rather adequately interpreted within the assumption of exponential modulation function in the context of Kubo-Rothschield theory and indicate that the system experiences an intermediate dynamical regime that gets only slower with an increase in the ionic radius of the cation-modifier. We found that the vibrational correlation functions of all glasses studied comply with the Rothschild approach assuming that the environmental modulation is described by a stretched exponential decay. The evolution of the dispersion parameter α with increasing ionic radius of the cation indicates the deviation from the model simple liquid indicating the reduction of the coherence decay in the perturbation potential as a result of local short lived aggregates. The results are discussed in the framework of the current phenomenological status of the field.

The Effect of Salt on the Complex Coacervation of Vinyl Polyelectrolytes

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

Perry, Sarah; Li, Yue; Priftis, Dimitrios

2014-06-01

Complex coacervation is an electrostatically-driven phase separation phenomenon that is utilized in a wide range of everyday applications and is of great interest for the creation of self-assembled materials. Here, we utilized turbidity to characterize the effect of salt type on coacervate formation using two vinyl polyelectrolytes, poly(acrylic acid sodium salt) (pAA) and poly(allylamine hydrochloride) (pAH), as simple models for industrial and biological coacervates. We confirmed the dominant role of salt valence on the extent of coacervate formation, while demonstrating the presence of significant secondary effects, which can be described by Hofmeister-like behavior. These results revealed the importance of ion-specificmore » interactions, which are crucial for the informed design of coacervate-based materials for use in complex ionic environments, and can enable more detailed theoretical investigations on the role of subtle electrostatic and thermodynamic effects in complex coacervation.« less

Effects of ionic strength on passive and iontophoretic transport of cationic permeant across human nail.

PubMed

Smith, Kelly A; Hao, Jinsong; Li, S Kevin

2009-06-01

Transport across the human nail under hydration can be modeled as hindered transport across aqueous pore pathways. As such, nail permselectivity to charged species can be manipulated by changing the ionic strength of the system in transungual delivery to treat nail diseases. The present study investigated the effects of ionic strength upon transungual passive and iontophoretic transport. Transungual passive and anodal iontophoretic transport experiments of tetraethylammonium ion (TEA) were conducted under symmetric conditions in which the donor and receiver had the same ionic strength in vitro. Experiments under asymmetric conditions were performed to mimic the in vivo conditions. Prior to the transport studies, TEA uptake studies were performed to assess the partitioning of TEA into the nail. Permselectivity towards TEA was inversely related to ionic strength in both passive and iontophoretic transport. The permeability and transference number of TEA were higher at lower ionic strengths under the symmetric conditions due to increased partitioning of TEA into the nail. Transference numbers were smaller under the asymmetric conditions compared with their symmetric counterparts. The results demonstrate significant ionic strength effects upon the partitioning and transport of a cationic permeant in transungual transport, which may be instrumental in the development of transungual delivery systems.

Theoretical and Numerical Modeling of faceted Ionic crystalline vesicles

NASA Astrophysics Data System (ADS)

Olvera de La Cruz, Monica

2007-03-01

Icosahedral shape is found in several natural structures including large viruses, large fullerenes and cationic-anionic vesicles. Faceting into icosahedral shape can occur in large crystalline membranes via elasticity theory. Icosahedral symmetry is found in small systems of particles with short-range interactions on a sphere. Dr G. Vernizzi and I show a novel electrostatic-driven mechanism of ionic crystalline shells faceting into icosahedral shapes even for systems with a small number of particles. Icosahedral shape is possible in cationic and anionic molecules adsorbed onto spherical interfaces, such as emulsions or other immiscible liquid droplets because the large concentration of charges at the interface can lead to ionic crystals on the curved interface. Such self-organized ionic structures favors the formation of flat surfaces. We find that these ionic crystalline shells can have lower energy when faceted into icosahedra along particular directions. Indeed, the ``ionic'' buckling is driven by preferred bending directions of the planar ionic structure, along which is more likely for the icosahedral shape to develop an edge. Since only certain orientations are allowed, rotational symmetry is broken. One can hope to exploit this mechanism to generate functional materials where, for instance, proteins with specific charge groups can orient at specific directions along an icosahedral cationic-anionic vesicle.

The magic of aqueous solutions of ionic liquids: ionic liquids as a powerful class of catanionic hydrotropes†

PubMed Central

Cláudio, Ana Filipa M.; Neves, Márcia C.; Shimizu, Karina; Canongia Lopes, José N.; Freire, Mara G.; Coutinho, João A. P.

2015-01-01

Hydrotropes are compounds able to enhance the solubility of hydrophobic substances in aqueous media and therefore are widely used in the formulation of drugs, cleaning and personal care products. In this work, it is shown that ionic liquids are a new class of powerful catanionic hydrotropes where both the cation and the anion synergistically contribute to increase the solubility of biomolecules in water. The effects of the ionic liquid chemical structures, their concentration and the temperature on the solubility of two model biomolecules, vanillin and gallic acid were evaluated and compared with the performance of conventional hydrotropes. The solubility of these two biomolecules was studied in the entire composition range, from pure water to pure ionic liquids, and an increase in the solubility of up to 40-fold was observed, confirming the potential of ionic liquids to act as hydrotropes. Using dynamic light scattering, NMR and molecular dynamics simulations, it was possible to infer that the enhanced solubility of the biomolecule in the IL aqueous solutions is related to the formation of ionic-liquid–biomolecules aggregates. Finally, it was demonstrated that hydrotropy induced by ionic liquids can be used to recover solutes from aqueous media by precipitation, simply by using water as an anti-solvent. The results reported here have a significant impact on the understanding of the role of ionic liquid aqueous solutions in the extraction of value-added compounds from biomass as well as in the design of novel processes for their recovery from aqueous media. PMID:26379471

Magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction of selenium for speciation in foods and beverages.

PubMed

Wang, Xiaojun; Wu, Long; Cao, Jiaqi; Hong, Xincheng; Ye, Rui; Chen, Weiji; Yuan, Ting

2016-07-01

A novel, simple and rapid method based on magnetic effervescent tablet-assisted ionic liquid dispersive liquid-liquid microextraction (MEA-IL-DLLME) followed by graphite furnace atomic absorption spectrometry (GFAAS) determination was established for the speciation of selenium in various food and beverage samples. In the procedure, a special magnetic effervescent tablet containing CO2 sources (sodium carbonate and sodium dihydrogenphosphate), ionic liquids and Fe3O4 magnetic nanoparticles (MNPs) was used to combine extractant dispersion and magnetic recovery procedures into a single step. The parameters influencing the microextraction efficiency, such as pH of the sample solution, volume of ionic liquid, amount of MNPs, concentration of the chelating agent, salt effect and matrix effect were investigated and optimised. Under the optimised conditions, the limits of detection (LODs) for Se(IV) were 0.021 μg l(-)(1) and the linear dynamic range was 0.05-5.0 μg l(-)(1). The relative standard deviation for seven replicate measurements of 1.0 μg l(-)(1) of Se(IV) was 2.9%. The accuracy of the developed method was evaluated by analysis of the standard reference materials (GBW10016 tea, GBW10017 milk powder, GBW10043 Liaoning rice, GBW10046 Henan wheat, GBW10048 celery). The proposed method was successfully applied to food and beverage samples including black tea, milk powder, mushroom, soybean, bamboo shoots, energy drink, bottled water, carbonated drink and mineral water for the speciation of Se(IV) and Se(VI) with satisfactory relative recoveries (92.0-108.1%).

Microwave-assisted ionic liquid homogeneous liquid-liquid microextraction coupled with high performance liquid chromatography for the determination of anthraquinones in Rheum palmatum L.

PubMed

Wang, Zhibing; Hu, Jianxue; Du, Hongxia; He, Shuang; Li, Qing; Zhang, Hanqi

2016-06-05

The microwave-assisted ionic liquid homogeneous liquid-liquid microextraction (MA-IL-HLLME) coupled with high performance liquid chromatography with diode array detection (HPLC-DAD) was developed for the determination of anthraquinones, including aloe-emodin, emodin, chrysophanol and physcion in root of Rheum palmatum L. Several experimental parameters influencing the extraction efficiency, including amount of sample, type and volume of ionic liquid, volume and pH value of extraction medium, microwave power and extraction time, concentration of NH4PF6 as well as centrifugal condition were optimized. When 140μL of ionic liquid ([C8MIM][BF4]) was used as an extraction solvent, target analytes can be extracted from sample matrix in one minute with the help of microwave irradiation. The MA-IL-HLLME is simple and quick. The calibration curves exhibited good linear relationship (r>0.9984). The limits of detection and quantification were in the range of 0.015-0.026 and 0.051-0.088μgmL(-1), respectively. The spiked recovery for each analyte was in the range of 81.13-93.07% with relative standard deviations lower than 6.89%. The present method is free of volatile organic solvents, and represents lower expenditures of sample, extraction time and solvent, compared with ultrasonic and heat reflux extraction. The results indicated that the present method can be successfully applied to the determination of anthraquinones in medicinal plant. Copyright © 2016 Elsevier B.V. All rights reserved.

Quantum dots and ionic liquid-sensitized effect as an efficient and green catalyst for the sensitive determination of glucose.

PubMed

Azizi, Seyed Naser; Chaichi, Mohammad Javad; Shakeri, Parmis; Bekhradnia, Ahmadreza

2015-07-05

A novel fluorescence (FL) method using water-soluble CdSe quantum dots (QDs) is proposed for the fluorometric determination of hydrogen peroxide and glucose. Water-soluble CdSe QDs were synthesized by using thioglycolic acid as stabilizer in aqueous solutions. The nanoparticles were structurally and optically characterized by X-ray powder diffraction (XRD), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR), UV-Vis absorption spectroscopy, photoluminescence (PL) emission spectroscopy and transmission electron microscope (TEM). Ionic liquid-sensitized effect in aqueous solution was then investigated. In the presence of ionic liquid as catalyst, H2O2 was decomposed into radical that could quench the fluorescence of CdSe QDs more efficiently and rapidly. Then the oxidization of glucose by glucose oxidase was coupled with the fluorescence quenching of CdSe QDs by H2O2 producer with ionic liquid catalyst, which can be used to detect glucose. Therefore, a new FL analysis system was developed for the determination of glucose. Under the optimum conditions, there is a good linear relationship between the relative PL emission intensity and the concentration of glucose in the range of 5.0×10(-7)-1.0×10(-4) M of glucose with a correlation coefficient (R(2)) of 0.9973. The limit of detection of this system was found to be 1.0×10(-7) M. This method is not only simple, sensitive and low cost, but also reliable for practical applications. Copyright © 2015. Published by Elsevier B.V.

Empirical Modeling of ICMEs Using ACE/SWICS Ionic Distributions

NASA Astrophysics Data System (ADS)

Rivera, Y.; Landi, E.; Lepri, S. T.; Gilbert, J. A.

2017-12-01

Coronal Mass Ejections (CMEs) are some of the largest, most energetic events in the solar system releasing an immense amount of plasma and magnetic field into the Heliosphere. The Earth-bound plasma plays a large role in space weather, causing geomagnetic storms that can damage space and ground based instrumentation. As a CME is released, the plasma experiences heating, expansion and acceleration; however, the physical mechanism supplying the heating as it lifts out of the corona still remains uncertain. From previous work we know the ionic composition of solar ejecta undergoes a gradual transition to a state where ionization and recombination processes become ineffective rendering the ionic composition static along its trajectory. This property makes them a good indicator of thermal conditions in the corona, where the CME plasma likely receives most of its heating. We model this so-called `freeze-in' process in Earth-directed CMEs using an ionization code to empirically determine the electron temperature, density and bulk velocity. `Frozen-in' ions from an ensemble of independently modeled plasmas within the CME are added together to fit the full range of observational ionic abundances collected by ACE/SWICS during ICME events. The models derived using this method are used to estimate the CME energy budget to determine a heating rate used to compare with a variety of heating mechanisms that can sustain the required heating with a compatible timescale.

Estimating inelastic heavy-particle - hydrogen collision data. II. Simplified model for ionic collisions and application to barium-hydrogen ionic collisions

NASA Astrophysics Data System (ADS)

Belyaev, Andrey K.; Yakovleva, Svetlana A.

2017-12-01

Aims: A simplified model is derived for estimating rate coefficients for inelastic processes in low-energy collisions of heavy particles with hydrogen, in particular, the rate coefficients with high and moderate values. Such processes are important for non-local thermodynamic equilibrium modeling of cool stellar atmospheres. Methods: The derived method is based on the asymptotic approach for electronic structure calculations and the Landau-Zener model for nonadiabatic transition probability determination. Results: It is found that the rate coefficients are expressed via statistical probabilities and reduced rate coefficients. It is shown that the reduced rate coefficients for neutralization and ion-pair formation processes depend on single electronic bound energies of an atomic particle, while the reduced rate coefficients for excitation and de-excitation processes depend on two electronic bound energies. The reduced rate coefficients are calculated and tabulated as functions of electronic bound energies. The derived model is applied to barium-hydrogen ionic collisions. For the first time, rate coefficients are evaluated for inelastic processes in Ba+ + H and Ba2+ + H- collisions for all transitions between the states from the ground and up to and including the ionic state. Tables with calculated data are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/608/A33

Large Electro-Optic Kerr Effect in Ionic Liquid Crystals: Connecting Features of Liquid Crystals and Polyelectrolytes.

PubMed

Schlick, M Christian; Kapernaum, Nadia; Neidhardt, Manuel M; Wöhrle, Tobias; Stöckl, Yannick; Laschat, Sabine; Giesselmann, Frank

2018-06-06

The electro-optic Kerr effect in simple dipolar fluids such as nitrobenzene has been widely applied in electro-optical phase modulators and light shutters. In 2005, the discovery of the large Kerr effect in liquid-crystalline blue phases (Y. Hisakado et al., Adv. Mater. 2005, 17, 96-98.) gave new directions to the search for advanced Kerr effect materials. Even though the Kerr effect is present in all transparent and optically isotropic media, it is well known that the effect can be anomalously large in complex fluids, namely in the isotropic phase of liquid crystals or in polyelectrolyte solutions. Herein, it is shown that the Kerr effect in the isotropic phase of ionic liquid crystals combines the effective counterion polarization mechanism found in polyelectrolytes and the unique pretransitional growth of the Kerr constant found in the isotropic phase of nematic liquid crystals. Maximum Kerr constants in the order of several 10 -11  m V -2 (ten times higher than the Kerr constant of the toxic nitrobenzene and less temperature sensitive than Kerr constants of nematic liquid crystals) make ionic liquid crystals attractive as new class of functional materials in low-speed Kerr effect applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An open circuit voltage equation enabling separation of cathode and anode polarization resistances of ceria electrolyte based solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Zhang, Yanxiang; Chen, Yu; Yan, Mufu

2017-07-01

The open circuit voltage (OCV) of solid oxide fuel cells is generally overestimated by the Nernst equation and the Wagner equation, due to the polarization losses at electrodes. Considering both the electronic conduction of electrolyte and the electrode polarization losses, we express the OCV as an implicit function of the characteristic oxygen pressure of electrolyte (p* [atm], at which the electronic and ionic conductivities are the same), and the relative polarization resistance of electrodes (rc = Rc/Ri and ra = Ra/Ri, where Ri/c/a [Ωcm2] denotes the ionic resistance of electrolyte, and the polarization resistances of cathode and anode, respectively). This equation approaches to the Wagner equation when the electrodes are highly active (rc and ra → 0), and approaches to the Nernst equation when the electrolyte is a purely ionic conductor (p* → 0). For the fuel cells whose OCV is well below the prediction of the Wagner equation, for example with thin doped ceria electrolyte, it is demonstrated that the combination of OCV and impedance spectroscopy measurements allows the determination of p*, Rc and Ra. This equation can serve as a simple yet powerful tool to study the internal losses in the cell under open circuit condition.

Determination of diflubenzuron and chlorbenzuron in fruits by combining acetonitrile-based extraction with dispersive liquid-liquid microextraction followed by high-performance liquid chromatography.

PubMed

Ruan, Chunqiang; Zhao, Xiang; Liu, Chenglan

2015-09-01

In this study, a simple and low-organic-solvent-consuming method combining an acetonitrile-partitioning extraction procedure followed by "quick, easy, cheap, effective, rugged and safe" cleanup with ionic-liquid-based dispersive liquid-liquid microextraction and high-performance liquid chromatography with diode array detection was developed for the determination of diflubenzuron and chlorbenzuron in grapes and pears. Ionic-liquid-based dispersive liquid-liquid microextraction was performed using the ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate as the extractive solvent and acetonitrile extract as the dispersive solvent. The main factors influencing the efficiency of the dispersive liquid-liquid microextraction were evaluated, including the extractive solvent type and volume and the dispersive solvent volume. The validation parameters indicated the suitability of the method for routine analyses of benzoylurea insecticides in a large number of samples. The relative recoveries at three spiked levels ranged between 98.6 and 109.3% with relative standard deviations of less than 5.2%. The limit of detection was 0.005 mg/kg for the two insecticides. The proposed method was successfully used for the rapid determination of diflubenzuron and chlorbenzuron residues in real fruit samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of an ionic liquid-based ultrasonic-assisted liquid-liquid microextraction method for sensitive determination of biogenic amines: application to the analysis of octopamine, tyramine and phenethylamine in beer samples.

PubMed

Huang, Ke-Jing; Jin, Chun-Xue; Song, Shi-Lin; Wei, Cai-Yun; Liu, Yan-Ming; Li, Jing

2011-03-15

A simple and efficient method, ionic liquid-based ultrasound-assisted liquid-liquid microextraction, has been developed for the determination of three biogenic amines including octopamine (OCT), tyramine (TYR) and phenethylamine (PHE). Fluorescence probe 2,6-dimethyl-4-quinolinecarboxylic acid N-hydroxysuccinimide ester was applied for derivatization of biogenic amines and high-performance liquid chromatography coupled with fluorescence detection was used for the determination of the derivatives. The factors affecting the extraction efficiency, such as the type and volume of ionic liquid, ultrasonication time and centrifugation time have been investigated in detail. Under the optimum conditions, linearity of the method was observed in the range of 0.5-50 μgmL(-1) for OCT and TYR, and 0.025-2.5 μgmL(-1) for PHE, respectively, with correlation coefficients (γ)>0.996. The limits of detection ranged from 0.25-50 ngmL(-1) (S/N=3). The spiked recoveries of three target compounds in beer samples were in the range of 90.2-114%. As a result, this method has been successfully applied for the sensitive determination of OCT, TYR and PHE in beer samples. Copyright © 2011 Elsevier B.V. All rights reserved.

Deconstruction of Malaysian agro-wastes with inexpensive and bifunctional triethylammonium hydrogen sulfate ionic liquid

NASA Astrophysics Data System (ADS)

Zahari, S. M. Shahrul Nizan Shikh; Amin, Alia Thuraya Mohd; Halim, Nurdiyana Mohd; Rosli, Farah Amanina; Halim, Wan Ibrahim Thani Abd; Samsukamal, Nur Asyiqin; Sasithran, Bavitiraa; Ariffin, Nur'Alyaa Zainal; Azman, Hazeeq Hazwan; Hassan, Nur Hasyareeda; Othman, Zetty Shafiqa

2018-06-01

Ionic liquids (ILs) are known to be very effective at deconstructing biomass, but, they are typically 5-20 times more expensive than molecular solvents; this is a major impediment to the utilisation of ILs in biorefinery applications. In view of this, this paper is the first to report a preliminary study on the use of inexpensive and bifunctional triethylammonium hydrogen sulfate ionic liquid, [N2220][HSO4] IL, in deconstructing two Malaysian agro-wastes, oil palm empty fruit bunches (OPEFB) and coconut husk. The [N2220][HSO4] IL was synthesised via simple acid-base neutralisation route between two inexpensive precursors: sulfuric acid, H2SO4, and triethylamine, N222. The results of deconstruction of OPEFB and coconut husk under the applied conditions, IL/H2O (80/20 wt/wt) at 120 °C for 2 h, proved that the IL provided bifunctional action as: a Brønsted acid catalyst that hydrolysed chemical bonds linking carbohydrate-rich-material (cellulose and hemicellulose) and lignin fractions, and; a delignification agent that dissolved lignin, separating the biopolymer from the carbohydrate-rich-material. The outcomes of this study indicate that the deconstruction of Malaysian agro-wastes for isolating valuable biopolymers can be performed in a more economical and effective way using the [N2220][HSO4] IL.

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.

Influence of droplet size, pH and ionic strength on endotoxin-triggered ordering transitions in liquid crystalline droplets

PubMed Central

Miller, Daniel S.; Abbott, Nicholas L.

2012-01-01

We report an investigation of ordering transitions that are induced in water-dispersed, micrometer-sized droplets of a thermotropic liquid crystal (LC) by the bacterial lipopolysaccharide endotoxin. We reveal that the ordering transitions induced by endotoxin – from a bipolar state of the droplets to a radial state – are strongly dependent on the size of the LC droplets. Specifically, as the diameters of the LC droplets increase from 2 μm to above 10 μm (in phosphate buffered saline with an ionic strength of 90 mM and a pH of 7.2), we measured the percentage of droplets exhibiting a radial configuration in the presence of 100 pg/mL endotoxin to decrease from 98 ± 1 % to 3 ± 2 %. In addition, we measured a decrease in either the ionic strength or pH of the aqueous phase to reduce the percentage of droplets exhibiting a radial configuration in the presence of endotoxin. These results, when interpreted within the context of a simple thermodynamic model that incorporates the contributions of elasticity and surface anchoring to the free energies of the LC droplets, lead us to conclude that (i) the elastic constant K24 plays a central role in determining the size-dependent response of the LC droplets to endotoxin, and (ii) endotoxin-triggered ordering transitions occur only under solution conditions (pH, ionic strength) where the combined contributions of elasticity and surface anchoring to the free energies of the bipolar and radial configurations of the LC droplets are similar in magnitude. Our analysis also suggests that the presence of endotoxin perturbs the free energies of the LC droplets by ~10−17 J/droplet, which is comparable to the standard free energy of self-association of ~103 endotoxin molecules. These results, when combined with prior reports of localization of endotoxin at the center of LC droplets, are consistent with the hypothesis that self-assembly of endotoxin within micrometer-sized LC droplets provides the driving force for the ordering transitions. Overall, these results advance our understanding of ordering transitions triggered by the interactions of analytes with LC droplets and, more broadly, provide guidance to the design of LC droplet systems as the basis of stimuli-responsive soft materials. PMID:23675387

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.

Water Conditioner

NASA Technical Reports Server (NTRS)

1991-01-01

A home use water treatment incorporates technology developed to purify water aboard Space Shuttle Orbiters. The General Ionics Model IQ Bacteriostatic Water Softener softens water and inhibits bacteria growth in the filtering unit. Ionics used NASA silver ion technology as a basis for development of a silver carbon dense enough to remain on top of the water softening resin bed.

Ionic charge accumulation at microscopic interfaces in filled composites

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

Zhu Yutao; Wang Xinheng; Xie Hengkun

1996-12-31

In this paper the charge accumulation process at microscopic interfaces in insulating materials filled with inorganic fillers is analyzed by using a unit model. Dynamic equations of interfacial ionic charge accumulation are proposed by the authors. The charge accumulation and its regulations are proved by TSC test results obtained on silica filled EPDM samples.

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.