Physicochemical properties and solubility of alkyl-(2-hydroxyethyl)-dimethylammonium bromide.

PubMed

Domańska, Urszula; Bogel-Łukasik, Rafał

2005-06-23

Quaternary ammonium salts, which are precursors of ionic liquids, have been prepared from N,N-dimethylethanolamine as a substrate. The paper includes specific basic characterization of synthesized compounds via the following procedures: nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectra, water content, mass spectroscopy (MS) spectra, temperatures of decompositions, basic thermodynamic properties of pure ionic liquids (the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition), and the difference in the solute heat capacity between the liquid and solid at the melting temperature determined by differential scanning calorimetry (DSC). The (solid + liquid) phase equilibria of binary mixtures containing (quaternary ammonium salt + water, or + 1-octanol) has been measured by a dynamic method over wide range of temperatures, from 230 K to 560 K. These data were correlated by means of the UNIQUAC ASM and modified nonrandom two-liquid NRTL1 equations utilizing parameters derived from the (solid + liquid) equilibrium. The partition coefficient of ionic liquid in the 1-octanol/water binary system has been calculated from the solubility results. Experimental partition coefficients (log P) were negative at three temperatures.

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.

Expanding the range of free calcium regulation in biological solutions.

PubMed

Dweck, David; Reyes-Alfonso, Avelino; Potter, James D

2005-12-15

Many biological systems use ethylene glycol bis (beta-aminoethylether)-N,N,N',N'-tetraacetic acid (EGTA) to regulate the free calcium concentration ([Ca(2+)](free)) in the presence of physiological levels of free Mg(2+) ([Mg(2+)](free)). Frequently, it is necessary to work at [Ca(2+)](free) beyond EGTA's buffering capabilities. Therefore, we have developed methods to extend the buffering range by adding nitrilotriacetic acid (NTA) to solutions containing EGTA. This extension results from NTA having a lower K'(dCa) than EGTA. Such equilibria are solved by pCa Calculator, a computer program designed to aid in the study of Ca(2+)-dependent physiological processes while accounting for the effects of pH, temperature, and ionic strength. With multiple chelators and pH buffers from which to choose, pCa Calculator calculates the total concentration of each species required to achieve specified free concentrations of Ca(2+), ATP, and Mg(2+). The program is intuitive, user-friendly, and flexible enough to fix or vary the [Mg-ATP(2-)] and ionic strength. Moreover, it can account for increases in experimental volume from calcium addition. A comparative analysis is reported for testing solutions in the presence and absence of NTA by measuring the calcium binding affinity of fluorescent cardiac troponin C. These findings demonstrate that EGTA, when used in conjunction with NTA, improves and expands the regulation of free calcium in solution.

Metal Complexation in Xylem Fluid 1

PubMed Central

White, Michael C.; Decker, A. Morris; Chaney, Rufus L.

1981-01-01

Xylem fluid was analyzed for numerous solutes to characterize chemically the sap as a medium for forming and transporting metal complexes. The stem exudate was collected hourly for 8 hours from topped 31-day-old soybean (Glycine max L. Merr.) and 46-day-old tomato (Lycopersicon esculentum Mill.) plants grown in normal (0.5 micromolar) and Za-phytotoxic nutrient solutions. Soybean plants were grown in the normal and high-Zn solutions for 24 days; tomato plants were grown for 32 days. The exudate was analyzed for seven organic acids, 22 amino acids, eight inorganic solutes, apparent ionic strength, and pH. Significant changes in many solutes occurred over the 8-hour sampling period. These fluctuations depended on plant species, individual solute, and Zn treatment, and demonstrated that extrapolation of xylem-fluid analyses to whole-plant xylem sap is valid only for sap samples collected shortly after topping a plant. Exudate pH decreased over the 8-hour period for both species; exudate ionic strength increased for tomato and decreased for soybean. At the normal-Zn treatment (0 to 1 hour), the highest acid micromolar concentrations in soybean exudate were: asparagine, 2,583; citric, 1,706; malic, 890; and malonic, 264. Under the same conditions, the highest acid micromolar concentrations in tomato exudate were: maleic, 1,206; malic, 628; glutamine, 522; citric, 301; and asparagine, 242. Cysteine and methionine were above detection limits only in soybean exudate. Zinc phytotoxicity caused significant changes in many solutes. The analyses reported here provide a comprehensive data base for further studies on metal-complex equilibria in xylem fluid. PMID:16661664

Thermodynamic characteristics of protolytic equilibria of L-serine in aqueous solutions

NASA Astrophysics Data System (ADS)

Kochergina, L. A.; Volkov, A. V.; Khokhlova, E. A.; Krutova, O. N.

2011-05-01

The heat effects of the reaction of aqueous solution of L-serine with aqueous solutions of HNO3 and KOH were determined by calorimetry at temperatures of 288.15, 298.15, and 308.15 K, and ionic strength values of 0.2, 0.5, and 1.0 (background electrolyte, KNO3). Standard thermodynamic characteristics (Δr H o, Δr G o, Δr S o, Δ C {/p o}) of the acid-base reactions in aqueous solutions of L-serine were calculated. The effect of the concentration of background electrolyte and temperature on the heats of dissociation of amino acid was considered. The combustion energy of L-serine by bomb calorimetry in the medium of oxygen was determined. The standard combustion and formation enthalpies of crystalline L-serine were calculated. The heats of dissolution of crystalline L-serine in water and solutions of potassium hydroxide at 298.15 K were measured by direct calorimetry. The standard enthalpies of formation of L-serine and products of its dissociation in aqueous solution were calculated.

Phase equilibria and crystal chemistry of rubidium niobates and rubidium tantalates

NASA Technical Reports Server (NTRS)

Minor, D. B.; Roth, R. S.; Parker, H. S.; Brower, W. S.

1977-01-01

The phase equilibria relations and crystal chemistry of portions of the Rb2O-Nb2O5 and Rb2O-Ta2O5 systems were investigated for structures potentially useful as ionic conductors. A hexagonal tungsten bronze-type (HTB) structure was found in both systems as well as three hexagonal phases with mixed HTB-pyrochlore type structures. Ion exchange experiments between various alkali ions are described for several phases. Unit cell dimensions and X-ray diffraction powder patterns are reported.

Liquid-vapor phase equilibria and the thermodynamic properties of 2-methylpropanol- n-alkyl propanoate solutions

NASA Astrophysics Data System (ADS)

Suntsov, Yu. K.; Goryunov, V. A.; Chuikov, A. M.; Meshcheryakov, A. V.

2016-08-01

The boiling points of solutions of five binary systems are measured via ebulliometry in the pressure range of 2.05-103.3 kPa. Equilibrium vapor phase compositions, the values of the excess Gibbs energies, enthalpies, and entropies of solution of these systems are calculated. Patterns in the changes of phase equilibria and thermodynamic properties of solutions are established, depending on the compositions and temperatures of the systems. Liquid-vapor equilibria in the systems are described using the equations of Wilson and the NRTL (Non-Random Two-Liquid Model).

Solution influence on biomolecular equilibria - Nucleic acid base associations

NASA Technical Reports Server (NTRS)

Pohorille, A.; Pratt, L. R.; Burt, S. K.; Macelroy, R. D.

1984-01-01

Various attempts to construct an understanding of the influence of solution environment on biomolecular equilibria at the molecular level using computer simulation are discussed. First, the application of the formal statistical thermodynamic program for investigating biomolecular equilibria in solution is presented, addressing modeling and conceptual simplications such as perturbative methods, long-range interaction approximations, surface thermodynamics, and hydration shell. Then, Monte Carlo calculations on the associations of nucleic acid bases in both polar and nonpolar solvents such as water and carbon tetrachloride are carried out. The solvent contribution to the enthalpy of base association is positive (destabilizing) in both polar and nonpolar solvents while negative enthalpies for stacked complexes are obtained only when the solute-solute in vacuo energy is added to the total energy. The release upon association of solvent molecules from the first hydration layer around a solute to the bulk is accompanied by an increase in solute-solvent energy and decrease in solvent-solvent energy. The techniques presented are expectd to displace less molecular and more heuristic modeling of biomolecular equilibria in solution.

Solubility of alkali metal halides in the ionic liquid [C4C1im][OTf].

PubMed

Kuzmina, O; Bordes, E; Schmauck, J; Hunt, P A; Hallett, J P; Welton, T

2016-06-28

The solubilities of the metal halides LiF, LiCl, LiBr, LiI, NaF, NaCl, NaBr, NaI, KF, KCl, KBr, KI, RbCl, CsCl, CsI, were measured at temperatures ranging from 298.15 to 378.15 K in the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([C4C1im][OTf]). Li(+), Na(+) and K(+) salts with anions matching the ionic liquid have also been investigated to determine how well these cations dissolve in [C4C1im][OTf]. This study compares the influence of metal cation and halide anion on the solubility of salts within this ionic liquid. The highest solubility found was for iodide salts, and the lowest solubility for the three fluoride salts. There is no outstanding difference in the solubility of salts with matching anions in comparison to halide salts. The experimental data were correlated employing several phase equilibria models, including ideal mixtures, van't Hoff, the λh (Buchowski) equation, the modified Apelblat equation, and the non-random two-liquid model (NRTL). It was found that the van't Hoff model gave the best correlation results. On the basis of the experimental data the thermodynamic dissolution parameters (ΔH, ΔS, and ΔG) were determined for the studied systems together with computed gas phase metathesis parameters. Dissolution depends on the energy difference between enthalpies of fusion and dissolution of the solute salt. This demonstrates that overcoming the lattice energy of the solid matrix is the key to the solubility of inorganic salts in ionic liquids.

Thermodynamic characteristics of protolytic equilibria in aqueous solutions of glycyl peptides

NASA Astrophysics Data System (ADS)

Gridchin, S. N.

2016-11-01

Protolytic equilibria in aqueous solutions of glycyl-DL-serine, glycyl-DL-threonine, and glycyl-DL-valine are investigated by means of potentiometry and calorimetry. Dissociation constants and heat effects of the above dipeptides are determined. Standard thermodynamic characteristics (p K°, Δdis G°, Δdis H°, Δdis S°) of the investigated equilibria are calculated. The obtained results are compared to corresponding data on relative compounds.

Kinetics and equilibria of lysozyme precipitation and crystallization in concentrated ammonium sulfate solutions.

PubMed

Cheng, Yu-Chia; Lobo, Raul F; Sandler, Stanley I; Lenhoff, Abraham M

2006-05-05

The kinetics and thermodynamics of lysozyme precipitation in ammonium sulfate solutions at pH 4 and 8 and room temperature were studied. X-ray powder diffraction (XRD) was used to characterize the structure of lysozyme precipitates. It was found that, if sufficient time was allowed, microcrystals developed following an induction period after initial lysozyme precipitation, even up to ionic strengths of 8 m and at acidic pH, where lysozyme is refractory to crystallization in ammonium sulfate. The full set of precipitation and crystallization data allowed construction of a phase diagram of lysozyme, showing the ammonium sulfate dependence. It suggests that precipitation may reflect a frustrated metastable liquid-liquid phase separation, which would allow this process to be understood within the framework of the generic phase diagram for proteins. The results also demonstrate that XRD, more frequently used for characterizing inorganic and organic polycrystalline materials, is useful both in characterizing the presence of crystals in the dense phase and in verifying the crystal form of proteins.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands.

PubMed

El-Sherif, Ahmed A; Shehata, Mohamed R; Shoukry, Mohamed M; Barakat, Mohammad H

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO(3)) using a potentiometric technique. The order of -ΔG(0) and -ΔH(0) was found to obey Co(2+) < Ni(2+) < Cu(2+) > Zn(2+), in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K.

Thermodynamic Investigation and Mixed Ligand Complex Formation of 1,4-Bis-(3-aminopropyl)-piperazine and Biorelevant Ligands

PubMed Central

El-Sherif, Ahmed A.; Shehata, Mohamed R.; Shoukry, Mohamed M.; Barakat, Mohammad H.

2012-01-01

Thermodynamic parameters for protonation of 1,4-bis(3-aminopropyl)-piperazine (BAPP) and its metal complexation with some divalent metal ions were determined in aqueous solution at constant ionic strength (0.1 M NaNO3) using a potentiometric technique. The order of –ΔG0 and –ΔH0 was found to obey Co2+ < Ni2+ < Cu2+ > Zn2+, in accordance with the Irving-Williams order. The formation equilibria of zinc (II) complexes and the ternary complexes Zn(BAPP)L, where L = amino acid, amides, or DNA constituents), have been investigated. Ternary complexes are formed by a simultaneous mechanism. The concentration distribution of the complexes in solution was evaluated as a function of pH. Stoichiometry and stability constants for the complexes formed are reported and discussed. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameter Δlog K. PMID:23226992

Thermodynamic characteristics of the protolytic equilibria of tetramethylenediamine- N,N,N', N'-tetraacetic acid

NASA Astrophysics Data System (ADS)

Gridchin, S. N.; Nikol'skii, V. M.

2014-04-01

The stepwise dissociation constants of tetramethylenediamine- N,N,N', N'-tetraacetic acid (H4L) are determined by means of potentiometry at 298.15 K and ionic strength values of 0.1, 0.5, and 1.0 (KNO3). The heat effects of the dissociation of the betaine groups of the complexone are measured by direct calorimetry. The standard thermodynamic characteristics of the protolytic equilibria of H4L are calculated via combined use of the results from thermochemical and potentiometric studies performed under identical experimental conditions. Our results are compared with the corresponding data on relative compounds.

Hydrostatic Equilibria of Rotating Stars with Realistic Equation of State

NASA Astrophysics Data System (ADS)

Yasutake, Nobutoshi; Fujisawa, Kotaro; Okawa, Hirotada; Yamada, Shoichi

Stars rotate generally, but it is a non-trivial issue to obtain hydrostatic equilibria for rapidly rotating stars theoretically, especially for baroclinic cases, in which the pressure depends not only on the density, but also on the temperature and compositions. It is clear that the stellar structures with realistic equation of state are the baroclinic cases, but there are not so many studies for such equilibria. In this study, we propose two methods to obtain hydrostatic equilibria considering rotation and baroclinicity, namely the weak-solution method and the strong-solution method. The former method is based on the variational principle, which is also applied to the calculation of the inhomogeneous phases, known as the pasta structures, in crust of neutron stars. We found this method might break the balance equation locally, then introduce the strong-solution method. Note that our method is formulated in the mass coordinate, and it is hence appropriated for the stellar evolution calculations.

Multi-objective Optimization Strategies Using Adjoint Method and Game Theory in Aerodynamics

NASA Astrophysics Data System (ADS)

Tang, Zhili

2006-08-01

There are currently three different game strategies originated in economics: (1) Cooperative games (Pareto front), (2) Competitive games (Nash game) and (3) Hierarchical games (Stackelberg game). Each game achieves different equilibria with different performance, and their players play different roles in the games. Here, we introduced game concept into aerodynamic design, and combined it with adjoint method to solve multi-criteria aerodynamic optimization problems. The performance distinction of the equilibria of these three game strategies was investigated by numerical experiments. We computed Pareto front, Nash and Stackelberg equilibria of the same optimization problem with two conflicting and hierarchical targets under different parameterizations by using the deterministic optimization method. The numerical results show clearly that all the equilibria solutions are inferior to the Pareto front. Non-dominated Pareto front solutions are obtained, however the CPU cost to capture a set of solutions makes the Pareto front an expensive tool to the designer.

Phase Equilibria and Crystallography of Ceramic Oxides

PubMed Central

Wong-Ng, W.; Roth, R. S.; Vanderah, T. A.; McMurdie, H. F.

2001-01-01

Research in phase equilibria and crystallography has been a tradition in the Ceramics Division at National Bureau of Standards/National Institute of Standatrds and Technology (NBS/NIST) since the early thirties. In the early years, effort was concentrated in areas of Portland cement, ceramic glazes and glasses, instrument bearings, and battery materials. In the past 40 years, a large portion of the work was related to electronic materials, including ferroelectrics, piezoelectrics, ionic conductors, dielectrics, microwave dielectrics, and high-temperature superconductors. As a result of the phase equilibria studies, many new compounds have been discovered. Some of these discoveries have had a significant impact on US industry. Structure determinations of these new phases have often been carried out as a joint effort among NBS/NIST colleagues and also with outside collaborators using both single crystal and neutron and x-ray powder diffraction techniques. All phase equilibria diagrams were included in Phase Diagrams for Ceramists, which are collaborative publications between The American Ceramic Society (ACerS) and NBS/NIST. All x-ray powder diffraction patterns have been included in the Powder Diffraction File (PDF). This article gives a brief account of the history of the development of the phase equilibria and crystallographic research on ceramic oxides in the Ceramics Division. Represented systems, particularly electronic materials, are highlighted. PMID:27500068

Computer modeling of the mineralogy of the Martian surface, as modified by aqueous alteration

NASA Technical Reports Server (NTRS)

Zolensky, M. E.; Bourcier, W. L.; Gooding, J. L.

1988-01-01

Mineralogical constraints can be placed on the Martian surface by assuming chemical equilibria among the surface rocks, atmosphere and hypothesized percolating groundwater. A study was made of possible Martian surface mineralogy, as modified by the action of aqueous alteration, using the EQ3/6 computer codes. These codes calculate gas fugacities, aqueous speciation, ionic strength, pH, Eh and concentration and degree of mineral saturation for complex aqueous systems. Thus, these codes are also able to consider mineralogical solid solutions. These codes are able to predict the likely alteration phases which will occur as the result of weathering on the Martian surface. Knowledge of the stability conditions of these phases will then assist in the definition of the specifications for the sample canister of the proposed Martian sample return mission. The model and its results are discussed.

Conductivity, A Simple Method to Probe Micellar Solutions

NASA Astrophysics Data System (ADS)

Bachofer, Steven J.

1996-09-01

A conductivity experiment on the tetradecyltrimethylammonium X-benzoate surfactants and the corresponding sodium X-benzoate salts demonstrates how this physical property can be applied to the study of the complex equilibria of ionic micellar aggregates. The surfactant CMC and fractional ionization constant (alpha) values are determined from the conductivity measurements. A student class studies the surfactants, in which a number of substituted benzoate counterions are utilized, and can be introduced to Quantitative Structure-Activity Relationships (QSAR) to explain the resulting CMC values. High quality data can be recorded with ease. The data from a student class illustrate that CMC values are sensitive to the hydrophobicity of the X-benzoate anion. However, hydrophobicity is not the only important parameter to be considered. The student class can propose other important factors with some additional reading of the colloidal literature.

The Permeability of the Sodium Channel to Metal Cations in Myelinated Nerve

PubMed Central

Hille, Bertil

1972-01-01

The relative permeability of sodium channels to eight metal cations is studied in myelinated nerve fibers. Ionic currents under voltage-clamp conditions are measured in Na-free solutions containing the test ion. Measured reversal potentials and the Goldman equation are used to calculate the permeability sequence: Na+ ≈ Li+ > Tl+ > K+. The ratio P K/P Na is 1/12. The permeabilities to Rb+, Cs+, Ca++, and Mg++ are too small to measure. The permeability ratios agree with observations on the squid giant axon and show that the reversal potential E Na differs significantly from the Nernst potential for Na+ in normal axons. Opening and closing rates for sodium channels are relatively insensitive to the ionic composition of the bathing medium, implying that gating is a structural property of the channel rather than a result of the movement or accumulation of particular ions around the channel. A previously proposed pore model of the channel accommodates the permeant metal cations in a partly hydrated form. The observed sequence of permeabilities follows the order expected for binding to a high field strength anion in Eisenman's theory of ion exchange equilibria. PMID:5025743

Textbook Forum: Equilibrium Constants of Chemical Reactions Involving Condensed Phases: Pressure Dependence and Choice of Standard State.

ERIC Educational Resources Information Center

Perlmutter-Hayman, Berta

1984-01-01

Problems of equilibria in condensed phases (particularly those involving solutes in dilute solutions) are encountered by students in their laboratory work; the thermodynamics of these equilibria is neglected in many textbooks. Therefore, several aspects of this topic are explored, focusing on pressure dependence and choice of standard state. (JN)

Thermodynamic assessment of hydrothermal alkali feldspar-mica-aluminosilicate equilibria

USGS Publications Warehouse

Sverjensky, D.A.; Hemley, J.J.; d'Angelo, W. M.

1991-01-01

The thermodynamic properties of minerals retrieved from consideration of solid-solid and dehydration equilibria with calorimetric reference values, and those of aqueous species derived from studies of electrolytes, are not consistent with experimentally measured high-temperature solubilities in the systems K2O- and Na2O-Al2O3-SiO2-H2O-HCl (e.g., K-fs - Ms - Qtz - K+ - H+). This introduces major inaccuracies into the computation of ionic activity ratios and the acidities of diagenetic, metamorphic, and magmatic hydrothermal fluids buffered by alkali silicate-bearing assemblages. We report a thermodynamic analysis of revised solubility equilibria in these systems that integrates the thermodynamic properties of minerals obtained from phase equilibria studies (Berman, 1988) with the properties of aqueous species calculated from a calibrated equation of state (Shock and Helgeson, 1988). This was achieved in two separate steps. First, new values of the free energies and enthalpies of formation at 25??C and 1 bar for the alkali silicates muscovite and albite were retrieved from the experimental solubility equilibria at 300??C and Psat. Because the latter have stoichiometric reaction coefficients different from those for solid-solid and dehydration equilibria, our procedure preserves exactly the relative thermodynamic properties of the alkali-bearing silicates (Berman, 1988). Only simple arithmetic adjustments of -1,600 and -1,626 (??500) cal/mol to all the K- and Na-bearing silicates, respectively, in Berman (1988) are required. In all cases, the revised values are within ??0.2% of calorimetric values. Similar adjustments were derived for the properties of minerals from Helgeson et al. (1978). Second, new values of the dissociation constant of HCl were retrieved from the solubility equilibria at temperatures and pressures from 300-600??C and 0.5-2.0 kbars using a simple model for aqueous speciation. The results agree well with the conductance-derived dissociation constants from Franck (1956a,b) for temperatures from 300-550??C. Compared to the conductance-derived results of Frantz and Marshall (1984), our dissociation constants agree well at the highest densities, but are greater at lower densities. At the lowest density, at 600??C and 1 kbar, the discrepancy of 0.9 log units is within the overall uncertainties associated with our experimental results and those associated with deriving dissociation constants from conductance measurements in highly associated solutions (Oelkers and Helgeson, 1988). Finally, we also report an equation of state fit to the standard thermodynamic properties of the aqueous HCl molecule that is consistent with a wide array of independently determined dissociation constants of HCl and permits interpolation and extrapolation of the dissociation constant of HCl to 1000??C and 5.0 kbars. ?? 1991.

Seasonal multiphase equilibria in the atmospheres of Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.

2017-12-01

At the extremely low temperatures in Titan's upper troposphere and on Pluto's surface, the atmospheres as a whole are subject to freeze into solid solutions, not pure ices. The presence of the solid phases introduces conditions with rich phase equilibria upon seasonal changes, even if the temperature undergoes only small changes. For the first time, the profile of atmospheric methane in Titan's troposphere will be reproduced complete with the solid solutions. This means that the freezing point, i.e. the altitude where the first solid phase appears, is determined. The seasonal change will also be evaluated both at the equator and the northern polar region. For Pluto, also for the first time, the seasonal solid-vapor equilibria will be evaluated. The fate of the two solid phases, the methane-rich and carbon-monoxide-rich solid solutions, will be analyzed upon temperature and pressure changes. Such investigations are enabled by the development of a molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, which includes solid solutions in its phase-equilibria calculations. The atmospheres of Titan and Pluto are modeled as ternary gas mixtures: nitrogen-methane-ethane and nitrogen-methane-carbon monoxide, respectively. Calculations using CRYOCHEM can provide us with compositions not only in two-phase equilibria, but also that in three-phase equilibria. Densities of all phases involved will also be calculated. For Titan, density inversion between liquid and solid phases will be identified and presented. In the inversion, the density of solid phase is less than that in the liquid phase. The method and results of this work will be useful for further investigations and modeling on the atmospheres of Titan, Pluto, and other bodies with similar conditions in the Solar System and beyond.

Tautomerism, Hammett σ, and QSAR

NASA Astrophysics Data System (ADS)

Martin, Yvonne Connolly

2010-06-01

A consideration of equilibrium model-based equations suggests that tautomeric equilibria do not markedly affect observed potency if the tautomer bound represents at least 50% of the compound in solution. Tautomeric equilibria can enhance or attenuate the correlation of potency with Hammett σ. Additionally, tautomeric equilibria can lead to a correlation of potency with σ even in the absence of a correlation of binding with σ.

One-dimensional models of quasi-neutral parallel electric fields

NASA Technical Reports Server (NTRS)

Stern, D. P.

1981-01-01

Parallel electric fields can exist in the magnetic mirror geometry of auroral field lines if they conform to the quasineutral equilibrium solutions. Results on quasi-neutral equilibria and on double layer discontinuities were reviewed and the effects on such equilibria due to non-unique solutions, potential barriers and field aligned current flows using as inputs monoenergetic isotropic distribution functions were examined.

Thermodynamic assessment of the U–La–O system

DOE PAGES

McMurray, J. W.; Shin, D.; Besmann, T. M.

2014-10-03

The CALPHAD methodology was used to develop a thermodynamic assessment of the U-La-O system. The solid solution and liquid phases are described with the compound energy formalism and the partially ionic two-sublattice liquid model respectively. A density functional theory (DFT) calculation for the lattice stability of the fictive lanthanum oxide fluorite structure compound is used to determine the Gibbs energies for the La containing end-members in the CEF model for U 1-yLa yO 2+x. Experimental thermodynamic and phase equilibria data were then used in optimizations to develop representations of the phases in the system that can be extended to includemore » other actinide and fission products to develop multi-component models. The models that comprise this assessment very well reproduce experimentally determined oxygen potentials and the observed phase relations for the U-La-O system.« less

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.

Acid-base characterization of 5-hydroxypyrazine-2-carboxylic acid and the role of ionic equilibria in the optimization of some process conditions for its biocatalytic production.

PubMed

Sak-Bosnar, M; Kovar, K

2005-10-01

This paper describes the use of potentiometric titration to determine the relevant acid-base properties of 5-hydroxypyrazine-2-carboxylic acid (5OH-PYCA), an important intermediate in the production of tuberculostatics. The data obtained were used for calculation of the dissociation constants of 5OH-PYCA. It was found that 5OH-PYCA dissociates in two steps, with the corresponding dissociation constants pK (a1)=3.42 and pK (a2)=7.96, designating 5OH-PYCA as a medium weak acid (1st step). The distribution diagram of dissociated species and the buffer-strength diagram of 5OH-PYCA provide useful information about its behaviour at different pH. The ionic equilibria data obtained can be used for selection of the optimum pH for biotransformation of pyrazine-2-carboxylic acid (PYCA) and for prediction of pH changes during the biotransformation. These data can also be used for selection of the optimum pH for precipitating 5OH-PYCA in downstream processing. All computations have been optimized by mathematical modelling using Solver.

Convergence to equilibrium of renormalised solutions to nonlinear chemical reaction–diffusion systems

NASA Astrophysics Data System (ADS)

Fellner, Klemens; Tang, Bao Quoc

2018-06-01

The convergence to equilibrium for renormalised solutions to nonlinear reaction-diffusion systems is studied. The considered reaction-diffusion systems arise from chemical reaction networks with mass action kinetics and satisfy the complex balanced condition. By applying the so-called entropy method, we show that if the system does not have boundary equilibria, i.e. equilibrium states lying on the boundary of R_+^N, then any renormalised solution converges exponentially to the complex balanced equilibrium with a rate, which can be computed explicitly up to a finite-dimensional inequality. This inequality is proven via a contradiction argument and thus not explicitly. An explicit method of proof, however, is provided for a specific application modelling a reversible enzyme reaction by exploiting the specific structure of the conservation laws. Our approach is also useful to study the trend to equilibrium for systems possessing boundary equilibria. More precisely, to show the convergence to equilibrium for systems with boundary equilibria, we establish a sufficient condition in terms of a modified finite-dimensional inequality along trajectories of the system. By assuming this condition, which roughly means that the system produces too much entropy to stay close to a boundary equilibrium for infinite time, the entropy method shows exponential convergence to equilibrium for renormalised solutions to complex balanced systems with boundary equilibria.

Dynamics of Axially Symmetric Perturbed Hamiltonians in 1:1:1 Resonance

NASA Astrophysics Data System (ADS)

Carrasco, D.; Palacián, J. F.; Vidal, C.; Vidarte, J.; Yanguas, P.

2018-03-01

We study the dynamics of a family of perturbed three-degree-of-freedom Hamiltonian systems which are in 1:1:1 resonance. The perturbation consists of axially symmetric cubic and quartic arbitrary polynomials. Our analysis is performed by normalisation, reduction and KAM techniques. Firstly, the system is reduced by the axial symmetry, and then, periodic solutions and KAM 3-tori of the full system are determined from the relative equilibria. Next, the oscillator symmetry is extended by normalisation up to terms of degree 4 in rectangular coordinates; after truncation of higher orders and reduction to the orbit space, some relative equilibria are established and periodic solutions and KAM 3-tori of the original system are obtained. As a third step, the reduction in the two symmetries leads to a one-degree-of-freedom system that is completely analysed in the twice reduced space. All the relative equilibria together with the stability and parametric bifurcations are determined. Moreover, the invariant 2-tori (related to the critical points of the twice reduced space), some periodic solutions and the KAM 3-tori, all corresponding to the full system, are established. Additionally, the bifurcations of equilibria occurring in the twice reduced space are reconstructed as quasi-periodic bifurcations involving 2-tori and periodic solutions of the full system.

Thermodynamic model for polyelectrolyte hydrogels.

PubMed

Arndt, Markus C; Sadowski, Gabriele

2014-09-04

The composition and swelling behavior of hydrogels may be dramatically influenced by external stimuli. Polyelectrolyte hydrogels consisting of charged polymers are particularly well-known for a high sensitivity to the presence of ionic species. For a thermodynamic description of such systems, the polyelectrolyte Perturbed-Chain Statistical Association Fluid Theory (pePC-SAFT) equation of state was augmented and merged with an extension of the modeling of hydrogels. This combined approach allowed for two effects to be taken into account: first, charges along the polymer chain and their interaction with mobile ions of the same or opposite charge in aqueous solutions and, second, the elastic interactions of swellable networks and their effect on Helmholtz energy and pressure. Thus, predictions of the degree of counterion condensation on the polymer chains could be made both for vapor-liquid equilibria of aqueous polyelectrolyte solutions and for polyelectrolyte hydrogels in aqueous salt solutions. The influence of temperature and molecular weight thereon was predicted successfully, and the impact of the degree of neutralization and the effect of additional salts were examined in comparison to literature data. With the inclusion of the influence of the Donnan potential, our model gave good predictions of swellable polyelectrolyte hydrogel systems in salt solutions. Poly(acrylic acid) and poly(methacrylic acid) gels were studied along with their corresponding sodium salts. Their swelling behavior in aqueous NaCl and NaNO3 solutions was examined.

Computing Nash equilibria through computational intelligence methods

NASA Astrophysics Data System (ADS)

Pavlidis, N. G.; Parsopoulos, K. E.; Vrahatis, M. N.

2005-03-01

Nash equilibrium constitutes a central solution concept in game theory. The task of detecting the Nash equilibria of a finite strategic game remains a challenging problem up-to-date. This paper investigates the effectiveness of three computational intelligence techniques, namely, covariance matrix adaptation evolution strategies, particle swarm optimization, as well as, differential evolution, to compute Nash equilibria of finite strategic games, as global minima of a real-valued, nonnegative function. An issue of particular interest is to detect more than one Nash equilibria of a game. The performance of the considered computational intelligence methods on this problem is investigated using multistart and deflection.

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

PubMed

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

2015-08-01

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

Separation and Recovery of a Hemicellulose-Derived Sugar Produced from the Hydrolysis of Biomass by an Acidic Ionic Liquid.

PubMed

da Costa Lopes, Andre M; Łukasik, Rafał M

2018-03-22

Biomass processing with ionic liquids (ILs) has been one of the most topical research areas in recent years. However, separation and recovery of biomass products and ILs are currently a challenge. Recovery of produced monosaccharides from an IL postreaction solution and the possibility to reuse the IL are strongly required to guarantee the sustainability of biomass processing. The present study demonstrates a novel approach that aims at separating a biomass hemicellulose-derived product, namely, xylose, and 1-ethyl-3-methylimidazolium hydrogensulfate ([emim][HSO 4 ]). High polarity of a postreaction system composed of xylose, IL, and water is one of the major hindrances in the separation performance. A proposed solution is fine-tuning of the system polarity by the addition of moderately polar acetonitrile. To scrutinize the potential of xylose and IL separation, phase equilibria of a system constituted by [emim][HSO 4 ], water, and acetonitrile were studied. Additionally, preparative chromatography experiments with alumina as a stationary phase were performed to determine the conditions required for efficient separation of the sugar and the IL by selective adsorption of xylose on alumina in detriment of IL. The amount and treatment of the stationary phase, eluent polarity, and amount of loaded sample were also scrutinized in this study. Treatment of alumina was considered as a necessary step to achieve recovery yields of 90.8 and 98.1 wt % for the IL and xylose, respectively, as separate fractions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterizing the Nash equilibria of three-player Bayesian quantum games

NASA Astrophysics Data System (ADS)

Solmeyer, Neal; Balu, Radhakrishnan

2017-05-01

Quantum games with incomplete information can be studied within a Bayesian framework. We analyze games quantized within the EWL framework [Eisert, Wilkens, and Lewenstein, Phys Rev. Lett. 83, 3077 (1999)]. We solve for the Nash equilibria of a variety of two-player quantum games and compare the results to the solutions of the corresponding classical games. We then analyze Bayesian games where there is uncertainty about the player types in two-player conflicting interest games. The solutions to the Bayesian games are found to have a phase diagram-like structure where different equilibria exist in different parameter regions, depending both on the amount of uncertainty and the degree of entanglement. We find that in games where a Pareto-optimal solution is not a Nash equilibrium, it is possible for the quantized game to have an advantage over the classical version. In addition, we analyze the behavior of the solutions as the strategy choices approach an unrestricted operation. We find that some games have a continuum of solutions, bounded by the solutions of a simpler restricted game. A deeper understanding of Bayesian quantum game theory could lead to novel quantum applications in a multi-agent setting.

On the manifestation of coexisting nontrivial equilibria leading to potential well escapes in an inhomogeneous floating body

NASA Astrophysics Data System (ADS)

Sequeira, Dane; Wang, Xue-She; Mann, B. P.

2018-02-01

This paper examines the bifurcation and stability behavior of inhomogeneous floating bodies, specifically a rectangular prism with asymmetric mass distribution. A nonlinear model is developed to determine the stability of the upright and tilted equilibrium positions as a function of the vertical position of the center of mass within the prism. These equilibria positions are defined by an angle of rotation and a vertical position where rotational motion is restricted to a two dimensional plane. Numerical investigations are conducted using path-following continuation methods to determine equilibria solutions and evaluate stability. Bifurcation diagrams and basins of attraction that illustrate the stability of the equilibrium positions as a function of the vertical position of the center of mass within the prism are generated. These results reveal complex stability behavior with many coexisting solutions. Static experiments are conducted to validate equilibria orientations against numerical predictions with results showing good agreement. Dynamic experiments that examine potential well hopping behavior in a waveflume for various wave conditions are also conducted.

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

PubMed

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

2012-01-01

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

Morse Theory and Relative Equilibria in the Planar n-Vortex Problem

NASA Astrophysics Data System (ADS)

Roberts, Gareth E.

2018-04-01

Morse theoretical ideas are applied to the study of relative equilibria in the planar n-vortex problem. For the case of positive circulations, we prove that the Morse index of a critical point of the Hamiltonian restricted to a level surface of the angular impulse is equal to the number of pairs of real eigenvalues of the corresponding relative equilibrium periodic solution. The Morse inequalities are then used to prove the instability of some families of relative equilibria in the four-vortex problem with two pairs of equal vorticities. We also show that, for positive circulations, relative equilibria cannot accumulate on the collision set.

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

DOE PAGES

Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.

2017-05-12

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

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

Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.

To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less

Complexation equilibria and spectrophotometric determination of iron(III) with 1-amino-4-hydroxyanthraquinone.

PubMed

Abu-Bakr, M S; Sedaira, H; Hashem, E Y

1994-10-01

The complex equilibria of iron(III) with 1-amino-4-hydroxyanthraquinone (AMHA) were studied spectrophotometrically in 40% (v/v) ethanol and an ionic strength of 0.1M (NaClO(4)). The complexation reactions were demonstrated and characterized using graphical logarithmic analysis of the absorbance-pH graphs. A simple, rapid, selective and sensitive method for the spectrophotometric determination of trace amounts of Fe(III) is developed based on the formation of Fe(AMHA) complex at pH 2.5 (lambda(max) = 640 nm, epsilon approximately = 2.1 x 10(4) L. mol(-1) . cm(-1)) in the presence of a large number of foreign ions. Interferences caused by palladium(II) was masked by the addition of cyanide ions. The method has been applied to the determination of iron in some synthetic samples and polymetallic iron ores.

Stability of Inhomogeneous Equilibria of Hamiltonian Continuous Media Field Theories

NASA Astrophysics Data System (ADS)

Hagstrom, George

2013-10-01

There are a wide variety of 1 + 1 Hamiltonian continuous media field theories that exhibit phase space pattern formation. In plasma physics, the most famous of these is the Vlasov-Poisson equation, but other examples include the incompressible Euler equation in two-dimensions and the Hamiltonian Mean Field (or XY) model. One of the characteristic phenomenon that occurs in systems described by these equations is the formation of cat's eye patterns in phase space as a result of the nonlinear saturation of instabilities. Corresponding to each of these cat's eyes is a spatially inhomogeneous equilibrium solution of the underlying model, in plasma physics these are called BGK modes, but analogous solutions exist in all of the above systems. Here we analyze the stability of inhomogeneous equilibria in the Hamiltonian Mean Field model and in the Single Wave model, which is an equation that was derived to provide a model of the formation of electron holes in plasmas. We use action angle variables and the properties of elliptic functions to analyze the resulting dispersion relation construct linearly stable inhomogeneous equilibria for in the limit of small numbers of particles and study the behavior of solutions near these equilibria. Work supported by USDOE grant no. DE-FG02-ER53223.

Quasi-simultaneous Measurements of Ionic Currents by Vibrating Probe and pH Distribution by Ion-selective Microelectrode

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

Isaacs, H.S.; Lamaka, S.V.; Taryba, M.

2011-01-01

This work reports a new methodology to measure quasi-simultaneously the local electric fields and the distribution of specific ions in a solution via selective microelectrodes. The field produced by the net electric current was detected using the scanning vibrating electrode technique (SVET) with quasi-simultaneous measurements of pH with an ion-selective microelectrode (pH-SME). The measurements were performed in a validation cell providing a 48 ?m diameter Pt wire cross section as a source of electric current. A time lag between acquiring each current density and pH data-point was 1.5 s due to the response time of pH-SME. The quasi-simultaneous SVET-pH measurementsmore » that correlate electrochemical oxidation-reduction processes with acid-base chemical equilibria are reported for the first time. No cross-talk between the vibrating microelectrode and the ion-selective microelectrode could be detected under given experimental conditions.« less

Generalization of Solovev’s approach to finding equilibrium solutions for axisymmetric plasmas with flow

NASA Astrophysics Data System (ADS)

M, S. CHU; Yemin, HU; Wenfeng, GUO

2018-03-01

Solovev’s approach of finding equilibrium solutions was found to be extremely useful for generating a library of linear-superposable equilibria for the purpose of shaping studies. This set of solutions was subsequently expanded to include the vacuum solutions of Zheng, Wootton and Solano, resulting in a set of functions {SOLOVEV_ZWS} that were usually used for all toroidally symmetric plasmas, commonly recognized as being able to accommodate any desired plasma shapes (complete-shaping capability). The possibility of extending the Solovev approach to toroidal equilibria with a general plasma flow is examined theoretically. We found that the only meaningful extension is to plasmas with a pure toroidal rotation and with a constant Mach number. We also show that the simplification ansatz made to the current profiles, which was the basis of the Solovev approach, should be applied more systematically to include an internal boundary condition at the magnetic axis; resulting in a modified and more useful set {SOLOVEV_ZWSm}. Explicit expressions of functions in this set are given for equilibria with a quasi-constant current density profile, with a toroidal flow at a constant Mach number and with specific heat capacity 1. The properties of {SOLOVEV_ZWSm} are studied analytically. Numerical examples of achievable equilibria are demonstrated. Although the shaping capability of the set {SOLOVE_ZWSm} is quite extensive, it nevertheless still does not have complete shaping capability, particularly for plasmas with negative curvature points on the plasma boundary such as the doublets or indented bean shaped tokamaks.

Osmotic regulation of gene action.

PubMed

Douzou, P

1994-03-01

Most reactions involved in gene translation systems are ionic-dependent and may be explained in electrostatic terms. However, a number of observations of equilibria and rate processes making up the overall reactions clearly indicate that there is still an enormous gap between the rough picture of the mechanism of ionic regulation and the detailed behavior of reactions at the molecular level that hold the key to specific mechanisms. The present paper deals with possible osmotic contributions arising from the gel state of gene systems that are complementary to, and interdependent of, electrostatic contributions. This treatment, although still oversimplified, explains many previous observations by relating them to a general osmotic mechanism and suggests experimental approaches to studying the mechanisms of gene regulation in organelle-free and intact systems.

Jump conditions in transonic equilibria

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

Guazzotto, L.; Betti, R.; Jardin, S. C.

2013-04-15

In the present paper, the numerical calculation of transonic equilibria, first introduced with the FLOW code in Guazzotto et al.[Phys. Plasmas 11, 604 (2004)], is critically reviewed. In particular, the necessity and effect of imposing explicit jump conditions at the transonic discontinuity are investigated. It is found that 'standard' (low-{beta}, large aspect ratio) transonic equilibria satisfy the correct jump condition with very good approximation even if the jump condition is not explicitly imposed. On the other hand, it is also found that high-{beta}, low aspect ratio equilibria require the correct jump condition to be explicitly imposed. Various numerical approaches aremore » described to modify FLOW to include the jump condition. It is proved that the new methods converge to the correct solution even in extreme cases of very large {beta}, while they agree with the results obtained with the old implementation of FLOW in lower-{beta} equilibria.« less

Magnetospheric Reconnection in Modified Current-Sheet Equilibria

NASA Astrophysics Data System (ADS)

Newman, D. L.; Goldman, M. V.; Lapenta, G.; Markidis, S.

2012-10-01

Particle simulations of magnetic reconnection in Earth's magnetosphere are frequently initialized with a current-carrying Harris equilibrium superposed on a current-free uniform background plasma. The Harris equilibrium satisfies local charge neutrality, but requires that the sheet current be dominated by the hotter species -- often the ions in Earth's magnetosphere. This constraint is not necessarily consistent with observations. A modified kinetic equilibrium that relaxes this constraint on the currents was proposed by Yamada et al. [Phys. Plasmas., 7, 1781 (2000)] with no background population. These modified equilibria were characterized by an asymptotic converging or diverging electrostatic field normal to the current sheet. By reintroducing the background plasma, we have developed new families of equilibria where the asymptotic fields are suppressed by Debye shielding. Because the electrostatic potential profiles of these new equilibria contain wells and/or barriers capable of spatially isolating different populations of electrons and/or ions, these solutions can be further generalized to include classes of asymmetric kinetic equilibria. Examples of both symmetric and asymmetric equilibria will be presented. The dynamical evolution of these equilibria, when perturbed, will be further explored by means of implicit 2D PIC reconnection simulations, including comparisons with simulations employing standard Harris-equilibrium initializations.

Experimental investigation of the phase equilibria in the carbon dioxide-propane-3 M MDEA system

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

Jou, F.Y.; Mather, A.E.; Otto, F.D.

1995-07-01

The treating of liquefied petroleum gas (LPG) to remove carbon dioxide and hydrogen sulfide using aqueous alkanolamine solutions is an important aspect of gas processing. One of the amines used in the natural gas industry is methyldiethanolamine (MDEA). Measurements of the phase equilibria in the carbon dioxide-propane-3 M MDEA system have been made at 25 and 40 C at pressures up to 15.5 MPa. Vapor-liquid, liquid-liquid, and vapor-liquid-liquid equilibria were determined. The vapor-liquid equilibrium data were compared with the model of Deshmukh and Mather.

Multiple Equilibria and Endogenous Cycles in a Non-Linear Harrodian Growth Model

NASA Astrophysics Data System (ADS)

Commendatore, Pasquale; Michetti, Elisabetta; Pinto, Antonio

The standard result of Harrod's growth model is that, because investors react more strongly than savers to a change in income, the long run equilibrium of the economy is unstable. We re-interpret the Harrodian instability puzzle as a local instability problem and integrate his model with a nonlinear investment function. Multiple equilibria and different types of complex behaviour emerge. Moreover, even in the presence of locally unstable equilibria, for a large set of initial conditions the time path of the economy is not diverging, providing a solution to the instability puzzle.

a Theoretical Study of Coherent Structures in Nonneutral Plasma Columns

NASA Astrophysics Data System (ADS)

Lund, Steven M.

A ubiquitous feature of experimental and computer simulation studies of magnetically confined pure electron plasmas in cylindrical confinement devices is the formation of nonaxisymmetric (partial/partial theta ne 0) rotating equilibria. In this dissertation, nonaxisymmetric rotating equilibria are investigated theoretically for strongly magnetized, low-density (omega_sp{pe} {2}/omega_sp{ce}{2 } << 1) pure electron plasmas confined in a two-dimensional cylindrical geometry. These dynamic equilibria are also called rotating coherent structures, and are stationary (time-independent) in a frame of reference rotating with angular velocity omega_ {r} = const. about the cylinder axis (r = 0). Radial confinement of the pure electron plasma is provided by a uniform axial magnetic field B_0 {bf e}_{z}, and a grounded, perfectly conducting, cylindrical wall is located at radius r = r_{w}. The analysis is based on a nonrelativistic, guiding-center model in the cold-fluid limit (the continuity and Poisson equations) that treats the electrons as a massless fluid (m_{e} to 0) with E times B flow velocity V _{e} = -(c/B_0)nablaphi times {bf e}_{z}. Within this model, general rotating equilibria with electron density (n_{e} equiv n_{R}(r,theta-omega _{r}t) and electrostatic potential phi equiv phi_{R }(r,theta-omega_{r}t) have the property that the electron density is functionally related to the streamfunction psi _{R} = -ephi_{R} + omega_{r}(eB_0/2c)r^2 by n_{R} = n_{R }(psi_{R}). The streamfunction psi_{R} satisfies the nonlinear equilibrium equation nabla ^2psi_{R} = -4pi e^2n _{R}(psi_{R}) + 2omega_{r}eB_0/c with psi_{R} = omega _{r}(eB_0/2c)r_sp{w }{2} equiv psi_{w } = const. on the cylindrical wall at r = r_{w}. A general methodology for the solution of this equilibrium system is presented and several properties of rotating equilibria are analyzed. Following this analysis, two classes of nonaxisymmetric equilibria are investigated. These two classes of equilibria can have large amplitude (strongly nonaxisymmetric). First, a class of vortex-like rotating equilibria is analyzed that is characterized by a structured density profile that fills a confinement geometry with an inner conducting cylinder at radius r = r_{I} < r_ {w}. The streamfunction describing these vortex-like equilibria is derived exactly and analyzed in several relevant limits. Next, a physically motivated class of rotating equilibria with "waterbag" (step-function) density profiles and free plasma-vacuum interfaces is investigated. An integral equation formulation of the nonlinear equilibrium equation that describes general waterbag equilibria is developed. Then a numerical method that can be used to construct diverse varieties of solutions for highly nonlinear waterbag equilibria is formulated. This method is employed to examine two classes of nonaxisymmetric equilibria that are nonlinear extrapolations of well-known small-amplitude equilibria. These two classes of rotating equilibria bear strong similarities to coherent structures observed experimentally by Driscoll and Fine (Phys. Fluid B 2, 1359 (1990)). (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253 -1690.).

Spontaneous decay of periodic magnetostatic equilibria

DOE PAGES

East, William E.; Zrake, Jonathan; Yuan, Yajie; ...

2015-08-28

In order to understand the conditions which lead a highly magnetized, relativistic plasma to become unstable, and in such cases how the plasma evolves, we study a prototypical class of magnetostatic equilibria where the magnetic field satisfies ∇ x B = αB , where \\alpha is spatially uniform, on a periodic domain. Using numerical solutions we show that generic examples of such equilibria are unstable to ideal modes (including incompressible ones) which are marked by exponential growth in the linear phase. We characterize the unstable mode, showing how it can be understood in terms of merging magnetic and current structures,more » and explicitly demonstrate its instability using the energy principle. Following the nonlinear evolution of these solutions, we find that they rapidly develop regions with relativistic velocities and electric fields of comparable magnitude to the magnetic field, liberating magnetic energy on dynamical timescales and eventually settling into a configuration with the largest allowable wavelength. Furthermore, these properties make such solutions a promising setting for exploring the mechanisms behind extreme cosmic sources of gamma rays.« less

High-beta analytic equilibria in circular, elliptical, and D-shaped large aspect ratio axisymmetric configurations with poloidal and toroidal flows

NASA Astrophysics Data System (ADS)

López, O. E.; Guazzotto, L.

2017-03-01

The Grad-Shafranov-Bernoulli system of equations is a single fluid magnetohydrodynamical description of axisymmetric equilibria with mass flows. Using a variational perturbative approach [E. Hameiri, Phys. Plasmas 20, 024504 (2013)], analytic approximations for high-beta equilibria in circular, elliptical, and D-shaped cross sections in the high aspect ratio approximation are found, which include finite toroidal and poloidal flows. Assuming a polynomial dependence of the free functions on the poloidal flux, the equilibrium problem is reduced to an inhomogeneous Helmholtz partial differential equation (PDE) subject to homogeneous Dirichlet conditions. An application of the Green's function method leads to a closed form for the circular solution and to a series solution in terms of Mathieu functions for the elliptical case, which is valid for arbitrary elongations. To extend the elliptical solution to a D-shaped domain, a boundary perturbation in terms of the triangularity is used. A comparison with the code FLOW [L. Guazzotto et al., Phys. Plasmas 11(2), 604-614 (2004)] is presented for relevant scenarios.

On the critical temperature, normal boiling point, and vapor pressure of ionic liquids.

PubMed

Rebelo, Luis P N; Canongia Lopes, José N; Esperança, José M S S; Filipe, Eduardo

2005-04-07

One-stage, reduced-pressure distillations at moderate temperature of 1-decyl- and 1-dodecyl-3-methylimidazolium bistriflilamide ([Ntf(2)](-)) ionic liquids (ILs) have been performed. These liquid-vapor equilibria can be understood in light of predictions for normal boiling points of ILs. The predictions are based on experimental surface tension and density data, which are used to estimate the critical points of several ILs and their corresponding normal boiling temperatures. In contrast to the situation found for relatively unstable ILs at high-temperature such as those containing [BF(4)](-) or [PF(6)](-) anions, [Ntf(2)](-)-based ILs constitute a promising class in which reliable, accurate vapor pressure measurements can in principle be performed. This property is paramount for assisting in the development and testing of accurate molecular models.

High pressure study of water-salt systems, phase equilibria, partitioning, thermodynic properties and implication for large icy worlds hydrospheres.

NASA Astrophysics Data System (ADS)

Journaux, B.; Brown, J. M.; Abramson, E.; Petitgirard, S.; Pakhomova, A.; Boffa Ballaran, T.; Collings, I.

2017-12-01

Water salt systems are predicted to be present in deep hydrosphere inside water-rich planetary bodies, following water/rock chemical interaction during early differentiation stages or later hydrothermal activity. Unfortunately the current knowledge of the thermodynamic and physical properties of aqueous salt mixtures at high pressure and high temperature is still insufficient to allow realistic modeling of the chemical or dynamic of thick planetary hydrospheres. Recent experimental results have shown that the presence of solutes, and more particularly salts, in equilibrium with high pressure ices have large effects on the stability fields, buoyancy and chemistry of all the phases present at these extreme conditions. Effects currently being investigated by our research group also covers ice melting curve depressions that depend on the salt species and incorporation of solutes inside the crystallographic lattice of high pressure ices. Both of these could have very important implication at the planetary scale, enabling thicker/deeper liquid oceans, and allowing chemical transportation through the high pressure ice layer in large icy worlds. We will present the latest results obtained in-situ using diamond anvil cell, coupled with Synchrotron X-Ray diffraction, Raman Spectroscopy and optical observations, allowing to probe the crystallographic structure, equations of state, partitioning and phase boundary of high pressure ice VI and VII in equilibrium with Na-Mg-SO4-Cl ionic species at high pressures (1-10 GPa). The difference in melting behavior depending on the dissolved salt species was characterized, suggesting differences in ionic speciation at liquidus conditions. The solidus P-T conditions were also measured as well as an increase of lattice volumes interpreted as an outcome of ionic incorporation in HP ice during incongruent crystallization. The measured phase diagrams, lattice volumes and important salt incorporations suggest a more complex picture of the structure, dynamic and evolution of icy worlds hydrospheres that could allow, among others, deep liquid reservoirs, chemical transport at the solid state through HP ices layers and/or complex dynamic due to salt exsolutions at HP ices solid-solid phase boundaries.

Speciation and Structural Properties of Hydrothermal Solutions of Sodium and Potassium Sulfate Studied by Molecular Dynamics Simulations.

PubMed

Reimer, Joachim; Vogel, Frédéric; Steele-MacInnis, Matthew

2016-05-18

Aqueous solutions of salts at elevated pressures and temperatures play a key role in geochemical processes and in applications of supercritical water in waste and biomass treatment, for which salt management is crucial for performance. A major question in predicting salt behavior in such processes is how different salts affect the phase equilibria. Herein, molecular dynamics (MD) simulations are used to investigate molecular-scale structures of solutions of sodium and/or potassium sulfate, which show contrasting macroscopic behavior. Solutions of Na-SO4 exhibit a tendency towards forming large ionic clusters with increasing temperature, whereas solutions of K-SO4 show significantly less clustering under equivalent conditions. In mixed systems (Nax K2-x SO4 ), cluster formation is dramatically reduced with decreasing Na/(K+Na) ratio; this indicates a structure-breaking role of K. MD results allow these phenomena to be related to the characteristics of electrostatic interactions between K(+) and SO4 (2-) , compared with the analogous Na(+) -SO4 (2-) interactions. The results suggest a mechanism underlying the experimentally observed increasing solubility in ternary mixtures of solutions of Na-K-SO4 . Specifically, the propensity of sodium to associate with sulfate, versus that of potassium to break up the sodium-sulfate clusters, may affect the contrasting behavior of these salts. Thus, mutual salting-in in ternary hydrothermal solutions of Na-K-SO4 reflects the opposing, but complementary, natures of Na-SO4 versus K-SO4 interactions. The results also provide clues towards the reported liquid immiscibility in this ternary system. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solution landscapes in nematic microfluidics

NASA Astrophysics Data System (ADS)

Crespo, M.; Majumdar, A.; Ramos, A. M.; Griffiths, I. M.

2017-08-01

We study the static equilibria of a simplified Leslie-Ericksen model for a unidirectional uniaxial nematic flow in a prototype microfluidic channel, as a function of the pressure gradient G and inverse anchoring strength, B. We numerically find multiple static equilibria for admissible pairs (G , B) and classify them according to their winding numbers and stability. The case G = 0 is analytically tractable and we numerically study how the solution landscape is transformed as G increases. We study the one-dimensional dynamical model, the sensitivity of the dynamic solutions to initial conditions and the rate of change of G and B. We provide a physically interesting example of how the time delay between the applications of G and B can determine the selection of the final steady state.

Electric Current Filamentation Induced by 3D Plasma Flows in the Solar Corona

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

Nickeler, Dieter H.; Karlický, Marian; Kraus, Michaela

Many magnetic structures in the solar atmosphere evolve rather slowly, so they can be assumed as (quasi-)static or (quasi-)stationary and represented via magnetohydrostatic (MHS) or stationary magnetohydrodynamic (MHD) equilibria, respectively. While exact 3D solutions would be desired, they are extremely difficult to find in stationary MHD. We construct solutions with magnetic and flow vector fields that have three components depending on all three coordinates. We show that the noncanonical transformation method produces quasi-3D solutions of stationary MHD by mapping 2D or 2.5D MHS equilibria to corresponding stationary MHD states, that is, states that display the same field-line structure as themore » original MHS equilibria. These stationary MHD states exist on magnetic flux surfaces of the original 2D MHS states. Although the flux surfaces and therefore also the equilibria have a 2D character, these stationary MHD states depend on all three coordinates and display highly complex currents. The existence of geometrically complex 3D currents within symmetric field-line structures provides the basis for efficient dissipation of the magnetic energy in the solar corona by ohmic heating. We also discuss the possibility of maintaining an important subset of nonlinear MHS states, namely force-free fields, by stationary flows. We find that force-free fields with nonlinear flows only arise under severe restrictions of the field-line geometry and of the magnetic flux density distribution.« less

Free boundary skin current MHD (magnetohydrodynamic) equilibria

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

Reusch, M.F.

1988-02-01

Function theoretic methods in the complex plane are used to develop simple parametric hodograph formulae which generate sharp boundary equilibria of arbitrary shape. The related method of Gorenflo and Merkel is discussed. A numerical technique for the construction of solutions, based on one of the methods is presented. A study is made of the bifurcations of an equilibrium of general form. 28 refs., 9 figs.

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

PubMed

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

2014-12-11

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

Membrane separation of ionic liquid solutions

DOEpatents

Campos, Daniel; Feiring, Andrew Edward; Majumdar, Sudipto; Nemser, Stuart

2015-09-01

A membrane separation process using a highly fluorinated polymer membrane that selectively permeates water of an aqueous ionic liquid solution to provide dry ionic liquid. Preferably the polymer is a polymer that includes polymerized perfluoro-2,2-dimethyl-1,3-dioxole (PDD). The process is also capable of removing small molecular compounds such as organic solvents that can be present in the solution. This membrane separation process is suitable for drying the aqueous ionic liquid byproduct from precipitating solutions of biomass dissolved in ionic liquid, and is thus instrumental to providing usable lignocellulosic products for energy consumption and other industrial uses in an environmentally benign manner.

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.

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.

Constants and thermodynamics of the acid-base equilibria of triglycine in water-ethanol solutions containing sodium perchlorate at 298 K

NASA Astrophysics Data System (ADS)

Pham Tkhi, L.; Usacheva, T. R.; Tukumova, N. V.; Koryshev, N. E.; Khrenova, T. M.; Sharnin, V. A.

2016-02-01

The acid-base equilibrium constants for glycyl-glycyl-glycine (triglycine) in water-ethanol solvents containing 0.0, 0.1, 0.3, and 0.5 mole fractions of ethanol are determined by potentiometric titration at 298.15 K and an ionic strength of 0.1, maintained with sodium perchlorate. It is established that an increase in the ethanol content in the solvent reduces the dissociation constant of the carboxyl group of triglycine (increases p K 1) and increases the dissociation constant of the amino group of triglycine (decreases p K 2). It is noted that the weakening of the acidic properties of a triglycinium ion upon an increase of the ethanol content in the solvent is due to the attenuation of the solvation shell of the zwitterionic form of triglycine, and to the increased solvation of triglycinium ions. It is concluded that the acid strength of triglycine increases along with a rise in the EtOH content in the solvent, due to the desolvation of the tripeptide zwitterion and the enhanced solvation of protons.

MHD Studies of Advanced Tokamak Equilibria

NASA Astrophysics Data System (ADS)

Strumberger, E.

2005-10-01

Advanced tokamak scenarios are often characterized by an extremely reversed profile of the safety factor, q, and a fast toroidal rotation. ASDEX Upgrade type equilibria with toroidal flow are computed up to a toroidal Mach number of Mta= 0.5, and compared with the static solution. Using these equilibria, the stabilizing effect of differential toroidal rotation on double tearing modes (DTMs) is investigated. These studies show that the computation of equilibria with flow is necessary for toroidally rotating plasma with Mta>=0.2. The use of ρtor instead of ρpol as radial coordinate enables us also to investigate the stability of equilibria with current holes. For numerical reasons, the rotational transform, = 1/q, has to be unequal zero in the CASTOR$FLOW code, but values of a>=0.001 (qa<=1000) can be easily handled. Stability studies of DTMs in the presence of a current hole are presented. Tokamak equilibria are only approximately axisymmetric. The finite number of toroidal field coils destroys the perfect axisymmetry of the device, and the coils produce a short wavelength ripple in the magnetic field strength. This toroidal field ripple plays a crucial role for the loss of high energy particles. Therefore, three-dimensional tokamak equilibria with and without current holes are computed for various plasma beta values. In addition the influence of the plasma beta on the toroidal field ripple is investigated.

Theoretical models of non-Maxwellian equilibria for one-dimensional collisionless plasmas

NASA Astrophysics Data System (ADS)

Allanson, O.; Neukirch, T.; Wilson, F.; Troscheit, S.

2016-12-01

It is ideal to use exact equilibrium solutions of the steady state Vlasov-Maxwell system to intialise collsionless simulations. However, exact equilibrium distribution functions (DFs) for a given macroscopic configuration are typically unknown, and it is common to resort to using `flow-shifted' Maxwellian DFs in their stead. These DFs may be consistent with a macrosopic system with the target number density and current density, but could well have inaccurate higher order moments. We present recent theoretical work on the `inverse problem in Vlasov-Maxwell equilibria', namely calculating an exact solution of the Vlasov equation for a specific given magnetic field. In particular, we focus on one-dimensional geometries in Cartesian (current sheets) coordinates.1. From 1D fields to Vlasov equilibria: Theory and application of Hermite Polynomials: (O. Allanson, T. Neukirch, S. Troscheit and F. Wilson, Journal of Plasma Physics, 82, 905820306 (2016) [28 pages, Open Access] )2. An exact collisionless equilibrium for the Force-Free Harris Sheet with low plasma beta: (O. Allanson, T. Neukirch, F. Wilson and S. Troscheit, Physics of Plasmas, 22, 102116 (2015) [11 pages, Open Access])3. Neutral and non-neutral collisionless plasma equilibria for twisted flux tubes: The Gold-Hoyle model in a background field (O. Allanson, F. Wilson and T. Neukirch, (2016)) (accepted, Physics of Plasmas)

Evaluation of effects of pH and ionic strength on colloidal stability of IgG solutions by PEG-induced liquid-liquid phase separation.

PubMed

Thompson, Ronald W; Latypov, Ramil F; Wang, Ying; Lomakin, Aleksey; Meyer, Julie A; Vunnum, Suresh; Benedek, George B

2016-11-14

Colloidal stability of IgG antibody solutions is important for pharmaceutical and medicinal applications. Solution pH and ionic strength are two key factors that affect the colloidal stability of protein solutions. In this work, we use a method based on the PEG-induced liquid-liquid phase separation to examine the effects of pH and ionic strength on the colloidal stability of IgG solutions. We found that at high ionic strength (≥0.25M), the colloidal stability of most of our IgGs is insensitive to pH, and at low ionic strength (≤0.15M), all IgG solutions are much more stable at pH 5 than at pH 7. In addition, the PEG-induced depletion force is less efficient in causing phase separation at pH 5 than at pH 7. In contrast to the native inter-protein interaction of IgGs, the effect of depletion force on phase separation of the antibody solutions is insensitive to ionic strength. Our results suggest that the long-range electrostatic inter-protein repulsion at low ionic strength stabilizes the IgG solutions at low pH. At high ionic strength, the short-range electrostatic interactions do not make a significant contribution to the colloidal stability for most IgGs with a few exceptions. The weaker effect of depletion force at lower pH indicates a reduction of protein concentration in the condensed phase. This work advances our basic understanding of the colloidal stability of IgG solutions and also introduces a practical approach to measuring protein colloidal stability under various solution conditions.

SOILSOLN: A Program for Teaching Equilibria Modeling of Soil Solution Composition.

ERIC Educational Resources Information Center

Wolt, Jeffrey D.

1989-01-01

Presents a computer program for use in teaching ion speciation in soil solutions. Provides information on the structure of the program, execution, and software specifications. The program estimates concentrations of ion pairs, hydrolytic species, metal-organic complexes, and free ions in solutions. (Author/RT)

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

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

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

2015-12-08

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

Efficiency reduction and pseudo-convergence in replica exchange sampling of peptide folding unfolding equilibria

NASA Astrophysics Data System (ADS)

Denschlag, Robert; Lingenheil, Martin; Tavan, Paul

2008-06-01

Replica exchange (RE) molecular dynamics (MD) simulations are frequently applied to sample the folding-unfolding equilibria of β-hairpin peptides in solution, because efficiency gains are expected from this technique. Using a three-state Markov model featuring key aspects of β-hairpin folding we show that RE simulations can be less efficient than conventional techniques. Furthermore we demonstrate that one is easily seduced to erroneously assign convergence to the RE sampling, because RE ensembles can rapidly reach long-lived stationary states. We conclude that typical REMD simulations covering a few tens of nanoseconds are by far too short for sufficient sampling of β-hairpin folding-unfolding equilibria.

Tested Demonstrations. Color, Solubility, and Complex Ion Equilibria of Nickel (II) Species in Aqueous Solution.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.; And Others

1980-01-01

Presents three different procedures in which reagents are added in a specified order to a large beaker containing an aqueous solution of nickel sulfate. Complex ions of nickel (II) are prepared by using aqueous solutions of ammonia, ethylenediamine, dimethylglyoxime, and cyanide ion. (CS)

A conserved quantity in thin body dynamics

NASA Astrophysics Data System (ADS)

Hanna, J. A.; Pendar, H.

2016-02-01

Thin, solid bodies with metric symmetries admit a restricted form of reparameterization invariance. Their dynamical equilibria include motions with both rigid and flowing aspects. On such configurations, a quantity is conserved along the intrinsic coordinate corresponding to the symmetry. As an example of its utility, this conserved quantity is combined with linear and angular momentum currents to construct solutions for the equilibria of a rotating, flowing string, for which it is akin to Bernoulli's constant.

Free boundary skin current magnetohydrodynamic equilibria

NASA Astrophysics Data System (ADS)

Reusch, Michael F.

1988-10-01

Function theoretic methods in the complex plane are used to develop simple parametric hodograph formulas that generate sharp boundary equilibria of arbitrary shape. The related method of Gorenflo [Z. Angew. Math. Phys. 16, 279 (1965)] and Merkel (Ph.D. thesis, University of Munich, 1965) is discussed. A numerical technique for the construction of solutions, based on one of the methods, is presented. A study is made of the bifurcations of an equilibrium of general form.

Hydration and conformational equilibria of simple hydrophobic and amphiphilic solutes.

PubMed Central

Ashbaugh, H S; Kaler, E W; Paulaitis, M E

1998-01-01

We consider whether the continuum model of hydration optimized to reproduce vacuum-to-water transfer free energies simultaneously describes the hydration free energy contributions to conformational equilibria of the same solutes in water. To this end, transfer and conformational free energies of idealized hydrophobic and amphiphilic solutes in water are calculated from explicit water simulations and compared to continuum model predictions. As benchmark hydrophobic solutes, we examine the hydration of linear alkanes from methane through hexane. Amphiphilic solutes were created by adding a charge of +/-1e to a terminal methyl group of butane. We find that phenomenological continuum parameters fit to transfer free energies are significantly different from those fit to conformational free energies of our model solutes. This difference is attributed to continuum model parameters that depend on solute conformation in water, and leads to effective values for the free energy/surface area coefficient and Born radii that best describe conformational equilibrium. In light of these results, we believe that continuum models of hydration optimized to fit transfer free energies do not accurately capture the balance between hydrophobic and electrostatic contributions that determines the solute conformational state in aqueous solution. PMID:9675177

Electrodialytic in-line preconcentration for ionic solute analysis.

PubMed

Ohira, Shin-Ichi; Yamasaki, Takayuki; Koda, Takumi; Kodama, Yuko; Toda, Kei

2018-04-01

Preconcentration is an effective way to improve analytical sensitivity. Many types of methods are used for enrichment of ionic solute analytes. However, current methods are batchwise and include procedures such as trapping and elution. In this manuscript, we propose in-line electrodialytic enrichment of ionic solutes. The method can enrich ionic solutes within seconds by quantitative transfer of analytes from the sample solution to the acceptor solution under an electric field. Because of quantitative ion transfer, the enrichment factor (the ratio of the concentration in the sample and to that in the obtained acceptor solution) only depends on the flow rate ratio of the sample solution to the acceptor solution. The ratios of the concentrations and flow rates are equal for ratios up to 70, 20, and 70 for the tested ionic solutes of inorganic cations, inorganic anions, and heavy metal ions, respectively. The sensitivity of ionic solute determinations is also improved based on the enrichment factor. The method can also simultaneously achieve matrix isolation and enrichment. The method was successively applied to determine the concentrations of trace amounts of chloroacetic acids in tap water. The regulated concentration levels cannot be determined by conventional high-performance liquid chromatography with ultraviolet detection (HPLC-UV) without enrichment. However, enrichment with the present method is effective for determination of tap water quality by improving the limits of detection of HPLC-UV. The standard addition test with real tap water samples shows good recoveries (94.9-109.6%). Copyright © 2017 Elsevier B.V. All rights reserved.

Electroosmotic flow hysteresis for dissimilar ionic solutions

PubMed Central

Lim, An Eng; Lam, Yee Cheong

2015-01-01

Electroosmotic flow (EOF) with two or more fluids is commonly encountered in various microfluidics applications. However, no investigation has hitherto been conducted to investigate the hysteretic or flow direction-dependent behavior during the displacement flow of solutions with dissimilar ionic species. In this investigation, electroosmotic displacement flow involving dissimilar ionic solutions was studied experimentally through a current monitoring method and numerically through finite element simulations. The flow hysteresis can be characterized by the turning and displacement times; turning time refers to the abrupt gradient change of current-time curve while displacement time is the time for one solution to completely displace the other solution. Both experimental and simulation results illustrate that the turning and displacement times for a particular solution pair can be directional-dependent, indicating that the flow conditions in the microchannel are not the same in the two different flow directions. The mechanics of EOF hysteresis was elucidated through the theoretical model which includes the ionic mobility of each species, a major governing parameter. Two distinct mechanics have been identified as the causes for the EOF hysteresis involving dissimilar ionic solutions: the widening/sharpening effect of interfacial region between the two solutions and the difference in ion concentration distributions (and thus average zeta potentials) in different flow directions. The outcome of this investigation contributes to the fundamental understanding of flow behavior in microfluidic systems involving solution pair with dissimilar ionic species. PMID:25945139

Water structure and aqueous uranyl(VI) adsorption equilibria onto external surfaces of beidellite, montmorillonite, and pyrophyllite: results from molecular simulations.

PubMed

Greathouse, Jeffery A; Cygan, Randall T

2006-06-15

Molecular dynamics simulations were performed to provide a systematic study of aqueous uranyl adsorption onto the external surface of 2:1 dioctahedral clays. Our understanding of this key process is critical in predicting the fate of radioactive contaminants in natural groundwaters. These simulations provide atomistic detail to help explain experimental trends in uranyl adsorption onto natural media containing smectite clays. Aqueous uranyl concentrations ranged from 0.027 to 0.162 M. Sodium ions and carbonate ions (0.027-0.243 M) were also present in the aqueous regions to more faithfully model a stream of uranyl-containing groundwater contacting a mineral system comprised of Na-smectite. No adsorption occurred near the pyrophyllite surface, and there was little difference in uranyl adsorption onto the beidellite and montmorillonite, despite the difference in location of clay layer charge between the two. At low uranyl concentration, the pentaaquouranyl complex dominates in solution and readily adsorbs to the clay basal plane. At higher uranyl (and carbonate) concentrations, the mono(carbonato) complex forms in solution, and uranyl adsorption decreases. Sodium adsorption onto beidellite occurred both as inner- and outer-sphere surface complexes, again with little effect on uranyl adsorption. Uranyl surface complexes consisted primarily of the pentaaquo cation (85%) and to a lesser extent the mono(carbonato) species (15%). Speciation diagrams of the aqueous region indicate that the mono(carbonato)uranyl complex is abundant at high ionic strength. Oligomeric uranyl complexes are observed at high ionic strength, particularly near the pyrophyllite and montmorillonite surfaces. Atomic density profiles of water oxygen and hydrogen atoms are nearly identical near the beidellite and montmorillonite surfaces. Water structure therefore appears to be governed by the presence of adsorbed ions and not by the location of layer charge associated with the substrate. The water oxygen density near the pyrophyllite surface is similar to the other cases, but the hydrogen density profile indicates reduced hydrogen bonding between adsorbed water molecules and the surface.

Composite polarizability and the construction of an invariant function of refraction and mass density for solutions.

PubMed

Szymański, Krzysztof; Petrache, Horia I

2011-04-14

Re-examination of dynamical ionic polarizabilities in water solutions leads to the formulation of a solution function r(c), which combines the indices of refraction and mass densities of solutions. We show that this function should be independent of ionic concentration if the composite polarizabilities of hydrated solute clusters are constant. Using existing experimental data for a number of aqueous salt and organic solutions, we find that the r(c) function is either constant or varies linearly with concentration, in most cases with negligible slope. We use this function to compare ionic polarizabilities of crystals and aqueous solutions and to highlight how solute polarizabilities at infinite dilution scale with the electronic valence shell of cations and anions. The proposed r(c) function can be used generally to verify the consistency of experimental measurements and of simulation results, and it provides a test of assumptions in current theories of ionic polarizabilities.

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.

Gex-Model Using Local Area Fraction for Binary Electrolyte Systems

NASA Astrophysics Data System (ADS)

Haghtalab, Ali; Joda, Marzieh

2007-06-01

The correlation and prediction of phase equilibria of electrolyte systems are essential in the design and operation of many industrial processes such as downstream processing in biotechnology, desalination, hydrometallurgy, etc. In this research, the local composition non-random two liquid-nonrandom factor (NRTL-NRF) model of Haghtalab and Vera was extended for uni-univalent aqueous electrolyte solutions. Based on the assumptions of the NRTL-NRF model, excess Gibbs free energy ( g E) functions were derived for binary electrolyte systems. In this work, the local area fraction was applied and the modified model of NRTL-NRF was developed with either an equal or unequal surface area of an anion to the surface area of a cation. The modified NRTL-NRF models consist of two contributions, one due to long-range forces represented by the Debye-Hückel theory, and the other due to short-range forces, represented by local area fractions of species through nonrandom factors. Each model contains only two adjustable parameters per electrolyte. In addition, the model with unequal surface area of ionic species gives better results in comparison with the second new model with equal surface area of ions. The results for the mean activity coefficients for aqueous solutions of uni-univalent electrolytes at 298.15 K showed that the present model is more accurate than the original NRTL-NRF model.

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

High energy supercapattery with an ionic liquid solution of LiClO4.

PubMed

Yu, Linpo; Chen, George Z

2016-08-15

A supercapattery combining an ideally polarized capacitor-like electrode and a battery-like electrode is demonstrated theoretically and practically using an ionic liquid electrolyte containing 1-butyl-1-methylpyrrolidinium tri(pentafluoroethyl)trifluorophosphate (BMPyrrFAP), gamma-butyrolactone (γ-GBL) and LiClO4. The electrochemical deposition and dissolution of lithium metal on a platinum and glass carbon electrode were investigated in this ionic liquid solution. The CVs showed that the fresh electrochemically deposited lithium metal was stable in the electrolyte, which encouraged the investigation of this ionic liquid solution in a supercapattery with a lithium battery negative electrode. The active material counted specific energy of the supercapattery based on a lithium negative electrode and an activated carbon (Act-C) positive electrode could reach 230 W h kg(-1) under a galvanostatic charge-discharge current density of 1 mA cm(-2). The positive electrode material (Act-C) was also investigated by CV, AC impedance, SEM and BET. The non-uniform particle size and micropores dominated porous structure of the Act-C enabled its electric double layer capacitor (EDLC) behavior in the ionic liquid solution. The measured specific capacitance of the Act-C in this ionic liquid solution is higher than the same Act-C in aqueous solution, which indicates the Act-C can also perform well in the ionic liquid electrolyte.

Thermodynamic Modeling of Organic-Inorganic Aerosols with the Group-Contribution Model AIOMFAC

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Luo, B. P.; Peter, T.

2009-04-01

Liquid aerosol particles are - from a physicochemical viewpoint - mixtures of inorganic salts, acids, water and a large variety of organic compounds (Rogge et al., 1993; Zhang et al., 2007). Molecular interactions between these aerosol components lead to deviations from ideal thermodynamic behavior. Strong non-ideality between organics and dissolved ions may influence the aerosol phases at equilibrium by means of liquid-liquid phase separations into a mainly polar (aqueous) and a less polar (organic) phase. A number of activity models exists to successfully describe the thermodynamic equilibrium of aqueous electrolyte solutions. However, the large number of different, often multi-functional, organic compounds in mixed organic-inorganic particles is a challenging problem for the development of thermodynamic models. The group-contribution concept as introduced in the UNIFAC model by Fredenslund et al. (1975), is a practical method to handle this difficulty and to add a certain predictability for unknown organic substances. We present the group-contribution model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients), which explicitly accounts for molecular interactions between solution constituents, both organic and inorganic, to calculate activities, chemical potentials and the total Gibbs energy of mixed systems (Zuend et al., 2008). This model enables the computation of vapor-liquid (VLE), liquid-liquid (LLE) and solid-liquid (SLE) equilibria within one framework. Focusing on atmospheric applications we considered eight different cations, five anions and a wide range of alcohols/polyols as organic compounds. With AIOMFAC, the activities of the components within an aqueous electrolyte solution are very well represented up to high ionic strength. We show that the semi-empirical middle-range parametrization of direct organic-inorganic interactions in alcohol-water-salt solutions enables accurate computations of vapor-liquid and liquid-liquid equilibria. References Fredenslund, A., Jones, R. L., and Prausnitz, J. M.: Group-Contribution Estimation of Activity Coefficients in Nonideal Liquid Mixtures, AIChE J., 21, 1086-1099, 1975. Rogge, W. F., Mazurek, M. A., Hildemann, L. M., Cass, G. R., and Simoneit, B. R. T.: Quantification of Urban Organic Aerosols at a Molecular Level: Identification, Abundance and Seasonal Variation, Atmos. Environ., 27, 1309-1330, 1993. Zhang, Q. et al.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically influenced Northern Hemisphere midlatitudes, Geophys. Res. Lett., 34, L13 801, 2007. Zuend, A., Marcolli, C., Luo, B. P., and Peter, T.: A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients, Atmos. Chem. Phys., 8, 4559-4593, 2008.

Membrane contactor assisted extraction/reaction process employing ionic liquids

DOEpatents

Lin, Yupo J [Naperville, IL; Snyder, Seth W [Lincolnwood, IL

2012-02-07

The present invention relates to a functionalized membrane contactor extraction/reaction system and method for extracting target species from multi-phase solutions utilizing ionic liquids. One preferred embodiment of the invented method and system relates to an extraction/reaction system wherein the ionic liquid extraction solutions act as both extraction solutions and reaction mediums, and allow simultaneous separation/reactions not possible with prior art technology.

Microfluidic free-flow electrophoresis for the discovery and characterisation of calmodulin binding partners

NASA Astrophysics Data System (ADS)

Herling, Therese; Linse, Sara; Knowles, Tuomas

2015-03-01

Non-covalent and transient protein-ligand interactions are integral to cellular function and malfunction. Key steps in signalling and regulatory pathways rely on reversible non-covalent protein-protein binding or ion chelation. Here we present a microfluidic free-flow electrophoresis method for detecting and characterising protein-ligand interactions in solution. We apply this method to probe the binding equilibria of calmodulin, a central protein to calcium signalling pathways. In this study we characterise the specific binding of calmodulin to phosphorylase kinase, a known target, and creatine kinase, which we identify as a putative binding partner through a protein array screen and surface plasmon resonance experiments. We verify the interaction between calmodulin and creatine kinase in solution using free-flow electrophoresis and investigate the effect of calcium and sodium chloride on the calmodulin-ligand binding affinity in free solution without the presence of a potentially interfering surface. Our results demonstrate the general applicability of quantitative microfluidic electrophoresis to characterise binding equilibria between biomolecules in solution.

Phase equilibria of the magnesium sulfate-water system to 4 kbars

NASA Technical Reports Server (NTRS)

Hogenboom, D. L.; Kargel, J. S.; Ganasan, J. P.; Lee, L.

1993-01-01

Magnesium sulfate is the most abundant salt in carbonaceous chondrites, and it may be important in the low-temperature igneous evolution and aqueous differentiation of icy satellites and large chondritic asteroids. Accordingly, we are investigating high-pressure phase equilibria in MgSO4-H2O solutions under pressures up to four kbars. An initial report was presented two years ago. This abstract summarizes our results to date including studies of solutions containing 15.3 percent, 17 percent, and 22 percent MgSO4. Briefly, these results demonstrate that increasing pressure causes the eutectic and peritectic compositions to shift to much lower concentrations of magnesium sulfate, and the existence of a new low-density phase of magnesium sulfate hydrate.

A generalized procedure for the prediction of multicomponent adsorption equilibria

DOE PAGES

Ladshaw, Austin; Yiacoumi, Sotira; Tsouris, Costas

2015-04-07

Prediction of multicomponent adsorption equilibria has been investigated for several decades. While there are theories available to predict the adsorption behavior of ideal mixtures, there are few purely predictive theories to account for nonidealities in real systems. Most models available for dealing with nonidealities contain interaction parameters that must be obtained through correlation with binary-mixture data. However, as the number of components in a system grows, the number of parameters needed to be obtained increases exponentially. Here, a generalized procedure is proposed, as an extension of the predictive real adsorbed solution theory, for determining the parameters of any activity model,more » for any number of components, without correlation. This procedure is then combined with the adsorbed solution theory to predict the adsorption behavior of mixtures. As this method can be applied to any isotherm model and any activity model, it is referred to as the generalized predictive adsorbed solution theory.« less

Tension in Skinned Frog Muscle Fibers in Solutions of Varying Ionic Strength and Neutral Salt Composition

PubMed Central

Gordon, A. M.; Godt, R. E.; Donaldson, S. K. B.; Harris, C. E.

1973-01-01

The maximal calcium-activated isometric tension produced by a skinned frog single muscle fiber falls off as the ionic strength of the solution bathing this fiber is elevated declining to zero near 0.5 M as the ionic strength is varied using KCl. When other neutral salts are used, the tension always declines at high ionic strength, but there is some difference between the various neutral salts used. The anions and cations can be ordered in terms of their ability to inhibit the maximal calcium-activated tension. The order of increasing inhibition of tension (decreasing tension) at high ionic strength for anions is propionate- ≃ SO4 -- < Cl- < Br-. The order of increasing inhibition of calcium-activated tension for cations is K+ ≃ Na+ ≃ TMA+ < TEA+ < TPrA+ < TBuA+. The decline of maximal calcium-activated isometric tension with elevated salt concentration (ionic strength) can quantitatively explain the decline of isometric tetanic tension of a frog muscle fiber bathed in a hypertonic solution if one assumes that the internal ionic strength of a muscle fiber in normal Ringer's solution is 0.14–0.17 M. There is an increase in the base-line tension of a skinned muscle fiber bathed in a relaxing solution (no added calcium and 3 mM EGTA) of low ionic strength. This tension, which has no correlate in the intact fiber in hypotonic solutions, appears to be a noncalcium-activated tension and correlates more with a declining ionic strength than with small changes in [MgATP], [Mg], pH buffer, or [EGTA]. It is dependent upon the specific neutral salts used with cations being ordered in increasing inhibition of this noncalcium-activated tension (decreasing tension) as TPrA+ < TMA+ < K+ ≃ Na+. Measurements of potentials inside these skinned muscle fibers bathed in relaxing solutions produced occasional small positive values (<6 mV) which were not significantly different from zero. PMID:4543066

Hip-hop solutions of the 2N-body problem

NASA Astrophysics Data System (ADS)

Barrabés, Esther; Cors, Josep Maria; Pinyol, Conxita; Soler, Jaume

2006-05-01

Hip-hop solutions of the 2N-body problem with equal masses are shown to exist using an analytic continuation argument. These solutions are close to planar regular 2N-gon relative equilibria with small vertical oscillations. For fixed N, an infinity of these solutions are three-dimensional choreographies, with all the bodies moving along the same closed curve in the inertial frame.

Phase behaviour, interactions, and structural studies of (amines+ionic liquids) binary mixtures.

PubMed

Jacquemin, Johan; Bendová, Magdalena; Sedláková, Zuzana; Blesic, Marijana; Holbrey, John D; Mullan, Claire L; Youngs, Tristan G A; Pison, Laure; Wagner, Zdeněk; Aim, Karel; Costa Gomes, Margarida F; Hardacre, Christopher

2012-05-14

We present a study on the phase equilibrium behaviour of binary mixtures containing two 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide-based ionic liquids, [C(n)mim] [NTf(2)] (n=2 and 4), mixed with diethylamine or triethylamine as a function of temperature and composition using different experimental techniques. Based on this work, two systems showing an LCST and one system with a possible hourglass shape are measured. Their phase behaviours are then correlated and predicted by using Flory-Huggins equations and the UNIQUAC method implemented in Aspen. The potential of the COSMO-RS methodology to predict the phase equilibria was also tested for the binary systems studied. However, this methodology is unable to predict the trends obtained experimentally, limiting its use for systems involving amines in ionic liquids. The liquid-state structure of the binary mixture ([C(2)mim] [NTf(2)]+diethylamine) is also investigated by molecular dynamics simulation and neutron diffraction. Finally, the absorption of gaseous ethane by the ([C(2)mim][NTf(2)]+diethylamine) binary mixture is determined and compared with that observed in the pure solvents. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Room temperature electrodeposition of actinides from ionic solutions

DOEpatents

Hatchett, David W.; Czerwinski, Kenneth R.; Droessler, Janelle; Kinyanjui, John

2017-04-25

Uranic and transuranic metals and metal oxides are first dissolved in ozone compositions. The resulting solution in ozone can be further dissolved in ionic liquids to form a second solution. The metals in the second solution are then electrochemically deposited from the second solutions as room temperature ionic liquid (RTIL), tri-methyl-n-butyl ammonium n-bis(trifluoromethansulfonylimide) [Me.sub.3N.sup.nBu][TFSI] providing an alternative non-aqueous system for the extraction and reclamation of actinides from reprocessed fuel materials. Deposition of U metal is achieved using TFSI complexes of U(III) and U(IV) containing the anion common to the RTIL. TFSI complexes of uranium were produced to ensure solubility of the species in the ionic liquid. The methods provide a first measure of the thermodynamic properties of U metal deposition using Uranium complexes with different oxidation states from RTIL solution at room temperature.

Solubilization of water in water-in-oil microemulsions of kerosene

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

Andheria, A.P.; Bhagwat, S.S.

1995-04-01

The incorporation of water into fuels formulated as microemulsions can offer several advantages such as fire resistance, increased flash point, and improved air-fuel contact. To this end, phase equilibria of kerosene microemulsions employing ionic and nonionic surfactants such as sodium di-(2-ethylhexyl) sulfosuccinate (AOT), lauryl diethanolamide (LDEA), nonylphenol EO-4.5 (NPEO-4.5), sorbitan monolaurate (Span-20), and cetyltrimethylammonium bromide (CTAB), as well as cosurfactants such as n-pentanol, n-hexanol, and n-heptanol, were studied. The effect of the aromaticity of the oil phase on the solubilization of water was also investigated.

Thermodynamics study of the dimerization equilibria of rhodamine B and 6G in different ionic strengths by photometric titration and chemometrics method

NASA Astrophysics Data System (ADS)

Ghasemi, Jahanbakhsh; Niazi, Ali; Kubista, Mikael

2005-11-01

The dimerization constants of rhodamine B and 6G have been determined by studying the dependence of their absorption spectra on the temperature in the range 20-80 °C at different total concentrations of rhodamine B (5.89 × 10 -6 to 2.36 × 10 -4 M) and rhodamine 6G (2.34 × 10 -5 to 5.89 × 10 -4 M) and in different concentrations of LiCl, NaCl and KCl salts as supporting electrolytes. The monomer-dimer equilibrium of rhodamine B and 6G have been determined by chemometrics refinement of the absorption spectra obtained by thermometric titrations performed at different ionic strengths. The quantitative analysis of the data of undefined mixtures, was carried out by simultaneous resolution of the overlapping spectral bands in the whole set of absorption spectra. The dimerization constants are varied by changing the ionic strength and the degree of dimerization are decreased by increasing of the ionic strength of the medium. The enthalpy and entropy of the dimerization reactions were determined from the dependence of the equilibrium constants on the temperature (van't Hoff equation). From the thermodynamic results the TΔ S°-Δ H° plot was sketched. It shows a fairly good positive correlation which indicates the enthalpy-entropy compensation in the dimerization reactions (compensation effect).

Thermodynamics study of the dimerization equilibria of rhodamine B and 6G in different ionic strengths by photometric titration and chemometrics method.

PubMed

Ghasemi, Jahanbakhsh; Niazi, Ali; Kubista, Mikael

2005-11-01

The dimerization constants of rhodamine B and 6G have been determined by studying the dependence of their absorption spectra on the temperature in the range 20-80 degrees C at different total concentrations of rhodamine B (5.89 x 10(-6) to 2.36 x 10(-4)M) and rhodamine 6G (2.34 x 10(-5) to 5.89 x 10(-4)M) and in different concentrations of LiCl, NaCl and KCl salts as supporting electrolytes. The monomer-dimer equilibrium of rhodamine B and 6G have been determined by chemometrics refinement of the absorption spectra obtained by thermometric titrations performed at different ionic strengths. The quantitative analysis of the data of undefined mixtures, was carried out by simultaneous resolution of the overlapping spectral bands in the whole set of absorption spectra. The dimerization constants are varied by changing the ionic strength and the degree of dimerization are decreased by increasing of the ionic strength of the medium. The enthalpy and entropy of the dimerization reactions were determined from the dependence of the equilibrium constants on the temperature (van't Hoff equation). From the thermodynamic results the TDeltaS degrees -DeltaH degrees plot was sketched. It shows a fairly good positive correlation which indicates the enthalpy-entropy compensation in the dimerization reactions (compensation effect).

Quasi-Chemical PC-SAFT: An Extended Perturbed Chain-Statistical Associating Fluid Theory for Lattice-Fluid Mixtures.

PubMed

Parvaneh, Khalil; Shariati, Alireza

2017-09-07

In this study, a new modification of the perturbed chain-statistical associating fluid theory (PC-SAFT) has been proposed by incorporating the lattice fluid theory of Guggenheim as an additional term to the original PC-SAFT terms. As the proposed model has one more term than the PC-SAFT, a new mixing rule has been developed especially for the new additional term, while for the conventional terms of the PC-SAFT, the one-fluid mixing rule is used. In order to evaluate the proposed model, the vapor-liquid equilibria were estimated for binary CO 2 mixtures with 16 different ionic liquids (ILs) of the 1-alkyl-3-methylimidazolium family with various anions consisting of bis(trifluoromethylsulfonyl) imide, hexafluorophosphate, tetrafluoroborate, and trifluoromethanesulfonate. For a comprehensive comparison, three different modes (different adjustable parameters) of the proposed model were compared with the conventional PC-SAFT. Results indicate that the proposed modification of the PC-SAFT EoS is generally more reliable with respect to the conventional PC-SAFT in all the three proposed modes of vapor-liquid equilibria, giving good agreement with literature data.

Influence of aqueous media properties on aggregation and solubility of four structurally related meso-porphyrin photosensitizers evaluated by spectrophotometric measurements.

PubMed

Sobczyński, J; Tønnesen, H H; Kristensen, S

2013-02-01

Porphyrin photosensitizers tend to aggregate in aqueous solutions even in the micromolar concentration range. This is a challenge during formulation of e.g., parenteral preparations for photodynamic cancer therapy, or preparations for local or topical administration in antimicrobial photodynamic therapy. Monomerization is essential to achieve biocompatible drug formulations of high bioavailability and physiological response (i.e., photoreactivity) and low toxicity. The aggregation and solubilization of four structurally related meso-tetraphenyl porphyrin photosensitizers with nonionic (4-hydroxy), anionic (4-sulphonate; 4-carboxy) and cationic (4-trimethylanilinium) substituents were evaluated in various vehicles by use of UV-Vis spectroscopy. Substituents, overall charge and charge distribution influenced the pKa-values and interaction of the porphyrins with different solvents, excipients and impurities. Modification of medium polarity and solubilization by the nonionic surfactant Tween 80 adjusted the acid-base equilibria and increased the solubility by reduction of porphyrin aggregation. The selected porphyrins were sensitive towards ionic strength, temperature and inorganic impurities to various extents. The results will be further used during development of parenteral and topical formulations of porphyrin photosensitizers for use in photodynamic therapy of cancer and bacterial infections.

Phase-field modeling of chemical control of polarization stability and switching dynamics in ferroelectric thin films

DOE PAGES

Cao, Ye; Kalinin, Sergei V.

2016-12-15

Phase-field simulation (PFS) has revolutionized the understanding of domain structure and switching behavior in ferroelectric thin films and ceramics. Generally, PFS is based on the solution of (a set of) Landau-Ginzburg-Devonshire equations for a defined order parameter field(s) under physical boundary conditions (BCs) of fixed potential or charge. While well matched to the interfaces in bulk materials and devices, these BCs are generally not applicable to free ferroelectric surfaces. Here, we developed a self-consistent phase-field model with BCs based on electrochemical equilibria. We chose Pb(Zr 0.2Ti 0.8)O 3 ultrathin film consisting of (001) oriented single tetragonal domain ( Pz) asmore » a model system and systematically studied the effects of oxygen partial pressure, temperature, and surface ions on the ferroelectric state and compared it with the case of complete screening. We have further explored the polarization switching induced by the oxygen partial pressure and observed pronounced size effect induced by chemical screening. Finally, our paper thus helps to understand the emergent phenomena in ferroelectric thin films brought about by the electrochemical ionic surface compensations.« less

Phase-field modeling of chemical control of polarization stability and switching dynamics in ferroelectric thin films

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

Cao, Ye; Kalinin, Sergei V.

Phase-field simulation (PFS) has revolutionized the understanding of domain structure and switching behavior in ferroelectric thin films and ceramics. Generally, PFS is based on the solution of (a set of) Landau-Ginzburg-Devonshire equations for a defined order parameter field(s) under physical boundary conditions (BCs) of fixed potential or charge. While well matched to the interfaces in bulk materials and devices, these BCs are generally not applicable to free ferroelectric surfaces. Here, we developed a self-consistent phase-field model with BCs based on electrochemical equilibria. We chose Pb(Zr 0.2Ti 0.8)O 3 ultrathin film consisting of (001) oriented single tetragonal domain ( Pz) asmore » a model system and systematically studied the effects of oxygen partial pressure, temperature, and surface ions on the ferroelectric state and compared it with the case of complete screening. We have further explored the polarization switching induced by the oxygen partial pressure and observed pronounced size effect induced by chemical screening. Finally, our paper thus helps to understand the emergent phenomena in ferroelectric thin films brought about by the electrochemical ionic surface compensations.« less

A reversible conductivity modulation of azobenzene-based ionic liquids in aqueous solutions using UV/vis light.

PubMed

Li, Zhiyong; Yuan, Xiaoqing; Feng, Ying; Chen, Yongkui; Zhao, Yuling; Wang, Huiyong; Xu, Qingli; Wang, Jianji

2018-05-09

Photo-induced conductivity modulation of stimuli-responsive materials is of great importance from the viewpoint of fundamental research and technology. In this work, 5 new kinds of azobenzene-based photo-responsive ionic liquids were synthesized and characterized, and UV/vis light modulation of their conductivity was investigated in an aqueous solution. The factors affecting the conductivity modulation of the photo-responsive fluids, such as photo-isomerization efficiency, photo-regulation aggregation, concentration and chemical structure of the ionic liquids, were examined systematically. It was found that the conductivity of the ionic liquids in water exhibited a significant increase upon UV light irradiation and the ionic liquids with a shorter alkyl spacer in the cation showed a more remarkable photo-induced conductivity enhancement with a maximum increase of 150%. In addition, the solution conductivity was restored (or very close) to the initial value upon an alternative irradiation with visible light. Thus, the solution conductivity can be modulated using alternative irradiation with UV and visible light. Although the reversible photo-isomerization of the azobenzene group under UV/vis irradiation is the origin of the conductivity modulation, the photo-regulated aggregation of the ionic liquid in water is indispensable for the maximum degree of conductivity modulation because UV irradiation can weaken, even break the aggregated cis-isomers of the ionic liquids in an aqueous solution.

The nucleation rate surfaces design over diagram of phase equilibria and their applications for computational chemistry

NASA Astrophysics Data System (ADS)

Anisimov, M. P.

2016-12-01

One can find in scientific literature a pretty fresh idea of the nucleation rate surfaces design over the diagrams of phase equilibria. That idea looks like profitable for the nucleation theory development and for various practical applications where predictions of theory have no high enough accuracy for today. The common thermodynamics has no real ability to predict parameters of the first order phase transition. Nucleation experiment can be provided in very local nucleation conditions even the nucleation takes place from the critical line (in two-component case) down to the absolute zero temperature limit and from zero nucleation rates at phase equilibria up to the spinodal conditions. Theory predictions have low reliability as a rule. The computational chemistry has chance to make solution of that problem easier when a set of the used axiomatic statements will adapt enough progressive assumptions [1]. Semiempirical design of the nucleation rate surfaces over diagrams of phase equilibria have a potential ability to provide a reasonable quality information on nucleation rate for each channel of nucleation. Consideration and using of the nucleation rate surface topologies to optimize synthesis of a given phase of the target material can be available when data base on nucleation rates over diagrams of phase equilibria will be created.

Extremal equilibria for reaction-diffusion equations in bounded domains and applications

NASA Astrophysics Data System (ADS)

Rodríguez-Bernal, Aníbal; Vidal-López, Alejandro

We show the existence of two special equilibria, the extremal ones, for a wide class of reaction-diffusion equations in bounded domains with several boundary conditions, including non-linear ones. They give bounds for the asymptotic dynamics and so for the attractor. Some results on the existence and/or uniqueness of positive solutions are also obtained. As a consequence, several well-known results on the existence and/or uniqueness of solutions for elliptic equations are revisited in a unified way obtaining, in addition, information on the dynamics of the associated parabolic problem. Finally, we ilustrate the use of the general results by applying them to the case of logistic equations. In fact, we obtain a detailed picture of the positive dynamics depending on the parameters appearing in the equation.

Tautomeric equilibria in solutions of 1-methyl-2-phenacylbenzimidazoles

NASA Astrophysics Data System (ADS)

Skotnicka, Agnieszka; Czeleń, Przemysław; Gawinecki, Ryszard

2017-04-01

Until now the susceptibility of 1-methyl-2-phenacylbenzimidazoles to the proton transfer has not been carefully examined. There only have been selective trials to recognize tautomeric equilibrium of substituted compounds. Unfortunately, conclusions of these studies are often conflicting. Therefore, the aim of this work was to analyze the influence of the factors affecting the tautomeric processes of substituted 1-methyl-2-phenacylbenzimidazoles in solutions of chloroform by spectroscopic technique of 1H and 13C NMR. Complex equilibria may only take place when molecules of tautomeric species contain multiple basic and/or acidic centres. Analysis of NMR spectra show unequivocally that 1-methyl-2-phenacylbenzimidazoles (ketimine tautomeric form) are in equilibrium with (Z)-2-(1-methyl-1H-benzo[d]imidazol-2yl)-1-phenylethenols (enolimine).

Meyer-Overton reforged: The origins of alcohol and anesthetic potency in membranes as determined by a new NMR partitioning probe, benzyl alcohol

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

Janes, N.; Ma, L.; Hsu, J.W.

1992-01-01

The Meyer-Overton hypothesis--that anesthesia arises from the nonspecific action of solutes on membrane lipids--is reformulated using colligative thermodynamics. Configurational entropy, the randomness imparted by the solute through the partitioning process, is implicated as the energetic driving force that pertubs cooperative membrane equilibria. A proton NMR partitioning approach based on the anesthetic benzyl alcohol is developed to assess the reformulation. Ring resonances from the partitioned drug are shielded by 0.2 ppm and resolved from the free, aqueous drug. Free alcohol is quantitated in dilute lipid dispersions using an acetate internal standard. Cooperative equilibria in model dipalmitoyl lecithin membranes are examined withmore » changes in temperature and alcohol concentration. The L[sub [beta][prime

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.

Effect of the alkyl chain length on the rotational dynamics of nonpolar and dipolar solutes in a series of N-alkyl-N-methylmorpholinium ionic liquids.

PubMed

Khara, Dinesh Chandra; Kumar, Jaini Praveen; Mondal, Navendu; Samanta, Anunay

2013-05-02

Rotational dynamics of two dipolar solutes, 4-aminophthalimide (AP) and 6-propionyl-2-dimethylaminonaphthalene (PRODAN), and a nonpolar solute, anthracene, have been studied in N-alkyl-N-methylmorpholinium (alkyl = ethyl, butyl, hexyl, and octyl) bis(trifluoromethansulfonyl)imide (Tf2N) ionic liquids as a function of temperature and excitation wavelength to probe the microheterogeneous nature of these ionic liquids, which are recently reported to be more structured than the imidazolium ionic liquids (Khara and Samanta, J. Phys. Chem. B2012, 116, 13430-13438). Analysis of the measured rotational time constants of the solutes in terms of the Stokes-Einstein-Debye (SED) hydrodynamic theory reveals that with increase in the alkyl chain length attached to the cationic component of the ionic liquids, AP shows stick to superstick behavior, PRODAN rotation lies between stick and slip boundary conditions, whereas anthracene exhibits slip to sub slip behavior. The contrasting rotational dynamics of these probe molecules is a reflection of their location in distinct environments of the ionic liquids thus demonstrating the heterogeneity of these ionic liquids. The microheterogeneity of these media, in particular, those with the long alkyl chain, is further evidence from the excitation wavelength dependence study of the rotational diffusion of the dipolar probe molecules.

X-ray spectroscopy for chemistry in the 2-4 keV energy regime at the XMaS beamline: ionic liquids, Rh and Pd catalysts in gas and liquid environments, and Cl contamination in γ-Al2O3.

PubMed

Thompson, Paul B J; Nguyen, Bao N; Nicholls, Rachel; Bourne, Richard A; Brazier, John B; Lovelock, Kevin R J; Brown, Simon D; Wermeille, Didier; Bikondoa, Oier; Lucas, Christopher A; Hase, Thomas P A; Newton, Mark A

2015-11-01

The 2-4 keV energy range provides a rich window into many facets of materials science and chemistry. Within this window, P, S, Cl, K and Ca K-edges may be found along with the L-edges of industrially important elements from Y through to Sn. Yet, compared with those that cater for energies above ca. 4-5 keV, there are relatively few resources available for X-ray spectroscopy below these energies. In addition, in situ or operando studies become to varying degrees more challenging than at higher X-ray energies due to restrictions imposed by the lower energies of the X-rays upon the design and construction of appropriate sample environments. The XMaS beamline at the ESRF has recently made efforts to extend its operational energy range to include this softer end of the X-ray spectrum. In this report the resulting performance of this resource for X-ray spectroscopy is detailed with specific attention drawn to: understanding electrostatic and charge transfer effects at the S K-edge in ionic liquids; quantification of dilution limits at the Cl K- and Rh L3-edges and structural equilibria in solution; in vacuum deposition and reduction of [Rh(I)(CO)2Cl]2 to γ-Al2O3; contamination of γ-Al2O3 by Cl and its potential role in determining the chemical character of supported Rh catalysts; and the development of chlorinated Pd catalysts in `green' solvent systems. Sample environments thus far developed are also presented, characterized and their overall performance evaluated.

Ternary mixtures of ionic liquids for better salt solubility, conductivity and cation transference number improvement

PubMed Central

Karpierz, E.; Niedzicki, L.; Trzeciak, T.; Zawadzki, M.; Dranka, M.; Zachara, J.; Żukowska, G. Z.; Bitner-Michalska, A.; Wieczorek, W.

2016-01-01

We hereby present the new class of ionic liquid systems in which lithium salt is introduced into the solution as a lithium cation−glyme solvate. This modification leads to the reorganisation of solution structure, which entails release of free mobile lithium cation solvate and hence leads to the significant enhancement of ionic conductivity and lithium cation transference numbers. This new approach in composing electrolytes also enables even three-fold increase of salt concentration in ionic liquids. PMID:27767069

Relativistic Self-similar Equilibria and Non-axisymmetric Neutral Modes

NASA Astrophysics Data System (ADS)

Cai, Mike J.; Shu, F. H.

2002-05-01

We have constructed semi-analytic axisymmetric scale free solutions to Einstein field equations with perfect fluid matter source. These spacetimes are self-similar under the simultaneous transformation r'= ar and t'=a1-nt. We explored the two dimensional solution space parameterized by the rescaling index n and the isothermal sound speed γ 1/2. The isopycnic surfaces are in general toroids. As the equilibrium configuration rotates faster, an ergo region develops in the form of the exterior of a cone centered about the symmetry axis. The sequence of solution terminates when frame dragging becomes infinite and the ergo cone closes onto the axis. In the extreme flattening limit, we have also searched for non-axisymmetric neutral modes in a self-similar disk. Two separate sets of tracks are discovered in the solution space. One corresponds to the bifurcation points to non-axisymmetric equilibria, which is confined in the non-ergo solutions. The other track signals the onset of instability driven by gravitational radiation. These solutions are formally infinite in extent, and thus can not represent realistic astrophysical systems. However, if these properties do not alter qualitatively when the self-similar configurations are truncated, then these solutions may serve as initial data for dynamic collapse in super massive black hole formation.

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.

Conformational equilibria of alkanes in aqueous solution: relationship to water structure near hydrophobic solutes.

PubMed Central

Ashbaugh, H S; Garde, S; Hummer, G; Kaler, E W; Paulaitis, M E

1999-01-01

Conformational free energies of butane, pentane, and hexane in water are calculated from molecular simulations with explicit waters and from a simple molecular theory in which the local hydration structure is estimated based on a proximity approximation. This proximity approximation uses only the two nearest carbon atoms on the alkane to predict the local water density at a given point in space. Conformational free energies of hydration are subsequently calculated using a free energy perturbation method. Quantitative agreement is found between the free energies obtained from simulations and theory. Moreover, free energy calculations using this proximity approximation are approximately four orders of magnitude faster than those based on explicit water simulations. Our results demonstrate the accuracy and utility of the proximity approximation for predicting water structure as the basis for a quantitative description of n-alkane conformational equilibria in water. In addition, the proximity approximation provides a molecular foundation for extending predictions of water structure and hydration thermodynamic properties of simple hydrophobic solutes to larger clusters or assemblies of hydrophobic solutes. PMID:10423414

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

Acceptor-type hydroxide graphite intercalation compounds electrochemically formed in high ionic strength solutions.

PubMed

Miyazaki, Kohei; Iizuka, Asuka; Mikata, Koji; Fukutsuka, Tomokazu; Abe, Takeshi

2017-09-05

The intercalation of hydroxide ions (OH - ) into graphite formed graphite intercalation compounds (GICs) in high ionic strength solutions. GICs of solvated OH - anions with two water molecules (OH - ·2H 2 O) in alkaline aqueous solutions and GICs of only OH - anions in a molten NaOH-KOH salt solution were electrochemically synthesized.

Reliability of ionic polymer metallic composite for opto-mechanical applications

NASA Astrophysics Data System (ADS)

Yu, Chung-Yi; Su, Guo-Dung J.

2014-09-01

Electroactive polymer (EAP) is capable of exhibiting large shape changes in response to electrical stimulation. EAPs can produce large deformation with lower applied voltage for actuation applications. IPMC (Ionic Polymer Metal Composite) is a well-known ionic EAPs. It has numerous attractive advantages, such as low electrical energy consumption and light weight. The mechanism of IPMC actuator is due to the ionic diffusion when the voltage gradient is applied, so that the type of ionic solution has a large impact on the physical properties of IPMC. In this paper, the reliability tests of IPMC with non-aqueous ionic solution are demonstrated. Pt-IPMC with LiOH aqueous solution exhibits the best maximum displacement, but the water in LiOH solution is electrolyzed because of the low electrolysis voltage 1.23 V of water. To improve electrolysis problems and the operation time in the air, proper solvents including high electrolysis voltage and low vapor pressure should be considered. The reliability tests focus on the durability of IPMC in the air. The surface resistance, tip displacement and response time of IPMC are presented. More improvements of IPMC fabrication, such as Ag-IPMC, was developed in this paper.

The effect of topography on the evolution of unstable disturbances in a baroclinic atmosphere

NASA Technical Reports Server (NTRS)

Clark, J. H. E.

1985-01-01

A two layer spectral quasi-geostrophic model is used to simulate the effects of topography on the equilibria, their stability, and the long term evolution of incipient unstable waves. The flow is forced by latitudinally dependent radiative heating. Dissipation is in the form of Rayleigh friction. An analytical solution is found for the propagating finite amplitude waves which result from baroclinic instability of the zonal winds when topography is absent. The appearance of this solution for wavelengths just longer than the Rossby radius of deformation and disappearance of ultra-long wavelengths is interpreted in terms of the Hopf bifurcation theory. Simple dynamic and thermodynamic criteria for the existence of periodic Rossby solutions are presented. A Floquet stability analysis shows that the waves are neutral. The nature of the form drag instability of high index equilibria is investigated. The proximity of the equilibrium shear to a resonant value is essential for the instability, provided the equilibrium occurs at a slightly stronger shear than resonance.

High order finite volume WENO schemes for the Euler equations under gravitational fields

NASA Astrophysics Data System (ADS)

Li, Gang; Xing, Yulong

2016-07-01

Euler equations with gravitational source terms are used to model many astrophysical and atmospheric phenomena. This system admits hydrostatic balance where the flux produced by the pressure is exactly canceled by the gravitational source term, and two commonly seen equilibria are the isothermal and polytropic hydrostatic solutions. Exact preservation of these equilibria is desirable as many practical problems are small perturbations of such balance. High order finite difference weighted essentially non-oscillatory (WENO) schemes have been proposed in [22], but only for the isothermal equilibrium state. In this paper, we design high order well-balanced finite volume WENO schemes, which can preserve not only the isothermal equilibrium but also the polytropic hydrostatic balance state exactly, and maintain genuine high order accuracy for general solutions. The well-balanced property is obtained by novel source term reformulation and discretization, combined with well-balanced numerical fluxes. Extensive one- and two-dimensional simulations are performed to verify well-balanced property, high order accuracy, as well as good resolution for smooth and discontinuous solutions.

Solvation behaviour of L-leucine in aqueous ionic liquid at different temperatures: Volumetric approach

NASA Astrophysics Data System (ADS)

Sharma, Samriti; Sandarve, Sharma, Amit K.; Sharma, Meena

2018-05-01

For the investigation of interactions of L-leucine in aqueous solutions of an ionic liquid (1-butyl-3-methylimidazolium tetra fluoroborate [Bmim][BF4]) at atmospheric pressure over a temperature range of (293.15K to 313.16K), we use the volumetric approach. By using the density data we have calculated the apparent molar volume, VΦ, limiting apparent molar volume, V0Φ, the slope, Sv, partial molar volume of transfer, V0Φ,tr. The values of these acoustical parameters have been used for the interpretation of different interactions like hydrophilic-hydrophilic, hydrophilic-hydrophobic, ion hydrophilic, solute-solvent and solute-solute interactions in the amino acid and ionic liquid solutions.

Methods for separating medical isotopes using ionic liquids

DOEpatents

Luo, Huimin; Boll, Rose Ann; Bell, Jason Richard; Dai, Sheng

2014-10-21

A method for extracting a radioisotope from an aqueous solution, the method comprising: a) intimately mixing a non-chelating ionic liquid with the aqueous solution to transfer at least a portion of said radioisotope to said non-chelating ionic liquid; and b) separating the non-chelating ionic liquid from the aqueous solution. In preferred embodiments, the method achieves an extraction efficiency of at least 80%, or a separation factor of at least 1.times.10.sup.4 when more than one radioisotope is included in the aqueous solution. In particular embodiments, the method is applied to the separation of medical isotopes pairs, such as Th from Ac (Th-229/Ac-225, Ac-227/Th-227), or Ra from Ac (Ac-225 and Ra-225, Ac-227 and Ra-223), or Ra from Th (Th-227 and Ra-223, Th-229 and Ra-225).

Geostrophic tripolar vortices in a two-layer fluid: Linear stability and nonlinear evolution of equilibria

NASA Astrophysics Data System (ADS)

Reinaud, J. N.; Sokolovskiy, M. A.; Carton, X.

2017-03-01

We investigate equilibrium solutions for tripolar vortices in a two-layer quasi-geostrophic flow. Two of the vortices are like-signed and lie in one layer. An opposite-signed vortex lies in the other layer. The families of equilibria can be spanned by the distance (called separation) between the two like-signed vortices. Two equilibrium configurations are possible when the opposite-signed vortex lies between the two other vortices. In the first configuration (called ordinary roundabout), the opposite signed vortex is equidistant to the two other vortices. In the second configuration (eccentric roundabouts), the distances are unequal. We determine the equilibria numerically and describe their characteristics for various internal deformation radii. The two branches of equilibria can co-exist and intersect for small deformation radii. Then, the eccentric roundabouts are stable while unstable ordinary roundabouts can be found. Indeed, ordinary roundabouts exist at smaller separations than eccentric roundabouts do, thus inducing stronger vortex interactions. However, for larger deformation radii, eccentric roundabouts can also be unstable. Then, the two branches of equilibria do not cross. The branch of eccentric roundabouts only exists for large separations. Near the end of the branch of eccentric roundabouts (at the smallest separation), one of the like-signed vortices exhibits a sharp inner corner where instabilities can be triggered. Finally, we investigate the nonlinear evolution of a few selected cases of tripoles.

Physico-Chemical Properties and Phase Behaviour of Pyrrolidinium-Based Ionic Liquids

PubMed Central

Domańska, Urszula

2010-01-01

A review of the relevant literature on 1-alkyl-1-methylpyrrolidinium-based ionic liquids has been presented. The phase diagrams for the binary systems of {1-ethyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [EMPYR][CF3SO3] + water, or + 1-butanol} and for the binary systems of {1-propyl-1-methylpyrrolidinium trifluoromethanesulfonate (triflate) [PMPYR][CF3SO3] + water, or + an alcohol (1-butanol, 1-hexanol, 1-octanol, 1-decanol)} have been determined at atmospheric pressure using a dynamic method. The influence of alcohol chain length was discussed for the [PMPYR][CF3SO3]. A systematic decrease in the solubility was observed with an increase of the alkyl chain length of an alcohol. (Solid + liquid) phase equilibria with complete miscibility in the liquid phase region were observed for the systems involving water and alcohols. The solubility of the ionic liquid increases as the alkyl chain length on the pyrrolidinium cation increases. The correlation of the experimental data has been carried out using the Wilson, UNIQUAC and the NRTL equations. The phase diagrams reported here have been compared to the systems published earlier with the 1-alkyl-1-methylpyrrolidinium-based ionic liquids. The influence of the cation and anion on the phase behaviour has been discussed. The basic thermal properties of pure ILs, i.e., melting temperature and the enthalpy of fusion, the solid-solid phase transition temperature and enthalpy have been measured using a differential scanning microcalorimetry technique. PMID:20480044

Self-organization in a distributed coordination game through heuristic rules

NASA Astrophysics Data System (ADS)

Agarwal, Shubham; Ghosh, Diptesh; Chakrabarti, Anindya S.

2016-12-01

In this paper, we consider a distributed coordination game played by a large number of agents with finite information sets, which characterizes emergence of a single dominant attribute out of a large number of competitors. Formally, N agents play a coordination game repeatedly, which has exactly N pure strategy Nash equilibria, and all of the equilibria are equally preferred by the agents. The problem is to select one equilibrium out of N possible equilibria in the least number of attempts. We propose a number of heuristic rules based on reinforcement learning to solve the coordination problem. We see that the agents self-organize into clusters with varying intensities depending on the heuristic rule applied, although all clusters but one are transitory in most cases. Finally, we characterize a trade-off in terms of the time requirement to achieve a degree of stability in strategies versus the efficiency of such a solution.

Calculating the thermodynamic properties of aqueous solutions of alkali metal carboxylates

NASA Astrophysics Data System (ADS)

Rudakov, A. M.; Sergievskii, V. V.; Zhukova, T. V.

2014-06-01

A modified Robinson-Stokes equation with terms that consider the formation of ionic hydrates and associates is used to describe thermodynamic properties of aqueous solutions of electrolytes. The model is used to describe data on the osmotic coefficients of aqueous solutions of alkali metal carboxylates, and to calculate the mean ionic activity coefficients of salts and excess Gibbs energies. The key contributions from ionic hydration and association to the nonideality of solutions is determined by analyzing the contributions of various factors. Relations that connect the hydration numbers of electrolytes with the parameters of the Pitzer-Mayorga equation and a modified Hückel equation are developed.

Free energy and phase equilibria for the restricted primitive model of ionic fluids from Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Orkoulas, Gerassimos; Panagiotopoulos, Athanassios Z.

1994-07-01

In this work, we investigate the liquid-vapor phase transition of the restricted primitive model of ionic fluids. We show that at the low temperatures where the phase transition occurs, the system cannot be studied by conventional molecular simulation methods because convergence to equilibrium is slow. To accelerate convergence, we propose cluster Monte Carlo moves capable of moving more than one particle at a time. We then address the issue of charged particle transfers in grand canonical and Gibbs ensemble Monte Carlo simulations, for which we propose a biased particle insertion/destruction scheme capable of sampling short interparticle distances. We compute the chemical potential for the restricted primitive model as a function of temperature and density from grand canonical Monte Carlo simulations and the phase envelope from Gibbs Monte Carlo simulations. Our calculated phase coexistence curve is in agreement with recent results of Caillol obtained on the four-dimensional hypersphere and our own earlier Gibbs ensemble simulations with single-ion transfers, with the exception of the critical temperature, which is lower in the current calculations. Our best estimates for the critical parameters are T*c=0.053, ρ*c=0.025. We conclude with possible future applications of the biased techniques developed here for phase equilibrium calculations for ionic fluids.

Stern potential and Debye length measurements in dilute ionic solutions with electrostatic force microscopy.

PubMed

Kumar, Bharat; Crittenden, Scott R

2013-11-01

We demonstrate the ability to measure Stern potential and Debye length in dilute ionic solution with atomic force microscopy. We develop an analytic expression for the second harmonic force component of the capacitive force in an ionic solution from the linearized Poisson-Boltzmann equation. This allows us to calibrate the AFM tip potential and, further, obtain the Stern potential of sample surfaces. In addition, the measured capacitive force is independent of van der Waals and double layer forces, thus providing a more accurate measure of Debye length.

Thermodynamic studies of drug-alpha-cyclodextrin interactions in water at 298.15 K: promazine hydrochloride/chlorpromazine hydrochloride + alpha-cyclodextrin + H(2)O systems.

PubMed

Terdale, Santosh S; Dagade, Dilip H; Patil, Kesharsingh J

2007-12-06

Data on osmotic coefficients have been obtained for a binary aqueous solution of two drugs, namely, promazine hydrochloride (PZ) and chlorpromazine hydrochloride (CPZ) using a vapor pressure osmometer at 298.15 K. The observed critical micelle concentration (cmc) agrees excellently with the available literature data. The measurements are extended to aqueous ternary solutions containing fixed a concentration of alpha-cyclodextrin (alpha-CD) of 0.1 mol kg(-1) and varied concentrations (approximately 0.005-0.2 mol kg(-1)) of drugs at 298.15 K. It has been found that the cmc values increase by the addition of alpha-CD. The mean molal activity coefficients of the ions and the activity coefficient of alpha-CD in binary as well as ternary solutions were obtained, which have been further used to calculate the excess Gibbs free energies and transfer Gibbs free energies. The lowering of the activity coefficients of ions and of alpha-CD is attributed to the existence of host-guest (inclusion)-type complex equilibria. It is suggested that CPZ forms 2:1 and 1:1 complexed species with alpha-CD, while PZ forms only 1:1 complexed species. The salting constant (ks) values are determined at 298.15 K for promazine-alpha-CD and chlorpromazine-alpha-CD complexes, respectively, by following the method based on the application of the McMillan-Mayer theory of virial coefficients to transfer free energy data. It is noted that the presence of chlorine in the drug molecule imparts better complexing capacity, the effect of which gets attenuated as a result of hydrophobic interaction. The results are discussed from the point of view of associative equilibria before the cmc and complexed equilibria for binary and ternary solutions, respectively.

Ion-pairing dynamics of Li{sup +} and SCN{sup -} in dimethylformamide solution: Chemical exchange two-dimensional infrared spectroscopy

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

Lee, Kyung-Koo; Park, Kwang-Hee; Kwon, Donghyun

2011-02-14

Ultrafast two-dimensional infrared (2DIR) spectroscopy has been proven to be an exceptionally useful method to study chemical exchange processes between different vibrational chromophores under thermal equilibria. Here, we present experimental results on the thermal equilibrium ion pairing dynamics of Li{sup +} and SCN{sup -} ions in N,N-dimethylformamide. Li{sup +} and SCN{sup -} ions can form a contact ion pair (CIP). Varying the relative concentration of Li{sup +} in solution, we could control the equilibrium CIP and free SCN{sup -} concentrations. Since the CN stretch frequency of Li-SCN CIP is blue-shifted by about 16 cm{sup -1} from that of free SCN{supmore » -} ion, the CN stretch IR spectrum is a doublet. The temperature-dependent IR absorption spectra reveal that the CIP formation is an endothermic (0.57 kJ/mol) process and the CIP state has larger entropy by 3.12 J/(K mol) than the free ion states. Since the two ionic configurations are spectrally distinguishable, this salt solution is ideally suited for nonlinear IR spectroscopic investigations to study ion pair association and dissociation dynamics. Using polarization-controlled IR pump-probe methods, we first measured the lifetimes and orientational relaxation times of these two forms of ionic configurations. The vibrational population relaxation times of both the free ion and CIP are about 32 ps. However, the orientational relaxation time of the CIP, which is {approx}47 ps, is significantly longer than that of the free SCN{sup -}, which is {approx}7.7 ps. This clearly indicates that the effective moment of inertia of the CIP is much larger than that of the free SCN{sup -}. Then, using chemical exchange 2DIR spectroscopy and analyzing the diagonal peak and cross-peak amplitude changes with increasing the waiting time, we determined the contact ion pair association and dissociation time constants that are found to be 165 and 190 ps, respectively. The results presented and discussed in this paper are believed to be important, not only because the ion-pairing dynamics is one of the most fundamental physical chemistry problems but also because such molecular ion-ion interactions are of critical importance in understanding Hofmeister effects on protein stability.« less

Regenerable biocide delivery unit, volume 2

NASA Technical Reports Server (NTRS)

Atwater, James E.; Wheeler, Richard R., Jr.

1992-01-01

Source code for programs dealing with the following topics are presented: (1) life cycle test stand-parametric test stand control (in BASIC); (2) simultaneous aqueous iodine equilibria-true equilibrium (in C); (3) simultaneous aqueous iodine equilibria-pseudo-equilibrium (in C); (4) pseudo-(fast)-equilibrium with iodide initially present (in C); (5) solution of simultaneous iodine rate expressions (Mathematica); (6) 2nd order kinetics of I2-formic acid in humidity condensate (Mathematica); (7) prototype RMCV onboard microcontroller (CAMBASIC); (8) prototype RAM data dump to PC (in BASIC); and (9) prototype real time data transfer to PC (in BASIC).

Reclamation of niobium compounds from ionic liquid electrochemical polishing of superconducting radio frequency cavities

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

Recent research has shown that choline chloride (vitamin B4)-based solutions can be used as a greener alternative to acid-based electrochemical polishing solutions. This study demonstrated a successful method for electrochemical deposition of niobium compounds onto the surface of copper substrates using a novel choline chloride-based ionic liquid. Niobium ions present in the ionic liquid solution were dissolved into the solution prior to deposition via electrochemical polishing of solid niobium. A black coating was clearly visible on the surface of the Cu following deposition. This coating was analyzed using scanning electron microscopy (SEM), electron dispersive X-ray spectroscopy (EDX), atomic force microscopymore » (AFM), and X-ray fluorescence spectroscopy (XRF). This ionic liquid-based electrochemical deposition method effectively recycles previously dissolved niobium from electrochemical polishing of superconducting radio frequency (SRF) cavities.« less

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

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

Wixtrom, Alex I.; Buhler, Jessica E.; Reece, Charles E.

2013-06-01

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

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.

High-temperature experimental and thermodynamic modelling research on the pyrometallurgical processing of copper

NASA Astrophysics Data System (ADS)

Hidayat, Taufiq; Shishin, Denis; Decterov, Sergei A.; Hayes, Peter C.; Jak, Evgueni

2017-01-01

Uncertainty in the metal price and competition between producers mean that the daily operation of a smelter needs to target high recovery of valuable elements at low operating cost. Options for the improvement of the plant operation can be examined and decision making can be informed based on accurate information from laboratory experimentation coupled with predictions using advanced thermodynamic models. Integrated high-temperature experimental and thermodynamic modelling research on phase equilibria and thermodynamics of copper-containing systems have been undertaken at the Pyrometallurgy Innovation Centre (PYROSEARCH). The experimental phase equilibria studies involve high-temperature equilibration, rapid quenching and direct measurement of phase compositions using electron probe X-ray microanalysis (EPMA). The thermodynamic modelling deals with the development of accurate thermodynamic database built through critical evaluation of experimental data, selection of solution models, and optimization of models parameters. The database covers the Al-Ca-Cu-Fe-Mg-O-S-Si chemical system. The gas, slag, matte, liquid and solid metal phases, spinel solid solution as well as numerous solid oxide and sulphide phases are included. The database works within the FactSage software environment. Examples of phase equilibria data and thermodynamic models of selected systems, as well as possible implementation of the research outcomes to selected copper making processes are presented.

Rare earth metal-containing ionic liquids

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

Prodius, Denis; Mudring, Anja-Verena

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Rare earth metal-containing ionic liquids

DOE PAGES

Prodius, Denis; Mudring, Anja-Verena

2018-03-07

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

A stochastic cellular automata model of tautomer equilibria

NASA Astrophysics Data System (ADS)

Bowers, Gregory A.; Seybold, Paul G.

2018-03-01

Many chemical substances, including drugs and biomolecules, exist in solution not as a single species, but as a collection of tautomers and related species. Importantly, each of these species is an independent compoundwith its own specific biochemical and physicochemical properties. The species interconvert in a dynamic and often complicated manner, making modelling the overall species composition difficult. Agent-based cellular automata models are uniquely suited to meet this challenge, allowing the equilibria to be simulated using simple rulesand at the same time capturing the inherent stochasticity of the natural phenomenon. In the present example a stochastic cellular automata model is employed to simulate the tautomer equilibria of 9-anthrone and 9-anthrol in the presence of their common anion. The observed KE of the 9-anthrone ⇌ 9-anthrol tautomerisation along with the measured tautomer pKa values were used to model the equilibria at pH values 4, 7 and 10. At pH 4 and 7, the anthrone comprises >99% of the total species population, while at pH 10the anthrone and the anion each represent just under half of the total population. The advantages of the cellular automata approach over the customary coupled differential equation approach are discussed.

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

PubMed

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

2018-05-09

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

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

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

Simone, Peter M.; Lodge, Timothy P.

2008-08-26

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

Ionic association and solvation of the ionic liquid 1-hexyl-3-methylimidazolium chloride in molecular solvents revealed by vapor pressure osmometry, conductometry, volumetry, and acoustic measurements.

PubMed

Sadeghi, Rahmat; Ebrahimi, Nosaibah

2011-11-17

A systematic study of osmotic coefficient, conductivity, volumetric and acoustic properties of solutions of ionic liquid 1-hexyl-3-methylimidazolium chloride ([C(6)mim][Cl]) in various molecular solvents has been made at different temperatures in order to study of ionic association and solvation behavior of [C(6)mim][Cl] in different solutions. Precise measurements on electrical conductances of solutions of [C(6)mim][Cl] in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and acetonitrile at 293.15, 298.15, and 303.15 K are reported and analyzed with Barthel's low-concentration chemical model (lcCM) to obtain the limiting molar conductivities and association constants of this ionic liquid in the investigated solvents. Strong ion pairing was found for the ionic liquid in 2-propanol, 1-butanol, and 1-propanol, whereas ion association in acetonitrile, methanol and ethanol is rather weak and in water the ionic liquid is fully dissociated. In the second part of this work, the apparent molar volumes and isentropic compressibilities of [C(6)mim][Cl] in water, methanol, ethanol, acetonitrile, 1-propanol, 2-propanol, and 1-butanol are obtained at the 288.15-313.15 K temperature range at 5 K intervals at atmospheric pressure from the precise measurements of density and sound velocity. The infinite dilution apparent molar volume and isentropic compressibility values of the free ions and ion pairs of [C(6)mim][Cl] in the investigated solvents as well as the excess molar volume of the investigated solutions are determined and their variations with temperature and type of solvents are also studied. Finally, the experimental measurements of osmotic coefficient at 318.15 K for binary solutions of [C(6)mim][Cl] in water, methanol, ethanol, 2-propanol, and acetonitrile are taken using the vapor pressure osmometry (VPO) method and from which the values of the solvent activity, vapor pressure, activity coefficients, and Gibbs free energies are calculated. The results are interpreted in terms of ion association, ion-dipole interactions, and structural factors of the ionic liquid and investigated organic solvents. The ionic liquid is solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation.

Thermostable cellulases, and mutants thereof, capable of hydrolyzing cellulose in ionic liquid

DOEpatents

Sapra, Rajat; Datta, Supratim; Chen, Zhiwei; Holmes, Bradley M.; Simmons, Blake A.; Blanch, Harvey W.

2016-04-26

The present invention provides for a composition comprising an ionic liquid and a thermostable cellulose, and a method of hydrolyzing a cellulose, comprising: (a) providing a composition comprising a solution comprising an ionic liquid and a cellulose, and (b) introducing a thermostable cellulase to the solution, such that the cellulose is hydrolyzed by the cellulase. The present invention also provides for a Thermatoga maritima thermostable cellulase mutant with increased cellulase activity.

Recovery of sugars from ionic liquid biomass liquor by solvent extraction

DOEpatents

Brennan, Timothy Charles R.; Holmes, Bradley M.; Simmons, Blake A.; Blanch, Harvey W.

2015-10-13

The present invention provides for a composition comprising a solution comprising (a) an ionic liquid (IL) or ionic liquid-aqueous (ILA) phase and (b) an organic phase, wherein the solution comprises a sugar and a boronic acid. The present invention also provides for a method of removing a sugar from a solution, comprising: (a) providing a solution comprising (i) an IL or ILA phase and (ii) an organic phase, wherein the solution comprises an IL, a sugar and a boronic acid; (b) contacting the sugar with the boronic acid to form a sugar-boronic acid complex, (c) separating the organic phase and the aqueous phase, wherein the organic phase contains the sugar-boronic acid complex, and optionally (d) separating the sugar from the organic phase.

Liquid-vapor phase equilibria of three-component systems of propanol-2-propanoic acid esters

NASA Astrophysics Data System (ADS)

Suntsov, Yu. K.; Goryunov, V. A.; Chuikov, A. M.

2017-12-01

The boiling points of solutions of three-component systems formed by propanol-2 and propanoic acid esters are measured at different pressures by means of ebulliometry. The coefficients of the activity of the solutions' components are measured using Wilson and nonrandom two-liquid (NRTL) equations. The results from calculations are in line with the experimental data.

Ion-exchange sorption of silver(I) chloride complexes from aqueous HCl solutions

NASA Astrophysics Data System (ADS)

Kononova, O. N.; Duba, E. V.; Medovikov, D. V.; Efimova, A. S.; Ivanov, A. I.; Krylov, A. S.

2017-12-01

The ion-exchange sorption of silver(I) chloride complexes from 1-4 M aqueous solutions of HCl on a series of Purolite anionites with various functional groups was studied. The ion-exchange equilibria in the systems were found to be anomalous according to Raman spectroscopy, which does not significantly affect the sorption properties of the ionites.

Similarity considerations and conservation laws for magneto-static atmospheres

NASA Technical Reports Server (NTRS)

Webb, G. M.

1986-01-01

The equations of magnetohydrostatic equilibria for a plasma in a gravitational field are investigated analytically. For equilibria with one ignorable spatial coordinate, the equations reduce to a single nonlinear elliptic equation for the magnetic potential. Similarity solutions of the elliptic equation are obtained for the case of an isothermal atmosphere in a uniform gravitational field. The solutions are obtained from a consideration of the invariance group of the elliptic equation. The importance of symmetries of the elliptic equation also appears in the determination of conservation laws. It turns out that the elliptic equation can be written as a variational principle, and the symmetries of the variational functional lead (via Noether's theorem) to conservation laws for the equation. As an example of the application of the similarity solutions, a model magnetostatic atmosphere is constructed in which the current density J is proportional to the cube of the magnetic potential, and falls off exponentially with distance vertical to the base, with an 'e-folding' distance equal to the gravitational scale height. The solutions show the interplay between the gravitational force, the J x B force (B, magnetic field induction) and the gas pressure gradient.

Ionic Liquid as an Effective Additive for Rechargeable Magnesium Batteries

DOE PAGES

Pan, Baofei; Lau, Ka -Cheong; Vaughey, John T.; ...

2017-03-02

Here, the effect of the addition of an ionic liquid DEME•TFSI to an electrolyte solution of Mg(HMDS) 2-MgCl 2 in THF was studied electrochemically and spectroscopically. Reversible magnesium deposition/dissolution was achieved with the DEME•TFSI-modified electrolyte. This electrolyte shows higher ionic conductivity, and a linear relationship was observed between the ionic conductivity and the concentration of DEME•TFSI in THF solution of Mg(HMDS) 2-MgCl 2. Mg-Mo 6S 8 coin cells have also been successfully cycled using Mg(HMDS) 2-MgCl 2 electrolyte with the addition of DEME•TFSI. Raman and NMR spectroscopy suggest that DEME•TFSI facilitates magnesium deposition/dissolution by improving ionic conductivity of the electrolyte.

Simulating Osmotic Equilibria: A New Tool for Calculating Activity Coefficients in Concentrated Aqueous Salt Solutions.

PubMed

Bley, Michael; Duvail, Magali; Guilbaud, Philippe; Dufrêche, Jean-François

2017-10-19

Herein, a new theoretical method is presented for predicting osmotic equilibria and activities, where a bulk liquid and its corresponding vapor phase are simulated by means of molecular dynamics using explicit polarization. Calculated time-averaged number density profiles provide the amount of evaporated molecules present in the vapor phase and consequently the vapor-phase density. The activity of the solvent and the corresponding osmotic coefficient are determined by the vapor density at different solute concentrations with respect to the reference vapor density of the pure solvent. With the extended Debye-Hückel equation for the activity coefficient along with the corresponding Gibbs-Duhem relation, the activity coefficients of the solutes are calculated by fitting the osmotic coefficients. A simple model based on the combination of Poisson processes and Maxwell-Boltzmann velocity distributions is introduced to interpret statistical phenomena observed during the simulations, which are related to evaporation and recondensation. This method is applied to aqueous dysprosium nitrate [Dy(NO 3 ) 3 ] solutions at different concentrations. The obtained densities of the liquid bulk and the osmotic and activity coefficients are in good agreement with the experimental results for concentrated and saturated solutions. Density profiles of the liquid-vapor interface at different concentrations provide detailed insight into the spatial distributions of all compounds.

Group decisions in biodiversity conservation: implications from game theory.

PubMed

Frank, David M; Sarkar, Sahotra

2010-05-27

Decision analysis and game theory have proved useful tools in various biodiversity conservation planning and modeling contexts. This paper shows how game theory may be used to inform group decisions in biodiversity conservation scenarios by modeling conflicts between stakeholders to identify Pareto-inefficient Nash equilibria. These are cases in which each agent pursuing individual self-interest leads to a worse outcome for all, relative to other feasible outcomes. Three case studies from biodiversity conservation contexts showing this feature are modeled to demonstrate how game-theoretical representation can inform group decision-making. The mathematical theory of games is used to model three biodiversity conservation scenarios with Pareto-inefficient Nash equilibria: (i) a two-agent case involving wild dogs in South Africa; (ii) a three-agent raptor and grouse conservation scenario from the United Kingdom; and (iii) an n-agent fish and coral conservation scenario from the Philippines. In each case there is reason to believe that traditional mechanism-design solutions that appeal to material incentives may be inadequate, and the game-theoretical analysis recommends a resumption of further deliberation between agents and the initiation of trust--and confidence--building measures. Game theory can and should be used as a normative tool in biodiversity conservation contexts: identifying scenarios with Pareto-inefficient Nash equilibria enables constructive action in order to achieve (closer to) optimal conservation outcomes, whether by policy solutions based on mechanism design or otherwise. However, there is mounting evidence that formal mechanism-design solutions may backfire in certain cases. Such scenarios demand a return to group deliberation and the creation of reciprocal relationships of trust.

Isoenzymes.

ERIC Educational Resources Information Center

Daugherty, N. A.

1979-01-01

The uses of isoenzyme assays are reviewed as they relate to solutions of practical problems. Emphasizes their use of diagnostic tools in medicine, specifically in cardiac profiling. Suggests that principles of isoenzyme assays readily demonstrate molecular structure, acid-base equilibria, kinetics, and electrochemistry to general chemistry…

Sorption properties of algae Spirogyra sp. and their use for determination of heavy metal ions concentrations in surface water.

PubMed

Rajfur, Małgorzata; Kłos, Andrzej; Wacławek, Maria

2010-11-01

Kinetics of heavy-metal ions sorption by alga Spirogyra sp. was evaluated experimentally in the laboratory, using both the static and the dynamic approach. The metal ions--Mn(2+), Cu(2+), Zn(2+) and Cd(2+)--were sorbed from aqueous solutions of their salts. The static experiments showed that the sorption equilibria were attained in 30 min, with 90-95% of metal ions sorbed in first 10 min of each process. The sorption equilibria were approximated with the Langmuir isotherm model. The algae sorbed each heavy metal ions proportionally to the amount of this metal ions in solution. The experiments confirmed that after 30 min of exposition to contaminated water, the concentration of heavy metal ions in the algae, which initially contained small amounts of these metal ions, increased proportionally to the concentration of metal ions in solution. The presented results can be used for elaboration of a method for classification of surface waters that complies with the legal regulations. Copyright © 2010 Elsevier B.V. All rights reserved.

Stability and bifurcation analysis of three-species predator-prey model with non-monotonic delayed predator response

NASA Astrophysics Data System (ADS)

Balilo, Aldrin T.; Collera, Juancho A.

2018-03-01

In this paper, we consider delayed three-species predator-prey model with non-monotonic functional response where two predator populations feed on a single prey population. Response function in both predator populations includes a time delay which represents the gestation period of the predator populations. We call a positive equlibrium solution of the form E*S=(x*,y*,y*) as a symmetric equilibrium. The goal of this paper is to determine the effect of the difference in gestation periods of predator populations to the local dynamics of symmetric equilibria. Our results include conditions on the existence of equilibrium solutions, and stability and bifurcations of symmetric equilibria as the gestation periods of predator populations are varied. A numerical bifurcation analysis tool is also used to illustrate our results. Stability switch occurs at a Hopf bifurcation. Moreover, a branch of stable periodic solutions, obtained using numerical continuation, emerges from the Hopf bifurcation. This shows that the predator population with longer gestation period oscillates higher than the predator population with shorter gestation period.

Hybrid reconstruction of field-reversed configurations

NASA Astrophysics Data System (ADS)

Steinhauer, Loren; TAE Team

2016-10-01

Field-reversed configurations (FRC) are poorly represented by fluid-based models and require instead an ion-distribution function. Two such populations are needed since ``core'' ions are roughly restricted to the region inside the separatrix, whereas ``periphery'' ions can escape along open field lines. The Vlasov equation governs the distribution, the general solution to which is an arbitrary function of the constants of motion (Hamiltonian, canonical angular momentum). Only a small subset of such distributions are realistic in view of collisions, which smooth the distribution, and instabilities, which reorganize the field structure. Collisions and end loss are included if the distribution is a solution to the Fokker-Planck (FP) equation. Vlasov and FP solutions are nearly identical in weakly-collisional plasmas. Numerical construction of such equilibria requires solving both Ampere's law for the magnetic flux variable and the ponderous task of a full velocity-space integration at each point. The latter can be done analytically by expressing the distribution as the superposition of simple basis elements. This procedure allows rapid reconstruction of evolving equilibria based on limited diagnostic observables in FRC experiments.

The Tautomeric Equilibria of Thio-Analogues of Nucleic Acid Bases. Part 1. 2-Thiouracil: Background, Preparation of Model Compounds, and Gas Phase Proton Affinities

DTIC Science & Technology

1989-05-11

complilmentary publication for the present paper has studied the tautomeric equilibria by infrared spectroscopy . (Scheme 2 ) 5 Preparation of Compounds...4 6 292-2940C). 14 2 -Methylthio-4- pyrimidone (6).- To 2 -thiouracil (4) (12.8 g, 0.1 mol) and NaOH (7.6 g, 0.19 mol) in 200 ml of H20-EtOH (I : 1... pyrimidone (1i).- To a solution of 5N NaOH (44 ml, 220 mmol) containing 2 -thiouracil (4) (10.0 g, 78.0 mmol) at 0 CC was added dropwise dimethyl

On the stability of a class of isothermal, magnetostatic atmospheres. [in sun

NASA Technical Reports Server (NTRS)

Webb, G. M.; Ko, C. M.

1989-01-01

The stability of a class of isothermal magnetostatic atmospheres with one ignorable coordinate corresponding to a uniform gravitational field in a plane geometry is explored. Special attention is given to the stability of nonpotential equilibria that have the same magnetic field geometry as the potential equilibrium of the solution family. It is found that equilibria in which the source currents for the potential field are buried at large distances below the photospheric base are stable. Also considered is the stability of configurations in which the source currents for the potential field are located at a finite depth below the base.

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures.

PubMed

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina; Schröder, Christian

2017-01-13

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C 2 mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood-Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed.

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 simulation study of CS2 solutions in two related ionic liquids with dications and monocations

NASA Astrophysics Data System (ADS)

Lynden-Bell, R. M.; Quitevis, E. L.

2018-05-01

Atomistic simulations of solutions of CS2 in an ionic liquid, [C8(C1im)2 ] [NTf2]2, with a divalent cation and in the corresponding ionic liquid with a monovalent cation, [C4C1im][NTf2], were carried out. The low-frequency librational density of states of the CS2 was of particular interest in view of recent optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES). Compared to the monocation ionic liquid, the maximum shifts to higher frequencies in the dication ionic liquid under ambient conditions, but was found to be significantly pressure-dependent. CS2 molecules lie above and below the plane of the imidazolium rings and found to be close to the butyl tails of the monocation. The diffusion rates and embedding energies of solvent ions and CS2 in the two ionic liquids were measured.

CO2 Responsive Imidazolium-Type Poly(Ionic Liquid) Gels.

PubMed

Zhang, Jing; Xu, Dan; Guo, Jiangna; Sun, Zhe; Qian, Wenjing; Zhang, Ye; Yan, Feng

2016-07-01

Poly(ionic liquid) (PIL) gels with CO2 stimulus responsiveness have been synthesized through the copolymerization of an imidazolium-type ionic liquid monomer with 2-(dimethyl amino) ethyl methacrylate. Upon bubbling with CO2 gas, the prepared PIL solution is converted to a transparent and stable gel, which can be turned back to the initial solution state after N2 bubbling. The reversible sol-gel phase transition behavior is proved by the reversible values of viscosity and ionic conductivity. The possible mechanism for such a reversible sol-gel phase transition is demonstrated by NMR, conductivity, and rheological measurements. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental-Theoretical Approach to the Adsorption Mechanisms for Anionic, Cationic, and Zwitterionic Surfactants at the Calcite-Water Interface.

PubMed

Durán-Álvarez, Agustín; Maldonado-Domínguez, Mauricio; González-Antonio, Oscar; Durán-Valencia, Cecilia; Romero-Ávila, Margarita; Barragán-Aroche, Fernando; López-Ramírez, Simón

2016-03-22

The adsorption of surfactants (DTAB, SDS, and CAPB) at the calcite-water interface was studied through surface zeta potential measurements and multiscale molecular dynamics. The ground-state polarization of surfactants proved to be a key factor for the observed behavior; correlation was found between adsorption and the hard or soft charge distribution of the amphiphile. SDS exhibits a steep aggregation profile, reaching saturation and showing classic ionic-surfactant behavior. In contrast, DTAB and CAPB featured diversified adsorption profiles, suggesting interplay between supramolecular aggregation and desorption from the solid surface and alleviating charge buildup at the carbonate surface when bulk concentration approaches CMC. This manifests as an adsorption profile with a fast initial step, followed by a metastable plateau and finalizing with a sharp decrease and stabilization of surface charge. Suggesting this competition of equilibria, elicited at the CaCO3 surface, this study provides atomistic insight into the adsorption mechanism for ionic surfactants on calcite, which is in accordance with experimental evidence and which is a relevant criterion for developing enhanced oil recovery processes.

Extraction of organic compounds with room temperature ionic liquids.

PubMed

Poole, Colin F; Poole, Salwa K

2010-04-16

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

On Nash Equilibrium and Evolutionarily Stable States That Are Not Characterised by the Folk Theorem

PubMed Central

Li, Jiawei; Kendall, Graham

2015-01-01

In evolutionary game theory, evolutionarily stable states are characterised by the folk theorem because exact solutions to the replicator equation are difficult to obtain. It is generally assumed that the folk theorem, which is the fundamental theory for non-cooperative games, defines all Nash equilibria in infinitely repeated games. Here, we prove that Nash equilibria that are not characterised by the folk theorem do exist. By adopting specific reactive strategies, a group of players can be better off by coordinating their actions in repeated games. We call it a type-k equilibrium when a group of k players coordinate their actions and they have no incentive to deviate from their strategies simultaneously. The existence and stability of the type-k equilibrium in general games is discussed. This study shows that the sets of Nash equilibria and evolutionarily stable states have greater cardinality than classic game theory has predicted in many repeated games. PMID:26288088

Chemistry Notes.

ERIC Educational Resources Information Center

School Science Review, 1984

1984-01-01

Presents an experiment which links mass spectrometry to gas chromatography. Also presents a simulation of iron extraction using a ZX81 computer and discussions of Fehling versus Benedict's solutions, transition metal ammine complexes, electrochemical and other chemical series, and a simple model of dynamic equilibria. (JN)

Why Isn't My Rain as Acidic as Yours?

ERIC Educational Resources Information Center

Zajicek, O. T.

1985-01-01

Discusses three topics that have been improperly applied to the acidic precipitation issue. They are: (1) use of the pH scale; (2) acidity; and (3) solution equilibria of strong and weak acids. Implications for instruction are considered. (JN)

How to Compute Labile Metal-Ligand Equilibria

ERIC Educational Resources Information Center

de Levie, Robert

2007-01-01

The different methods used for computing labile metal-ligand complexes, which are suitable for an iterative computer solution, are illustrated. The ligand function has allowed students to relegate otherwise tedious iterations to a computer, while retaining complete control over what is calculated.

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.

A family of analytic equilibrium solutions for the Grad-Shafranov equation

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

Guazzotto, L.; Freidberg, J. P.

2007-11-15

A family of exact solutions to the Grad-Shafranov equation, similar to those described by Atanasiu et al. [C. V. Atanasiu, S. Guenter, K. Lackner, and I. G. Miron, Phys. Plasmas 11, 3510 (2004)], is presented. The solution allows for finite plasma aspect ratio, elongation and triangularity, while only requiring the evaluation of a small number of well-known hypergeometric functions. Plasma current, pressure, and pressure gradients are set to zero at the plasma edge. Realistic equilibria for standard and spherical tokamaks are presented.

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

PubMed

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

2015-02-03

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

Novel double-confined polymeric ionic liquids as sorbents for solid-phase microextraction with enhanced stability and durability in high-ionic-strength solution.

PubMed

Feng, Juanjuan; Sun, Min; Xu, Lili; Wang, Shuai; Liu, Xia; Jiang, Shengxiang

2012-12-14

Because of the occurrence of ion exchange between high-ionic-strength solution and anions of polymeric ionic liquids (PILs), PILs based solid-phase microextraction (SPME) fibers were rarely used in direct immersion mode to high-salt-added samples. In this work, a novel double-confined PIL sorbent was prepared by co-polymerization of cation and anion of 1-vinyl-3-octylimidzaolium p-styrenesulfonate (VOIm(+)SS(-)). The poly(VOIm(+)-SS(-)) was chemically bonded onto functionalized stainless steel wire via surface radical chain-transfer reaction. Stability of poly(VOIm(+)-SS(-)) in high-ionic-strength solution was investigated and compared with that of poly(1-vinyl-3-octylimidzaolium benzenesulfonate) (poly(VOIm(+)BS(-))) by elemental analysis of sulfur element, and results turned out that the poly(VOIm(+)-SS(-)) was more stable. Coupled to gas chromatography (GC), the poly(VOIm(+)-SS(-)) fiber was used to extract three sorts of compounds including anilines, phenols and phthalate esters in aqueous solution. The as-established method showed good linearity, low detection limits, and acceptable repeatability. The direct immersion SPME-GC method was applied to determine the model phthalate esters in bottled mineral water. The determination results were satisfactory. Copyright © 2012 Elsevier B.V. All rights reserved.

Conductometry of electrolyte solutions

NASA Astrophysics Data System (ADS)

Safonova, Lyubov P.; Kolker, Arkadii M.

1992-09-01

A review is given of the theories of the electrical conductance of electrolyte solutions of different ionic strengths and concentrations, and of the models of ion association. An analysis is made of the methods for mathematical processing of experimental conductometric data. An account is provided of various theories describing the dependence of the limiting value of the ionic electrical conductance on the properties of the solute and solvent. The bibliography includes 115 references.

Effect of ionic strength and presence of serum on lipoplexes structure monitorized by FRET

PubMed Central

Madeira, Catarina; Loura, Luís MS; Prieto, Manuel; Fedorov, Aleksander; Aires-Barros, M Raquel

2008-01-01

Background Serum and high ionic strength solutions constitute important barriers to cationic lipid-mediated intravenous gene transfer. Preparation or incubation of lipoplexes in these media results in alteration of their biophysical properties, generally leading to a decrease in transfection efficiency. Accurate quantification of these changes is of paramount importance for the success of lipoplex-mediated gene transfer in vivo. Results In this work, a novel time-resolved fluorescence resonance energy transfer (FRET) methodology was used to monitor lipoplex structural changes in the presence of phosphate-buffered saline solution (PBS) and fetal bovine serum. 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP)/pDNA lipoplexes, prepared in high and low ionic strength solutions, are compared in terms of complexation efficiency. Lipoplexes prepared in PBS show lower complexation efficiencies when compared to lipoplexes prepared in low ionic strength buffer followed by addition of PBS. Moreover, when serum is added to the referred formulation no significant effect on the complexation efficiency was observed. In physiological saline solutions and serum, a multilamellar arrangement of the lipoplexes is maintained, with reduced spacing distances between the FRET probes, relative to those in low ionic strength medium. Conclusion The time-resolved FRET methodology described in this work allowed us to monitor stability and characterize quantitatively the structural changes (variations in interchromophore spacing distances and complexation efficiencies) undergone by DOTAP/DNA complexes in high ionic strength solutions and in presence of serum, as well as to determine the minimum amount of potentially cytotoxic cationic lipid necessary for complete coverage of DNA. This constitutes essential information regarding thoughtful design of future in vivo applications. PMID:18302788

On the thermal behavior of model Li-Li xCoO 2 systems containing ionic liquids in standard electrolyte solutions

NASA Astrophysics Data System (ADS)

Larush, L.; Borgel, V.; Markevich, E.; Haik, O.; Zinigrad, E.; Aurbach, D.; Semrau, G.; Schmidt, M.

We report herein on the possibility of using ionic liquids (ILs) as additives to conventional electrolyte solutions, based on alkyl carbonates and LiPF 6 for attenuating thermal reactions in Li battery systems. As a model, a Li-Li 0.5CoO 2 system was used. The ionic liquids chosen included cations based on derivatives of pyrrolidinium and imidazolium, and the anions bioxalato borate (C 4O 8B -, BOB), (CH 3SO 2) 2N - (TFSI), and PF 3(C 2S 5) 3 - (FAP). The thermal behavior of solutions alone, solutions with Li metal, Li 0.5CoO 2 and Li metal + Li 0.5CoO 2 was studied. It was found that the presence of 10% of ILs, with derivatives of pyrrolidinium cations and FAP or TFSI anions in standard EC-DMC/LiPF 6 solutions, improves considerably the thermal stability of Li 0.5CoO 2 in electrolyte solutions. The onset temperatures of the thermal reactions of Li 0.5CoO 2 with solution species are higher and their heat evolution is considerably lower, when they contain these ionic liquids as additives. This finding opens the door for further studies and optimization of the use of selected ILs as additives that may improve the safety features of Li-ion batteries.

A coordinate free description of magnetohydrostatic equilibria

NASA Technical Reports Server (NTRS)

Martens, P. C. H.

1986-01-01

The question what geometrical restrictions are imposed on static magnetic fields by the magnetohydrostatic (MHS) equation is addressed. The general mathematical problem is therefore to determine the solutions of the MHS equations in the corona subject to an arbitrary normal component of the magnetic field at the boundary and arbitrary connectivity. What constraints the MHS equations impose on the geometry of the solutions, expressed in metric tensors, will be determined.

Metal biosorption equilibria in a ternary system

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

Chong, K.H.; Volesky, B.

Equilibrium metal uptake performance of a biosorbent prepared from Ascophyllum nodosum seaweed biomass was studied using aqueous solutions containing copper, cadmium, and zinc ions in binary and ternary mixtures. Triangular equilibrium diagrams can graphically represent all the ternary equilibrium sorption data. Application of the multicomponent Langmuir model to describe the three-metal system revealed its nonideal characteristics, whereby the value of apparent dissociation constants for the respective metals differed for each system. This restricted the prediction of the ternary equilibria from the binary systems. However, some predictions of the ternary system behavior from the model were consistent with experimental data andmore » with conclusions postulated from the three possible binary subsystems.« less

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

Organosilica Membrane with Ionic Liquid Properties for Separation of Toluene/H₂ Mixture.

PubMed

Hirota, Yuichiro; Maeda, Yohei; Yamamoto, Yusuke; Miyamoto, Manabu; Nishiyama, Norikazu

2017-08-03

In this study, we present a new concept in chemically stabilized ionic liquid membranes: an ionic liquid organosilica (ILOS) membrane, which is an organosilica membrane with ionic liquid-like properties. A silylated ionic liquid was used as a precursor for synthesis. The permselectivity, permeation mechanism, and stability of the membrane in the H₂/toluene binary system were then compared with a supported ionic liquid membrane. The membrane showed a superior separation factor of toluene/H₂ (>17,000) in a binary mixture system based on a solution-diffusion mechanism with improved durability over the supported ionic liquid membrane.

Application of ionic liquids based enzyme-assisted extraction of chlorogenic acid from Eucommia ulmoides leaves.

PubMed

Liu, Tingting; Sui, Xiaoyu; Li, Li; Zhang, Jie; Liang, Xin; Li, Wenjing; Zhang, Honglian; Fu, Shuang

2016-01-15

A new approach for ionic liquid based enzyme-assisted extraction (ILEAE) of chlorogenic acid (CGA) from Eucommia ulmoides is presented in which enzyme pretreatment was used in ionic liquids aqueous media to enhance extraction yield. For this purpose, the solubility of CGA and the activity of cellulase were investigated in eight 1-alkyl-3-methylimidazolium ionic liquids. Cellulase in 0.5 M [C6mim]Br aqueous solution was found to provide better performance in extraction. The factors of ILEAE procedures including extraction time, extraction phase pH, extraction temperatures and enzyme concentrations were investigated. Moreover, the novel developed approach offered advantages in term of yield and efficiency compared with other conventional extraction techniques. Scanning electronic microscopy of plant samples indicated that cellulase treated cell wall in ionic liquid solution was subjected to extract, which led to more efficient extraction by reducing mass transfer barrier. The proposed ILEAE method would develope a continuous process for enzyme-assisted extraction including enzyme incubation and solvent extraction process. In this research, we propose a novel view for enzyme-assisted extraction of plant active component, besides concentrating on enzyme facilitated cell wall degradation, focusing on improvement of bad permeability of ionic liquids solutions. Copyright © 2015 Elsevier B.V. All rights reserved.

Student Conceptions of Ionic Compounds in Solution and the Influences of Sociochemical Norms on Individual Learning

ERIC Educational Resources Information Center

Warfa, Abdi-Rizak M.

2013-01-01

Using the symbolic interactionist perspective that meaning is constituted as individuals interact with one another, this study examined how group thinking during cooperative inquiry-based activity on chemical bonding theories shaped and influenced college students' understanding of the properties of ionic compounds in solution. The analysis…

Aligned Carbon Nanotubes for Highly Efficient Energy Generation and Storage Devices

DTIC Science & Technology

2012-01-24

solution processing methods, including filtration, solution-casting, electrophoretic deposition, and Langmuir - Blodgett deposition. However, most...supercapacitors with environmentally friendly ionic liquid electrolytes. These new nanocomposite electrodes consist of the high-surface-area activated...carbons, carbon nanotubes, and ionic liquids as the integrated constituent components. The resultant composites show significantly improved charge

CHLORIDEDETERMINATION IN HIGH IONIC STRENGTH SOLUTION OF AMMONIUM ACETATE USING NEGATIVE ION ELECTRON SPRAY IONIZATION (HPLC/MS)

EPA Science Inventory

A precise ion chromatography method has been developed for the determination of chloride in high ionic strength ammonium acetate solutions (10-5 M-5 M) using sodium carbonate/sodium bicarbonate as eluent. Negative ion electrospray ionization (ESI) mass spectrometry was used for q...

Computational analysis of the solvation of coffee ingredients in aqueous ionic liquid mixtures† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6ra24736a Click here for additional data file.

PubMed Central

Zeindlhofer, Veronika; Khlan, Diana; Bica, Katharina

2017-01-01

In this paper, we investigate the solvation of coffee ingredients including caffeine, gallic acid as representative for phenolic compounds and quercetin as representative for flavonoids in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate [C2mim][OAc] at various concentrations. Due to the anisotropy of the solutes we show that classical Kirkwood–Buff theory is not appropriate to study solvation effects with increasing ionic liquid content. However, excess coordination numbers as well as the mean residence time of solvent molecules at the surface of the solutes can be determined by Voronoi tessellation. Since the volume of the hydration shells is also available by this method, solvation free energies will be discussed as a function of the ionic liquid concentration to yield a physical meaningful picture of solvation for the anisotropic solutes. Hydrogen bonding capabilities of the solutes and their relevance for experimental extraction yields from spent coffee grounds are also discussed. PMID:28496974

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

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

Kavun, V. Ya., E-mail: kavun@ich.dvo.ru; Uvarov, N.F.; Slobodyuk, A.B.

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K,more » these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.« less

Unique role of ionic liquid [bmin][BF 4] during curcumin-surfactant association and micellization of cationic, anionic and non-ionic surfactant solutions

NASA Astrophysics Data System (ADS)

Patra, Digambara; Barakat, Christelle

2011-09-01

Hydrophilic ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroburate, modified the properties of aqueous surfactant solutions associated with curcumin. Because of potential pharmaceutical applications as an antioxidant, anti-inflammatory and anti-carcinogenic agent, curcumin has received ample attention as potential drug. The interaction of curcumin with various charged aqueous surfactant solutions showed it exists in deprotonated enol form in surfactant solutions. The nitro and hydroxyl groups of o-nitrophenol interact with the carbonyl and hydroxyl groups of the enol form of curcumin by forming ground state complex through hydrogen bonds and offered interesting information about the nature of the interactions between the aqueous surfactant solutions and curcumin depending on charge of head group of the surfactant. IL[bmin][BF 4] encouraged early formation of micelle in case of cationic and anionic aqueous surfactant solutions, but slightly prolonged micelle formation in the case of neutral aqueous surfactant solution. However, for curcumin IL [bmin][BF 4] favored strong association (7-fold increase) with neutral surfactant solution, marginally supported association with anionic surfactant solution and discouraged (˜2-fold decrease) association with cationic surfactant solution.

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

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

PubMed

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

2017-04-01

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

Polyelectrolyte multilayer assembly as a function of pH and ionic strength using the polysaccharides chitosan and heparin.

PubMed

Boddohi, Soheil; Killingsworth, Christopher E; Kipper, Matt J

2008-07-01

The goal of this work is to explore the effects of solution ionic strength and pH on polyelectrolyte multilayer (PEM) assembly, using biologically derived polysaccharides as the polyelectrolytes. We used the layer-by-layer (LBL) technique to assemble PEM of the polysaccharides heparin (a strong polyanion) and chitosan (a weak polycation) and characterized the sensitivity of the PEM composition and layer thickness to changes in processing parameters. Fourier-transform surface plasmon resonance (FT-SPR) and spectroscopic ellipsometry provided in situ and ex situ measurements of the PEM thickness, respectively. Vibrational spectroscopy and X-ray photoelectron spectroscopy (XPS) provided details of the chemistry (i.e., composition, electrostatic interactions) of the PEM. We found that when PEM were assembled from 0.2 M buffer, the PEM thickness could be increased from less than 2 nm per bilayer to greater than 4 nm per bilayer by changing the solution pH; higher and lower ionic strength buffer solutions resulted in narrower ranges of accessible thickness. Molar composition of the PEM was not very sensitive to solution pH or ionic strength, but pH did affect the interactions between the sulfonates in heparin and amines in chitosan when PEM were assembled from 0.2 M buffer. Changes in the PEM thickness with pH and ionic strength can be interpreted through descriptions of the charge density and conformation of the polyelectrolyte chains in solution.

Transport and remobilization of multi-walled carbon nanotubes in porous media during dynamic saturation change

NASA Astrophysics Data System (ADS)

Sharma, P.

2012-04-01

Nanotechnology is one of the most important technologies in this century and it is evoking a new industrial revolution. Carbon nanotubes (CNTs) are important engineered nanoparticles with unique and beneficial properties. As a result, CNT has been used in a wide range of commercial products including electronics, optical devices and drug delivery leading to their disposal in the natural environment. Literature studies have investigated the mobility of CNTs in saturated porous media under differing physical and chemical conditions. However CNT transport in temporarily changing porous media water content has not been investigated thus far (a common scenario with rainfall/infiltration events in the vadose zone). This study investigated the mobilization of multi-walled CNTs (MCNTs) in repeated wetting and drying cycles with varying flow rates and ionic strength of the inflow solution. Imbibition-drainage-imbibition cycle experiments suggest that MCNTs mobilization increased with increase in flow rates. MCNTs mobilization occurred only with first imbibition events at low ionic strengths however less mobilization happened for higher ionic strength inflow solution in the first imbibition cycle and additional MCNTs were found in the outflow solution in second imbibition cycle, using low ionic strength solution. This observation was likely due to the attachment force between MCNTs and sand surface. Most of the MCNT mobilization occurred during liquid-gas interface movement with less chance of MCNTs to jump the energy barrier at higher ionic strength solution. As a result, less detachment of MCNTs occurred from the sand surface during drainage.

Untangling the Diverse Interior and Multiple Exterior Guest Interactions of a Supramolecular Host by the Simultaneous Analysis of Complementary Observables.

PubMed

Sgarlata, Carmelo; Raymond, Kenneth N

2016-07-05

The entropic and enthalpic driving forces for encapsulation versus sequential exterior guest binding to the [Ga4L6](12-) supramolecular host in solution are very different, which significantly complicates the determination of these thermodynamic parameters. The simultaneous use of complementary techniques, such as NMR, UV-vis, and isothermal titration calorimetry, enables the disentanglement of such multiple host-guest interactions. Indeed, data collected by each technique measure different components of the host-guest equilibria and together provide a complete picture of the solution thermodynamics. Unfortunately, commercially available programs do not allow for global analysis of different physical observables. We thus resorted to a novel procedure for the simultaneous refinement of multiple parameters (ΔG°, ΔH°, and ΔS°) by treating different observables through a weighted nonlinear least-squares analysis of a constrained model. The refinement procedure is discussed for the multiple binding of the Et4N(+) guest, but it is broadly applicable to the deconvolution of other intricate host-guest equilibria.

Multidimensional equilibria and their stability in copolymer-solvent mixtures

NASA Astrophysics Data System (ADS)

Glasner, Karl; Orizaga, Saulo

2018-06-01

This paper discusses localized equilibria which arise in copolymer-solvent mixtures. A free boundary problem associated with the sharp-interface limit of a density functional model is used to identify both lamellar and concentric domain patterns composed of a finite number of layers. Stability of these morphologies is studied through explicit linearization of the free boundary evolution. For the multilayered lamellar configuration, transverse instability is observed for sufficiently small dimensionless interfacial energies. Additionally, a crossover between small and large wavelength instabilities is observed depending on whether solvent-polymer or monomer-monomer interfacial energy is dominant. Concentric domain patterns resembling multilayered micelles and vesicles exhibit bifurcations wherein they only exist for sufficiently small dimensionless interfacial energies. The bifurcation of large radii vesicle solutions is studied analytically, and a crossover from a supercritical case with only one solution branch to a subcritical case with two is observed. Linearized stability of these configurations shows that azimuthal perturbation may lead to instabilities as interfacial energy is decreased.

Calculating Pressure-Driven Current Near Magnetic Islands for 3D MHD Equilibria

NASA Astrophysics Data System (ADS)

Radhakrishnan, Dhanush; Reiman, Allan

2016-10-01

In general, 3D MHD equilibria in toroidal plasmas do not result in nested pressure surfaces. Instead, islands and chaotic regions appear in the equilibrium. Near small magnetic islands, the pressure varies within the flux surfaces, which has a significant effect on the pressure-driven current, introducing singularities. Previously, the MHD equilibrium current near a magnetic island was calculated, including the effect of ``stellarator symmetry,'' wherein the singular components of the pressure-driven current vanish [A. H. Reiman, Phys. Plasmas 23, 072502 (2016)]. Here we first solve for pressure in a cylindrical plasma from the heat diffusion equation, after adding a helical perturbation. We then numerically calculate the corresponding Pfirsch-Schluter current. At the small island limit, we compare the pressure-driven current with the previously calculated solution, and far from the island, we recover the solution for nested flux surfaces. Lastly, we compute the current for a toroidal plasma for symmetric and non-symmetric geometries.

Benzimidazole acrylonitriles as multifunctional push-pull chromophores: Spectral characterisation, protonation equilibria and nanoaggregation in aqueous solutions

NASA Astrophysics Data System (ADS)

Horak, Ema; Vianello, Robert; Hranjec, Marijana; Krištafor, Svjetlana; Zamola, Grace Karminski; Steinberg, Ivana Murković

2017-05-01

Heterocyclic donor-π-acceptor molecular systems based on an N,N-dimethylamino phenylacrylonitrile benzimidazole skeleton have been characterised and are proposed for potential use in sensing applications. The benzimidazole moiety introduces a broad spectrum of useful multifunctional properties to the system including electron accepting ability, pH sensitivity and compatibility with biomolecules. The photophysical characterisation of the prototropic forms of these chromophores has been carried out in both solution and on immobilisation in polymer films. The experimental results are further supported by computational determination of pKa values. It is noticed that compound 3 forms nanoaggregates in aqueous solutions with aggregation-induced emission (AIE) at 600 nm. All the systems demonstrate spectral pH sensitivity in acidic media which shifts towards near-neutral values upon immobilisation in polymer films or upon aggregation in an aqueous environment (compound 3). The structure-property relationships of these functional chromophores, involving their spectral characteristics, acid-base equilibria, pKa values and aggregation effects have been determined. Potential applications of the molecules as pH and biomolecular sensors are proposed based on their pH sensitivity and AIE properties.

Equilibrium swelling properties of polyampholytic hydrogels

NASA Astrophysics Data System (ADS)

English, Anthony E.; Mafé, Salvador; Manzanares, José A.; Yu, Xiahong; Grosberg, Alexander Yu.; Tanaka, Toyoichi

1996-06-01

The role of counter ions and ion dissociation in establishing the equilibrium swelling of balanced and unbalanced polyampholytic hydrogels has been investigated experimentally and theoretically. The swelling dependence on both the net charge offset and the external bath salt concentration has been examined using an acrylamide based polyampholytic hydrogels. By careful consideration of the swelling kinetics, we illustrate the effects of ion dissociation equilibria and counter ion shielding in polyampholytic hydrogels near their balance point where both polyelectrolyte and polyampholyte effects are present. The theory considers a Flory type swelling model where the Coulombic interactions between fixed ions in the hydrogel resemble those of an ionic solid with a Debye screening factor. Theoretical predictions from this model are in qualitative agreement with our experimental results.

Rotational diffusion of nonpolar and ionic solutes in 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides: is solute rotation always influenced by the length of the alkyl chain on the imidazolium cation?

PubMed

Gangamallaiah, V; Dutt, G B

2012-10-25

In an attempt to find out whether the length of the alkyl chain on the imidazolium cation has a bearing on solute rotation, temperature-dependent fluorescence anisotropies of three structurally similar solutes have been measured in a series of 1-alkyl-3-methylimidazolium (alkyl = methyl, ethyl, propyl, butyl, and hexyl) bis(trifluoromethylsulfonyl)imides. Solute-solvent coupling constants obtained from the experimentally measured reorientation times with the aid of Stokes-Einstein-Debye hydrodynamic theory indicate that there is no influence of the length of the alkyl chain on the rotation of nonpolar, anionic, and cationic solutes 9-phenylanthracene (9-PA), fluorescein (FL), and rhodamine 110 (R110), respectively. It has also been noticed that the rotational diffusion of 9-PA is closer to the predictions of slip hydrodynamics, whereas the rotation of negatively charged FL and positively charged R110 is almost identical and follows stick hydrodynamics in these ionic liquids. Despite having similar shape and size, ionic solutes rotate slower by a factor of 3-4 compared to the nonpolar solute. Interplay of specific and electrostatic interactions between FL and the imidazolium cation of the ionic liquids, and between R110 and the bis(trifluoromethylsulfonyl)imide anion, appear to be responsible for the observed behavior. These results are an indication that the length of the alkyl chain on the imidazolium cation does not alter their physical properties in a manner that has an effect on solute rotation.

Particle paths and phase plane for time-dependent similarity solutions of the one-dimensional Vlasov-Maxwell equations

NASA Technical Reports Server (NTRS)

Roberts, Dana Aaron; Abraham-Shrauner, Barbara

1987-01-01

The phase trajectories of particles in a plasma described by the one-dimensional Vlasov-Maxwell equations are determined qualitatively, analyzing exact general similarity solutions for the cases of temporally damped and growing (sinusoidal or localized) electric fields. The results of numerical integration in both untransformed and Lie-group point-transformed coordinates are presented in extensive graphs and characterized in detail. The implications of the present analysis for the stability of BGK equilibria are explored, and the existence of nonlinear solutions arbitrarily close to and significantly different from the BGK solutions is demonstrated.

Synthesis and reactivity of TADDOL-based chiral Fe(II) PNP pincer complexes-solution equilibria between κ(2)P,N- and κ(3)P,N,P-bound PNP pincer ligands.

PubMed

Holzhacker, Christian; Stöger, Berthold; Carvalho, Maria Deus; Ferreira, Liliana P; Pittenauer, Ernst; Allmaier, Günter; Veiros, Luis F; Realista, Sara; Gil, Adrià; Calhorda, Maria José; Müller, Danny; Kirchner, Karl

2015-08-07

Treatment of anhydrous FeX2 (X = Cl, Br) with 1 equiv. of the asymmetric chiral PNP pincer ligands PNP-R,TAD (R = iPr, tBu) with an R,R-TADDOL (TAD) moiety afforded complexes of the general formula [Fe(PNP)X2]. In the solid state these complexes adopt a tetrahedral geometry with the PNP ligand coordinated in κ(2)P,N-fashion, as shown by X-ray crystallography and Mössbauer spectroscopy. Magnetization studies led to a magnetic moment very close to 4.9μB reflecting the expected four unpaired d-electrons (quintet ground state). In solution there are equilibria between [Fe(κ(3)P,N,P-PNP-R,TAD)X2] and [Fe(κ(2)P,N-PNP-R,TAD)X2] complexes, i.e., the PNP-R,TAD ligand is hemilabile. At -50 °C these equilibria are slow and signals of the non-coordinated P-TAD arm of the κ(2)P,N-PNP-R,TAD ligand can be detected by (31)P{(1)H} NMR spectroscopy. Addition of BH3 to a solution of [Fe(PNP-iPr,TAD)Cl2] leads to selective boronation of the pendant P-TAD arm shifting the equilibrium towards the four-coordinate complex [Fe(κ(2)P,N-PNP-iPr,TAD(BH3))Cl2]. DFT calculations corroborate the existence of equilibria between four- and five-coordinated complexes. Addition of CO to [Fe(PNP-iPr,TAD)X2] in solution yields the diamagnetic octahedral complexes trans-[Fe(κ(3)P,N,P-PNP-iPr,TAD)(CO)X2], which react further with Ag(+) salts in the presence of CO to give the cationic complexes trans-[Fe(κ(3)P,N,P-PNP-iPr,TAD)(CO)2X](+). CO addition most likely takes place at the five coordinate complex [Fe(κ(3)P,N,P-PNP-iPr,TAD)X2]. The mechanism for the CO addition was also investigated by DFT and the most favorable path obtained corresponds to the rearrangement of the pincer ligand first from a κ(2)P,N- to a κ(3)P,N,P-coordination mode followed by CO coordination to [Fe(κ(3)P,N,P-PNP-iPr,TAD)X2]. Complexes bearing tBu substituents do not react with CO. Moreover, in the solid state none of the tetrahedral complexes are able to bind CO.

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

PubMed

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

2011-03-14

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

Methods for applying microchannels to separate methane using liquid absorbents, especially ionic liquid absorbents from a mixture comprising methane and nitrogen

DOEpatents

Tonkovich, Anna Lee Y [Dublin, OH; Litt, Robert D [Westerville, OH; Dongming, Qiu [Dublin, OH; Silva, Laura J [Plain City, OH; Lamont, Micheal Jay [Plain City, OH; Fanelli, Maddalena [Plain City, OH; Simmons, Wayne W [Plain city, OH; Perry, Steven [Galloway, OH

2011-10-04

Methods of using microchannel separation systems including absorbents to improve thermal efficiency and reduce parasitic power loss. Energy is typically added to desorb methane and then energy or heat is removed to absorb methane using a working solution. The working solution or absorbent may comprise an ionic liquid, or other fluids that demonstrate a difference in affinity between methane and nitrogen in a solution.

Simultaneous extraction and HPLC determination of 3-indole butyric acid and 3-indole acetic acid in pea plant by using ionic liquid-modified silica as sorbent.

PubMed

Sheikhian, Leila; Bina, Sedigheh

2016-01-15

In this study, ionic liquid-modified silica was used as sorbent for simultaneous extraction and preconcentration of 3-indole butyric acid and 3-indole acetic acid in pea plants. The effect of some parameters such as pH and ionic strength of sample solution, amount of sorbent, flow rate of aqueous sample solution and eluent solution, concentration of eluent solution, and temperature were studied for each hormone solution. Percent extraction of 3-indole butyric acid and 3-indole acetic acid was strongly affected by pH of aqueous sample solution. Ionic strength of aqueous phase and temperature showed no serious effects on extraction efficiency of studied plant hormones. Obtained breakthrough volume was 200mL for each of studied hormones. Preconcentration factor for spectroscopic and chromatographic determination of studied hormones was 100 and 4.0×10(3) respectively. Each solid sorbent phase was reusable for almost 10 times of extraction/stripping procedure. Relative standard deviations of extraction/stripping processes of 3-indole butyric acid and 3-indole acetic acid were 2.79% and 3.66% respectively. The calculated limit of detections for IBA and IAA were 9.1×10(-2)mgL(-1) and 1.6×10(-1)mgL(-1) respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Existence and exponential stability of traveling waves for delayed reaction-diffusion systems

NASA Astrophysics Data System (ADS)

Hsu, Cheng-Hsiung; Yang, Tzi-Sheng; Yu, Zhixian

2018-03-01

The purpose of this work is to investigate the existence and exponential stability of traveling wave solutions for general delayed multi-component reaction-diffusion systems. Following the monotone iteration scheme via an explicit construction of a pair of upper and lower solutions, we first obtain the existence of monostable traveling wave solutions connecting two different equilibria. Then, applying the techniques of weighted energy method and comparison principle, we show that all solutions of the Cauchy problem for the considered systems converge exponentially to traveling wave solutions provided that the initial perturbations around the traveling wave fronts belong to a suitable weighted Sobolev space.

Effect of Ionic Strength and Surface Charge Density on the Kinetics of Cellulose Nanocrystal Thin Film Swelling.

PubMed

Reid, Michael S; Kedzior, Stephanie A; Villalobos, Marco; Cranston, Emily D

2017-08-01

This work explores cellulose nanocrystal (CNC) thin films (<50 nm) and particle-particle interactions by investigating film swelling in aqueous solutions with varying ionic strength (1-100 mM). CNC film hydration was monitored in situ via surface plasmon resonance, and the kinetics of liquid uptake were quantified. The contribution of electrostatic double-layer forces to film swelling was elucidated by using CNCs with different surface charges (anionic sulfate half ester groups, high and low surface charge density, and cationic trimethylammonium groups). Total water uptake in the thin films was found to be independent of ionic strength and surface chemistry, suggesting that in the aggregated state van der Waals forces dominate over double-layer forces to hold the films together. However, the rate of swelling varied significantly. The water uptake followed Fickian behavior, and the measured diffusion constants decreased with the ionic strength gradient between the film and the solution. This work highlights that nanoparticle interactions and dispersion are highly dependent on the state of particle aggregation and that the rate of water uptake in aggregates and thin films can be tailored based on surface chemistry and solution ionic strength.

DNA surface hybridization regimes

PubMed Central

Gong, Ping; Levicky, Rastislav

2008-01-01

Surface hybridization reactions, in which sequence-specific recognition occurs between immobilized and solution nucleic acids, are routinely carried out to quantify and interpret genomic information. Although hybridization is fairly well understood in bulk solution, the greater complexity of an interfacial environment presents new challenges to a fundamental understanding, and hence application, of these assays. At a surface, molecular interactions are amplified by the two-dimensional nature of the immobilized layer, which focuses the nucleic acid charge and concentration to levels not encountered in solution, and which impacts the hybridization behavior in unique ways. This study finds that, at low ionic strengths, an electrostatic balance between the concentration of immobilized oligonucleotide charge and solution ionic strength governs the onset of hybridization. As ionic strength increases, the importance of electrostatics diminishes and the hybridization behavior becomes more complex. Suppression of hybridization affinity constants relative to solution values, and their weakened dependence on the concentration of DNA counterions, indicate that the immobilized strands form complexes that compete with hybridization to analyte strands. Moreover, an unusual regime is observed in which the surface coverage of immobilized oligonucleotides does not significantly influence the hybridization behavior, despite physical closeness and hence compulsory interactions between sites. These results are interpreted and summarized in a diagram of hybridization regimes that maps specific behaviors to experimental ranges of ionic strength and probe coverage. PMID:18381819

Development of an automated experimental setup for the study of ionic-exchange kinetics. Application to the ionic adsorption, equilibrium attainment and dissolution of apatite compounds.

PubMed

Thomann, J M; Gasser, P; Bres, E F; Voegel, J C; Gramain, P

1990-02-01

An ion-selective electrode and microcomputer-based experimental setup for the study of ionic-exchange kinetics between a powdered solid and the solution is described. The equipment is composed of easily available commercial devices and a data acquisition and regularization computer program is presented. The system, especially developed to investigate the ionic adsorption, equilibrium attainment and dissolution of hard mineralized tissues, provides good reliable results by taking into account the volume changes of the reacting solution and the electrode behaviour under different experimental conditions, and by avoiding carbonation of the solution. A second computer program, using the regularized data and the experimental parameters, calculates the quantities of protons consumed and calcium released in the case of equilibrium attainment and dissolution of apatite-like compounds. Finally, typical examples of ion-exchange and dissolution kinetics under constant pH of enamel and synthetic hydroxyapatite are examined.

The solvation structures of cellulose microfibrils in ionic liquids.

PubMed

Mostofian, Barmak; Smith, Jeremy C; Cheng, Xiaolin

2011-12-01

The use of ionic liquids for non-derivatized cellulose dissolution promises an alternative method for the thermochemical pretreatment of biomass that may be more efficient and environmentally acceptable than more conventional techniques in aqueous solution. Here, we performed equilibrium MD simulations of a cellulose microfibril in the ionic liquid 1-butyl-3-methylimidazolium chloride (BmimCl) and compared the solute structure and the solute-solvent interactions at the interface with those from corresponding simulations in water. The results indicate a higher occurrence of solvent-exposed orientations of cellulose surface hydroxymethyl groups in BmimCl than in water. Moreover, spatial and radial distribution functions indicate that hydrophilic surfaces are a preferred site of interaction between cellulose and the ionic liquid. In particular, hydroxymethyl groups on the hydrophilic fiber surface adopt a different conformation from their counterparts oriented towards the fiber's core. Furthermore, the glucose units with these solvent-oriented hydroxymethyls are surrounded by the heterocyclic organic cation in a preferred parallel orientation, suggesting a direct and distinct interaction scheme between cellulose and BmimCl.

Effects of ionic concentration gradient on electroosmotic flow mixing in a microchannel.

PubMed

Peng, Ran; Li, Dongqing

2015-02-15

Effects of ionic concentration gradient on electroosmotic flow (EOF) mixing of one stream of a high concentration electrolyte solution with a stream of a low concentration electrolyte solution in a microchannel are investigated numerically. The concentration field, flow field and electric field are strongly coupled via concentration dependent zeta potential, dielectric constant and electric conductivity. The results show that the electric field and the flow velocity are non-uniform when the concentration dependence of these parameters is taken into consideration. It is also found that when the ionic concentration of the electrolyte solution is higher than 1M, the electrolyte solution essentially cannot enter the channel due to the extremely low electroosmotic flow mobility. The effects of the concentration dependence of zeta potential, dielectric constant and electric conductivity on electroosmotic flow mixing are studied. Copyright © 2014 Elsevier Inc. All rights reserved.

Phase equilibria in a system of aqueous arginine with an octane solution of sulfonic acid

NASA Astrophysics Data System (ADS)

Kuvaeva, Z. I.; Koval'chuk, I. V.; Vodop'yanova, L. A.; Soldatov, V. S.

2013-05-01

The extraction of arginine (Arg) from aqueous salt (0.1 M NaCl) solutions with a sulfo extractant in a wide range of pH values and amino acid concentrations was studied. The 0.1 M solution of dinonylnaphthalenesulfonic acid (HD) in octane was used as an extractant. The degree of extraction was found to be high at pH 0.8-9.0. This can be explained by the effect of additional intermolecular interactions in the extractant phase involving the guanidine group of Arg.

Understanding and modulating opalescence and viscosity in a monoclonal antibody formulation

PubMed Central

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

2014-01-01

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

Hydration thermodynamics of the SWy-1 montmorillonite saturated with alkali and alkaline-earth cations: A predictive model

NASA Astrophysics Data System (ADS)

Vieillard, Philippe; Blanc, Philippe; Fialips, Claire I.; Gailhanou, Hélène; Gaboreau, Stéphane

2011-10-01

The aim of the present work was to study the thermodynamic equilibria between water and a homo-ionic montmorillonite SWy-1 saturated by different cations. The choice of this smectite is justified by the large set of experimental data available from the literature for eight different interlayer cations: Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, Sr 2+, and Ba 2+. In particular, studies by Cases et al. (1992, 1997) and Bérend et al. (1995) are providing heat of adsorption data, pairs of desorption-adsorption isotherms, and information about the partition of adsorption-desorption water molecules between external surfaces and internal spaces. By calculating the effective amount of hydration water as the difference between the so-called gravimetric water and the surface covering water, a thermodynamic model was then developed, based on the concept of Ransom and Helgeson (1994) considering an asymmetric subregular binary solid solution between a fully hydrated and a anhydrous smectite. A set of six thermodynamic parameters ( ΔH∘hyd,S∘hyd and four Margules parameters) was extracted by a least square method from measurements of enthalpies of adsorption and paired adsorption-desorption isotherms for each interlayer cation. These six initial parameters were then used to determine a complete set of standard thermodynamic hydration parameters ( ΔH∘hyd,ΔG∘hyd,ΔS∘hyd, heat capacity, molar volume, and number of interlayer H 2O) and quantify, for each cation, the number of moles of hydration water molecules as a function of relative humidity and temperature. The validation of the standard state thermodynamic properties of hydration for each end member was carried out using three approaches: (1) a comparison with experimental isotherms obtained on hetero-ionic and homo-ionic SWy-1 smectite at different temperatures; (2) a comparison with the experimental integral enthalpy and entropy of hydration of the SWy-1 smectite; and (3) a comparison with experimental isotherms acquired on various smectites (Upton, MX80, Arizona) with different layer charges. Eventually, the present work demonstrates that, from a limited number of measurements, it is possible to provide the hydration thermodynamic parameters for hydrated smectites with different compositions and under different conditions of temperature and relative humidity, using the newly developed predictive model.

Can the scaling behavior of electric conductivity be used to probe the self-organizational changes in solution with respect to the ionic liquid structure? The case of [C8MIM][NTf2].

PubMed

Paluch, Marian; Wojnarowska, Zaneta; Goodrich, Peter; Jacquemin, Johan; Pionteck, Jürgen; Hensel-Bielowka, Stella

2015-08-28

Electrical conductivity of the supercooled ionic liquid [C8MIM][NTf2], determined as a function of temperature and pressure, highlights strong differences in its ionic transport behavior between low and high temperature regions. To date, the crossover effect which is very well known for low molecular van der Waals liquids has been rarely described for classical ionic liquids. This finding highlights that the thermal fluctuations could be dominant mechanisms driving the dramatic slowing down of ion motions near Tg. An alternative way to analyze separately low and high temperature dc-conductivity data using a density scaling approach was then proposed. Based on which a common value of the scaling exponent γ = 2.4 was obtained, indicating that the applied density scaling is insensitive to the crossover effect. By comparing the scaling exponent γ reported herein along with literature data for other ionic liquids, it appears that γ decreases by increasing the alkyl chain length on the 1-alkyl-3-methylimidazolium-based ionic liquids. This observation may be related to changes in the interaction between ions in solution driven by an increase in the van der Waals type interaction by increasing the alkyl chain length on the cation. This effect may be related to changes in the ionic liquid nanostructural organization with the alkyl chain length on the cation as previously reported in the literature based on molecular dynamic simulations. In other words, the calculated scaling exponent γ may be then used as a key parameter to probe the interaction and/or self-organizational changes in solution with respect to the ionic liquid structure.

Simultaneous Nanoscale Surface Charge and Topographical Mapping.

PubMed

Perry, David; Al Botros, Rehab; Momotenko, Dmitry; Kinnear, Sophie L; Unwin, Patrick R

2015-07-28

Nanopipettes are playing an increasingly prominent role in nanoscience, for sizing, sequencing, delivery, detection, and mapping interfacial properties. Herein, the question of how to best resolve topography and surface charge effects when using a nanopipette as a probe for mapping in scanning ion conductance microscopy (SICM) is addressed. It is shown that, when a bias modulated (BM) SICM scheme is used, it is possible to map the topography faithfully, while also allowing surface charge to be estimated. This is achieved by applying zero net bias between the electrode in the SICM tip and the one in bulk solution for topographical mapping, with just a small harmonic perturbation of the potential to create an AC current for tip positioning. Then, a net bias is applied, whereupon the ion conductance current becomes sensitive to surface charge. Practically this is optimally implemented in a hopping-cyclic voltammetry mode where the probe is approached at zero net bias at a series of pixels across the surface to reach a defined separation, and then a triangular potential waveform is applied and the current response is recorded. Underpinned with theoretical analysis, including finite element modeling of the DC and AC components of the ionic current flowing through the nanopipette tip, the powerful capabilities of this approach are demonstrated with the probing of interfacial acid-base equilibria and high resolution imaging of surface charge heterogeneities, simultaneously with topography, on modified substrates.

Electrospinning biopolymers from ionic liquids requires control of different solution properties than volatile organic solvents

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

Zavgorodnya, Oleksandra; Shamshina, Julia L.; Bonner, Jonathan R.

Here, we report the correlation between key solution properties and spinability of chitin from the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C 2mim][OAc]), and the similarities and differences to electrospinning solutions of non-ionic polymers in volatile organic compounds (VOCs). We found that when electrospinning is conducted from ILs, conductivity and surface tension are not the key parameters regulating spinability, while solution viscosity and polymer concentration are. Contrarily, for electrospinning of polymers from VOCs, solution conductivity and viscosity have been reported to be among some of the most important factors controlling fiber formation. For chitin electrospun from [C 2mim][OAc], we found bothmore » a critical chitin concentration required for continuous fiber formation (> 0.20 wt%) and a required viscosity for the spinning solution (between ca. 450 – 1500 cP). The high viscosities of the biopolymer-IL solutions made it possible to electrospin solutions with low, less than 1 wt% of polymer concentration and produce thin fibers without the need to adjust the electrospinning parameters. These results suggest new prospects for the control of fiber architecture in non-woven mats, which is crucial for materials performance.« less

Electrospinning biopolymers from ionic liquids requires control of different solution properties than volatile organic solvents

DOE PAGES

Zavgorodnya, Oleksandra; Shamshina, Julia L.; Bonner, Jonathan R.; ...

2017-04-27

Here, we report the correlation between key solution properties and spinability of chitin from the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([C 2mim][OAc]), and the similarities and differences to electrospinning solutions of non-ionic polymers in volatile organic compounds (VOCs). We found that when electrospinning is conducted from ILs, conductivity and surface tension are not the key parameters regulating spinability, while solution viscosity and polymer concentration are. Contrarily, for electrospinning of polymers from VOCs, solution conductivity and viscosity have been reported to be among some of the most important factors controlling fiber formation. For chitin electrospun from [C 2mim][OAc], we found bothmore » a critical chitin concentration required for continuous fiber formation (> 0.20 wt%) and a required viscosity for the spinning solution (between ca. 450 – 1500 cP). The high viscosities of the biopolymer-IL solutions made it possible to electrospin solutions with low, less than 1 wt% of polymer concentration and produce thin fibers without the need to adjust the electrospinning parameters. These results suggest new prospects for the control of fiber architecture in non-woven mats, which is crucial for materials performance.« less

Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries

DOE PAGES

Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; ...

2016-11-25

Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange currentmore » density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li 2S 8 and Li 2S 4).« less

Homogeneous Liquid–Liquid Extraction of Rare Earths with the Betaine—Betainium Bis(trifluoromethylsulfonyl)imide Ionic Liquid System

PubMed Central

Hoogerstraete, Tom Vander; Onghena, Bieke; Binnemans, Koen

2013-01-01

Several fundamental extraction parameters such as the kinetics and loading were studied for a new type of metal solvent extraction system with ionic liquids. The binary mixture of the ionic liquid betainium bis(trifluoromethylsulfonyl)imide and water shows thermomorphic behavior with an upper critical solution temperature (UCST), which can be used to avoid the slower mass transfer due to the generally higher viscosity of ionic liquids. A less viscous homogeneous phase and mixing on a molecular scale are obtained when the mixture is heated up above 55 °C. The influence of the temperature, the heating and cooling times, were studied for the extraction of neodymium(III) with betaine. A plausible and equal extraction mechanism is proposed in bis(trifluoromethylsulfonyl)imide, nitrate, and chloride media. After stripping of the metals from the ionic liquid phase, a higher recovery of the ionic liquid was obtained by salting-out of the ionic liquid fraction lost by dissolution in the aqueous phase. The change of the upper critical solution temperature by the addition of HCl or betaine was investigated. In addition, the viscosity was measured below and above the UCST as a function of the temperature. PMID:24169434

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation

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

Chopade, Sujay A.; Anderson, Evan L.; Schmidt, Peter W.

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethylmore » sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.« less

Interaction of indole-papaverine with DNA in solutions of various ionic strength

NASA Astrophysics Data System (ADS)

Travkina, V. I.; Moroshkina, E. B.; Osinnikova, D. N.

2017-11-01

Interaction of synthetic alkaloid of isoquinoline series, which is an analogue of the biologically active compound papaverine, was studied by spectral, microcalorimetric, optical and hydrodynamic methods at different ionic strengths of medium. It was found that the investigated compound may interact with DNA in various ways depending on the ratio of ligand - DNA concentrations and ionic strength of solution (μ). When μ = 0.001, indole-papaverine intercalates into the double helix of DNA. The increase of μ resulted in a decrease of the affinity of the compound to DNA and a change its binding method.

CAN FLUORIDATION AFFECT LEAD (II) IN POTABLE WATER? HEXAFLUOROSILICATE AND FLUORIDE EQUILIBRIA IN AQUEOUS SOLUTION

EPA Science Inventory

Recent reports have attempted to show that fluoridating potable water is linked to increased levels of lead(II) in the blood. We examine these claims in light of the established science and critically evaluate their significance. The completeness of hexafluorosilicate hydrolysi...

Unified Approximations: A New Approach for Monoprotic Weak Acid-Base Equilibria

ERIC Educational Resources Information Center

Pardue, Harry; Odeh, Ihab N.; Tesfai, Teweldemedhin M.

2004-01-01

The unified approximations reduce the conceptual complexity by combining solutions for a relatively large number of different situations into just two similar sets of processes. Processes used to solve problems by either the unified or classical approximations require similar degrees of understanding of the underlying chemical processes.

Influence of Hofmeister ions on the structure of proline-based peptide models: A combined experimental and molecular modeling study

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

Brohl, Andreas; Albrecht, Benjamin; Zhang, Yong

Here, the influence of three sodium salts, covering a wide range of the Hofmeister series, on the conformation of three proline-based peptide models in aqueous solution is examined using a combination of nuclear magnetic resonance spectroscopy and molecular dynamics simulations. The anions preferentially interact with the cis conformers of the peptide models, which is rationalized by the respective electrostatic potential surfaces. These preferred interactions have a strong impact on the thermodynamics of the cis/trans equilibria, leading to a higher population of the cis conformers. In distinct cases, these equilibria are nearly independent of temperature, showing that the salts are alsomore » able to stabilize the conformers over wide temperature ranges.« less

Influence of Hofmeister Ions on the Structure of Proline-Based Peptide Models: A Combined Experimental and Molecular Modeling Study.

PubMed

Bröhl, Andreas; Albrecht, Benjamin; Zhang, Yong; Maginn, Edward; Giernoth, Ralf

2017-03-09

The influence of three sodium salts, covering a wide range of the Hofmeister series, on the conformation of three proline-based peptide models in aqueous solution is examined using a combination of nuclear magnetic resonance spectroscopy and molecular dynamics simulations. The anions preferentially interact with the cis conformers of the peptide models, which is rationalized by the respective electrostatic potential surfaces. These preferred interactions have a strong impact on the thermodynamics of the cis/trans equilibria, leading to a higher population of the cis conformers. In distinct cases, these equilibria are nearly independent of temperature, showing that the salts are also able to stabilize the conformers over wide temperature ranges.

Shot noise perturbations and mean first passage times between stable states.

PubMed

Drury, Kevin L S

2007-08-01

Predicting crossings between stable states is a central issue in population biology. Crossings from low-density to high-density equilibria are often associated with pest outbreaks, while the opposite crossings are often associated with population collapse of harvested species. Here I use a simple, bistable model to demonstrate a technique for estimating mean first passage times (MFPT) of thresholds, including boundaries between stable equilibria. The approach is based on stochastic "shot-noise" perturbations to the population and the MFPTs compare favorably with mean crossing times from Monte Carlo numerical solutions of the stochastically perturbed model. This agreement suggests that MFPT approximations can be used to quantify expected effects of species manipulations, whether the goal is pest control or sustainable harvest.

Influence of Hofmeister ions on the structure of proline-based peptide models: A combined experimental and molecular modeling study

DOE PAGES

Brohl, Andreas; Albrecht, Benjamin; Zhang, Yong; ...

2017-02-13

Here, the influence of three sodium salts, covering a wide range of the Hofmeister series, on the conformation of three proline-based peptide models in aqueous solution is examined using a combination of nuclear magnetic resonance spectroscopy and molecular dynamics simulations. The anions preferentially interact with the cis conformers of the peptide models, which is rationalized by the respective electrostatic potential surfaces. These preferred interactions have a strong impact on the thermodynamics of the cis/trans equilibria, leading to a higher population of the cis conformers. In distinct cases, these equilibria are nearly independent of temperature, showing that the salts are alsomore » able to stabilize the conformers over wide temperature ranges.« less

Transport and Retention of TiO2 Rutile Nanoparticles in Saturated Porous Media: Influence of Solution pH, Ionic Strength, and the Presence of Humic Acid

EPA Science Inventory

The influence of solution pH, ionic strength, and varying concentrations of the Suwannee River Humic Acid (SRHA) on the transport of titanium dioxide (TiO2, rutile) nanoparticle aggregates (nTiO2) in saturated porous media was investigated through systematically examining the tra...

Analysis of Voltammetric Half-Wave Potentials in Low Ionic Strength Solutions and Voltammetric Measurement of Ion Impurity Concentrations

DTIC Science & Technology

1990-11-17

voltammetric response. As will be developed in this paper , the ability to observe sigmoidally shaped voltammograms requires a minimum number of solution ions...polished with I 4im diamond paste (Buehler). Similar results ,vere obtained using both methods of electrode construction. Precise values of the electrode...impurities in the bulk of the solution that can serve as an electrolyte, Cimp * We will assume for simplicity that all ionic i f11urities are 1: 1

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.

Effect of Pressure-Induced Changes in the Ionization Equilibria of Buffers on Inactivation of Escherichia coli and Staphylococcus aureus by High Hydrostatic Pressure

PubMed Central

Gayán, Elisa; Condón, Santiago; Álvarez, Ignacio; Nabakabaya, Maria

2013-01-01

Survival rates of Escherichia coli and Staphylococcus aureus after high-pressure treatment in buffers that had large or small reaction volumes (ΔV°), and which therefore underwent large or small changes in pH under pressure, were compared. At a low buffer concentration of 0.005 M, survival was, as expected, better in MOPS (morpholinepropanesulfonic acid), HEPES, and Tris, whose ΔV° values are approximately 5.0 to 7.0 cm3 mol−1, than in phosphate or dimethyl glutarate (DMG), whose ΔV° values are about −25 cm3 mol−1. However, at a concentration of 0.1 M, survival was unexpectedly better in phosphate and DMG than in MOPS, HEPES, or Tris. This was because the baroprotective effect of phosphate and DMG increased much more rapidly with increasing concentration than it did with MOPS, HEPES, or Tris. Further comparisons of survival in solutions of salts expected to cause large electrostriction effects (Na2SO4 and CaCl2) and those causing lower electrostriction (NaCl and KCl) were made. The salts with divalent ions were protective at much lower concentrations than salts with monovalent ions. Buffers and salts both protected against transient membrane disruption in E. coli, but the molar concentrations necessary for membrane protection were much lower for phosphate and Na2SO4 than for HEPES and NaCl. Possible protective mechanisms discussed include effects of electrolytes on water compressibility and kosmotropic and specific ion effects. The results of this systematic study will be of considerable practical significance in studies of pressure inactivation of microbes under defined conditions but also raise important fundamental questions regarding the mechanisms of baroprotection by ionic solutes. PMID:23624471

Kinetic Studies of Reactions in Solution Using Fast Mass Spectrometry

DTIC Science & Technology

2013-08-13

dicyanamide ionic liquids Hypergolic fuels, or hypergols, can be ignited by exposure to an oxidizing agent under ambient conditions and are a common...DCA) based ionic liquids are a less volatile alternative that are less viscous than most ionic liquids ; however, ignition of these compounds...Condensates upon Hypergolic Ignition of Dicyanamide Ionic Liquids ," Angew. Chem. Int. Ed. 50, 8634–8637 (2011). (7) R. H. Perry, D. I. Bellovin, E

Oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system up to 0.7 mol/kg ionic strength at 25 °C

USGS Publications Warehouse

Kim, Sang-Tae; Gebbinck, Christa Klein; Mucci, Alfonso; Coplen, Tyler B.

2014-01-01

To investigate the oxygen isotope systematics in the aragonite-CO2-H2O-NaCl system, witherite (BaCO3) was precipitated quasi-instantaneously and quantitatively from Na-Cl-Ba-CO2 solutions of seawater-like ionic strength (I = 0.7 mol/kg) at two pH values (~7.9 and ~10.6) at 25 °C. The oxygen isotope composition of the witherite and the dissolved inorganic carbon speciation in the starting solution were used to estimate the oxygen isotope fractionations between HCO3¯ and H2O as well as between CO3 2 and H2O. Given the analytical error on the oxygen isotope composition of the witherite and uncertainties of the parent solution pH and speciation, oxygen isotope fractionation between NaHCO3° and HCO3¯, as well as between NaCO3¯ and CO3 2, is negligible under the experimental conditions investigated. The influence of dissolved NaCl concentration on the oxygen isotope fractionation in the aragonite-CO2-H2O-NaCl system also was investigated at 25 °C. Aragonite was precipitated from Na-Cl-Ca-Mg-(B)-CO2 solutions of seawater-like ionic strength using passive CO2 degassing or constant addition methods. Based upon our new experimental observations and published experimental data from lower ionic strength solutions by Kim et al. (2007b), the equilibrium aragonite-water oxygen isotope fractionation factor is independent of the ionic strength of the parent solution up to 0.7 mol/kg. Hence, our study also suggests that the aragonite precipitation mechanism is not affected by the presence of sodium and chloride ions in the parent solution over the range of concentrations investigated.

Controlling adsorption and passivation properties of bovine serum albumin on silica surfaces by ionic strength modulation and cross-linking.

PubMed

Park, Jae Hyeon; Sut, Tun Naw; Jackman, Joshua A; Ferhan, Abdul Rahim; Yoon, Bo Kyeong; Cho, Nam-Joon

2017-03-29

Understanding the physicochemical factors that influence protein adsorption onto solid supports holds wide relevance for fundamental insights into protein structure and function as well as for applications such as surface passivation. Ionic strength is a key parameter that influences protein adsorption, although how its modulation might be utilized to prepare well-coated protein adlayers remains to be explored. Herein, we investigated how ionic strength can be utilized to control the adsorption and passivation properties of bovine serum albumin (BSA) on silica surfaces. As protein stability in solution can influence adsorption kinetics, the size distribution and secondary structure of proteins in solution were first characterized by dynamic light scattering (DLS), nanoparticle tracking analysis (NTA), and circular dichroism (CD) spectroscopy. A non-monotonic correlation between ionic strength and protein aggregation was observed and attributed to colloidal agglomeration, while the primarily α-helical character of the protein in solution was maintained in all cases. Quartz crystal microbalance-dissipation (QCM-D) experiments were then conducted in order to track protein adsorption onto silica surfaces as a function of ionic strength, and the measurement responses indicated that total protein uptake at saturation coverage is lower with increasing ionic strength. In turn, the QCM-D data and the corresponding Voigt-Voinova model analysis support that the surface area per bound protein molecule is greater with increasing ionic strength. While higher protein uptake under lower ionic strengths by itself did not result in greater surface passivation under subsequent physiologically relevant conditions, the treatment of adsorbed protein layers with a gluteraldehyde cross-linking agent stabilized the bound protein in this case and significantly improved surface passivation. Collectively, our findings demonstrate that ionic strength modulation influences BSA adsorption uptake on account of protein spreading and can be utilized in conjunction with covalent cross-linking strategies to prepare well-coated protein adlayers for improved surface passivation.

Characterization and Detection of ϵ-Berge-Zhukovskii Equilibria

PubMed Central

Lung, Rodica Ioana; Suciu, Mihai; Gaskó, Noémi; Dumitrescu, D.

2015-01-01

The Berge-Zhukovskii equilibrium is an alternate solution concept in non-cooperative game theory that formalizes cooperation in a noncooperative setting. In this paper, the ϵ-Berge-Zhukovskii equilibrium is introduced and characterized by using a generative relation. The generative relation also provides a solution to the problem of computing the ϵ-Berge-Zhukovskii equilibrium for large games, by using evolutionary algorithms. Numerical examples illustrate the approach and provide a possible application for this equilibrium concept. PMID:26177217

Ion mobility and transport properties of bismuth fluoride-containing solid solutions with tysonite-type structure

NASA Astrophysics Data System (ADS)

Kavun, V. Ya.; Uvarov, N. F.; Slobodyuk, A. B.; Merkulov, E. B.; Polyantsev, M. M.

2018-07-01

The ion mobility and conductivity of solid solutions with tysonite-type structure obtained by doping bismuth trifluoride with lead (II) fluoride, and zirconium and bismuth oxides have been studied using 19F NMR, X-ray diffraction analysis, and impedance spectroscopy. The types of ionic motions in the fluoride sublattice of the synthesized solid solutions in the temperature range 150-450 K have been determined and the energy of their activation has been estimated. Due to high ionic conductivity, above 10-2 S/cm at 570 K, these solid solutions can be considered as superionic conductors.

Sorption of phenol and alkylphenols from aqueous solution onto organically modified montmorillonite and applications of dual-mode sorption model

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

Huh, J.K.; Song, D.I.; Jeon, Y.W.

2000-01-01

Single- and multisolute competitive sorptions were carried out in a batch reactor to investigate the uptake of phenol, 4-methylphenol (MeP), 2,4-dimethylphenol (DMeP), and 4-ethylphenol (EtP) dissolved in water at 25 C onto organically modified montmorillonite. Hexadecyltrimethylammonium (HDTMA) cation was exchanged for metal cations on the montmorillonite to the extent of the cation-exchange capacity (CEC) of the montmorillonite to prepare HDTMA-montmorillonite, changing its surface property from hydrophilic to organophilic. It was observed from the experimental results that the adsorption affinity on HDTMA-montmorillonite was in the order 4-EtP {approx} 2,4-DMeP > 4-MeP > phenol. The Langmuir, dual-mode sorption (DS), and Redlich-Peterson (RP)more » models were used to analyze the single-solute sorption equilibria. The competitive Langmuir model (CLM), competitive dual-mode sorption model (CDSM), and ideal adsorbed solution theory (IAST), coupled with the single-solute models (i.e., Langmuir, DS, and RP models), were used to predict the multisolute competitive sorption equilibria. All the models considered in this work yielded favorable representations of both single- and multisolute sorption behaviors. DSM, CDSM, and IAST coupled with the DSM were found to be other satisfactory models to describe the single- and multisolute sorption of the phenolic compounds onto HDTMA-montmorillonite.« less

Miscibility and Speciation in the Water/carbon Dioxide System

NASA Astrophysics Data System (ADS)

Abramson, E.; Bollengier, O.; Brown, J. M.

2017-12-01

We have been exploring fluid-fluid solubilities and speciation in mixed systems of CO2-H2O. Fluid-fluid immiscibility extends to the highest pressures and temperatures yet explored (7 GPa, 700K). In this region, commonly used COH fluid models agree neither with the data nor among themselves. The range of immiscibility is extended by addition of NaCl, but miscibility limits determined in preliminary experiments are not as expected from extrapolation of lower pressure (<0.2 GPa) results. For majority-water systems (XCO2<0.5) an abrupt increase of solubility with pressure is linked to an observed change in speciation as CO2(aq) reacts with water. The identity of the newly formed species is, as of the writing of this abstract, unknown, but presumed to be either H2CO3 or HCO3-. A reasonable match between the observed equilibria and an application of HKF theory suggests that the new species is, indeed, HCO3-, but with a Raman frequency shifted from that found in the dilute aqueous solution. Application of HKF theory to the CO2(f)-CO2(aq) equilibrium suffers from an incompatibility of the usual formulation of the theory with known molar volumes of CO2(f) at higher pressures. On the basis of these studies we conclude that models of CO2-H2O fluids must take into account major changes in speciation, and that simple equations-of-state, of a few fitted parameters, will not afford an adequate description of such fluids. "First principles" models, tested against real data, seem more likely to yield the desired results. This statement extends as well to the calculation of the dielectric constants of these mixed fluids, the basis of ionic solution chemistry. Further, semi-empirical formulations of solution thermodynamics, which function well at pressures of kbars, ought to be re-worked for use over larger pressure ranges.

Dissecting ion-specific dielectric spectra of sodium-halide solutions into solvation water and ionic contributions.

PubMed

Rinne, Klaus F; Gekle, Stephan; Netz, Roland R

2014-12-07

Using extensive equilibrium molecular dynamics simulations we determine the dielectric spectra of aqueous solutions of NaF, NaCl, NaBr, and NaI. The ion-specific and concentration-dependent shifts of the static dielectric constants and the dielectric relaxation times match experimental results very well, which serves as a validation of the classical and non-polarizable ionic force fields used. The purely ionic contribution to the dielectric response is negligible, but determines the conductivity of the salt solutions. The ion-water cross correlation contribution is negative and reduces the total dielectric response by about 5%-10% for 1 M solutions. The dominating water dielectric response is decomposed into different water solvation shells and ion-pair configurations, by this the spectral blue shift and the dielectric decrement of salt solutions with increasing salt concentration is demonstrated to be primarily caused by first-solvation shell water. With rising salt concentration the simulated spectra show more pronounced deviations from a single-Debye form and can be well described by a Cole-Cole fit, in quantitative agreement with experiments. Our spectral decomposition into ionic and different water solvation shell contributions does not render the individual contributions more Debye-like, this suggests the non-Debye-like character of the dielectric spectra of salt solutions not to be due to the superposition of different elementary relaxation processes with different relaxation times. Rather, the non-Debye-like character is likely to be an inherent spectral signature of solvation water around ions.

Method of forming catalyst layer by single step infiltration

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

Gerdes, Kirk; Lee, Shiwoo; Dowd, Regis

Provided herein is a method for electrocatalyst infiltration of a porous substrate, of particular use for preparation of a cathode for a solid oxide fuel cell. The method generally comprises preparing an electrocatalyst infiltrate solution comprising an electrocatalyst, surfactant, chelating agent, and a solvent; pretreating a porous mixed ionic-electric conductive substrate; and applying the electrocatalyst infiltration solution to the porous mixed ionic-electric conductive substrate.

Electrodeionization method

DOEpatents

Lin, YuPo J.; Hestekin, Jamie; Arora, Michelle; St. Martin, Edward J.

2004-09-28

An electrodeionization method for continuously producing and or separating and/or concentrating ionizable organics present in dilute concentrations in an ionic solution while controlling the pH to within one to one-half pH unit method for continuously producing and or separating and/or concentrating ionizable organics present in dilute concentrations in an ionic solution while controlling the pH to within one to one-half pH unit.

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.

The Effect of Ionic Strength on the Solubility of an Electrolyte

ERIC Educational Resources Information Center

Willey, Joan D.

2004-01-01

A simple experiment was conducted for studying and demonstrating visually and dramatically the effect of ionic strength on the solubility of an electrolyte is described. It is seen that the experiment visually illustrates the effect of ionic strength on electrolyte solubility by the appearance of the two solutions and by the difference in the…

Selective and Responsive Nanopore-Filled Membranes

DTIC Science & Technology

2011-03-14

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

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

Quantifying the effect of ionic screening with protein-decorated graphene transistors

PubMed Central

Ping, Jinglei; Xi, Jin; Saven, Jeffery G.; Liu, Renyu; Charlie Johnson, A. T.

2015-01-01

Liquid-based applications of biomolecule-decorated field-effect transistors (FETs) range from biosensors to in vivo implants. A critical scientific challenge is to develop a quantitative understanding of the gating effect of charged biomolecules in ionic solution and how this influences the readout of the FETs. To address this issue, we fabricated protein-decorated graphene FETs and measured their electrical properties, specifically the shift in Dirac voltage, in solutions of varying ionic strength. We found excellent quantitative agreement with a model that accounts for both the graphene polarization charge and ionic screening of ions adsorbed on the graphene as well as charged amino acids associated with the immobilized protein. The technique and analysis presented here directly couple the charging status of bound biomolecules to readout of liquid-phase FETs fabricated with graphene or other two-dimensional materials. PMID:26626969

Accelerating Multiagent Reinforcement Learning by Equilibrium Transfer.

PubMed

Hu, Yujing; Gao, Yang; An, Bo

2015-07-01

An important approach in multiagent reinforcement learning (MARL) is equilibrium-based MARL, which adopts equilibrium solution concepts in game theory and requires agents to play equilibrium strategies at each state. However, most existing equilibrium-based MARL algorithms cannot scale due to a large number of computationally expensive equilibrium computations (e.g., computing Nash equilibria is PPAD-hard) during learning. For the first time, this paper finds that during the learning process of equilibrium-based MARL, the one-shot games corresponding to each state's successive visits often have the same or similar equilibria (for some states more than 90% of games corresponding to successive visits have similar equilibria). Inspired by this observation, this paper proposes to use equilibrium transfer to accelerate equilibrium-based MARL. The key idea of equilibrium transfer is to reuse previously computed equilibria when each agent has a small incentive to deviate. By introducing transfer loss and transfer condition, a novel framework called equilibrium transfer-based MARL is proposed. We prove that although equilibrium transfer brings transfer loss, equilibrium-based MARL algorithms can still converge to an equilibrium policy under certain assumptions. Experimental results in widely used benchmarks (e.g., grid world game, soccer game, and wall game) show that the proposed framework: 1) not only significantly accelerates equilibrium-based MARL (up to 96.7% reduction in learning time), but also achieves higher average rewards than algorithms without equilibrium transfer and 2) scales significantly better than algorithms without equilibrium transfer when the state/action space grows and the number of agents increases.

Illite equilibria in solutions: III. A re-interpretation of the data of Sass et al. (1987)

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

Aja, S.U.

1991-11-01

In a recent solubility study of Goose Lake and Beavers Bend illite, SASS et al. (1987) inferred the existence of three components of natural illites (K{sub 0.24}/O{sub 10}(OH){sub 2}), (K{sub 0.67}/O{sub 10}(OH){sub 2}), and (K{sub 0.90}/O{sub 10}(OH){sub 2}) which were interpreted to be smectite, illite, and K-mica, respectively. They also speculated that illite-smectite equilibrium is metastable under diagenetic conditions except between 90 and 110C where it is stabilized by an ordering transition. A re-interpretation of the data of SASS et al. (1987) indicates that the solubility-controlling phases have the following K atoms per half cell: 0.29, 0.52, 0.69, 0.084, andmore » 1.0. Furthermore, solution equilibration investigations of kaolinite-microcline mixtures have shown that these two minerals do not coexist stably. Thus, the question of an ordering transition whose main effect is to stabilize illite-smectite equilibria relative to kaolinite-microcline assemblage does not arise.« less

Acid-base properties of the N3 ruthenium(II) solar cell sensitizer: a combined experimental and computational analysis.

PubMed

Pizzoli, Giuliano; Lobello, Maria Grazia; Carlotti, Benedetta; Elisei, Fausto; Nazeeruddin, Mohammad K; Vitillaro, Giuseppe; De Angelis, Filippo

2012-10-14

We report a combined spectro-photometric and computational investigation of the acid-base equilibria of the N3 solar cell sensitizer [Ru(dcbpyH(2))(2)(NCS)(2)] (dcbpyH(2) = 4,4'-dicarboxyl-2,2' bipyridine) in aqueous/ethanol solutions. The absorption spectra of N3 recorded at various pH values were analyzed by Single Value Decomposition techniques, followed by Global Fitting procedures, allowing us to identify four separate acid-base equilibria and their corresponding ground state pK(a) values. DFT/TDDFT calculations were performed for the N3 dye in solution, investigating the possible relevant species obtained by sequential deprotonation of the four dye carboxylic groups. TDDFT excited state calculations provided UV-vis absorption spectra which nicely agree with the experimental spectral shapes at various pH values. The calculated pK(a) values are also in good agreement with experimental data, within <1 pK(a) unit. Based on the calculated energy differences a tentative assignment of the N3 deprotonation pathway is reported.

Thermoresponsive light scattering device utilizing surface behavior effects between polyimide and an ionic liquid-water mixture exhibiting lower critical solution temperature (LCST)-type phase separation

NASA Astrophysics Data System (ADS)

Goda, Kazuya; Takatoh, Kohki; Funasako, Yusuke; Inokuchi, Makoto

2018-06-01

We proposed a thermoresponsive light scattering device that utilizes the surface behavior between polyimide and an ionic liquid-water mixture exhibiting lower critical solution temperature (LCST)-type phase separation. The LCST behavior for an ionic liquid device utilizing the polyimide with and without alkyl side chains was investigated. In the here-reported ionic liquid device that utilized the polyimide with alkyl side chains, [nBu4P][CF3COO] droplets were generated by phase separation—they were predominantly formed at the alkyl surface by a surface pinning effect. A stable transmittance in the opaque state could be obtained with this device. In contrast, an ionic liquid device using polyimide without alkyl side chains deteriorated transmittance in the opaque state because there was no surface pinning effect. Additionally, the viewing angle, contrast ratio, and heat cycle testing of this ionic liquid device with polyimide with alkyl side chains were also investigated. The results indicated that no parallax was obtained and that the ionic liquid device has a stable transmittance (verified by heat cycle testing). This unique device is expected to find use in the smart window applications that are activated by temperature changes.

Chain Conformation of Phosphorycholine-based Zwitterionic Polymer Brushes in Aqueous Solutions

NASA Astrophysics Data System (ADS)

Mao, Jun; Yu, Jing; Lee, Sungsik; Yuan, Guangcui; Satija, Sushil; Chen, Wei; Tirrell, Matthew

Polyzwitterionic brushes are resistant to nonspecific accumulation of proteins and microorganisms, making them excellent candidates for antifouling applications. It is well-known that polyzwitterions exhibit the so-called antipolyelectrolyte effect: Polyzwitterionic brushes would adopt a collapsed conformation at a low ionic strength due to the electrostatic inter/intra-chain association; whereas at a high ionic strength, they would exhibit an extended conformation because the electrostatic inter/intra-chain dipole-dipole interaction is weakened. However, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) is a unique member in polyzwitterionic families. Its ultrahigh affinity to water leads to no detectable shrinks in aqueous solutions even at low ionic strengths. In this study, we synthesized highly dense PMPC brushes via surface initiated radical polymerization and systematically investigate their conformational behaviors at solid-liquid interfaces in the presence of multivalent counterions, combining X-ray and neutron scattering and force measurements. We have demonstrated that despite no obvious changes of the entire lengths of extended PMPC brushes in aqueous solutions, the chain conformations including, but not limited to, polyzwitterion distribution and charge correlation, varied, dependent on salt types, ionic strengths and ion valences.

HCl, KCl and KOH solvation resolved solute-solvent interactions and solution surface stress

NASA Astrophysics Data System (ADS)

Zhang, Xi; Xu, Yan; Zhou, Yong; Gong, Yinyan; Huang, Yongli; Sun, Chang Q.

2017-11-01

An incorporation of the hydrogen bond (O:Hsbnd O or HB) cooperativity notion, contact angle detection, and the differential phonon spectrometrics (DPS) has enabled us to gain refined information on the HCl, KCl and KOH solvation resolved solute-solvent molecular interactions and the solution surface stresses. Results show that ionic polarization stiffens the solvent Hsbnd O bond phonon from 3200 to 3480 cm-1 in the hydration shells. The HO- in alkaline solution, however, shares not only the same Hsbnd O phonon redshift of compressed water from 3200 to < 3100 cm-1 but also the dangling bonds of H2O surface featured at 3610 cm-1. Salt and alkaline solvation enhances the solution surface stress by K+ and Cl- ionic polarization. The excessive H+ proton in acid solution forms a H↔H anti-HB that depresses the solution surface stress, instead. The solute capability of transforming the fraction of the O:Hsbnd O bonds of the solvent matrix is featured by: fH = 0 and fx ∝ 1-exp(-C/C0) (x = HO-, K+ and Cl-) towards saturation. Exercises not only confirm the presence of the H↔H anti-HB point fragilization, the O:⇔:O super-HB point compression, and ionic polarization dominating the performance of the respective HCl, KOH, and KCl solutions, but also demonstrate the power of the DPS that enables high resolution of solute-solute-solvent interactions and correlation between HB relaxation and solution surface stress.

The effect of delays on filament oscillations and stability

NASA Astrophysics Data System (ADS)

van den Oord, G. H. J.; Schutgens, N. A. J.; Kuperus, M.

1998-11-01

We discuss the linear response of a filament to perturbations, taking the finite communication time between the filament and the photosphere into account. The finite communication time introduces delays in the system. Recently Schutgens (1997ab) investigated the solutions of the delay equation for vertical perturbations. In this paper we expand his analysis by considering also horizontal and coupled oscillations. The latter occur in asymmetric coronal fields. We also discuss the effect of Alfven wave emission on filament oscillations and show that wave emission is important for stabilizing filaments. We introduce a fairly straightforward method to study the solutions of delay equations as a function of the filament-photosphere communication time. A solution can be described by a linear combination of damped harmonic oscillations each characterized by a frequency, a damping/growth time and, accordingly, a quality factor. As a secondary result of our analysis we show that, within the context of line current models, Kippenhahn/Schlüter-type filament equilibria can never be stable in the horizontal and the vertical direction at the same time but we also demonstrate that Kuperus/Raadu-type equilibria can account for both an inverse or a normal polarity signature. The diagnostic value of our analysis for determining, e.g., the filament current from observations of oscillating filaments is discussed.

Connecting the solution chemistry of PbI2 and MAI: a cyclodextrin-based supramolecular approach to the formation of hybrid halide perovskites.

PubMed

Masi, Sofia; Aiello, Federica; Listorti, Andrea; Balzano, Federica; Altamura, Davide; Giannini, Cinzia; Caliandro, Rocco; Uccello-Barretta, Gloria; Rizzo, Aurora; Colella, Silvia

2018-03-28

The evolution from solvated precursors to hybrid halide perovskite films dictates most of the photophysical and optoelectronic properties of the final polycrystalline material. Specifically, the complex equilibria and the importantly different solubilities of lead iodide (PbI 2 ) and methylammonium iodide (MAI) induce inhomogeneous crystal growth, often leading to a defect dense film showing non-optimal optoelectronic properties and intrinsic instability. Here, we explore a supramolecular approach based on the use of cyclodextrins (CDs) to modify the underlying solution chemistry. The peculiar phenomenon demonstrated is a tunable complexation between different CDs and MA + cations concurrent to an out of cage PbI 2 intercalation, representing the first report of a connection between the solvation equilibria of the two perovskite precursors. The optimal conditions in terms of CD cavity size and polarity translate to a neat enhancement of PbI 2 solubility in the reaction media, leading to an equilibration of the availability of the precursors in solution. The macroscopic result of this is an improved nucleation process, leading to a perovskite material with higher crystallinity, better optical properties and improved moisture resistance. Remarkably, the use of CDs presents a great potential for a wide range of device-related applications, as well as for the development of tailored composite materials.

Experimental investigation and application of the equilibrium rutile + orthopyroxene = quartz + ilmenite

USGS Publications Warehouse

Hayob, J.L.; Bohlen, S.R.; Essene, E.J.

1993-01-01

Equilibria in the Sirf (Silica-Ilmenite-Rutile-Ferrosilite) system: {Mathematical expression} have been calibrated in the range 800-1100?? C and 12-26 kbar using a piston-cylinder apparatus to assess the potential of the equilibria for geobarometry in granulite facies assemblages that lack garnet. Thermodynamic calculations indicate that the two end-member equilibria involving quartz + geikielite = rutile + enstatite, and quartz + ilmenite = rutile + ferrosilite, are metastable. We therefore reversed equilibria over the compositional range Fs40-70, using Ag80Pd20 capsules with {Mathematical expression} buffered at or near iron-wu??stite. Ilmenite compositions coexisting with orthopyroxene are {Mathematical expression} of 0.06 to 0.15 and {Mathematical expression} of 0.00 to 0.01, corresponding to KD values of 13.3, 10.2, 9.0 and 8.0 (??0.5) at 800, 900, 1000 and 1100?? C, respectively, where KD=(XMg/XFe)Opx/(XMg/XFe)Ilm. Pressures have been calculated using equilibria in the Sirf system for granulites from the Grenville Province of Ontario and for granulite facies xenoliths from central Mexico. Pressures are consistent with other well-calibrated geobarometers for orthopyroxeneilmenite pairs from two Mexican samples in which oxide textures appear to represent equilibrium. Geologically unreasonable pressures are obtained, however, where oxide textures are complex. Application of data from this study on the equilibrium distribution of iron and magnesium between ilmenite and orthopyroxene suggests that some ilmenite in deep crustal xenoliths is not equilibrated with coexisting pyroxene, while assemblages from exposed granulite terranes have reequilibrated during retrogression. The Sirf equilibria are sensitive to small changes in composition and may be used for determination of activity/composition (a/X) relations of orthopyroxene if an ilmenite model is specified. A symmetric regular solution model has been used for orthopyroxene in conjunction with activity models for ilmenite available from the literature to calculate a/X relations in orthopyroxene of intermediate composition. Data from this study indicate that FeSiO3-MgSiO3 orthopyroxene exhibits small, positive deviations from ideality over the range 800-1100??C. ?? 1993 Springer-Verlag.

The role of electrostatics in protein-protein interactions of a monoclonal antibody.

PubMed

Roberts, D; Keeling, R; Tracka, M; van der Walle, C F; Uddin, S; Warwicker, J; Curtis, R

2014-07-07

Understanding how protein-protein interactions depend on the choice of buffer, salt, ionic strength, and pH is needed to have better control over protein solution behavior. Here, we have characterized the pH and ionic strength dependence of protein-protein interactions in terms of an interaction parameter kD obtained from dynamic light scattering and the osmotic second virial coefficient B22 measured by static light scattering. A simplified protein-protein interaction model based on a Baxter adhesive potential and an electric double layer force is used to separate out the contributions of longer-ranged electrostatic interactions from short-ranged attractive forces. The ionic strength dependence of protein-protein interactions for solutions at pH 6.5 and below can be accurately captured using a Deryaguin-Landau-Verwey-Overbeek (DLVO) potential to describe the double layer forces. In solutions at pH 9, attractive electrostatics occur over the ionic strength range of 5-275 mM. At intermediate pH values (7.25 to 8.5), there is a crossover effect characterized by a nonmonotonic ionic strength dependence of protein-protein interactions, which can be rationalized by the competing effects of long-ranged repulsive double layer forces at low ionic strength and a shorter ranged electrostatic attraction, which dominates above a critical ionic strength. The change of interactions from repulsive to attractive indicates a concomitant change in the angular dependence of protein-protein interaction from isotropic to anisotropic. In the second part of the paper, we show how the Baxter adhesive potential can be used to predict values of kD from fitting to B22 measurements, thus providing a molecular basis for the linear correlation between the two protein-protein interaction parameters.

The thermodynamic water retention capacity of solutions and gels.

PubMed

Borchard, W; Jablonski, P

2003-01-01

The thermodynamic water retention capacity (WRC) has been defined and applied to different heterogeneous phase equilibria. This definition includes others known from the literature for testing heterogeneous systems. For the type of a real solution it is shown that at constant values of temperature and pressure the WRC is related to the difference of the chemical potential of water between the original state and the state after having applied a constraint. The dependence of WRC on concentration of a solute is predicted to be described by an e-function which has been experimentally confirmed in the literature.

On the adequacy of modeling the concentration dependences of the activity coefficients for the components of solutions

NASA Astrophysics Data System (ADS)

Sergievskii, V. V.; Rudakov, A. M.

2006-11-01

An analysis of the accepted methods for calculating the activity coefficients for the components of binary aqueous solutions was performed. It was demonstrated that the use of the osmotic coefficients in auxiliary calculations decreases the accuracy of estimates of the activity coefficients. The possibility of calculating the activity coefficient of the solute from the concentration dependence of the water activity was examined. It was established that, for weak electrolytes, the interpretation of data on heterogeneous equilibria within the framework of the standard assumption that the dissociation is complete encounters serious difficulties.

Influence of ionic strength and OH(-) ion concentration on the Cu(II) complex formation with EDTA in alkaline solutions.

PubMed

Norkus, E; Vaskelis, A; Zakaite, I

1996-03-01

D.c. polarographic data show that the complex formation of copper ions with EDTA depends markedly on the ionic strength of the solution at pH 8-10. This is primarily associated with the dependence of the fourth deprotonization constant of EDTA on the solution ionic strength: when it increases from 0.4 to 3.4, the pK(a4) value decreases from 9.5 to 8.2. According to polarographic and spectrophotometric data the degree of Cu(II) complexation increases at pH>10 due to transformation of the complex CuY(2-) to the more stable CuY(OH)(3-) (Y(4-), a fully deprotonized anion of EDTA), but it decreases with increase in alkalinity in a highly alkaline solution (pH>13.5). The latter result could be explained by the decrease in the EDTA anion activity. The calculated values of the activity coefficient are lower than 0.05 at pH>14.

External and internal guest binding of a highly charged supramolecular host in water: deconvoluting the very different thermodynamics.

PubMed

Sgarlata, Carmelo; Mugridge, Jeffrey S; Pluth, Michael D; Tiedemann, Bryan E F; Zito, Valeria; Arena, Giuseppe; Raymond, Kenneth N

2010-01-27

NMR, UV-vis, and isothermal titration calorimetry (ITC) measurements probe different aspects of competing host-guest equilibria as simple alkylammonium guest molecules interact with both the exterior (ion-association) and interior (encapsulation) of the [Ga(4)L(6)](12-) supramolecular assembly in water. Data obtained by each independent technique measure different components of the host-guest equilibria and only when analyzed together does a complete picture of the solution thermodynamics emerge. Striking differences between the internal and external guest binding are found. External binding is enthalpy driven and mainly due to attractive interactions between the guests and the exterior surface of the assembly while encapsulation is entropy driven as a result of desolvation and release of solvent molecules from the host cavity.

Calculation of Phase Equilibria in the Y2O3-Yb2O3-ZrO2 System

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Liu, Zi-Kui; Kaufman, Larry; Zhang, Fan

2001-01-01

Rare earth oxide stabilized zirconias find a wide range of applications. An understanding of phase equilibria is essential to all applications. In this study, the available phase boundary data and thermodynamic data is collected and assessed. Calphad-type databases are developed to completely describe the Y2O3-ZrO2, Yb2O3-ZrO2, and Y2O3-Yb2O3 systems. The oxide units are treated as components and regular and subregular solution models are used. The resultant calculated phase diagrams show good agreement with the experimental data. Then the binaries are combined to form the database for the Y2O3-Yb2O3-ZrO2 psuedo-ternary.

Submicrometer Emitter ESI Tips for Native Mass Spectrometry of Membrane Proteins in Ionic and Nonionic Detergents

NASA Astrophysics Data System (ADS)

Susa, Anna C.; Lippens, Jennifer L.; Xia, Zijie; Loo, Joseph A.; Campuzano, Iain D. G.; Williams, Evan R.

2018-01-01

Native mass spectrometry (native-MS) of membrane proteins typically requires a detergent screening protocol, protein solubilization in the preferred detergent, followed by protein liberation from the micelle by collisional activation. Here, submicrometer nano-ESI emitter tips are used for native-MS of membrane proteins solubilized in both nonionic and ionic detergent solutions. With the submicrometer nano-ESI emitter tips, resolved charge-state distributions of membrane protein ions are obtained from a 150 mM NaCl, 25 mM Tris-HCl with 1.1% octyl glucoside solution. The relative abundances of NaCl and detergent cluster ions at high m / z are significantly reduced with the submicrometer emitters compared with larger nano-ESI emitters that are commonly used. This technique is beneficial for significantly decreasing the abundances (by two to three orders of magnitude compared with the larger tip size: 1.6 μm) of detergent cluster ions formed from aqueous ammonium acetate solutions containing detergents that can overlap with the membrane protein ion signal. Resolved charge-state distributions of membrane protein ions from aqueous ammonium acetate solutions containing ionic detergents were obtained with the submicrometer nano-ESI emitters; this is the first report of native-MS of membrane proteins solubilized by ionic detergents. [Figure not available: see fulltext.

Submicrometer Emitter ESI Tips for Native Mass Spectrometry of Membrane Proteins in Ionic and Nonionic Detergents.

PubMed

Susa, Anna C; Lippens, Jennifer L; Xia, Zijie; Loo, Joseph A; Campuzano, Iain D G; Williams, Evan R

2018-01-01

Native mass spectrometry (native-MS) of membrane proteins typically requires a detergent screening protocol, protein solubilization in the preferred detergent, followed by protein liberation from the micelle by collisional activation. Here, submicrometer nano-ESI emitter tips are used for native-MS of membrane proteins solubilized in both nonionic and ionic detergent solutions. With the submicrometer nano-ESI emitter tips, resolved charge-state distributions of membrane protein ions are obtained from a 150 mM NaCl, 25 mM Tris-HCl with 1.1% octyl glucoside solution. The relative abundances of NaCl and detergent cluster ions at high m /z are significantly reduced with the submicrometer emitters compared with larger nano-ESI emitters that are commonly used. This technique is beneficial for significantly decreasing the abundances (by two to three orders of magnitude compared with the larger tip size: 1.6 μm) of detergent cluster ions formed from aqueous ammonium acetate solutions containing detergents that can overlap with the membrane protein ion signal. Resolved charge-state distributions of membrane protein ions from aqueous ammonium acetate solutions containing ionic detergents were obtained with the submicrometer nano-ESI emitters; this is the first report of native-MS of membrane proteins solubilized by ionic detergents. Graphical Abstract.

Heat-induced morphological transformation of gold nanodumbbells in ionic surfactant solutions

NASA Astrophysics Data System (ADS)

Wen, Ting-Chun; Lu, Chung-Wen; Hsieh, Wei-Chi; Chang, Sheng-Te; Yang, Ya-Ting; Deng, Jin-Pei

2018-01-01

The thermal stability of gold nanodumbbells (NDs) is studied in aqueous solution of ionic surfactants. It is found in aqueous solution of cetyltrimethylammonium bromide that the blue-shift of longitudinal surface plasmon resonance band of gold NDs occurs at 75 °C and the new gold nanorods (NRs) with shortened aspect ratio are formed at the same time. The aspect ratio of the generated gold NRs gradually decreases and finally approaches ∼1.7 after repeated processing. Similarly, the same results are also obtained in aqueous solution of sodium dodecyl sulfate at room temperature. Mechanism is proposed for the shape transformation of gold NDs.

Diffuse sorption modeling.

PubMed

Pivovarov, Sergey

2009-04-01

This work presents a simple solution for the diffuse double layer model, applicable to calculation of surface speciation as well as to simulation of ionic adsorption within the diffuse layer of solution in arbitrary salt media. Based on Poisson-Boltzmann equation, the Gaines-Thomas selectivity coefficient for uni-bivalent exchange on clay, K(GT)(Me(2+)/M(+))=(Q(Me)(0.5)/Q(M)){M(+)}/{Me(2+)}(0.5), (Q is the equivalent fraction of cation in the exchange capacity, and {M(+)} and {Me(2+)} are the ionic activities in solution) may be calculated as [surface charge, mueq/m(2)]/0.61. The obtained solution of the Poisson-Boltzmann equation was applied to calculation of ionic exchange on clays and to simulation of the surface charge of ferrihydrite in 0.01-6 M NaCl solutions. In addition, a new model of acid-base properties was developed. This model is based on assumption that the net proton charge is not located on the mathematical surface plane but diffusely distributed within the subsurface layer of the lattice. It is shown that the obtained solution of the Poisson-Boltzmann equation makes such calculations possible, and that this approach is more efficient than the original diffuse double layer model.

Magnetical hollow fiber bar collection of extract in homogenous ionic liquid microextraction of triazine herbicides in water samples.

PubMed

Wang, Kun; Jiang, Jia; Kang, Mingqin; Li, Dan; Zang, Shuang; Tian, Sizhu; Zhang, Hanqi; Yu, Aimin; Zhang, Ziwei

2017-04-01

The homogeneous ionic liquid microextraction combined with magnetical hollow fiber bar collection was developed for extracting triazine herbicides from water samples. These analytes were separated and determined by high performance liquid chromatography. The triazines were quickly extracted into ionic liquid microdroplets dispersed in solution, and then these microdroplets were completely collected with magnetical hollow fiber bars; the pores of which were impregnated with hydrophobic ionic liquid, which makes the phase separation simplified with no need of centrifugation. Some experimental parameters, such as the type of ionic liquid, ultrasonic immersion time of hollow fiber, pH of sample solution, volume of hydrophilic ionic liquid, amount of ion-pairing agent NH 4 PF 6 , NaCl concentration, number of magnetical hollow fiber bar, stirring rate, and collection time were investigated and optimized. When the present method was applied to the analysis of real water samples, the precision and recoveries of six triazine herbicides vary from 0.1 to 9.2% and 73.4 to 118.5%, respectively. The detection limits for terbumeton, ametryn, prometryn, terbutryn, trietazine, and dimethametryn were 0.48, 0.15, 0.15, 0.14, 0.35, and 0.16 μg L -1 , respectively.

The Co-Sb-Ga System: Isoplethal Section and Thermodynamic Modeling

NASA Astrophysics Data System (ADS)

Gierlotka, Wojciech; Chen, Sinn-wen; Chen, Wei-an; Chang, Jui-shen; Snyder, G. Jeffrey; Tang, Yinglu

2015-04-01

The Co-Sb-Ga ternary system is an important thermoelectric material system, and its phase equilibria are in need of further understanding. The CoSb3-GaSb isoplethal section is experimentally determined in this study. Phase equilibria of the ternary Co-Sb-Ga system are assessed, and the system's thermodynamic models are developed. In addition to the terminal phases and liquid phase, there are six binary intermediate phases and a ternary Co3Sb2Ga4 phase. The Ga solution in the CoSb3 compound is described by a dual-site occupation (GaVF) x Co4Sb12- x/2(GaSb) x/2 model. Phase diagrams are calculated using the developed thermodynamic models, and a reaction scheme is proposed based on the calculation results. The calculated results are in good agreement with the experimentally determined phase diagrams, including the CoSb3-GaSb isoplethal section, the liquidus projection, and an isothermal section at 923 K (650 °C). The dual-site occupation (GaVF) x Co4Sb12- x/2(GaSb) x/2 model gives good descriptions of both phase equilibria and thermoelectric properties of the CoSb3 phase with Ga doping.

Phase relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

USGS Publications Warehouse

Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.

1992-01-01

The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.

The influence of ionic strength on carbonate-based spectroscopic barometry for aqueous fluids: an in-situ Raman study on Na2CO3-NaCl solutions

PubMed Central

Wu, Jia; Wang, Shixia; Zheng, Haifei

2016-01-01

The Raman wavenumber of the symmetric stretching vibration of carbonate ion (ν1-CO32−) was measured in three aqueous solutions containing 2.0 mol·L−1 Na2CO3 and 0.20, 0.42, or 0.92 mol·L−1 NaCl, respectively, from 122 to 1538 MPa at 22 °C using a moissanite anvil cell. The ν1 Raman signal linearly shifted to higher wavenumbers with increasing pressure. Most importantly, the slope of ν1-CO32− Raman frequency shift (∂ν1/∂P)I was independent of NaCl concentration. Moreover, elevated ionic strength was found to shift the apparent outline of the carbonate peak toward low wavenumbers, possibly by increasing the proportion of the contact ion pair NaCO3−. Further investigations revealed no cross-interaction between the pressure effect and the ionic strength effect on the Raman spectra, possibly because the distribution of different ion-pair species in the carbonate equilibrium was largely pressure-independent. These results suggested that the ionic strength should be incorporated as an additional constraint for measuring the internal pressure of various solution-based systems. Combining the ν1-CO32− Raman frequency slope with the pressure herein with the values for the temperature or the ionic strength dependencies determined from previous studies, we developed an empirical equation that can be used to estimate the pressure of carbonate-bearing aqueous solutions. PMID:27982064

Dissecting ion-specific dielectric spectra of sodium-halide solutions into solvation water and ionic contributions

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

Rinne, Klaus F.; Netz, Roland R.; Gekle, Stephan

2014-12-07

Using extensive equilibrium molecular dynamics simulations we determine the dielectric spectra of aqueous solutions of NaF, NaCl, NaBr, and NaI. The ion-specific and concentration-dependent shifts of the static dielectric constants and the dielectric relaxation times match experimental results very well, which serves as a validation of the classical and non-polarizable ionic force fields used. The purely ionic contribution to the dielectric response is negligible, but determines the conductivity of the salt solutions. The ion-water cross correlation contribution is negative and reduces the total dielectric response by about 5%-10% for 1 M solutions. The dominating water dielectric response is decomposed into differentmore » water solvation shells and ion-pair configurations, by this the spectral blue shift and the dielectric decrement of salt solutions with increasing salt concentration is demonstrated to be primarily caused by first-solvation shell water. With rising salt concentration the simulated spectra show more pronounced deviations from a single-Debye form and can be well described by a Cole-Cole fit, in quantitative agreement with experiments. Our spectral decomposition into ionic and different water solvation shell contributions does not render the individual contributions more Debye-like, this suggests the non-Debye-like character of the dielectric spectra of salt solutions not to be due to the superposition of different elementary relaxation processes with different relaxation times. Rather, the non-Debye-like character is likely to be an inherent spectral signature of solvation water around ions.« less

[Determination of Chloride Salt Solution by NIR Spectroscopy].

PubMed

Zhang, Bin; Chen, Jian-hong; Jiao, Ming-xing

2015-07-01

Determination of chloride salt solution by near infrared spectrum plays a very important role in Biomedicine. The near infrared spectrum analysis of Sodium chloride, potassium chloride, calcium chloride aqueous solution shows that the concentration change of chloride salt can affect hydrogen bond, resulting in the variation of near infrared spectrum of water. The temperature influence on NIR spectrum has been decreased by choosing reasonable wavelength range and the wavelength where the temperature effects are zero (isosbestic point). Chlorine salt prediction model was established based on partial least squares method and used for predicting the concentration of the chlorine ion. The impact on near infrared spectrum of the cation ionic radius, the number of ionic charge, the complex effect of ionic in water has also discussed in this article and the reason of every factor are analysed. Experimental results show that the temperature and concentration will affect the near-infrared spectrum of the solution, It is found that the effect of temperature plays the dominant role at low concentrations of chlorine salt; rather, the ionic dominates at high concentration. Chloride complexes are formed in aqueous solution, It has an effect on hydrogen bond of water combining with the cations in chlorine salt solution, Comparing different chloride solutions at the same concentration, the destruction effects of chloride complexes and catnions on the hydrogen bond of water increases in the sequences: CaCl2 >NaCl>KC. The modeling result shows that the determination coefficients (R2) = 99.97%, the root mean square error of cross validation (RM- SECV) = 4.51, and the residual prediction deviation (RPD) = 62.7, it meets the daily requirements of biochemical detection accuracy.

Precipitation of thin-film organic single crystals by a novel crystal growth method using electrospray and ionic liquid film

NASA Astrophysics Data System (ADS)

Ueda, Hiroyuki; Takeuchi, Keita; Kikuchi, Akihiko

2018-04-01

We report an organic single crystal growth technique, which uses a nonvolatile liquid thin film as a crystal growth field and supplies fine droplets containing solute from the surface of the liquid thin film uniformly and continuously by electrospray deposition. Here, we investigated the relationships between the solute concentration of the supplied solution and the morphology and size of precipitated crystals for four types of fluorescent organic low molecule material [tris(8-hydroxyquinoline)aluminum (Alq3), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), N,N‧-bis(3-methylphenyl)-N,N‧-diphenylbenzidine (TPD), and N,N-bis(naphthalene-1-yl)-N,N-diphenyl-benzidine (NPB)] using an ionic liquid as the nonvolatile liquid. As the concentration of the supplied solution decreased, the morphology of precipitated crystals changed from dendritic or leaf shape to platelike one. At the solution concentration of 0.1 mg/ml, relatively large platelike single crystals with a diagonal length of over 100 µm were obtained for all types of material. In the experiment using ionic liquid and dioctyl sebacate as nonvolatile liquids, it was confirmed that there is a clear positive correlation between the maximum volume of the precipitated single crystal and the solubility of solute under the same solution supply conditions.

Ionic current rectification in organic solutions with quartz nanopipettes.

PubMed

Yin, Xiaohong; Zhang, Shudong; Dong, Yitong; Liu, Shujuan; Gu, Jing; Chen, Ye; Zhang, Xin; Zhang, Xianhao; Shao, Yuanhua

2015-09-01

The study of behaviors of ionic current rectification (ICR) in organic solutions with quartz nanopipettes is reported. ICR can be observed even in organic solutions using quartz pipettes with diameters varied from several to dozens of nanometers, and the direction of ICR is quite different from the ICR observed in aqueous phase. The influences of pore size, electrolyte concentration, and surface charge on the ICR have been investigated carefully. Water in organic solutions affects the direction and extent of ICR significantly. Mechanisms about the formation of an electrical double layer (EDL) on silica in organic solutions with different amount of water have been proposed. An improved method, which can be employed to detect trace water in organic solutions, has been implemented based on Au ultramicroelectrodes with cathodic differential pulse stripping voltammetry.

Adsorption mechanism for xanthene dyes to cellulose granules.

PubMed

Tabara, Aya; Yamane, Chihiro; Seguchi, Masaharu

2012-01-01

The xanthene dyes, erythrosine, phloxine, and rose bengal, were adsorbed to charred cellulose granules. The charred cellulose granules were preliminarily steeped in ionic (NaOH, NaCl, KOH, KCl, and sodium dodecyl sulfate (SDS)), nonionic (glucose, sucrose, and ethanol), and amphipathic sucrose fatty acid ester (SFAE) solutions, and adsorption tests on the dye to the steeped and charred cellulose granules were conducted. Almost none of the dye was adsorbed when the solutions of ionic and amphipathic molecules were used, but were adsorbed in the case of steeping in the nonionic molecule solutions. Thin-layer chromatography (TLC) and the Fourier transform infra-red (FT-IR) profiles of SFAE which was adsorbed to the charred cellulose granules and extracted by ethyl ether suggested the presence of hydrophobic sites on the surface of the charred cellulose granules. We confirmed that the xanthene dyes could bind to the charred cellulose granules by ionic and hydrophobic bonds.

Hermite Polynomials and the Inverse Problem for Collisionless Equilibria

NASA Astrophysics Data System (ADS)

Allanson, O.; Neukirch, T.; Troscheit, S.; Wilson, F.

2017-12-01

It is long established that Hermite polynomial expansions in either velocity or momentum space can elegantly encode the non-Maxwellian velocity-space structure of a collisionless plasma distribution function (DF). In particular, Hermite polynomials in the canonical momenta naturally arise in the consideration of the 'inverse problem in collisionless equilibria' (IPCE): "for a given macroscopic/fluid equilibrium, what are the self-consistent Vlasov-Maxwell equilibrium DFs?". This question is of particular interest for the equilibrium and stability properties of a given macroscopic configuration, e.g. a current sheet. It can be relatively straightforward to construct a formal solution to IPCE by a Hermite expansion method, but several important questions remain regarding the use of this method. We present recent work that considers the necessary conditions of non-negativity, convergence, and the existence of all moments of an equilibrium DF solution found for IPCE. We also establish meaningful analogies between the equations that link the microscopic and macrosopic descriptions of the Vlasov-Maxwell equilibrium, and those that solve the initial value problem for the heat equation. In the language of the heat equation, IPCE poses the pressure tensor as the 'present' heat distribution over an infinite domain, and the non-Maxwellian features of the DF as the 'past' distribution. We find sufficient conditions for the convergence of the Hermite series representation of the DF, and prove that the non-negativity of the DF can be dependent on the magnetisation of the plasma. For DFs that decay at least as quickly as exp(-v^2/4), we show non-negativity is guaranteed for at least a finite range of magnetisation values, as parameterised by the ratio of the Larmor radius to the gradient length scale. 1. O. Allanson, T. Neukirch, S. Troscheit & F. Wilson: From one-dimensional fields to Vlasov equilibria: theory and application of Hermite polynomials, Journal of Plasma Physics, 82, 905820306, 2016 2. O. Allanson, S. Troscheit & T. Neukirch: The inverse problem for collisionless plasma equilibria (invited paper for IMA Journal of Applied Mathematics, under review)

Ionic solutions of two-dimensional materials

NASA Astrophysics Data System (ADS)

Cullen, Patrick L.; Cox, Kathleen M.; Bin Subhan, Mohammed K.; Picco, Loren; Payton, Oliver D.; Buckley, David J.; Miller, Thomas S.; Hodge, Stephen A.; Skipper, Neal T.; Tileli, Vasiliki; Howard, Christopher A.

2017-03-01

Strategies for forming liquid dispersions of nanomaterials typically focus on retarding reaggregation, for example via surface modification, as opposed to promoting the thermodynamically driven dissolution common for molecule-sized species. Here we demonstrate the true dissolution of a wide range of important 2D nanomaterials by forming layered material salts that spontaneously dissolve in polar solvents yielding ionic solutions. The benign dissolution advantageously maintains the morphology of the starting material, is stable against reaggregation and can achieve solutions containing exclusively individualized monolayers. Importantly, the charge on the anionic nanosheet solutes is reversible, enables targeted deposition over large areas via electroplating and can initiate novel self-assembly upon drying. Our findings thus reveal a unique solution-like behaviour for 2D materials that enables their scalable production and controlled manipulation.

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

Preparation and evaluation of surface-bonded tricationic ionic liquid silica as stationary phases for high-performance liquid chromatography.

PubMed

Qiao, Lizhen; Shi, Xianzhe; Lu, Xin; Xu, Guowang

2015-05-29

Two tricationic ionic liquids were prepared and then bonded onto the surface of supporting silica materials through "thiol-ene" click chemistry as new stationary phases for high-performance liquid chromatography. The obtained columns of tricationic ionic liquids were evaluated respectively in the reversed-phase liquid chromatography (RPLC) mode and hydrophilic interaction liquid chromatography (HILIC) mode, and possess ideal column efficiency of 80,000 plates/m in the RPLC mode with naphthalene as the test solute. The tricationic ionic liquid stationary phases exhibit good hydrophobic and shape selectivity to hydrophobic compounds, and RPLC retention behavior with multiple interactions. In the HILIC mode, the retention and selectivity were evaluated through the efficient separation of nucleosides and bases as well as flavonoids, and the typical HILIC retention behavior was demonstrated by investigating retention changes of hydrophilic solutes with water volume fraction in mobile phase. The results show that the tricationic ionic liquid columns possess great prospect for applications in analysis of hydrophobic and hydrophilic samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Ionic Effects on Supercritical CO2-Brine Interfacial Tensions: Molecular Dynamics Simulations and a Universal Correlation with Ionic Strength, Temperature, and Pressure.

PubMed

Zhao, Lingling; Ji, Jiayuan; Tao, Lu; Lin, Shangchao

2016-09-13

For geological CO2 storage in deep saline aquifers, the interfacial tension (IFT) between supercritical CO2 and brine is critical for the storage security and design of the storage capacitance. However, currently, no predictive model exists to determine the IFT of supercritical CO2 against complex electrolyte solutions involving various mixed salt species at different concentrations and compositions. In this paper, we use molecular dynamics (MD) simulations to investigate the effect of salt ions on the incremental IFT at the supercritical CO2-brine interface with respect to that at the reference supercritical CO2-water interface. Supercritical CO2-NaCl solution, CO2-CaCl2 solution and CO2-(NaCl+CaCl2) mixed solution systems are simulated at 343 K and 20 MPa under different salinities and salt compositions. We find that the valence of the cations is the primary contributor to the variation in IFT, while the Lennard-Jones potentials for the cations pose a smaller impact on the IFT. Interestingly, the incremental IFT exhibits a general linear correlation with the ionic strength in the above three electrolyte systems, and the slopes are almost identical and independent of the solution types. Based on this finding, a universal predictive formula for IFTs of CO2-complex electrolyte solution systems is established, as a function of ionic strength, temperature, and pressure. The predicted IFTs using the established formula agree perfectly (with a high statistical confidence level of ∼96%) with a wide range of experimental data for CO2 interfacing with different electrolyte solutions, such as those involving MgCl2 and Na2SO4. This work provides an efficient and accurate route to directly predict IFTs in supercritical CO2-complex electrolyte solution systems for practical engineering applications, such as geological CO2 sequestration in deep saline aquifers and other interfacial systems involving complex electrolyte solutions.

Diffusion anisotropy of poor metal solute atoms in hcp-Ti

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

Scotti, Lucia, E-mail: lxs234@bham.ac.uk; Mottura, Alessandro, E-mail: a.mottura@bham.ac.uk

2015-05-28

Atom migration mechanisms influence a wide range of phenomena: solidification kinetics, phase equilibria, oxidation kinetics, precipitation of phases, and high-temperature deformation. In particular, solute diffusion mechanisms in α-Ti alloys can help explain their excellent high-temperature behaviour. The purpose of this work is to study self- and solute diffusion in hexagonal close-packed (hcp)-Ti, and its anisotropy, from first-principles using the 8-frequency model. The calculated diffusion coefficients show that diffusion energy barriers depend more on bonding characteristics of the solute rather than the size misfit with the host, while the extreme diffusion anisotropy of some solute elements in hcp-Ti is a resultmore » of the bond angle distortion.« less

Lithium-Based High Energy Density Flow Batteries

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); West, William C. (Inventor); Kindler, Andrew (Inventor); Smart, Marshall C. (Inventor)

2014-01-01

Systems and methods in accordance with embodiments of the invention implement a lithium-based high energy density flow battery. In one embodiment, a lithium-based high energy density flow battery includes a first anodic conductive solution that includes a lithium polyaromatic hydrocarbon complex dissolved in a solvent, a second cathodic conductive solution that includes a cathodic complex dissolved in a solvent, a solid lithium ion conductor disposed so as to separate the first solution from the second solution, such that the first conductive solution, the second conductive solution, and the solid lithium ionic conductor define a circuit, where when the circuit is closed, lithium from the lithium polyaromatic hydrocarbon complex in the first conductive solution dissociates from the lithium polyaromatic hydrocarbon complex, migrates through the solid lithium ionic conductor, and associates with the cathodic complex of the second conductive solution, and a current is generated.

Analysis of stability and bifurcations of fixed points and periodic solutions of a lumped model of neocortex with two delays

PubMed Central

2012-01-01

A lumped model of neural activity in neocortex is studied to identify regions of multi-stability of both steady states and periodic solutions. Presence of both steady states and periodic solutions is considered to correspond with epileptogenesis. The model, which consists of two delay differential equations with two fixed time lags is mainly studied for its dependency on varying connection strength between populations. Equilibria are identified, and using linear stability analysis, all transitions are determined under which both trivial and non-trivial fixed points lose stability. Periodic solutions arising at some of these bifurcations are numerically studied with a two-parameter bifurcation analysis. PMID:22655859

A simplified analytic form for generation of axisymmetric plasma boundaries

DOE PAGES

Luce, Timothy C.

2017-02-23

An improved method has been formulated for generating analytic boundary shapes as input for axisymmetric MHD equilibria. This method uses the family of superellipses as the basis function, as previously introduced. The improvements are a simplified notation, reduction of the number of simultaneous nonlinear equations to be solved, and the realization that not all combinations of input parameters admit a solution to the nonlinear constraint equations. The method tests for the existence of a self-consistent solution and, when no solution exists, it uses a deterministic method to find a nearby solution. As a result, examples of generation of boundaries, includingmore » tests with an equilibrium solver, are given.« less

A simplified analytic form for generation of axisymmetric plasma boundaries

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

Luce, Timothy C.

An improved method has been formulated for generating analytic boundary shapes as input for axisymmetric MHD equilibria. This method uses the family of superellipses as the basis function, as previously introduced. The improvements are a simplified notation, reduction of the number of simultaneous nonlinear equations to be solved, and the realization that not all combinations of input parameters admit a solution to the nonlinear constraint equations. The method tests for the existence of a self-consistent solution and, when no solution exists, it uses a deterministic method to find a nearby solution. As a result, examples of generation of boundaries, includingmore » tests with an equilibrium solver, are given.« less

Long-range electrostatic screening in ionic liquids

PubMed Central

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

2015-01-01

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

Ionic current devices-Recent progress in the merging of electronic, microfluidic, and biomimetic structures.

PubMed

Koo, Hyung-Jun; Velev, Orlin D

2013-05-09

We review the recent progress in the emerging area of devices and circuits operating on the basis of ionic currents. These devices operate at the intersection of electrochemistry, electronics, and microfluidics, and their potential applications are inspired by essential biological processes such as neural transmission. Ionic current rectification has been demonstrated in diode-like devices containing electrolyte solutions, hydrogel, or hydrated nanofilms. More complex functions have been realized in ionic current based transistors, solar cells, and switching memory devices. Microfluidic channels and networks-an intrinsic component of the ionic devices-could play the role of wires and circuits in conventional electronics.

Electrical, structural, thermal and electrochemical properties of corn starch-based biopolymer electrolytes.

PubMed

Liew, Chiam-Wen; Ramesh, S

2015-06-25

Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF6) and ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) are prepared by solution casting technique. Temperature dependence-ionic conductivity studies reveal Vogel-Tamman-Fulcher (VTF) relationship which is associated with free volume theory. Ionic liquid-based biopolymer electrolytes show lower glass transition temperature (Tg) than ionic liquid-free biopolymer electrolyte. X-ray diffraction (XRD) studies demonstrate higher amorphous region of ionic liquid-added biopolymer electrolytes. In addition, the potential stability window of the biopolymer electrolyte becomes wider and stable up to 2.9V. Conclusively, the fabricated electric double layer capacitor (EDLC) shows improved electrochemical performance upon addition of ionic liquid into the biopolymer electrolyte. The specific capacitance of EDLC based on ionic liquid-added polymer electrolyte is relatively higher than that of ionic liquid-free polymer electrolyte as depicted in cyclic voltammogram. Copyright © 2015 Elsevier Ltd. All rights reserved.

Method and apparatus for lysing and processing algae

DOEpatents

Chew, Geoffrey; Reich, Alton J.; Dykes, Jr., H. Waite H.; Di Salvo, Roberto

2013-03-05

Methods and apparatus for processing algae are described in which a hydrophilic ionic liquid is used to lyse algae cells at lower temperatures than existing algae processing methods. A salt or salt solution is used as a separation agent and to remove water from the ionic liquid, allowing the ionic liquid to be reused. The used salt may be dried or concentrated and reused. The relatively low lysis temperatures and recycling of the ionic liquid and salt reduce the environmental impact of the algae processing while providing biofuels and other useful products.

Theoretical interpretation of the limiting electric conductivity in ionic solution

NASA Astrophysics Data System (ADS)

Fraenkel, Dan

2017-12-01

The physical essence of the limiting equivalent ionic conductivity in solution, λ0i, has been a continuing challenge over almost a century. Here I briefly present an ab initio theoretical treatment providing (1) a new insight into the nature of λ0i, and (2) a mathematical formula for computing λ0i. In the new treatment, one assumes that any chosen ion i is surrounded by a spherical body of oriented solvent dipoles carrying the charge of the counterion, and the bulk solvent is a continuum with no molecular detail. λ0i is thus the result of the tandem operation, at hydrodynamic equilibrium, of the dipole body's electrophoretic and relaxation forces exerted on the drifting ion. λ0i is found to be proportional to the radius of ion i, and independent of the ionic charge. From experimental λ0i's, the ion radius can be computed as 'electric radius.' An electric ion-radius scale so derived compares well with other ion-size scales. The current theory expresses λ0i using only universal constants and unitary factors of the ionic solution, and it sheds new light on the fundamental nature of ion and charge transport in a polar liquid medium.

Synthesis, structure, and ionic conductivity of solid solution, Li10+δM1+δP2-δS12 (M = Si, Sn).

PubMed

Hori, Satoshi; Suzuki, Kota; Hirayama, Masaaki; Kato, Yuki; Saito, Toshiya; Yonemura, Masao; Kanno, Ryoji

2014-01-01

Solid solutions of the silicon and tin analogous phases of the superionic conductor Li(10)MP(2)S(12) (M = Si, Sn) were synthesized by a conventional solid-state reaction in an evacuated silica tube at 823 K. The ranges of the solid solutions were determined to be 0.20 < δ < 0.43 and -0.25 < δ < -0.01 in Li(10+δ)M(1+δ)P(2-δ)S(12) (0.525 ≤k≤ 0.60 and 0.67 ≤k≤ 0.75 in Li(4-k)M(1-k)PkS(4)) for the Si and Sn systems, respectively. The ionic conductivity of these systems varied as a function of the changing M ions: the Si and Sn systems showed lower conductivity than the Ge system, Li(10+δ)Ge(1+δ)P(2-δ)S(12). The conductivity change for different elements might be due to the lattice size and lithium content affecting the ionic conduction. The relationship between ionic conduction, structure, and lithium concentration is discussed based on the structural and electrochemical information for the silicon, germanium, and tin systems.

Cycling and rate performance of Li-LiFePO 4 cells in mixed FSI-TFSI room temperature ionic liquids

NASA Astrophysics Data System (ADS)

Lewandowski, A. P.; Hollenkamp, A. F.; Donne, S. W.; Best, A. S.

A study is conducted of the performance of lithium iron(II) phosphate, LiFePO 4, as a cathode material in a lithium secondary battery that features an ionic liquid electrolyte solution and a metallic lithium anode. The electrolyte solution comprises an ionic liquid of a N-methyl-N-alkyl-pyrrolidinium (alkyl = n-propyl or n-butyl) cation and either the bis(fluorosulfonyl)imide [(FSO 2) 2N -] or bis(trifluoromethanesulfonyl)imide [(F 3CSO 2) 2N -] anion, together with 0.5 mol kg -1 of lithium bis(trifluoromethanesulfonyl)imide salt. For N-methyl-N-propyl-pyrrolidinium bis(fluorosulfonyl)imide, coin cells discharging at rates of C/10 and 4C yield specific capacities of 153 and 110 mAh g -1, respectively, at an average coulombic efficiency of 99.8%. This performance is maintained for over 400 cycles at 50 °C and therefore indicates that these electrolyte solutions support long-term cycling of both LiFePO 4 and metallic lithium while, due to the negligible volatility of ionic liquids, surrounding the lithium in an inherently safe, non-flammable medium.

In situ chemical degradation of DNAPLS in contaminated soils and sediments

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

Gates, D.D.; Korte, N.E.; Siegrist, R.L.

1996-08-01

An emerging approach to in situ treatment of organic contaminants is chemical degradation. The specific processes discussed in this chapter are in situ chemical oxidation using either hydrogen peroxide (H{sub 2}O{sub 2}) or potassium permanganate (KMnO{sub 4}) and in situ dechlorination of halogenated hydrocarbons using zero-valence base metals such as iron. These technologies are primarily chemical treatment processes, where the treatment goal is to manipulate the chemistry of the subsurface environment in such a manner that the contaminants of interest are destroyed and/or rendered non-toxic. Chemical properties that can be altered include pH, ionic strength, oxidation and reduction potential, andmore » chemical equilibria. In situ contaminant destruction processes alter or destroy contaminants in place and are typically applied to compounds that can be either converted to innocuous species such as CO{sub 2} and water, or can be degraded to species that are non-toxic or amenable to other in situ processes (i.e., bioremediation). With in situ chemical oxidation, the delivery and distribution of chemical reagents are critical to process effectiveness. In contrast, published approaches for the use of zero valence base metals suggest passive approaches in which the metals are used in a permeable reaction wall installed in situ in the saturated zone. Both types of processes are receiving increasing attention and are being applied both in technology demonstration and as final solutions to subsurface contaminant problems. 43 refs., 9 figs., 1 tab.« less

Volumetric Properties and Fluid Phase Equilibria of CO2 + H2O

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

Capobianco, Ryan; Gruszkiewicz, Miroslaw; Wesolowski, David J

2013-01-01

The need for accurate modeling of fluid-mineral processes over wide ranges of temperature, pressure and composition highlighted considerable uncertainties of available property data and equations of state, even for the CO2 + H2O binary system. In particular, the solubility, activity, and ionic dissociation equilibrium data for the CO2-rich phase, which are essential for understanding dissolution/precipitation, fluid-matrix reactions, and solute transport, are uncertain or missing. In this paper we report the results of a new experimental study of volumetric and phase equilibrium properties of CO2 + H2O, to be followed by measurements for bulk and confined multicomponent fluid mixtures. Mixture densitiesmore » were measured by vibrating tube densimetry (VTD) over the entire composition range at T = 200 and 250 C and P = 20, 40, 60, and 80 MPa. Initial analysis of the mutual solubilities, determined from volumetric data, shows good agreement with earlier results for the aqueous phase, but finds that the data of Takenouchi and Kennedy (1964) significantly overestimated the solubility of water in supercritical CO2 (by a factor of more than two at 200 C). Resolving this well-known discrepancy will have a direct impact on the accuracy of predictive modeling of CO2 injection in geothermal reservoirs and geological carbon sequestration through improved equations of state, needed for calibration of predictive molecular-scale models and large-scale reactive transport simulations.« less

Ion-solvation structure and battery electrode characteristics of nonflammable organic electrolytes based on tris(trifluoroethyl)phosphate dissolving lithium salts.

PubMed

Todorov, Yanko Marinov; Fujii, Kenta; Yoshimoto, Nobuko; Hirayama, Daisuke; Aoki, Masahiro; Mimura, Hideyuki; Morita, Masayuki

2017-11-29

The structure and properties of lithium salt solutions based on tris(2,2,2-trifluoroethyl)phosphate (TFEP) solvent have been studied to design a safer electrolyte system for large-sized lithium-ion battery applications. Influences of the ionic structure on the polarization behavior of the LiCoO 2 (LCO) positive electrode were investigated. The ionic conductivity and viscosity of the solution consisting of lithium salts dissolved in TFEP, LiX/TFEP (X = PF 6 , BF 4 and TFSA) (TFSA = (CF 3 SO 2 ) 2 N), were measured. The results suggest that the ion-solvation structure greatly depends on the anionic species in the salt. Spectroscopic measurements also support the conclusion that the Li + -solvation structure varies with the lithium salts. The differences in the ionic structure of LiX/TFEP influence the electrochemical oxidation potential of the solution and the polarization behavior of the LCO electrode. The overvoltage for Li-desertion/insertion from/into LCO in LiX/TFEP, being much higher than that observed in conventional LIB electrolyte solutions, shows the order of BF 4 < PF 6 < TFSA. The addition of ethylene carbonate (EC) to LiX/TFEP increases the ionic conductivity, which is probably caused by changes in the Li + -solvation structure in TFEP. The overvoltage for the Li-desertion/insertion of LCO is much lowered by the addition of EC to LiX/TFEP.

A new class of problems in the calculus of variations

NASA Astrophysics Data System (ADS)

Ekeland, Ivar; Long, Yiming; Zhou, Qinglong

2013-11-01

This paper investigates an infinite-horizon problem in the one-dimensional calculus of variations, arising from the Ramsey model of endogeneous economic growth. Following Chichilnisky, we introduce an additional term, which models concern for the well-being of future generations. We show that there are no optimal solutions, but that there are equilibrium strateges, i.e. Nash equilibria of the leader-follower game between successive generations. To solve the problem, we approximate the Chichilnisky criterion by a biexponential criterion, we characterize its equilibria by a pair of coupled differential equations of HJB type, and we go to the limit. We find all the equilibrium strategies for the Chichilnisky criterion. The mathematical analysis is difficult because one has to solve an implicit differential equation in the sense of Thom. Our analysis extends earlier work by Ekeland and Lazrak.

Global stability and pattern formation in a nonlocal diffusive Lotka-Volterra competition model

NASA Astrophysics Data System (ADS)

Ni, Wenjie; Shi, Junping; Wang, Mingxin

2018-06-01

A diffusive Lotka-Volterra competition model with nonlocal intraspecific and interspecific competition between species is formulated and analyzed. The nonlocal competition strength is assumed to be determined by a diffusion kernel function to model the movement pattern of the biological species. It is shown that when there is no nonlocal intraspecific competition, the dynamics properties of nonlocal diffusive competition problem are similar to those of classical diffusive Lotka-Volterra competition model regardless of the strength of nonlocal interspecific competition. Global stability of nonnegative constant equilibria are proved using Lyapunov or upper-lower solution methods. On the other hand, strong nonlocal intraspecific competition increases the system spatiotemporal dynamic complexity. For the weak competition case, the nonlocal diffusive competition model may possess nonconstant positive equilibria for some suitably large nonlocal intraspecific competition coefficients.

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.

Solid-State Ionic Diodes Demonstrated in Conical Nanopores

DOE PAGES

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

2017-02-27

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

The Effect of Ionic Strength on the Haemolytic Activity of Complement

PubMed Central

Wardlaw, A. C.; Walker, H. G.

1963-01-01

The haemolytic activity of guinea-pig complement has been measured in isotonic solutions of various ionic strengths in the range 0.034–0.28 and shown to be maximum at an ionic strength close to 0.08. Haemolytic activity was virtually abolished at ionic strength 0.034, while at 0.28, the complement titre was only about 20 per cent of the value found at the physiological ionic strength 0.155. NaCl, KCl, LiBr and K2SO4 were the electrolytes used to provide ionic strength, and sucrose, mannitol and inositol the non-electrolytes used to maintain isotonicity. Nine permutations of the four electrolytes with the three non-electrolytes were tested and gave similar results. Human and rabbit complements also showed optimum haemolytic activity at ionic strength 0.08–0.10. PMID:13998876

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

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

PubMed

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

2018-05-01

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

Elucidation of ionic interactions in the protic ionic liquid solutions by isothermal titration calorimetry.

PubMed

Rai, Gitanjali; Kumar, Anil

2014-04-17

The strong hydrogen-bonded network noted in protic ionic liquids (PILs) may lead to stronger interactions of the ionic entities of PILs with solvents (water, methanol, ethylene glycol, dimethylsulfoxide (DMSO), N,N'-dimethylformamide (DMF)) as compared with those of aprotic ionic liquids (APILs). The PILs used in this work are 1-methylimidazolium tetrafluoroborate, 2-methylpyridinium tetrafluoroborate, and N-methylpyrrolodinium tetrafluoroborate in comparison to 1-butyl-3-methylimidazolium tetrafluoroborate, which is classified as an APIL. In this work, the excess partial molar enthalpy, H(E)IL obtained from isothermal calorimetric titrations at 298.15 K is used to probe the nature of interactions of the PIL cations with solvent molecules against those present in APIL-solvent systems. This work also reports interesting flip-flopping in the thermal behavior of these PIL-solvent systems depending upon the structure of the cationic ring of a PIL. In some cases, these flip-flops are the specific fingerprints for specific PILs in a common solvent environment. The excess partial molar enthalpy at infinite dilution, H(E,∞)IL, of these PILs bears a critical dependence on the solvent properties. An analysis of relative apparent molar enthalpies, ϕL, of the PIL solutions by the ion interaction model of Pitzer yields important information on ionic interactions of these systems.

The truthful signalling hypothesis: an explicit general equilibrium model.

PubMed

Hausken, Kjell; Hirshleifer, Jack

2004-06-21

In mating competition, the truthful signalling hypothesis (TSH), sometimes known as the handicap principle, asserts that higher-quality males signal while lower-quality males do not (or else emit smaller signals). Also, the signals are "believed", that is, females mate preferentially with higher-signalling males. Our analysis employs specific functional forms to generate analytic solutions and numerical simulations that illuminate the conditions needed to validate the TSH. Analytic innovations include: (1) A Mating Success Function indicates how female mating choices respond to higher and lower signalling levels. (2) A congestion function rules out corner solutions in which females would mate exclusively with higher-quality males. (3) A Malthusian condition determines equilibrium population size as related to per-capita resource availability. Equilibria validating the TSH are achieved over a wide range of parameters, though not universally. For TSH equilibria it is not strictly necessary that the high-quality males have an advantage in terms of lower per-unit signalling costs, but a cost difference in favor of the low-quality males cannot be too great if a TSH equilibrium is to persist. And although the literature has paid less attention to these points, TSH equilibria may also fail if: the quality disparity among males is too great, or the proportion of high-quality males in the population is too large, or if the congestion effect is too weak. Signalling being unprofitable in aggregate, it can take off from a no-signalling equilibrium only if the trait used for signalling is not initially a handicap, but instead is functionally useful at low levels. Selection for this trait sets in motion a bandwagon, whereby the initially useful indicator is pushed by male-male competition into the domain where it does indeed become a handicap.

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.

Excessive Counterion Condensation on Immobilized ssDNA in Solutions of High Ionic Strength

PubMed Central

Rant, Ulrich; Arinaga, Kenji; Fujiwara, Tsuyoshi; Fujita, Shozo; Tornow, Marc; Yokoyama, Naoki; Abstreiter, Gerhard

2003-01-01

We present experiments on the bias-induced release of immobilized, single-stranded (ss) 24-mer oligonucleotides from Au-surfaces into electrolyte solutions of varying ionic strength. Desorption is evidenced by fluorescence measurements of dye-labeled ssDNA. Electrostatic interactions between adsorbed ssDNA and the Au-surface are investigated with respect to 1), a variation of the bias potential applied to the Au-electrode; and 2), the screening effect of the electrolyte solution. For the latter, the concentration of monovalent salt in solution is varied from 3 to 1600 mM. We find that the strength of electric interaction is predominantly determined by the effective charge of the ssDNA itself and that the release of DNA mainly occurs before the electrochemical double layer has been established at the electrolyte/Au interface. In agreement with Manning's condensation theory, the measured desorption efficiency (ηrel) stays constant over a wide range of salt concentrations; however, as the Debye length is reduced below a value comparable to the axial charge spacing of the DNA, ηrel decreases substantially. We assign this effect to excessive counterion condensation on the DNA in solutions of high ionic strength. In addition, the relative translational diffusion coefficient of ssDNA in solution is evaluated for different salt concentrations. PMID:14645075

Excessive counterion condensation on immobilized ssDNA in solutions of high ionic strength.

PubMed

Rant, Ulrich; Arinaga, Kenji; Fujiwara, Tsuyoshi; Fujita, Shozo; Tornow, Marc; Yokoyama, Naoki; Abstreiter, Gerhard

2003-12-01

We present experiments on the bias-induced release of immobilized, single-stranded (ss) 24-mer oligonucleotides from Au-surfaces into electrolyte solutions of varying ionic strength. Desorption is evidenced by fluorescence measurements of dye-labeled ssDNA. Electrostatic interactions between adsorbed ssDNA and the Au-surface are investigated with respect to 1), a variation of the bias potential applied to the Au-electrode; and 2), the screening effect of the electrolyte solution. For the latter, the concentration of monovalent salt in solution is varied from 3 to 1600 mM. We find that the strength of electric interaction is predominantly determined by the effective charge of the ssDNA itself and that the release of DNA mainly occurs before the electrochemical double layer has been established at the electrolyte/Au interface. In agreement with Manning's condensation theory, the measured desorption efficiency (etarel) stays constant over a wide range of salt concentrations; however, as the Debye length is reduced below a value comparable to the axial charge spacing of the DNA, etarel decreases substantially. We assign this effect to excessive counterion condensation on the DNA in solutions of high ionic strength. In addition, the relative translational diffusion coefficient of ssDNA in solution is evaluated for different salt concentrations.

Effects of ionic strength and ion pairing on (plant-wide) modelling of anaerobic digestion.

PubMed

Solon, Kimberly; Flores-Alsina, Xavier; Mbamba, Christian Kazadi; Volcke, Eveline I P; Tait, Stephan; Batstone, Damien; Gernaey, Krist V; Jeppsson, Ulf

2015-03-01

Plant-wide models of wastewater treatment (such as the Benchmark Simulation Model No. 2 or BSM2) are gaining popularity for use in holistic virtual studies of treatment plant control and operations. The objective of this study is to show the influence of ionic strength (as activity corrections) and ion pairing on modelling of anaerobic digestion processes in such plant-wide models of wastewater treatment. Using the BSM2 as a case study with a number of model variants and cationic load scenarios, this paper presents the effects of an improved physico-chemical description on model predictions and overall plant performance indicators, namely effluent quality index (EQI) and operational cost index (OCI). The acid-base equilibria implemented in the Anaerobic Digestion Model No. 1 (ADM1) are modified to account for non-ideal aqueous-phase chemistry. The model corrects for ionic strength via the Davies approach to consider chemical activities instead of molar concentrations. A speciation sub-routine based on a multi-dimensional Newton-Raphson (NR) iteration method is developed to address algebraic interdependencies. The model also includes ion pairs that play an important role in wastewater treatment. The paper describes: 1) how the anaerobic digester performance is affected by physico-chemical corrections; 2) the effect on pH and the anaerobic digestion products (CO2, CH4 and H2); and, 3) how these variations are propagated from the sludge treatment to the water line. Results at high ionic strength demonstrate that corrections to account for non-ideal conditions lead to significant differences in predicted process performance (up to 18% for effluent quality and 7% for operational cost) but that for pH prediction, activity corrections are more important than ion pairing effects. Both are likely to be required when precipitation is to be modelled. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rotational dynamics of coumarin-153 and 4-aminophthalimide in 1-ethyl-3-methylimidazolium alkylsulfate ionic liquids: effect of alkyl chain length on the rotational dynamics.

PubMed

Das, Sudhir Kumar; Sarkar, Moloy

2012-01-12

Rotational dynamics of two neutral organic solutes, coumarin-153 (C-153) and 4-aminophthalimide (AP), with only the latter having hydrogen-bond-donating ability, has been investigated in a series of 1-ethyl-3-methylimidazolium alkyl sulfate ionic liquids as a function of temperature. The ionic liquids differ only in the length of the linear alkyl side chain (alkyl = ethyl, butyl, hexyl, and octyl) on the anionic moiety. The present study has been undertaken to examine the role of alkyl side chains on the rotational dynamics of the two solutes in these ionic liquids. Analysis of the results using Stokes-Einstein-Debye hydrodynamic theory indicates that the rotational dynamics of C-153 lies between the stick and slip boundary condition in the ethyl analogue and finally reaches subslip condition as in case of the octyl substituent. The observed rotational behavior of C-153 has been explained on the basis of an increase in the size of the solvent, which offers lower friction for solute rotation. On the other hand, AP shows superstick behavior in the ethyl system and exceeds the stick limit in the octyl derivative. Superstick behavior of AP has been attributed to the specific hydrogen-bonding interaction between AP and the sulfate moiety. Proton NMR investigation confirms the hydrogen-bonding interaction between the N-H hydrogen of AP and the ionic liquid. The decrease in rotational coupling constant values for AP with increasing length of alkyl side chains has been attributed to the decrease in the solute-solvent-specific interaction with an increase in the alkyl side chain length on the sulfate moiety.

Catenaries in viscous fluid

NASA Astrophysics Data System (ADS)

Hanna, James; Chakrabarti, Brato

2015-11-01

Slender structures live in fluid flows across many scales, from towed instruments to plant blades to microfluidic valves. The present work details a simple model of a flexible structure in a uniform flow. We present analytical solutions for the translating, axially flowing equilibria of strings subjected to a uniform body force and linear drag forces. This is an extension of the classical catenaries to a five-parameter family of solutions, represented as trajectories in angle-curvature ``phase space.'' Limiting cases include neutrally buoyant towed cables and freely sedimenting flexible filaments. Now at University of California, San Diego.

Crystallization of pure anhydrous polymorphs of carbamazepine by solution enhanced dispersion with supercritical fluids (SEDS).

PubMed

Edwards, A D; Shekunov, B Y; Kordikowski, A; Forbes, R T; York, P

2001-08-01

Pure anhydrous polymorphs of carbamazepine were prepared by solution-enhanced dispersion with supercritical fluids (SEDS). Crystallization of the polymorphs was studied. Mechanisms are proposed that consider the thermodynamics of carbamazepine, supersaturation in the SEDS process, and the binary phase equilibria of organic solvents and the carbon dioxide antisolvent. alpha-Carbamazepine was crystallized at high supersaturations and low temperatures, beta-carbamazepine crystallized from a methanol-carbon dioxide phase split, and gamma-carbamazepine crystallized via nucleation at high temperatures and low supersaturation. Copyright 2001 Wiley-Liss, Inc.

Controlling Ionic Transport for Device Design in Synthetic Nanopores

NASA Astrophysics Data System (ADS)

Kalman, Eric Boyd

Polymer nanopores present a number of behaviors not seen in microscale systems, such as ion current rectification, ionic selectivity, size exclusion and potential dependent ion concentrations in and near the pore. The existence of these effects stems from the small size of nanopores with respect to the characteristic length scales of surface interactions at the interface between the nanopore surface and the solution within it. The large surface-to-volume ratio due to the nanoscale geometry of a nanopore, as well as similarity in scale between geometry and interaction demands the solution interact with the nanopore walls. As surfaces in solution almost always carry residual charge, these surface forces are primarily the electrostatic interactions between the charge groups on the pore surface and the ions in solution. These interactions may be used by the experimentalist to control ionic transport through synthetic nanopores, and use them as a template for the construction of devices. In this research, we present our work on creating a number of ionic analogs to seminal electronic devices, specifically diodes, and transistors, by controlling ionic transport through the electrostatic interactions between a single synthetic nanopore and ions. Control is achieved by "doping" the effective charge carrier concentration in specific regions of the nanopore through manipulation of the pore's surface charge. This manipulation occurs through two mechanisms: chemical modification of the surface charge and electrostatic manipulation of the local internal nanopore potential using a gate electrode. Additionally, the innate selectivity of the charged nanopores walls allows for the separation of charges in solution. This well-known effect, which spawns measureable quantities, the streaming potential and current, has been used to create nanoscale water desalination membranes. We attempt to create a device using membranes with large nanopore densities for the desalination of water which should theoretically outperform currently available devices, as through our previous work we have developed techniques allowing for transport manipulation not current accessible in traditional membrane motifs.

Evolution of Osmolyte Systems.

ERIC Educational Resources Information Center

Banfalvi, Gaspar

1991-01-01

Osmotic aspects of aqueous solutions that are usually disregarded in biochemistry textbooks are presented. This article discusses the osmolarity of seawater, evolution of organisms over geological time, ionic adaptation of cells, ionic concentrations in bacteria, osmolytes and blood electrolytes in water-stressed organisms and land vertebrates,…

Ionic liquids behave as dilute electrolyte solutions

PubMed Central

Gebbie, Matthew A.; Valtiner, Markus; Banquy, Xavier; Fox, Eric T.; Henderson, Wesley A.; Israelachvili, Jacob N.

2013-01-01

We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends. PMID:23716690

Determination of triazine herbicides in juice samples by microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction coupled with high-performance liquid chromatography.

PubMed

Su, Rui; Li, Dan; Wu, Lijie; Han, Jing; Lian, Wenhui; Wang, Keren; Yang, Hongmei

2017-07-01

A novel microextraction method, termed microwave-assisted ionic liquid/ionic liquid dispersive liquid-liquid microextraction, has been developed for the rapid enrichment and analysis of triazine herbicides in fruit juice samples by high-performance liquid chromatography. Instead of using hazardous organic solvents, two kinds of ionic liquids, a hydrophobic ionic liquid (1-hexyl-3-methylimidazolium hexafluorophosphate) and a hydrophilic ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate), were used as the extraction solvent and dispersion agent, respectively, in this method. The extraction procedure was induced by the formation of cloudy solution, which was composed of fine drops of 1-hexyl-3-methylimidazolium hexafluorophosphate dispersed entirely into sample solution with the help of 1-butyl-3-methylimidazolium tetrafluoroborate. In addition, an ion-pairing agent (NH 4 PF 6 ) was introduced to improve recoveries of the ionic liquid phase. Several experimental parameters that might affect the extraction efficiency were investigated. Under the optimum experimental conditions, the linearity for determining the analytes was in the range of 5.00-250.00 μg/L, with the correlation coefficients of 0.9982-0.9997. The practical application of this effective and green method is demonstrated by the successful analysis of triazine herbicides in four juice samples, with satisfactory recoveries (76.7-105.7%) and relative standard deviations (lower than 6.6%). In general, this method is fast, effective, and robust to determine triazine herbicides in juice samples. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Equilibrium II: Acids and Bases. Independent Learning Project for Advanced Chemistry (ILPAC). Unit P3.

ERIC Educational Resources Information Center

Inner London Education Authority (England).

This unit on equilibrium is one of 10 first year units produced by the Independent Learning Project for Advanced Chemistry (ILPAC). The unit, which consists of two levels, focuses on the application of equilibrium principles to equilibria involving weak acids and bases, including buffer solutions and indicators. Level one uses Le Chatelier's…

Individual and Co Transport Study of Titanium Dioxide NPs and Zinc Oxide NPs in Porous Media

PubMed Central

Kumari, Jyoti; Mathur, Ankita; Rajeshwari, A.; Venkatesan, Arthi; S, Satyavati; Pulimi, Mrudula; Chandrasekaran, Natarajan; Nagarajan, R.; Mukherjee, Amitava

2015-01-01

The impact of pH and ionic strength on the mobility (individual and co-transport) and deposition kinetics of TiO2 and ZnO NPs in porous media was systematically investigated in this study. Packed column experiments were performed over a series of environmentally relevant ionic strengths with both NaCl (0.1−10 mM) and CaCl2 (0.01–0.1mM) solutions and at pH 5, 7, and 9. The transport of TiO2 NPs at pH 5 was not significantly affected by ZnO NPs in solution. At pH 7, a decrease in TiO2 NP transport was noted with co-existence of ZnO NPs, while at pH 9 an increase in the transport was observed. At pH 5 and 7, the transport of ZnO NPs was decreased when TiO2 NPs was present in the solution, and at pH 9, an increase was noted. The breakthrough curves (BTC) were noted to be sensitive to the solution chemistries; the decrease in the breakthrough plateau with increasing ionic strength was observed under all examined pH (5, 7, and 9). The retention profiles were the inverse of the plateaus of BTCs, as expected from mass balance considerations. Overall, the results from this study suggest that solution chemistries (ionic strength and pH) are likely the key factors that govern the individual and co-transport behavior of TiO2 and ZnO NPs in sand. PMID:26252479

Effects of surfactants on lipase structure, activity, and inhibition.

PubMed

Delorme, Vincent; Dhouib, Rabeb; Canaan, Stéphane; Fotiadu, Frédéric; Carrière, Frédéric; Cavalier, Jean-François

2011-08-01

Lipase inhibitors are the main anti-obesity drugs prescribed these days, but the complexity of their mechanism of action is making it difficult to develop new molecules for this purpose. The efficacy of these drugs is known to depend closely on the physico-chemistry of the lipid-water interfaces involved and on the unconventional behavior of the lipases which are their target enzymes. The lipolysis reaction which occurs at an oil-water interface involves complex equilibria between adsorption-desorption processes, conformational changes and catalytic mechanisms. In this context, surfactants can induce significant changes in the partitioning of the enzyme and the inhibitor between the water phase and lipid-water interfaces. Surfactants can be found at the oil-water interface where they compete with lipases for adsorption, but also in solution in the form of micellar aggregates and monomers that may interact with hydrophobic parts of lipases in solution. These various interactions, combined with the emulsification and dispersion of insoluble substrates and inhibitors, can either promote or decrease the activity and the inhibition of lipases. Here, we review some examples of the various effects of surfactants on lipase structure, activity and inhibition, which show how complex the various equilibria involved in the lipolysis reaction tend to be.

On application of asymmetric Kan-like exact equilibria to the Earth magnetotail modeling

NASA Astrophysics Data System (ADS)

Korovinskiy, Daniil B.; Kubyshkina, Darya I.; Semenov, Vladimir S.; Kubyshkina, Marina V.; Erkaev, Nikolai V.; Kiehas, Stefan A.

2018-04-01

A specific class of solutions of the Vlasov-Maxwell equations, developed by means of generalization of the well-known Harris-Fadeev-Kan-Manankova family of exact two-dimensional equilibria, is studied. The examined model reproduces the current sheet bending and shifting in the vertical plane, arising from the Earth dipole tilting and the solar wind nonradial propagation. The generalized model allows magnetic configurations with equatorial magnetic fields decreasing in a tailward direction as slow as 1/x, contrary to the original Kan model (1/x3); magnetic configurations with a single X point are also available. The analytical solution is compared with the empirical T96 model in terms of the magnetic flux tube volume. It is found that parameters of the analytical model may be adjusted to fit a wide range of averaged magnetotail configurations. The best agreement between analytical and empirical models is obtained for the midtail at distances beyond 10-15 RE at high levels of magnetospheric activity. The essential model parameters (current sheet scale, current density) are compared to Cluster data of magnetotail crossings. The best match of parameters is found for single-peaked current sheets with medium values of number density, proton temperature and drift velocity.

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

PubMed

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

2018-06-06

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

Studies of bio-mimetic medium of ionic and non-ionic micelles by a simple charge transfer fluorescence probe N,N-dimethylaminonapthyl-(acrylo)-nitrile

NASA Astrophysics Data System (ADS)

Samanta, Anuva; Paul, Bijan Kumar; Guchhait, N.

2011-05-01

In this report we have studied micellization process of anionic, cationic and non-ionic surfactants using N,N-dimethylaminonapthyl-(acrylo)-nitrile (DMANAN) as an external fluorescence probe. Micropolarity, microviscosity, critical micellar concentration of these micelles based on steady state absorption and fluorescence and time resolved emission spectroscopy of the probe DMANAN show that the molecule resides in the micelle-water interface for ionic micelles and in the core for the non-ionic micelle. The effect of variation of pH of the micellar solution as well as fluorescence quenching measurements of DMANAN provide further support for the location of the probe in the micelles.

Ionic Attachment as a Feasible Approach to Heterogenizing Anionic Solution Catalysts. The Carbonylation of Methanol,

DTIC Science & Technology

1980-08-01

carbonylation of methanol to acetic acid reaction is well suited for a demonstration of the feasibility and value of ionically binding a catalyst to a...approximate doubling of the reaction rate. This result suggests that a liquid flow system design in which there is a large catalyst to methanol ratio could...Heterogenizing Anionic Solution Catalysts . The Carbonylation of Methanol by Russell S. Drago, Eric D. Nyberg, Anton El A’mma and Alan Zombeck ABSTRACT -’Few

Vapor-Liquid Equilibria of Imidazolium Ionic Liquids with Cyano Containing Anions with Water and Ethanol.

PubMed

Khan, Imran; Batista, Marta L S; Carvalho, Pedro J; Santos, Luís M N B F; Gomes, José R B; Coutinho, João A P

2015-08-13

Isobaric vapor-liquid equilibria of 1-butyl-3-methylimidazolium thiocyanate ([C4C1im][SCN]), 1-butyl-3-methylimidazolium dicyanamide ([C4C1im][N(CN)2]), 1-butyl-3-methylimidazolium tricyanomethanide ([C4C1im][C(CN)3]), and 1-ethyl-3-methylimidazolium tetracyanoborate ([C2C1im][B(CN)4]), with water and ethanol were measured over the whole concentration range at 0.1, 0.07, and 0.05 MPa. Activity coefficients were estimated from the boiling temperatures of the binary systems, and the data were used to evaluate the ability of COSMO-RS for describing these molecular systems. Aiming at further understanding the molecular interactions on these systems, molecular dynamics (MD) simulations were performed. On the basis of the interpretation of the radial and spatial distribution functions along with coordination numbers obtained through MD simulations, the effect of the increase of CN-groups in the IL anion in its capability to establish hydrogen bonds with water and ethanol was evaluated. The results obtained suggest that, for both water and ethanol systems, the anion [N(CN)2](-) presents the higher ability to establish favorable interactions due to its charge, and that the ability of the anions to interact with the solvent, decreases with further increasing of the number of cyano groups in the anion. The ordering of the partial charges in the nitrogen atoms from the CN-groups in the anions agrees with the ordering obtained for VLE and activity coefficient data.

Supramolecular Assembly of a Biomineralizing Antimicrobial Peptide in Coarse-Grained Monte Carlo Simulations (Postprint)

DTIC Science & Technology

2010-07-05

aqueous solutions at a wide pH range.7 Silica forms rapidly at room temperature in the absence of other ionic catalysts or cofactors (buffers, salts...and other ionic species) that are normally required with in vitro biosilica synthesis. The silaffins are uniquely functionalized; serine residues are...alkaline conditions mimic the properties of the poly- ionic modifications on native silaffins.13,14 The zwitterionic properties facilitate intermolecular

Ionic liquids for addressing unmet needs in healthcare

PubMed Central

Agatemor, Christian; Ibsen, Kelly N.; Tanner, Eden E. L.

2018-01-01

Abstract Advances in the field of ionic liquids have opened new applications beyond their traditional use as solvents into other fields especially healthcare. The broad chemical space, rich with structurally diverse ions, and coupled with the flexibility to form complementary ion pairs enables task‐specific optimization at the molecular level to design ionic liquids for envisioned functions. Consequently, ionic liquids now are tailored as innovative solutions to address many problems in medicine. To date, ionic liquids have been designed to promote dissolution of poorly soluble drugs and disrupt physiological barriers to transport drugs to targeted sites. Also, their antimicrobial activity has been demonstrated and could be exploited to prevent and treat infectious diseases. Metal‐containing ionic liquids have also been designed and offer unique features due to incorporation of metals. Here, we review application‐driven investigations of ionic liquids in medicine with respect to current status and future potential. PMID:29376130

Evaporation-based Ge/.sup.68 Ga Separation

DOEpatents

Mirzadeh, Saed; Whipple, Richard E.; Grant, Patrick M.; O'Brien, Jr., Harold A.

1981-01-01

Micro concentrations of .sup.68 Ga in secular equilibrium with .sup.68 Ge in strong aqueous HCl solution may readily be separated in ionic form from the .sup.68 Ge for biomedical use by evaporating the solution to dryness and then leaching the .sup.68 Ga from the container walls with dilute aqueous solutions of HCl or NaCl. The chloro-germanide produced during the evaporation may be quantitatively recovered to be used again as a source of .sup.68 Ga. If the solution is distilled to remove any oxidizing agents which may be present as impurities, the separation factor may easily exceed 10.sup.5. The separation is easily completed and the .sup.68 Ga made available in ionic form in 30 minutes or less.

Structural, thermodynamic, and electrical properties of polar fluids and ionic solutions on a hypersphere: Results of simulations

NASA Astrophysics Data System (ADS)

Caillol, J. M.; Levesque, D.

1992-01-01

The reliability and the efficiency of a new method suitable for the simulations of dielectric fluids and ionic solutions is established by numerical computations. The efficiency depends on the use of a simulation cell which is the surface of a four-dimensional sphere. The reliability originates from a charge-charge potential solution of the Poisson equation in this confining volume. The computation time, for systems of a few hundred molecules, is reduced by a factor of 2 or 3 compared to this of a simulation performed in a cubic volume with periodic boundary conditions and the Ewald charge-charge potential.

Reversible water uptake/release by thermoresponsive polyelectrolyte hydrogels derived from ionic liquids.

PubMed

Deguchi, Yuki; Kohno, Yuki; Ohno, Hiroyuki

2015-06-07

Thermoresponsive polyelectrolyte hydrogels, derived from tetra-n-alkylphosphonium 3-sulfopropyl methacrylate-type ionic liquid monomers, show reversible water uptake/release, in which the gels absorb/desorb water for at least ten cycles via a lower critical solution temperature-type phase transition.

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

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

Wu, Boning; Liang, Min; Zmich, Nicole

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

Photoinduced Bimolecular Electron Transfer in Ionic Liquids: Cationic Electron Donors

DOE PAGES

Wu, Boning; Liang, Min; Zmich, Nicole; ...

2018-01-29

Recently, we have reported a systematic study of photoinduced electron-transfer reactions in ionic liquid solvents using neutral and anionic electron donors and a series of cyano-substituted anthracene acceptors [Wu, B.; Maroncelli, M.; Castner, E. W., Jr.Photoinduced Bimolecular Electron Transfer in Ionic Liquids. J. Am. Chem. Soc.139, 2017, 14568]. In this paper, we report complementary results for a cationic class of 1-alkyl-4-dimethylaminopyridinium electron donors. Reductive quenching of cyano-substituted anthracene fluorophores by these cationic quenchers is studied in solutions of acetonitrile and the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Varying the length of the alkyl chain permits tuning of the quencher diffusivities in solution.more » The observed quenching kinetics are interpreted using a diffusion-reaction analysis. Finally, together with results from the prior study, these results show that the intrinsic electron-transfer rate constant does not depend on the quencher charge in this family of reactions.« less

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

Method and apparatus for processing algae

DOEpatents

Chew, Geoffrey; Reich, Alton J.; Dykes, Jr., H. Waite; Di Salvo, Roberto

2012-07-03

Methods and apparatus for processing algae are described in which a hydrophilic ionic liquid is used to lyse algae cells. The lysate separates into at least two layers including a lipid-containing hydrophobic layer and an ionic liquid-containing hydrophilic layer. A salt or salt solution may be used to remove water from the ionic liquid-containing layer before the ionic liquid is reused. The used salt may also be dried and/or concentrated and reused. The method can operate at relatively low lysis, processing, and recycling temperatures, which minimizes the environmental impact of algae processing while providing reusable biofuels and other useful products.

Effect of Cerium(III) and ionic liquids on the clouding behavior of Triton X-100 micelles

NASA Astrophysics Data System (ADS)

Sen, Indrani Das; Negi, Charu; Jayaram, Radha V.

2018-04-01

In the present study, the effect of Ce(III) on the clouding behavior of Triton X-100 has been investigated in the presence and absence of imidazolium based ionic liquids of varying chain length and counter ions. Thermodynamic parameters of clouding were calculated to comprehend the underlying interactions between the surfactant and the additives. The cloud point (CP) of Triton X-100 was found to increase with the concentration of Ce(III) and that of the ionic liquids studied. This increase of CP reflects the solubilization of the ionic liquids in the micellar solution1.

Signaling equilibria in sensorimotor interactions.

PubMed

Leibfried, Felix; Grau-Moya, Jordi; Braun, Daniel A

2015-08-01

Although complex forms of communication like human language are often assumed to have evolved out of more simple forms of sensorimotor signaling, less attention has been devoted to investigate the latter. Here, we study communicative sensorimotor behavior of humans in a two-person joint motor task where each player controls one dimension of a planar motion. We designed this joint task as a game where one player (the sender) possesses private information about a hidden target the other player (the receiver) wants to know about, and where the sender's actions are costly signals that influence the receiver's control strategy. We developed a game-theoretic model within the framework of signaling games to investigate whether subjects' behavior could be adequately described by the corresponding equilibrium solutions. The model predicts both separating and pooling equilibria, in which signaling does and does not occur respectively. We observed both kinds of equilibria in subjects and found that, in line with model predictions, the propensity of signaling decreased with increasing signaling costs and decreasing uncertainty on the part of the receiver. Our study demonstrates that signaling games, which have previously been applied to economic decision-making and animal communication, provide a framework for human signaling behavior arising during sensorimotor interactions in continuous and dynamic environments. Copyright © 2015 Elsevier B.V. All rights reserved.

Determination of melanterite-rozenite and chalcanthite-bonattite equilibria by humidity measurements at 0.1 MPa

USGS Publications Warehouse

Chou, I.-Ming; Seal, R.R.; Hemingway, B.S.

2002-01-01

Melanterite (FeSO4??7H2O)-rozenite (FeSO4??4H2O) and chalcanthite (CuSO4??5H2O)-bonattite (CuSO4??3H2O) equilibria were determined by humidity measurements at 0.1 MPa. Two methods were used; one is the gas-flow-cell method (between 21 and 98 ??C), and the other is the humidity-buffer method (between 21 and 70 ??C). The first method has a larger temperature uncertainty even though it is more efficient. With the aid of humidity buffers, which correspond to a series of saturated binary salt solutions, the second method yields reliable results as demonstrated by very tight reversals along each humidity buffer. These results are consistent with those obtained by the first method, and also with the solubility data reported in the literature. Thermodynamic analysis of these data yields values of 29.231 ?? 0.025 and 22.593 ?? 0.040 kJ/mol for standard Gibbs free energy of reaction at 298.15 K and 0.1 MPa for melanterite-rozenite and chalcanthite-bonattite equilibria, respectively. The methods used in this study hold great potential for unraveling the thermodynamic properties of sulfate salts involved in dehydration reactions at near ambient conditions.

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.

Fluorescent probe studies of polarity and solvation within room temperature ionic liquids: a review.

PubMed

Pandey, Shubha; Baker, Sheila N; Pandey, Siddharth; Baker, Gary A

2012-09-01

Ionic liquids display an array of useful and sometimes unconventional, solvent features and have attracted considerable interest in the field of green chemistry for the potential they hold to significantly reduce environmental emissions. Some of these points have a bearing on the chemical reactivity of these systems and have also generated interest in the physical and theoretical aspects of solvation in ionic liquids. This review presents an introduction to the field of ionic liquids, followed by discussion of investigations into the solvation properties of neat ionic liquids or mixed systems including ionic liquids as a major or minor component. The ionic liquid based multicomponent systems discussed are composed of other solvents, other ionic liquids, carbon dioxide, surfactants or surfactant solutions. Although we clearly focus on fluorescence spectroscopy as a tool to illuminate ionic liquid systems, the issues discussed herein are of general relevance to discussions of polarity and solvent effects in ionic liquids. Transient solvation measurements carried out by means of time-resolved fluorescence measurements are particularly powerful for their ability to parameterize the kinetics of the solvation process in ionic liquids and are discussed as well.

Concentration Fluctuations and Capacitive Response in Dense Ionic Solutions.

PubMed

Uralcan, Betul; Aksay, Ilhan A; Debenedetti, Pablo G; Limmer, David T

2016-07-07

We use molecular dynamics simulations in a constant potential ensemble to study the effects of solution composition on the electrochemical response of a double layer capacitor. We find that the capacitance first increases with ion concentration following its expected ideal solution behavior but decreases upon approaching a pure ionic liquid in agreement with recent experimental observations. The nonmonotonic behavior of the capacitance as a function of ion concentration results from the competition between the independent motion of solvated ions in the dilute regime and solvation fluctuations in the concentrated regime. Mirroring the capacitance, we find that the characteristic decay length of charge density correlations away from the electrode is also nonmonotonic. The correlation length first decreases with ion concentration as a result of better electrostatic screening but increases with ion concentration as a result of enhanced steric interactions. When charge fluctuations induced by correlated ion-solvent fluctuations are large relative to those induced by the pure ionic liquid, such capacitive behavior is expected to be generic.

Preconcentration of aqueous dyes through phase-transfer liquid-phase microextraction with a room-temperature ionic liquid.

PubMed

Chen, Hsiu-Liang; Chang, Shuo-Kai; Lee, Chia-Ying; Chuang, Li-Lin; Wei, Guor-Tzo

2012-09-12

In this study, we employed the room-temperature ionic liquid [bmim][PF(6)] as both ion-pair agent and an extractant in the phase-transfer liquid-phase microextraction (PTLPME) of aqueous dyes. In the PTLPME method, a dye solution was added to the extraction solution, comprising a small amount of [bmim][PF(6)] in a relatively large amount of CH(2)Cl(2), which serves as the disperser solvent to an extraction solution. Following extraction, CH(2)Cl(2) was evaporated from the extractant, resulting in the extracted dyes being concentrated in a small volume of the ionic liquid phase to increase the enrichment factor. The enrichment factors of for the dye Methylene Blue, Neutral Red, and Methyl Red were approximately 500, 550 and 400, respectively; their detection limits were 0.014, 0.43, and 0.02 μg L(-1), respectively, with relative standard deviations of 4.72%, 4.20%, and 6.10%, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

Halide Ions Effects on Surface Excess of Long Chain Ionic Liquids Water Solutions

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

Wang, Wenjie; Sung, Woongmo; Ao, Mingqi

2013-10-07

The interfacial structure and composition of water solutions with alkylimidazolium ionic liquids varying in their halide anions ([C12mim][X], X = Cl and I) were investigated by X-ray near-total-reflection fluorescence spectroscopy and X-ray reflectivity measurements. We demonstrate that X-ray fluorescence and reflectivity techniques provide a more direct measurement of surface adsorption. Furthermore, we show that for [C12mim][Cl] and [C12mim][I] solutions with mixed inorganic salts (NaI, NaCl), I– ions replace Cl– above the critical micelle concentration (CMC) of [C12mim][Cl] at much lower concentrations of NaI, whereas NaCl concentrations a hundred times higher than the CMC of [C12mim][I] only partially replace the I–more » at the interface. Our surface-sensitive X-ray diffraction and spectroscopy provide two independent tools to directly determine the surface adsorption of ionic surfactants and the interfacial composition of the surface films.« less

Connecting the solution chemistry of PbI2 and MAI: a cyclodextrin-based supramolecular approach to the formation of hybrid halide perovskites† †Electronic supplementary information (ESI) available: Experimental section; Section 1: solution characterization; Section 2: solar cell optimization and characterization; Section 3: thin film characterization; Section 4: advanced structural characterization. See DOI: 10.1039/c7sc05095j

PubMed Central

Masi, Sofia; Aiello, Federica; Listorti, Andrea; Balzano, Federica; Altamura, Davide; Giannini, Cinzia; Caliandro, Rocco; Uccello-Barretta, Gloria

2018-01-01

The evolution from solvated precursors to hybrid halide perovskite films dictates most of the photophysical and optoelectronic properties of the final polycrystalline material. Specifically, the complex equilibria and the importantly different solubilities of lead iodide (PbI2) and methylammonium iodide (MAI) induce inhomogeneous crystal growth, often leading to a defect dense film showing non-optimal optoelectronic properties and intrinsic instability. Here, we explore a supramolecular approach based on the use of cyclodextrins (CDs) to modify the underlying solution chemistry. The peculiar phenomenon demonstrated is a tunable complexation between different CDs and MA+ cations concurrent to an out of cage PbI2 intercalation, representing the first report of a connection between the solvation equilibria of the two perovskite precursors. The optimal conditions in terms of CD cavity size and polarity translate to a neat enhancement of PbI2 solubility in the reaction media, leading to an equilibration of the availability of the precursors in solution. The macroscopic result of this is an improved nucleation process, leading to a perovskite material with higher crystallinity, better optical properties and improved moisture resistance. Remarkably, the use of CDs presents a great potential for a wide range of device-related applications, as well as for the development of tailored composite materials. PMID:29732103

Interactions of N,N'-dimethylaminoethanol with steel surfaces in alkaline and chlorine containing solutions

NASA Astrophysics Data System (ADS)

Welle, A.; Liao, J. D.; Kaiser, K.; Grunze, M.; Mäder, U.; Blank, N.

1997-10-01

Formulations based on dilute aqueous solutions of N,N'-dimethylethanolamine (DMEA) are used to protect reinforcement steel bars ('rebar') in concrete from corrosion. In a previous paper we discussed the usefulness of X-ray photoelectron spectroscopy (XPS) to detect DMEA adsorbed from solution and the application of secondary neutral mass spectrometry (SNMS) to study migration of DMEA through a cement matrix. In this report we present XPS data of DMEA adsorbed on steel surfaces from alkaline and chlorine containing solutions of variable concentration range and discuss models for the interaction of DMEA with the oxidized steel surface and the mechanism of corrosion inhibition of DMEA. DMEA is strongly bonded to the steel surface and displaces ionic species from the substrate/solution interface hence protecting the ironoxide surface from ionic attack.

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

Bhattacharya, Raghu N.

An electroplating solution and method for producing an electroplating solution containing a gallium salt, an ionic compound and a solvent that results in a gallium thin film that can be deposited on a substrate.

How Does the Alkyl Chain Length of an Ionic Liquid Influence Solute Rotation in the Presence of an Electrolyte?

PubMed

Prabhu, Sugosh R; Dutt, G B

2016-12-29

Fluorescence anisotropies of a nonpolar solute, 9-phenylanthracene (9-PA), have been measured in 1-alkyl-3-methylimidazolium (alkyl = methyl, butyl, octyl, and dodecyl) bis(trifluoromethylsulfonyl)imides ([RMIM][Tf 2 N]) with varying amounts (0-0.3 mole fraction) of lithium bis(trifluoromethylsulfonyl)imide (LiTf 2 N). This study has been carried out to understand how the length of the alkyl chain and the concentration of the electrolyte influence the rotational diffusion of a nonpolar solute. It has been observed that the addition of an electrolyte to the ionic liquid increases the bulk viscosity of the system significantly, as the Li + cations strongly coordinate with the [Tf 2 N] anions in the polar domains. The reorientation times of 9-PA have been analyzed with the aid of Stokes-Einstein-Debye hydrodynamic (SED) theory, and they fall within the broad limits set by the hydrodynamic slip and stick boundary conditions. However, deviations from the SED theory have been noticed upon addition of LiTf 2 N, and the influence of the electrolyte is more pronounced in the case of ionic liquids with shorter alkyl chains. The observed trends have been rationalized in terms of electrolyte-induced structural changes in these ionic liquids.

Voltammetry and conductivity of a polyether-pyridinium room temperature molten salt electrolyte and of its polymer electrolyte solutions in polydimethylsiloxane

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

Pyati, R.; Murray, R.W.

1996-02-01

This report describes the synthesis, microelectrode voltammetry, and ionic conductivity of a new room temperature molten salt N-(methoxy(ethoxy){sub 2}ethyl)pyridinium p-toluene sulfonate (abbreviated as[Py(E{sub 3}M){sup +}][Tos{sup {minus}}]) and of its solution in a hydroxy-terminated polydimethylsiloxane. Both ionically conductive liquids (conductivity = 1 {times} 10{sup {minus}4} {Omega}{sup {minus}1} cm{sup {minus}1}) exhibit voltammetric potential windows of about 1.5 V. The negative potential limit is determined by the reduction of the [Py(E{sub 3}M){sup +}] pyridinium species, with subsequent radical coupling to form a voltammetrically observed viologen dimer. The estimated diffusivities of the [Py(E{sub 3}M){sup +}] species, of a diethyleneglycol-tailed ferrocene redox solute studied, andmore » by application of Nernst-Einstein relation to the ionic charge carriers, all lie in the 10{sup {minus}7} to 10{sup {minus}8} cm{sup 2}/s range. Viscosities and glass transition thermal observations are reported as is the fit of the temperature dependencies of ionic conductivity in [Py(E{sub 3}M){sup +}][Tos{sup {minus}}] and in [Py(E{sub 3}M){sup +}][TOS{sup {minus}}]/PDMS mixtures to Vogel-Tamman-Fulcher predictions.« less

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

PubMed

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

2013-06-15

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

Monosilicide-disilicide-silicon phase equilibria in the nickel-platinum-silicon and nickel-palladium-silicon systems

NASA Astrophysics Data System (ADS)

Loomans, M. E.; Chi, D. Z.; Chua, S. J.

2004-10-01

Bulk-phase equilibria in Ni-rich/Si-rich alloys of the Ni-Pt-Si and Ni-Pd-Si systems were investigated. Results suggest that a bulk monosilicide solid solution, containing up to at least 11 at. pct Pt, exists in the Ni-Pt-Si system. Monosilicides containing more than 11 at. pct Pt were not examined. Results from both ternary systems point convincingly to the existence of a NiSi+Si↔NiSi2 eutectoid reaction near 700 °C in the Ni-Si binary system; data from the Ni-Pt-Si system, which yield the more accurate determination of the eutectoid temperature, place it at roughly 710 °C. The Pt and Pd concentrations of monosilicide in equilibrium with disilicide and Si were measured using energy-dispersive spectrometry (EDS) and were found to increase with temperature.

Planar attitude motion of a satellite with a variable mass distribution in field of gravity of attracting center

NASA Astrophysics Data System (ADS)

Burov, Alexander; Kosenko, Ivan

2018-05-01

Dynamics of a spacecraft with a variable mass distribution in a central field of Newtonian attraction is considered. Using another viewpoint one can regard sufficiently compact formation instead of a spacecraft. This formation can vary distances between its particular spacecrafts thus implementing pulsing motions of the system as a whole. Within the so-called "satellite approximation" the equations of spatial attitude motion are obtained. Rules of the mass redistribution providing prescribed in advance attitude motions are indicated. For classes of relative equilibria previously found and existing under appropriate rules of the mass redistribution, stability study is performed. The investigation splits into two topics: (a) general dynamical consideration for the planar attitude satellite motion with use of the KAM theory; (b) constructing the families of periodic solutions represented by means of convergent series in powers of eccentricity and describing satellite motions emanating from its relative equilibria.

The presence of functional groups key for biodegradation in ionic liquids: effect on gas solubility.

PubMed

Deng, Yun; Morrissey, Saibh; Gathergood, Nicholas; Delort, Anne-Marie; Husson, Pascale; Costa Gomes, Margarida F

2010-03-22

The effect of the incorporation of either ester or ester and ether functions into the side chain of an 1-alkyl-3-methylimidazolium cation on the physico-chemical properties of ionic liquids containing bis(trifluoromethylsulfonyl)imide or octylsulfate anions is studied. It is believed that the introduction of an ester function into the cation of the ionic liquids greatly increases their biodegradability. The density of three such ionic liquids is measured as a function of temperature, and the solubility of four gases-carbon dioxide, ethane, methane, and hydrogen-is determined between 303 K and 343 K and at pressures close to atmospheric level. Carbon dioxide is the most soluble gas, followed by ethane and methane; the mole fraction solubilities vary from 1.8 x 10(-3) to 3.7 x 10(-2). These solubilities are of the same order of magnitude as those determined for alkylimidazolium-based ionic liquids. The chemical modification of the alkyl side chain does not result in a significant change of the solvation properties of the ionic liquid. All of the solubilities decrease with increasing temperature, corresponding to an exothermal solvation process. From the variation of this property with temperature, the thermodynamic functions of solvation (Gibbs energy, enthalpy, and entropy) are calculated and provide information about the solute-solvent interactions and the molecular structure of the solutions.

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

PubMed Central

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

2017-01-01

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

Refinement of current monitoring methodology for electroosmotic flow assessment under low ionic strength conditions

PubMed Central

Saucedo-Espinosa, Mario A.; Lapizco-Encinas, Blanca H.

2016-01-01

Current monitoring is a well-established technique for the characterization of electroosmotic (EO) flow in microfluidic devices. This method relies on monitoring the time response of the electric current when a test buffer solution is displaced by an auxiliary solution using EO flow. In this scheme, each solution has a different ionic concentration (and electric conductivity). The difference in the ionic concentration of the two solutions defines the dynamic time response of the electric current and, hence, the current signal to be measured: larger concentration differences result in larger measurable signals. A small concentration difference is needed, however, to avoid dispersion at the interface between the two solutions, which can result in undesired pressure-driven flow that conflicts with the EO flow. Additional challenges arise as the conductivity of the test solution decreases, leading to a reduced electric current signal that may be masked by noise during the measuring process, making for a difficult estimation of an accurate EO mobility. This contribution presents a new scheme for current monitoring that employs multiple channels arranged in parallel, producing an increase in the signal-to-noise ratio of the electric current to be measured and increasing the estimation accuracy. The use of this parallel approach is particularly useful in the estimation of the EO mobility in systems where low conductivity mediums are required, such as insulator based dielectrophoresis devices. PMID:27375813

Relationship Between Equilibrium Forms of Lysozyme Crystals and Precipitant Anions

NASA Technical Reports Server (NTRS)

Nadarajah, Arunan

1996-01-01

Molecular forces, such as electrostatic, hydrophobic, van der Waals and steric forces, are known to be important in determining protein interactions. These forces are affected by the solution conditions and changing the pH, temperature or the ionic strength of the solution can sharply affect protein interactions. Several investigations of protein crystallization have shown that this process is also strongly dependent on solution conditions. As the ionic strength of the solution is increased, the initially soluble protein may either crystallize or form an amorphous precipitate at high ionic strengths. Studies done on the model protein hen egg white lysozyme have shown that different crystal forms can be easily and reproducibly obtained, depending primarily on the anion used to desolubilize the protein. In this study we employ pyranine to probe the effect of various anions on the water structure. Additionally, lysozyme crystallization was carried out at these conditions and the crystal form was determined by X-ray crystallography. The goal of the study was to understand the physico-chemical basis for the effect of changing the anion concentration on the equilibrium form of lysozyme crystals. It will also verify the hypothesis that the anions, by altering the bulk water structure in the crystallizing solutions, alter the surface energy of the between the crystal faces and the solution and, consequently, the equilibrium form of the crystals.

Rotational diffusion of nondipolar and charged solutes in alkyl-substituted imidazolium triflimides: effect of C2 methylation on solute rotation.

PubMed

Prabhu, Sugosh R; Dutt, G B

2014-08-07

Rotational diffusion of a nondipolar solute 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and a charged solute rhodamine 110 (R110) has been investigated in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM][Tf2N]) and 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide ([BMMIM][Tf2N]) to understand the influence of the C2 methylation on solute rotation. The measured reorientation times of the nondipolar solute DMDPP are similar in both the ionic liquids and follow Stokes-Einstein-Debye hydrodynamic theory with slip hydrodynamics. In contrast, rotational diffusion of the charged solute R110 in [BMIM][Tf2N] obeys stick hydrodynamics due to specific interactions with the anion of the ionic liquid. Nevertheless, the intriguing result of this study is that the reorientation times of R110 in [BMMIM][Tf2N] deviate significantly from the predictions of stick hydrodynamics, especially at ambient temperatures. The solute-solvent boundary condition parameter Cobs, which is defined as the ratio of the measured reorientation time to the one calculated using the SED theory with stick boundary condition, for R110 is lower by a factor of 2 in [BMMIM][Tf2N] compared to [BMIM][Tf2N] at 298 K. Upon increasing the temperature, Cobs gradually increases and eventually matches with that obtained in [BMIM][Tf2N] at 348 K. It has been well established that methylation of the C2 position in [BMMIM][Tf2N] switches off the main hydrogen-bonding interaction between the anion and the cation, but increases the Coulombic interactions. As a consequence of the enhanced interionic interactions between the cation and anion of the ionic liquid, specific interactions between R110 and [Tf2N] diminish leading to the faster rotation of the solute. However, such an influence is not apparent in case of DMDPP as it does not experience specific interactions with either the cation or the anion of these ionic liquids.

Influence of MRI contrast media on histamine release from mast cells.

PubMed

Kun, Tomasz; Jakubowski, Lucjusz

2012-07-01

Mast cells, owing to diversity of secreted mediators, play a crucial role in the regulation of inflammatory response. Together with basophils, mast cells constitute a central pathogenetic element of anaphylactic (IgE-dependent) and anaphylactoid (IgE-independent) reactions. In severe cases, generalized degranulation of mast cells may cause symptoms of anaphylactic shock. The influence of the classical, iodine-based contrast media on mastocyte degranulation has been fully described. Our objective was to determine the influence of the gadolinium-based MRI contrast media on histamine release from mast cells and to compare the activity of ionic and non-ionic preparations of contrast media. To determine the intensity of mast cell degranulation, we used an experimental model based on mastocytes isolated from rat peritoneal fluid. Purified suspensions of mast cells were incubated with various concentrations of Gd-DTPA and Gd-DTPA-BMA, and solutions of PEG 600 which served as a non-toxic osmotic stimulus. The intensity of mast cell activation was presented as mean percentage of histamine released from cells after incubation. The obtained results demonstrate that both ionic and non-ionic preparations of the MRI contrast media are able to induce mast cell degranulation in vitro. It was also proved that the non-ionic MRI contrast media stimulate mast cells markedly more weakly than ionic contrast media at identical concentration. The aforementioned results may suggest a more profitable safety profile of the non-ionic contrast preparations. We may also conclude that triggering of mast cell degranulation after incubation with the solutions of MRI contrast media results from non-specific osmotic stimulation and direct toxicity of free ionic residues.

The radiation chemistry of ionic liquids: A review

DOE PAGES

Mincher, Bruce J.; Wishart, James F.

2014-07-03

Ionic liquids have received increasing attention as media for radiochemical separations. Recent literature includes examinations of the efficiencies and mechanisms of the solvent extraction of lanthanides, actinides and fission products into ionic liquid solutions. For radiochemical applications, including as replacement solvents for nuclear fuel reprocessing, a thorough understanding of the radiation chemistry of ionic liquids will be required. Such an understanding can be achieved based on a combination of steady-state radiolysis experiments coupled with post-irradiation product identification and pulse-radiolysis experiments to acquire kinetic information. These techniques allow for the elucidation of radiolytic mechanisms. This contribution reviews the current ionic liquidmore » radiation chemistry literature as it affects separations, with these considerations in mind.« less

Active chemisorption sites in functionalized ionic liquids for carbon capture.

PubMed

Cui, Guokai; Wang, Jianji; Zhang, Suojiang

2016-07-25

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

Asymmetric kinetic equilibria: Generalization of the BAS model for rotating magnetic profile and non-zero electric field

NASA Astrophysics Data System (ADS)

Dorville, Nicolas; Belmont, Gérard; Aunai, Nicolas; Dargent, Jérémy; Rezeau, Laurence

2015-09-01

Finding kinetic equilibria for non-collisional/collisionless tangential current layers is a key issue as well for their theoretical modeling as for our understanding of the processes that disturb them, such as tearing or Kelvin Helmholtz instabilities. The famous Harris equilibrium [E. Harris, Il Nuovo Cimento Ser. 10 23, 115-121 (1962)] assumes drifting Maxwellian distributions for ions and electrons, with constant temperatures and flow velocities; these assumptions lead to symmetric layers surrounded by vacuum. This strongly particular kind of layer is not suited for the general case: asymmetric boundaries between two media with different plasmas and different magnetic fields. The standard method for constructing more general kinetic equilibria consists in using Jeans theorem, which says that any function depending only on the Hamiltonian constants of motion is a solution to the steady Vlasov equation [P. J. Channell, Phys. Fluids (1958-1988) 19, 1541 (1976); M. Roth et al., Space Sci. Rev. 76, 251-317 (1996); and F. Mottez, Phys. Plasmas 10, 1541-1545 (2003)]. The inverse implication is however not true: when using the motion invariants as variables instead of the velocity components, the general stationary particle distributions keep on depending explicitly of the position, in addition to the implicit dependence introduced by these invariants. The standard approach therefore strongly restricts the class of solutions to the problem and probably does not select the most physically reasonable. The BAS (Belmont-Aunai-Smets) model [G. Belmont et al., Phys. Plasmas 19, 022108 (2012)] used for the first time the concept of particle accessibility to find new solutions: considering the case of a coplanar-antiparallel magnetic field configuration without electric field, asymmetric solutions could be found while the standard method can only lead to symmetric ones. These solutions were validated in a hybrid simulation [N. Aunai et al., Phys. Plasmas (1994-present) 20, 110702 (2013)], and more recently in a fully kinetic simulation as well [J. Dargent and N. Aunai, Phys. Plasmas (submitted)]. Nevertheless, in most asymmetric layers like the terrestrial magnetopause, one would indeed expect a magnetic field rotation from one direction to another without going through zero [J. Berchem and C. T. Russell, J. Geophys. Res. 87, 8139-8148 (1982)], and a non-zero normal electric field. In this paper, we propose the corresponding generalization: in the model presented, the profiles can be freely imposed for the magnetic field rotation (although restricted to a 180 rotation hitherto) and for the normal electric field. As it was done previously, the equilibrium is tested with a hybrid simulation.

Acid-base properties of brown seaweed biomass considered as a Donnan gel. A model reflecting electrostatic effects and chemical heterogeneity.

PubMed

Rey-Castro, Carlos; Lodeiro, Pablo; Herrero, Roberto; Sastre de Vicente, Manuel E

2003-11-15

Brown seaweeds are interesting materials to be used as biosorbents for heavy metals due to their high binding ability and low cost. The study of the passive biosorption of protons on this kind of materials and its dependency on pH, ionic strength, and medium composition is essential for the practical application of brown algae in wastewater treatment. This work reports the results of the study of the proton binding equilibria of dead biomass from the seaweeds Sargassum muticum, Cystoseira baccata, and Saccorhiza polyschides by potentiometric titration with a glass electrode in the pH range between 2 and 8. Two different salts, NaCl and KNO3, in concentrations ranging from 0.05 to 2 mol x L(-1), were used as background electrolytes. The influence of the ionic strength was accounted for by means of the Donnan model in combination with the master curve approach. Different empirical expressions to describe the swelling behavior of the biosorbent were tested. On the basis of the intrinsic affinity distribution analysis a unimodal Langmuir-Freundlich isotherm was selected to describe the proton binding properties. The results show very little influence of the type of salt. The ionic strength dependency of the proton binding is very similar for the three species, and average empirical expressions of the Donnan volume are proposed. The maximum proton binding capacities obtained ranged between 2.4 and 2.9 mol x kg(-1), with average intrinsic proton affinity constants between 3.1 and 3.3, and heterogeneity parameters of ca. 0.5 for S. muticum and C. baccata, and slightly higher (ca. 0.7) for S. polyschides. The combined Langmuir-Freundlich equation and Donnan model allowed a good description of the experimental charge vs pH curves obtained.

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

EPA Science Inventory

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

Reactions of Starch in Ionic Liquids

USDA-ARS?s Scientific Manuscript database

We found that starches are found to be soluble at 80 ºC in ionic liquids such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and 1-butyl-3-methylimidazolium dicyanamide (BMIMdca) in concentration up to 10% (w/w). Higher concentrations of biopolymers in these novel solvents resulted in solutions w...

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…

Deposition kinetics of extracellular polymeric substances (EPS) on silica in monovalent and divalent salts.

PubMed

Zhu, Pingting; Long, Guoyu; Ni, Jinren; Tong, Meiping

2009-08-01

The deposition kinetics of extracellular polymeric substances (EPS) on silica surfaces were examined in both monovalent and divalent solutions under a variety of environmentally relevant ionic strength and pH conditions by employing a quartz crystal microbalance with dissipation (DCM-D). Soluble EPS (SEPS) and bound EPS (BEPS) were extracted from four bacterial strains with different characteristics. Maximum favorable deposition rates (k(fa)) were observed for all EPS at low ionic strengths in both NaCl and CaCl2 solutions. With the increase of ionic strength, k(fa) decreased due to the simultaneous occurrence of EPS aggregation in solutions. Deposition efficiency (alpha; the ratio of deposition rates obtained under unfavorable versus corresponding favorable conditions) for all EPS increased with increasing ionic strength in both NaCl and CaCl2 solutions, which agreed with the trends of zeta potentials and was consistent with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. Comparison of alpha for SEPS and BEPS extracted from the same strain showed that the trends of alpha did not totally agree with trends of zeta potentials, indicating the deposition kinetics of EPS on silica surfaces were not only controlled by DLVO interactions, but also non-DLVO forces. Close comparison of alpha for EPS extracted from different sources showed alpha increased with increasing proteins to polysaccharides ratio. Subsequent experiments for EPS extracted from the same strain but with different proteins to polysaccharides ratios and from activated sludge also showed that alpha were largest for EPS with greatest proteins to polysaccharides ratio. Additional experiments for pure protein and solutions with different pure proteins to pure saccharides ratios further corroborated that larger proteins to polysaccharides ratio resulted in greater EPS deposition.

New recommendations for measuring collagen solubility.

PubMed

Latorre, María E; Lifschitz, Adrian L; Purslow, Peter P

2016-08-01

The heat-solubility of intramuscular collagen is usually conducted in 1/4 Ringer's solution at pH7.4, despite this ionic strength and pH being inappropriate for post-rigor meat. The current work studied the percentage of soluble collagen and hydrothermal isometric tension characteristics of perimysial strips on bovine semitendinosus muscles in either 1/4 Ringer's solution, distilled water, PBS, or a solution of the same salt concentration as 1/4 Ringer's but at pH5.6. Values of % soluble collagen were lower at pH7.4 than 5.6. Increasing ionic strength reduced % soluble collagen. The maximum perimysial isometric tension was independent of the bathing medium, but the percent relaxation was higher at pH7.4 than at pH5.6, and increased with ionic strength of the media. It is recommended that future measurements of collagen solubility and tests on connective tissue components of post-rigor meat should be carried out in a solution of concentrations NaCl and KCl equivalent to those in 1/4 Ringer's, but at pH5.6, a pH relevant to post-rigor meat. Copyright © 2016 Elsevier Ltd. All rights reserved.

Fractionation of poly(methacrylic acid) and poly(vinyl pyridine) in aqueous and organic mobile phases by multidetector thermal field-flow fractionation.

PubMed

Greyling, Guilaume; Pasch, Harald

2017-08-25

Multidetector thermal field-flow fractionation (ThFFF) is shown to be a versatile characterisation platform that can be used to characterise hydrophilic polymers in a variety of organic and aqueous solutions with various ionic strengths. It is demonstrated that ThFFF fractionates isotactic and syndiotactic poly(methacrylic acid) (PMAA) as well as poly(2-vinyl pyridine) (P2VP) and poly(4-vinyl pyridine) (P4VP) according to microstructure in organic solvents and that the ionic strength of the mobile phase has no influence on the retention behaviour of the polymers. With regard to aqueous solutions, it is shown that, despite the weak retention, isotactic and syndiotactic PMAA show different retention behaviours which can qualitatively be attributed to microstructure. Additionally, it is shown that the ionic strength of the mobile phase has a significant influence on the thermal diffusion of polyelectrolytes in aqueous solutions and that the addition of an electrolyte is essential to achieve a microstructure-based separation of P2VP and P4VP in aqueous solutions. Copyright © 2017 Elsevier B.V. All rights reserved.

Potential of Zero Charge and Its Temperature Derivative for Au(111) Electrode|Alkanethiol SAM|1.0 M Aqueous Electrolyte Solution Interfaces: Impact of Electrolyte Solution Ionic Strength and Its Effect on the Structure of the Modified Electrode|Electrolyte Solution Interface

DOE PAGES

Smalley, John F.

2017-04-06

In this study, we demonstrate how small and rapid temperature perturbations (produced by the indirect laser-induced temperature jump (ILIT) technique) of solid metal electrode|electrolyte solution interfaces may be used to determine the potential of zero (total) charge (E pzc) and its temperature derivativemore » $$\\left(\\frac{dEpzc}{dT}\\right)$$ of Au(111) electrode surfaces modified by alkanethiol self-assembled monolayers in contact with high ionic strength (i.e., 1.0 M) aqueous electrolyte solutions. The E pzc’s measured for two different types of SAMs (made from either HS(CH 2) n-1CH 3 (5 ≤ n ≤ 12, E pzc = -(0.99 ± 0.12) V vs SSCE) or HS(CH 2) nOH (3 ≤ n ≤ 16, E pzc = (0.46 ± 0.22) V vs SSCE)) are considerably different than those measured previously at much lower electrolyte solution ionic strengths. For mixed monolayers made from both HS(CH 2) n-1CH 3 and HS(CH 2) nFc (where Fc refers to ferrocene), the difference in Epzc decreases as a function of the surface concentration of the Fc moiety (i.e., [Fc]), and it completely disappears at a surprisingly small [Fc] (~4.0 × 10 –11 mol cm –2). These observations for the Au(111)|hydrophobic (neat and mixed) SAM|aqueous electrolyte solution interfaces, along with the surface potentials (g Sml(dip)) evaluated for the contacting electrolyte solution surfaces of these interfaces, are consistent with a structure for the water molecule components of these surfaces where there is a net orientation of the dipoles of these molecules. Accordingly, the negative (oxygen) ends of these molecules point toward the SAM surface. The positive values of g Sml(dip) evaluated for hydrophilic SAM (e.g., made from HS(CH 2) nOH)|aqueous electrolyte solution interfaces) also indicate that the structure of these interfaces is similar to that of the hydrophobic interfaces. However, g Sml(dip) decreases with increasing ionic strength for the hydrophilic interfaces, while it increases with increasing ionic strength for the hydrophobic interfaces. The data (and calculations) reported in the present work and other studies of hydrophobic (and hydrophilic)|aqueous solution interfaces are as yet insufficient to support a complete explanation for the effects of ionic strength observed in the present study. Nevertheless, an analysis based upon the value of $$\\left(\\frac{dEpzc}{dT}\\right)$$ (= (0.51 ± 0.12) mV/K, essentially the same for SAMs made from both HS(CH 2) n-1CH 3 and HS(CH 2) nOH), determined in the present study provides a further indication that upon formation of the SAM there is a partial charge transfer of electrons from the relevant gold atoms on the Au(111) surface to the sulfur atoms of the alkanethiols.« less

Structure and equilibria of Ca 2+-complexes of glucose and sorbitol from multinuclear ( 1H, 13C and 43Ca) NMR measurements supplemented with molecular modelling calculations

NASA Astrophysics Data System (ADS)

Pallagi, A.; Dudás, Cs.; Csendes, Z.; Forgó, P.; Pálinkó, I.; Sipos, P.

2011-05-01

Ca 2+-complexation of D-glucose and D-sorbitol have been investigated with the aid of multinuclear ( 1H, 13C and 43Ca) NMR spectroscopy and ab initio quantum chemical calculations. Formation constants of the forming 1:1 complexes have been estimated from one-dimensional 13C NMR spectra obtained at constant ionic strength (1 M NaCl). Binding sites were identified from 2D 1H- 43Ca NMR spectra. 2D NMR measurements and ab initio calculations indicated that Ca 2+ ions were bound in a tridentate manner via the glycosidic OH, the ethereal oxygen in the ring and the OH on the terminal carbon for the α- and β-anomers of glucose and for sorbitol simultaneous binding of four hydroxide moieties (C1, C2, C4 and C6) was suggested.

SEPARATION OF PLUTONIUM FROM FISSION PRODUCTS BY A COLLOID REMOVAL PROCESS

DOEpatents

Schubert, J.

1960-05-24

A method is given for separating plutonium from uranium fission products. An acidic aqueous solution containing plutonium and uranium fission products is subjected to a process for separating ionic values from colloidal matter suspended therein while the pH of the solution is maintained between 0 and 4. Certain of the fission products, and in particular, zirconium, niobium, lanthanum, and barium are in a colloidal state within this pH range, while plutonium remains in an ionic form, Dialysis, ultracontrifugation, and ultrafiltration are suitable methods of separating plutonium ions from the colloids.

Electrochemical Deposition of Niobium onto the Surface of Copper Using a Novel Choline Chloride-Based Ionic Liquid

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

Wixtroma, Alex I.; Buhlera, Jessica E.; Reece, Charles E.

2013-06-01

Recent research has shown that choline chloride-based solutions can be used to replace acid-based electrochemical polishing solutions. In this study niobium metal was successfully deposited on the surface of copper substrate via electrochemical deposition using a novel choline chloride-based ionic liquid. The niobium metal used for deposition on the Cu had been dissolved in the solution from electrochemical polishing of a solid niobium piece prior to the deposition. The visible coating on the surface of the Cu was analyzed using scanning electron microscopy (SEM) and electron dispersive x-ray spectroscopy (EDX). This deposition method effectively recycles previously dissolved niobium from electrochemicalmore » polishing.« less

Numerical Solution of the Extended Nernst-Planck Model.

PubMed

Samson; Marchand

1999-07-01

The main features of a numerical model aiming at predicting the drift of ions in an electrolytic solution upon a chemical potential gradient are presented. The mechanisms of ionic diffusion are described by solving the extended Nernst-Planck system of equations. The electrical coupling between the various ionic fluxes is accounted for by the Poisson equation. Furthermore, chemical activity effects are considered in the model. The whole system of nonlinear equations is solved using the finite-element method. Results yielded by the model for simple test cases are compared to those obtained using an analytical solution. Applications of the model to more complex problems are also presented and discussed. Copyright 1999 Academic Press.

Experimental determination of solubilities of di-calcium ethylenediaminetetraacetic acid hydrate [Ca2C10H12N2O8·7H2O(s)] in NaCl and MgCl2 solutions to high ionic strengths and its Pitzer model: Applications to geological disposal of nuclear waste and other low temperature environments

DOE PAGES

Xiong, Yongliang; Kirkes, Leslie; Westfall, Terry

2017-04-01

In this study, solubility measurements on di-calcium ethylenediaminetetraacetic acid [Ca 2C 10H 12N 2O 8(s), abbreviated as Ca 2EDTA(s)] as a function of ionic strength are conducted in NaCl solutions up to I = 5.0 mol•kg –1 and in MgCl 2 solutions up to I = 7.5 mol•kg –1, at room temperature (22.5 ± 0.5oC).

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Amphiphilic zinc phthalocyanine photosensitizers: synthesis, photophysicochemical properties and in vitro studies for photodynamic therapy.

PubMed

Çakır, Dilek; Göksel, Meltem; Çakır, Volkan; Durmuş, Mahmut; Biyiklioglu, Zekeriya; Kantekin, Halit

2015-05-28

Peripherally and non-peripherally tetra-substituted zinc(ii) phthalocyanines bearing 2-(2-{2-[3-(dimethylamino)phenoxy]ethoxy}ethoxy)ethoxy and 2-(2-{2-[3-(diethylamino)phenoxy]ethoxy}ethoxy)ethoxy groups (, , and ) were synthesized by cyclotetramerization of the corresponding phthalonitriles (, , and ). Their quaternized ionic derivatives (, , and ) were also synthesized by the reaction of them with methyl iodide. The novel compounds were characterized by using standard spectroscopic techniques such as FT-IR, (1)H NMR, (13)C NMR, UV-vis, mass and elemental analyses. The obtained quaternized phthalocyanines (, , and ) showed amphiphilic behaviour with excellent solubility in both organic and aqueous solutions, which makes them potential photosensitizers for use in photodynamic therapy (PDT) of cancer. The photophysical (fluorescence quantum yields and lifetimes) and photochemical (singlet oxygen and photodegradation quantum yields) properties of these novel phthalocyanines were studied in DMSO for both non-ionic and ionic quaternized derivatives. However, these properties were examined in both DMSO and phosphate buffer solution (PBS) for quaternized ionic phthalocyanines. The effects of the positions of substituents (peripheral or non-peripheral) and the quaternization of the nitrogen atoms on the substituents about their photophysical and photochemical properties were also compared in this study. The bovine serum albumin (BSA) binding behaviours of the studied quaternized ionic zinc(ii) phthalocyanines were also described in PBS solutions. The quaternized phthalocyanines (, , and ) successfully displayed light-dependent photodamage in HeLa and HuH-7 cancer cells in photodynamic therapy treatment. The photosensitivity and the intensity of damage were found directly related to the concentration of the photosensitizers.

Calculating Equilibrium Constants in the SnCl2-H2O-NaOH System According to Potentiometric Titration Data

NASA Astrophysics Data System (ADS)

Maskaeva, L. N.; Fedorova, E. A.; Yusupov, R. A.; Markov, V. F.

2018-05-01

The potentiometric titration of tin chloride SnCl2 is performed in the concentration range of 0.00009-1.1 mol/L with a solution of sodium hydroxide NaOH. According to potentiometric titration data based on modeling equilibria in the SnCl2-H2O-NaOH system, basic equations are generated for the main processes, and instability constants are calculated for the resulting hydroxo complexes and equilibrium constants of low-soluble tin(II) compounds. The data will be of interest for specialists in the field of theory of solutions.

The Spectral Web of stationary plasma equilibria. II. Internal modes

NASA Astrophysics Data System (ADS)

Goedbloed, J. P.

2018-03-01

The new method of the Spectral Web to calculate the spectrum of waves and instabilities of plasma equilibria with sizeable flows, developed in the preceding Paper I [Goedbloed, Phys. Plasmas 25, 032109 (2018)], is applied to a collection of classical magnetohydrodynamic instabilities operating in cylindrical plasmas with shear flow or rotation. After a review of the basic concepts of the complementary energy giving the solution path and the conjugate path, which together constitute the Spectral Web, the cylindrical model is presented and the spectral equations are derived. The first example concerns the internal kink instabilities of a cylindrical force-free magnetic field of constant α subjected to a parabolic shear flow profile. The old stability diagram and the associated growth rate calculations for static equilibria are replaced by a new intricate stability diagram and associated complex growth rates for the stationary model. The power of the Spectral Web method is demonstrated by showing that the two associated paths in the complex ω-plane nearly automatically guide to the new class of global Alfvén instabilities of the force-free configuration that would have been very hard to predict by other methods. The second example concerns the Rayleigh-Taylor instability of a rotating theta-pinch. The old literature is revisited and shown to suffer from inconsistencies that are remedied. The most global n = 1 instability and a cluster sequence of more local but much more unstable n =2 ,3 ,…∞ modes are located on separate solution paths in the hydrodynamic (HD) version of the instability, whereas they merge in the MHD version. The Spectral Web offers visual demonstration of the central position the HD flow continuum and of the MHD Alfvén and slow magneto-sonic continua in the respective spectra by connecting the discrete modes in the complex plane by physically meaningful curves towards the continua. The third example concerns the magneto-rotational instability (MRI) thought to be operating in accretion disks about black holes. The sequence n =1 ,2 ,… of unstable MRIs is located on one continuous solution path, but also on infinitely many separate loops ("pancakes") of the conjugate path with just one MRI on each of them. For narrow accretion disks, those sequences are connected with the slow magneto-sonic continuum, which is far away though from the marginal stability transition. In this case, the Spectral Web method is the first to effectively incorporate the MRIs into the general MHD spectral theory of equilibria with background flows. Together, the three examples provide compelling evidence of the computational power of the Spectral Web Method.

Two-craft Coulomb formation study about circular orbits and libration points

NASA Astrophysics Data System (ADS)

Inampudi, Ravi Kishore

This dissertation investigates the dynamics and control of a two-craft Coulomb formation in circular orbits and at libration points; it addresses relative equilibria, stability and optimal reconfigurations of such formations. The relative equilibria of a two-craft tether formation connected by line-of-sight elastic forces moving in circular orbits and at libration points are investigated. In circular Earth orbits and Earth-Moon libration points, the radial, along-track, and orbit normal great circle equilibria conditions are found. An example of modeling the tether force using Coulomb force is discussed. Furthermore, the non-great-circle equilibria conditions for a two-spacecraft tether structure in circular Earth orbit and at collinear libration points are developed. Then the linearized dynamics and stability analysis of a 2-craft Coulomb formation at Earth-Moon libration points are studied. For orbit-radial equilibrium, Coulomb forces control the relative distance between the two satellites. The gravity gradient torques on the formation due to the two planets help stabilize the formation. Similar analysis is performed for along-track and orbit-normal relative equilibrium configurations. Where necessary, the craft use a hybrid thrusting-electrostatic actuation system. The two-craft dynamics at the libration points provide a general framework with circular Earth orbit dynamics forming a special case. In the presence of differential solar drag perturbations, a Lyapunov feedback controller is designed to stabilize a radial equilibrium, two-craft Coulomb formation at collinear libration points. The second part of the thesis investigates optimal reconfigurations of two-craft Coulomb formations in circular Earth orbits by applying nonlinear optimal control techniques. The objective of these reconfigurations is to maneuver the two-craft formation between two charged equilibria configurations. The reconfiguration of spacecraft is posed as an optimization problem using the calculus of variations approach. The optimality criteria are minimum time, minimum acceleration of the separation distance, minimum Coulomb and electric propulsion fuel usage, and minimum electrical power consumption. The continuous time problem is discretized using a pseudospectral method, and the resulting finite dimensional problem is solved using a sequential quadratic programming algorithm. The software package, DIDO, implements this approach. This second part illustrates how pseudospectral methods significantly simplify the solution-finding process.

Social Interactions under Incomplete Information: Games, Equilibria, and Expectations

NASA Astrophysics Data System (ADS)

Yang, Chao

My dissertation research investigates interactions of agents' behaviors through social networks when some information is not shared publicly, focusing on solutions to a series of challenging problems in empirical research, including heterogeneous expectations and multiple equilibria. The first chapter, "Social Interactions under Incomplete Information with Heterogeneous Expectations", extends the current literature in social interactions by devising econometric models and estimation tools with private information in not only the idiosyncratic shocks but also some exogenous covariates. For example, when analyzing peer effects in class performances, it was previously assumed that all control variables, including individual IQ and SAT scores, are known to the whole class, which is unrealistic. This chapter allows such exogenous variables to be private information and models agents' behaviors as outcomes of a Bayesian Nash Equilibrium in an incomplete information game. The distribution of equilibrium outcomes can be described by the equilibrium conditional expectations, which is unique when the parameters are within a reasonable range according to the contraction mapping theorem in function spaces. The equilibrium conditional expectations are heterogeneous in both exogenous characteristics and the private information, which makes estimation in this model more demanding than in previous ones. This problem is solved in a computationally efficient way by combining the quadrature method and the nested fixed point maximum likelihood estimation. In Monte Carlo experiments, if some exogenous characteristics are private information and the model is estimated under the mis-specified hypothesis that they are known to the public, estimates will be biased. Applying this model to municipal public spending in North Carolina, significant negative correlations between contiguous municipalities are found, showing free-riding effects. The Second chapter "A Tobit Model with Social Interactions under Incomplete Information", is an application of the first chapter to censored outcomes, corresponding to the situation when agents" behaviors are subjected to some binding restrictions. In an interesting empirical analysis for property tax rates set by North Carolina municipal governments, it is found that there is a significant positive correlation among near-by municipalities. Additionally, some private information about its own residents is used by a municipal government to predict others' tax rates, which enriches current empirical work about tax competition. The third chapter, "Social Interactions under Incomplete Information with Multiple Equilibria", extends the first chapter by investigating effective estimation methods when the condition for a unique equilibrium may not be satisfied. With multiple equilibria, the previous model is incomplete due to the unobservable equilibrium selection. Neither conventional likelihoods nor moment conditions can be used to estimate parameters without further specifications. Although there are some solutions to this issue in the current literature, they are based on strong assumptions such as agents with the same observable characteristics play the same strategy. This paper relaxes those assumptions and extends the all-solution method used to estimate discrete choice games to a setting with both discrete and continuous choices, bounded and unbounded outcomes, and a general form of incomplete information, where the existence of a pure strategy equilibrium has been an open question for a long time. By the use of differential topology and functional analysis, it is found that when all exogenous characteristics are public information, there are a finite number of equilibria. With privately known exogenous characteristics, the equilbria can be represented by a compact set in a Banach space and be approximated by a finite set. As a result, a finite-state probability mass function can be used to specify a probability measure for equilibrium selection, which completes the model. From Monte Carlo experiments about two types of binary choice models, it is found that assuming equilibrium uniqueness can bring in estimation biases when the true value of interaction intensity is large and there are multiple equilibria in the data generating process.

Disinfection of Spacecraft Potable Water Systems by Passivation with Ionic Silver

NASA Technical Reports Server (NTRS)

Birmele, Michele N.; McCoy, LaShelle e.; Roberts, Michael S.

2011-01-01

Microbial growth is common on wetted surfaces in spacecraft environmental control and life support systems despite the use of chemical and physical disinfection methods. Advanced control technologies are needed to limit microorganisms and increase the reliability of life support systems required for long-duration human missions. Silver ions and compounds are widely used as antimicrobial agents for medical applications and continue to be used as a residual biocide in some spacecraft water systems. The National Aeronautics and Space Administration (NASA) has identified silver fluoride for use in the potable water system on the next generation spacecraft. Due to ionic interactions between silver fluoride in solution and wetted metallic surfaces, ionic silver is rapidly depleted from solution and loses its antimicrobial efficacy over time. This report describes research to prolong the antimicrobial efficacy of ionic silver by maintaining its solubility. Three types of metal coupons (lnconel 718, Stainless Steel 316, and Titanium 6AI-4V) used in spacecraft potable water systems were exposed to either a continuous flow of water amended with 0.4 mg/L ionic silver fluoride or to a static, pre-treatment passivation in 50 mg/L ionic silver fluoride with or without a surface oxidation pre-treatment. Coupons were then challenged in a high-shear, CDC bioreactor (BioSurface Technologies) by exposure to six bacteria previously isolated from spacecraft potable water systems. Continuous exposure to 0.4 mg/L ionic silver over the course of 24 hours during the flow phase resulted in a >7-log reduction. The residual effect of a 24-hour passivation treatment in 50 mg/L of ionic silver resulted in a >3-log reduction, whereas a two-week treatment resulted in a >4-log reduction. Results indicate that 0.4 mg/L ionic silver is an effective biocide against many bacteria and that a prepassivation of metal surfaces with silver can provide additional microbial control.

Ionic liquid as an electrolyte additive for high performance lead-acid batteries

NASA Astrophysics Data System (ADS)

Deyab, M. A.

2018-06-01

The performance of lead-acid battery is improved in this work by inhibiting the corrosion of negative battery electrode (lead) and hydrogen gas evolution using ionic liquid (1-ethyl-3-methylimidazolium diethyl phosphate). The results display that the addition of ionic liquid to battery electrolyte (5.0 M H2SO4 solution) suppresses the hydrogen gas evolution to very low rate 0.049 ml min-1 cm-2 at 80 ppm. Electrochemical studies show that the adsorption of ionic liquid molecules on the lead electrode surface leads to the increase in the charge transfer resistance and the decrease in the double layer capacitance. I also notice a noteworthy improvement of battery capacity from 45 mAh g-1 to 83 mAh g-1 in the presence of ionic liquid compound. Scanning electron microscopy and energy dispersive X-ray analysis confirm the adsorption of ionic liquid molecules on the battery electrode surface.

Electrochemical characterisation of a lithium-ion battery electrolyte based on mixtures of carbonates with a ferrocene-functionalised imidazolium electroactive ionic liquid.

PubMed

Forgie, John C; El Khakani, Soumia; MacNeil, Dean D; Rochefort, Dominic

2013-05-28

Electrolytic solutions of lithium-ion batteries can be modified with additives to improve their stability and safety. Electroactive molecules can be used as such additives to act as an electron (redox) shuttle between the two electrodes to prevent overcharging. The electroactive ionic liquid, 1-ferrocenylmethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (TFSI), was synthesised and its electrochemical properties were investigated when diluted with ethylene carbonate-diethyl carbonate solvent at various concentrations. Cyclic voltammetry data were gathered to determine the redox potential, diffusion coefficient and heterogeneous rate constants of the electroactive imidazolium TFSI ionic liquid in the carbonate solution. The properties of this molecule as an additive in lithium battery electrolytes were studied in standard coin cells with a metallic Li anode and a Li4Ti5O12 cathode.

Long-Term Experimental Determination of Solubilities of Micro-Crystalline Nd(III) Hydroxide in High Ionic Strength Solutions: Applications to Nuclear Waste Management [A Pitzer Model for Am(III)/Nd(III) hydroxide solubility in NaCl-H 2O at 298.15 K to high ionic strengths: Experimental validation and model applications

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

Xiong, Yongliang; Kirkes, Leslie Dawn; Marrs, Cassandra

In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH) 3(micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3(micro cr), avoiding the possibility of phase change.

Long-Term Experimental Determination of Solubilities of Micro-Crystalline Nd(III) Hydroxide in High Ionic Strength Solutions: Applications to Nuclear Waste Management [A Pitzer Model for Am(III)/Nd(III) hydroxide solubility in NaCl-H 2O at 298.15 K to high ionic strengths: Experimental validation and model applications

DOE PAGES

Xiong, Yongliang; Kirkes, Leslie Dawn; Marrs, Cassandra

2017-12-01

In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH) 3(micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3(micro cr), avoiding the possibility of phase change.

Ionic Liquids as Quasihydrostatic Pressure Media for Diamond Anvil Cell Experiments

NASA Astrophysics Data System (ADS)

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

2012-02-01

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

Changes in apparent molar water volume and DKP solubility yield insights on the Hofmeister effect.

PubMed

Payumo, Alexander Y; Huijon, R Michael; Mansfield, Deauna D; Belk, Laurel M; Bui, Annie K; Knight, Anne E; Eggers, Daryl K

2011-12-15

This study examines the properties of a 4 × 2 matrix of aqueous cations and anions at concentrations up to 8.0 M. The apparent molar water volume, as calculated by subtracting the mass and volume of the ions from the corresponding solution density, was found to exceed the molar volume of ice in many concentrated electrolyte solutions, underscoring the nonideal behavior of these systems. The solvent properties of water were also analyzed by measuring the solubility of diketopiperazine (DKP) in 2.000 M salt solutions prepared from the same ion combinations. Solution rankings for DKP solubility were found to parallel the Hofmeister series for both cations and anions, whereas molar water volume concurred with the cation series only. The results are discussed within the framework of a desolvation energy model that attributes solute-specific changes in equilibria to solute-dependent changes in the free energy of bulk water.

Changes in Apparent Molar Water Volume and DKP Solubility Yield Insights on the Hofmeister Effect

PubMed Central

Payumo, Alexander Y.; Huijon, R. Michael; Mansfield, Deauna D.; Belk, Laurel M.; Bui, Annie K.; Knight, Anne E.; Eggers, Daryl K.

2011-01-01

This study examines the properties of a 4 × 2 matrix of aqueous cations and anions at concentrations up to 8.0 M. The apparent molar water volume, as calculated by subtracting the mass and volume of the ions from the corresponding solution density, was found to exceed the molar volume of ice in many concentrated electrolyte solutions, underscoring the non-ideal behavior of these systems. The solvent properties of water were also analyzed by measuring the solubility of diketopiperazine (DKP) in 2.000 M salt solutions prepared from the same ion combinations. Solution rankings for DKP solubility were found to parallel the Hofmeister series for both cations and anions, whereas molar water volume concurred with the cation series only. The results are discussed within the framework of a desolvation energy model that attributes solute-specific changes in equilibria to solute-dependent changes in the free energy of bulk water. PMID:22029390

Water-enhanced solvation of organic solutes in ketone and ester solvents

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

Lee, J.H.; Brunt, V. van; King, C.J.

1994-05-01

Previous research has shown that the solubilities of dicarboxylic acids in certain electron-donor solvents are substantially increased in the presence of water. Information on solubilities, liquid-liquid equilibria and maximum-boiling ternary azeotropes was screened so as to identify other systems where codissolved water appears to enhance solvation of organic solutes in solvents. Several carboxylic acids, an alcohol, diols, and phenols were selected for examination as solutes in ketone and ester solvents. Effects of water upon solute solubilities and volatilities were measured. Results showed that water-enhanced solvation is greatest for carboxylic acids. Solute activity coefficients decreased by factors of 2--3, 6--8, andmore » 7--10 due to the presence of water for mono-, di and tricarboxylic acids, respectively. Activity coefficients decreased by a factor of about 1.5 for ethanol and 1,2-propanediol as solutes. Water-enhanced solvation of phenols is small, when existent.« less

Aquifer modification: an approach to improve the mobility of nanoscale zero-valent iron particles used for in situ groundwater remediation

NASA Astrophysics Data System (ADS)

MicicBatka, Vesna; Schmid, Doris; Marko, Florian; Velimirovic, Milica; Wagner, Stephan; von der Kammer, Frank; Hofmann, Thilo

2015-04-01

Successful emplacement of nanoscale zero-valent iron (nZVI) within the contaminated source zone is a prerequisite for the use of nZVI technology in groundwater remediation. Emplacement of nZVI is influenced i.e., by the injection technique and the injection velocity applied, as well as by the mobility of nZVI in the subsurface. Whereas processes linked to the injection can be controlled by the remediation practitioners, the mobility of nZVI in the subsurface remains limited. Even though mobility of nZVI is somewhat improved by surface coating with polyelectrolytes, it is still greatly affected by the groundwater composition and physical and chemical heterogeneities of aquifer grains. In order to promote mobility of nZVI it is needed to alter the surface charge heterogeneities of aquifer grains. Modifying the aquifer grain's surfaces by means of polyelectrolyte coating is an approach proposed to increase the overall negative surface charge of the aquifer grain surfaces, hinder deposition of nZVI onto aquifer grains, and finally promote nZVI mobility. In this study the effect of different polyelectrolytes on the nZVI mobility is tested in natural sands deriving from real brownfield sites that are proposed to be remediated using the nZVI technology. Sands collected from brownfield sites were characterized in terms of grain size distribution, mineralogical and chemical composition, and organic carbon content. Furthermore, surface charge of these sands was determined in both, low- and high ionic strength background solutions. Finally, changes of the sand's surface charges were examined after addition of the proposed aquifer modifiers, lignin sulfonate and humic acid. Surface charge of brownfield sands in low ionic strength background solution is more negative compared to that in high ionic strength background solution. An increase in negative surface potential of brownfield sand was recorded when aquifer modifiers were applied in a background solution with low ionic strength, indicating their potential to improve nZVI mobility under comparable environmental conditions. In contrast, no significant change of the surface potential of brownfield sand was observed when aquifer modifiers were applied in a background solution with high ionic strength. The potential of the aquifer modifiers to promote the mobility of nZVI was furthermore tested in flow-through columns, starting with the one filled with natural quartz sand with rough surface, low ionic strength background solutions and pre-injecting lignin sulfonate in concentration of 50 mg/L. The preliminary results showed that the pre-injection of lignin sulfonate does increase mobility of nZVI under this experimental condition. Further mobility tests will be carried out in order to elucidate the potential of the aquifer modifiers to promote the mobility of nZVI in sands with a complex mineralogy and in the background solutions with varying ionic strength, in order to account for the condition that resemble those at polluted sites. This research receives funding from the European Union's Seventh Framework Programme FP7/2007-2013 under grant agreement n°309517.

Kinetic description of rotating Tokamak plasmas with anisotropic temperatures in the collisionless regime

NASA Astrophysics Data System (ADS)

Cremaschini, Claudio; Tessarotto, Massimo

2011-11-01

A largely unsolved theoretical issue in controlled fusion research is the consistent kinetic treatment of slowly-time varying plasma states occurring in collisionless and magnetized axisymmetric plasmas. The phenomenology may include finite pressure anisotropies as well as strong toroidal and poloidal differential rotation, characteristic of Tokamak plasmas. Despite the fact that physical phenomena occurring in fusion plasmas depend fundamentally on the microscopic particle phase-space dynamics, their consistent kinetic treatment remains still essentially unchallenged to date. The goal of this paper is to address the problem within the framework of Vlasov-Maxwell description. The gyrokinetic treatment of charged particles dynamics is adopted for the construction of asymptotic solutions for the quasi-stationary species kinetic distribution functions. These are expressed in terms of the particle exact and adiabatic invariants. The theory relies on a perturbative approach, which permits to construct asymptotic analytical solutions of the Vlasov-Maxwell system. In this way, both diamagnetic and energy corrections are included consistently into the theory. In particular, by imposing suitable kinetic constraints, the existence of generalized bi-Maxwellian asymptotic kinetic equilibria is pointed out. The theory applies for toroidal rotation velocity of the order of the ion thermal speed. These solutions satisfy identically also the constraints imposed by the Maxwell equations, i.e., quasi-neutrality and Ampere's law. As a result, it is shown that, in the presence of nonuniform fluid and EM fields, these kinetic equilibria can sustain simultaneously toroidal differential rotation, quasi-stationary finite poloidal flows and temperature anisotropy.

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.

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.

Performance of carbon-carbon supercapacitors based on organic, aqueous and ionic liquid electrolytes

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Olejniczak, Angelika; Galinski, Maciej; Stepniak, Izabela

Properties of capacitors working with the same carbon electrodes (activated carbon cloth) and three types of electrolytes: aqueous, organic and ionic liquids were compared. Capacitors filled with ionic liquids worked at a potential difference of 3.5 V, their solutions in AN and PC were charged up to the potential difference of 3 V, classical organic systems to 2.5 V and aqueous to 1 V. Cyclic voltammetry, galvanostatic charging/discharging and impedance spectroscopy were used to characterize these capacitors. The highest specific energy was recorded for the device working with ionic liquids, while the highest power is characteristic for the device filled with aqueous H 2SO 4 electrolyte. Aqueous electrolytes led to energy density an order of magnitude lower in comparison to that characteristic of ionic liquids.

Development and Implementation of Carbon Nanofoam Cathode Structures for Magnesium-Hydrogen Peroxide Semi-Fuel Cells

DTIC Science & Technology

2008-05-05

ionic solution) or a solid ionic conductor (e.g. Nafion ). An external circuit electronically connects the anode and cathode to each other. The...polymers. Aerogels could be the first nanoarchitectures, dating back to the 1930’s when Steven Kistler recognized a technique to remove liquid from a

State-of-the-Art pH Electrode Quality Control for Measurements of Acidic, Low Ionic Strength Waters.

ERIC Educational Resources Information Center

Stapanian, Martin A.; Metcalf, Richard C.

1990-01-01

Described is the derivation of the relationship between the pH measurement error and the resulting percentage error in hydrogen ion concentration including the use of variable activity coefficients. The relative influence of the ionic strength of the solution on the percentage error is shown. (CW)

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.

Exploring the role of ionic liquids to tune the polymorphic outcome of organic compounds.

PubMed

Zeng, Qingying; Mukherjee, Arijit; Müller, Peter; Rogers, Robin D; Myerson, Allan S

2018-02-14

While molecular solvents are commonly used in the screening of polymorphs, the choices are often restricted. Ionic liquids (ILs) - also referred as designer solvents - have immense possibility in this regard because of their wide flexibility of tunability. More importantly, the interactions among the IL components are completely unique compared to those present in the molecular solvents. In this context, we have chosen tetrolic acid (TA) and isonicotinamide (INA), which showed solution-structure link in molecular solvents in the past, as probes to investigate the role of imidazolium based ionic liquids in the polymorphism of these two systems and whether the different solute-solvent interactions in ILs affect the polymorphic outcome. It is observed that the selected imidazolium-based ILs, with varying anion basicity have influenced the crystallization outcome by the interaction between ILs and model compounds. Later, we have utilized the concept of double salt ionic liquids (DSIL) for INA, a penta-morphic system, to investigate the variation in the polymorphic outcome. This approach helped to obtain the forms that were otherwise inaccessible in ILs.

Ionic association and solvation in solutions of magnesium and nickel perchlorates in acetonitrile

NASA Astrophysics Data System (ADS)

Kalugin, O. N.; Agieienko, V. N.; Otroshko, N. A.; Moroz, V. V.

2009-02-01

The paper presents the conductometric data on solutions of Mg(ClO4)2 and Ni(ClO4)2 in acetonitrile over the temperature ranges 5-55°C for Mg(ClO4)2 and 25-75°C for Ni(ClO4)2. The extended Lee-Wheaton equation for unsymmetrical electrolytes was used to determine the limiting equivalent conductivities of the Mg2+, Ni2+, and ClO{4/-} ions and first-step ionic association constants with the formation of [KtClO4]+ ion pairs. Lower ionic association constants for Ni(ClO4)2 compared with Mg(ClO4)2 were a consequence of stronger non-Coulomb repulsion in the formation of [KtClO4]+ ion pairs because of the formation of a firmer solvation shell by the nickel compared with magnesium cation. The structure-dynamic parameter of ionic solvation was estimated. It was found that spatial-time correlations in the nearest environment of ions increased in the series ClO{4/-} > Mg2+ > Ni2+.

Spectroscopic investigation of the effect of salt on binding of tartrazine with two homologous serum albumins: quantification by use of the Debye-Hückel limiting law and observation of enthalpy-entropy compensation.

PubMed

Bolel, Priyanka; Datta, Shubhashis; Mahapatra, Niharendu; Halder, Mintu

2012-08-30

Formation of ion pair between charged molecule and protein can lead to interesting biochemical phenomena. We report the evolution of thermodynamics of the binding of tartrazine, a negatively charged azo colorant, and serum albumins with salt. The dye binds predominantly electrostatically in low buffer strengths; however, on increasing salt concentration, affinity decreases considerably. The calculated thermodynamic parameters in high salt indicate manifestation of nonelectrostatic interactions, namely, van der Waals force and hydrogen bonding. Site-marker competitive binding studies and docking simulations indicate that the dye binds with HSA in the warfarin site and with BSA at the interface of warfarin and ibuprofen binding sites. The docked poses indicate nearby amino acid positive side chains, which are possibly responsible for electrostatic interaction. Using the Debye-Hückel interionic attraction theory for binding equilibria, it is shown that, for electrostatic binding the calculated free energy change increases linearly with square root of ionic strength. Also UV-vis, fluorescence, CD data indicate a decrease of interaction with salt concentration. This study quantitatively relates how ionic strength modulates the strength of the protein-ligand electrostatic interaction. The binding enthalpy and entropy have been found to compensate one another. The enthalpy-entropy compensation (EEC), general property of weak intermolecular interactions, has been discussed.

NADP-dependent malate dehydrogenase (decarboxylating) from sugar cane leaves. Kinetic properties of different oligomeric structures.

PubMed

Iglesias, A A; Andreo, C S

1990-09-24

NADP-dependent malate dehydrogenase (decarboxylating) from sugar cane leaves was inhibited by increasing the ionic strength in the assay medium. The inhibitory effect was higher at pH 7.0 than 8.0, with median inhibitory concentrations (IC50) of 89 mM and 160 mM respectively, for inhibition by NaCl. Gel-filtration experiments indicated that the enzyme dissociated into dimers and monomers when exposed to high ionic strength (0.3 M NaCl). By using the enzyme-dilution approach in the absence and presence of 0.3 M NaCl, the kinetic properties of each oligomeric species of the protein was determined at pH 7.0 and 8.0. Tetrameric, dimeric and monomeric structures were shown to be active but with different V and Km values. The catalytic efficiency of the oligomers was tetramer greater than dimer greater than monomer, and each quaternary structure exhibited higher activity at pH 8.0 than 7.0. Dissociation constants for the equilibria between the different oligomeric forms of the enzyme were determined. It was established that Kd values were affected by pH and Mg2+ levels in the medium. Results suggest that the distinct catalytic properties of the different oligomeric forms of NADP-dependent malate dehydrogenase and changes in their equilibrium could be the molecular basis for an efficient physiological regulation of the decarboxylation step of C4 metabolism.

Ruthenium nanoparticles in ionic liquids: structural and stability effects of polar solutes.

PubMed

Salas, Gorka; Podgoršek, Ajda; Campbell, Paul S; Santini, Catherine C; Pádua, Agílio A H; Costa Gomes, Margarida F; Philippot, Karine; Chaudret, Bruno; Turmine, Mireille

2011-08-14

Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface.

In-situ ionic liquid dispersive liquid-liquid microextraction using a new anion-exchange reagent combined Fe3O4 magnetic nanoparticles for determination of pyrethroid pesticides in water samples.

PubMed

Fan, Chen; Liang, You; Dong, Hongqiang; Ding, Guanglong; Zhang, Wenbing; Tang, Gang; Yang, Jiale; Kong, Dandan; Wang, Deng; Cao, Yongsong

2017-07-04

In this work, in-situ ionic liquid dispersive liquid-liquid microextraction combined ultrasmall Fe 3 O 4 magnetic nanoparticles was developed as a kind of pretreatment method to detect pyrethroid pesticides in water samples. New anion-exchange reagents including Na[DDTC] and Na[N(CN) 2 ] were optimized for in-situ extraction pyrethroids, which showed enhanced microextraction performance. Pyrethroids were enriched by hydrophilic ionic liquid [P 4448 ][Br] (aqueous solution, 200 μL, 0.2 mmol mL -1 ) reaction in-situ with anion-exchange reagent Na[N(CN) 2 ] (aqueous solution, 300 μL, 0.2 mmol mL -1 ) forming hydrophobic ionic liquid as extraction agent in water sample (10 mL). Ultrasmall superparamagnetic iron oxide nanoparticles (30 mg) were used to collect the mixture of ionic liquid and pyrethroids followed by elution with acetonitrile. The extraction of ionic liquid strategies was unique and efficiently fulfilled with high enrichment factors (176-213) and good recoveries (80.20-117.31%). The method was successively applied to the determination of pyrethroid pesticides in different kinds of water samples with the limits of detection ranged from 0.16 to 0.21 μg L -1 . The proposed method is actually nanometer-level microextraction (average size 80 nm) with the advantages of simplicity, rapidity, and sensitivity. Copyright © 2017 Elsevier B.V. All rights reserved.

Kadomtsev−Petviashvili equation for a flow of highly nonisothermal collisionless plasma

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

Movsesyants, Yu. B., E-mail: yumovsesyants@gmail.com; Rukhadze, A. A., E-mail: rukh@fpl.gpi.ru; Tyuryukanov, P. M.

2016-01-15

It is shown that the equations of two-fluid electrodynamics for a cold ions flow and Boltzmann electrons in the vicinity of the ion-sound point can be reduced to the Kadomtsev−Petviashvili equation. Examples of two-dimensional equilibria with pole singularities obtained by exactly solving the equations are presented. An exact self-similar solution describing a two-dimensional transonic flow and having no pole singularities is found.

Kadomtsev-Petviashvili equation for a flow of highly nonisothermal collisionless plasma

NASA Astrophysics Data System (ADS)

Movsesyants, Yu. B.; Rukhadze, A. A.; Tyuryukanov, P. M.

2016-01-01

It is shown that the equations of two-fluid electrodynamics for a cold ions flow and Boltzmann electrons in the vicinity of the ion-sound point can be reduced to the Kadomtsev-Petviashvili equation. Examples of two-dimensional equilibria with pole singularities obtained by exactly solving the equations are presented. An exact self-similar solution describing a two-dimensional transonic flow and having no pole singularities is found.

Collision Index and Stability of Elliptic Relative Equilibria in Planar {n}-body Problem

NASA Astrophysics Data System (ADS)

Hu, Xijun; Ou, Yuwei

2016-12-01

It is well known that a planar central configuration of the {n}-body problem gives rise to solutions where each particle moves on a specific Keplerian orbit while the totality of the particles move on a homographic motion. When the eccentricity {e} of the Keplerian orbit belongs in {[0,1)}, following Meyer and Schmidt, we call such solutions elliptic relative equilibria (shortly, ERE). In order to study the linear stability of ERE in the near-collision case, namely when {1-e} is small enough, we introduce the collision index for planar central configurations. The collision index is a Maslov-type index for heteroclinic orbits and orbits parametrised by half-lines that, according to the definition given by Hu and Portaluri (An index theory for unbounded motions of Hamiltonian systems, Hu and Portaluri (2015, preprint)), we shall refer to as half-clinic orbits and whose definition in this context, is essentially based on a blow up technique in the case {e=1}. We get the fundamental properties of collision index and approximation theorems. As applications, we give some new hyperbolic criteria and prove that, generically, the ERE of minimal central configurations are hyperbolic in the near-collision case, and we give a detailed analysis of Euler collinear orbits in the near-collision case.

Rapid nondestructive spectrometric measurement of temperature-dependent gas-liquid solubility equilibria.

PubMed

Ma, Jian; Dasgupta, Purnendu K; Yang, Bingcheng

2011-02-01

Gas-liquid solubility equilibria (Henry's Law behavior) are of basic interest to many different areas. Temperature-dependent aqueous solubilities of various organic compounds are of fundamental importance in many branches of environmental science. In a number of situations, the gas/dissolved solute of interest has characteristic spectroscopic absorption that is distinct from that of the solvent. For such cases, we report facile nondestructive rapid measurement of the temperature-dependent Henry's law constant (K(H)) in a static sealed spectrometric cell. Combined with a special cell design, multiwavelength measurement permits a large range of K(H) to be spanned. It is possible to derive the K(H) values from the absorbance measured in the gas phase only, the liquid phase only (preferred), and both phases. Underlying principles are developed, and all three approaches are illustrated for a solute like acetone in water. A thermostatic spectrophotometer cell compartment, widely used and available, facilitates rapid temperature changes and allows rapid temperature-dependent equilibrium measurements. Applicability is shown for both acetone and methyl isobutyl ketone. Very little sample is required for the measurement; the K(H) for 4-hydroxynonenal, a marker for oxidative stress, is measured to be 56.9 ± 2.6 M/atm (n = 3) at 37.4 °C with 1 mg of the material available.

Electrochemical detection of DNA damage induced by acrylamide and its metabolite at the graphene-ionic liquid-Nafion modified pyrolytic graphite electrode.

PubMed

Qiu, Yanyan; Qu, Xiangjin; Dong, Jing; Ai, Shiyun; Han, Ruixia

2011-06-15

A new electrochemical biosensor for directly detecting DNA damage induced by acrylamide (AA) and its metabolite was presented in this work. The graphene-ionic liquid-Nafion modified pyrolytic graphite electrode (PGE) was prepared, and then horseradish peroxidase (HRP) and natural double-stranded DNA were alternately assembled on the modified electrode by the layer-by-layer method. The PGE/graphene-ionic liquid-Nafion and the construction of the (HRP/DNA)(n) film were characterized by electrochemical impedance spectroscopy. With the guanine signal in DNA as an indicator, the damage of DNA was detected by differential pulse voltammetry after PGE/graphene-ionic liquid-Nafion/(HRP/DNA)(n) was incubated in AA solution or AA+H(2)O(2) solution at 37°C. This method provides a new model to mimic and directly detect DNA damage induced by chemical pollutants and their metabolites in vitro. The results indicated that, in the presence of H(2)O(2), HRP was activated and catalyzed the transformation of AA to glycidamide, which could form DNA adducts and induce more serious damage of DNA than AA. In order to further verify these results, UV-vis spectrophotometry was also used to investigate DNA damage induced by AA and its metabolites in solution and the similar results were obtained. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of the interfacial tension and ionic strength on the thermodynamic barrier associated to the benzocaine insertion into a cell membrane.

PubMed

López Cascales, J J; Oliveira Costa, S D

2013-02-01

The insertion of local anaesthetics into a cell membrane is a key aspect for explaining their activity at a molecular level. It has been described how the potency and response time of local anaesthetics is improved (for clinical applications) when they are dissolved in a solution of sodium bicarbonate. With the aim of gaining insight into the physico-chemical principles that govern the action mechanism of these drugs at a molecular level, simulations of benzocaine in binary lipid bilayers formed by DPPC/DPPS were carried out for different ionic strengths of the aqueous solution. From these molecular dynamic simulations, we observed how the thermodynamic barrier associated with benzocaine insertion into the lipid bilayers diminished exponentially as the fraction of DPPS in the bilayer increased, especially when the ionic strength of the aqueous solution increased. In line with these results, we also observed how this thermodynamic barrier diminished exponentially with the phospholipid/water interfacial tension. Copyright © 2012 Elsevier B.V. All rights reserved.

Peroxidase-mediated polymerization of 1-naphthol: impact of solution pH and ionic strength.

PubMed

Bhandari, Alok; Xu, Fangxiang; Koch, David E; Hunter, Robert P

2009-01-01

Peroxidase-mediated oxidation has been proposed as a treatment method for naphthol-contaminated water. However, the impact of solution chemistry on naphthol polymerization and removal has not been documented. This research investigated the impact of pH and ionic strength on peroxidase-mediated removal of 1-naphthol in completely mixed batch reactors. The impact of hydrogen peroxide to 1-naphthol ratio and activity of horseradish peroxidase was also studied. Size exclusion chromatography was used to estimate the molecular weight distribution of oligomeric products, and liquid chromatography/mass spectrometry was used to estimate product structure. Naphthol transformation decreased with ionic strength, and substrate removal was lowest at neutral pHs. Solution pH influenced the size and the composition of the oligomeric products. An equimolar ratio of H(2)O(2):naphthol was sufficient for optimal naphthol removal. Polymerization products included naphthoquinones and oligomers derived from two, three, and four naphthol molecules. Our results illustrate the importance of water chemistry when considering a peroxidase-based approach for treatment of naphthol-contaminated waters.

3-D simulation of nanopore structure for DNA sequencing.

PubMed

Park, Jun-Mo; Pak, Y Eugene; Chun, Honggu; Lee, Jong-Ho

2012-07-01

In this paper, we propose a method for simulating nanopore structure by using conventional 3-D simulation tool to mimic the I-V behavior of the nanopore structure. In the simulation, we use lightly doped silicon for ionic solution where some parameters like electron affinity and dielectric constant are fitted to consider the ionic solution. By using this method, we can simulate the I-V behavior of nanopore structure depending on the location and the size of the sphere shaped silicon oxide which is considered to be an indicator of a DNA base. In addition, we simulate an Ionic Field Effect Transistor (IFET) which has basically the nanopore structure, and show that the simulated curves follow sufficiently the I-V behavior of the measurement data. Therefore, we think it is reasonable to apply parameter modeling mentioned above to simulate nanopore structure. The key idea is to modify electron affinity of silicon which is used to mimic the KCl solution to avoid band bending and depletion inside the nanopore. We could efficiently utilize conventional 3-D simulation tool to simulate the I-V behavior of nanopore structures.

Effects of humic acid and solution chemistry on the aggregation and dispersion of carboxyl-functionalized carbon black nanoparticles

NASA Astrophysics Data System (ADS)

Hwang, G.; Gomez-Flores, A.; Choi, S.; Han, Y., , Dr; Kim, H.

2017-12-01

The influence of humic acid, ionic strength and ionic species on the aggregation and dispersion of carboxyl-functionalized carbon black nanoparticles (CB-NPs) was systemically investigated in aqueous media. The experimental conditions of stability tests were selected to the changes in the solution chemistry (0.1-10 mM NaCl and 0.01-1 mM CaCl2) and in the presence/absence of humic acid (1 and 5 mg L-1) in an aquatic environment. The CB-NPs suspension was more rapidly settled in NaCl solution than in CaCl2. Specifically, in the case of NaCl, the aggregation rate of CB-NPs increased with ionic strength. Contrary, CB-NPs dispersed in CaCl2 were insensitive to the aggregation as the ionic strength increased; that was because specific adsorption of the divalent cation Ca2+ occurred since the zeta potential of the CB-NPs is reversed to a positive charge with increasing of the ionic strength. It was confirmed that humic acid greatly influences the stability of the CB-NPs. In particular, the dispersion of CB-NPs was improved in the whole range of ionic strengths of NaCl as well as of CaCl2. To support the results, the interaction energy between CB-NPs was calculated for each condition by using the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) and modified-DLVO theories. In the presence of humic acid, the improved stability of CB-NPs is attributed to the steric repulsive force.This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2015R1D1A3A01020766), the Ministry of Education (MOE) and National Research Foundation of Korea (NRF) through the Human Resource Training Project for Regional Innovation (2015H1C1A1035930) and Korea Energy and Mineral Resources Engineering Program (KEMREP).

The structure investigations of dehydroacetic acid and 1,8-diaminonaphthalene condensation product by NMR, MS, and X-ray measurements

NASA Astrophysics Data System (ADS)

Kołodziej, B.; Morawiak, M.; Kamieński, B.; Schilf, W.

2016-05-01

A new unexpected product of condensation reaction of 1,8-diaminonaphthalene (DAN) and carbonyl compound (here: dehydroacetic acid (dha)) was synthesized. Discussion about the molecular structure of possible products of this reaction was done on the base of NMR studies. The structure of the titled product in both DMSO solution and in the solid state was resolved by analysis of its spectral data (X-ray structure analysis, multinuclear NMR in solution and solid state spectra) and MS measurements. The presented studies provided clear evidence that the titled product exists in diluted DMSO solution as the mixture of two kinetic free ionic species whereas in concentrated DMSO solution as well as in the solid state this system forms associated ionic pairs bonded together by hydrogen bonds.

Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

PubMed Central

Ma, Xingmao; Uddin, Sheikh

2013-01-01

The strong affinity of carbon nanotubes (CNTs) to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength) and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB) from multi-walled carbon nanotubes (MWNTs). The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH < 7 vs. pH > 7). In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs. PMID:28348336

On the application of ionic liquids for rechargeable Li batteries: High voltage systems

NASA Astrophysics Data System (ADS)

Borgel, V.; Markevich, E.; Aurbach, D.; Semrau, G.; Schmidt, M.

We examined the possible use of the following ionic liquids all having the same anion, bis(trifluoromethylsulfonyl)imide (TFSI) and the following cations: 1-hexyl-3-methyl imidazolium (HMITFSI), 1-(2-methoxyethyl)-3-methyl imidazolium (MEMITFSI), N-ethyl- NN-dimethyl-2-methoxyethylammonium (EDMETFSI), 1-methyl-1-butylpyrrolidinium (BMPTFSI), and 1-methyl-1-propylpiperidinium (MPPpTFSI) solutions with LiTFSI (the source of Li ions), as electrolyte systems for 5 V, rechargeable battery systems with Li metal anodes and LiMn 1.5Ni 0.5O 4 spinel cathodes. Standard solution based on alkyl carbonates and LiPF 6 was examined in this respect for comparison. The ionic liquids (ILs) based on derivatives of piperidinium and pyrrolidinium demonstrate a very wide electrochemical window (up to 5.5 V) and they can be compatible with lithium metal anodes. At low potentials in the presence of Li ions in solutions (or on Li metal surfaces), TFSI anions are reduced to insoluble Li compounds which passivate Li, noble metal and graphite electrodes in the Li salt/IL solutions. The mechanism, kinetics and effectiveness of electrodes' passivation in these systems depend on the nature of both IL and electrode used. It was possible to demonstrate reversible behavior of Li/LiMn 1.5Ni 0.5O 4 cells (4.8 V) with solutions based on BMPTFSI and MPPpTFSI. Possible parasitic anodic reactions upon charging at the high potentials are much lower in the ILs than in standard solutions.

Hydrogen exchange equilibria in thiols.

PubMed

Hofstetter, Dustin; Thalmann, Basil; Nauser, Thomas; Koppenol, Willem H

2012-09-17

Cysteine, cysteinyl-glycine, glutathione, phenylalanyl-cysteinyl-glycine, and histidyl-cysteinyl-glycine were dissolved in acidic and neutral D(2)O in the presence of the radical generator 2,2'-azobis(2-methylpropionamidine) dihydrochloride and radical mediator compounds (benzyl alcohol and 2-propanol). An exchange of H-atoms by D-atoms took place in these peptides due to intramolecular H-abstraction equilibria. NMR measurements allow one to follow the extent of H-D exchanges and to identify the sites where these exchanges take place. Significant exchanges occur in acidic media in GSH at positions Glu-β and Glu-γ, in Phe-Cys-Gly at positions Phe ortho, Phe-β, Cys-α, Cys-β, and Gly-α, and in His-Cys-Gly at positions His H1, His H2, His β, Cys β, and Gly α. In neutral media, exchanges occur in Cys-Gly at position Cys β and in GSH at position Cys α. Phe-Cys-Gly and His-Cys-Gly were not examined in neutral media. Sites participating in the radical exchange equilibria are highly dependent on structure and pH; the availability of electron density in the form of lone pairs appears to increase the extent of exchange. Interestingly, and unexpectedly, 2D NMR experiments show that GSH rearranges itself in acidic solution: the signals shift, but their patterns do not change. The formation of a thiolactone from Gly and Cys residues matches the changes observed.

Acquisition and evaluation of thermodynamic data for morenosite-retgersite equilibria at 0.1 MPa

USGS Publications Warehouse

Chou, I.-Ming; Seal, R.R.

2003-01-01

Metal-sulfate salts in mine drainage environments commonly occur as solid solutions containing Fe, Cu, Mg, Zn, Al, Mn, Ni, Co, Cd, and other elements. Thermodynamic data for some of the end-member salts containing Fe, Cu, Zn, and Mg have been collected and evaluated previously, and the present study extends to the system containing Ni. Morenosite (NiSO4-7H2O)-retgersite (NiSO4-6H2O) equilibria were determined along five humidity buffer curves at 0.1 MPa and between 5 and 22??C. Reversals along these humidity-buffer curves yield In K = 17.58-6303.35/T, where K is the equilibrium constant, and T is temperature in K. The derived standard Gibbs free energy of reaction is 8.84 kJ/mol, which agrees very well with the values of 8.90, 8.83, and 8.85 kJ/mol based on the vapor pressure measurements of Schumb (1923), Bonnell and Burridge (1935), and Stout et al. (1966). respectively. This value also agrees reasonably well with the values of 8.65 and 9.56 kJ/mol calculated from the data compiled by Wagman et al. (1982) and DeKock (1982), respectively. The temperature-humidity relationships defined by this study for dehydration equilibria between morenosite and retgersite explain the more common occurrence of retgersite relative to morenosite in nature.

Competition and equilibria in electricity markets based on two-settlement system: A conjectural variation approach

NASA Astrophysics Data System (ADS)

Watts, David

This dissertation studies electricity markets based on two-settlement systems and applies the concept of conjectural variation (CV) as a tool for representing different levels of competitiveness in the market. Some recent theoretical works are addressed to support the use of CV as a solution concept. A notion of consistency is introduced to make the level of competitiveness of the market endogenous, and allows finding consistent CV equilibria and the corresponding conditions for existence of equilibria. First, a case is studied in which firms hold exogenous levels of forward commitments. Then, backward induction and sub-game perfection are used to solve sequentially for the spot and forward market equilibrium. This allows analyzing how firms take positions in the forward market, based on considering their later impact on the spot market. It is concluded that positions taken in the forward market depend largely on firms expectations about the competitiveness of both the spot and the forward market. Forward markets are welfare enhancing even if they are not as competitive as the associated spot market as long as they are not too oligopolistie. The above formulation is used to model a dynamic scenario to analyze market stability, linking this research to Dr. Alvarado's earlier research on market stability. This brings about interesting trade offs between market power and market stability.

Benzoic Acid and Chlorobenzoic Acids: Thermodynamic Study of the Pure Compounds and Binary Mixtures With Water.

PubMed

Reschke, Thomas; Zherikova, Kseniya V; Verevkin, Sergey P; Held, Christoph

2016-03-01

Benzoic acid is a model compound for drug substances in pharmaceutical research. Process design requires information about thermodynamic phase behavior of benzoic acid and its mixtures with water and organic solvents. This work addresses phase equilibria that determine stability and solubility. In this work, Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) was used to model the phase behavior of aqueous and organic solutions containing benzoic acid and chlorobenzoic acids. Absolute vapor pressures of benzoic acid and 2-, 3-, and 4-chlorobenzoic acid from literature and from our own measurements were used to determine pure-component PC-SAFT parameters. Two binary interaction parameters between water and/or benzoic acid were used to model vapor-liquid and liquid-liquid equilibria of water and/or benzoic acid between 280 and 413 K. The PC-SAFT parameters and 1 binary interaction parameter were used to model aqueous solubility of the chlorobenzoic acids. Additionally, solubility of benzoic acid in organic solvents was predicted without using binary parameters. All results showed that pure-component parameters for benzoic acid and for the chlorobenzoic acids allowed for satisfying modeling phase equilibria. The modeling approach established in this work is a further step to screen solubility and to predict the whole phase region of mixtures containing pharmaceuticals. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Thermodynamics of aggregate formation between a non-ionic polymer and ionic surfactants: An isothermal titration calorimetric study.

PubMed

Patel, Salin Gupta; Bummer, Paul M

2017-01-10

This report examines the energetics of aggregate formation between hydroxypropyl methylcellulose (HPMC) and model ionic surfactants including sodium dodecyl sulfate (SDS) at pharmaceutically relevant concentrations using the isothermal titration calorimetry (ITC) technique and a novel treatment of calorimetric data that accounts for the various species formed. The influence of molecular weight of HPMC, temperature and ionic strength of solution on the aggregate formation process was explored. The interaction between SDS and HPMC was determined to be an endothermic process and initiated at a critical aggregation concentration (CAC). The SDS-HPMC interactions were observed to be cooperative in nature and dependent on temperature and ionic strength of the solution. Molecular weight of HPMC significantly shifted the interaction parameters between HPMC and SDS such that at the highest molecular weight (HPMC K-100M;>240kDa), although the general shape of the titration curve (enthalpogram) was observed to remain similar, the critical concentration parameters (CAC, polymer saturation concentration (C sat ) and critical micelle concentration (CMC)) were significantly altered and shifted to lower concentrations of SDS. Ionic strength was also observed to influence the critical concentration parameters for the SDS-HPMC aggregation and decreased to lower SDS concentrations with increasing ionic strength for both anionic and cationic surfactant-HPMC systems. From these data, other thermodynamic parameters of aggregation such as ΔH agg ° , ΔG agg ° , H agg ° , ΔS agg ° , and ΔC p were calculated and utilized to postulate the hydrophobic nature of SDS-HPMC aggregate formation. The type of ionic surfactant head group (anionic vs. cationic i.e., dodecyltrimethylammonium bromide (DTAB)) was found to influence the strength of HPMC-surfactant interactions wherein a distinct CAC signifying the strength of HPMC-DTAB interactions was not observed. The interpretation of the microcalorimetric data at different temperatures and ionic strengths while varying properties of polymer and surfactant was a very effective tool in investigating the nature and energetics of HPMC and ionic surfactant interactions. Copyright © 2016 Elsevier B.V. All rights reserved.

Colloid Mobilization in a Fractured Soil: Effect of Pore-Water Exchange between Preferential Flow Paths and Soil Matrix.

PubMed

Mohanty, Sanjay K; Saiers, James E; Ryan, Joseph N

2016-03-01

Exchange of water and solutes between contaminated soil matrix and bulk solution in preferential flow paths has been shown to contribute to the long-term release of dissolved contaminants in the subsurface, but whether and how this exchange can affect the release of colloids in a soil are unclear. To examine this, we applied rainfall solutions of different ionic strength on an intact soil core and compared the resulting changes in effluent colloid concentration through multiple sampling ports. The exchange of water between soil matrix and the preferential flow paths leading to each port was characterized on the basis of the bromide (conservative tracer) breakthrough time at the port. At individual ports, two rainfalls of a certain ionic strength mobilized different amounts of colloids when the soil was pre-exposed to a solution of lower or higher ionic strength. This result indicates that colloid mobilization depended on rainfall solution history, which is referred as colloid mobilization hysteresis. The extent of hysteresis was increased with increases in exchange of pore water and solutes between preferential flow paths and matrix. The results indicate that the soil matrix exchanged the old water from the previous infiltration with new infiltrating water during successive infiltration and changed the pore water chemistry in the preferential flow paths, which in turn affected the release of soil colloids. Therefore, rainfall solution history and soil heterogeneity must be considered to assess colloid mobilization in the subsurface. These findings have implications for the release of colloids, colloid-associated contaminants, and pathogens from soils.

Thermodynamics of Coupled Folding in the Interaction of Archaeal RNase P Proteins RPP21 and RPP29

PubMed Central

Xu, Yiren; Oruganti, Sri Vidya; Gopalan, Venkat; Foster, Mark P.

2014-01-01

We have used isothermal titration calorimetry (ITC) to identify and describe binding-coupled equilibria in the interaction between two protein subunits of archaeal ribonuclease P (RNase P). In all three domains of life, RNase P is a ribonucleoprotein complex that is primarily responsible for catalyzing the Mg2+-dependent cleavage of the 5′ leader sequence of precursor tRNAs during tRNA maturation. In archaea, RNase P has been shown to be composed of one catalytic RNA and up to five proteins, four of which associate in the absence of RNA as two functional heterodimers, POP5-RPP30 and RPP21-RPP29. NMR studies of the Pyrococcus furiosus RPP21 and RPP29 proteins in their free and complexed states provided evidence for significant protein folding upon binding. ITC experiments were performed over a range of temperatures, ionic strengths, pH values and in buffers with varying ionization potential, and with a folding-deficient RPP21 point mutant. These experiments revealed a negative heat capacity change (ΔCp), nearly twice that predicted from surface accessibility calculations, a strong salt dependence to the interaction and proton release at neutral pH, but a small net contribution from these to the excess ΔCp. We considered potential contributions from protein folding and burial of interfacial water molecules based on structural and spectroscopic data. We conclude that binding-coupled protein folding is likely responsible for a significant portion of the excess ΔCp. These findings provide novel structural-thermodynamic insights into coupled equilibria that enable specificity in macromolecular assemblies. PMID:22243443

Spectrophotometric studies on the complexation equilibria of Ni and Pb with 2-carboxy-2-hydroxy-5'-sulfo-formazylbenzene. Simultaneous determination of trace amounts of Ni and Pb.

PubMed

Hashem, Elham Y; Abu-Bakr, Mohamed S; Hussain, Sawsan M

2004-01-01

Spectrophotometric studies have been made to investigate the reaction of Nickel and Lead with 2-carboxy-2'-hydroxy-5'-sulfoformazyl-benzene (zincon) in 50%(v/v) ethanol-water at 25 degrees C and an ionic strength of 0.1 M NaClO4. A complete picture of the complexation equilibria in the pH range (4.2-12.0) for nickel and (1.9-11.5) for lead are presented. Simple, rapid, selective and sensitive methods for the spectro-photometric determination of nickel and lead has been developed based on the color reaction of their complexes with zincon. The methods allow the determination of 4.69 microg mL(-1) of nickel at pH = 6.3 (lambdamax = 665 nm) and 10.3 microg ml(-1) of lead at pH = 5.6 (lambdamax = 610 nm). The apparent molar absorptivities were epsilon = 1.3 x 10(4) L mol(-1) cm(-1) for nickel and epsilon = 0.6 x 10(4) L mol(-1) cm(-1) for lead. The interference of a large number of foreign ions and complexing agents has been studied. Thiosulphate, as masking agent allows the simultaneous determination of nickel and lead in the presence of high concentrations of copper. Ascorbic acid, sodium cyanide and or sodium fluoride provide the elimination of many other interferences. The methods have been applied successfully to the simultaneous determination of nickel and lead in an aluminium and non-ferrous alloy.

PHAST--a program for simulating ground-water flow, solute transport, and multicomponent geochemical reactions

USGS Publications Warehouse

Parkhurst, David L.; Kipp, Kenneth L.; Engesgaard, Peter; Charlton, Scott R.

2004-01-01

The computer program PHAST simulates multi-component, reactive solute transport in three-dimensional saturated ground-water flow systems. PHAST is a versatile ground-water flow and solute-transport simulator with capabilities to model a wide range of equilibrium and kinetic geochemical reactions. The flow and transport calculations are based on a modified version of HST3D that is restricted to constant fluid density and constant temperature. The geochemical reactions are simulated with the geochemical model PHREEQC, which is embedded in PHAST. PHAST is applicable to the study of natural and contaminated ground-water systems at a variety of scales ranging from laboratory experiments to local and regional field scales. PHAST can be used in studies of migration of nutrients, inorganic and organic contaminants, and radionuclides; in projects such as aquifer storage and recovery or engineered remediation; and in investigations of the natural rock-water interactions in aquifers. PHAST is not appropriate for unsaturated-zone flow, multiphase flow, density-dependent flow, or waters with high ionic strengths. A variety of boundary conditions are available in PHAST to simulate flow and transport, including specified-head, flux, and leaky conditions, as well as the special cases of rivers and wells. Chemical reactions in PHAST include (1) homogeneous equilibria using an ion-association thermodynamic model; (2) heterogeneous equilibria between the aqueous solution and minerals, gases, surface complexation sites, ion exchange sites, and solid solutions; and (3) kinetic reactions with rates that are a function of solution composition. The aqueous model (elements, chemical reactions, and equilibrium constants), minerals, gases, exchangers, surfaces, and rate expressions may be defined or modified by the user. A number of options are available to save results of simulations to output files. The data may be saved in three formats: a format suitable for viewing with a text editor; a format suitable for exporting to spreadsheets and post-processing programs; or in Hierarchical Data Format (HDF), which is a compressed binary format. Data in the HDF file can be visualized on Windows computers with the program Model Viewer and extracted with the utility program PHASTHDF; both programs are distributed with PHAST. Operator splitting of the flow, transport, and geochemical equations is used to separate the three processes into three sequential calculations. No iterations between transport and reaction calculations are implemented. A three-dimensional Cartesian coordinate system and finite-difference techniques are used for the spatial and temporal discretization of the flow and transport equations. The non-linear chemical equilibrium equations are solved by a Newton-Raphson method, and the kinetic reaction equations are solved by a Runge-Kutta or an implicit method for integrating ordinary differential equations. The PHAST simulator may require large amounts of memory and long Central Processing Unit (CPU) times. To reduce the long CPU times, a parallel version of PHAST has been developed that runs on a multiprocessor computer or on a collection of computers that are networked. The parallel version requires Message Passing Interface, which is currently (2004) freely available. The parallel version is effective in reducing simulation times. This report documents the use of the PHAST simulator, including running the simulator, preparing the input files, selecting the output files, and visualizing the results. It also presents four examples that verify the numerical method and demonstrate the capabilities of the simulator. PHAST requires three input files. Only the flow and transport file is described in detail in this report. The other two files, the chemistry data file and the database file, are identical to PHREEQC files and the detailed description of these files is found in the PHREEQC documentation.

A network thermodynamic method for numerical solution of the Nernst-Planck and Poisson equation system with application to ionic transport through membranes.

PubMed

Horno, J; González-Caballero, F; González-Fernández, C F

1990-01-01

Simple techniques of network thermodynamics are used to obtain the numerical solution of the Nernst-Planck and Poisson equation system. A network model for a particular physical situation, namely ionic transport through a thin membrane with simultaneous diffusion, convection and electric current, is proposed. Concentration and electric field profiles across the membrane, as well as diffusion potential, have been simulated using the electric circuit simulation program, SPICE. The method is quite general and extremely efficient, permitting treatments of multi-ion systems whatever the boundary and experimental conditions may be.

Competitive adsorption from mixed hen egg-white lysozyme/surfactant solutions at the air-water interface studied by tensiometry, ellipsometry, and surface dilational rheology.

PubMed

Alahverdjieva, V S; Grigoriev, D O; Fainerman, V B; Aksenenko, E V; Miller, R; Möhwald, H

2008-02-21

The competitive adsorption at the air-water interface from mixed adsorption layers of hen egg-white lysozyme with a non-ionic surfactant (C10DMPO) was studied and compared to the mixture with an ionic surfactant (SDS) using bubble and drop shape analysis tensiometry, ellipsometry, and surface dilational rheology. The set of equilibrium and kinetic data of the mixed solutions is described by a thermodynamic model developed recently. The theoretical description of the mixed system is based on the model parameters for the individual components.

Effect of oxidation state and ionic strength on sorption of actinides (Th, U, Np, Am) to geologic media [Abstract and References Only

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

Dittrich, Timothy M.; Richmann, Michael K.; Reed, Donald T.

2015-10-30

The degree of conservatism in the estimated sorption partition coefficients (K ds) used in a performance assessment model is being evaluated based on a complementary batch and column method. The main focus of this work is to investigate the role of ionic strength, solution chemistry, and oxidation state (III-VI) in actinide sorption to dolomite rock. Based on redox conditions and solution chemistry expected at the WIPP, possible actinide species include Pu(III), Pu(IV), U(IV), U(VI), Np(IV), Np(V), Am(III), and Th(IV).

Higher-order structures assembly of gold nanorods caused by captopril in high ionic strength solutions.

PubMed

Shen, Sufen; Zhao, Huawen; Huang, Chengzhi; Wu, Liping

2010-02-01

The ability to construct self-assembled architectures is essential for the exploration of nanoparticle-structured properties. It is one of good strategies by employing molecule-modificated nanoparticles to prepare new materials with particular properties. Herein, we found that captopril (Cap), a biocompatible medicament, could adjust and control the formation of self-assembled gold nanorods (Au-NRs) in high ionic strength solutions. The assembly is in higher-order structures containing both end-to-end and side-by-side orientations. Furthermore, these structures of Au-NRs could be served as plasmonic waveguide in future biological nanodevices.

Releasing effects in flame photometry: Determination of calcium

USGS Publications Warehouse

Dinnin, J.I.

1960-01-01

Strontium, lanthanum, neodymium, samarium, and yttrium completely release the flame emission of calcium from the depressive effects of sulfate, phosphate, and aluminate. Magnesium, beryllium, barium, and scandium release most of the calcium emission. These cations, when present in high concentration, preferentially form compounds with the depressing anions when the solution is evaporated rapidly in the flame. The mechanism of the interference and releasing effects is explained on the basis of the chemical equilibria in the evaporating droplets of solution and is shown to depend upon the nature of the compounds present in the aqueous phase of the solution. The need for background correction techniques is stressed. The releasing effect is used in the determination of calcium in silicate rocks without the need for separations.

Enhanced photophysics of conjugated polymers

DOEpatents

Chen, Liaohai [Argonne, IL; Xu, Su [Santa Clara, CA; McBranch, Duncan [Santa Fe, NM; Whitten, David [Santa Fe, NM

2003-05-27

The addition of oppositely charged surfactant to fluorescent ionic conjugated polymer forms a polymer-surfactant complex that exhibits at least one improved photophysical property. The conjugated polymer is a fluorescent ionic polymer that typically has at least one ionic side chain or moiety that interacts with the specific surfactant selected. The photophysical property improvements may include increased fluorescence quantum efficiency, wavelength-independent emission and absorption spectra, and more stable fluorescence decay kinetics. The complexation typically occurs in a solution of a polar solvent in which the polymer and surfactant are soluble, but it may also occur in a mixture of solvents. The solution is commonly prepared with a surfactant molecule:monomer repeat unit of polymer ratio ranging from about 1:100 to about 1:1. A polymer-surfactant complex precipitate is formed as the ratio approaches 1:1. This precipitate is recoverable and usable in many forms.

INORGANIC AND ORGANIC ONIUM SALTS

DTIC Science & Technology

The nitrosonium NO ion absorbs in the infrared between 1/2400 and 1/ 2150 cm. Salts of complex fluoro-acids absorb at higher frequencies than salts...halide adducts generally contain nitrosonium ions . Hexaphenylditin does not undergo marked heterolytic dissociation in nitromethane solution...influencing the covalent-ionic equilibrium are discussed. Infrared spectrum nitrosonium ion ; ionic character in lattice and position nitrosonium ion absorption

Ionic tracer movement through a Wyoming snowpack

Treesearch

Roger C. Bales; Richard A. Sommerfeld; David G. Kebler

1990-01-01

A meltwater ionic pulse with initial concentrations of 5-10 or more times the average was observed in lysimeters set at the base of a 2-m snowpack in an unpolluted, alpine watershed. Both background chemical species and added tracers exhibited the initial pulse. About 10 days after the onset of meltwater release, solute concentrations collected in the lysimeters...

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

DTIC Science & Technology

2011-03-29

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

Effects of ionic strength on the antimicrobial photodynamic efficiency of methylene blue.

PubMed

Núñez, Silvia Cristina; Garcez, Aguinaldo Silva; Kato, Ilka Tiemy; Yoshimura, Tania Mateus; Gomes, Laércio; Baptista, Maurício Silva; Ribeiro, Martha Simões

2014-03-01

Antimicrobial photodynamic therapy (APDT) may become a useful clinical tool to treat microbial infections, and methylene blue (MB) is a well-known photosensitizer constantly employed in APDT studies, and although MB presents good efficiency in antimicrobial studies, some of the MB photochemical characteristics still have to be evaluated in terms of APDT. This work aimed to evaluate the role of MB solvent's ionic strength regarding dimerization, photochemistry, and photodynamic antimicrobial efficiency. Microbiological survival fraction assays on Escherichia coli were employed to verify the solution's influence on MB antimicrobial activity. MB was evaluated in deionized water and 0.9% saline solution through optical absorption spectroscopy; the solutions were also analysed via dissolved oxygen availability and reactive oxygen species (ROS) production. Our results show that bacterial reduction was increased in deionized water. Also we demonstrated that saline solution presents less oxygen availability than water, the dimer/monomer ratio for MB in saline is smaller than in water and MB presented a higher production of ROS in water than in 0.9% saline. Together, our results indicate the importance of the ionic strength in the photodynamic effectiveness and point out that this variable must be taken into account to design antimicrobial studies and to evaluate similar studies that might present conflicting results.

Application of a thiourea-containing task-specific ionic liquid for the solid-phase extraction cleanup of lead ions from red lipstick, pine leaves, and water samples.

PubMed

Saljooqi, Asma; Shamspur, Tayebeh; Mohamadi, Maryam; Mostafavi, Ali

2014-07-01

Here, task-specific ionic liquid solid-phase extraction is proposed for the first time. In this approach, a thiourea-functionalized ionic liquid is immobilized on the solid sorbent, multiwalled carbon nanotubes. These modified nanotubes packed into a solid-phase extraction column are used for the selective extraction and preconcentration of ultra-trace amounts of lead(II) from aqueous samples prior to electrothermal atomic absorption spectroscopy determination. The thiourea functional groups act as chelating agents for lead ions retaining them and so, give the selectivity to the sorbent. Elution of the retained ions can be performed using an acidic thiourea solution. The effects of experimental parameters including pH of the aqueous solution, type and amount of eluent, and the flow rates of sample and eluent solutions on the separation efficiency are investigated. The linear dependence of absorbance of lead on its concentration in the initial solution is in the range of 0.5-40.0 ng/mL with the detection limit of 0.13 ng/mL (3(Sb)/m, n = 10). The proposed method is applicable to the analysis of red lipstick, pine leaves, and water samples for their lead contents. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acid-base equilibria inside amine-functionalized mesoporous silica.

PubMed

Yamaguchi, Akira; Namekawa, Manato; Kamijo, Toshio; Itoh, Tetsuji; Teramae, Norio

2011-04-15

Acid-base equilibria and effective proton concentration inside a silica mesopore modified with a trimethyl ammonium (TMAP) layer were studied by steady-state fluorescence experiments. The mesoporous silica with a dense TMAP layer (1.4 molecules/nm(2)) was prepared by a post grafting of N-trimethoxysilylpropyl-N,N,N-trimethylammonium at surfactant-templated mesoporous silica (diameter of silica framework =3.1 nm). The resulting TMAP-modified mesoporous silica strongly adsorbed of anionic fluorescence indicator dyes (8-hydroxypyrene-1,3,6-trisulfonate (pyranine), 8-aminopyrene-1,3,6-trisulfonate (APTS), 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid disulfuric acid (TPPS), 2-naphthol-3,6-disulfonate (2NT)) and fluorescence excitation spectra of these dyes within TMAP-modified mesoporous silica were measured by varying the solution pH. The fluorescence experiments revealed that the acid-base equilibrium reactions of all pH indicator dyes within the TMAP-modified silica mesopore were quite different from those in bulk water. From the analysis of the acid-base equilibrium of pyranine, the following relationships between solution pH (pH(bulk)) and the effective proton concentration inside the pore (pH(pore)) were obtained: (1) shift of pH(pore) was 1.8 (ΔpH(pore)=1.8) for the pH(bulk) change from 2.1 to 9.1 (ΔpH(bulk)=7.0); (2) pH(pore) was not simply proportional to pH(bulk); (3) the inside of the TMAP-modified silica mesopore was suggested to be in a weak acidic or neutral condition when pH(bulk) was changed from 2.0 to 9.1. Since these relationships between pH(bulk) and pH(pore) could explain the acid-base equilibria of other pH indicator dyes (APTS, TPPS, 2NT), these relationships were inferred to describe the effective proton concentration inside the TMAP-modified silica mesopore. © 2011 American Chemical Society

Large Deviations and Transitions Between Equilibria for Stochastic Landau-Lifshitz-Gilbert Equation

NASA Astrophysics Data System (ADS)

Brzeźniak, Zdzisław; Goldys, Ben; Jegaraj, Terence

2017-11-01

We study a stochastic Landau-Lifshitz equation on a bounded interval and with finite dimensional noise. We first show that there exists a pathwise unique solution to this equation and that this solution enjoys the maximal regularity property. Next, we prove the large deviations principle for the small noise asymptotic of solutions using the weak convergence method. An essential ingredient of the proof is the compactness, or weak to strong continuity, of the solution map for a deterministic Landau-Lifschitz equation when considered as a transformation of external fields. We then apply this large deviations principle to show that small noise can cause magnetisation reversal. We also show the importance of the shape anisotropy parameter for reducing the disturbance of the solution caused by small noise. The problem is motivated by applications from ferromagnetic nanowires to the fabrication of magnetic memories.

Linear adsorption of nonionic organic compounds from water onto hydrophilic minerals: Silica and alumina

USGS Publications Warehouse

Su, Y.-H.; Zhu, Y.-G.; Sheng, G.; Chiou, C.T.

2006-01-01

To characterize the linear adsorption phenomena in aqueous nonionic organic solute-mineral systems, the adsorption isotherms of some low-molecular- weightnonpolar nonionic solutes (1,2,3-trichlorobenzene, lindane, phenanthrene, and pyrene) and polar nonionic solutes (1,3-dinitrobenzene and 2,4-dinitrotoluene) from single-and binary-solute solutions on hydrophilic silica and alumina were established. Toward this objective, the influences of temperature, ionic strength, and pH on adsorption were also determined. It is found that linear adsorption exhibits low exothermic heats and practically no adsorptive competition. The solute-solid configuration and the adsorptive force consistent with these effects were hypothesized. For nonpolar solutes, the adsorption occurs presumably by London (dispersion) forces onto a water film above the mineral surface. For polar solutes, the adsorption is also assisted by polar-group interactions. The reduced adsorptive forces of solutes with hydrophilic minerals due to physical separation by the water film and the low fractions of the water-film surface covered by solutes offer a theoretical basis for linear solute adsorption, low exothermic heats, and no adsorptive competition. The postulated adsorptive forces are supported by observations that ionic strength or pH poses no effect on the adsorption of nonpolar solutes while it exhibits a significant effect on the uptake of polar solutes. ?? 2006 American Chemical Society.

Nonideality in diffusion of ionic and hydrophobic solutes and pair dynamics in water-acetone mixtures of varying composition.

PubMed

Gupta, Rini; Chandra, Amalendu

2007-07-14

We have performed a series of molecular dynamics simulations of water-acetone mixtures containing either an ionic solute or a neutral hydrophobic solute to study the extent of nonideality in the dynamics of these solutes with variation of composition of the mixtures. The diffusion coefficients of the charged solutes, both cationic and anionic, are found to change nonmonotonically with the composition of the mixtures showing strong nonideality of their dynamics. Also, the extent of nonideality in the diffusion of these charged solutes is found to be similar to the nonideality that is observed for the diffusion and orientational relaxation of water and acetone molecules in these mixtures which show a somewhat similar changes in the solvation characteristics of charged and dipolar solutes with changes of composition of water-acetone mixtures. The diffusion of the hydrophobic solute, however, shows a monotonic increase with increase of acetone concentration showing its different solvation characteristics as compared to the charged and dipolar solutes. The links between the nonideality in diffusion and solvation structures are further confirmed through calculations of the relevant solute-solvent and solvent-solvent radial distribution functions for both ionic and hydrophobic solutes. We have also calculated various pair dynamical properties such as the relaxation of water-water and acetone-water hydrogen bonds and residence dynamics of water molecules in water and acetone hydration shells. The lifetimes of both water-water and acetone-water hydrogen bonds and also the residence times of water molecules are found to increase steadily with increase in acetone concentration. No maximum or minimum was found in the composition dependence of these pair dynamical quantities. The lifetimes of water-water hydrogen bonds are always found to be longer than that of acetone-water hydrogen bonds in these mixtures. The residence times of water molecules are also found to follow a similar trend.

On the Preparation of Buffer Solutions.

ERIC Educational Resources Information Center

Thomson, Bruce M.; Kessick, Michael A.

1981-01-01

Presents a method, suitable for use on programmable calculators, which allows calculation of the pH and ionic strength (I) of a mixed solution of salts of an acid or amounts necessary to produce a solution of a particular pH and I. Includes limitations when using the calculations described. (SK)

Macroscopic experimental and modeling evaluation of selenite and selenate adsorption mechanisms on gibbsite

USDA-ARS?s Scientific Manuscript database

Selenite Se(IV) and selenate Se(VI) selenium adsorption behavior was investigated on gibbsite as a function of solution pH and solution ionic strength. Adsorption of both Se redox states decreased with increasing solution pH. Electrophoretic mobility measurements showed downward shifts in point of...

On the composition dependence of faceting behaviour of primary phases during solidification

NASA Astrophysics Data System (ADS)

Saroch, Mamta; Dubey, K. S.; Ramachandrarao, P.

1993-02-01

The entropy of solution of the primary aluminium-rich phase in the aluminium-tin melts has been evaluated as a function of temperature using available thermodynamic and phase equilibria data with a view to understand the faceting behaviour of this phase. It was noticed that the range of compositions in which alloys of aluminium and tin yield a faceted primary phase is correlated with the domain of compositions over which the entropy of solution shows a strong temperature dependence. It is demonstrated that both a high value of the entropy of solution and a strong temperature dependence of it are essential for providing faceting. A strong temperature dependence of the entropy of solution is in turn a consequence of negligible liquidus slope and existence of retrograde solubility. The AgBi and AgPb systems have similar features.

Optimization of neural network for ionic conductivity of nanocomposite solid polymer electrolyte system (PEO-LiPF 6-EC-CNT)

NASA Astrophysics Data System (ADS)

Johan, Mohd Rafie; Ibrahim, Suriani

2012-01-01

In this study, the ionic conductivity of a nanocomposite polymer electrolyte system (PEO-LiPF 6-EC-CNT), which has been produced using solution cast technique, is obtained using artificial neural networks approach. Several results have been recorded from experiments in preparation for the training and testing of the network. In the experiments, polyethylene oxide (PEO), lithium hexafluorophosphate (LiPF 6), ethylene carbonate (EC) and carbon nanotubes (CNT) are mixed at various ratios to obtain the highest ionic conductivity. The effects of chemical composition and temperature on the ionic conductivity of the polymer electrolyte system are investigated. Electrical tests reveal that the ionic conductivity of the polymer electrolyte system varies with different chemical compositions and temperatures. In neural networks training, different chemical compositions and temperatures are used as inputs and the ionic conductivities of the resultant polymer electrolytes are used as outputs. The experimental data is used to check the system's accuracy following the training process. The neural network is found to be successful for the prediction of ionic conductivity of nanocomposite polymer electrolyte system.

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

Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

2016-09-01

Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

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

PubMed

de Oliveira, Heitor Fernando Nunes; Rinaldi, Roberto

2015-05-11

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

A shell-resolved analysis of preferential solvation of coffee ingredients in aqueous mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate

NASA Astrophysics Data System (ADS)

Zeindlhofer, Veronika; Berger, Magdalena; Steinhauser, Othmar; Schröder, Christian

2018-05-01

Ionic liquids increase the solubility of various coffee ingredients in aqueous solution but little is known about the underlying mechanism. Kirkwood-Buff integrals as well as the potential of mean force indicate that the imidazolium cations are accumulated at the surface of the solutes, removing water molecules from the solute surface. Although hydrogen bonding of the anions to hydroxy groups of the solutes can be detected, their concentration at the surface is less enhanced compared to the cations. The decomposition into solvation shells by Voronoi tessellation reveals that structural features are only observed in the first solvation shell. Nevertheless, the depletion of water and the excess concentration of the ions and, in particular, of the cations are visible in the next solvation shells as well. Therefore, classical arguments of hydrotropic theory fail to explain this behavior.

Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

NASA Astrophysics Data System (ADS)

Ali, H. M.; Iedema, M.; Yu, X.-Y.; Cowin, J. P.

2014-06-01

The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium chloride (brine) particles was studied by utilizing a cross flow mini-reactor. The reaction kinetics were followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely CCSEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry's law solubility of H2O2 in brine solutions to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to, eventually, a mixed NaHSO4 plus H2SO4 brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted using established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the dependence of the Henry's law constant of H2O2 on ionic strength.

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

PubMed

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

2011-06-30

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

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.

Microelectrode voltammetry of multi-electron transfers complicated by coupled chemical equilibria: a general theory for the extended square scheme.

PubMed

Laborda, Eduardo; Gómez-Gil, José María; Molina, Angela

2017-06-28

A very general and simple theoretical solution is presented for the current-potential-time response of reversible multi-electron transfer processes complicated by homogeneous chemical equilibria (the so-called extended square scheme). The expressions presented here are applicable regardless of the number of electrons transferred and coupled chemical processes, and they are particularized for a wide variety of microelectrode geometries. The voltammetric response of very different systems presenting multi-electron transfers is considered for the most widely-used techniques (namely, cyclic voltammetry, square wave voltammetry, differential pulse voltammetry and steady state voltammetry), studying the influence of the microelectrode geometry and the number and thermodynamics of the (electro)chemical steps. Most appropriate techniques and procedures for the determination of the 'interaction' between successive transfers are discussed. Special attention is paid to those situations where homogeneous chemical processes, such as protonation, complexation or ion association, affect the electrochemical behaviour of the system by different stabilization of the oxidation states.

A new problem in mathematical physics associated with the problem of coherent phase transformation

NASA Astrophysics Data System (ADS)

Grinfeld, M. A.

1985-06-01

The description of heterogeneous coherent phase equilibria in an elastic single component system is shown to lead, in the approximation of small intrinsic deformation, to a new problem in mathematical physics with an unknown bound. The low order terms of the resulting system of equilibrium equations coincide with the equations of the classical linear theory of elasticity (generally speaking, anisotropic); however, the problem remains strongly nonlinear overall, inasmuch as it contains an unknown bound and a boundary condition on it which is quadratic with respect to translation. The formulas obtained are used to find certain explicit solutions to the boundary problems. As an example, the problem of heterogeneous equilibria in an infinite rectangular isotropic beam with free faces and constant loading on the surfaces x squared = const can be examined. A modeling problem for the asymptote of small intrinsic deformation during coherent phase transformation is presented as a scalar analog of the vector problem considered initially.

Dynamics of a neutral delay equation for an insect population with long larval and short adult phases

NASA Astrophysics Data System (ADS)

Gourley, Stephen A.; Kuang, Yang

We present a global study on the stability of the equilibria in a nonlinear autonomous neutral delay differential population model formulated by Bocharov and Hadeler. This model may be suitable for describing the intriguing dynamics of an insect population with long larval and short adult phases such as the periodical cicada. We circumvent the usual difficulties associated with the study of the stability of a nonlinear neutral delay differential model by transforming it to an appropriate non-neutral nonautonomous delay differential equation with unbounded delay. In the case that no juveniles give birth, we establish the positivity and boundedness of solutions by ad hoc methods and global stability of the extinction and positive equilibria by the method of iteration. We also show that if the time adjusted instantaneous birth rate at the time of maturation is greater than 1, then the population will grow without bound, regardless of the population death process.

Collisionless current sheet equilibria

NASA Astrophysics Data System (ADS)

Neukirch, T.; Wilson, F.; Allanson, O.

2018-01-01

Current sheets are important for the structure and dynamics of many plasma systems. In space and astrophysical plasmas they play a crucial role in activity processes, for example by facilitating the release of magnetic energy via processes such as magnetic reconnection. In this contribution we will focus on collisionless plasma systems. A sensible first step in any investigation of physical processes involving current sheets is to find appropriate equilibrium solutions. The theory of collisionless plasma equilibria is well established, but over the past few years there has been a renewed interest in finding equilibrium distribution functions for collisionless current sheets with particular properties, for example for cases where the current density is parallel to the magnetic field (force-free current sheets). This interest is due to a combination of scientific curiosity and potential applications to space and astrophysical plasmas. In this paper we will give an overview of some of the recent developments, discuss their potential applications and address a number of open questions.

Phase equilibria in the Bi 2TeO 5Bi 2SeO 5 system and a high temperature neutron powder diffraction study of Bi 2SeO 5

NASA Astrophysics Data System (ADS)

Dityatyev, Oleg A.; Smidt, Peer; Stefanovich, Sergey Yu; Lightfoot, Philip; Dolgikh, Valery A.; Opperman, Heinrich

2004-09-01

Phase equilibria in the Bi 2TeO 5Bi 2SeO 5 system were studied by X-ray, DTA and second harmonic generation (SHG). The samples were synthesized by solid state reactions of the Bi, Te and Se oxides. The phase diagram is interpreted as a quasibinary peritectic one with wide ranges of solid solutions on the basis of both compounds. The SHG study showed Bi 2SeO 5 to undergo a phase transition at about 250 °C. Neutron diffraction (25-650 °C) showed no major changes in the structure of Bi 2SeO 5 at high temperatures. However, the analysis of the oxygen atom thermal factors and site occupancies suggested that the mechanism of the phase transformation is an order-disorder transition involving reorientation of the SeO 3 group.

Axisymmetric plasma equilibria in a Kerr metric

NASA Astrophysics Data System (ADS)

Elsässer, Klaus

2001-10-01

Plasma equilibria near a rotating black hole are considered within the multifluid description. An isothermal two-component plasma with electrons and positrons or ions is determined by four structure functions and the boundary conditions. These structure functions are the Bernoulli function and the toroidal canonical momentum per mass for each species. The quasi-neutrality assumption (no charge density, no toroidal current) allows to solve Maxwell's equations analytically for any axisymmetric stationary metric, and to reduce the fluid equations to one single scalar equation for the stream function \\chi of the positrons or ions, respectively. The basic smallness parameter is the ratio of the skin depth of electrons to the scale length of the metric and fluid quantities, and, in the case of an electron-ion plasma, the mass ratio m_e/m_i. The \\chi-equation can be solved by standard methods, and simple solutions for a Kerr geometry are available; they show characteristic flow patterns, depending on the structure functions and the boundary conditions.

Experimental tests of linear and nonlinear three-dimensional equilibrium models in DIII-D

DOE PAGES

King, Josh D.; Strait, Edward J.; Lazerson, Samuel A.; ...

2015-07-01

DIII-D experiments using new detailed magnetic diagnostics show that linear, ideal magnetohydrodynamics (MHD) theory quantitatively describes the magnetic structure (as measured externally) of three-dimensional (3D) equilibria resulting from applied fields with toroidal mode number n = 1, while a nonlinear solution to ideal MHD force balance, using the VMEC code, requires the inclusion of n ≥ 1 to achieve similar agreement. Moreover, these tests are carried out near ITER baseline parameters, providing a validated basis on which to exploit 3D fields for plasma control development. We determine scans of the applied poloidal spectrum and edge safety factors which confirm thatmore » low-pressure, n = 1 non-axisymmetric tokamak equilibria are a single, dominant, stable eigenmode. But, at higher beta, near the ideal kink mode stability limit in the absence of a conducting wall, the qualitative features of the 3D structure are observed to vary in a way that is not captured by ideal MHD.« less

Torsten Almén (1931-2016): the father of non-ionic iodine contrast media.

PubMed

Nyman, Ulf; Ekberg, Olle; Aspelin, Peter

2016-09-01

The Swedish radiologist Torsten Almén is the first clinical radiologist ever to have made a fundamental contribution to intravascular contrast medium design, the development of non-ionic contrast media. He became emotionally triggered by the patients' severe pain each time he injected the ionic "high-osmolar" contrast media when performing peripheral arteriographies in the early 1960s. One day he got a flash of genius that combined the observation of pain, a pathophysiological theory and how to eliminate it with suitable contrast media chemistry. After self-studies in chemistry he developed the concept of iodine contrast media not dissociating into ions in solution to reduce their osmolality and even reach plasma isotonicity. He offered several pharmaceutical companies his concept of mono- and polymeric non-ionic agents but without response, since it was considered against the chemical laws of that time. Contrast media constructed as salts and dissociating into ions in solution was regarded an absolute necessity to achieve high enough water solubility and concentration for diagnostic purposes. Finally a small Norwegian company, Nyegaard & Co., took up his idea 1968 and together they developed the essentially painless "low-osmolar" monomeric non-ionic metrizamide (Amipaque) released in 1974 and iohexol (Omipaque) in 1982 followed by the "iso-osmolar" dimeric non-ionic iodixanol (Visipaque) released in 1993. This has implied a profound paradigm shift with regard to reduction of both hypertonic and chemotoxic side effects, which have been a prerequisite for the today's widespread use of contrast medium-enhanced CT and advanced endovascular interventional techniques even in fragile patients. © The Foundation Acta Radiologica 2016.

Asymmetric kinetic equilibria: Generalization of the BAS model for rotating magnetic profile and non-zero electric field

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

Dorville, Nicolas, E-mail: nicolas.dorville@lpp.polytechnique.fr; Belmont, Gérard; Aunai, Nicolas

Finding kinetic equilibria for non-collisional/collisionless tangential current layers is a key issue as well for their theoretical modeling as for our understanding of the processes that disturb them, such as tearing or Kelvin Helmholtz instabilities. The famous Harris equilibrium [E. Harris, Il Nuovo Cimento Ser. 10 23, 115–121 (1962)] assumes drifting Maxwellian distributions for ions and electrons, with constant temperatures and flow velocities; these assumptions lead to symmetric layers surrounded by vacuum. This strongly particular kind of layer is not suited for the general case: asymmetric boundaries between two media with different plasmas and different magnetic fields. The standard methodmore » for constructing more general kinetic equilibria consists in using Jeans theorem, which says that any function depending only on the Hamiltonian constants of motion is a solution to the steady Vlasov equation [P. J. Channell, Phys. Fluids (1958–1988) 19, 1541 (1976); M. Roth et al., Space Sci. Rev. 76, 251–317 (1996); and F. Mottez, Phys. Plasmas 10, 1541–1545 (2003)]. The inverse implication is however not true: when using the motion invariants as variables instead of the velocity components, the general stationary particle distributions keep on depending explicitly of the position, in addition to the implicit dependence introduced by these invariants. The standard approach therefore strongly restricts the class of solutions to the problem and probably does not select the most physically reasonable. The BAS (Belmont-Aunai-Smets) model [G. Belmont et al., Phys. Plasmas 19, 022108 (2012)] used for the first time the concept of particle accessibility to find new solutions: considering the case of a coplanar-antiparallel magnetic field configuration without electric field, asymmetric solutions could be found while the standard method can only lead to symmetric ones. These solutions were validated in a hybrid simulation [N. Aunai et al., Phys. Plasmas (1994-present) 20, 110702 (2013)], and more recently in a fully kinetic simulation as well [J. Dargent and N. Aunai, Phys. Plasmas (submitted)]. Nevertheless, in most asymmetric layers like the terrestrial magnetopause, one would indeed expect a magnetic field rotation from one direction to another without going through zero [J. Berchem and C. T. Russell, J. Geophys. Res. 87, 8139–8148 (1982)], and a non-zero normal electric field. In this paper, we propose the corresponding generalization: in the model presented, the profiles can be freely imposed for the magnetic field rotation (although restricted to a 180 rotation hitherto) and for the normal electric field. As it was done previously, the equilibrium is tested with a hybrid simulation.« less

Coatable Li4 SnS4 Solid Electrolytes Prepared from Aqueous Solutions for All-Solid-State Lithium-Ion Batteries.

PubMed

Choi, Young Eun; Park, Kern Ho; Kim, Dong Hyeon; Oh, Dae Yang; Kwak, Hi Ram; Lee, Young-Gi; Jung, Yoon Seok

2017-06-22

Bulk-type all-solid-state lithium-ion batteries (ASLBs) for large-scale energy-storage applications have emerged as a promising alternative to conventional lithium-ion batteries (LIBs) owing to their superior safety. However, the electrochemical performance of bulk-type ASLBs is critically limited by the low ionic conductivity of solid electrolytes (SEs) and poor ionic contact between the active materials and SEs. Herein, highly conductive (0.14 mS cm -1 ) and dry-air-stable SEs (Li 4 SnS 4 ) are reported, which are prepared using a scalable aqueous-solution process. An active material (LiCoO 2 ) coated by solidified Li 4 SnS 4 from aqueous solutions results in a significant improvement in the electrochemical performance of ASLBs. Side-effects of the exposure of LiCoO 2 to aqueous solutions are minimized by using predissolved Li 4 SnS 4 solution. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rheological properties of concentrated solutions of gelatin in an ionic liquid 1-ethyl-3-methylimidazolium dimethyl phosphate.

PubMed

Horinaka, Jun-Ichi; Okamoto, Arisa; Takigawa, Toshikazu

2016-10-01

Rheological properties of gelatin solutions were examined in concentrated regions. Gelatin species from porcine skin and from bovine bone were dissolved in an ionic liquid 1-ethyl-3-methylimidazolium dimethyl phosphate. The dynamic viscoelasticity data for the solutions exhibited rubbery plateaus, indicating the existence of entanglement coupling between gelatin chains in the solutions. From the analogy with rubber elasticity, assuming that the molecular weight between entanglements (Me) is the average mesh size of the entanglement network, Me for gelatin in the solutions were determined from the heights of the rubbery plateaus. Then the value of Me in the molten state (Me,melt), a material constant reflecting the chemical structure of polymer species, for gelatin was estimated to be 8.7×10(3). Compared to synthetic polyamides whose Me,melt were known, Me,melt for gelatin was significantly larger, which could be explained by the densely repeating amide bonds composing gelatin. Copyright © 2016 Elsevier B.V. All rights reserved.

Colloid transport in porous media: impact of hyper-saline solutions.

PubMed

Magal, Einat; Weisbrod, Noam; Yechieli, Yoseph; Walker, Sharon L; Yakirevich, Alexander

2011-05-01

The transport of colloids suspended in natural saline solutions with a wide range of ionic strengths, up to that of Dead Sea brines (10(0.9) M) was explored. Migration of microspheres through saturated sand columns of different sizes was studied in laboratory experiments and simulated with mathematical models. Colloid transport was found to be related to the solution salinity as expected. The relative concentration of colloids at the columns outlet decreased (after 2-3 pore volumes) as the solution ionic strength increased until a critical value was reached (ionic strength > 10(-1.8) M) and then remained constant above this level of salinity. The colloids were found to be mobile even in the extremely saline brines of the Dead Sea. At such high ionic strength no energetic barrier to colloid attachment was presumed to exist and colloid deposition was expected to be a favorable process. However, even at these salinity levels, colloid attachment was not complete and the transport of ∼ 30% of the colloids through the 30-cm long columns was detected. To further explore the deposition of colloids on sand surfaces in Dead Sea brines, transport was studied using 7-cm long columns through which hundreds of pore volumes were introduced. The resulting breakthrough curves exhibited a bimodal shape whereby the relative concentration (C/C(0)) of colloids at the outlet rose to a value of 0.8, and it remained relatively constant (for the ∼ 18 pore volumes during which the colloid suspension was flushed through the column) and then the relative concentration increased to a value of one. The bimodal nature of the breakthrough suggests different rates of colloid attachment. Colloid transport processes were successfully modeled using the limited entrapment model, which assumes that the colloid attachment rate is dependent on the concentration of the attached colloids. Application of this model provided confirmation of the colloid aggregation and their accelerated attachment during transport through soil in high salinity solution. Copyright © 2011 Elsevier Ltd. All rights reserved.

Fabrication of ionic liquid electrodeposited Cu--Sn--Zn--S--Se thin films and method of making

DOEpatents

Bhattacharya, Raghu Nath

2016-01-12

A semiconductor thin-film and method for producing a semiconductor thin-films comprising a metallic salt, an ionic compound in a non-aqueous solution mixed with a solvent and processing the stacked layer in chalcogen that results in a CZTS/CZTSS thin films that may be deposited on a substrate is disclosed.

Ionic association of lithium salts in propylene carbonate/ 1,2-dimethoxyethane mixed systems for lithium batteries

NASA Astrophysics Data System (ADS)

Ishikawa, Masashi; Wen, Shi-Qui; Matsuda, Yoshiharu

1993-06-01

The ionic association constants of lithium perchlorate, lithium trifluoremethylsulfate, lithium hexafluorophosphate, and lithium tetrafluoroborate have been determined experimentally (by Shedlovsky's method) in various mixtures of propylene carbonate and 1,2-dimethoxyethane as typical electrolyte systems for rechargeable lithium batteries. The association constants vary extensively for different mixing ratios of propylene to 1,2-dimethoxyethane and for different species of salts. These values are compared with the theoretical values as predicted by the Fuoss and Bjerrum equations. On the basis of this comparison and some physical properties of the solution, the variation in the ionic association constants may be ascribed to the charge of ionic association species, i.e., a contact ion-pair and a solvent-separated ion-pair.

Glass formation, ionic conductivity, and conductivity/viscosity decoupling, in LiAlCl{sub 4} + LiClO{sub 4} and LiAlCl{sub 4} + LiAlCl{sub 3}{center_dot}imide solutions

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

Videa, M.; Angeli, C.A.

As part of a search for chemically and electrochemically stable ambient temperature molten lithium salt systems the authors have investigated the properties of solutions of LiAlCl{sub 4} with various second components. In this paper they review the factors which determine the ambient temperature conductivity and report results for two systems, one of which satisfies the stability requirements although failing to provide the high conductivities which are needed for a successful ambient temperature Li battery electrolyte. These ionic solutions appear to be very fragile liquids. Evidence is found for a mixing incompatibility of polarizable and nonpolarizable components of binary melts.

Motion of Molecular Probes and Viscosity Scaling in Polyelectrolyte Solutions at Physiological Ionic Strength

PubMed Central

Sozanski, Krzysztof; Wisniewska, Agnieszka; Kalwarczyk, Tomasz; Sznajder, Anna; Holyst, Robert

2016-01-01

We investigate transport properties of model polyelectrolyte systems at physiological ionic strength (0.154 M). Covering a broad range of flow length scales—from diffusion of molecular probes to macroscopic viscous flow—we establish a single, continuous function describing the scale dependent viscosity of high-salt polyelectrolyte solutions. The data are consistent with the model developed previously for electrically neutral polymers in a good solvent. The presented approach merges the power-law scaling concepts of de Gennes with the idea of exponential length scale dependence of effective viscosity in complex liquids. The result is a simple and applicable description of transport properties of high-salt polyelectrolyte solutions at all length scales, valid for motion of single molecules as well as macroscopic flow of the complex liquid. PMID:27536866

Ion concentration in micro and nanoscale electrospray emitters.

PubMed

Yuill, Elizabeth M; Baker, Lane A

2018-06-01

Solution-phase ion transport during electrospray has been characterized for nanopipettes, or glass capillaries pulled to nanoscale tip dimensions, and micron-sized electrospray ionization emitters. Direct visualization of charged fluorophores during the electrospray process is used to evaluate impacts of emitter size, ionic strength, analyte size, and pressure-driven flow on heterogeneous ion transport during electrospray. Mass spectrometric measurements of positively- and negatively-charged proteins were taken for micron-sized and nanopipette emitters under low ionic strength conditions to further illustrate a discrepancy in solution-driven transport of charged analytes. A fundamental understanding of analyte electromigration during electrospray, which is not always considered, is expected to provide control over selective analyte depletion and enrichment, and can be harnessed for sample cleanup. Graphical abstract Fluorescence micrographs of ion migration in nanoscale pipettes while solution is electrosprayed.

Molecular crowding has no effect on the dilution thermodynamics of the biologically relevant cation mixtures.

PubMed

Głogocka, Daria; Przybyło, Magdalena; Langner, Marek

2017-04-01

The ionic composition of intracellular space is rigorously maintained in the expense of high-energy expenditure. It has been recently postulated that the cytoplasmic ionic composition is optimized so the energy cost of the fluctuations of calcium ion concentration is minimized. Specifically, thermodynamic arguments have been produced to show that the presence of potassium ions at concentrations higher than 100 mM reduce extend of the energy dissipation required for the dilution of calcium cations. No such effect has been measured when sodium ions were present in the solution or when the other divalent cation magnesium was diluted. The experimental observation has been interpreted as the indication of the formation of ionic clusters composed of calcium, chloride and potassium. In order to test the possibility that such clusters may be preserved in biological space, the thermodynamics of ionic mixtures dilution in solutions containing albumins and model lipid bilayers have been measured. Obtained thermograms clearly demonstrate that the energetics of calcium/potassium mixture is qualitatively different from calcium/sodium mixture indicating that the presence of the biologically relevant quantities of proteins and membrane hydrophilic surfaces do not interfere with the properties of the intracellular aqueous phase.

Poly(Ionic Liquid) Semi-Interpenetrating Network Multi-Responsive Hydrogels

PubMed Central

Tudor, Alexandru; Florea, Larisa; Gallagher, Simon; Burns, John; Diamond, Dermot

2016-01-01

Herein we describe poly(ionic liquid) hydrogel actuators that are capable of responding to multiple stimuli, namely temperature, ionic strength and white light irradiation. Using two starting materials, a crosslinked poly ionic liquid (PIL) and a linear poly(N-isopropylacrylamide-co-spiropyran-co-acrylic acid), several semi-interpenetrating (sIPN) hydrogels were synthesised. The dimensions of hydrogels discs were measured before and after applying the stimuli, to quantify their response. Samples composed of 100% crosslinked PIL alone showed an average area reduction value of ~53% when the temperature was raised from 20 °C to 70 °C, ~24% when immersed in 1% w/w NaF salt solution and no observable photo-response. In comparison, sIPNs containing 300% w/w linear polymer showed an average area reduction of ~45% when the temperature was raised from 20 °C to 70 °C, ~36% when immersed in 1% NaF w/w salt solution and ~10% after 30 min exposure to white light irradiation, respectively. Moreover, by varying the content of the linear component, fine-control over the photo-, thermo- and salt response, swelling-deswelling rate and mechanical properties of the resulting sIPN was achieved. PMID:26861339

[Verification of a decrease in the rigidity of the phage lambda DNA polymeric chain in low ionic strength aqueous solutions by testing the polymer-polymer interlink interactions].

PubMed

Arutiunian, A V; Ivanova, M A; Kurliand, D I; Kapshin, Iu S; Landa, S B; Poshekhonov, S T; Drobchenko, E A; Shevelev, I V

2011-01-01

Changes in the rigidity of the polymetric chain of phage lambda double-strand DNA have been studied by laser correlation spectroscopy. It was shown that, as the ionic strength increases, the effect of the screening of the hydrodynamic interaction of the links of the polymeric chain specific for polymeric coils arises in a DNA solution. It is assumed that the screening occurs when the threshold of the overlapping of DNA coils is achieved. The overlapping of coils is the result of a previously observed significant rise of DNA coil size from abnormally small DNA coils in low ionic strength buffers (about 10(-2) M Na+ or less) to maximum possible large coils in the 5SSC and 5SSC-like buffers. Further analysis of the far interlink interactions in linear lambda phage DNA coils in similar buffers at pH 7 and 4 confirms the earlier proposal about the role of H+ ions in the appearance of abnormally small DNA coils. The abnormal decrease in the DNA coil size in low ionic strength buffers is not a specific feature of lambda phage DNA only.

Conductivity and spectroscopic investigation of bis(trifluoromethanesulfonyl)imide solution in ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide.

PubMed

Yu, Lei; Pizio, Benjamin S; Vaden, Timothy D

2012-06-07

Protic ionic liquids (PILs) are promising alternatives to water for swelling Nafion as a fuel cell proton exchange membrane (PEM). PILs can significantly improve the high-temperature performance of a PEM. The proton dissociation and solvation mechanisms in a PIL, which are keys to understanding the proton transportation and conductivity, have not been fully explored. In this paper, we used FTIR, Raman, and electronic spectroscopy with computational simulation techniques to explore the spectroscopic properties of bis(trifluoromethanesulfonyl)imide (HTFSI) solutions in 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) ionic liquid at concentrations from ∼0.1 to as high as ∼1.0 M. Solution conductivities were measured at room temperature and elevated temperatures up to ∼65 °C. The solution structure and properties depend on the concentration of HTFSI. At lower concentration, around 0.1 M, the HTFSI solution has higher conductivity than pure BMITFSI. However, the conductivity decreases when the concentration increases from 0.1 to 1.0 M. Temperature-dependent conductivities followed the Vogel-Fulcher-Tamman equation at all concentrations. Conductivity and spectroscopy results elucidate the complicated ionization and solvation mechanism of HTFSI in BMITFSI solutions. Raman spectroscopy and density functional theory (DFT) calculations are consistent with the complete ionization of HTFSI to generate solvated H(+) at low concentrations. FTIR, Raman, and electronic spectroscopic results as well as DFT computational simulation indicated that when the concentration is as high as 1.0 M, a significant amount of TFSI(-) is protonated, most likely at the imide nitrogen.

Ultrafast fluorescence upconversion technique and its applications to proteins.

PubMed

Chosrowjan, Haik; Taniguchi, Seiji; Tanaka, Fumio

2015-08-01

The basic principles and main characteristics of the ultrafast time-resolved fluorescence upconversion technique (conventional and space-resolved), including requirements for nonlinear crystals, mixing spectral bandwidth, acceptance angle, etc., are presented. Applications to flavoproteins [wild-type (WT) FMN-binding protein and its W32Y, W32A, E13R, E13K, E13Q and E13T mutants] and photoresponsive proteins [WT photoactive yellow protein and its R52Q mutant in solution and as single crystals] are demonstrated. For flavoproteins, investigations elucidating the effects of ionic charges on ultrafast electron transfer (ET) dynamics are summarized. It is shown that replacement of the ionic amino acid Glu13 and the resulting modification of the electrostatic charge distribution in the protein chromphore-binding pocket substantially alters the ultrafast fluorescence quenching dynamics and ET rate in FMN-binding protein. It is concluded that, together with donor-acceptor distances, electrostatic interactions between ionic photoproducts and other ionic groups in the proteins are important factors influencing the ET rates. In WT photoactive yellow protein and the R52Q mutant, ultrafast photoisomerization dynamics of the chromophore (deprotonated trans-p-coumaric acid) in liquid and crystal phases are investigated. It is shown that the primary dynamics in solution and single-crystal phases are quite similar; hence, the photocycle dynamics and structural differences observed at longer time scales arise mostly from the structural restraints imposed by the crystal lattice rigidity versus the flexibility in solution. © 2014 FEBS.

Static axisymmetric equilibria in general relativistic magnetohydrodynamics

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

Nunez, Manuel

2008-01-15

While the definition of static equilibria is not clear in a general relativistic context, in many cases of astrophysical interest a natural 3+1 split exists which allows us to define physically meaningful spatial and temporal coordinates. We study the possibility of axisymmetric magnetohydrodynamic equilibria in this setting. The presence of a nontrivial shift velocity provides a constraint not present in the Newtonian case, while the momentum equation may be set in a Grad-Shafranov-like form with the presence of additional terms involving the space-time metric coefficients. It is found that whenever the magnetic field or the shift velocity possesses poloidal component,more » the existence of even local static equilibria demands that the metric parameters satisfy such strong conditions that these equilibria are extremely unlikely. Only very particular cases such as purely toroidal fields and shifts yield existence of equilibria, provided we are able to choose arbitrarily the plasma pressure and density.« less

Aqueous Binary Lanthanide(III) Nitrate Ln(NO3)3 Electrolytes Revisited: Extended Pitzer and Bromley Treatments

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

Chatterjee, Sayandev; Campbell, Emily L.; Neiner, Doinita

To date, only limited thermodynamic models describing activity coefficients of the aqueous solutions of lanthanide ions are available. This work expands the existing experimental osmotic coefficient data obtained by classical isopiestic technique for the aqueous binary trivalent lanthanide nitrate Ln(NO3)3 solutions using a combination of water activity and vapor pressure osmometry measurements. The combined osmotic coefficient database for each aqueous lanthanide nitrate at 25°C, consisting of literature available data as well as data obtained in this work, was used to test the validity of Pitzer and Bromley thermodynamic models for the accurate prediction of mean molal activity coefficients of themore » Ln(NO3)3 solutions in wide concentration ranges. The new and improved Pitzer and Bromley parameters were calculated. It was established that the Ln(NO3)3 activity coefficients in the solutions with ionic strength up to 12 mol kg-1 can be estimated by both Pitzer and single-parameter Bromley models, even though the latter provides for more accurate prediction, particularly in the lower ionic strength regime (up to 6 mol kg-1). On the other hand for the concentrated solutions, the extended three-parameter Bromley model can be employed to predict the Ln(NO3)3 activity coefficients with remarkable accuracy. The accuracy of the extended Bromley model in predicting the activity coefficients was greater than ~95% and ~90% for all solutions with the ionic strength up to 12 mol kg-1 and and 20 mol kg-1, respectively. This is the first time that the activity coefficients for concentrated lanthanide solutions have been predicted with such a remarkable accuracy.« less

Development and Characterization of Poly(1-vinylpyrrolidone-co-vinyl acetate) Copolymer Based Polymer Electrolytes

PubMed Central

Sa'adun, Nurul Nadiah; Subramaniam, Ramesh; Kasi, Ramesh

2014-01-01

Gel polymer electrolytes (GPEs) are developed using poly(1-vinylpyrrolidone-co-vinyl acetate) [P(VP-co-VAc)] as the host polymer, lithium bis(trifluoromethane) sulfonimide [LiTFSI] as the lithium salt and ionic liquid, and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide [EMImTFSI] by using solution casting technique. The effect of ionic liquid on ionic conductivity is studied and the optimum ionic conductivity at room temperature is found to be 2.14 × 10−6 S cm−1 for sample containing 25 wt% of EMImTFSI. The temperature dependence of ionic conductivity from 303 K to 353 K exhibits Arrhenius plot behaviour. The thermal stability of the polymer electrolyte system is studied by using thermogravimetric analysis (TGA) while the structural and morphological properties of the polymer electrolyte is studied by using Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction analysis (XRD), respectively. PMID:25431781

Apparent Ionic Charge in Electrolyte and Polyelectrolyte Solutions

ERIC Educational Resources Information Center

Magdelenat, H.; And Others

1978-01-01

Compares average displacements of charged particles under thermal motion alone with those obtained by the action of an external electric field to develop a concept of "apparent charge" to approximate actual structural charge in an electrolyte solution. (SL)

Mixed mosaic membranes prepared by layer-by-layer assembly for ionic separations.

PubMed

Rajesh, Sahadevan; Yan, Yu; Chang, Hsueh-Chia; Gao, Haifeng; Phillip, William A

2014-12-23

Charge mosaic membranes, which possess distinct cationic and anionic domains that traverse the membrane thickness, are capable of selectively separating dissolved salts from similarly sized neutral solutes. Here, the generation of charge mosaic membranes using facile layer-by-layer assembly methodologies is reported. Polymeric nanotubes with pore walls lined by positively charged polyethylenimine moieties or negatively charged poly(styrenesulfonate) moieties were prepared via layer-by-layer assembly using track-etched membranes as sacrificial templates. Subsequently, both types of nanotubes were deposited on a porous support in order to produce mixed mosaic membranes. Scanning electron microscopy demonstrates that the facile deposition techniques implemented result in nanotubes that are vertically aligned without overlap between adjacent elements. Furthermore, the nanotubes span the thickness of the mixed mosaic membranes. The effects of this unique nanostructure are reflected in the transport characteristics of the mixed mosaic membranes. The hydraulic permeability of the mixed mosaic membranes in piezodialysis operations was 8 L m(-2) h(-1) bar(-1). Importantly, solute rejection experiments demonstrate that the mixed mosaic membranes are more permeable to ionic solutes than similarly sized neutral molecules. In particular, negative rejection of sodium chloride is observed (i.e., the concentration of NaCl in the solution that permeates through a mixed mosaic membrane is higher than in the initial feed solution). These properties illustrate the ability of mixed mosaic membranes to permeate dissolved ions selectively without violating electroneutrality and suggest their utility in ionic separations.

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

Gilbert, Kimberly; Bennett, Philip C.; Wolfe, Will

Dissolution of CO2 into deep subsurface brines for carbon sequestration is regarded as one of the few viable means of reducing the amount of CO2 entering the atmosphere. Ions in solution partially control the amount of CO2 that dissolves, but the mechanisms of the ion's influence are not clearly understood and thus CO2 solubility is difficult to predict. In this study, CO2 solubility was experimentally determined in water, NaCl, CaCl2, Na2SO4, and NaHCO3 solutions and a mixed brine similar to the Bravo Dome natural CO2 reservoir; ionic strengths ranged up to 3.4 molal, temperatures to 140 °C, and CO2 pressuresmore » to 35.5 MPa. Increasing ionic strength decreased CO2 solubility for all solutions when the salt type remained unchanged, but ionic strength was a poor predictor of CO2 solubility in solutions with different salts. A new equation was developed to use ion hydration number to calculate the concentration of electrostricted water molecules in solution. Dissolved CO2 was strongly correlated (R2 = 0.96) to electrostricted water concentration. Strong correlations were also identified between CO2 solubility and hydration enthalpy and hydration entropy. These linear correlation equations predicted CO2 solubility within 1% of the Bravo Dome brine and within 10% of two mixed brines from literature (a 10 wt % NaCl + KCl + CaCl2 brine and a natural Na+, Ca2+, Cl- type brine with minor amounts of Mg2+, K+, Sr2+ and Br-).« less

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

PubMed

Aparicio, Santiago; Alcalde, Rafael; Atilhan, Mert

2010-05-06

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

Vibrational Spectroscopy of Ionic Liquids.

PubMed

Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C

2017-05-24

Vibrational spectroscopy has continued use as a powerful tool to characterize ionic liquids since the literature on room temperature molten salts experienced the rapid increase in number of publications in the 1990's. In the past years, infrared (IR) and Raman spectroscopies have provided insights on ionic interactions and the resulting liquid structure in ionic liquids. A large body of information is now available concerning vibrational spectra of ionic liquids made of many different combinations of anions and cations, but reviews on this literature are scarce. This review is an attempt at filling this gap. Some basic care needed while recording IR or Raman spectra of ionic liquids is explained. We have reviewed the conceptual basis of theoretical frameworks which have been used to interpret vibrational spectra of ionic liquids, helping the reader to distinguish the scope of application of different methods of calculation. Vibrational frequencies observed in IR and Raman spectra of ionic liquids based on different anions and cations are discussed and eventual disagreements between different sources are critically reviewed. The aim is that the reader can use this information while assigning vibrational spectra of an ionic liquid containing another particular combination of anions and cations. Different applications of IR and Raman spectroscopies are given for both pure ionic liquids and solutions. Further issues addressed in this review are the intermolecular vibrations that are more directly probed by the low-frequency range of IR and Raman spectra and the applications of vibrational spectroscopy in studying phase transitions of ionic liquids.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

Conductivity of gel polymer electrolytes doped with solutions of phosphonic acid or protic ionic liquids

NASA Astrophysics Data System (ADS)

Shmukler, Liudmila E.; Fadeeva, Yuliya A.; Glushenkova, Ekaterina V.; Nguyen, Van Thuc; Safonova, Liubov P.

2018-04-01

The proton-conducting gel electrolytes (PCGEs) based on PMMA, PVdF or PVdF-HFP doped with solutions of phosphonic acid or ammonium based protic ionic liquids (PILs) in DMF have been synthesized. Rather high values of the conductivity (10-4-10-3 S cm-1) have been reached at low dopant concentrations (up to 1 mol l-1). The influence of the nature of both polymeric matrix and dopant as well as dopant concentration on the conductivity values was discussed. It was established that the dependence of conductivity on the nature of dopant, but not the polymeric matrix, was more pronounced.

Dielectric constant of ionic solutions: a field-theory approach.

PubMed

Levy, Amir; Andelman, David; Orland, Henri

2012-06-01

We study the variation of the dielectric response of a dielectric liquid (e.g. water) when a salt is added to the solution. Employing field-theoretical methods, we expand the Gibbs free energy to first order in a loop expansion and calculate self-consistently the dielectric constant. We predict analytically the dielectric decrement which depends on the ionic strength in a complex way. Furthermore, a qualitative description of the hydration shell is found and is characterized by a single length scale. Our prediction fits rather well a large range of concentrations for different salts using only one fit parameter related to the size of ions and dipoles.

Solution structure of detergent micelles at conditions relevant to membrane protein crystallization.

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

Littrell, K.; Thiyagarajan, P.; Tiede, D.

1999-07-02

In this study small angle neutron scattering was used to characterize the formation of micelles in aqueous solutions of the detergents DMG and SPC as a function of detergent concentration and ionic strength of the solvent. The effects on the micelle structure of the additives glycerol and PEG, alone as well as in combination typical for actual membrane protein crystallization, were also explored. This research suggests that the micelles are cigar-like in form at the concentrations studied. The size of the micelles was observed to increase with increasing ionic strength but decrease with the addition of glycerol or PEG.

Molecular interactions in high conductive gel electrolytes based on low molecular weight gelator.

PubMed

Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

2017-03-15

Organic ionic gel (OIG) electrolytes, also known as gel electrolytes or ionogels are one example of modern functional materials with the potential to use in wide range of electrochemical applications. The functionality of OIGs arises from the thermally reversible solidification of electrolytes or ionic liquids and their superior ionic conductivity. To understand and to predict the properties of these systems it is important to get the knowledge about the interactions on molecular level between the solid gelator matrix and the electrolyte solution. This paper reports the spectroscopic studies (FT-IR, UV-Vis and Raman) of the gel electrolyte based on low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside and solution of quaternary ammonium salt, tetramethylammonium bromide. The solidification process was based on sol-gel technique. Below characteristic temperature, defined as gel to sol phase transition temperature, T gs , the samples were solid-like and showed high conductivity values of the same order as observed for pure liquid electrolytes. The investigations were performed for a OIGs in a wide range of molar concentrations of the electrolyte solution. Copyright © 2016 Elsevier Inc. All rights reserved.

A molecular dynamics simulation study of dynamic process and mesoscopic structure in liquid mixture systems

NASA Astrophysics Data System (ADS)

Yang, Peng

The focus of this dissertation is the Molecular Dynamics (MD) simulation study of two different systems. In thefirst system, we study the dynamic process of graphene exfoliation, particularly graphene dispersion using ionic surfactants (Chapter 2). In the second system, we investigate the mesoscopic structure of binary solute/ionic liquid (IL) mixtures through the comparison between simulations and corresponding experiments (Chapter 3 and 4). In the graphene exfoliation study, we consider two separation mechanisms: changing the interlayer distance and sliding away the relative distance of two single-layer graphene sheets. By calculating the energy barrier as a function of separation (interlayer or sliding-away) distance and performing sodium dodecyl sulfate (SDS) structure analysis around graphene surface in SDS surfactant/water + bilayer graphene mixture systems, we find that the sliding-away mechanism is the dominant, feasible separation process. In this process, the SDS-graphene interaction gradually replaces the graphene-graphene Van der Waals (VdW) interaction, and decreases the energy barrier until almost zero at critical SDS concentration. In solute/IL study, we investigate nonpolar (CS2) and dipolar (CH 3CN) solute/IL mixture systems. MD simulation shows that at low concentrations, IL is nanosegregated into an ionic network and nonpolar domain. It is also found that CS2 molecules tend to be localized into the nonpolar domain, while CH3CN interacts with nonpolar domain as well as with the charged head groups in the ionic network because of its amphiphilicity. At high concentrations, CH3CN molecules eventually disrupt the nanostructural organization. This dissertation is organized in four chapters: (1) introduction to graphene, ionic liquids and the methodology of MD; (2) MD simulation of graphene exfoliation; (3) Nanostructural organization in acetonitrile/IL mixtures; (4) Nanostructural organization in carbon disulfide/IL mixtures; (5) Conclusions. Results of MD simulations of liquid mixture systems car-ried out in this research explain observed experiments and show the details of nanostructural organizations in small solute molecules/IL mixture. Additionally, the research successfully reveals the correct mechanism of graphene exfoliation process in liquid solution. (This will be summarized in Chapter 5.) The research presented in this dissertation enhances our understanding of the microscopic behaviors in complex liquid systems as well as the theoretical method to explore them.

Topological constraints and the existence of force-free fields

NASA Technical Reports Server (NTRS)

Antiochos, S. K.

1986-01-01

A fundamental problem in plasma theory is the question of the existence of MHD equilibria. The issue of topological constraints is of crucial importance for the problem of the existence of equilibria. Heuristic methods are used to discuss the coronal wrapping pattern. It is concluded that for a given set of footpoint positions the wrapping pattern in the corona is completely fixed. The topological constraints are included in the boundary conditions on the Euler potentials and impost no additional restrictions on possible equilibria. Although this does not prove that equilibria always exist, it does show that the force-free problem is not overdetermined and that existence of equilibria is still an open question.

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

Bunkin, N F; Shkirin, A V; Burkhanov, I S

Aqueous NaCl solutions with different concentrations have been investigated by dynamic scattering of laser radiation. It is experimentally shown that these solutions contain scattering particles with a wide size distribution in a range of ∼10 – 100 nm. The experimental results indirectly confirm the existence of quasi-stable gas nanobubbles in the bulk of aqueous ionic solutions. (light scattering)

Macroscopic experimental and modeling evaluation of selenite and selenate adsorption mechanisms on gibbsite

USDA-ARS?s Scientific Manuscript database

Selenite Se(IV) and selenate Se(VI) adsorption behavior was investigated on gibbsite as a function of solution pH and solution ionic strength. Adsorption of both Se redox states decreased with increasing solution pH. Electrophoretic mobility measurements showed downward shifts in point of zero cha...

Generator for ionic gallium-68 based on column chromatography

DOEpatents

Neirinckx, Rudi D.; Davis, Michael A.

1981-01-01

A physiologically acceptable solution of gallium-68 fluorides, having an activity of 0.1 to 50 millicuries per milliliter of solution is provided. The solution is obtained from a generator comprising germanium-68 hexafluoride bound to a column of an anion exchange resin which forms gallium-68 in situ by eluting the column with an acid solution to form a solution containing .sup.68 Ga-fluorides. The solution then is neutralized prior to administration.

[The Influence of Different Ionic Concentration in Cell Physiological Solution on Temperature Measurement by Near Infrared].

PubMed

Zheng, Yu; Chen, Xiong; Zhou, Mei; Wang, Meng-jun; Wang, Jin-hai; Li, Gang; Cui, Jun

2015-10-01

It is important to real-timely monitor and control the temperature of cell physiological solution in patch clamp experiments, which can eliminate the uncertainty due to temperature and improve the measurement accuracy. This paper studies the influence of different ions at different concentrations in the physiological solution on precision of a temperature model by using near infrared spectroscopy and chemometrics method. Firstly, we prepared twelve sample solutions respectively with the solutes of CaCl2, KCl and NaCl at four kinds of concentrations, and collected the spectra of different solutions at the setting temperature range 20-40 degrees C, the range of the spectra is 9 615-5 714 cm(-1). Then we divided the spectra of each solution at different temperatures into two parts (a training set and a prediction set) by three methods. Interval partial least squares method was used to select an effective wavelength range and develop calibration models between the spectra in the selected range and temperature velues. The experimental results show that RMSEP of CaCl2 solution with 0.25 g x mL(-1) is maximum, the result of the three tests are 0.386 3, 0.303 7 and 0.337 2 degrees C, RMSEP of NaCl with 0.005 g x mL(-1) solution is minimum, the result of the three tests are 0.220 8, 0.155 3 and 0.145 2 degrees C. The experimental results indicate that Ca2+ has the greatest influence on the accuracy of the temperature model of the cell physiological solution, then K+, and Na+ has the least influence. And with the ionic concentration increasing, the model accuracy decreases. Therefore; when we build the temperature model of cell physiological solution, it is necessary to change the proportion of the three kinds of main ions in cell physiological solution reasonably in order to correct the effects of different ionic concentrations in physiological solution and improve the accuracy of temperature measurements by near infrared spectroscopy.

Existence of equilibria in articulated bearings

NASA Astrophysics Data System (ADS)

Buscaglia, G.; Ciuperca, I.; Hafidi, I.; Jai, M.

2007-04-01

The existence of equilibrium solutions for a lubricated system consisting of an articulated body sliding over a flat plate is considered. Though this configuration is very common (it corresponds to the popular tilting-pad thrust bearings), the existence problem has only been addressed in extremely simplified cases, such as planar sliders of infinite width. Our results show the existence of at least one equilibrium for a quite general class of (nonplanar) slider shapes. We also extend previous results concerning planar sliders.

Critical Factors for the Transition from Chromate to Chromate-Free Corrosion Protection

DTIC Science & Technology

2005-06-15

sub-ambient temperature. Local Cr-rich deposits (location b) are located on grain boundaries or pre- 3 existing metal ridge. Microchemical analysis ...form the framework for this review. AQUEOUS CHEMISTRY Cr6+ is readily hydrolyzed in aqueous solution and exists as an oxoanion in all but...involved in the reaction equilibria shown in Eqs. 2-4. The key results from this analysis are the following: • In acidic environments (pH 2-4

Attractors in complex networks

NASA Astrophysics Data System (ADS)

Rodrigues, Alexandre A. P.

2017-10-01

In the framework of the generalized Lotka-Volterra model, solutions representing multispecies sequential competition can be predictable with high probability. In this paper, we show that it occurs because the corresponding "heteroclinic channel" forms part of an attractor. We prove that, generically, in an attracting heteroclinic network involving a finite number of hyperbolic and non-resonant saddle-equilibria whose linearization has only real eigenvalues, the connections corresponding to the most positive expanding eigenvalues form part of an attractor (observable in numerical simulations).

Attractors in complex networks.

PubMed

Rodrigues, Alexandre A P

2017-10-01

In the framework of the generalized Lotka-Volterra model, solutions representing multispecies sequential competition can be predictable with high probability. In this paper, we show that it occurs because the corresponding "heteroclinic channel" forms part of an attractor. We prove that, generically, in an attracting heteroclinic network involving a finite number of hyperbolic and non-resonant saddle-equilibria whose linearization has only real eigenvalues, the connections corresponding to the most positive expanding eigenvalues form part of an attractor (observable in numerical simulations).

Noninvasive quantitative measurement of colloid transport in mesoscale porous media using time lapse fluorescence imaging.

PubMed

Bridge, Jonathan W; Banwart, Steven A; Heathwaite, A Louise

2006-10-01

We demonstrate noninvasive quantitative imaging of colloid and solute transport at millimeter to decimeter (meso-) scale. Ultraviolet (UV) excited fluorescent solute and colloid tracers were independently measured simultaneously during co-advection through saturated quartz sand. Pulse-input experiments were conducted at constant flow rates and ionic strengths 10(-3), 10(-2) and 10(-1) M NaCl. Tracers were 1.9 microm carboxylate latex microspheres and disodium fluorescein. Spatial moments analysis was used to quantify relative changes in mass distribution of the colloid and solute tracers over time. The solute advected through the sand at a constant velocity proportional to flow rate and was described well by a conservative transport model (CXTFIT). In unfavorable deposition conditions increasing ionic strength produced significant reduction in colloid center of mass transport velocity over time. Velocity trends correlated with the increasing fraction of colloid mass retained along the flowpath. Attachment efficiencies (defined by colloid filtration theory) calculated from nondestructive retained mass data were 0.013 +/- 0.03, 0.09 +/- 0.02, and 0.22 +/- 0.05 at 10(-3), 10(-2), and 10(-1) M ionic strength, respectively, which compared well with previously published data from breakthrough curves and destructive sampling. Mesoscale imaging of colloid mass dynamics can quantify key deposition and transport parameters based on noninvasive, nondestructive, spatially high-resolution data.

Lignin fate and characterization during ionic liquid biomass pretreatment for renewable chemicals and fuels production

Treesearch

Noppadon Sathitsuksanoh; Kevin M. Holtman; Daniel J. Yelle; Trevor Morgan; Vitalie Stavila; Jeffrey Pelton; Harvey Blanch; Blake A. Simmons; Anthe George

2014-01-01

The fate of lignin from wheat straw, Miscanthus, and Loblolly pine after pretreatment by a non-toxic and recyclable ionic liquid (IL), [C2mim][OAc], followed by enzymatic hydrolysis was investigated. The lignin partitioned into six process streams, each of which was quantified and analyzed by a combination of a novel solution-state two-dimensional (2D) nuclear magnetic...