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Sample records for ionic solutions strategies

  1. General strategy for biodetection in high ionic strength solutions using transistor-based nanoelectronic sensors

    PubMed Central

    Gao, Ning; Zhou, Wei; Jiang, Xiaocheng; Hong, Guosong; Fu, Tian-Ming; Lieber, Charles M.

    2015-01-01

    Transistor-based nanoelectronic sensors are capable of label-free real-time chemical and biological detection with high sensitivity and spatial resolution, although the short Debye screening length in high ionic strength solutions has made difficult applications relevant to physiological conditions. Here, we describe a new and general strategy to overcome this challenge for field-effect transistor (FET) sensors that involves incorporating a porous and biomolecule permeable polymer layer on the FET sensor. This polymer layer increases the effective screening length in the region immediately adjacent to the device surface, and thereby enables detection of biomolecules in high ionic strength solutions in real-time. Studies of silicon nanowire (SiNW) field-effect transistors (FETs) with additional polyethylene glycol (PEG) modification show that prostate specific antigen (PSA) can be readily detected in solutions with phosphate buffer (PB) concentrations as high as 150 mM, while similar devices without PEG modification only exhibit detectable signals for concentrations ≤ 10 mM. Concentration-dependent measurements exhibited real-time detection of PSA with a sensitivity of at least 10 nM in ~130 mM ionic strength PB with linear response up to the highest (1000 nM) PSA concentrations tested. The current work represents an important step toward general application of nanoelectronic detectors for biochemical sensing in physiological environments, and is expected to open up exciting opportunities for in-vitro and in-vivo biological sensing relevant to basic biology research through medicine. PMID:25664395

  2. Aqueous Biphasic Systems Based on Salting-Out Polyethylene Glycol or Ionic Solutions: Strategies for Actinide or Fission Product Separations

    SciTech Connect

    Rogers, Robin D.; Gutowski, Keith E.; Griffin, Scott T.; Holbrey, John D.

    2004-03-29

    Aqueous biphasic systems can be formed by salting-out (with kosmotropic, waterstructuring salts) water soluble polymers (e.g., polyethylene glycol) or aqueous solutions of a wide range of hydrophilic ionic liquids based on imidazolium, pyridinium, phosphonium and ammonium cations. The use of these novel liquid/liquid biphases for separation of actinides or other fission products associated with nuclear wastes (e.g., pertechnetate salts) has been demonstrated and will be described in this presentation.

  3. Membrane separation of ionic liquid solutions

    SciTech Connect

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

    2015-09-01

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

  4. Electroosmotic flow hysteresis for dissimilar ionic solutions.

    PubMed

    Lim, An Eng; Lim, Chun Yee; Lam, Yee Cheong

    2015-03-01

    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

  5. 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

  6. Ionic solutes impact collagen scaffold bioactivity.

    PubMed

    Pawelec, K M; Husmann, A; Wardale, R J; Best, S M; Cameron, R E

    2015-02-01

    The structure of ice-templated collagen scaffolds is sensitive to many factors. By adding 0.5 wt% of sodium chloride or sucrose to collagen slurries, scaffold structure could be tuned through changes in ice growth kinetics and interactions of the solute and collagen. With ionic solutes (sodium chloride) the entanglements of the collagen molecule decreased, leading to fibrous scaffolds with increased pore size and decreased attachment of chondrocytes. With non-ionic solutes (sucrose) ice growth was slowed, leading to significantly reduced pore size and up-regulated cell attachment. This highlights the large changes in structure and biological function stimulated by solutes in ice-templating systems. PMID:25649518

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

    SciTech Connect

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

    2015-12-08

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

  8. DNA denaturation in ionic solution

    NASA Astrophysics Data System (ADS)

    Maity, Arghya; Singh, Amar; Singh, Navin

    2016-05-01

    Salt or cations, present in solution play an important role in DNA denaturation and folding kinetics of DNA helix. In this work we study the thermal melting of double stranded DNA (dsDNA) molecule using Peyrard Bishop Dauxois (PBD) model. We modify the potential of H-bonding between the bases of the complimentary strands to introduce the salt and solvent effect. We choose different DNA sequences having different contents of GC pairs and calculate the melting temperatures. The melting temperature increases logarithmically with the salt concentration of the solution. The more GC base pairs in the chain enhance the stability of DNA chain at a fix salt concentration. The obtained results are in good accordance with experimental findings.

  9. 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

  10. Neutral polyampholyte in an ionic solution

    NASA Astrophysics Data System (ADS)

    Diehl, Alexandre; Barbosa, Marcia C.; Levin, Yan

    1996-12-01

    The behavior of a neutral polyampholyte (PA) chain with N monomers, in an ionic solution, is analyzed in the framework of the full Debye-Hückel-Bjerrum-Flory (DHBjF) theory. A PA chain, that in addition to the neutral monomers, also contains an equal number of positively and negatively charged monomers, is dissolved in an ionic solution. For high concentrations of salt and at high temperatures, the PA exists in an extended state. As the temperature is decreased, the electrostatic energy becomes more relevant and at a T=Tθ the system collapses into a dilute globular state, or microelectrolyte. This state contains a concentration of salt higher than the surrounding medium. As the temperature is decreased even further, association between the monomers of the polymer and the ions of the salt becomes relevant and there is a crossover from this globular state to a low temperature extended state. For low densities of salt, the system is collapsed for almost all temperatures and exhibits a first-order phase transition to an extended state at an unphysical low temperature.

  11. On the theory of ionic solutions.

    PubMed

    Olivares, W; McQuarrie, D A

    1975-02-01

    One of the purposes of this paper is to assess the degree of applicability of the nonlinear Poisson-Boltzmann equation. In order to do this we compare the thermodynamic properties calculated through this equation with Monte Carlo data on 1-1 and 2-2 electrolytes described by the restricted primitive model, in which the ions are modeled by hard spheres with a coulombic potential and the solvent is modeled as a continuum dielectric medium of uniform dielectric constant epsilon. We choose Monte Carlo data rather than real experimental data since all parameters are completely specified and there is no liberty for "adjustment." Thus this serves as a definitive test. In addition, we present a simple but numerically accurate alternative approximation scheme which is not only numerically superior to the Poisson-Boltzmann equation but avoids the necessity of solving a nonlinear partial differential equation which is approximate in the first place. The new approximation scheme that is presented here is suggested by recent developments in the statistical mechanical theories of ionic solutions which are reviewed in the Introduction. Although these theories themselves yield exceedingly good comparison with experimental (Monte Carlo) data, they involve fairly advanced theoretical and mathematical techniques and do not appear to be readily solvable for other than very simple geometries. The two approximations suggested here require only the solution of the linear Debye-Hückel equation, which has been solved for a variety of systems. These two approximations are simple to apply and yield good thermodynamic properties up to concentrations of 2 M for the restricted primitive model. In addition, they have a sound theoretical foundation and are offered as a substitute for the difficult-to-solve nonlinear Poisson-Boltzmann equation. PMID:1111632

  12. "Switchable water": aqueous solutions of switchable ionic strength.

    PubMed

    Mercer, Sean M; Jessop, Philip G

    2010-04-26

    "Salting out" is a standard method for separating water-soluble organic compounds from water. In this method, adding a large amount of salt to the aqueous solution forces the organic compound out of the aqueous phase. However, the method can not be considered sustainable because it creates highly salty water. A greener alternative would be a method that allows reversible salting out. Herein, we describe aqueous solutions of switchable ionic strength. Aqueous solutions of a diamine in water have essentially zero ionic strength but are converted by CO(2) into solutions of high ionic strength. The change is reversible. Application to the reversible salting out of THF from water is described. PMID:20186910

  13. Adsorption Kinetics at Silica Gel/Ionic Liquid Solution Interface.

    PubMed

    Flieger, Jolanta; Tatarczak-Michalewska, Małgorzata; Groszek, Anna; Blicharska, Eliza; Kocjan, Ryszard

    2015-01-01

    A series of imidazolium and pyridinium ionic liquids with different anions (Cl(-), Br(-), BF₄(-), PF₆(-)) has been evaluated for their adsorption activity on silica gel. Quantification of the ionic liquids has been performed by the use of RP-HPLC with organic-aqueous eluents containing an acidic buffer and a chaotropic salt. Pseudo-second order kinetic models were applied to the experimental data in order to investigate the kinetics of the adsorption process. The experimental data showed good fitting with this model, confirmed by considerably high correlation coefficients. The adsorption kinetic parameters were determined and analyzed. The relative error between the calculated and experimental amount of ionic liquid adsorbed at equilibrium was within 7%. The effect of various factors such as initial ionic liquid concentration, temperature, kind of solvent, kind of ionic liquid anion and cation on adsorption efficiency were all examined in a lab-scale study. Consequently, silica gel showed better adsorptive characteristics for imidazolium-based ionic liquids with chaotropic anions from aqueous solutions in comparison to pyridinium ionic liquids. The adsorption was found to decrease with the addition of organic solvents (methanol, acetonitrile) but it was not sensitive to the change of temperature in the range of 5-40 °C. PMID:26690392

  14. Electric birefringence anomaly of solutions of ionically charged anisometric particles.

    PubMed

    Hoffmann, H; Gräbner, Dieter

    2015-02-01

    The term "electric birefringence anomaly" is known as the electric birefringence (EB) signal that occurs in solutions of ionically charged anisometric particles in a narrow concentration region. The signal is of opposite sign to the normal birefringence that occurs below and above this narrow concentration region. The normal electric birefringence signals in the dilute and more concentrated regions are due to the orientation of the particles in the direction of the applied electric field. The origin for the anomalous signal was not completely understood until now. The article summarises previous results in which the anomalous results had been observed but not well understood. It shows that the birefringence anomaly occurs in systems as diverse as micellar solutions, polyelectrolytes, solutions of clays, viruses and fibres. In all these systems the anomaly signals are present at the concentration when the length of the colloidal particles including the thickness of the electric double layer are about the same as the mean distance between the colloidal particles. Under these conditions the electric double layers of the particles overlap along the main axis of the particles but not in the direction across the particles. As a consequence of this situation a dipole is built up across the particles by the migration of the counter-ions of the particles in the electric field and this dipole leads to an orientation of the particles perpendicular to the electric field. The anomalous signal can usually be observed simultaneously with the normal signal. The amplitude of the anomalous signal can be larger than the amplitude of the normal signal. As a consequence the total birefringence changes its sign in the anomalous concentration region. The anomaly signal of the clays can also be explained by a fluctuating dipole around the particles, which is due to the fact that the centre of the ionic charges of the particles does not fall on the centre of the ionic charge of the counter

  15. Phase Behavior and Ionic Conductivity of Concentrated Solutions of Polystyrene-Poly(ethylene oxide) Diblock Copolymers in an Ionic Liquid

    SciTech Connect

    Simone, Peter M.; Lodge, Timothy P.

    2010-03-16

    Concentrated solutions of poly(styrene-b-ethylene oxide) (PS-PEO) diblock copolymers were prepared using the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMI][TFSI] as the solvent. The self-assembled microstructures adopted by the copolymer solutions have been characterized using small-angle X-ray scattering. Lyotropic mesophase transitions were observed, with a progression from hexagonally packed cylinders of PEO, to lamellae, to hexagonally packed cylinders of PS upon increasing [EMI][TFSI] content. The change in lamellar domain spacing with ionic liquid concentration was found to be comparable to that reported for other block copolymers in strongly selective solvents. The ionic conductivity of the concentrated PS-PEO/[EMI][TFSI] solutions was measured via impedance spectroscopy, and ranged from 1 x 10{sup -7} to 1 x 10{sup -3} S/cm at temperatures from 25-100 C. Additionally, the ionic conductivity of the solutions was found to increase with both ionic liquid concentration and molecular weight of the PEO blocks. The ionic conductivity of PEO homopolymer/[EMI][TFSI] solutions was also measured in order to compare the conductivity of the PS-PEO solutions to the expected limit for a lamellar sample with randomly oriented microstructure grains.

  16. Concentration Fluctuations and Capacitive Response in Dense Ionic Solutions.

    PubMed

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

    2016-07-01

    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. PMID:27259040

  17. 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

  18. Parameterization of lattice spacings for lipid multilayers in ionic solutions

    NASA Astrophysics Data System (ADS)

    Petrache, Horia; Johnson, Merrell; Harries, Daniel; Seifert, Soenke

    Lipids, which are molecules found in biological cells, form highly regular layered structures called multilamellar lipid vesicles (MLVs). The repeat lattice spacings of MLVs depend on van der Waals and electrostatic forces between neighboring membranes and are sensitive to the presence of salt. For example, addition of salt ions such as sodium and potassium makes the MLVs swell, primarily due to changes in electrical polarizabilities. However, a more complicated behavior is found in some ionic solutions such as those containing lithium ions. Using x-ray scattering, we show experimentally how the interactions between membranes depend on the type of monovalent ions and construct parameterizations of MLVs swelling curves that can help analyze van der Waals interactions.

  19. Dielectric response of triplex DNA in ionic solution from simulations.

    PubMed Central

    Yang, L; Weerasinghe, S; Smith, P E; Pettitt, B M

    1995-01-01

    We have analyzed a 1.2-ns molecular dynamics simulation of 51 mM d(CG.G)7 with 21 Na+ counter-ions and 1 M NaCl in water. Via the dipole fluctuations, the dielectric constant for the DNA is found to be around 16, whereas that for the bases and sugars combined is only 3. The dielectric constant for water in this system is 41, which is much smaller than 71 for pure SPC/E water, because of the strong restriction imposed on the motion of water molecules by the DNA and the ions. Also addressed in the present work are several technical issues related to the calculation of the dipole moment of an ionic solution from molecular dynamics simulations using periodic boundary conditions. PMID:8534822

  20. Thermodynamic studies of ionic hydration and interactions for amino acid ionic liquids in aqueous solutions at 298.15 K.

    PubMed

    Dagade, Dilip H; Madkar, Kavita R; Shinde, Sandeep P; Barge, Seema S

    2013-01-31

    Amino acid ionic liquids are a special class of ionic liquids due to their unique acid-base behavior, biological significance, and applications in different fields such as templates in synthetic chemistry, stabilizers for biological macromolecules, etc. The physicochemical properties of these ionic liquids can easily be altered by making the different combinations of amino acids as anion along with possible cation modification which makes amino acid ionic liquids more suitable to understand the different kinds of molecular and ionic interactions with sufficient depth so that they can provide fruitful information for a molecular level understanding of more complicated biological processes. In this context, volumetric and osmotic coefficient measurements for aqueous solutions containing 1-ethyl-3-methylimidazolium ([Emim]) based amino acid ionic liquids of glycine, alanine, valine, leucine, and isoleucine are reported at 298.15 K. From experimental osmotic coefficient data, mean molal activity coefficients of ionic liquids were estimated and analyzed using the Debye-Hückel and Pitzer models. The hydration numbers of ionic liquids in aqueous solutions were obtained using activity data. Pitzer ion interaction parameters are estimated and compared with other electrolytes reported in the literature. The nonelectrolyte contribution to the aqueous solutions containing ionic liquids was studied by calculating the osmotic second virial coefficient through an application of the McMillan-Mayer theory of solution. It has been found that the second osmotic virial coefficient which includes volume effects correlates linearly with the Pitzer ion interaction parameter estimated independently from osmotic data as well as the hydrophobicity of ionic liquids. The enthalpy-entropy compensation effect, explained using the Starikov-Nordén model of enthalpy-entropy compensation, and partial molar entropy analysis for aqueous [Emim][Gly] solutions are made by using experimental Gibb

  1. Borohydride ionic liquids and borane/ionic-liquid solutions as hypergolic fuels with superior low ignition-delay times.

    PubMed

    Li, Songqing; Gao, Haixiang; Shreeve, Jean'ne M

    2014-03-10

    In propellant systems, fuels of choice continue to be hydrazine and its derivatives, even though they comprise a class of acutely carcinogenic and toxic substances which exhibit rather high vapor pressures and require expensive handling procedures and costly safety precautions. Hypergolic ionic liquids tend to have low volatility and high thermal and chemical stability, and often exhibit wide liquid ranges, which could allow the use of these substances as bipropellant fuels under a variety of conditions. A new family of borohydride ionic liquids and borane-ionic-liquid solutions is described which meets nearly all of the desired important criteria for well-performing fuels. They exhibit ignition-delay times that are superior to that of any known hypergolic ionic liquid and may thus be legitimate replacements for hydrazine and its derivatives. PMID:24604814

  2. Cellulose aerogel from ionic liquid solution dried by silylation

    NASA Astrophysics Data System (ADS)

    Rein, Dmitry; Cohen, Yachin

    2011-03-01

    Aerogels are a class of materials characterised by a highly porous structure with low solids content. There is much interest in cellulose aerogel (aerocellulose) as a biodegradable and sustainable material. Cellulose lyogel can be fabricated from its solution in ionic liquids (IL) by coagulation with a nonsolvent such as water. However, subsequent drying capillary forces in the gel pores that result in severe shrinkage and pore closure. The use of supercritical fluids for drying or freeze-drying entails high equipment and energy requirements. We describe the fabrication and structure of aerocellulose fabricated from IL solution with a simple novel drying process: Addition of a compatible reactive agent (trimethylchlorosilane) and its diffusion into the water-swollen cellulose hydrogel pores results in a reaction with water as well as the pore surface hydroxyl groups. The remaining hydrophobic compound (hexamethyldisiloxane-HMDS), which fills the initially hydrophilic cellulose hydrogel pores, has a low intrinsic surface tension in the pores allowing easy drying with minimal shrinkage. Furthermore it allows modification of the pore surface and even fabrication of cellulose-polysiloxane composites. Relations between aerocellolose processing conditions and the resulting structural features will be discussed.

  3. Ultrasound response of aqueous poly(ionic liquid) solution.

    PubMed

    Li, Kai; Kobayashi, Takaomi

    2016-05-01

    Ultrasound (US) effects on aqueous poly(ionic liquid) (PIL) solution were investigated using viscosity and FT-IR spectroscopy after exposure to US of 23, 43, and 96 kHz frequencies at 50 W. The viscosity of the poly(1-vinyl-3-butyl-imidazolium chloride) (PIL) aqueous solution decreased during exposure to US. It then increased gradually within about 10 min as US stopped. The aqueous PIL behavior was then observed using FT-IR spectroscopy. The US exposure enhanced the FT-IR band intensity of the OH stretching. The band intensity returned to its original value after the US stopped. These results responded cyclically to the US on/off. Analysis of the FT-IR spectra revealed that US influenced the breakage and reformation of hydrogen bonds in the PIL and water. Two-dimensional correlation and deconvolution were used to analyze the change of components in the region of 3000-3700 cm(-1) for US exposure. Results of these analyses suggest that US exposure might break hydrogen bonds between PIL segments and water. In the absence of US, hydrogen bonds reformation was also observed between the PIL and water. PMID:26597539

  4. Single Molecule Electrochemical Detection in Aqueous Solutions and Ionic Liquids.

    PubMed

    Byers, Joshua C; Paulose Nadappuram, Binoy; Perry, David; McKelvey, Kim; Colburn, Alex W; Unwin, Patrick R

    2015-10-20

    Single molecule electrochemical detection (SMED) is an extremely challenging aspect of electroanalytical chemistry, requiring unconventional electrochemical cells and measurements. Here, SMED is reported using a "quad-probe" (four-channel probe) pipet cell, fabricated by depositing carbon pyrolytically into two diagonally opposite barrels of a laser-pulled quartz quadruple-barreled pipet and filling the open channels with electrolyte solution, and quasi-reference counter electrodes. A meniscus forms at the end of the probe covering the two working electrodes and is brought into contact with a substrate working electrode surface. In this way, a nanogap cell is produced whereby the two carbon electrodes in the pipet can be used to promote redox cycling of an individual molecule with the substrate. Anticorrelated currents generated at the substrate and tip electrodes, at particular distances (typically tens of nanometers), are consistent with the detection of single molecules. The low background noise realized in this droplet format opens up new opportunities in single molecule electrochemistry, including the use of ionic liquids, as well as aqueous solution, and the quantitative assessment and analysis of factors influencing redox cycling currents, due to a precisely known gap size. PMID:26398675

  5. Solvent effects on the polar network of ionic liquid solutions

    NASA Astrophysics Data System (ADS)

    Bernardes, Carlos E. S.; Shimizu, Karina; Canongia Lopes, José N.

    2015-05-01

    Molecular dynamics simulations were used to probe mixtures of ionic liquids (ILs) with common molecular solvents. Four types of systems were considered: (i) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide plus benzene, hexafluorobenzene or 1,2-difluorobenzene mixtures; (ii) choline-based ILs plus ether mixtures (iii) choline-based ILs plus n-alkanol mixtures; and (iv) 1-butyl-3-methylimidazolium nitrate and 1-ethyl-3-methylimidazolium ethyl sulfate aqueous mixtures. The results produced a wealth of structural and aggregation information that highlight the resilience of the polar network of the ILs (formed by clusters of alternating ions and counter-ions) to the addition of different types of molecular solvent. The analysis of the MD data also shows that the intricate balance between different types of interaction (electrostatic, van der Waals, H-bond-like) between the different species present in the mixtures has a profound effect on the morphology of the mixtures at a mesoscopic scale. In the case of the IL aqueous solutions, the present results suggest an alternative interpretation for very recently published x-ray and neutron diffraction data on similar systems.

  6. Solvent effects on the polar network of ionic liquid solutions.

    PubMed

    Bernardes, Carlos E S; Shimizu, Karina; Canongia Lopes, José N

    2015-05-20

    Molecular dynamics simulations were used to probe mixtures of ionic liquids (ILs) with common molecular solvents. Four types of systems were considered: (i) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide plus benzene, hexafluorobenzene or 1,2-difluorobenzene mixtures; (ii) choline-based ILs plus ether mixtures (iii) choline-based ILs plus n-alkanol mixtures; and (iv) 1-butyl-3-methylimidazolium nitrate and 1-ethyl-3-methylimidazolium ethyl sulfate aqueous mixtures. The results produced a wealth of structural and aggregation information that highlight the resilience of the polar network of the ILs (formed by clusters of alternating ions and counter-ions) to the addition of different types of molecular solvent. The analysis of the MD data also shows that the intricate balance between different types of interaction (electrostatic, van der Waals, H-bond-like) between the different species present in the mixtures has a profound effect on the morphology of the mixtures at a mesoscopic scale. In the case of the IL aqueous solutions, the present results suggest an alternative interpretation for very recently published x-ray and neutron diffraction data on similar systems. PMID:25923649

  7. Polyelectrolyte and carbon nanotube multilayers made from ionic liquid solutions

    NASA Astrophysics Data System (ADS)

    Nakashima, Takuya; Zhu, Jian; Qin, Ming; Ho, Szushen; Kotov, Nicholas A.

    2010-10-01

    The inevitable contact of substrates with water during the traditional practice of layer-by-layer assembly (LBL) creates problems for multiple potential applications of LBL films in electronics. To resolve this issue, we demonstrate here the possibility of a LBL process using ionic liquids (ILs), which potentially eliminates corrosion and hydration processes related to aqueous media and opens additional possibilities in structural control of LBL films. ILs are also considered to be one of the best ``green'' processing solvents, and hence, are advantageous in respect to traditional organic solvents. Poly(ethyleneimine) (PEI) and poly(sodium styrenesulfonate) (PSS) were dispersed in a hydrophilic IL and successfully deposited in the LBL fashion. To produce electroactive thin films with significance to electronics, a similar process was realized for PSS-modified single-walled carbon nanotubes (SWNT-PSS) and poly(vinyl alcohol) (PVA). Characterization of the coating using standard spectroscopy and microscopy techniques typical of the multilayer field indicated that there are both similarities and differences in the structure and properties of LBL films build from ILs and aqueous solutions. The films exhibited electrical conductivity of 102 S m-1 with transparency as high as 98% for visible light, which is comparable to similar parameters for many carbon nanotube and graphene films prepared by both aqueous LBL and other methods.The inevitable contact of substrates with water during the traditional practice of layer-by-layer assembly (LBL) creates problems for multiple potential applications of LBL films in electronics. To resolve this issue, we demonstrate here the possibility of a LBL process using ionic liquids (ILs), which potentially eliminates corrosion and hydration processes related to aqueous media and opens additional possibilities in structural control of LBL films. ILs are also considered to be one of the best ``green'' processing solvents, and hence, are

  8. Influence of ionic strength on poly(diallyldimethylammonium chloride) macromolecule conformations in electrolyte solutions.

    PubMed

    Adamczyk, Zbigniew; Jamroży, Krzysztof; Batys, Piotr; Michna, Aneta

    2014-12-01

    Conformations of poly(diallyldimethylammonium chloride), PDADMAC, molecules in electrolyte solutions were experimentally evaluated by dynamic light scattering (DLS), micro-electrophoretic and viscosity measurements. The role of ionic strength varied within 10(-4) and 2M was systematically studied. The diffusion coefficient of the polymer molecules was equal to 1.3×10(-7)cm(2)s(-1) for the ionic strength range 5×10(-4) to 10(-2)M decreasing slightly for higher ionic strength. This corresponds to the hydrodynamic diameter of 38.5nm. Using the diffusion coefficient and the electrophoretic mobility data, the electrokinetic charge on PDADMAC molecules was calculated as a function of ionic strength. It was positive and varied between 84 and 51 elementary charges. This gives the effective ionization degree of the macromolecule equal to 13% and 8% for ionic strength of 5×10(-4) and 0.15M, respectively. Additional information about macromolecule conformation was derived from the viscosity measurements of dilute PDADMAC solutions. The intrinsic viscosity derived from these measurements decreased abruptly with ionic strength from 3400 for 10(-4)M to 100 for 2M, NaCl solutions. By extrapolating the hydrodynamic diameter and intrinsic viscosity data to zero ionic strength the polyelectrolyte molecule contour length of 240nm and the backbone diameter of 0.85nm were predicted. On the other hand, the decrease in the intrinsic viscosity for higher ionic strength was attributed to changes in macromolecule conformations to more collapsed ones. The experimental results were interpreted by molecular dynamics modeling of PDADMAC chain conformations in electrolyte solutions where the ionic strength effect and the effective ionization degree were considered. A quantitative agreement was attained for lower ionic strength range proving that the combined DLS and viscosity measurements furnish reliable information about macromolecule conformations in electrolyte solution. PMID:25265546

  9. Modeling colloid and microorganism transport and release with transients in solution ionic strength

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The transport and fate of colloids, microorganisms, and nanoparticles in subsurface environments is strongly influenced by transients in solution ionic strength (IS). A sophisticated dual-permeability transport model that is capable of simulating exponential, hyperexponential, uniform, and nonmonot...

  10. Molecular solutes in ionic liquids: a structural perspective.

    PubMed

    Pádua, Agílio A H; Costa Gomes, Margarida F; Canongia Lopes, José N A

    2007-11-01

    Understanding physicochemical properties of ionic liquids is important for their rational use in extractions, reactions, and other applications. Ionic liquids are not simple fluids: their ions are generally asymetric, flexible, with delocalized electrostatic charges, and available in a wide variety. It is difficult to capture their subtle properties with models that are too simplistic. Molecular simulation using atomistic force fields, which describe structures and interactions in detail, is an excellent tool to gain insights into their liquid-state organization, how they solvate different compounds, and what molecular factors determine their properties. The identification of certain ionic liquids as self-organized phases, with aggregated nonpolar and charged domains, provides a new way to interpret the solvation and structure of their mixtures. Many advances are the result of a successful interplay between experiment and modeling, possible in this field where none of the two methodologies had a previous advance. PMID:17661440

  11. 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. PMID:27228429

  12. Maillard reaction products from chitosan-xylan ionic liquid solution.

    PubMed

    Luo, Yuqiong; Ling, Yunzhi; Wang, Xiaoying; Han, Yang; Zeng, Xianjie; Sun, Runcang

    2013-10-15

    A facile method is reported to prepare Maillard reaction products (MRPs) from chitosan and xylan in co-solvent ionic liquid. UV absorbance and fluorescence changes were regarded as indicators of the occurrence of Maillard reaction. FT-IR, NMR, XRD and TG were used to investigate the structure of chitosan-xylan conjugate. The results revealed that when chitosan reacted with xylan in ionic liquid, the hydrogen bonds in chitosan were destroyed, the facts resulted in the formation of chitosan-xylan MRPs. Moreover, when the mass ratio of chitosan to xylan was 1:1, the Maillard reaction proceeded easily. In addition, relatively high antioxidant property was also noted for the chitosan-xylan conjugate with mass ratio 1:1. So the obtained chitosan-xylan MRP is a promising antioxidant agent for food industry. PMID:23987419

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

    PubMed

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

    2007-05-10

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

  14. Security solutions: strategy and architecture

    NASA Astrophysics Data System (ADS)

    Seto, Myron W. L.

    2002-04-01

    Producers of banknotes, other documents of value and brand name goods are being presented constantly with new challenges due to the ever increasing sophistication of easily-accessible desktop publishing and color copying machines, which can be used for counterfeiting. Large crime syndicates have also shown that they have the means and the willingness to invest large sums of money to mimic security features. To ensure sufficient and appropriate protection, a coherent security strategy has to be put into place. The feature has to be appropriately geared to fight against the different types of attacks and attackers, and to have the right degree of sophistication or ease of authentication depending upon by whom or where a check is made. Furthermore, the degree of protection can be considerably increased by taking a multi-layered approach and using an open platform architecture. Features can be stratified to encompass overt, semi-covert, covert and forensic features.

  15. 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. PMID:26148000

  16. Two-dimensional ultrafast vibrational spectroscopy of azides in ionic liquids reveals solute-specific solvation.

    PubMed

    Dutta, Samrat; Ren, Zhe; Brinzer, Thomas; Garrett-Roe, Sean

    2015-10-28

    The stereochemistry and the reaction rates of bimolecular nucleophilic substitution reactions involving azides in ionic liquids are governed by solute-solvent interactions. Two-dimensional ultrafast vibrational spectroscopy (2D-IR) shows that the picosecond dynamics of inorganic azides are substantially slower than organic azides in a series of homologous imidazolium ionic liquids. In water, both organic and inorganic azides spectrally diffuse with a ∼2 ps time constant. In the aprotic solvent tetrahydrofuran, both kinds of azides spectrally diffuse on a timescale >5 ps. In ionic liquids, like 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]), organic azides spectrally diffuse with a 2-4 ps time constant, and inorganic azides spectrally diffuse with a >40 ps time constant. Such a striking difference suggests that neutral (organic) and charged (inorganic) azides are incorporated in the ionic liquids with different solvation structures. PMID:26193916

  17. Influence of Lithium Solutes on Double-Layer Structure of Ionic Liquids.

    PubMed

    Smith, Alexander M; Perkin, Susan

    2015-12-01

    The ionic liquid-electrode interface has attracted much recent interest owing to its importance for development of energy storage devices; however, the important step of adding electro-active ions is not yet well understood at the molecular level. Using direct force measurements across confined electrolyte films, we study the effect of added lithium-ion solute on the double-layer structure of an ionic liquid electrolyte with molecular resolution. We find anionic clusters involving lithium can persist adjacent to the surfaces, and in many cases, this inhibits direct adsorption of lithium ions to the negative surface. Two apparently similar ionic liquid solvents show diverging properties, with one facilitating and the other preventing direct Li-ion adsorption onto the negative surface. The results have implications for the selection of ionic liquids as electrolytes in lithium-ion batteries. PMID:26580815

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

    NASA Astrophysics Data System (ADS)

    Warfa, Abdi-Rizak M.

    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 revealed the development of sociochemical norms and specific ways of reasoning about chemical ideas that led to shifts in student thinking and understanding of the nature of dissolved ionic solids. The analysis similarly revealed two kinds of teacher-initiated discourses, dialogical and monologic, that impacted student learning differently. I discuss the nature of this teacher-initiated discourse and number of moves, such as confirming, communicative, and re-orienting, that the course instructor made to communicate to students what counts as justifiable chemical reasoning and appropriate representations of chemical knowledge. I further describe the use of sociochemical dialogues as lens to study the ways in which chemistry instructors and students develop normative ways of reasoning and chemical justifications. Because the activity was designed as an intervention to target student misconceptions about ionic bonding, I also examined the extent to which the activity elicited and corrected commonly found student chemical misconceptions. To do so, student-generated particulate drawings were coded qualitatively into one of four broad themes: i) use of molecular framework with discrete atoms, ii) use of ionic framework with discrete ionic species, iii) use of quasi-ionic framework with partial ionic-molecular thinking, or iv) use of an all-encompassing "other" category. The findings suggested the intervention significantly improved students' conceptual knowledge of ionic compounds in solution - there was statistically significant increase in the number of drawings using ionic and quasi-ionic frameworks in the pre-activity vs. post

  19. Thermodynamic and Ultrasonic Properties of Ascorbic Acid in Aqueous Protic Ionic Liquid Solutions

    PubMed Central

    Singh, Vickramjeet; Sharma, Gyanendra; Gardas, Ramesh L.

    2015-01-01

    In this work, we report the thermodynamic and ultrasonic properties of ascorbic acid (vitamin C) in water and in presence of newly synthesized ammonium based protic ionic liquid (diethylethanolammonium propionate) as a function of concentration and temperature. Apparent molar volume and apparent molar isentropic compression, which characterize the solvation state of ascorbic acid (AA) in presence of protic ionic liquid (PIL) has been determined from precise density and speed of sound measurements at temperatures (293.15 to 328.15) K with 5 K interval. The strength of molecular interactions prevailing in ternary solutions has been discussed on the basis of infinite dilution partial molar volume and partial molar isentropic compression, corresponding volume of transfer and interaction coefficients. Result has been discussed in terms of solute-solute and solute-solvent interactions occurring between ascorbic acid and PIL in ternary solutions (AA + water + PIL). PMID:26009887

  20. Sensitivity of nanostructure in charged cubosomes to phase changes triggered by ionic species in solution.

    PubMed

    Liu, Qingtao; Dong, Yao-Da; Hanley, Tracey L; Boyd, Ben J

    2013-11-19

    The phase behavior of dispersions comprising mixed ionic surfactant and phytantriol was precisely controlled by varying the ionic surfactant content in the mixed lipid and the ionic strength in the system. Two important trends in the phase transition of the mixed lipid systems were identified: (1) An increase in the ionic surfactant content increased the curvature of the self-assembled system toward the hydrophobic region, resulting in the phase transition from cubic phase to lamellar phase. (2) An increase in ionic strength decreased repulsion between the headgroups of the ionic surfactant, resulting in a phase transition from lamellar phase to cubic phase. The phase transitions were confirmed using small-angle X-ray scattering and cryo-TEM and were strongly correlated with the visual turbidity of the dispersions. The lipid mixture with anionic surfactant showed high sensitivity to multivalent cations for triggering the phase transition, which may be a potential strategy to develop a detection/treatment system for toxic multivalent metallic cations such as chromium. PMID:24111826

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

    PubMed

    Mester, Zoltan; Panagiotopoulos, Athanassios Z

    2015-01-28

    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 predictions 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. PMID:25637995

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

    SciTech Connect

    Mester, Zoltan; Panagiotopoulos, Athanassios Z.

    2015-01-28

    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 predictions 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.

  3. 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)

  4. 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…

  5. Kinetics and mass spectrometric measurements of myoglobin unfolding in aqueous ionic liquid solutions.

    PubMed

    Miller, Miranda C; Hanna, Sylvia L; DeFrates, Kelsey G; Fiebig, Olivia C; Vaden, Timothy D

    2016-04-01

    Recent studies have characterized the effects of aqueous ionic liquids on myoglobin unfolding for the broader purposes of understanding their effects on protein structures, stabilities, and ultimately biocompatibilities for future applications. Here, we investigated the effects of four different ionic liquids (ILs) on the thermal stability, unfolding kinetics, and tertiary shape of myoglobin. We compared results for four different ILs: 1-butyl-3-methyl imidazolium tetrafluoroborate (BMIBF4); 1-butyl-3-methyl pyrrolidinium tetrafluoroborate (PyrrBF4); 1-ethyl-3-methyl imidazolium acetate (EMIAc); and tetramethylguanidinium acetate (TMGAc). Results showed that ILs accelerate myoglobin unfolding kinetics both through aqueous solution ionic strength effects and ionic liquid-specific effects. Arrhenius plots of observed rate constants reveal that some ILs lower the energy barrier to unfolding, possibly by destabilizing the native protein state. The magnitude of these ionic liquid effects correlates with their effects on protein thermodynamic stabilities. Hydrogen-deuterium exchange (HDX) experiments using ESI-MS showed that myoglobin exhibits a more open, and presumably less stable, tertiary shape in aqueous IL solutions. Overall, BMIBF4 and TMGAc exhibit the strongest effect on the myoglobin stability, unfolding rate, and tertiary structure while PyrrBF4 and EMIAc have weaker effects under our experimental conditions. PMID:26751398

  6. Ionic liquid solutions as extractive solvents for value-added compounds from biomass

    PubMed Central

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

    2014-01-01

    In the past few years, the number of studies regarding the application of ionic liquids (ILs) as alternative solvents to extract value-added compounds from biomass has been growing. Based on an extended compilation and analysis of the data hitherto reported, the main objective of this review is to provide an overview on the use of ILs and their mixtures with molecular solvents for the extraction of value-added compounds present in natural sources. The ILs (or IL solutions) investigated as solvents for the extraction of natural compounds, such as alkaloids, flavonoids, terpenoids, lipids, among others, are outlined. The extraction techniques employed, namely solid–liquid extraction, and microwave-assisted and ultrasound-assisted extractions, are emphasized and discussed in terms of extraction yields and purification factors. Furthermore, the evaluation of the IL chemical structure and the optimization of the process conditions (IL concentration, temperature, biomass–solvent ratio, etc.) are critically addressed. Major conclusions on the role of the ILs towards the extraction mechanisms and improved extraction yields are additionally provided. The isolation and recovery procedures of the value-added compounds are ascertained as well as some scattered strategies already reported for the IL solvent recovery and reusability. Finally, a critical analysis on the economic impact versus the extraction performance of IL-based methodologies was also carried out and is here presented and discussed. PMID:25516718

  7. Plutonium (IV) complexation by nitrate in acid solutions of ionic strengths from 2 to 19 molal

    SciTech Connect

    Berg, J.M.; Veirs, D.K.; Vaughn, R.B.; Cisneros, M.A.; Smith, C.A.

    1997-09-01

    Titrations of Pu(IV) with HNO{sub 3} in a series of aqueous HClO{sub 4} solutions ranging in ionic strength from 2 to 19 molal were followed using absorption spectrophotometry. The Pu 5f-5f spectra in the visible and near IR range change with complex formation. At each ionic strength, a series of spectra were obtained by varying nitrate concentration. Each series was deconvoluted into spectra f Pu{sup 4+}(aq), Pu(NO{sub 3}){sup 3+} and Pu(NO{sub 3}){sub 2}{sup 2+} complexes, and simultaneously their formation constants were determined. When corrected for the incomplete dissociation of nitric acid, the ionic strength dependence of each formation constant can be described by two parameters, {beta}{sup 0} and {Delta}{var_epsilon} using the formulae of specific ion interaction theory. The difficulties with extending this analysis to higher nitrate coordination numbers are discussed.

  8. 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. PMID:21603700

  9. Solubilities of Solutes in Ionic Liquids from a SimplePerturbed-Hard-Sphere Theory

    SciTech Connect

    Qin, Yuan; Prausnitz, John M.

    2005-09-20

    In recent years, several publications have provided solubilities of ordinary gases and liquids in ionic liquids. This work reports an initial attempt to correlate the experimental data using a perturbed-hard-sphere theory; the perturbation is based on well-known molecular physics when the solution is considered as a dielectric continuum. For this correlation, the most important input parameters are hard-sphere diameters of the solute and of the cation and anion that constitute the ionic liquid. In addition, the correlation uses the solvent density and the solute's polarizability and dipole and quadrupole moments, if any. Dispersion-energy parameters are obtained from global correlation of solubility data. Results are given for twenty solutes in several ionic liquids at normal temperatures; in addition, some results are given for gases in two molten salts at very high temperatures. Because the theory used here is much simplified, and because experimental uncertainties (especially for gaseous solutes) are often large, the accuracy of the correlation presented here is not high; in general, predicted solubilities (Henry's constants) agree with experiment to within roughly {+-} 70%. As more reliable experimental data become available, modifications in the characterizing parameters are likely to improve accuracy. Nevertheless, even in its present form, the correlation may be useful for solvent screening in engineering design.

  10. Fabrication of carbon nanotube high-frequency nanoelectronic biosensor for sensing in high ionic strength solutions.

    PubMed

    Kulkarni, Girish S; Zhong, Zhaohui

    2013-01-01

    The unique electronic properties and high surface-to-volume ratios of single-walled carbon nanotubes (SWNT) and semiconductor nanowires (NW) make them good candidates for high sensitivity biosensors. When a charged molecule binds to such a sensor surface, it alters the carrier density in the sensor, resulting in changes in its DC conductance. However, in an ionic solution a charged surface also attracts counter-ions from the solution, forming an electrical double layer (EDL). This EDL effectively screens off the charge, and in physiologically relevant conditions ~100 millimolar (mM), the characteristic charge screening length (Debye length) is less than a nanometer (nm). Thus, in high ionic strength solutions, charge based (DC) detection is fundamentally impeded. We overcome charge screening effects by detecting molecular dipoles rather than charges at high frequency, by operating carbon nanotube field effect transistors as high frequency mixers. At high frequencies, the AC drive force can no longer overcome the solution drag and the ions in solution do not have sufficient time to form the EDL. Further, frequency mixing technique allows us to operate at frequencies high enough to overcome ionic screening, and yet detect the sensing signals at lower frequencies. Also, the high transconductance of SWNT transistors provides an internal gain for the sensing signal, which obviates the need for external signal amplifier. Here, we describe the protocol to (a) fabricate SWNT transistors, (b) functionalize biomolecules to the nanotube, (c) design and stamp a poly-dimethylsiloxane (PDMS) micro-fluidic chamber onto the device, and (d) carry out high frequency sensing in different ionic strength solutions. PMID:23912795

  11. Fabrication of Carbon Nanotube High-Frequency Nanoelectronic Biosensor for Sensing in High Ionic Strength Solutions

    PubMed Central

    Kulkarni, Girish S.; Zhong, Zhaohui

    2013-01-01

    The unique electronic properties and high surface-to-volume ratios of single-walled carbon nanotubes (SWNT) and semiconductor nanowires (NW) 1-4 make them good candidates for high sensitivity biosensors. When a charged molecule binds to such a sensor surface, it alters the carrier density5 in the sensor, resulting in changes in its DC conductance. However, in an ionic solution a charged surface also attracts counter-ions from the solution, forming an electrical double layer (EDL). This EDL effectively screens off the charge, and in physiologically relevant conditions ~100 millimolar (mM), the characteristic charge screening length (Debye length) is less than a nanometer (nm). Thus, in high ionic strength solutions, charge based (DC) detection is fundamentally impeded6-8. We overcome charge screening effects by detecting molecular dipoles rather than charges at high frequency, by operating carbon nanotube field effect transistors as high frequency mixers9-11. At high frequencies, the AC drive force can no longer overcome the solution drag and the ions in solution do not have sufficient time to form the EDL. Further, frequency mixing technique allows us to operate at frequencies high enough to overcome ionic screening, and yet detect the sensing signals at lower frequencies11-12. Also, the high transconductance of SWNT transistors provides an internal gain for the sensing signal, which obviates the need for external signal amplifier. Here, we describe the protocol to (a) fabricate SWNT transistors, (b) functionalize biomolecules to the nanotube13, (c) design and stamp a poly-dimethylsiloxane (PDMS) micro-fluidic chamber14 onto the device, and (d) carry out high frequency sensing in different ionic strength solutions11. PMID:23912795

  12. A novel strategy for preparing mechanically robust ionically cross-linked alginate hydrogels.

    PubMed

    Jejurikar, Aparna; Lawrie, Gwen; Martin, Darren; Grøndahl, Lisbeth

    2011-04-01

    The properties of alginate films modified using two cross-linker ions (Ca(2+) and Ba(2+)), comparing two separate cross-linking techniques (the traditional immersion (IM) method and a new strategy in a pressure-assisted diffusion (PD) method), are evaluated. This was achieved through measuring metal ion content, water uptake and film stability in an ionic solution ([Ca(2+)] = 2 mM). Characterization of the internal structure and mechanical properties of hydrated films were established by cryogenic scanning electron microscopy and tensile testing, respectively. It was found that gels formed by the PD technique possessed greater stability and did not exhibit any delamination after 21 day immersion as compared to gels formed by the IM technique. The Ba(2+) cross-linked gels possessed significantly higher cross-linking density as reflected in lower water content, a more dense internal structure and higher Young's modulus compared to Ca(2+) cross-linked gels. For the Ca(2+) cross-linked gels, a large improvement in the mechanical properties was observed in gels produced by the PD technique and this was attributed to thicker pore walls observed within the hydrogel structure. In contrast, for the Ba(2+) cross-linked gels, the PD technique resulted in gels that had lower tensile strength and strain energy density and this was attributed to phase separation and larger macropores in this gel. PMID:21436510

  13. An electric impedance based microelectromechanical system flow sensor for ionic solutions

    PubMed Central

    Ayliffe, H Edward; Rabbitt, RD

    2008-01-01

    Microfluidic devices with channel cross sections measuring 4 × 10 μm2 instrumented with gold microelectrodes were used to sense flow rates of ionic solutions on the basis of electric impedance (EI) measured perpendicular to the flow. Negative pressures were applied to access ports of the microdevices to generate flow of saline solutions (physiologic concentrations 0.9%) through the micro-EI recording zone with flow rates between 2.4 and 4.8 μl min−1. The EI spectra (100 Hz–20 MHz) recorded under flow conditions were compared with the no-flow condition. Changes in the magnitude of EI (at 350 Hz) for flow rates as low as 2.4 μl min−1 were statistically significant compared with the no-flow condition. The observed dependence of EI on flow rate is attributed to the relative difference between the rate of migration of charge-balancing electrolyte ions to the electrode surface and the rate of removal of the same ions by forced convection. An electrochemical convection–diffusion model was used to study the observed dependence on flow. Simulations support the conceptual model that passing DC current from the gold electrodes into the ionic solution results in an increase in ionic concentration near the electrode surface (due to the inward migration of counter-balancing ions). When the fluid flow rates increase, these counter-balancing ions are replaced by the bulk solution, thereby lowering the average ionic concentration within the recording zone. This local concentration drop results in an increase in the real part of the impedance. PMID:19672321

  14. Ionic Behavior in Highly Concentrated Aqueous Solutions Nanoconfined between Discretely Charged Silicon Surfaces.

    PubMed

    Qiu, Yinghua; Ma, Jian; Chen, Yunfei

    2016-05-17

    Through molecular dynamics simulations considering thermal vibration of surface atoms, ionic behaviors in concentrated NaCl solutions confined between discretely charged silicon surfaces have been investigated. The electric double layer structure was found to be sensitive to the density and distribution of surface charges. Due to the discreteness of the surface charge, a slight charge inversion appeared which depended on the surface charge density, bulk concentration, and confinement. In the nanoconfined NaCl solutions concentrated from 0.2 to 4.0 M, the locations of accumulation layers for Na(+) and Cl(-) ions remained stable, but their peak values increased. The higher the concentration was, the more obvious the charge inversion appeared. In 4.0 M NaCl solution, Na(+) and Cl(-) ions show obvious alternating layered distributions which may correspond to the solidification found in experiments. By changing surface separation, the confinement had a large effect on the ionic distribution. As both surfaces approached each other, many ions and water molecules were squeezed out of the confined space. Two adjacent layers in ion or water distribution profiles can be forced closer to each other and merge together. From ionic hydration analysis, the coordination number of Na(+) ions in highly confined space was much lower than that in the bulk. PMID:27137990

  15. Stabilization of urinary THC solutions with a simple non-ionic surfactant.

    PubMed

    Welsh, Eric R; Snyder, J Jacob; Klette, Kevin L

    2009-01-01

    To stabilize urinary solutions against adsorptive loss of metabolites of Delta9-tetrahydrocannabinol (THC), a non-ionic surfactant, Tergitol, was investigated to reduce the need for special handling and storage of such solutions. Addition of surfactant up to 20 times the critical micelle concentration (CMC) did not adversely affect the analytical process. Yet, at only two times CMC, surfactant was found to mitigate adsorptive loss of THC analytes under a variety of storage and handling conditions including exposure to glass and plastic surfaces, after storage in a refrigerator or freezer, and at reduced pH, where adsorptive losses were expected to be significant. On average, micellar solubilization of analyte increased the assayed concentration by 10% with a range of 3 to 20%, depending on condition, relative to solutions without surfactant. Solutions with surfactant did not fail (i.e., deviate in concentration by +/-20%) over a 49-week period, whereas those without surfactant failed by 21 weeks. These results indicate that addition of small amounts of non-ionic surfactant to solutions of urinary THC metabolites is a simple method to improve both the accuracy and precision of analyte concentrations, as determined by gas chromatography-mass spectrometry, in such solutions by mitigating adsorptive losses during storage and handling events. PMID:19161669

  16. Ionic strength effects on the photodegradation reactions of riboflavin in aqueous solution.

    PubMed

    Ahmad, Iqbal; Anwar, Zubair; Ali, Syed Abid; Hasan, Khwaja Ali; Sheraz, Muhammad Ali; Ahmed, Sofia

    2016-04-01

    A study of the effect of ionic strength on the photodegradation reactions (photoreduction and photoaddition) of riboflavin (RF) in phosphate buffer (pH7.0) has been carried out using a specific multicomponent spectrometric method. It has been found that the rates of photodegradation reactions of RF are dependent upon the ionic strength of the solutions at different buffer concentrations. The apparent first-order rate constants (kobs) for the photodegradation of riboflavin at ionic strengths of 0.1-0.5 (0.5M phosphate) lie in the range of 7.35-30.32×10(-3)min(-1). Under these conditions, the rate constants for the formation of the major products, lumichrome (LC) by photoreduction pathway, and cyclodehydroriboflavin (CDRF) by photoaddition pathway, are in the range of 3.80-16.03 and 1.70-6.07×10(-3)min(-1), respectively. A linear relationship has been observed between log kobs and √μ/1+√μ. A similar plot of log k/ko against √μ yields a straight line with a value of ~+1 for ZAZB showing the involvement of a charged species in the rate determining step. NaCl appears to promote the photodegradation reactions of RF probably by an excited state interaction. The implications of ionic strength on RF photodegradation by different pathways and flavin-protein interactions have been discussed. PMID:26910851

  17. Structural effects of anions and cations on the aggregation behavior of ionic liquids in aqueous solutions.

    PubMed

    Wang, Huiyong; Wang, Jianji; Zhang, Shibiao; Xuan, Xiaopeng

    2008-12-25

    The formation of ionic liquids aggregates in aqueous solution is of great importance to the future applications of ionic liquids. In this work, aggregation behavior of 1-alkyl-3-methylimidazolium salts [C8mim]X (X = Cl, Br, [NO3], [CH3COO], [CF3COO], [CF3SO3], and [ClO4]), 1-octyl-4-methylpyridinium bromide (4m-[C8pyr]Br), and 1-methyl-1-octylpyrrolidinium ([C8mpyrr]Br) has been investigated in aqueous solutions by conductivity, volume, fluorescence, dynamic light scattering, and transmission electron microscopy. The critical aggregation concentration (CAC), ionization degree of the aggregates alpha, the standard Gibbs energy of aggregation deltaG(m)degrees, the average aggregation number N, the apparent molar volumes at critical aggregation concentration V(phi,CAC), the apparent molar volumes in aggregation phase V(phi)mic, and the change of the apparent molar volumes upon aggregation deltaV(phi,m), have been derived from the experimental data for these ionic liquids. It is found that both nature of the anions and ring type of the cations significantly affect the aggregation in aqueous solution. The anionic effect basically follows the Hofmeister series, and the ability of anionic hydration is predominant for the aggregation behavior of the ionic liquids. Hydrophobicity and steric hindrance of the cations as well as binding strength of the cations with the anions are suggested to play important roles in the aggregation of [C8mim]Br, 4m-[C8pyr]Br, and [C8mpyrr]Br. The investigated ILs were found to form spherical aggregates. Structures of anions and cations have very weak effects on the morphology, but they do affect the aggregate sizes. PMID:19367863

  18. J-aggregation of ionic liquid solutions of meso-tetrakis(4-sulfonatophenyl)porphyrin

    SciTech Connect

    Ali, Maroof; Kumar, Vinod; Baker, Sheila N; Baker, Gary A; Pandey, Siddharth

    2010-01-01

    The title porphyrin was dissolved in the hydrophilic ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF4], and triggered to assemble into J-aggregates by the addition of incremental volumes of water containing various amounts of acid (0.1, 0.2, or 1.0 M HCl). In contrast to recent studies, the current investigation is unique in that it centers on media that contain a predominant ionic liquid component (2.9 5.4 M [bmim][BF4]), as opposed to an aqueous electrolyte containing a small fraction of ionic liquid as dissociated solute. Complex aggregation and underlying photophysical behavior are revealed from absorption spectroscopy, steady-state fluorescence, and resonance light scattering studies. Upon addition of aqueous HCl, the efficient formation of H4TPPS2 J-aggregates from the diprotonated form of meso-tetrakis(4-sulfonatophenyl)porphyrin (H2TPPS4) occurs in [bmim][BF4]-rich media in a manner highly dependent upon the acidity, TPPS concentration, and solvent composition. The unique features of TPPS aggregation in this ionic liquid were elucidated, including the surprising disassembly of J-aggregates at higher aqueous contents, and our results are described qualitatively in terms of the molecular exciton theory. Finally, the potential of this system for the optical sensing of water at a sensitivity below 0.5 wt% is demonstrated. Overall, our findings accentuate how little is known about functional self-assembly within ionic liquids and suggest a number of avenues for exploring this completely untouched research landscape.

  19. Peptides in the presence of aqueous ionic liquids: tunable co-solutes as denaturants or protectants?

    PubMed

    Lesch, Volker; Heuer, Andreas; Tatsis, Vasileios A; Holm, Christian; Smiatek, Jens

    2015-10-21

    We studied the stability of a small β-hairpin peptide under the influence of an aqueous 1-ethyl-3-methylimidazolium acetate ([EMIM](+)[ACE](-)) solution via all-atom molecular dynamics simulations in combination with metadynamics. Our free energy results indicate a denaturation of the peptide structure in the presence of the ionic liquid which is validated by a significant broadening of the end-to-end distance. The radial distribution functions between the ions and the peptide were used for the calculation of the preferential binding coefficients in terms of the Kirkwood-Buff theory. A significant structure dependent binding behavior of acetate to the peptide was found which can be interpreted as the main reason for the denaturation of the native conformation. The outcomes of our simulations allow us to propose a simple mechanism to explain the unfolding of the peptide with regard to the specific properties of ionic liquids. Our results are in good agreement with experimental findings and demonstrate the benefits of ionic liquids as tunable co-solutes with regard to their influence on protein structural properties. PMID:26377364

  20. High-Strength Composite Fibers from Cellulose-Lignin Blends Regenerated from Ionic Liquid Solution.

    PubMed

    Ma, Yibo; Asaadi, Shirin; Johansson, Leena-Sisko; Ahvenainen, Patrik; Reza, Mehedi; Alekhina, Marina; Rautkari, Lauri; Michud, Anne; Hauru, Lauri; Hummel, Michael; Sixta, Herbert

    2015-12-01

    Composite fibres that contain cellulose and lignin were produced from ionic liquid solutions by dry-jet wet spinning. Eucalyptus dissolving pulp and organosolv/kraft lignin blends in different ratios were dissolved in the ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate to prepare a spinning dope from which composite fibres were spun successfully. The composite fibres had a high strength with slightly decreasing values for fibres with an increasing share of lignin, which is because of the reduction in crystallinity. The total orientation of composite fibres and SEM images show morphological changes caused by the presence of lignin. The hydrophobic contribution of lignin reduced the vapour adsorption in the fibre. Thermogravimetric analysis curves of the composite fibres reveal the positive effect of the lignin on the carbonisation yield. Finally, the composite fibre was found to be a potential raw material for textile manufacturing and as a precursor for carbon fibre production. PMID:26542190

  1. Dielectric spectra broadening as the signature of dipole-matrix interaction. II. Water in ionic solutions.

    PubMed

    Levy, Evgeniya; Puzenko, Alexander; Kaatze, Udo; Ben Ishai, Paul; Feldman, Yuri

    2012-03-21

    In this, the second part of our series on the dielectric spectrum symmetrical broadening of water, we consider ionic aqueous solutions. If in Part I, dipole-dipole interaction was the dominant feature, now ion-dipole interplay is shown to be the critical element in the dipole-matrix interaction. We present the results of high-frequency dielectric measurements of different concentrations of NaCl/KCl aqueous solutions. We observed Cole-Cole broadening of the main relaxation peak of the solvent in the both electrolytes. The 3D trajectory approach (described in detail in Part I) is applied in order to highlight the differences between the dynamics and structure of solutions of salts on one hand and dipolar solutes on the other hand. PMID:22443773

  2. Bioreduction and precipitation of uranium in ionic liquid aqueous solution by Clostridium sp.

    PubMed

    Zhang, C; Dodge, C J; Malhotra, S V; Francis, A J

    2013-05-01

    The ionic liquids, 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], N-ethylpyridiniumtrifluoroacetate [EtPy][CF3COO] and N-ethylpyridiniumtetrafluoroborate [EtPy][BF4], affected the reduction and precipitation of uranium by Clostridium sp. to a varying degree. Characterization of uranium association with the ionic liquids showed that uranium formed a monodentate complex with the anion BF4(-) and PF6(-) of [EtPy][BF4] and [BMIM][PF6], respectively; and a bidentate complex with carboxylate of [EtPy][CF3COO]. Bioreduction of U(VI) was influenced by the type of complex formed: monodentate complexes were readily reduced whereas the bidentate complex of U(VI) with [CF3COO] was recalcitrant. [EtPy][BF4] affected the rate and extent of precipitation of the reduced uranium; at higher concentration the reduced U(IV) remained in the solution phase. The results suggest that by tuning the properties of ionic liquids they may be valuable candidates for uranium biotreatment. PMID:23566468

  3. 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.

  4. Predicting hardness of covalent/ionic solid solution from first-principles theory

    NASA Astrophysics Data System (ADS)

    Hu, Q. M.; Kádas, K.; Hogmark, S.; Yang, R.; Johansson, B.; Vitos, L.

    2007-09-01

    We introduce a hardness formula for the multicomponent covalent and ionic solid solutions. This expression is tested on nitride spinel materials A3N4 (A=C,Si,Ge) and applied to titanium nitrogen carbide (TiN1-xCx with 0⩽x ⩽1), off-stoichiometric transition-metal nitride (TiN1-x and VN1-x with x ⩽0.25), and B-doped semiconductors (C1-xBx, Si1-xBx, and Ge1-xBx with x ⩽0.1). In all cases, the theoretical hardness is in good agreement with experiments.

  5. Lorentz effect imaging of ionic currents in solution using correct values for ion mobility

    NASA Astrophysics Data System (ADS)

    Wijesinghe, Ranjith S.; Roth, Bradley J.

    2010-06-01

    Truong and his colleagues have recently published a paper introducing a new method called Lorentz effect imaging (LEI) to detect ionic currents in a solution. Their main goal was to prove that the Lorentz force acting on ions in the presence of a static magnetic field could be used as a contrast mechanism to measure neural currents with magnetic resonance imaging. However, they failed to use the correct values for the ion mobilities. In this investigation, we have used correct ion mobility values and show that LEI cannot be used as a contrast mechanism to directly image neural currents.

  6. Solute diffusion in ionic liquids, NMR measurements and comparisons to conventional solvents.

    PubMed

    Kaintz, Anne; Baker, Gary; Benesi, Alan; Maroncelli, Mark

    2013-10-01

    Diffusion coefficients of a variety of dilute solutes in the series of 1-alkyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imides ([Prn1][Tf2N], n = 3, 4, 6, 8, and 10), trihexyltetracedecylphosphonium bis(trifluoromethanesulfonyl)imide [P14,666][Tf2N], and assorted imidazolium ionic liquids are measured using pulsed field gradient (1)H NMR. These data, combined with available literature data, are used to try to uncover the solute and solvent characteristics most important in determining tracer diffusion rates. Discussion is framed in terms of departures from simple hydrodynamic predictions for translational friction using the ratio ζobs/ζSE, where ζobs is the observed friction, determined from the measured diffusion coefficient D via ζobs = kBT/D, and ζSE = 6πηR is the Stokes friction on a sphere of radius R (determined from the solute van der Waals volume) in a solvent with viscosity η. In the case of neutral solutes, the primary determinant of whether hydrodynamic predictions are accurate is the relative size of solute versus solvent molecules. A single correlation, albeit with considerable scatter, is found between ζobs/ζSE and the ratio of solute-to-solvent van der Waals volumes, ζobs/ζSE = {1 + a(VU/VV)(-p)}, with constants a = 1.93 and p = 1.88. In the case of small solutes, the observed friction is over 100-fold smaller than predictions of hydrodynamic models. The dipole moment of the solute has little effect on the friction, whereas solute charge has a marked effect. For monovalent solutes of size comparable to or smaller than the solvent ions, the observed friction is comparable to or even greater than what is predicted by hydrodynamics. These general trends are shown to be quite similar to what is observed for tracer diffusion in conventional solvents. PMID:23968276

  7. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    DOE PAGESBeta

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulkmore » IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.« less

  8. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    SciTech Connect

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

  9. True molecular solutions of natural cellulose in the binary ionic liquid-containing solvent mixtures.

    PubMed

    Rein, Dmitry M; Khalfin, Rafail; Szekely, Noemi; Cohen, Yachin

    2014-11-01

    Evidence is presented for the first time of true molecular dissolution of cellulose in binary mixtures of common polar organic solvents with ionic liquid. Cryogenic transmission electron microscopy, small-angle neutron-, X-ray- and static light scattering were used to investigate the structure of cellulose solutions in mixture of dimethyl formamide and 1-ethyl-3-methylimidazolium acetate. Structural information on the dissolved chains (average molecular weight ∼ 5 × 10(4)g/mol; gyration radius ∼ 36 nm, persistence length ∼ 4.5 nm), indicate the absence of significant aggregation of the dissolved chains and the calculated value of the second virial coefficient ∼ 2.45 × 10(-2)mol ml/g(2) indicates that this solvent system is a good solvent for cellulose. More facile dissolution of cellulose could be achieved in solvent mixtures that exhibit the highest electrical conductivity. Highly concentrated cellulose solution in pure ionic liquid (27 wt.%) prepared according to novel method, utilizing the rapid evaporation of a volatile co-solvent in binary solvent mixtures at superheated conditions, shows insignificant cellulose molecular aggregation. PMID:25129726

  10. Motion of Molecular Probes and Viscosity Scaling in Polyelectrolyte Solutions at Physiological Ionic Strength.

    PubMed

    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

  11. 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

  12. Ionic conductivity of dual-phase polymer electrolytes comprised of NBR/SBR latex films swollen with lithium salt solutions

    SciTech Connect

    Matsumoto, Morihiko; Ichino, Toshihiro; Rutt, J.S.; Nishi, Shiro . NTT Interdisciplinary Research Lab.)

    1994-08-01

    Dual-phase polymer electrolytes (DPE) with high ionic conductivity and good mechanical strength were prepared by swelling poly(acrylonitrile-co-butadiene) rubber (NBR) and poly(styrene-co-butadiene) rubber (SBR) mixed latex films with lithium salt solutions (e.g., 1M LiClO[sub 4]/[gamma]-butyrolactone). The latex films retain particle morphology in the solid state. The NBR phase (formed from fused NBR latex particles) is polar and is impregnated selectively with polar lithium salt solutions, yielding ion-conductive channels, whereas the SBR phase (formed from fused SBR latex particles) is nonpolar and is not impregnated, providing a mechanically supportive matrix. The ionic conductivity of the DPE increased dramatically with increasing content of lithium salt solution, and higher amounts of solution were imbibed with increasing content of NBR relative to SBR. Several factors which affect the ionic conductivity of this system were examined, and the highest ionic conductivity (>10[sup [minus]3] S/cm) was obtained when either an NBR/SBR 70/30 (w/w) or a 50/50 (w/w) latex film was saturated with 1M LiClO[sub 4]/[gamma]-BL solution or 1M LiClO[sub 4]/[gamma]-BL/DME solution. Ion-conductive behavior changed critically with increasing lithium salt solution uptake. At low levels of lithium salt solution uptake, evidence suggested that ionic conductivity of the absorbed lithium salt solution was strongly influenced by the presence of the NBR in the ion-conductive channel, but at higher levels, the effects of the NBR were reduced and free'' lithium salt solution was present.

  13. 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. PMID:23127811

  14. Comparison of interionic/intermolecular vibrational dynamics between ionic liquids and concentrated electrolyte solutions.

    PubMed

    Fujisawa, Tomotsumi; Nishikawa, Keiko; Shirota, Hideaki

    2009-12-28

    In this study, we have compared the interionic/intermolecular vibrational dynamics of ionic liquids (ILs) and concentrated electrolyte solutions measured by femtosecond optically heterodyne-detected Raman-induced Kerr effect spectroscopy. A typical anion in ILs, bis(trifluoromethanesulfonyl)amide ([NTf(2)](-)), has been chosen as the anion for the sample ILs and concentrated electrolyte solutions. ILs used in this study are 1-butyl-3-methylimidazolium, 1-butylpyridinium, N-butyl-N,N,N-triethylammonium, and 1-butyl-1-methylpyrrolidinium with [NTf(2)](-). Li[NTf(2)] solutions (approximately 3.3 M) of water, methanol, propylene carbonate, and poly(ethylene glycol) have been selected as control samples. Kerr transients of the ILs and electrolyte solutions show intra- and interionic/intermolecular vibrational dynamics followed by slow picosecond overdamped relaxation. Fourier transform Kerr spectra have shown a difference in the relative intensities of intraionic vibrational bands of [NTf(2)](-) (280-350 cm(-1)) between the ILs and electrolyte solutions. The origin of the difference is attributed to the change in the conformational equilibrium between cisoid and transoid forms of [NTf(2)](-), which is caused by a favorable stabilization of dipolar cisoid form due to Li(+) and dipolar solvent molecules in the electrolyte solutions. Low-frequency Kerr spectra (0-200 cm(-1)) exhibit unique features with the variation of cation and solvent species. The aromatic ILs have a prominent high-frequency librational motion at about 100 cm(-1) in contrast to the case for the nonaromatic ones. The common structure of the spectra observed at about 20 cm(-1) likely comes from an interionic motion of [NTf(2)](-). The nonaromatic ILs allow a fair comparison with the electrolyte solutions of propylene carbonate and poly(ethylene glycol) because of the structural similarities. The comparison based on the first moment of the interionic/intermolecular vibrational spectrum suggests the

  15. Comparison of interionic/intermolecular vibrational dynamics between ionic liquids and concentrated electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Fujisawa, Tomotsumi; Nishikawa, Keiko; Shirota, Hideaki

    2009-12-01

    In this study, we have compared the interionic/intermolecular vibrational dynamics of ionic liquids (ILs) and concentrated electrolyte solutions measured by femtosecond optically heterodyne-detected Raman-induced Kerr effect spectroscopy. A typical anion in ILs, bis(trifluoromethanesulfonyl)amide ([NTf2]-), has been chosen as the anion for the sample ILs and concentrated electrolyte solutions. ILs used in this study are 1-butyl-3-methylimidazolium, 1-butylpyridinium, N-butyl-N,N,N-triethylammonium, and 1-butyl-1-methylpyrrolidinium with [NTf2]-. Li[NTf2] solutions (˜3.3M) of water, methanol, propylene carbonate, and poly(ethylene glycol) have been selected as control samples. Kerr transients of the ILs and electrolyte solutions show intra- and interionic/intermolecular vibrational dynamics followed by slow picosecond overdamped relaxation. Fourier transform Kerr spectra have shown a difference in the relative intensities of intraionic vibrational bands of [NTf2]- (280-350 cm-1) between the ILs and electrolyte solutions. The origin of the difference is attributed to the change in the conformational equilibrium between cisoid and transoid forms of [NTf2]-, which is caused by a favorable stabilization of dipolar cisoid form due to Li+ and dipolar solvent molecules in the electrolyte solutions. Low-frequency Kerr spectra (0-200 cm-1) exhibit unique features with the variation of cation and solvent species. The aromatic ILs have a prominent high-frequency librational motion at about 100 cm-1 in contrast to the case for the nonaromatic ones. The common structure of the spectra observed at about 20 cm-1 likely comes from an interionic motion of [NTf2]-. The nonaromatic ILs allow a fair comparison with the electrolyte solutions of propylene carbonate and poly(ethylene glycol) because of the structural similarities. The comparison based on the first moment of the interionic/intermolecular vibrational spectrum suggests the stronger interionic/intermolecular interaction in

  16. Critical behaviour of ionic solutions in non-polar solvents with a liquid - liquid phase transition

    NASA Astrophysics Data System (ADS)

    Schröer, W.; Kleemeier, M.; Plikat, M.; Weiss, V.; Wiegand, S.

    1996-11-01

    Turbidity measurements showing crossover from mean-field to Ising criticality have been reported by Narayanan and Pitzer for the liquid - liquid phase transition in ionic solutions of alkyl-ammonium picrates in higher alcohols. The Ising region was found to increase with the dielectric permittivity D for solvents with 4 < D < 8. It was conjectured that the Ising region becomes too small to be observed for lower values of D, which is in accordance with the finding of mean-field criticality in the system triethylhexylammonium triethylhexylborate 0953-8984/8/47/023/img1 in diphenyl ether 0953-8984/8/47/023/img2, where 0953-8984/8/47/023/img3. In order to check this hypothesis, we investigate solutions of salts in non-protonating solvents with D<2.5. The systems are tetrabutylammonium naphthyl sulphonate 0953-8984/8/47/023/img4 in toluene and tributylheptylammonium dodecyl sulphate 0953-8984/8/47/023/img5 in cyclohexane. The location of the critical points in the corresponding state diagram is in general agreement with the model system of charged hard spheres in a dielectric continuum, i.e. the restricted primitive model (RPM). However, changes of 0953-8984/8/47/023/img6 by minute variations of the salt and of the solvent (toluene, xylene, ethylbenzene) cannot be explained by the RPM. We report measurements of the phase diagram and light-scattering results. The amplitudes of the correlation length are up to an order of magnitude larger than those typically found in non-ionic fluids. For the new systems, but also for the solution of 0953-8984/8/47/023/img7 in 0953-8984/8/47/023/img8, Ising criticality is found in the region of 0953-8984/8/47/023/img9.

  17. Physical properties and intermolecular dynamics of an ionic liquid compared with its isoelectronic neutral binary solution.

    PubMed

    Shirota, Hideaki; Castner, Edward W

    2005-10-27

    In this study, we address the following question about room-temperature ionic liquids (RTILs). Are the properties of a RTIL more dependent on the charges of the molecular ions or on the fact that the liquid is a complex mixture of two species, one or both of which are asymmetric? To address this question and to better understand the interactions and dynamics in RTILs, we have prepared the organic ionic liquid 1-methoxyethylpyridinium dicyanoamide (MOEPy(+)/DCA(-)) and compared this RTIL with the analogous isoelectronic binary solution, comprised of equal parts of 1-methoxyethylbenzene (MOEBz) and dicyanomethane (DCM). In essence, we have created a RTIL and a nearly identical neutral pair in which we have effectively turned off the charges. To understand the intermolecular interactions in both of these liquids, we have characterized the bulk density and shear viscosity. Using femtosecond optical Kerr effect spectroscopy, we have also characterized the intermolecular vibrational dynamics and diffusive reorientation. To verify that the shape, polarizability, and electronic structure of the RTIL ions and the components of the neutral pair are truly quite similar, we have carried out density functional theory calculations on the individual molecular ion and neutral species. PMID:16866386

  18. Self-assembly in aqueous solutions of a non-ionic hydrotrope

    NASA Astrophysics Data System (ADS)

    Subramanian, Deepa

    Hydrotropes are amphiphilic molecules, too small to cause spontaneous self-assembly towards equilibrium mesoscale structures in aqueous solutions, but they form dynamic, noncovalent assemblies, which may create microscopic regions of lowered polarity. This enhances the solubilization of hydrophobic compounds, also known as solubilizates, in aqueous solutions and may cause further aggregation to larger structures. In this work, unusual mesoscopic properties of aqueous solutions of a non-ionic hydrotrope, namely tertiary butyl alcohol (TBA) have been investigated by light scattering, microscopy, and chromatography. Aqueous TBA solutions show anomalous thermodynamic and structural properties in the range of concentrations 3-8 mol % TBA and temperatures 0-25 °C. These anomalies appear to be associated with short-lived, short-ranged micelle-like structural fluctuations, distinctly different from usual concentration fluctuations in non-ideal solutions. Molecular dynamics simulations and neutron-scattering experiments show clustering of TBA molecules on a nanometer scale, interacting through hydrogen bonds with a shell of water molecules. In this concentration range, TBA aqueous solutions, although macroscopically homogeneous, occasionally show the presence of "mysterious" inhomogeneities on a 100 nm scale. We have found that the emergence of such inhomogeneities strongly correlates with impurities present in commercial TBA samples. Experiments with controlled addition of a third component, such as propylene oxide, isobutyl alcohol, or cyclohexane, reveal the mechanism of formation of these inhomogeneities through stabilization of micelle-like fluctuations by a solubilizate. These structures are long-lived, i.e., stable from a few days up to many months. We have confirmed that mesoscale structures in aqueous solutions can be generated from self-assembly of small molecules, without involvement of surfactants or polymers. This kind of self-assembly may potentially result

  19. Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

    SciTech Connect

    Yao, Yi; Berkowitz, Max L. E-mail: ykanai@unc.edu; Kanai, Yosuke E-mail: ykanai@unc.edu

    2015-12-28

    The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicate that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na{sup +} and K{sup +} ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

  20. Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

    NASA Astrophysics Data System (ADS)

    Yao, Yi; Berkowitz, Max L.; Kanai, Yosuke

    2015-12-01

    The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicate that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na+ and K+ ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

  1. Effect of ionic liquid treatment on the structures of lignins in solutions

    SciTech Connect

    Cheng, Gang; Kent, Michael S; He, Lilin; Varanasi, Patanjali; Dibble, Dean; Melnichenko, Yuri B; Simmons, Blake; Singh, Seema

    2012-01-01

    The solution structures of three types of isolated lignin - organosolv (OS), Kraft (K), and low sulfonate (LS) - before and after treatment with 1-ethyl-3-methylimidazolium acetate were studied using small-angle neutron scattering (SANS) and dynamic light scattering (DLS) over a concentration range of 0.3-2.4 wt %. The results indicate that each of these lignins is comprised of aggregates of well-defined basal subunits, the shapes and sizes of which, in D{sub 2}O and DMSO-d{sub 6}, are revealed using these techniques. LS lignin contains a substantial amount of nanometer-scale individual subunits. In aqueous solution these subunits have a well-defined elongated shape described well by ellipsoidal and cylindrical models. At low concentration the subunits are highly expanded in alkaline solution, and the effect is screened with increasing concentration. OS lignin dissolved in DMSO was found to consist of a narrow distribution of aggregates with average radius 200 {+-} 30 nm. K lignin in DMSO consists of aggregates with a very broad size distribution. After ionic liquid (IL) treatment, LS lignin subunits in alkaline solution maintained the elongated shape but were reduced in size. IL treatment of OS and K lignins led to the release of nanometer-scale subunits with well-defined size and shape.

  2. Accurate integral equation theory for the central force model of liquid water and ionic solutions

    NASA Astrophysics Data System (ADS)

    Ichiye, Toshiko; Haymet, A. D. J.

    1988-10-01

    The atom-atom pair correlation functions and thermodynamics of the central force model of water, introduced by Lemberg, Stillinger, and Rahman, have been calculated accurately by an integral equation method which incorporates two new developments. First, a rapid new scheme has been used to solve the Ornstein-Zernike equation. This scheme combines the renormalization methods of Allnatt, and Rossky and Friedman with an extension of the trigonometric basis-set solution of Labik and co-workers. Second, by adding approximate ``bridge'' functions to the hypernetted-chain (HNC) integral equation, we have obtained predictions for liquid water in which the hydrogen bond length and number are in good agreement with ``exact'' computer simulations of the same model force laws. In addition, for dilute ionic solutions, the ion-oxygen and ion-hydrogen coordination numbers display both the physically correct stoichiometry and good agreement with earlier simulations. These results represent a measurable improvement over both a previous HNC solution of the central force model and the ex-RISM integral equation solutions for the TIPS and other rigid molecule models of water.

  3. Solute-solvent hydrogen-bonding in room temperature ionic liquids studied by Raman spectroscopy.

    PubMed

    Kobayashi, Akira; Osawa, Koji; Terazima, Masahide; Kimura, Yoshifumi

    2012-10-21

    The vibrational frequencies of the C=O + C=C band of diphenylcyclopropenone and the NH(2) stretching band of p-aminobenzonitrile were determined in various room temperature ionic liquids (RTILs). The vibrational frequency shifts of the C=O + C=C stretching mode were compared with Kamlet α values, and frequency shifts of the NH(2) stretching mode were compared with Kamlet β values. A nearly linear relationship was obtained for both parameters, although the solvatochromic parameters were more sensitive to changes of the cation species. Vibrational frequency calculations of a 1 : 1 cluster of p-aminobenzonitrile with the RTIL anions using DFT theory reproduced the observed frequency shifts of the NH(2) stretching mode fairly well. The frequency shifts of the CN stretching mode were well reproduced by the linear combination of dipolarity parameters, the hydrogen-bond donating and accepting parameters determined by the Raman shift of the solute molecule. PMID:22968223

  4. In situ crystallization of ionic liquid [Emim][PF6] from methanol solution under high pressure.

    PubMed

    Li, Haining; Su, Lei; Zhu, Xiang; Cheng, Xuerui; Yang, Kun; Yang, Guoqiang

    2014-07-24

    The solubility of 1-ethyl-3-methylimidazolium hexafluorophosphate ([Emim][PF6]) in methanol under high pressure is newly measured quantitatively according to the correlation between the ratios of Raman intensity and the concentrations. In situ crystallization and cation conformation of [Emim][PF6] from methanol solution under high pressure have been investigated by using Raman spectroscopy in detail. Remarkably, crystal polymorphism was observed and two crystalline phases (phases I and II) coexisted under high pressure up to ∼ 1.4 GPa. However, only phase II was obtained by recrystallization at ∼ 2 GPa. Our findings may facilitate the development of an effective way for crystallization and purification of ionic liquids under high pressure. PMID:24968114

  5. Accurate measurements of thermodynamic properties of solutes in ionic liquids using inverse gas chromatography.

    PubMed

    Mutelet, Fabrice; Jaubert, Jean-Noël

    2006-01-13

    Activity coefficients at infinite dilution of 29 organic compounds in two room temperature ionic liquids were determined using inverse gas chromatography. The measurements were carried out at different temperatures between 323.15 and 343.15K. To establish the influence of concurrent retention mechanisms on the accuracy of activity coefficients at infinite dilution for 1-butyl-3-methylimidazolium octyl sulfate and 1-ethyl-3-methylimidazolium tosylate, phase loading studies of the net retention volume per gram of packing as a function of the percent phase loading were used. It is shown that most of the solutes are retained largely by partition with a small contribution from adsorption on 1-butyl-3-methylimidazolium octyl sulfate and that the n-alkanes are retained predominantly by interfacial adsorption on 1-ethyl-3-methylimidazolium tosylate. PMID:16310203

  6. The structure of ionic aqueous solutions at interfaces: An intrinsic structure analysis

    NASA Astrophysics Data System (ADS)

    Bresme, Fernando; Chacón, Enrique; Tarazona, Pedro; Wynveen, Aaron

    2012-09-01

    We investigate the interfacial structure of ionic solutions consisting of alkali halide ions in water at concentrations in the range 0.2-1.0 molal and at 300 K. Combining molecular dynamics simulations of point charge ion models and a recently introduced computational approach that removes the averaging effect of interfacial capillary waves, we compute the intrinsic structure of the aqueous interface. The interfacial structure is more complex than previously inferred from the analysis of mean profiles. We find a strong alternating double layer structure near the interface, which depends on the cation and anion size. Relatively small changes in the ion diameter disrupt the double layer structure, promoting the adsorption of anions or inducing the density enhancement of small cations with diameters used in simulation studies of lithium solutions. The density enhancement of the small cations is mediated by their strong water solvation shell, with one or more water molecules "anchoring" the ion to the outermost water layer. We find that the intrinsic interfacial electrostatic potential features very strong oscillations with a minimum at the liquid surface that is ˜4 times stronger than the electrostatic potential in the bulk. For the water model employed in this work, SPC/E, the electrostatic potential at the water surface is ˜-2 V, equivalent to ˜80 kBT (for T = 300 K), much stronger than previously considered. Furthermore, we show that the utilization of the intrinsic surface technique provides a route to extract ionic potentials of mean force that are not affected by the thermal fluctuations, which limits the accuracy of most past approaches including the popular umbrella sampling technique.

  7. 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

    2015-09-01

    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. PMID:26388373

  8. Multigrid solution strategies for adaptive meshing problems

    NASA Technical Reports Server (NTRS)

    Mavriplis, Dimitri J.

    1995-01-01

    This paper discusses the issues which arise when combining multigrid strategies with adaptive meshing techniques for solving steady-state problems on unstructured meshes. A basic strategy is described, and demonstrated by solving several inviscid and viscous flow cases. Potential inefficiencies in this basic strategy are exposed, and various alternate approaches are discussed, some of which are demonstrated with an example. Although each particular approach exhibits certain advantages, all methods have particular drawbacks, and the formulation of a completely optimal strategy is considered to be an open problem.

  9. Students' Use of "Look Back" Strategies in Multiple Solution Methods

    ERIC Educational Resources Information Center

    Lee, Shin-Yi

    2016-01-01

    The purpose of this study was to investigate the relationship between both 9th-grade and 1st-year undergraduate students' use of "look back" strategies and problem solving performance in multiple solution methods, the difference in their use of look back strategies and problem solving performance in multiple solution methods, and the…

  10. Enhanced catalytic performance of Pd catalyst for formic acid electrooxidation in ionic liquid aqueous solution

    NASA Astrophysics Data System (ADS)

    Feng, Yuan-Yuan; Yin, Qian-Ying; Lu, Guo-Ping; Yang, Hai-Fang; Zhu, Xiao; Kong, De-Sheng; You, Jin-Mao

    2014-12-01

    A protic ionic liquid (IL), n-butylammonium nitrate (N4NO3), is prepared and employed as the electrolyte for formic acid electrooxidation reaction (FAOR) on Pd catalysts. The oxidation peak potential of FAOR in the IL solution shows about a 200 mV negative shift as compared with those in traditional H2SO4/HClO4 electrolytes, suggesting that FAOR can be more easily carried out on Pd catalysts in IL media. The catalytic properties of Pd toward FAOR are not only dependent on the concentration of IL, as a consequence of the varied electronic conductivity of the IL solution, but also on the high potential limit of the cyclic voltammograms. When the Pd catalyst is cycled up to 1.0 V (vs. SCE), which induces a significant oxidation of Pd, it shows ca. 4.0 times higher activity than that not subjected to the Pd oxidation (up to 0.6 V). The Pd oxides, which are more easily formed in IL solution than in traditional H2SO4/HClO4 electrolytes, may play a crucial role in increasing the catalytic activities of Pd toward FAOR. Our work would shed new light on the mechanism of FAOR and highlight the potential applications of IL as green and environment-friendly electrolytes in fuel cells and other technologies.

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

    PubMed

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

    2016-02-01

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

  12. 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.

  13. Theoretical insights into the properties of amino acid ionic liquids in aqueous solution.

    PubMed

    Zhu, Xueying; Ai, Hongqi

    2016-07-01

    This report presents a systematic investigation of the interactions of water molecule(s) with a series of amino acid cations (Gly(+), Ala(+), Val(+), and Leu(+)), halogen anions (Cl(-), Br(-), BF4 (-), and PF6 (-)), and clusters (GlyCl) n (n = 1-5). The results reveal that H-bonds between amino acid ionic liquids (AAILs) and water molecules are crucial to the properties of aqueous solution of AAILs. The properties of AAIL in water solution depend on the alkyl chain of the amino acid cation, the size of the halogen anion, and the number of water molecules, which provides a certain theoretical basis for the design and application of new AAILs. A series of calculations for some different models showed that quadruple-GlyCl hydrate represents a basic unit for the Gly-water binary system, and can be employed as the simplest model for studying an AAIL-water cluster. On the basis of this model, the effects of water on the hygroscopicity, speed of solubility, viscosity, density, solution enthalpy, and polarity of the AAIL were also predicted. Most importantly, unlike traditional ILs, the novel GlyCl-type AAIL favors interaction of its cationic part, rather than its anionic part, with surrounding water molecules, thus amino acid cationic ILs expand the types of IL available, increasing the choice of ILs for different purposes. We hope that the application of this AAIL in many fields will lead to optimization of this class of compound and be of benefit to the environment. Graphical Abstract Quadruple-GlyCl hydrate represents the basic unit for a GlyCl-water binary system, which can be employed as the simplest model for studying an amino acid ionic liquid (AAIL)-water cluster. The effects of available water on some properties of AAIL are predicted. GlyCl-type AAIL is a novel IL, which prefers its cationic part over its anionic part for interaction with surrounding water molecules. The properties of AAIL in water solution can be adjusted by varying the ion used and the

  14. 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...

  15. Delineating solute-solvent interactions in binary mixtures of ionic liquids in molecular solvents and preferential solvation approach.

    PubMed

    Khupse, Nageshwar D; Kumar, Anil

    2011-02-01

    The effect of solute-solvent and solvent-solvent interactions on the preferential solvation of solvatochromic indicators in binary mixtures of ionic liquids with molecular solvents has been investigated. The binary mixtures of the pyridinium-based ionic liquids 1-butylpyridinium tetrafluoroborate ([BP][BF4]), 1-butyl-3-methylpyridinium tetrafluoroborate ([3-MBP][BF4]), and 1-butyl-4-methylpyridinium tetrafluoroborate ([4-MBP][BF4]) with molecular solvents like water, methanol, and dichloromethane have been selected for this investigation. The effect of addition of ionic liquids to molecular solvents on the polarity parameters E(T)(N), Kamlet-Taft parameters, hydrogen bond donor ability (HBD) (α), hydrogen bond acceptor ability (HBA) (β), and polarizability (π*) was obtained. The polarity parameters of the mixture display nonideality on addition of ionic liquids to water and dichloromethane. On the other hand, strong synergetic effects were seen in the ionic liquid-methanol binary mixtures. The preferential solvation models have been employed to analyze the collected data in order to achieve information on solute-solvent interactions in these binary mixtures. PMID:21142058

  16. Pairing mechanism among ionic liquid ions in aqueous solutions. A molecular dynamics study

    SciTech Connect

    Annapureddy, Harsha V.; Dang, Liem X.

    2013-07-18

    In this study, we carried out molecular dynamics simulations to examine the molecular mechanism for ionic liquid pair association in aqueous solutions. We chose the commonly studied imidazolium-based ionic liquid pairs. We computed potentials of mean force (PMF) for four systems—1,3-dimethlylimidazoliumchloride; 1,3-dimethlylimidazolium iodide; 1-methly-3-octylimidazolium chloride; and 1-methly-3-octylimidazolium iodide. Our PMF studies show a stronger interaction for the ion pairs of systems involving dimethlylimidazolium as the cation species compared to that of the systems containing octylimidazolium. This result indicates a decrease in ion-pair association as the cation alkyl tail length increases. We also studied the kinetics of ion-pair dissociation using different rate theories such as the Grote-Hynes and Kramer’s theories. As expected, the computed rate results significantly deviated from results obtained from transition state theory because it does not account for dynamical solvent effects. Dissociative barrier curvatures are found to be very small for the systems investigated because the transmission coefficients computed using Grote-Hynes theory and Kramer’s theory are approximately equal. Our analysis of the rotational dynamics of cations revealed that the time scales for molecular reorientation are longer for cations with longer alkyl tails. This work was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is a multiprogram national laboratory operated for DOE by Battelle. The calculations were carried out using computer resources provided by BES.

  17. Solvent extraction of lanthanides and yttrium from aqueous solution with methylimidazole in an ionic liquid.

    PubMed

    Shen, Yinglin; Li, Wenkui; Wu, Jianrong; Li, Shun; Luo, Huimin; Dai, Sheng; Wu, Wangsuo

    2014-07-14

    1-Methylimidazole (1-MIM) and 2-methylimidazole (2-MIM) are miscible in water and imidazolium based ionic liquids (ILs), and can coordinate with soft metal ions. This paper reports a novel solvent extraction process for trivalent lanthanides and yttrium from aqueous solutions into ILs, which was promoted by a hydrophilic 1-MIM or 2-MIM. Slope analysis confirmed that MIM in ILs formed a 1 : 1 complex with La(3+) and Y(3+) and a 1 : 4 complex with Eu(3+) and Lu(3+), depending on the atomic number of the metal and the metal-ligand interactions that have been characterized by FTIR spectroscopy and ESI-MS. The effect of nitrate concentration on the extraction of lanthanides with 1-MIM in ILs was analysed. It indicated that nitrate anions were involved in the extraction process. Under the same conditions, the extraction of lanthanides with MIM into n-pentanol was carried out. The extractability was by far lower than that obtained in ILs. Both cationic exchange and neutral solvation mechanisms occurred in ILs and only the neutral solvation mechanism occurred in n-pentanol, which were demonstrated by the extraction tests and the structure of extracted species determined by ESI-MS. The competitive extraction in ILs showed good selectivity for lanthanides compared to alkali metals and alkaline earth cations. After extraction, lanthanides could be stripped very easily from the ionic liquid phase with dilute nitric acid. From the temperature dependence data, the thermodynamic parameter values (ΔH, ΔS and ΔG) were calculated. The results indicated that the extraction reactions were spontaneous and went through an endothermic process. PMID:24854623

  18. Crafting Elegant Solutions: Strategies for Conflict Resolution.

    ERIC Educational Resources Information Center

    Koch, Susan J.; Decker, Robert H.

    1993-01-01

    The conflict-resolution technique of interpersonal negotiation involves five steps: (1) state your positive intentions; (2) define, analyze, and discuss the problem; (3) summarize progress; (4) explore alternative solutions; and (5) set a time for follow-up. (MLF)

  19. Role of specific interactions on the rotational diffusion of organic solutes in a protic ionic liquid-propylammonium nitrate.

    PubMed

    Karve, Lalita; Dutt, G B

    2012-08-01

    Rotational diffusion of two pairs of structurally similar organic solutes has been examined in a protic ionic liquid, n-propylammonium nitrate (PAN), to understand the influence of specific interactions on solute rotation. It has been observed that the rotation of the nondipolar solute, 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP) in PAN is 30-50% slower compared to its structurally similar counterpart 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP). Analysis of the data using Stokes-Einstein-Debye hydrodynamic theory indicates that the measured reorientation times of DMDPP and DPP are between the stick and slip limits. Furthermore, the rotation of the hydrogen bond accepting solute DMDPP was found to be 60% slower compared to the predictions of slip hydrodynamics, which has been rationalized on the basis of specific interactions between the solute and n-propylammonium cation of the ionic liquid. DPP, on the other hand, experiences specific interactions with both the anion and the cation of the ionic liquid due to the presence of hydrogen bond donating as well as accepting groups, resulting in slower rotation compared to DMDPP. The reorientation times of the ionic solutes fluorescein (FL) and rhodamine 110 (R110) are almost identical and closer to the predictions of stick hydrodynamics. The observed behavior is a consequence of the anionic solute FL and the cationic solute R110 experiencing hydrogen bonding interactions with n-propylammonium cation and nitrate anion, respectively. An attempt has also been made to rationalize these trends in terms of hydrogen bond acidity and basicity of PAN with the aid of existing scales, such as Kamlet-Taft and the Abraham model. PMID:22755511

  20. Rotational diffusion of neutral and charged solutes in 1-butyl-3-methylimidazolium-based ionic liquids: influence of the nature of the anion on solute rotation.

    PubMed

    Karve, Lalita; Dutt, G B

    2012-02-16

    Temperature-dependent fluorescence anisotropies of two organic solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and rhodamine 110 (R110), have been measured in 1-butyl-3-methylimidazolium ([bmim(+)])-based ionic liquids containing the anions hexafluorophosphate ([PF(6)(-)]), bis(trifluoromethylsulfonyl)imide ([Tf(2)N(-)]), tetrafluoroborate ([BF(4)(-)]), trifluoromethanesulfonate ([TfO(-)]), and nitrate ([NO(3)(-)]). This data has been used in conjunction with the recently published results (Dutt, G. B. J. Phys. Chem. B2010, 114, 8971) for the same solutes in [bmim(+)] tris(pentafluoroethyl)trifluorophosphate ([FAP(-)]) to understand the influence of various anions on solute rotation. The boundary condition parameter C(obs), which has been obtained from the analysis of the data using Stokes-Einstein-Debye hydrodynamic theory, for the neutral solute DMDPP is more or less the same in all the ionic liquids. Moreover, C(obs) values are close to the predictions of slip boundary condition, which indicates that solvent viscosity alone governs the rotation of DMDPP. In contrast, for R110, which experiences specific interactions with the anions of the ionic liquids, the C(obs) values are close to stick hydrodynamics. It has also been noticed that the C(obs) values vary with the nature of the anion and this variation correlates with the hydrogen bond basicities of the anions of the ionic liquids. PMID:22233259

  1. Photodegradation mechanism and rate improvement of chlorinated aromatic dye in non-ionic surfactant solutions.

    PubMed

    Ma, C W; Chu, W

    2001-07-01

    A typical insoluble chlorinated aromatic dye (CAD), disperse red (DR), was used to explore the reaction mechanism and kinetics of photodegradation in non-ionic surfactant solutions. The use of an additional hydrogen source and photosensitizer is also studied to improve the decay rates. The decay rate of dye in surfactants depends on the Km of surfactants and their ability to offering an effective hydrogen source. The photodegradation of CAD can be divided into three stages: the initial lag stage. the fast degradation stage and the final retardation stage. The lag stage will vanish and the decay rates of dye can be greatly improved by 2.5-3.6 times after adding an additional hydrogen source (NaBH4) or photosensitizer (acetone) to the surfactant micellar solution. However, the use of an additional hydrogen source or photosensitizer has dosage limitations in such applications. The photoreduction of DR is the main reaction mechanism, in which photodechlorination is observed first with the generation of HCI as the final product, then followed by photodecolorization by breaking the azo bond of the chromophore. PMID:11394780

  2. Influence of Solute Charge and Pyrrolidinium Ionic Liquid Alkyl Chain Length on Probe Rotational Reorientation Dynamics

    SciTech Connect

    Guo, Jianchang; Mahurin, Shannon Mark; Baker, Gary A; Hillesheim, Patrick C; Dai, Sheng; Shaw, Robert W

    2014-01-01

    In recent years, the effect of molecular charge on the rotational dynamics of probe solutes in room temperature ionic liquids (RTILs) has been a subject of growing interest. For the purpose of extending our understanding of charged solute behavior within RTILs, we have studied the rotational dynamics of three illustrative xanthene fluorescent probes within a series of N-alkylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Cnmpyr][Tf2N]) RTILs with different n-alkyl chain lengths (n = 3, 4, 6, 8, or 10) using time-resolved fluorescence anisotropy decay. The rotational dynamics of the neutral probe rhodamine B dye lies between the stick and slip boundary conditions due to the influence of specific hydrogen bonding interactions. The rotation of the negatively-charged sulforhodamine 640 is slower than that of its positively-charged counterpart rhodamine 6G. An analysis based upon Stokes-Einstein-Debye hydrodynamics indicates that SR640 adheres to stick boundary conditions due to specific interactions, whereas the faster rotation of R6G is attributed to weaker electrostatic interactions. No dependence of the rotational dynamics on the solvent alkyl chain length was observed for any of the three dyes, suggesting that the specific interactions between dyes and RTILs are independent of this solvent parameter.

  3. Reorientational dynamics of charged and neutral solutes in 1-alkyl-3-methylimidazoilum bis(trifluoromethylsulfonyl)imide ionic liquids: Realization of ionic component of hydrogen bond

    NASA Astrophysics Data System (ADS)

    Sahu, Prabhat Kumar; Sarkar, Moloy

    2016-05-01

    Role of electrostatic interaction on rotational relaxation dynamics of two charged solutes, sodium 8-methoxypyrene-1,3,6-trisulfonate (MPTS), 1-pyrenesulfonic acid sodium salt (1-PSA) and neutral perylene has been studied in two structurally similar but chemically distinguishable imidazolium-based ionic liquids (ILs). Analysis of the results reveals that rotational relaxation of MPTS is significantly hindered even in the IL where acidic C2-H of the imidazolium moiety is replaced by the methyl group. Moreover, rotational relaxation of neutral perylene is found to be faster than mononegative 1-PSA which is again observed to be faster than that of tri-negative MPTS in the same ILs.

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

    PubMed

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

    2010-11-25

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

  5. Effect of solution temperature, pH and ionic strength on dye adsorption onto Magellanic peat.

    PubMed

    Sepulveda, Luisa Antonia; Santana, Cesar Costapinto

    2013-01-01

    The aim of this research was to study the effect of the solution temperature, pH and ionic strength on the adsorption of the Basic Blue 3 (BB3) and Acid Black 1 (AB1) dyes in Magellanic peat. The peat used was physically characterized as fibrous, of low decomposition level, without the presence of crystalline material and with a highly porous morphology. The functional groups with major concentration in the surface adsorbent were the carboxylics and phenolics, with values of 0.91 and 0.47 mmol/g, respectively. The results of the batch assays showed that the adsorption of the AB1 dye was strongly dependent of electrical charge density on the surface, contrary to what occurred to the BB3 dye, because the interactions between the dyes and carboxylic groups of the peat could be either electrostatic or non-electrostatic. The Langmuir, Freundlich and Sips isotherm models were fitted to the experimental data; among them, the Sips model presented the best adjustment quality. The maximum adsorption capacities for BB3 and AB1 dyes were 33.1 and 33.7 mg/g, respectively. The adsorption of BB3 dye onto Magellan peat has an exothermic behaviour, obtaining an adsorption enthalpy of -3.44 kJ/mol. Contrarily the adsorption of AB1 has an adsorption enthalpy of 56.76 kJ/mol. PMID:23837348

  6. The Amphiphilic Character of Cellulose Molecules in True Solution in Solvent Mixtures Containing Ionic Liquid and its Utilization in Emulsification

    NASA Astrophysics Data System (ADS)

    Napso, Sofia; Cohen, Yachin; Rein, Dmitry; Khalfin, Rafail; Szekely, Noemi

    2015-03-01

    Cellulose is the most abundant renewable material in nature that is utilized as a raw material for fabrication of synthetic products. Although it is not soluble in common solvents, there is significant interest in the use of solvent mixtures containing ionic liquids (IL) and polar organic solvents for cellulose dissolution. We present evidence for true molecular dissolution of cellulose in binary mixtures of common polar organic solvents with an ionic liquid, using cryogenic transmission electron microscopy, small-angle neutron-, x-ray- and static light scattering. In particular, the measured low values of the molecular, gyration radius and persistence length indicate the absence of significant aggregation of the dissolved chains. We conjecture that the dissolved cellulose chains are amphiphilic. This can be inferred from the facile fabrication of cellulose-encapsulated colloidal oil-in-water or water-in-oil dispersions. This may be done by mixing water, oil and cellulose solution in an ionic liquid. A more practical alternative is to form first a hydrogel from the cellulose/ionic liquid solution by coagulation with water and applying it to sonicated water/oil or oil/water mixtures. Apparently the dissolution/ regeneration process affords higher mobility to the cellulose molecules so an encapsulation coating can be formed at the water-oil interface.

  7. Where are ionic liquid strategies most suited in the pursuit of chemicals and energy from lignocellulosic biomass?

    PubMed

    Sun, Ning; Rodríguez, Héctor; Rahman, Mustafizur; Rogers, Robin D

    2011-02-01

    Certain ionic liquids have been shown to dissolve cellulose, other biopolymers, and even raw biomass under relatively mild conditions. This particular ability of some ionic liquids, accompanied by a series of concurrent advantages, enables the development of improved processing strategies for the manufacturing of a plethora of biopolymer-based advanced materials. The more recent discoveries of dissolution of lignocellulosic materials (e.g., wood) in ionic liquids, with at least partial separation of the major constituent biopolymers, suggest further paths towards the achievement of a truly sustainable chemical and energy economy based on the concept of a biorefinery which provides chemicals, materials, and energy. Nonetheless, questions remain about the use of ionic liquids and the advisability of introducing any new process which utilizes bulk synthetic chemicals which have to be made, disposed of, and prevented from entering the environment. In this article, we discuss our own journey from the discovery of the dissolution of cellulose in ionic liquids to the cusp of an enabling technology for a true biorefinery and consider some of the key questions which remain. PMID:21170465

  8. Optimality criteria solution strategies in multiple constraint design optimization

    NASA Technical Reports Server (NTRS)

    Levy, R.; Parzynski, W.

    1981-01-01

    Procedures and solution strategies are described to solve the conventional structural optimization problem using the Lagrange multiplier technique. The multipliers, obtained through solution of an auxiliary nonlinear optimization problem, lead to optimality criteria to determine the design variables. It is shown that this procedure is essentially equivalent to an alternative formulation using a dual method Lagrangian function objective. Although mathematical formulations are straight-forward, successful applications and computational efficiency depend upon execution procedure strategies. Strategies examined, with application examples, include selection of active constraints, move limits, line search procedures, and side constraint boundaries.

  9. Using UCST Ionic Liquid as a Draw Solute in Forward Osmosis to Treat High-Salinity Water.

    PubMed

    Zhong, Yujiang; Feng, Xiaoshuang; Chen, Wei; Wang, Xinbo; Huang, Kuo-Wei; Gnanou, Yves; Lai, Zhiping

    2016-01-19

    The concept of using a thermoresponsive ionic liquid (IL) with an upper critical solution temperature (UCST) as a draw solute in forward osmosis (FO) was successfully demonstrated here experimentally. A 3.2 M solution of protonated betaine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf2N]) was obtained by heating and maintaining the temperature above 56 °C. This solution successfully drew water from high-salinity water up to 3.0 M through FO. When the IL solution cooled to room temperature, it spontaneously separated into a water-rich phase and an IL-rich phase: the water-rich phase was the produced water that contained a low IL concentration, and the IL-rich phase could be used directly as the draw solution in the next cycle of the FO process. The thermal stability, thermal-responsive solubility, and UV-vis absorption spectra of the IL were also studied in detail. PMID:26649525

  10. First observation of rich lamellar structures formed by a single-tailed amphiphilic ionic liquid in aqueous solutions.

    PubMed

    Shi, Lijuan; Wei, Ying; Sun, Nan; Zheng, Liqiang

    2013-12-18

    It was found for the first time that rich lamellar structures are formed by a single-tailed amphiphilic ionic liquid (IL), 1-dodecyl-3-methylimidazolium β-naphthalene sulfonate ([C12mim][Nsa]), in aqueous solutions without any additives. With increasing IL concentration, spontaneous transition from micelles to unilamellar and multilamellar vesicles, planar bilayers, and then to lamellar liquid crystals occurs. PMID:24166649

  11. Coagulation of chitin and cellulose from 1-ethyl-3-methylimidazolium acetate ionic-liquid solutions using carbon dioxide.

    PubMed

    Barber, Patrick S; Griggs, Chris S; Gurau, Gabriela; Liu, Zhen; Li, Shan; Li, Zengxi; Lu, Xingmei; Zhang, Suojiang; Rogers, Robin D

    2013-11-18

    Chemisorption of carbon dioxide by 1-ethyl-3-methylimidazolium acetate ([C2 mim][OAc]) provides a route to coagulate chitin and cellulose from [C2 mim][OAc] solutions without the use of high-boiling antisolvents (e.g., water or ethanol). The use of CO2 chemisorption as an alternative coagulating process has the potential to provide an economical and energy-efficient method for recycling the ionic liquid. PMID:24115399

  12. Lower critical solution temperature (LCST) phase behaviour of an ionic liquid and its control by supramolecular host-guest interactions.

    PubMed

    Dong, Shengyi; Heyda, Jan; Yuan, Jiayin; Schalley, Christoph A

    2016-06-28

    Lower critical solution temperature (LCST) phase behaviour of an imidazolium-based ionic liquid is reported, which can be controlled by concentration, the choice of cation, anion and solvent, and by supramolecular host-guest complex formation. Molecular dynamics simulations provide insight into the molecular basis of this LCST phenomenon. This thermo-responsive system has potential applications in cloud point extraction processes. PMID:27253850

  13. Doped ionic liquid crystals as effective weakly alignment media for polar solutes

    NASA Astrophysics Data System (ADS)

    Di Pietro, Maria Enrica; Celebre, Giorgio; De Luca, Giuseppina

    2016-06-01

    The ionic liquid crystal 1-dodecyl-3-methylimidazolium tetrafluoroborate slightly doped with water is presented as a promising NMR alignment medium for the measurement of residual dipolar couplings for polar molecules dissolved therein.

  14. Doped ionic liquid crystals as effective weakly alignment media for polar solutes.

    PubMed

    Di Pietro, Maria Enrica; Celebre, Giorgio; De Luca, Giuseppina

    2016-06-01

    The ionic liquid crystal 1-dodecyl-3-methylimidazolium tetrafluoroborate slightly doped with water is presented as a promising NMR alignment medium for the measurement of residual dipolar couplings for polar molecules dissolved therein. PMID:27128198

  15. Structure and dynamics of POPC bilayers in water solutions of room temperature ionic liquids

    SciTech Connect

    Benedetto, Antonio; Bingham, Richard J.; Ballone, Pietro

    2015-03-28

    Molecular dynamics simulations in the NPT ensemble have been carried out to investigate the effect of two room temperature ionic liquids (RTILs), on stacks of phospholipid bilayers in water. We consider RTIL compounds consisting of chloride ([bmim][Cl]) and hexafluorophosphate ([bmim][PF{sub 6}]) salts of the 1-buthyl-3-methylimidazolium ([bmim]{sup +}) cation, while the phospholipid bilayer is made of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). Our investigations focus on structural and dynamical properties of phospholipid and water molecules that could be probed by inelastic and quasi-elastic neutron scattering measurements. The results confirm the fast incorporation of [bmim]{sup +} into the lipid phase already observed in previous simulations, driven by the Coulomb attraction of the cation for the most electronegative oxygens in the POPC head group and by sizeable dispersion forces binding the neutral hydrocarbon tails of [bmim]{sup +} and of POPC. The [bmim]{sup +} absorption into the bilayer favours the penetration of water into POPC, causes a slight but systematic thinning of the bilayer, and further stabilises hydrogen bonds at the lipid/water interface that already in pure samples (no RTIL) display a lifetime much longer than in bulk water. On the other hand, the effect of RTILs on the diffusion constant of POPC (D{sub POPC}) does not reveal a clearly identifiable trend, since D{sub POPC} increases upon addition of [bmim][Cl] and decreases in the [bmim][PF{sub 6}] case. Moreover, because of screening, the electrostatic signature of each bilayer is only moderately affected by the addition of RTIL ions in solution. The analysis of long wavelength fluctuations of the bilayers shows that RTIL sorption causes a general decrease of the lipid/water interfacial tension and bending rigidity, pointing to the destabilizing effect of RTILs on lipid bilayers.

  16. Ionic liquids by proton transfer: vapor pressure, conductivity, and the relevance of DeltapKa from aqueous solutions.

    PubMed

    Yoshizawa, Masahiro; Xu, Wu; Angell, C Austen

    2003-12-17

    We describe the behavior of the conductivity, viscosity, and vapor pressure of various binary liquid systems in which proton transfer occurs between neat Brönsted acids and bases to form salts with melting points below ambient. Such liquids form an important subgroup of the ionic liquid (IL) class of reaction media and electrolytes on which so much attention is currently being focused. Such "protic ionic liquids" exhibit a wide range of thermal stabilities. We find a simple relation between the limit set by boiling, when the total vapor pressure reaches one atm, and the difference in pK(a) value for the acid and base determined in dilute aqueous solutions. For DeltapK(a) values above 10, the boiling point elevation becomes so high (>300 degrees C) that preemptive decomposition prevents its measurement. The completeness of proton transfer in such cases is suggested by the molten salt-like values of the Walden product, which is used to distinguish good from poor ionic liquids. For the good ionic liquids, the hydrogen bonding of acid molecules to the proton-transfer anion is strong enough that boiling points, but not melting points, may maximize at the hydrogen-bonded dianion composition. High boiling liquids of this type constitute an interesting class of high-temperature protonic acid that may have high-temperature fuel cell applications. PMID:14664586

  17. Fast solute diffusivity in ionic liquids with silyl or siloxane groups studied by the transient grating method

    NASA Astrophysics Data System (ADS)

    Endo, Takatsugu; Nemugaki, Shinya; Matsushita, Yuki; Sakai, Yasuhiro; Ozaki, Hiroaki; Hiejima, Yusuke; Kimura, Yoshifumi; Takahashi, Kenji

    2016-06-01

    To achieve ionic liquids (ILs) that show fast solute diffusivity independent of viscosity domination, sixteen ILs containing Si or Si-O-Si groups (SiILs) were synthesized. Diffusion coefficients of three solute molecules with different molecular sizes, i.e., CO, diphenylacetylene, and diphenylcyclopropenone, were determined in SiILs using the transient grating method and the results were compared to other solvent system. SiILs showed distinguishably faster diffusivity for the smallest solute, CO, than conventional ILs at the same viscosity, particularly in the high viscosity region. Based on previous results and our estimation, three plausible factors exists that contribute to the faster solute diffusivity in SiILs, i.e., the flexibility of the Si or Si-O-Si group, decreased interaction between the cation and the solute, and increased free volume because of the bulky structure.

  18. Concentration dependence of ionic conductance measured with ion-selective sub-micro pipette probes in aqueous sodium and potassium chloride solutions

    NASA Astrophysics Data System (ADS)

    Son, J. W.; Takami, T.; Lee, J.-K.; Kawai, T.; Park, B. H.

    2011-07-01

    Selective ionic currents in aqueous sodium and potassium chloride solutions with concentrations from 0.01 M to 1.0 M were measured using sub-micro pipette probes in which a poly(vinyl chloride) film containing crown ethers selectively filtered sodium or potassium ions. The selective ionic currents were monitored with a sub-picoampere current measurement system developed from the techniques of TΩ-gap impedance scanning tunneling microscopy. The ionic currents increased with the concentration of the corresponding solution, and thus these sub-micro pipette probes can be applied to detect local ionic concentration of a specific ion in living cells with ionic concentration higher than 0.1 M.

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

    SciTech Connect

    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 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.

  20. Solubilisation of myosin in a solution of low ionic strength L-histidine: Significance of the imidazole ring.

    PubMed

    Chen, Xing; Zou, Yufeng; Han, Minyi; Pan, Lihua; Xing, Tong; Xu, Xinglian; Zhou, Guanghong

    2016-04-01

    Myosin, a major muscle protein, can be solubilised in a low ionic strength solution containing L-histidine (His). To elucidate which chemical constituents in His are responsible for this solubilisation, we investigated the effects of 5mM His, imidazole (Imi), L-α-alanine (Ala), 1-methyl-L-histidine (M-his) and L-carnosine (Car) on particle properties of myosin suspensions and conformational characteristics of soluble myosin at low ionic strength (1 mM KCl, pH 7.5). His, Imi and Car, each containing an imidazole ring, were able to induce a myosin suspension, which had small particle size species and high absolute zeta potential, thus increasing the solubility of myosin. His, Imi and Car affected the tertiary structure and decreased the α-helix content of soluble myosin. Therefore, the imidazole ring of His appeared to be the significant chemical constituent in solubilising myosin at low ionic strength solution, presumably by affecting its secondary structure. PMID:26593463

  1. 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. PMID:27311506

  2. The solvent dependence of ionic properties in solution in the limit of infinite dilution

    NASA Astrophysics Data System (ADS)

    Fawcett, W. Ronald

    1998-10-01

    The dependence of the Gibbs solvation energy and limiting ionic conductance for simple ions on the solvent nature is discussed for a collection of data in 18 polar solvents both protic and aprotic. It is shown that the Gibbs solvation energy depends on the acidity and basicity of the solvent, concepts based on a detailed quantum mechanical description of the solvent molecule and its interaction with ions in its vicinity. On the other hand, ionic mobility, after correction for solvent viscosity, depends on the size of the surrounding molecules, and to a lesser extent on their acid-base properties.

  3. Simulation of ionic surfaces from an absolutely convergent solution of the Madelung problem

    SciTech Connect

    Wolf, D.

    1995-04-01

    The classic Madelung problem is cast into an absolutely convergent form that is readily evaluated by direct lattice summation, revealing a net r{sup {minus}5} range of the net Coulomb potential in ionic crystals and liquids. The realization that Coulomb interactions in condensed systems can actually be rather short ranged (provided the system is overall neutral) leads to the prediction, verified by computer simulations for rocksalt-structure surfaces, that all surfaces in predominantly ionic crystals should be fundamentally reconstructed. The work also provides a conceptual framework for the theoretical treatment of polar surfaces, as demonstrated for the case of the (111) surfaces of NaCl and MgO.

  4. Thin liquid films from aqueous solutions of non-ionic polymeric surfactants.

    PubMed

    Exerowa, Dotchi; Platikanov, Dimo

    2009-01-01

    The conditions of formation and stability of foam, emulsion, and wetting films from aqueous solutions of non-ionic polymeric surfactants have been established. Two types of polymeric surfactants - PEO-PPO-PEO three-block copolymers (A-B-A type) and hydrophobically modified inulin graft polymer (AB(n) type) - have been explored. Information about surface forces and nanoscale phenomena in aqueous films containing polymeric surfactants was obtained using the micro-interferometric technique and the Thin Liquid Film-Pressure Balance Technique. Two types of surface forces, which determine the stability of the foam and emulsion films, have been distinguished, namely: DLVO-forces at low electrolyte concentrations and non-DLVO-forces at high electrolyte concentrations. Non-DLVO-forces are steric surface forces of the brush-to-brush and loop-to-loop interaction type according to De Gennes. A substantial difference in the behavior of these two film types has been established and in the case of O/W emulsion films transitions to Newton black film (NBF) have been observed. These films are very stable and so are the respective emulsions. In contrast the wetting films are relatively thicker compared to emulsion films, and their thickness depends on the concentration of the AB(n) polymeric surfactant. The steric repulsion of the loops and tails of the polymeric surfactant determine the film thickness of wetting films on a hydrophilic solid surface. For solid surfaces with different degrees of hydrophobicity the wetting films are stable only at high polymer concentrations and low degree of hydrophobicity. Otherwise the films are unstable and rupture. Two types of bilayer emulsion films have been distinguished for the first time. One type is related to the brush-to-brush or loop-to-loop interactions according to De Gennes. The other type is a NBF where the forces are also steric between strongly hydrated brush and loops but they are short-range forces acting in a two

  5. Manipulation of ionic liquid anion-solute-antisolvent interactions for the purification of acetaminophen.

    PubMed

    Weber, C C; Kunov-Kruse, A J; Rogers, R D; Myerson, A S

    2015-03-11

    Hydrogen bond donating cosolvents have been shown to significantly reduce the solubility of acetaminophen (AAP) in ionic liquids containing the acetate anion. Reduced solubility arises from competition for solvation by the acetate anion and can be used for the design of advanced separation techniques, illustrated by the crystallization of AAP. PMID:25673089

  6. An elastic rod model to evaluate effects of ionic concentration on equilibrium configuration of DNA in salt solution.

    PubMed

    Xiao, Ye; Huang, Zaixing; Wang, Shengnan

    2014-03-01

    As a coarse-gained model, a super-thin elastic rod subjected to interfacial interactions is used to investigate the condensation of DNA in a multivalent salt solution. The interfacial traction between the rod and the solution environment is determined in terms of the Young-Laplace equation. Kirchhoff's theory of elastic rod is used to analyze the equilibrium configuration of a DNA chain under the action of the interfacial traction. Two models are established to characterize the change of the interfacial traction and elastic modulus of DNA with the ionic concentration of the salt solution, respectively. The influences of the ionic concentration on the equilibrium configuration of DNA are discussed. The results show that the condensation of DNA is mainly determined by competition between the interfacial energy and elastic strain energy of the DNA itself, and the interfacial traction is one of forces that drive DNA condensation. With the change of concentration, the DNA segments will undergo a series of alteration from the original configuration to the condensed configuration, and the spiral-shape appearing in the condensed configuration of DNA is independent of the original configuration. PMID:24691983

  7. Studies of laccase from Trametes versicolor in aqueous solutions of several methylimidazolium ionic liquids.

    PubMed

    Domínguez, Alberto; Rodríguez, Oscar; Tavares, Ana Paula M; Macedo, Eugenia A; Longo, María Asunción; Sanromán, María Angeles

    2011-08-01

    Stability and kinetic behavior of laccase from Trametes versicolor in the presence of several ionic liquids from the methylimidazolium family have been investigated. In general laccase stability diminished as the size of the alkylic substitute in the methylimidazolium ring increased. Higher concentrations of ionic liquids caused more destabilization than lower ones. Thus, low concentrations of [C(2)mim(+)][EtSO(4)(-)] allowed maintaining enzymatic stability. [C(4)mim(+)][Cl(-)] appeared to have a stabilizing effect on laccase, as little activity decay was observed within three weeks. Kinetic studies indicated that both [C(2)mim(+)][EtSO(4)(-)] and [C(4)mim(+)][Cl(-)] inhibited laccase activity, although 10-fold more [C(2)mim(+)][EtSO(4)(-)] than [C(4)mim(+)][Cl(-)] was required to cause the same degree of inhibition. A kinetic model was developed to represent the experimental data. PMID:21669518

  8. Effect of Oxygen-containing Functional Groups on Protein Stability in Ionic Liquid Solutions

    NASA Technical Reports Server (NTRS)

    Turner, Megan B.; Holbrey, John D.; Spear, Scott K.; Pusey, Marc L.; Rogers, Robin D.

    2004-01-01

    The ability of functionalized ionic liquids (ILs) to provide an environment of increased stability for biomolecules has been studied. Serum albumin is an inexpensive, widely available protein that contributes to the overall colloid osmotic blood pressure within the vascular system. Albumin is used in the present study as a marker of biomolecular stability in the presence of various ILs in a range of concentrations. The incorporation of hydroxyl functionality into the methylimidazolium-based cation leads to increased protein stability detected by fluorescence spectroscopy and circular dichroic (CD) spectrometry.

  9. Structure of ionic interfaces from an absolutely convergent solution of the Madelung problem

    SciTech Connect

    Wolf, D.

    1994-09-01

    The classic Madelung problem, i.e., the divergence associated with the r{sup -1} term in the Coulomb potential of condensed ionic systems, was cast into an absolutely convergent form that is readily evaluated by direct lattice summation, revealing a net r{sup -5} range of this potential. The realization that Coulomb interactions in condensed systems can actually be rather short ranged (if the system is overall neutral) permits novel physical insights into their structure and energetics to be gained. As an example, it was demonstrated that an understanding of the range and the nature of the convergence of the Coulomb potential leads naturally to the prediction, verified by computer simulations for rocksalt-structured surfaces, that all surfaces in predominantly ionic materials should be fundamentally reconstructed. The work also provides a conceptual framework for the theoretical treatment of polar surfaces and interfaces, as demonstrated for the case of the (111) stacking fault and of the (111) twin boundary in the rocksalt structure.

  10. Phase equilibria and modeling of ammonium ionic liquid, C2NTf2, solutions.

    PubMed

    Domańska, Urszula; Marciniak, Andrzej; Królikowski, Marek

    2008-01-31

    Novel quaternary ammonium ionic liquid, ethyl(2-hydroxyethyl)dimethylammonium bis(trifluomethylsulfonyl)imide (C2NTf2), has been prepared from N,N-dimethylethanolamine as a substrate. The paper includes a specific basic characterization of the synthesized compound by NMR and the basic thermophysical properties: the melting point, enthalpy of fusion, enthalpy of solid-solid phase transition, glass transition determined by the differential scanning calorimetry (DSC), temperature of decomposition, and water content. The density of the new compound was measured. The solid-liquid or liquid-liquid phase equilibria of binary mixtures containing {C2NTf2+water or an alcohol (propan-1-ol, butan-1-ol, hexan-1-ol, octan-1-ol, decan-1-ol), aromatic hydrocarbons (benzene, toluene), aliphatic hydrocarbons (n-hexane, n-octane), dimethylsulfoxide (DMSO), or tetrahydrofuran (THF)} have been measured by a dynamic method in a wide range of temperatures from 230 to 430 K. These data were correlated by means of the nonrandom two-liquid (NRTL) equation utilizing temperature-dependent parameters derived from the solid-liquid or liquid-liquid equilibrium. From the solubility results, the negative value of the partition coefficient of ionic liquid in binary system octan-1-ol/water (log P) at 298.15 K has been calculated. PMID:18179194

  11. Thermal stability and immersion solution dependence of second-order nonlinear optical ionically self-assembled films

    NASA Astrophysics Data System (ADS)

    Figura, Charles; Neyman, Patrick J.; Marciu, Daniela; Brands, Charles; Murray, Mandy A.; Hair, Steve; Davis, Rick M.; Miller, Michael B.; Heflin, James R.

    2000-05-01

    Polymeric films fabricated from ionically self-assembled monolayers (ISAMs) spontaneously from in a noncentrosymmetric structure requisite for a nonzero second order nonlinear optical (NLO) susceptibility, (chi) (2), without the need for electric field poling. ISAM NLO films exhibit excellent long-term temporal stability of (chi) (2), having shown no decay over a period of nearly three years. They are also remarkably stable at elevated temperatures. While (chi) (2) decreases by 20 percent as the temperature is raised to 150 degrees C, total recovery of the susceptibility is observed upon cooling, demonstrating that the decrease is not due to an irreversible randomization of the chromophore alignment. The thickness, orientational order, and NLO response are found to be strongly dependent on the pH and ionic strength of the solutions form which the films are deposited. The largest (chi) (2) values are observed in films with the smallest bilayer thickness. This suggests that polar orientation is obtained primarily at the interfaces between adjacent layers rather than throughout a full monolayer.

  12. Release and formation of surface-localized ionic clusters (SLICs) into phospholipid rafts from colloidal solutions during coalescence.

    PubMed

    Lestage, David J; Urban, Marek W

    2005-03-15

    Stimuli-responsive behavior of phospholipids in the presence of ionic surfactants utilized in synthesis of MMA/nBA colloidal particles was investigated. Utilizing 1-myristoyl-2-hydroxy-sn-glycero-phosphocholine (MHPC) phospholipid, and sodium dioctyl sulfosuccinate (SDOSS) surfactant as dispersing media in H(2)O, narrow unimodal particle size distributions of methyl methacrylate (MMA)/n-butyl acrylate (nBA) copolymers were synthesized. The particle diameters were 154 nm when a SDOSS/MHPC mixture was used and 161 nm using MHPC as the only surface-stabilizing species. When such colloidal dispersions are exposed to 1.7, 3.3, and 6.7 mM aqueous CaCl(2) and KCl electrolyte solutions, surface-localized ionic clusters are generated at the film-air interface that may serve as lipid rafts composed of crystalline phases of MHPC deposited on poly(MMA)/nBA films. These studies illustrate that it is possible to control release and morphology developments of surface phospholipid rafts on artificial surfaces. PMID:15752001

  13. Convection Induced by High Frequency Rotating Magnetic Field in Ionic Aqueous Solutions

    NASA Technical Reports Server (NTRS)

    Volz, Martin P.; Mazuruk, Konstantin

    2000-01-01

    Rotating magnetic fields (RMF) have found applications in modern metallurgy. Examples are casting and semiconductor crystal growth technology. Rotating convective flows can also be induced in ionic fluids. Due to optical transparency, these fluids offer a great opportunity to visualize convection. In this work, we investigate the dynamics of convection induced by a high frequency (100 kHz range) RMF. A dye injected into a cylindrical column of salty water serves as an indicator of the flow. The developed technique has been used to study mixing phenomena induced by a RMF both when the direc'tion of the field rotation is constant and when it is alternated. Optical recording has been used to analyze this process. A numerical model describing RMF mixing in the laminar regime will also be presented.

  14. Investigation of the colloidal Cr2O3 removal possibilities from aqueous solution using the ionic polyamino acid block copolymers.

    PubMed

    Ostolska, Iwona; Wiśniewska, Małgorzata

    2015-06-15

    Disposal of the environmentally dangerous metal oxide suspensions from the waste water is an essential problem. The polymers adsorption can be one of the most effective and suitable methods. In the presented paper the ionic diblock copolymers impact on the Cr2O3 suspensions was investigated. The copolymer adsorption layers structure was determined on the basis of the adsorption and electrokinetic (surface charge density and zeta potential) tests. The polymers adsorption amount was measured using the static method from aqueous solutions. Additionally, the application of the turbidimetric method enabled determination of the interactions between the system constituents. Analysis of this data allows the estimation of the most probable stabilization (or destabilization) mechanism of the Cr2O3 suspensions in the presence of the studied macromolecular compounds. Hence, the Cr2O3 suspensions are unstable in the presence of the anionic copolymer at pH 3 and the cationic one in the alkaline medium. PMID:25746566

  15. Kinetics of gypsum crystal growth from high ionic strength solutions: A case study of Dead Sea - seawater mixtures

    NASA Astrophysics Data System (ADS)

    Reznik, Itay J.; Gavrieli, Ittai; Antler, Gilad; Ganor, Jiwchar

    2011-04-01

    Gypsum precipitation kinetics were examined from a wide range of chemical compositions (11ionic strengths (4.75-10 m) and saturation state with respect to gypsum (1.16-1.74) in seeded batch experiments of mixtures of Ca 2+-rich Dead Sea brine and SO42--rich seawater. Despite the variability in the experimental solutions, a single general rate law was formulated to describe the heterogeneous precipitation rate of gypsum from these mixtures: Ratehet=k1·(Ω0.5-1)10+k2·(Ω0.5-1)2mol ms, where k1 and k2 are heterogeneous rate coefficients (mol s -1 m -2) that vary as a function of the solution compositions, and is the saturation state with respect to gypsum. It is suggested that two parallel mechanisms control the heterogeneous precipitation rate. Under closer-to-equilibrium conditions, the reaction is dominated by a mechanism best described as a 2nd order reaction with respect to Ω0.5 - 1, which fits to the predictions of both the Burton Cabrera and Frank (BCF) crystal growth theory ( Burton et al., 1951) and other layer-by-layer growth mechanisms ( Goto and Ridge, 1967; Van Rosmalen et al., 1981; Bosbach and Rammensee, 1994). Under further-away-from-equilibrium conditions, the reaction is dominated by an apparent 10th order reaction. A conceptual model for gypsum growth kinetics is presented. The model is based on the 2nd order kinetic coefficients determined in the present study and data from the literature and is valid under a wide range of ionic strengths and Ca/SO42- ratios. According to this model, the integration of SO42- to kinks on the surface of the growing crystals is the rate-limiting step in the precipitation reaction. At ionic strengths above 8.5 m the precipitation rate of gypsum is enhanced, possibly due to the formation of CaSO4° ion pairs and/or a decrease in hydration frequencies.

  16. Does addition of an electrolyte influence the rotational diffusion of nondipolar solutes in a protic ionic liquid?

    PubMed

    Prabhu, Sugosh R; Dutt, G B

    2015-05-21

    Rotational diffusion of two structurally similar nondipolar solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP), has been examined in ethylammonium nitrate-lithium nitrate (EAN-LiNO3) mixtures to understand the influence of added electrolyte on the local environment experienced by the solute molecules. The measured reorientation times of both DMDPP and DPP in EAN-LiNO3 mixtures fall within the broad limits set by the hydrodynamic slip and stick boundary conditions. The hydrogen bond accepting DMDPP and the hydrogen bond donating DPP experience specific interactions with the cation and anion of the ionic liquid, respectively. Addition of LiNO3 (0.1 and 0.2 mole fraction) to EAN induces only viscosity related effects on the rotational diffusion of the two nondipolar solutes. These observations suggest that the local environment experienced by DMDPP and DPP in EAN is not altered upon the addition of LiNO3. Our results are consistent with the structural details available in the literature for EAN-LiNO3 mixtures. PMID:25914928

  17. Optimizing the crowding strategy: sugar-based ionic micelles in the dilute-to-condensed regime.

    PubMed

    Del Favero, Elena; Brocca, Paola; Rondelli, Valeria; Motta, Simona; Raudino, Antonio; Cantu', Laura

    2014-08-01

    In the present study, we explore the effect of concentration on micelles made by different gangliosides, which are ionic biological glycolipids bearing multisugar headgroups with huge steric hindrance. Moreover, strong preferential interactions exist among like-conformer headgroups that can keep the ganglioside micelles in a trapped configuration. We extend the well-known ionic-amphiphiles paradigm, where local condensation and micelle crowding are matched by forming larger aggregates at increasing concentration. In fact, we force the balance between interparticle and intraparticle interactions while allowing for like conformers to modulate rebalancing. In the vast experimental framework, obtained by Small Angle X-ray scattering (SAXS) experiments, a theoretical model, accounting for a collective conformational transition of the bulky headgroups, is developed and successfully tested. It allows us to shed some light on the nature and coupling of the intermolecular forces involved in the interactions among glycolipid micelles. Energy minimization leads to complex behavior of the aggregation number on increasing concentration, fully consistent with the experimental landscape. From a biological perspective, this result could be reflected in the properties of ganglioside-enriched rafts on cell membranes, with a nonlinear structural response to approaching bodies such as charged proteins. PMID:25035176

  18. A general solution strategy of modified power method for higher mode solutions

    NASA Astrophysics Data System (ADS)

    Zhang, Peng; Lee, Hyunsuk; Lee, Deokjung

    2016-01-01

    A general solution strategy of the modified power iteration method for calculating higher eigenmodes has been developed and applied in continuous energy Monte Carlo simulation. The new approach adopts four features: 1) the eigen decomposition of transfer matrix, 2) weight cancellation for higher modes, 3) population control with higher mode weights, and 4) stabilization technique of statistical fluctuations using multi-cycle accumulations. The numerical tests of neutron transport eigenvalue problems successfully demonstrate that the new strategy can significantly accelerate the fission source convergence with stable convergence behavior while obtaining multiple higher eigenmodes at the same time. The advantages of the new strategy can be summarized as 1) the replacement of the cumbersome solution step of high order polynomial equations required by Booth's original method with the simple matrix eigen decomposition, 2) faster fission source convergence in inactive cycles, 3) more stable behaviors in both inactive and active cycles, and 4) smaller variances in active cycles. Advantages 3 and 4 can be attributed to the lower sensitivity of the new strategy to statistical fluctuations due to the multi-cycle accumulations. The application of the modified power method to continuous energy Monte Carlo simulation and the higher eigenmodes up to 4th order are reported for the first time in this paper.

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

    PubMed

    Cui, Guokai; Wang, Jianji; Zhang, Suojiang

    2016-07-25

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

  20. 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...

  1. Influence of Ionic Inorganic Solutes on Self-Assembly and Polymerization Processes Related to Early Forms of Life: Implications for a Prebiotic Aqueous Medium

    NASA Astrophysics Data System (ADS)

    Monnard, Pierre-Alain; Apel, Charles L.; Kanavarioti, Anastassia; Deamer, David W.

    2002-06-01

    A commonly accepted view is that life began in a marine environment, which would imply the presence of inorganic ions such as Na+, Cl-, Mg2+, Ca2+, and Fe2+. We have investigated two processes relevant to the origin of life - membrane self-assembly and RNA polymerization - and established that both are adversely affected by ionic solute concentrations much lower than those of contemporary oceans. In particular, monocarboxylic acid vesicles, which are plausible models of primitive membrane systems, are completely disrupted by low concentrations of divalent cations, such as magnesium and calcium, and by high sodium chloride concentrations as well. Similarly, a nonenzymatic, nontemplated polymerization of activated RNA monomers in ice/eutectic phases (in a solution of low initial ionic strength) yields oligomers with >80% of the original monomers incorporated, but polymerization in initially higher ionic strength aqueous solutions is markedly inhibited. These observations suggest that cellular life may not have begun in a marine environment because the abundance of ionic inorganic solutes would have significantly inhibited the chemical and physical processes that lead to self-assembly of more complex molecular systems.

  2. Impact of ionic liquids in aqueous solution on bacterial plasma membranes studied with molecular dynamics simulations.

    PubMed

    Lim, Geraldine S; Zidar, Jernej; Cheong, Daniel W; Jaenicke, Stephan; Klähn, Marco

    2014-09-01

    The impact of five different imidazolium-based ionic liquids (ILs) diluted in water on the properties of a bacterial plasma membrane is investigated using molecular dynamics (MD) simulations. Cations considered are 1-octyl-3-methylimidazolium (OMIM), 1-octyloxymethyl-3-methylimidazolium (OXMIM), and 1-tetradecyl-3-methylimidazolium (TDMIM), as well as the anions chloride and lactate. The atomistic model of the membrane bilayer is designed to reproduce the lipid composition of the plasma membrane of Gram-negative Escherichia coli. Spontaneous insertion of cations into the membrane is observed in all ILs. Substantially more insertions of OMIM than of OXMIM occur and the presence of chloride reduces cation insertions compared to lactate. In contrast, anions do not adsorb onto the membrane surface nor diffuse into the bilayer. Once inserted, cations are oriented in parallel to membrane lipids with cation alkyl tails embedded into the hydrophobic membrane core, while the imidazolium-ring remains mostly exposed to the solvent. Such inserted cations are strongly associated with one to two phospholipids in the membrane. The overall order of lipids decreased after OMIM and OXMIM insertions, while on the contrary the order of lipids in the vicinity of TDMIM increased. The short alkyl tails of OMIM and OXMIM generate voids in the bilayer that are filled by curling lipids. This cation induced lipid disorder also reduces the average membrane thickness. This effect is not observed after TDMIM insertions due to the similar length of cation alkyl chain and the fatty acids of the lipids. This lipid-mimicking behavior of inserted TDMIM indicates a high membrane affinity of this cation that could lead to an enhanced accumulation of cations in the membrane over time. Overall, the simulations reveal how cations are inserted into the bacterial membrane and how such insertions change its properties. Moreover, the different roles of cations and anions are highlighted and the fundamental

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

    PubMed

    Umapathi, Reddicherla; Attri, Pankaj; Venkatesu, Pannuru

    2014-06-01

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

  4. Colloid release and clogging in porous media: Effects of solution ionic strength and flow velocity.

    PubMed

    Torkzaban, Saeed; Bradford, Scott A; Vanderzalm, Joanne L; Patterson, Bradley M; Harris, Brett; Prommer, Henning

    2015-10-01

    The release and retention of in-situ colloids in aquifers play an important role in the sustainable operation of managed aquifer recharge (MAR) schemes. The processes of colloid release, retention, and associated permeability changes in consolidated aquifer sediments were studied by displacing native groundwater with reverse osmosis-treated (RO) water at various flow velocities. Significant amounts of colloid release occurred when: (i) the native groundwater was displaced by RO-water with a low ionic strength (IS), and (ii) the flow velocity was increased in a stepwise manner. The amount of colloid release and associated permeability reduction upon RO-water injection depended on the initial clay content of the core. The concentration of released colloids was relatively low and the permeability reduction was negligible for the core sample with a low clay content of about 1.3%. In contrast, core samples with about 6 and 7.5% clay content exhibited: (i) close to two orders of magnitude increase in effluent colloid concentration and (ii) more than 65% permeability reduction. Incremental improvement in the core permeability was achieved when the flow velocity increased, whereas a short flow interruption provided a considerable increase in the core permeability. This dependence of colloid release and permeability changes on flow velocity and colloid concentration was consistent with colloid retention and release at pore constrictions due to the mechanism of hydrodynamic bridging. A mathematical model was formulated to describe the processes of colloid release, transport, retention at pore constrictions, and subsequent permeability changes. Our experimental and modeling results indicated that only a small fraction of the in-situ colloids was released for any given change in the IS or flow velocity. Comparison of the fitted and experimentally measured effluent colloid concentrations and associated changes in the core permeability showed good agreement, indicating that the

  5. Solution of the nonlinear Poisson-Boltzmann equation: Application to ionic diffusion in cementitious materials

    SciTech Connect

    Arnold, J.; Kosson, D.S.; Garrabrants, A.; Meeussen, J.C.L.; Sloot, H.A. van der

    2013-02-15

    A robust numerical solution of the nonlinear Poisson-Boltzmann equation for asymmetric polyelectrolyte solutions in discrete pore geometries is presented. Comparisons to the linearized approximation of the Poisson-Boltzmann equation reveal that the assumptions leading to linearization may not be appropriate for the electrochemical regime in many cementitious materials. Implications of the electric double layer on both partitioning of species and on diffusive release are discussed. The influence of the electric double layer on anion diffusion relative to cation diffusion is examined.

  6. NMR Water Self-Diffusion and Relaxation Studies on Sodium Polyacrylate Solutions and Gels in Physiologic Ionic Solutions.

    PubMed

    Bai, Ruiliang; Basser, Peter J; Briber, Robert M; Horkay, Ferenc

    2014-03-15

    Water self-diffusion coefficients and longitudinal relaxation rates in sodium polyacrylate solutions and gels were measured by NMR, as a function of polymer content and structure in a physiological concentration range of monovalent and divalent cations, Ca(2+) and Na(+). Several physical models describing the self-diffusion of the solvent were applied and compared. A free-volume model was found to be in good agreement with the experimental results over a wide range of polymer concentrations. The longitudinal relaxation rate exhibited linear dependence on polymer concentration below a critical concentration and showed non-linear behavior at higher concentrations. Both the water self-diffusion and relaxation were less influenced by the polymer in the gel state than in the uncrosslinked polymer solutions. The effect of Na(+) on the mobility of water molecules was practically undetectable. By contrast, addition of Ca(2+) strongly increased the longitudinal relaxation rate while its effect on the self-diffusion coefficient was much less pronounced. PMID:24409001

  7. Aggregation Behavior of Imidazolium-Based Surface-Active Ionic Liquids with Photoresponsive Cinnamate Counterions in the Aqueous Solution.

    PubMed

    Bi, Yanhui; Zhao, Liuchen; Hu, Qiongzheng; Gao, Yan'an; Yu, Li

    2015-11-24

    Two imidazolium-based surface active ionic liquids (SAILs) with photoresponsive cinnamate aromatic counterions, viz. 1-dodecyl-3-methylimidazolium cinnamate ([C12mim][CA]) and 1-dodecyl-3-methylimidazolium para-hydroxy-cinnamate ([C12mim][PCA]), were newly synthesized, and their self-assembly behaviors in aqueous solutions were systematically explored. Results of surface tension and conductivity measurements show that both [C12mim][CA] and [C12mim][PCA] display a superior surface activity in aqueous solutions compared to the common imidazolium-based SAIL, 1-dodecyl-3-methylimidazolium bromide (C12mimBr), which implies the incorporation of cinnamate aromatic counterions can promote the micellar formation. Furthermore, [C12mim][CA] shows higher surface activity due to the higher hydrophobicity of its counterion in comparison to [C12mim][PCA] that has a hydroxyl group. Both hexagonal liquid-crystalline phase (H1) and cubic liquid-crystalline phase (V2) were constructed in the [C12mim][CA] aqueous solutions. In contrast, the [C12mim][PCA]/H2O system only exhibits a single hexagonal liquid-crystalline phase (H1) in a broad concentration region. These lyotropic liquid crystal (LLC) phases were comprehensively characterized by polarized optical microscopy (POM), small-angle X-ray scattering (SAXS), and rheometer. Investigation on the temperature-dependent self-assembly nanostructures demonstrates that the higher temperature leads to a looser arrangement. Under UV irradiation, trans-cis photoisomerization of the phenylalkene group results in inferior surface activity of the prepared SAILs in aqueous solution with higher cmc values. Moreover, UV light irradiation induces obvious change of the structural parameters without altering the LLC phases. This work is expected to enrich the investigations of phase behaviors formed in SAILs systems and receive particular attention due to their unique properties and potential applications in drug delivery, biochemistry, materials

  8. Effect of low viscous nondipolar solvent on the rotational diffusion of structurally similar nondipolar solutes in an ionic liquid.

    PubMed

    Prabhu, Sugosh R; Dutt, G B

    2015-02-01

    Fluorescence anisotropies of two structurally similar nondipolar solutes, 2,5-dimethyl-1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DMDPP) and 1,4-dioxo-3,6-diphenylpyrrolo[3,4-c]pyrrole (DPP), have been measured in 1-methyl-3-octylimidazolium hexafluorophosphate-dibenzyl ether ([MOIM][PF6]-DBE) mixtures to understand how the addition of a low viscous nondipolar solvent influences solute rotation. The data when analyzed with Stokes-Einstein-Debye hydrodynamic theory reveals that the measured reorientation times of DMDPP are closer to the predictions of slip boundary condition, whereas those of DPP follow stick hydrodynamics. This outcome arises due to specific interactions between DPP and the solvent medium. Nevertheless, the important result of this study is that the rotational diffusion of DMDPP becomes gradually slower with an increase in the mole fraction of DBE (xDBE) for a given viscosity and temperature. In contrast, such a trend is not noticed for the hydrogen-bond donating solute DPP. Instead, two sets of reorientation times have been obtained, one corresponding to xDBE = 0.0-0.2 and the other xDBE = 0.4-1.0. The results for DMDPP have been rationalized on the basis of the organized structure of [MOIM][PF6], which attains homogeneity at the microscopic level with an increase in xDBE. In case of DPP, however, the propensity of the solute to be in the neighborhood of DBE, as a consequence of its stronger hydrogen bond accepting ability compared to the ionic liquid, appears to be the reason for the observed behavior. PMID:25581072

  9. Extraction of Cesium Ions from Aqueous Solutions Using Calix[4]arene-bis(tert-octylbenzo-crown-6) in Ionic Liquids

    SciTech Connect

    Luo, Huimin; Dai, Sheng; Bonnesen, Peter V; Buchanan III, A C; Holbrey, John D; Bridges, Nicholas J; Rogers, Robin D

    2004-01-01

    Solvent extraction of cesium ions from aqueous solution to hydrophobic ionic liquids without the introduction of an organophilic anion in the aqueous phase was demonstrated using calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) as an extractant. The selectivity of this extraction process toward cesium ions and the use of a sacrificial cation exchanger (NaBPh{sub 4}) to control loss of imidazolium cation to the aqueous solutions by ion exchange have been investigated.

  10. Development of tropine-salt aqueous two-phase systems and removal of hydrophilic ionic liquids from aqueous solution.

    PubMed

    Wu, Haoran; Yao, Shun; Qian, Guofei; Song, Hang

    2016-08-26

    A novel aqueous two-phase systems (ATPS) composed of a small molecule organic compound tropine and an organic or inorganic salt aqueous solution has been developed for the first time. The phase behavior of tropine-salt ATPS was systemically investigated and the phase equilibrium data were measured in different temperatures and concentrations and correlated by the Merchuk equation with satisfactory results. The detection of the conductivity and particle size proved the formation of micelle in the process of forming tropine-salt ATPS. The separation application of the ATPS was assessed with the removal of hydrophilic benzothiazolium-based ionic liquids (ILs) from aqueous solution. The result showed that ILs were effectively extracted into the top tropine-rich phase. Finally, ILs in the top tropine-rich phase were further separated by the means of adsorption-desorption with DM301 macroporous resin and ethanol. The method of novel tropine-salt ATPS combined with adsorption-desorption is demonstrated a promising alternative thought and approach for the removal or recovery of hydrophilic compounds from aqueous media and also could provide a potential application for bio-separation. PMID:27485150

  11. Electrostatics in ionic solution : work and energy, charge regulation, and in homogeneous surfaces

    NASA Astrophysics Data System (ADS)

    Boon, N. J. H.

    2012-01-01

    This thesis concerns the electrostatic properties of charged objects that are immersed into an ionic solvent, for example water with dissolved salt. Typically, the ions inside such a solvent form layers of countercharge close to the charged objects, causing `screening' of the charges. By employing Density Functional Theory (DFT) one is able integrate out the degrees of freedom of the ions and find relations that describe the effective electrostatic properties of the charged objects. One finds that for a large parameter regime the electrostatic potential everywhere in the solvent should satisfy the well established Poisson-Boltzmann equation. We study the electrostatic capacity of porous electrodes in salt water, and derive a method to reversibly extract electric energy from salinity gradients that occur for example at an estuary where sea- and river water meet. However, in the main part of this thesis we consider charged colloidal particles, and study the effect of internal porosity as well as heterogeneities in the surface-charge density (patchy particles) on colloid-colloid interactions. In a far-field analysis we derive equations that describe these interactions for particles with nonvanishing multipole moments, for example `Janus' colloids with a strong dipole component. If such particles locally have a high surface charge density, then the nonlinear dependence of the counterion density on the local charge density leads to a generalisation of charge renormalisation from purely monopolar to dipolar, quadrupolar, etc., including `mode couplings'. In a more detailed approach, which turns out to be important for colloidal particles at smaller distances from each other, we consider the chemical processes that lead to surface charge, and specify a parameter regime in which charging can be described by a single `chargeability' parameter. As we show in this thesis, the phase diagrams we obtain within this regime have many similarities with a `constant surface potential

  12. Dependence of the dielectric constant of electrolyte solutions on ionic concentration: A microfield approach

    NASA Astrophysics Data System (ADS)

    Gavish, Nir; Promislow, Keith

    2016-07-01

    We present a microfield approach for studying the dependence of the orientational polarization of the water in aqueous electrolyte solutions upon the salt concentration and temperature. The model takes into account the orientation of the solvent dipoles due to the electric field created by ions, and the effect of thermal fluctuations. The model predicts a dielectric functional dependence of the form ɛ (c ) =ɛw-β L (3 α c /β ) ,β =ɛw-ɛms , where L is the Langevin function, c is the salt concentration, ɛw is the dielectric of pure water, ɛms is the dielectric of the electrolyte solution at the molten salt limit, and α is the total excess polarization of the ions. The functional form gives a remarkably accurate description of the dielectric constant for a variety of salts and a wide range of concentrations.

  13. Dependence of the dielectric constant of electrolyte solutions on ionic concentration: A microfield approach.

    PubMed

    Gavish, Nir; Promislow, Keith

    2016-07-01

    We present a microfield approach for studying the dependence of the orientational polarization of the water in aqueous electrolyte solutions upon the salt concentration and temperature. The model takes into account the orientation of the solvent dipoles due to the electric field created by ions, and the effect of thermal fluctuations. The model predicts a dielectric functional dependence of the form ɛ(c)=ɛ_{w}-βL(3αc/β),β=ɛ_{w}-ɛ_{ms}, where L is the Langevin function, c is the salt concentration, ɛ_{w} is the dielectric of pure water, ɛ_{ms} is the dielectric of the electrolyte solution at the molten salt limit, and α is the total excess polarization of the ions. The functional form gives a remarkably accurate description of the dielectric constant for a variety of salts and a wide range of concentrations. PMID:27575183

  14. Evaluation of the tapered PMMA fiber sensor response due to the ionic interaction within electrolytic solutions

    NASA Astrophysics Data System (ADS)

    Batumalay, M.; Rahman, H. A.; Kam, W.; Ong, Y. S.; Ahmad, F.; Zakaria, R.; Harun, S. W.; Ahmad, H.

    2014-01-01

    A tapered plastic multimode fiber (PMMA) optical sensor is proposed and demonstrated for continuous monitoring of solutions based on different concentration of sodium chloride and glucose in deionized water The tapered PMMA fiber was fabricated using an etching method involving deionized water and acetone to achieve a waist diameter and length of 0.45 mm and 10 mm, respectively, and was used to investigate the effect of straight, U-shape, and knot shape against concentration for both sodium chloride and glucose. The results show that there is a strong dependence of the electrolytic and non-electrolytic nature of the chemical solutions on the sensor output. It is found that the sensitivity of the sodium chloride concentration sensor with the straight tapered fiber probe was 0.0023 mV/%, which was better than the other probe arrangements of U-shape and knot. Meanwhile, the glucose sensor performs with the highest sensitivity of 0.0026 mV/wt % with the knot-shaped tapered fiber probe. In addition, a tapered PMMA probe which was coated by silver film was fabricated and demonstrated using calcium hypochlorite (G70) solution. The working mechanism of such a device is based on the observed increment in the transmission of the sensor that is immersed in solutions of higher concentration. As the concentration varies from 0 ppm to 6 ppm, the output voltage of the sensor increases linearly from 3.61 mV to 4.28 mV with a sensitivity of 0.1154 mV/ppm and a linearity of more than 99.47%. The silver film coating increases the sensitivity of the proposed sensor due to the effective cladding refractive index, which increases with the coating and thus allows more light to be transmitted from the tapered fiber.

  15. Investigation of the Ionic Hydration in Aqueous Salt Solutions by Soft X-ray Emission Spectroscopy.

    PubMed

    Jeyachandran, Y L; Meyer, F; Benkert, A; Bär, M; Blum, M; Yang, W; Reinert, F; Heske, C; Weinhardt, L; Zharnikov, M

    2016-08-11

    Understanding the molecular structure of the hydration shells and their impact on the hydrogen bond (HB) network of water in aqueous salt solutions is a fundamentally important and technically relevant question. In the present work, such hydration effects were studied for a series of representative salt solutions (NaCl, KCl, CaCl2, MgCl2, and KBr) by soft X-ray emission spectroscopy (XES) and resonant inelastic soft X-ray scattering (RIXS). The oxygen K-edge XES spectra could be described with three components, attributed to initial state HB configurations in pure water, water molecules that have undergone an ultrafast dissociation initiated by the X-ray excitation, and water molecules in contact with salt ions. The behavior of the individual components, as well as the spectral shape of the latter component, has been analyzed in detail. In view of the role of ions in such effects as protein denaturation (i.e., the Hofmeister series), we discuss the ion-specific nature of the hydration shells and find that the results point to a predominant role of anions as compared to cations. Furthermore, we observe a concentration-dependent suppression of ultrafast dissociation in all salt solutions, associated with a significant distortion of intact HB configurations of water molecules facilitating such a dissociation. PMID:27442708

  16. 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

  17. Cr(VI) transport via a supported ionic liquid membrane containing CYPHOS IL101 as carrier: system analysis and optimization through experimental design strategies.

    PubMed

    Rodríguez de San Miguel, Eduardo; Vital, Xóchitl; de Gyves, Josefina

    2014-05-30

    Chromium(VI) transport through a supported liquid membrane (SLM) system containing the commercial ionic liquid CYPHOS IL101 as carrier was studied. A reducing stripping phase was used as a mean to increase recovery and to simultaneously transform Cr(VI) into a less toxic residue for disposal or reuse. General functions which describe the time-depending evolution of the metal fractions in the cell compartments were defined and used in data evaluation. An experimental design strategy, using factorial and central-composite design matrices, was applied to assess the influence of the extractant, NaOH and citrate concentrations in the different phases, while a desirability function scheme allowed the synchronized optimization of depletion and recovery of the analyte. The mechanism for chromium permeation was analyzed and discussed to contribute to the understanding of the transfer process. The influence of metal concentration was evaluated as well. The presence of different interfering ions (Ca(2+), Al(3+), NO3(-), SO4(2-), and Cl(-)) at several Cr(VI): interfering ion ratios was studied through the use of a Plackett and Burman experimental design matrix. Under optimized conditions 90% of recovery was obtained from a feed solution containing 7mgL(-1) of Cr(VI) in 0.01moldm(-3) HCl medium after 5h of pertraction. PMID:24751491

  18. Factors influencing the formation of polybromide monoanions in solutions of ionic liquid bromide salts.

    PubMed

    Easton, Max E; Ward, Antony J; Chan, Bun; Radom, Leo; Masters, Anthony F; Maschmeyer, Thomas

    2016-03-01

    Six different bromide salts - tetraethylammonium bromide ([N2,2,2,2]Br, Br), 1-ethyl-1-methylpiperidinium bromide ([C2MPip]Br, Br), 1-ethyl-1-methylpyrrolidinium bromide ([C2MPyrr]Br, Br), 1-ethyl-3-methylimidazolium bromide ([C2MIm]Br, Br), 1-ethylpyridinium bromide ([C2Py]Br, Br), and 1-(2-hydroxyethyl)pyridinium bromide ([C2OHPy]Br, Br) - were studied in regards to their capacity to form polybromide monoanion products on addition of molecular bromine in acetonitrile solutions. Using complementary spectroscopic and computational methods for the examination of tribromide and pentabromide anion formation, key factors influencing polybromide sequestration were identified. Here, we present criteria for the targeted synthesis of highly efficient bromine sequestration agents. PMID:26890026

  19. Dependence of the osmotic coefficients and average ionic activity coefficients on hydrophobic hydration in solutions

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    The model that considers the nonideality of aqueous solutions of electrolytes with allowance for independent contributions of hydration of ions of various types and electrostatic interactions was substantiated using the cluster ion model. The empirical parameters in the model equations were found to be the hydrophilic and hydrophobic hydration numbers of ions in the standard state and the dispersion of their distribution over the stoichiometric coefficients. A mathematically adequate description of the concentration dependences of the osmotic coefficients and average ion activity coefficients of electrolytes was given for several systems. The difference in the rate of the decrease in the hydrophilic and hydrophobic hydration numbers of ions leads to extremum concentration dependences of the osmotic coefficients, which were determined by other authors from isopiestic data for many electrolytes and did not find explanation.

  20. NOVEL STRATEGIES FOR THE SYNTHESIS OF IONIC LIQUIDS IN AN ENVIRONMENTALLY FRIENDLY MANNER

    EPA Science Inventory

    The collaborative research effort established between the U. S. Environmental Protection Agency (USEPA) and Kreido Laboratories has focused on the development of reaction strategies for the synthesis of chemicals and materials in a green and sustainable manner. One such area of ...

  1. On the Relationship between Solution Strategies in Two Mental Rotation Tasks

    ERIC Educational Resources Information Center

    Janssen, Anne B.; Geiser, Christian

    2010-01-01

    Individual differences in solution strategies have frequently been reported for different measures of mental rotation (MR) ability. In the present study (N=346 German students), we investigated the relationship between solution strategies on two tests commonly used to identify different patterns of strategies: the Mental Rotations Test (MRT;…

  2. Aggregation behavior of 1-dodecyl-3-methylimidazolium bromide in aqueous solution: effect of ionic liquids with aromatic anions.

    PubMed

    Gu, Yingqiu; Shi, Lijuan; Cheng, Xiyuan; Lu, Fei; Zheng, Liqiang

    2013-05-28

    The effects of ionic liquids (ILs), 1-butyl-3-methylimidazolium methylsulfonate (bmimMsa), 1-butyl-3-methylimidazolium benzenesulfonate (bmimBsa), and 1-butyl-3-methylimidazolium 2-naphthalenesulfonate (bmimNsa), on the aggregation behavior of 1-dodecyl-3-methylimidazolium bromide (C12mimBr) in aqueous solution were investigated by surface tension, dynamic light scattering measurements, and (1)H NMR spectroscopy. The ability to promote the surfactant aggregation is in the order bmimNsa > bmimBsa > bmimMsa. Nevertheless, only bmimNsa distinctly reduces both the CMC value and the surface tension at CMC. Due to the penetration of C10H7SO3(-)anions into the surfactant aggregate, bmimNsa is found to induce a phase transition from micelles to vesicles, whereas the other ILs only slightly increase the sizes of micelles. The combined effect of intermolecular interactions, such as hydrophobic effect, electrostatic attractions, and π-π stacking interactions, is supposed to be responsible for this structural transformation, in which π-π stacking plays an important role. PMID:23642150

  3. The effect of hydration on the micromechanics of regenerated cellulose fibres from ionic liquid solutions of varying draw ratios.

    PubMed

    Bulota, M; Michud, A; Hummel, M; Hughes, M; Sixta, H

    2016-10-20

    Regenerated cellulose fibres - Ioncell-F, have been prepared with different draw ratios from cellulose solution in 1,5-diazabicyclo[4.3.0]non-5-ene-1-ium acetate ([DBNH]OAc) ionic liquid. Properties of the fibres were investigated in dry and wet conditions. The stiffness of fibres decreased on average 5 times upon the hydration while the tensile strength remained at around 70% of the initial value. The effect of hydration on the deformation mechanisms and mechanical properties was addressed using Raman spectroscopy. Bands located at 1095cm(-1) and 1414cm(-1) corresponding to the glucosidic linkage C-O-C and side groups C-O-H were followed upon straining. Raman band shifts were observed indicating molecular deformations. Moreover, the hydration of fibres altered the shifting rates implying changes in the molecular micromechanics. It is suggested that hydration affects inter-chain hydrogen bonds thus resulting in the slippage of the chains and lower stiffness of fibres. Some discrepancies from the series aggregate model have been observed which is indicative of changes in the deformation mechanisms upon hydration of the fibres. PMID:27474661

  4. Ion-water wires in imidazolium-based ionic liquid/water solutions induce unique trends in density.

    PubMed

    Ghoshdastidar, Debostuti; Senapati, Sanjib

    2016-03-28

    Ionic liquid/water binary mixtures are rapidly gaining popularity as solvents for dissolution of cellulose, nucleobases, and other poorly water-soluble biomolecules. Hence, several studies have focused on measuring the thermophysical properties of these versatile mixtures. Among these, 1-ethyl-3-methylimidazolium ([emim]) cation-based ILs containing different anions exhibit unique density behaviours upon addition of water. While [emim][acetate]/water binary mixtures display an unusual rise in density with the addition of low-to-moderate amounts of water, those containing the [trifluoroacetate] ([Tfa]) anion display a sluggish decrease in density. The density of [emim][tetrafluoroborate] ([emim][BF4])/water mixtures, on the other hand, declines rapidly in close accordance with the experimental reports. Here, we unravel the structural basis underlying this unique density behavior of [emim]-based IL/water mixtures using all-atom molecular dynamics (MD) simulations. The results revealed that the distinct nature of anion-water hydrogen bonded networks in the three systems was a key in modulating the observed unique density behaviour. Vast expanses of uninterrupted anion-water-anion H-bonded stretches, denoted here as anion-water wires, induced significant structuring in [emim][Ac]/water mixtures that resulted in the density rise. Conversely, the presence of intermittent large water clusters disintegrated the anion-water wires in [emim][Tfa]/water and [emim][BF4]/water mixtures to cause a monotonic density decrease. The differential nanostructuring affected the dynamics of the solutions proportionately, with the H-bond making and breaking dynamics found to be greatly retarded in [emim][Ac]/water mixtures, while it exhibited a faster relaxation in the other two binary solutions. PMID:26911708

  5. Colloidal stability of hydrophobic nanoparticles in ionic surfactant solutions: definition of the critical dispersion concentration.

    PubMed

    Dederichs, Thomas; Möller, Martin; Weichold, Oliver

    2009-02-17

    The dispersion stability diagrams of hydrophobic boehmite nanoparticles in aqueous n-alkyltrimethylammonium bromide solutions (alkyl chain lengths 10-16) were studied over a wide range of particle and surfactant concentrations. The surfactant molecules adsorb tail-on on the particle surface, which provides the colloidal stability through electrostatic repulsion. In the stable region of each diagram, bimodal particle size distributions (50 and 500 nm) are found at lower surfactant concentration, which give way to monomodal distributions (50 nm) at higher concentration. This deagglomeration is connected with the cmc of the surfactants and can be explained by a desorption of counterions from the self-assembled surfactant layer. The desorption is caused by changes in the counterion concentration upon micellization. At low particle concentrations, the transition from the intermediate to the stable region, that is, the disappearance of the precipitate, occurs at a constant surfactant concentration. This concentration is introduced as the "critical dispersion concentration" (cdc), this being the lowest required concentration of a surfactant that is necessary to disperse the hydrophobic particles. The logarithm of the cdc shows a linear dependence on the surfactant chain length, thus a cmc-analogous behavior. The ratio cdc/cmc decreases with increasing surfactant chain length, indicating that long-chain surfactants are more efficient in dispersing nanoparticles than are their lower homologues. The existence of a system-specific critical cdc/cmc ratio, beyond which stable dispersions cannot be obtained, is proposed, which explains the disability of short-chain surfactants to disperse colloids. PMID:19146423

  6. Parallel partitioning strategies for the adaptive solution of conservation laws

    SciTech Connect

    Devine, K.D.; Flaherty, J.E.; Loy, R.M.

    1995-12-31

    We describe and examine the performance of adaptive methods for Solving hyperbolic systems of conservation laws on massively parallel computers. The differential system is approximated by a discontinuous Galerkin finite element method with a hierarchical Legendre piecewise polynomial basis for the spatial discretization. Fluxes at element boundaries are computed by solving an approximate Riemann problem; a projection limiter is applied to keep the average solution monotone; time discretization is performed by Runge-Kutta integration; and a p-refinement-based error estimate is used as an enrichment indicator. Adaptive order (p-) and mesh (h-) refinement algorithms are presented and demonstrated. Using an element-based dynamic load balancing algorithm called tiling and adaptive p-refinement, parallel efficiencies of over 60% are achieved on a 1024-processor nCUBE/2 hypercube. We also demonstrate a fast, tree-based parallel partitioning strategy for three-dimensional octree-structured meshes. This method produces partition quality comparable to recursive spectral bisection at a greatly reduced cost.

  7. Homogeneous liquid-liquid extraction of metal ions with non-fluorinated bis(2-ethylhexyl)phosphate ionic liquids having a lower critical solution temperature in combination with water.

    PubMed

    Depuydt, Daphne; Liu, Liwang; Glorieux, Christ; Dehaen, Wim; Binnemans, Koen

    2015-09-28

    Ionic liquids with an ether-functionalised cation and the bis(2-ethylhexyl)phosphate anion show thermomorphic behaviour in water, with a lower critical solution temperature. These ionic liquids are useful for homogeneous liquid-liquid extraction of first-row (3d) transition metals. PMID:26255754

  8. Determination of solute partition behavior with room-temperature ionic liquid based micellar gas-liquid chromatography stationary phases using the pseudophase model.

    PubMed

    Lantz, Andrew W; Pino, Verónica; Anderson, Jared L; Armstrong, Daniel W

    2006-05-19

    The use of micelles in ionic liquid based gas-chromatography stationary phases was evaluated using equations derived for a "three-phase" model. This model allows the determination of all three partition coefficients involved in the system, and elucidates the micellar contribution to retention and selectivity. Four types of micellar-ionic liquid columns were examined in this study: 1-butyl-3-methylimidazolium chloride with sodium dodecylsulfate or dioctyl sulfosuccinate, and 1-butyl-3-methylimidazolium hexafluorophosphate with polyoxyethylene-100-stearyl ether or polyoxyethylene-23-lauryl ether. The partition coefficients were measured for a wide range of probe molecules capable of a variety of types and magnitudes of interactions. In general, most probe molecules preferentially partitioned to the micellar pseudophase over the bulk ionic liquid component of the stationary phase. Therefore, addition of surfactant to the stationary phase usually resulted in greater solute retention. It is also shown that the selectivity of the stationary phase is significantly altered by the presence of micelles, either by enhancing or lessening the separation. The effects of surfactant on the interaction parameters of the stationary phase are determined using the Abraham solvation parameter model. The addition of sodium dodecylsulfate and dioctyl sulfosuccinate to 1-butyl-3-methylimidazolium chloride stationary phases generally increased the phase's hydrogen bond basicity and increased the level of dispersion interaction. Polyoxyethylene-100-stearyl ether and polyoxyethylene-23-lauryl ether surfactants, however, enhanced the pi-pi/n-pi, polarizability/dipolarity, and hydrogen bond basicity interactions of 1-butyl-3-methylimidazolium hexafluorophosphate to a greater degree than the ionic surfactants with 1-butyl-3-methylimidazolium chloride. However, these nonionic surfactants appeared to hinder the ability of the stationary phase to interact with solutes via dispersion forces

  9. EFFECTS OF PH, SOLID/SOLUTION RATIO, IONIC STRENGTH, AND ORGANIC ACIDS ON PB AND CD 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 organic acids. Variables included pH, ionic strength, metal concentrat...

  10. Wormlike micelles with photoresponsive viscoelastic behavior formed by surface active ionic liquid/azobenzene derivative mixed solution.

    PubMed

    Bi, Yanhui; Wei, Hongtu; Hu, Qiongzheng; Xu, Wenwen; Gong, Yanjun; Yu, Li

    2015-04-01

    The UV-light-stimulated self-assembly behavior of a surface active ionic liquid (SAIL), 1-hexadecyl-3-methylimidazolium bromide (C16mimBr), with an azobenzene derivative, sodium azobenzene 4-carboxylate (AzoCOONa), was investigated in aqueous solution. The properties and structures of the aggregates, formed at a concentration ratio equal to 2:1 ([C16mimBr]:[AzoCOONa]), were comprehensively characterized by rheometer and cryogenic transmission electron microscopy. Initially, viscoelastic wormlike micelles with a viscosity of 0.65 Pa·s were constructed in the C16mimBr/AzoCOONa system. Upon irradiation by UV light (365 nm), particularly fascinating is that the wormlike micelles become much longer and more entangled, exhibiting a high viscosity of 6.9 Pa·s. This can be attributed to photoisomerization of the AzoCOONa molecule from trans to cis form. It is the first time that, with exposure to UV or visible light, the aggregate type of the photoresponsive system has remained unchanged, with only a change of internal property parameters. The cation-π interaction prevailing over the hydrophobic interaction and electrostatic interaction between C16mimBr and AzoCOONa molecules is supposed to be responsible for this peculiar phase behavior. The wormlike micelles constructed with the SAIL and photosensitive additive exhibit controllable viscoelastic behavior in the photoresponsive process. In addition, the average contour length of wormlike micelles was found to slightly decrease with the increase of temperature. We expect this system will receive particular attention due to its unique properties and potential applications in drug delivery, biochemistry, and materials science, etc. PMID:25763685

  11. Activity coefficients at infinite dilution measurements for organic solutes and water in the ionic liquid 1-(3-hydroxypropyl)pyridinium trifluorotris(perfluoroethyl)phosphate.

    PubMed

    Marciniak, Andrzej; Wlazło, Michał

    2010-05-27

    The activity coefficients at infinite dilution, gamma(13)(infinity), for 37 solutes, alkanes, alkenes, alkynes, cycloalkanes, aromatic hydrocarbons, alcohols, thiophene, ethers, ketones, and water, in the ionic liquid 1-(3-hydroxypropyl)pyridinium trifluorotris(perfluoroethyl)phosphate [N-C(3)OHPY][FAP] were determined by gas-liquid chromatography at the temperatures from 308.15 to 358.15 K. The partial molar excess enthalpies at infinite dilution values DeltaH(1)(E,infinity) were calculated from the experimental gamma(13)(infinity) values obtained over the temperature range. The selectivities for aliphatics/aromatics hydrocarbons separation problem were calculated from the gamma(13)(infinity) values and compared to the literature values for other ionic liquids, N-methylpyrrolidone (NMP) and sulfolane. It was found that the investigated [N-C(3)OHPY][FAP] ionic liquid shows much higher selectivity and capacity at infinite dilution than the generally used organic solvents such as NMP, sulfolane, and other ionic liquids. PMID:20429540

  12. Universal charge quenching and stability of proteins in 1-methyl-3-alkyl (hexyl/octyl) imidazolium chloride ionic liquid solutions.

    PubMed

    Rawat, Kamla; Bohidar, H B

    2012-09-13

    This study reports pH dependent stability of protein dispersions of five common proteins, bovine serum albumin (BSA), human serum albumin (HSA), immunoglobulin (IgG), β-lactoglobulin (β-Lg), and gelatin-B (Gel-B), all having isoelectric pH, pI ≈ 5, in room temperature ionic liquid solutions of 1-methyl-3-alkyl (hexyl/octyl) imidazolium chloride (concentration 0-0.2% w/v). Molecular hydrophobicity index, (H-index = hydrophobicity/hydrophilicity) of these molecules spanned the range 0.43-0.87. Electrophoretic characteristics, surface tension data and hydrodynamic size information revealed that IL solutions provide dispersion stability owing to specific protein-IL binding which did not alter their pI values though their surface charge was considerably screened. Change in maximum (ζ(max)) and minimum (ζ(min)) zeta potential values observed at pH ~3 (maximum protonated state) and pH ~8 (maximum deprotonated state) could be described universally as function of IL concentration, c as Δζ(x) = [1 - exp(-ac)] where Δζ(x) is either |(ζ(max) - ζ(w))|/ζ(w) or |(ζ(min) - ζ(w))|/ζ(w), and ζ(w) is the corresponding value in water. Tensiometry data showed two major stages of protein-IL interactions: (i) for c < cmc of IL, the IL molecules selectively bind with imidazolium cation through electrostatic forces forming protein-IL (complex) and (ii) for c> cmc free IL-aggregates begin to form. Similarly, we can define Δγ(x) as either |(γ(max) - γ(w))|/γ(w) at pH 3 or |(γ(min) - γ(w))|/γ(w) at pH 8. Both Δζ(x) and Δγ(x) showed linear dependence with c, Δγ(min, max) (or Δζ(min, max)) = (1 - K(γ) (or K(ζ)) H-index), where the slopes K(ζ) and K(γ) defined intermolecular interactions. Hydrodynamic radii data revealed protein stabilization, circular dichroism spectra implied retention of secondary structures, and Raman spectra confirmed a marginal increase in water structure. Results concluded that selective binding of IL molecules to protein surface in

  13. A new strategy to determine the protein mutation site using matrix-assisted laser desorption ionization in-source decay: derivatization by ionic liquid.

    PubMed

    Guo, Mengzhe; Zhai, Yixing; Guo, Cheng; Liu, Yaqin; Tang, Daoquan; Pan, Yuanjiang

    2015-03-20

    Matrix-assisted laser desorption ionization (MALDI) time-of-flight mass spectrometry (TOF-MS) can be considered as state of the art in the field of proteins and peptides analysis. In this work, we have designed an ionic liquid derivative strategy to obtain abundant fragment ions in MALDI in-source decay (ISD) and used the analysis of angiogenin with mutation in the fortieth (K40I) as an instance. Firstly, we have synthesized two types of ionic liquids, 3-allyl-4-methyl-1H-imidazol-3-ium and 4-methyl-3-(pent-4-yn-1-yl)-1H-imidazol-3-ium. Then in the light-catalyzed reaction, the alkenyl ionic liquid can open the disulfide bond of K40I protein and add to the thiol. And the derived protein can process in-source decay under the effect of ionic liquid group to produce c-z type ions. Additionally this fragmentation is potentiated to support widely range of fragment ions which can cover the location of mutation. Our results have supplied a new top-down method about how to analyze the mutation or even post-translational modification of proteins in MALDI mass spectrometry. PMID:25732582

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

    PubMed Central

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

    2012-01-01

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

  15. Accelerated Transport of 90Sr Following a Release of High Ionic Strength Solution in Vadose Zone Sediments

    SciTech Connect

    Laurence Hull; Annette Schafer

    2008-05-01

    Numerical simulation of cation exchange and mineral precipitation / dissolution reactions using the multiphase reactive geochemical transport code TOUGHREACT has provided important insight into the distribution of 90Sr between layers of geologic strata in a complex vadose zone at the U. S. Department of Energy’s Idaho National Laboratory. During a transfer operation in November 1972, 70.4 m3 of acidic, high ionic strength liquid containing 15,900 Ci of 90Sr was released over five days into alluvial gravels 137 m above the Snake River Plain Aquifer. Sampling data from perched water zones 33 m below the release contain very high levels of 90Sr as do soil samples obtained nearer the point of release. Use of traditional simulation approaches using laboratory measured constant partitioning coefficients (Kd) cannot simultaneously explain perched water and soil concentrations. To address the discrepancy, a reactive transport approach was adopted to include competitive cation exchange, dissolution / precipitation of calcite, carbon dioxide gas production and transport, and gibbsite precipitation. Simulation results using this model suggest that some of the 90Sr could have been transported very rapidly immediately after the release with the acceleration facilitated by competition with high sodium concentrations in the released liquid, by calcium dissolved from calcite, and to a lesser extent by formation of aqueous complexes with nitrate. It is known that once the leading edge of the liquid assemblage was flushed from the alluvium, the mobility of the remaining 90Sr decreased significantly in the absence of the competing cations. Calculations indicate that there should be a net increase in calcite, suggesting that 90Sr could be entrained in the mineral lattice, but insufficient field data exists for confirmation. Sensitivity studies show that the ion exchange capacity and the Na/Sr ion exchange selectivity coefficients were the most sensitive parameters. Because of the

  16. Accelerated transport of 90Sr following a release of high ionic strength solution in vadose zone sediments

    NASA Astrophysics Data System (ADS)

    Hull, Laurence C.; Schafer, Annette L.

    2008-04-01

    Numerical simulation of cation exchange and mineral precipitation/dissolution reactions using the multiphase reactive geochemical transport code TOUGHREACT has provided important insight into the distribution of 90Sr among layers of geologic strata in a complex vadose zone at the U. S. Department of Energy's Idaho National Laboratory. During a transfer operation in November 1972, 70.4 m 3 of acidic, high ionic strength liquid containing 15,900 Ci of 90Sr was released over five days into alluvial gravels 137 m above the Snake River Plain Aquifer. Sampling data from perched water zones 33 m below the release contain very high levels of 90Sr as do soil samples obtained nearer the point of release. Use of traditional simulation approaches using laboratory-measured constant partitioning coefficients ( Kd) cannot simultaneously explain perched water and soil concentrations. To address the discrepancy, a reactive transport approach was adopted to include competitive cation exchange, dissolution/precipitation of calcite, carbon dioxide gas production and transport, and gibbsite precipitation. Simulation results using this model suggest that some of the 90Sr could have been transported very rapidly immediately after the release with the acceleration facilitated by competition for cation exchange sites with high sodium concentrations in the released liquid and calcium dissolved from calcite, and to a lesser extent by formation of aqueous complexes with nitrate. Once the leading edge of the liquid assemblage was flushed from the alluvium, the mobility of the remaining 90Sr decreased significantly in the absence of the competing cations. Calculations indicate that there should be a net increase in calcite, suggesting that 90Sr could be entrained in the mineral lattice, but insufficient field data exist for confirmation. Sensitivity studies show that the cation exchange selectivity coefficients were the most sensitive individual parameters determining the 90Sr distribution

  17. Accelerated transport of (90)Sr following a release of high ionic strength solution in vadose zone sediments.

    PubMed

    Hull, Laurence C; Schafer, Annette L

    2008-04-28

    Numerical simulation of cation exchange and mineral precipitation/dissolution reactions using the multiphase reactive geochemical transport code TOUGHREACT has provided important insight into the distribution of (90)Sr among layers of geologic strata in a complex vadose zone at the U. S. Department of Energy's Idaho National Laboratory. During a transfer operation in November 1972, 70.4 m(3) of acidic, high ionic strength liquid containing 15,900 Ci of (90)Sr was released over five days into alluvial gravels 137 m above the Snake River Plain Aquifer. Sampling data from perched water zones 33 m below the release contain very high levels of (90)Sr as do soil samples obtained nearer the point of release. Use of traditional simulation approaches using laboratory-measured constant partitioning coefficients (K(d)) cannot simultaneously explain perched water and soil concentrations. To address the discrepancy, a reactive transport approach was adopted to include competitive cation exchange, dissolution/precipitation of calcite, carbon dioxide gas production and transport, and gibbsite precipitation. Simulation results using this model suggest that some of the (90)Sr could have been transported very rapidly immediately after the release with the acceleration facilitated by competition for cation exchange sites with high sodium concentrations in the released liquid and calcium dissolved from calcite, and to a lesser extent by formation of aqueous complexes with nitrate. Once the leading edge of the liquid assemblage was flushed from the alluvium, the mobility of the remaining (90)Sr decreased significantly in the absence of the competing cations. Calculations indicate that there should be a net increase in calcite, suggesting that (90)Sr could be entrained in the mineral lattice, but insufficient field data exist for confirmation. Sensitivity studies show that the cation exchange selectivity coefficients were the most sensitive individual parameters determining the (90)Sr

  18. Dissolving Polymers in Ionic Liquids.

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John

    2009-03-01

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

  19. 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...

  20. Study of a Li-air battery having an electrolyte solution formed by a mixture of an ether-based aprotic solvent and an ionic liquid

    NASA Astrophysics Data System (ADS)

    Cecchetto, Laura; Salomon, Mark; Scrosati, Bruno; Croce, Fausto

    2012-09-01

    Recent studies have clearly demonstrated that cyclic and linear carbonates are unstable when used in rechargeable Li-air batteries employing aprotic solvents mostly due to the cathodic formation of superoxide during the oxygen reduction reaction. In particular, it has been ascertained that nucleophilic attack by superoxide anion radical, O2-rad , at O-alkyl carbon is a common mechanism of decomposition of organic carbonates. Moreover, theoretical calculations showed that ether chemical functionalities are stable against nucleophilic substitution induced by superoxide. Aim of this study is to report on a new electrolyte solution for Li-air battery formed by a mixture of an ether-based aprotic solvent with an ionic liquid (IL). The IL-based electrolyte was obtained by mixing the pure ionic liquid N-methyl-(n-butyl) pyrrolidinium bis(trifluoromethane sulfonyl) imide (here denoted as PYR14TFSI) to a 0.91 M solution of lithium triflate (LiCF3SO3) in tetra ethylene glycol dimethyl etcher (TEGDME). We observed that the presence of IL beneficially affects the kinetics and the reversibility of the oxygen reactions involved at the cathode. The most significant result being a lower overvoltage for the charge reaction, compared to a Li/air cell containing the same electrolyte solution without IL.

  1. Strategies of Successful Synthesis Solutions: Mapping, Mechanisms, and More

    ERIC Educational Resources Information Center

    Bodé, Nicholas E.; Flynn, Alison B.

    2016-01-01

    Organic synthesis problems require the solver to integrate knowledge and skills from many parts of their courses. Without a well-defined, systematic method for approaching them, even the strongest students can experience difficulties. Our research goal was to identify the most successful problem-solving strategies and develop associated teaching…

  2. Managerial Solutions: An Exercise in Developing Successful Communication Strategies.

    ERIC Educational Resources Information Center

    Hufman, Melody

    Noting that every business person needs good communication skills, whether managers and employees, superordinates and subordinates, this paper outlines an exercise to teach students to set objectives, develop criteria, analyze perspectives, and implement successful communication strategies. The total time for the exercise is 2 hours and the number…

  3. Nuclear Data for Astrophysics: Resources, Challenges, Strategies, and Software Solutions

    SciTech Connect

    Smith, Michael Scott; Lingerfelt, Eric J; Nesaraja, Caroline D; Hix, William Raphael; Roberts, Luke F; Koura, Hiroyuki; Fuller, George M; Tytler, David

    2008-01-01

    One of the most exciting utilizations of nuclear data is to help unlock the mysteries of the Cosmos -- the creation of the chemical elements, the evolution and explosion of stars, and the origin and fate of the Universe. There are now many nuclear data sets, tools, and other resources online to help address these important questions. However, numerous serious challenges make it important to develop strategies now to ensure a sustainable future for this work. A number of strategies are advocated, including: enlisting additional manpower to evaluate the newest data; devising ways to streamline evaluation activities; and improving communication and coordination between existing efforts. Software projects are central to some of these strategies. Examples include: creating a virtual ''pipeline'' leading from the nuclear laboratory to astrophysics simulations; improving data visualization and management to get the most science out of the existing datasets; and creating a nuclear astrophysics data virtual (online) community. Recent examples will be detailed, including the development of two first-generation software pipelines, the Computational Infrastructure for Nuclear Astrophysics for stellar astrophysics and the bigbangonline suite of codes for cosmology, and the coupling of nuclear data to sensitivity studies with astrophysical simulation codes to guide future research.

  4. Local Solutions for National Challenges? Exploring Local Solutions through the Case of a National Succession Planning Strategy

    ERIC Educational Resources Information Center

    Collins, Mike

    2013-01-01

    The notion of localism and decentralization in national policy has come increasingly to the fore in recent years. The national succession planning strategy for headteachers in England introduced by the National College for School Leadership promoted "local solutions for a national challenge". This article deals with some aspects of the…

  5. A Sustainable Approach to the Stereoselective Synthesis of Diazaheptacyclic Cage Systems Based on a Multicomponent Strategy in an Ionic Liquid.

    PubMed

    Suresh Kumar, Raju; Almansour, Abdulrahman I; Arumugam, Natarajan; Altaf, Mohammad; Menéndez, José Carlos; Kumar, Raju Ranjith; Osman, Hasnah

    2016-01-01

    The microwave-assisted three-component reactions of 3,5-bis(E)-arylmethylidene]tetrahydro-4(1H)-pyridinones, acenaphthenequinone and cyclic α-amino acids in an ionic liquid, 1-butyl-3-methylimidazolium bromide, occurred through a domino sequence affording structurally intriguing diazaheptacyclic cage-like compounds in excellent yields. PMID:26840282

  6. Multiresolution strategies for the numerical solution of optimal control problems

    NASA Astrophysics Data System (ADS)

    Jain, Sachin

    There exist many numerical techniques for solving optimal control problems but less work has been done in the field of making these algorithms run faster and more robustly. The main motivation of this work is to solve optimal control problems accurately in a fast and efficient way. Optimal control problems are often characterized by discontinuities or switchings in the control variables. One way of accurately capturing the irregularities in the solution is to use a high resolution (dense) uniform grid. This requires a large amount of computational resources both in terms of CPU time and memory. Hence, in order to accurately capture any irregularities in the solution using a few computational resources, one can refine the mesh locally in the region close to an irregularity instead of refining the mesh uniformly over the whole domain. Therefore, a novel multiresolution scheme for data compression has been designed which is shown to outperform similar data compression schemes. Specifically, we have shown that the proposed approach results in fewer grid points in the grid compared to a common multiresolution data compression scheme. The validity of the proposed mesh refinement algorithm has been verified by solving several challenging initial-boundary value problems for evolution equations in 1D. The examples have demonstrated the stability and robustness of the proposed algorithm. The algorithm adapted dynamically to any existing or emerging irregularities in the solution by automatically allocating more grid points to the region where the solution exhibited sharp features and fewer points to the region where the solution was smooth. Thereby, the computational time and memory usage has been reduced significantly, while maintaining an accuracy equivalent to the one obtained using a fine uniform mesh. Next, a direct multiresolution-based approach for solving trajectory optimization problems is developed. The original optimal control problem is transcribed into a

  7. Potentiometric investigation of the effect of the pH on the ionic transfer of some amino acids at the interface between two immiscible electrolyte solutions.

    PubMed

    Spătaru, Tanta; Spătaru, Nicolae; Bonciocat, Nicolae; Luca, Constantin

    2004-04-01

    The effect of the pH on the ionic transfer of glycine and beta-alanine at the interface between two immiscible electrolyte solutions (ITIES) was investigated by a simple potentiometric method. Upon addition of small amounts of solution containing the investigated amino acids, a variation of the potential drop across the interface was recorded, which was found to be pH-dependent. This behavior was explained in terms of a preferential orientation of the amino acid molecules at the ITIES, induced by the different lipoficility of the functional groups. The results enabled the measurement of this voltage variation to be used as the basis for a simple and rapid method for determining the isoelectric point of the investigated compounds. The agreement between the pH(i) values thus estimated and those reported in the literature suggests the possibility of using the method for the interpretation of processes occurring at the level of biological membranes. PMID:14990327

  8. Protic ionic liquid-induced changes in the properties of aqueous triton X-100-CTAB surfactant solution: Solvent and rotational relaxation studies

    NASA Astrophysics Data System (ADS)

    Rao, Vishal Govind; Brahmachari, Udita; Mandal, Sarthak; Ghosh, Surajit; Banerjee, Chiranjib; Sarkar, Nilmoni

    2012-11-01

    We have investigated the effect of protic ionic liquid, N,N-Dimethylethanolammonium formate (DAF) addition on Triton X-100-cetyltrimethylammonium bromide (CTAB) mixed micellar solution. We have shown the effect of DAF addition on the size and zeta potential of the mixed micellar aggregates using dynamic light scattering measurements. The steady-state and time-resolved fluorescence spectroscopy have been used to investigate the effect of increasing CTAB/Triton X-100 ratio and DAF addition on the solvent and rotational relaxation of Coumarin-153 in CTAB-Triton X-100 mixed micellar solutions. The average solvation time decreases with increasing CTAB/Triton X-100 ratio and increases with the addition of DAF.

  9. Principal role of the stepwise aggregation mechanism in ionic surfactant solutions near the critical micelle concentration. Molecular dynamics study.

    PubMed

    Burov, Stanislav V; Vanin, Alexandr A; Brodskaya, Elena N

    2009-08-01

    The validity of the assumption on the predominant contribution of the stepwise processes to the ionic micelle formation/destruction in the vicinity of critical micelle concentration was investigated by molecular dynamics simulation. A coarse-grained model was used to describe the surfactant/water mixture. The cluster size distribution was estimated directly from molecular dynamics simulations or obtained from a reduced set of kinetic equations. The good agreement between two approaches shows that the neglect of the terms responsible for cluster fusion/fission is fully justified and that such processes are less important than stepwise aggregation. PMID:19591445

  10. The Partitioning of Americium and the Lanthanides Using Tetrabutyldiglycolamide (TBDGA) in Octanol and in Ionic Liquid Solution

    SciTech Connect

    M.E. Mincher; D.L. Quach; Y.J. Liao; B.J. Mincher; C.M. Wai

    2012-11-01

    Separations among the lanthanides and the separation of Am from the lanthanides remain challenging, and research in this area continues to expand. The separation of adjacent lanthanides is of interest to high-tech industries because individual lanthanides have specialized uses and are in short supply. In nuclear fuel cycle applications Am would be incorporated into fast reactor fuels, yet the lanthanides are not desired. In this work the diamide N,N,N',N'-tetrabutyldiglycolamide (TBDGA) was investigated as a ligand for lanthanide and Am solvent extraction in both molecular and room temperature ionic liquid (RTIL) diluents. The RTIL [C4MIM][Tf2N-] showed very high extraction efficiency for these trivalent metals from low nitric acid concentrations, while the molecular diluent 1-octanol showed high extraction efficiency at high acid concentrations. This was attributed to the extraction of ionic nitrate complexes by the RTIL, whereas 1-octanol extracted neutral nitrate complexes. TBDGA in RTIL did not provide adequate separation factors for Am/lanthanide partitioning, but 1-octanol did show reasonable separation possibilities. Lanthanide intergroup separations appeared to be feasible in both diluents, but with higher separation factors from 1-octanol.

  11. Numerical strategies for the solution of inverse problems

    NASA Astrophysics Data System (ADS)

    Hebber (Haber), Eldad

    This thesis deals with the numerical solutions of linear and nonlinear inverse problems. The goal of this thesis is to review and develop new techniques for solving such problems. In so doing, the computations tools for solving inverse problems are comprehensively studied. The thesis can be divided into two parts. In the first part, linear inverse theory is dealt with. Methods to estimate noise and efficiently invert large and full matrixes are reviewed and developed. Emphasis is given to Generalized Cross Validation (GCV) for noise estimation, and to Krylov space methods for efficient methods to invert large systems. This part is summarized by applying and comparing the methods developed on linear inverse problems which arise in gravity and tomography. In the second part of this thesis, extensive use of the linear algebra and the noise estimation methods which were developed in the first part of the thesis is made. A review of the current methods to carry out nonlinear inverse problems is given. A test example is constructed to demonstrate that these methods may fail. Next, a new algorithm for solving nonlinear inverse problems is developed. The algorithm is based on the ability to differentiate between correlated errors which comes from the linearization, and non-correlated noise which comes from the measurement. Based on these two types of noise, a regularization procedure which has two parts is developed. The first part is made of global regulation, to deal with the measurement noise, and the second part is made from a local regularization, to deal with the nonlinearity. The thesis demonstrates that GCV can be used in order to determine the measurement noise, and the Damped Gauss-Newton method can be used in order to deal with the local nonlinear terms. Another aspect of nonlinear inverse theory which is developed in this work concerns approximate sensitivities. A new formulation is suggested for the approximate sensitivities and bounds are calculated using

  12. Solubility and modeling acid-base properties of adrenaline in NaCl aqueous solutions at different ionic strengths and temperatures.

    PubMed

    Bretti, Clemente; Cigala, Rosalia Maria; Crea, Francesco; De Stefano, Concetta; Vianelli, Giuseppina

    2015-10-12

    Solubility and acid-base properties of adrenaline were studied in NaCl aqueous solutions at different ionic strengths (0ionic strength was modeled by means of the Debye-Hückel type equation and of the SIT (Specific ion Interaction Theory) approach. The specific interaction parameters of the ion pairs were also reported. For the protonation constants, the following thermodynamic values at infinite dilution were obtained: T=298.15 K, logK1(H0)=10.674±0.018 and logK2(H0)=8.954±0.022; T=310.15K, logK1(H0)=10.355±0.018 and logK2(H0)=8.749±0.030. PMID:26122929

  13. Fixation of CO2 by electrocatalytic reduction and electropolymerization in ionic liquid-H2O solution.

    PubMed

    Chu, Daobao; Qin, Guoxu; Yuan, Ximei; Xu, Mai; Zheng, Peng; Lu, Jia

    2008-01-01

    The electrocatalytic synthesis of low-density polyethylene (LDPE) from carbon dioxide on a nanostructured (ns)TiO2 film electrode was investigated by controlled potential electrolysis in a solvent mixture of water and the ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMI]BF4) at room temperature under ambient pressure. Under these conditions, the nsTiO2 film is remarkably efficient and selective for the electroreduction of CO2. The current efficiency for the formation of the electrolytic product is about 8-14% at -1.50 V (vs SCE). The electrocatalytic activity of the electrode in the electrochemical reduction of CO2 was investigated by cyclic voltammetry (CV), and the probable electrode reaction mechanism is discussed. PMID:18605207

  14. Communication: Collective dynamics of room-temperature ionic liquids and their Li ion solutions studied by high-resolution inelastic X-ray scattering

    NASA Astrophysics Data System (ADS)

    Fujii, Kenta; Shibayama, Mitsuhiro; Yamaguchi, Tsuyoshi; Yoshida, Koji; Yamaguchi, Toshio; Seki, Shiro; Uchiyama, Hiroshi; Baron, Alfred Q. R.; Umebayashi, Yasuhiro

    2013-04-01

    High-resolution inelastic X-ray scattering (IXS) measurements were performed for room-temperature ionic liquids (ILs) of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide and bis(fluorosulfonyl)amide, [C2mIm+][TFSA-] and [C2mIm+][FSA-], respectively, at ambient temperature. The observed spectra as a function of Q of 1.4-6 nm-1 can be ascribed to quasi-elastic and inelastic scatterings, so that they are well represented with the fitting by using the Lorentz and the damped harmonic oscillator model functions to yield the dynamic structure factors. It was found in the intermediate scattering function, F(Q, t) that both ILs show the relaxation at t < 10 ps. The IXS measurements were also made on [C2mIm+][TFSA-] and [C2mIm+][FSA-] solutions dissolving Li salt. It is suggested that the adding of Li salt to IL significantly prolongs the relaxation time.

  15. Inkjet-printed gold nanoparticle chemiresistors: influence of film morphology and ionic strength on the detection of organics dissolved in aqueous solution.

    PubMed

    Chow, Edith; Herrmann, Jan; Barton, Christopher S; Raguse, Burkhard; Wieczorek, Lech

    2009-01-19

    The influence of film morphology on the performance of inkjet-printed gold nanoparticle chemiresistors has been investigated. Nanoparticles deposited from a single-solvent system resulted in a "coffee ring"-like structure with most of the materials deposited at the edge. It was shown that the uniformity of the film could be improved if the nanoparticles were deposited from a mixture of solvents comprising N-methyl-2-pyrrolidone and water. Electrical conductivity measurements showed that both "coffee ring" and "flat" films were qualitatively similar suggesting that the films have similar nanoscale structures. To form the functional chemiresistor device, the 4-(dimethylamino)pyridine coating on the nanoparticle was exchanged with 1-hexanethiol to provide a hydrophobic sensing layer. The performance of 1-hexanethiol coated gold nanoparticle chemiresistors to small organic molecules, toluene, dichloromethane and ethanol dissolved in 1 M KCl in regard to changes in impedance and response times was unaffected by the film morphology. For larger hydrocarbons such as octane, the rate of uptake of the analyte into the film was significantly faster when the flatter nanoparticle film was used as opposed to the "coffee ring" film which has a thicker edge. Furthermore, the presence of potassium and chloride ions in the solution media does not significantly affect the impedance of the nanoparticle film at 1 Hz (<2% variation in film impedance over more than four orders of magnitude change in ionic strength). However, the ionic strength of the media affected the partitioning of the analyte into the hydrophobic nanoparticle film. The response of the sensor was found to increase with an increased salt concentration due to a salting-out of the analyte from the solution. PMID:19100893

  16. Structural characterization of zinc(II) chloride in aqueous solution and in the protic ionic liquid ethyl ammonium nitrate by x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    D'Angelo, Paola; Zitolo, Andrea; Ceccacci, Francesca; Caminiti, Ruggero; Aquilanti, Giuliana

    2011-10-01

    Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the species and structures existing in a series of ZnCl2-H2O-NaCl solutions with different chloride/zinc ratios and in a solution of ZnCl2 in the protic ionic liquid ethyl ammonium nitrate (EAN). The average coordination numbers and distances of zinc species were determined from the analysis of the EXAFS data. In aqueous solution the number of chloride ions tightly bounded to Zn2+ is significantly related to the chloride/zinc ratio, and no inner complex formation between Zn2+ and Cl- ions has been detected for low ZnCl2 concentration (0.1 and 0.2 M). Conversely, in the same concentration range (0.13 M) the ZnCl2 species do not dissociate in EAN and the Zn2+ first coordination shell has two chloride ions and is completed by two oxygen atoms of the nitrate anion. The results of this investigation show that notwithstanding the existence of similar characteristics between EAN and water, the solvation properties of the two solvents are markedly different.

  17. Ammonium ionic liquid as modulator of the critical micelle concentration of ammonium surfactant at aqueous solution: conductimetric and dynamic light scattering (DLS) studies.

    PubMed

    Sifaoui, Hocine; Lugowska, Katarzyna; Domańska, Urszula; Modaressi, Ali; Rogalski, Marek

    2007-10-15

    We report measurements of self aggregation in aqueous solution of an ionic liquid (IL), didecyl-dimethylammonium nitrate ([DDA][NO(3)]) and a surfactant hexadecyl-trimethylammonium bromide (CTAB) and of mixtures of these two salts. The electrical conductivity and dynamic light scattering (DLS) measurements were used for the characterization of the aggregation process. The conductivity measurements were performed at three temperatures. The critical micelle concentration (CMC) was determined at different temperatures and at different ratio of two salts. The effect of IL on the micellization of CTAB has been discussed. Our results suggest that organized structures formed by CTAB and [DDA][NO(3)] self assembly in domains of several hundred nanometers size. The micellar solubility of the salicylic acid in mixed salt aqueous solutions was determined to probe the physical properties of these assemblies. We have observed, that the micellar solubility enhancement was only slightly influenced by the nature of micelles present in aqueous solution. This proves that salicylic acid solubilization is enthalpy driven. PMID:17618639

  18. Complexation study of NpO{sub 2}{sup +} and UO{sub 2}{sup 2+} ions with several organic ligands in aqueous solutions of high ionic strength

    SciTech Connect

    Borkowski, M.; Lis, S.; Choppin, G.R.

    1995-09-01

    The acid dissociation constants, pK{sub a}, and the stability constants for NpO{sub 2}{sup +} and UO{sub 2}{sup 2+} have been measured for certain organic ligands [acetate, {alpha}-hydroxyisobutyrate, lactate, ascorbate, oxalate, citrate, EDTA, 8-hydroxyquinoline, 1, 10-phenanthroline, and thenoyltrifluoroacetone] in 5 m (NaCl) ionic strength solution. The pK{sub a} values were determined by potentiometry or spectrometry. These methods, as well as solvent extraction with {sup 233}U and {sup 237}Np radiotracers, were used to measure the stability constants of the 1:1 and 1:2 complexes of dioxo cations. These constants were used to estimate the concentrations required to result in 10 % competition with hydrolysis in the 5 m NaCl solution. Such estimates are of value in assessing the solubility from radioactive waste of AnO{sub 2}{sup +} and AnO{sub 2}{sup 2+} in brine solutions in contact with nuclear waste in a salt-bed repository.

  19. Geometry of ionic arrangements and magnetic interactions in ordered ferri-ilmenite solid solutions and its effect on low-T magnetic behavior

    NASA Astrophysics Data System (ADS)

    Robinson, Peter; Fabian, Karl; McEnroe, Suzanne A.

    2010-05-01

    The magnetic properties of metastable chemically ordered ilmenite-rich Fe2O3-FeTiO3 solid solutions in the temperature range 500-0 K represent a complex amalgam of the incompatible properties of the end-members. While hematite is controlled by adjacent layer antiferromagnetic interactions, ilmenite is controlled by double-layer antiferromagnetic interactions. The complex geometry of the exchange-coupled ions is visualized, and tentative explanations of property changes with temperature are provided by schematic 2-D ionic images along a common (1 1 -2 0) plane showing the exchange interactions in the end-members and in Ilm 90, 80, and 70 solid solutions, accompanied by parallel temperature- and frequency-dependent susceptibility diagrams. To provide a larger-scale visualization of the extent of exchange clusters and networks, 3-D images of Ilm 95, 90, 85, 80, 75, and 70 containing 2592 atomic positions were also constructed. Both types of images together provide a conceptual overview of the physical mechanisms governing this complex solid-solution system and its low-temperature magnetic behavior. Even though the geometric approach does not in itself provide a quantitative model of physical properties, it is an indispensable prerequisite for designing realistic quantitative models, judging their validity, and interpreting model results. It also supplies information on the distributions, numbers, and orientations of magnetic exchange interactions, which can become guidelines for more sophisticated calculations.

  20. Self adaptive solution strategies: Locally bound constrained Newton Raphson solution algorithms

    NASA Technical Reports Server (NTRS)

    Padovan, Joe

    1991-01-01

    A summary is given of strategies which enable the automatic adjustment of the constraint surfaces recently used to extend the range and numerical stability/efficiency of nonlinear finite element equation solvers. In addition to handling kinematic and material induced nonlinearity, both pre-and postbuckling behavior can be treated. The scheme employs localized bounds on various hierarchical partitions of the field variables. These are used to resize, shape, and orient the global constraint surface, thereby enabling essentially automatic load/deflection incrementation. Due to the generality of the approach taken, it can be implemented in conjunction with the constraints of an arbitrary functional type. To benchmark the method, several numerical experiments are presented. These include problems involving kinematic and material nonlinearity, as well as pre- and postbuckling characteristics. Also included is a list of papers published in the course of the work.

  1. Anisole Nitration During Gamma-Irradiation of Aqueous Nitrite and Nitrate Solutions: Free Radical Versus Ionic Mechanisms

    SciTech Connect

    Gracy Elias; Bruce J. Mincher; Leigh R. Martin; Stephen P. Mezyk; Thomas D. Cullen

    2010-04-01

    The nitration of aromatic compounds in the condensed phase is of interest to nuclear waste treatment applications. This chapter discusses our investigation of radiolytic aromatic nitration mechanisms in the condensed phase toward understanding the nitration products created during nuclear fuel reprocessing. The nitration reactions of anisole, a model aromatic compound, were studied in ?-irradiated acidic nitrate, neutral nitrate, and neutral nitrite solutions. The nitrated anisole product distributions were the same with and without radiation in acidic solution, although more products were formed with radiation. In the irradiated acidic condensed phase, radiation-enhanced nitrous acid-catalyzed nitrosonium ion electrophilic aromatic substitution followed by oxidation reactions dominated over radical addition reactions. Neutral nitrate anisole solutions were dominated by mixed nitrosonium/nitronium ion electrophilic aromatic substitution reactions, but with lower product yields. Irradiation of neutral nitrite anisole solution resulted in a statistical substitution pattern for nitroanisole products, suggesting non-electrophilic free radical reactions involving the •NO2 radical.

  2. Charging and aggregation of latex particles in aqueous solutions of ionic liquids: towards an extended Hofmeister series.

    PubMed

    Oncsik, Tamas; Desert, Anthony; Trefalt, Gregor; Borkovec, Michal; Szilagyi, Istvan

    2016-03-01

    The effect of ionic liquid (IL) constituents and other monovalent salts on the stability of polystyrene latex particles was studied by electrophoresis and light scattering in dilute aqueous suspensions. The surface charge and the aggregation rate were both sensitive to the type of ion leading to different critical coagulation concentration (CCC) values. Systematic variation of the type of IL cation and anion allows us to place these ions within the Hofmeister series. We find that the dicyanoamide anion should be placed between iodide and thiocyanate, while all 1-alkyl-3-methylimidazolium cations can be positioned to the left of the tetramethylammonium and ammonium ions. The hydrophobicity of the 1-butyl-1-methylpyrrolidinium (BMPL(+)) ion is intermediate between 1-ethyl-3-methylimidazolium (EMIM(+)) and 1-butyl-3-methylimidazolium (BMIM(+)). With increasing alkyl chain length, the 1-alkyl-3-methylimidazolium cations adsorb on the latex particles very strongly, and 1-hexyl-3-methylimidazolium (HMIM(+)) and 1-octyl-3-methylimidazolium (OMIM(+)) lead to pronounced charge reversal and to an intermediate restabilization region. PMID:26902948

  3. A Long-Life Lithium Ion Battery with Enhanced Electrode/Electrolyte Interface by Using an Ionic Liquid Solution.

    PubMed

    Elia, Giuseppe Antonio; Ulissi, Ulderico; Mueller, Franziska; Reiter, Jakub; Tsiouvaras, Nikolaos; Sun, Yang-Kook; Scrosati, Bruno; Passerini, Stefano; Hassoun, Jusef

    2016-05-10

    In this paper, we report an advanced long-life lithium ion battery, employing a Pyr14 TFSI-LiTFSI non-flammable ionic liquid (IL) electrolyte, a nanostructured tin carbon (Sn-C) nanocomposite anode, and a layered LiNi1/3 Co1/3 Mn1/3 O2 (NMC) cathode. The IL-based electrolyte is characterized in terms of conductivity and viscosity at various temperatures, revealing a Vogel-Tammann-Fulcher (VTF) trend. Lithium half-cells employing the Sn-C anode and NMC cathode in the Pyr14 TFSI-LiTFSI electrolyte are investigated by galvanostatic cycling at various temperatures, demonstrating the full compatibility of the electrolyte with the selected electrode materials. The NMC and Sn-C electrodes are combined into a cathode-limited full cell, which is subjected to prolonged cycling at 40 °C, revealing a very stable capacity of about 140 mAh g(-1) and retention above 99 % over 400 cycles. The electrode/electrolyte interface is further characterized through a combination of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations upon cell cycling. The remarkable performances reported here definitively indicate that IL-based lithium ion cells are suitable batteries for application in electric vehicles. PMID:26990320

  4. Ionic Blocks

    ERIC Educational Resources Information Center

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

    2008-01-01

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

  5. Influence of Design Training and Spatial Solution Strategies on Spatial Ability Performance

    ERIC Educational Resources Information Center

    Lin, Hanyu

    2016-01-01

    Numerous studies have reported that spatial ability improves through training. This study investigated the following: (1) whether design training enhances spatial ability and (2) whether differing solution strategies are applied or generated following design training. On the basis of these two research objectives, this study divided the…

  6. Cognitive and Neural Determinants of Response Strategy in the Dual-Solution Plus-Maze Task

    ERIC Educational Resources Information Center

    De Leonibus, Elvira; Costantini, Vivian J. A.; Massaro, Antonio; Mandolesi, Georgia; Vanni, Valentina; Luvisetto, Siro; Pavone, Flaminia; Oliverio, Alberto; Mele, Andrea

    2011-01-01

    Response strategy in the dual-solution plus maze is regarded as a form of stimulus-response learning. In this study, by using an outcome devaluation procedure, we show that it can be based on both action-outcome and stimulus-response habit learning, depending on the amount of training that the animals receive. Furthermore, we show that…

  7. A Cascade Optimization Strategy for Solution of Difficult Multidisciplinary Design Problems

    NASA Technical Reports Server (NTRS)

    Patnaik, Surya N.; Coroneos, Rula M.; Hopkins, Dale A.; Berke, Laszlo

    1996-01-01

    A research project to comparatively evaluate 10 nonlinear optimization algorithms was recently completed. A conclusion was that no single optimizer could successfully solve all 40 problems in the test bed, even though most optimizers successfully solved at least one-third of the problems. We realized that improved search directions and step lengths, available in the 10 optimizers compared, were not likely to alleviate the convergence difficulties. For the solution of those difficult problems we have devised an alternative approach called cascade optimization strategy. The cascade strategy uses several optimizers, one followed by another in a specified sequence, to solve a problem. A pseudorandom scheme perturbs design variables between the optimizers. The cascade strategy has been tested successfully in the design of supersonic and subsonic aircraft configurations and air-breathing engines for high-speed civil transport applications. These problems could not be successfully solved by an individual optimizer. The cascade optimization strategy, however, generated feasible optimum solutions for both aircraft and engine problems. This paper presents the cascade strategy and solutions to a number of these problems.

  8. Structure and stability of phospholipid bilayers hydrated by a room-temperature ionic liquid/water solution: a neutron reflectometry study.

    PubMed

    Benedetto, Antonio; Heinrich, Frank; Gonzalez, Miguel A; Fragneto, Giovanna; Watkins, Erik; Ballone, Pietro

    2014-10-23

    Neutron reflectometry (NR) measurements were carried out to probe the structure and stability of two model biomembranes consisting of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) and 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) phospholipid bilayers hydrated by water solutions of two prototypical room-temperature ionic liquids (RTILs), namely, 1-butyl-3-methyl-imidazolium chloride ([bmim][Cl]) and choline chloride ([Chol][Cl]) at concentrations of 0.1 M and 0.5 M, respectively. The raw data were analyzed by fitting a distribution of scattering length densities arising from the different chemical species in the system. The results of this analysis show that (a) for all systems and concentrations that we considered, the thickness of the bilayers shrinks by ∼1 Å upon dissolving the ionic liquid into water and that (b) the RTIL ions enter the bilayer, finding their way to a preferred location in the lipid range that is nearly independent of the lipid and of the [bimim](+) or [Chol](+) choice. The volume fraction of RTIL sorbed in/on the bilayer, however, does depend on the lipid, but, again, is the same for [bmim][Cl] and for [Chol][Cl]. Thus, the RTIL occupies ∼5% of the bilayer volume in POPC, rising to ∼10% in DMPC. Repeating the measurements and data analysis after rinsing in pure water shows that the changes in the bilayer due to the RTIL sorption are irreversible and that a measurable amount of IL remains in the lipid fraction, that is, ∼2.5% of the bilayer volume in POPC and ∼8% in DMPC. PMID:25251987

  9. One-pot synthesis of SnO{sub 2}/reduced graphene oxide nanocomposite in ionic liquid-based solution and its application for lithium ion batteries

    SciTech Connect

    Gu, Changdong Zhang, Heng; Wang, Xiuli; Tu, Jiangping

    2013-10-15

    Graphical abstract: - Highlights: • A facile and low-temperature method is developed for SnO{sub 2}/graphene composite. • Synthesis performed in a choline chloride-based ionic liquid. • The composite shows an enhanced cycling stability as anode for Li-ion batteries. • 4 nm SnO{sub 2} nanoparticles mono-dispersed on the surface of reduced graphene oxide. - Abstract: A facile and low-temperature method is developed for SnO{sub 2}/graphene composite which involves an ultrasonic-assistant oxidation–reduction reaction between Sn{sup 2+} and graphene oxide in a choline chloride–ethylene glycol based ionic liquid under ambient conditions. The reaction solution is non-corrosive and environmental-friendly. Moreover, the proposed technique does not require complicated infrastructures and heat treatment. The SnO{sub 2}/graphene composite consists of about 4 nm sized SnO{sub 2} nanoparticles with cassiterite structure mono-dispersed on the surface of reduced graphene oxide. As anode for lithium-ion batteries, the SnO{sub 2}/graphene composite shows a satisfying cycling stability (535 mAh g{sup −1} after 50 cycles @100 mA g{sup −1}), which is significantly prior to the bare 4 nm sized SnO{sub 2} nanocrsytals. The graphene sheets in the hybrid nanostructure could provide a segmentation effect to alleviate the volume expansion of the SnO{sub 2} and restrain the small and active Sn-based particles aggregating into larger and inactive clusters during cycling.

  10. In Silico Calculation of Infinite Dilution Activity Coefficients of Molecular Solutes in Ionic Liquids: Critical Review of Current Methods and New Models Based on Three Machine Learning Algorithms.

    PubMed

    Paduszyński, Kamil

    2016-08-22

    The aim of the paper is to address all the disadvantages of currently available models for calculating infinite dilution activity coefficients (γ(∞)) of molecular solutes in ionic liquids (ILs)-a relevant property from the point of view of many applications of ILs, particularly in separations. Three new models are proposed, each of them based on distinct machine learning algorithm: stepwise multiple linear regression (SWMLR), feed-forward artificial neural network (FFANN), and least-squares support vector machine (LSSVM). The models were established based on the most comprehensive γ(∞) data bank reported so far (>34 000 data points for 188 ILs and 128 solutes). Following the paper published previously [J. Chem. Inf. Model 2014, 54, 1311-1324], the ILs were treated in terms of group contributions, whereas the Abraham solvation parameters were used to quantify an impact of solute structure. Temperature is also included in the input data of the models so that they can be utilized to obtain temperature-dependent data and thus related thermodynamic functions. Both internal and external validation techniques were applied to assess the statistical significance and explanatory power of the final correlations. A comparative study of the overall performance of the investigated SWMLR/FFANN/LSSVM approaches is presented in terms of root-mean-square error and average absolute relative deviation between calculated and experimental γ(∞), evaluated for different families of ILs and solutes, as well as between calculated and experimental infinite dilution selectivity for separation problems benzene from n-hexane and thiophene from n-heptane. LSSVM is shown to be a method with the lowest values of both training and generalization errors. It is finally demonstrated that the established models exhibit an improved accuracy compared to the state-of-the-art model, namely, temperature-dependent group contribution linear solvation energy relationship, published in 2011 [J. Chem

  11. Facilitated transport of Cu with hydroxyapatite nanoparticles in saturated sand: Effects of solution ionic strength and composition

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Column experiments were conducted to investigate the facilitated transport of Cu in association with hydroxyapatite nanoparticles (nHAP) in water-saturated quartz sand at different solution concentrations of NaCl (0 to 100 mM) or CaCl2 (0.1 to 1.0 mM). The experimental breakthrough curves and retent...

  12. Kinetic Growth of Ultralong Metastable Zincblende MnSe Nanowires Catalyzed by a Fast Ionic Conductor via a Solution-Solid-Solid Mechanism.

    PubMed

    Zhang, Li; Yang, Qing

    2016-07-13

    The metastable semiconductor phase allows for the exploration of unusual properties and functionalities of abnormal structures, although it is often difficult to prevent thermodynamic transformations to lower energy structures from higher, unfavored energy states. Here, we show for the first time the preparation of high-quality ultralong metastable zincblende (ZB)-MnSe nanowires with a four-coordinate structure via solution-solid-solid (SSS) growth in a mild solution-phase synthetic environment (120-220 °C) in the presence of a trace amount of Ag(I). The metastable ZB-MnSe nanowires are stabilized kinetically due to the catalysis of early formed body-centered cubic (bcc) fast-ionic (superionic) Ag2Se nanocrystals from the Ag(I) source, and the ZB-MnSe nanowires grow epitaxially along the ⟨110⟩ axis rather than the ⟨111⟩ axis, as commonly observed for typical four-coordinate Grimm-Sommerfeld bonding solids. Our method provides a new route for the growth of metastable nanostructures. PMID:27254244

  13. Concentration and temperature induced dual-responsive wormlike micelle to hydrogel transition in ionic liquid-type surfactant [C₁₆imC₉]Br aqueous solution without additives.

    PubMed

    Hu, Yimin; Ge, Lingling; Han, Jie; Guo, Rong

    2015-07-28

    A highly viscoelastic fluid formed by the ionic liquid-type surfactant 1-hexadecyl-3-nonyl imidazolium bromide ([C16imC9]Br) in water in the absence of any additive was studied. The phase behavior and morphology of aggregates were studied by a combination of rheological techniques, small-angle X-ray scattering (SAXS), cryo-etch-scanning electron microscopy (cryo-etch-SEM) and freeze-fractured transmission electron microscopy (FF-TEM). [C16imC9]Br aqueous solutions showed interesting rheological behavior as a function of both concentration and temperature, which invoked a transition between wormlike micelles and hydrogels. With the increase in [C16imC9]Br concentration, the aqueous solution could form viscoelastic wormlike micelles (50-80 mM), hydrogels (90-110 mM) and wormlike micelles (120-180 mM). As the temperature increased, the hydrogels (90-110 mM) could also transit to wormlike micelles. The unusual phase transition between wormlike micelles and elastic hydrogels was postulated to be the change of the average micellar length. PMID:26059909

  14. PbSe films by ion exchange of synthetic plumbonacrite layers immersed in a selenium ionic solution

    NASA Astrophysics Data System (ADS)

    Mendívil-Reynoso, T.; Ochoa-Landín, R.; Ramírez-Rodríguez, L. P.; Gutierrez-Acosta, K.; Ramírez-Bon, R.; Castillo, S. J.

    2016-06-01

    Plumbonacrite is a lead compound with chemical formula Pb10(CO3)6(OH)6O, where several groups can be substituted by ion exchange in mild conditions. Plumbonacrite layers can be deposited by means of the chemical bath deposition technique. In this work it is studied the structural and morphological evolution of a plumbonacrite layer as a function of the immersion time in an aqueous solution containing Se-2 ions. The 1.39 μm thick plumbonacrite layer was chemically deposited on a glass substrate and immersed in an aqueous solution with Se-2 ions for 10, 20, 30 and 50 min. The as grown plumbonacrite layer as well as the immersed ones were analyzed by X-rays Diffraction, Scanning Electron Microscopy and Raman Spectroscopy measurements. The results show that the plumbonacrite layer is gradually converted to PbSe one by ion exchange process, where Se-2 ions substitute the groups of plumbonacrite.

  15. Ab initio molecular dynamics study of polarization effects on ionic hydration in aqueous AlCl3 solution

    NASA Astrophysics Data System (ADS)

    Ikeda, Takashi; Hirata, Masaru; Kimura, Takaumi

    2003-12-01

    The solvation shell structure and dynamics of Al3+ and Cl- in an aqueous solution of 0.8 M AlCl3 are studied under ambient conditions by using an ab initio molecular dynamics method. The solvation structures obtained from our ab initio simulations are in good agreement with the experimental ones for both Al3+ and Cl-. A detailed analysis of intramolecular geometry of hydration waters and dipole moments of the ingredients shows that the polarization has substantial effects on the structures and dynamics of both the cation and anion hydration shells. Implications for metal hydrolysis of Al3+ will also be given.

  16. X-ray absorption spectroscopy studies of ionic association in aqueous solutions of zinc bromide from normal to critical conditions

    NASA Astrophysics Data System (ADS)

    Simonet, V.; Calzavara, Y.; Hazemann, J. L.; Argoud, R.; Geaymond, O.; Raoux, D.

    2002-08-01

    Ion-pairing and dehydration phenomena occurring in ZnBr2 aqueous solutions from normal to critical T, P conditions were investigated by x-ray absorption spectroscopy. The respective influences of temperature, pressure, and concentration were studied. The evolution of the density of solute ions, probed by the height of the absorption edge, allowed us to get information on phase diagrams and salt precipitation. The average structural evolution deduced from extended x-ray absorption fine structure was related to the formation of complexes identified from x-ray absorption near edge structure analysis. Consequently, in noncritical conditions, an increase of temperature or concentration produces dehydration and ion-pairing, while a rise of pressure destroys the ion-pairs. In contrast, concentration and pressure have weaker effects on the local order in high P, T conditions. Moreover, ion pairing formation is found not to be specifically enhanced when the fluid is close to supercritical conditions as it also occurs at lower temperatures. In a discussion, the modifications induced by a variation of the different structural parameters are related to the macroscopic properties of the solvent.

  17. Internal configuration and electric potential in planar negatively charged lipid head group region in contact with ionic solution.

    PubMed

    Lebar, Alenka Maček; Velikonja, Aljaž; Kramar, Peter; Iglič, Aleš

    2016-10-01

    The lipid bilayer composed of negatively charged lipid 1-palmitoyl-3-oleoyl-sn-glycero-3-phosphatidylserine (POPS) in contact with an aqueous solution of monovalent salt ions was studied theoretically by using the mean-field modified Langevin-Poisson-Boltzmann (MLPB) model. The MLPB results were tested by using molecular dynamic (MD) simulations. In the MLPB model the charge distribution of POPS head groups is theoretically described by the negatively charged surface which accounts for negatively charged phosphate groups, while the positively charged amino groups and negatively charged carboxylate groups are assumed to be fixed on the rod-like structures with rotational degree of freedom. The spatial variation of relative permittivity, which is not considered in the well-known Gouy-Chapman (GC) model or in MD simulations, is thoroughly derived within a strict statistical mechanical approach. Therefore, the spatial dependence and magnitude of electric potential within the lipid head group region and its close vicinity are considerably different in the MLPB model from the GC model. The influence of the bulk salt concentration and temperature on the number density profiles of counter-ions and co-ions in the lipid head group region and aqueous solution along with the probability density function for the lipid head group orientation angle was compared and found to be in qualitative agreement in the MLPB and MD models. PMID:27209203

  18. Molecular basis of high viscosity in concentrated antibody solutions: Strategies for high concentration drug product development.

    PubMed

    Tomar, Dheeraj S; Kumar, Sandeep; Singh, Satish K; Goswami, Sumit; Li, Li

    2016-01-01

    Effective translation of breakthrough discoveries into innovative products in the clinic requires proactive mitigation or elimination of several drug development challenges. These challenges can vary depending upon the type of drug molecule. In the case of therapeutic antibody candidates, a commonly encountered challenge is high viscosity of the concentrated antibody solutions. Concentration-dependent viscosity behaviors of mAbs and other biologic entities may depend on pairwise and higher-order intermolecular interactions, non-native aggregation, and concentration-dependent fluctuations of various antibody regions. This article reviews our current understanding of molecular origins of viscosity behaviors of antibody solutions. We discuss general strategies and guidelines to select low viscosity candidates or optimize lead candidates for lower viscosity at early drug discovery stages. Moreover, strategies for formulation optimization and excipient design are also presented for candidates already in advanced product development stages. Potential future directions for research in this field are also explored. PMID:26736022

  19. Finite Time Merton Strategy under Drawdown Constraint: A Viscosity Solution Approach

    SciTech Connect

    Elie, R.

    2008-12-15

    We consider the optimal consumption-investment problem under the drawdown constraint, i.e. the wealth process never falls below a fixed fraction of its running maximum. We assume that the risky asset is driven by the constant coefficients Black and Scholes model and we consider a general class of utility functions. On an infinite time horizon, Elie and Touzi (Preprint, [2006]) provided the value function as well as the optimal consumption and investment strategy in explicit form. In a more realistic setting, we consider here an agent optimizing its consumption-investment strategy on a finite time horizon. The value function interprets as the unique discontinuous viscosity solution of its corresponding Hamilton-Jacobi-Bellman equation. This leads to a numerical approximation of the value function and allows for a comparison with the explicit solution in infinite horizon.

  20. Application of evolution strategies for the solution of an inverse problem in near-field optics.

    PubMed

    Macías, Demetrio; Vial, Alexandre; Barchiesi, Dominique

    2004-08-01

    We introduce an inversion procedure for the characterization of a nanostructure from near-field intensity data. The method proposed is based on heuristic arguments and makes use of evolution strategies for the solution of the inverse problem as a nonlinear constrained-optimization problem. By means of some examples we illustrate the performance of our inversion method. We also discuss its possibilities and potential applications. PMID:15330475

  1. Probing solute-solvent interaction in 1-ethyl-3-methylimidazolium-based room temperature ionic liquids: A time-resolved fluorescence anisotropy study.

    PubMed

    Das, Sudhir Kumar; Sarkar, Moloy

    2014-03-01

    Rotational diffusion of two organic solutes, coumarin153 (C153) and 4-aminophthalimide (AP) has been investigated in four ionic liquids (ILs), viz. 1-ethyl-3-methylimidazolium trifluoroacetate (EMIMTFA), 1-ethyl-3-methylimidazolium ethylsulfate (EMIMESU), 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMTFB) and 1-ethyl-3-methylimidazolium tetracyanoborate (EMIMTCB), as a function of temperature. Between the two probes, AP can act as hydrogen-bond-donor to the solvents having hydrogen bond acceptor ability. The results indicate that the rotational dynamics of C153 is mainly governed by the viscosity of the medium. On the other hand, the rotational motion of AP is found to be significantly hindered in the ILs depending on the nature of anions of the ILs. Rotational coupling constant values for AP in the ILs follow the order TFA > ESU > TCB > TFB. The slower rotational motion of AP in these ILs has been attributed to the specific hydrogen bonding interaction between AP and anions of ILs. PMID:24158315

  2. Ionic liquids as electrolytes for non-aqueous solutions electrochemical supercapacitors in a temperature range of 20 °C-80 °C

    NASA Astrophysics Data System (ADS)

    Zhang, Lei; Tsay, Ken; Bock, Christina; Zhang, Jiujun

    2016-08-01

    To increase the operating temperature of the supercapacitors (SCs) without compromising their high cycle-life, several typical fluoro- and non-fluoro containing ionic liquids (EMI-mesylate, EMI-hydrogen sulfate, PP13-triflate, PP13-TFSI, and EMI-TFSI, as shown in Fig. 1) are studied as the electrolytes to prepare organic solutions for SC performance measurements using a two-electrode cell. Both cyclic voltammograms and charge/discharge curves at various temperatures such as 20, 40, 60 and 80 °C are collected. At 60 °C, the increased performance order in both rating and cyclability measurements are found to be as follows: 1) EMI-hydrogen sulfate < PP13-TFSI < EMI-mesylate < PP13-triflate < EMI-TFSI for rating; and 2) EMI-hydrogen sulfate < EMI-mesylate < PP13-Triflate < PP13-TFSI < EMI-TFSI for life-time. The fluoro-containing group of ILs, i.e., PP13-Triflate, PP13-TFSI and EMI-TFSI can give a specific capacitance between 100 and 170 F/g for various scan rates for a conventional carbon electrode, and an extended lifetime test of 10, 000 cycles with a capacitance degradation of less than 10%, indicating that these two ion liquids can be used for SC electrolytes operated at high temperature.

  3. Effect of cation type, alkyl chain length, adsorbate size on adsorption kinetics and isotherms of bromide ionic liquids from aqueous solutions onto microporous fabric and granulated activated carbons.

    PubMed

    Hassan, Safia; Duclaux, Laurent; Lévêque, Jean-Marc; Reinert, Laurence; Farooq, Amjad; Yasin, Tariq

    2014-11-01

    The adsorption from aqueous solution of imidazolium, pyrrolidinium and pyridinium based bromide ionic liquids (ILs) having different alkyl chain lengths was investigated on two types of microporous activated carbons: a fabric and a granulated one, well characterized in terms of surface chemistry by "Boehm" titrations and pH of point of zero charge measurements and of porosity by N2 adsorption at 77 K and CO2 adsorption at 273 K. The influence of cation type, alkyl chain length and adsorbate size on the adsorption properties was analyzed by studying kinetics and isotherms of eight different ILs using conductivity measurements. Equilibrium studies were carried out at different temperatures in the range [25-55 °C]. The incorporation of ILs on the AC porosity was studied by N2 adsorption-desorption measurements at 77 K. The experimental adsorption isotherms data showed a good correlation with the Langmuir model. Thermodynamic studies indicated that the adsorption of ILs onto activated carbons was an exothermic process, and that the removal efficiency increased with increase in alkyl chain length, due to the increase in hydrophobicity of long chain ILs cations determined with the evolution of the calculated octanol-water constant (Kow). The negative values of free energies indicated that adsorption of ILs with long chain lengths having hydrophobic cations was more spontaneous at the investigated temperatures. PMID:24929502

  4. Learning to solve a problem: a microanalysis of the solution strategies of children with learning disabilities.

    PubMed

    Wansart, W L

    1990-03-01

    Ten subjects with learning disabilities and 10 normally achieving subjects, aged 10-5 to 12-5 years, were videotaped while attempting to solve the Tower of Hanoi problem (see Karat, 1982; Piaget, 1976; Simon, 1975). A microanalysis of their problem-solving activities provided a descriptive taxonomy used to analyze what, in fact, individual subjects did when constructing a solution strategy, and to categorize and compare changes in strategy. The results indicated that as a group the normally achieving subjects reached more sophisticated levels of strategy use (p less than .05). However, if the focus of the comparison is on an analysis of how learning proceeded in individuals, then the subjects with learning disabilities appear to be similar to the normally achieving subjects. There was no evidence in these subjects of the popular conception that individuals with learning disabilities are inactive, passive, or maladaptive in their attempts to learn to solve a problem. PMID:2313189

  5. Preparation of non-aggregating aqueous fullerenes in highly saline solutions with a biocompatible non-ionic polymer

    NASA Astrophysics Data System (ADS)

    Aich, Nirupam; Boateng, Linkel K.; Flora, Joseph R. V.; Saleh, Navid B.

    2013-10-01

    Size-tunable stable aqueous fullerenes were prepared with different concentrations of biocompatible block-copolymer pluronic (PA) F-127, ranging from 0.001% to 1% (w/v). Size uniformity increased with the increase in PA concentration, yielding optimum 58.8 ± 5.6 and 61.8 ± 5.6 nm nC60s and nC70s, respectively (0.10%w/v PA), as observed using a dynamic light scattering technique. Fullerene aqueous suspensions also manifested enhanced stability in saline solution, Dulbecco’s modified Eagle medium (DMEM), and Roswell Park Memorial Institute (RPMI) culture medium. Transmission electron microscopy was performed to elaborate on the morphology and size specificity of fullerene clusters. Physicochemical characterizations of the suspended fullerenes were performed through UV-vis spectroscopy and electrophoretic mobility measurements. PA molecules showed size restriction by encasement, as observed via molecular dynamics simulations. Such solubilization with controllable size and non-aggregating behavior can facilitate application enhancement and mechanistic environmental and toxicological studies of size-specific fullerenes.

  6. Monte Carlo simulation for the potential of mean force between ionic colloids in solutions of asymmetric salts

    SciTech Connect

    Wu, J.Z.; Bratko, D.; Blanch, H.W.; Prausnitz, J.M. |

    1999-10-01

    A new technique for Monte Carlo sampling of the hard-sphere collision force has been applied to study the interaction between a pair of spherical macroions in primitive-model electrolyte solutions with valences 1:2, 2:1, and 2:2. Macroions of the same charge can attract each other in the presence of divalent counterions, in analogy with earlier observations for planar and cylindrical geometries. The attraction is most significant at intermediate counterion concentrations. In contrast to the entropic depletion force between neutral particles, attraction between macroions is of energetic origin. The entropic contribution to the potential of mean force is generally repulsive at conditions corresponding to aqueous colloids with or without salt. For systems with divalent counterions, the potentials of mean force predicted by mean-field approximations like the Derjaguin{endash}Landau{endash}Verwey{endash}Overbeek (DLVO) theory or the Sogami{endash}Ise (SI) theory are qualitatively different from those observed in the simulations. However, for systems with monovalent counterions, predictions of DLVO theory are in fair agreement with simulation results. {copyright} {ital 1999 American Institute of Physics.}

  7. Removal of malachite green dye from aqueous solution using mesoporous silica synthesized from 1-octyl-3-methylimidazolium chloride ionic liquid

    NASA Astrophysics Data System (ADS)

    Ekka, Basanti; Nayak, Soumitra Ranjan; Dash, Priyabrat; Patel, Raj Kishore

    2016-04-01

    In this research, mesoporous silica was synthesized via a modified sol-gel route using 1-octyl-3-methylimidazolium chloride and was employed to remove malachite green (MG) dye from aqueous solution. Subsequently, this material was characterized and identified by different techniques such as Fourier transform infrared spectroscopy (FT-IR), N2 adsorption-desorption method, scanning electron microscopy (SEM), and thermosgravimetric analysis (TGA). Unique properties such as high surface area and pore diameter, in addition to highly reactive atoms and presence of various functional groups make the mesoporous silica possible for efficient removal of malachite green (MG). In batch experimental set-up, optimum conditions for quantitative removal of MG by mesoporous silica was attained by varying different variables such as adsorbent dosage, initial dye concentration, contact time, and pH. Optimum values were set as pH of 8.0, 0.5 g of adsorbent at contact time of 120 min. The adsorption of MG follows the pseudo-second-order rate equation. Equilibrium data fitted well with the Freundlich model at all amount of adsorbent, while maximum adsorption capacity was 5.981 mg g-1 for 0.5 g mesoporous silica synthesized in IL.

  8. Extraction of silver(I) from aqueous solutions in the absence and presence of copper(II) with a methimazole-based ionic liquid.

    PubMed

    Reyna-González, Juan M; Torriero, Angel A J; Siriwardana, Amal I; Burgar, Iko M; Bond, Alan M

    2011-08-21

    The ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf(2)], facilitates the efficient extraction of silver(I) from aqueous media via interaction with both the cation and anion components of the IL. Studies with a conventional aqueous-IL two phase system as well as microextraction of silver(I) by a thick IL film adhered to an electrode monitored in situ by cyclic voltammetry, established that [mimSBu][NTf(2)] can extract electroactive silver(I) ions from an aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu](+), which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of silver(I) further increase the acidity of the aqueous phase as a consequence of coordination with the IL cation component. Voltammetric and (1)H and (13)C NMR techniques have been used to establish the nature of the silver(I) complexes extracted, and show that the form of interaction with the IL differs from that outlined previously for the extraction of copper(II). Insights on the competition established when silver(I) is extracted in the presence of copper(II) are provided. Finally, it is noted that metallic silver can be directly electrodeposited at the electrode surface after extraction of silver(I) into [mimSBu][NTf(2)] and that back extraction of silver(I) into aqueous media is achieved by addition of an acidic aqueous solution. PMID:21727953

  9. Solubility of B-Nb2O5 and the Hydrolysis of Niobium(V) in Aqueous Solution as a Function of Temperature and Ionic Strength

    SciTech Connect

    Peiffert, C; Nguyen-Trung, Chinh {nmn}; Palmer, Donald; Laval, J. P.; Giffaut, E.

    2010-01-01

    B-Nb{sub 2}O{sub 5} was recrystallized from commercially available oxide, and XRD analyses indicated that it is stable in contact with solutions over the pH range 0 to 9, whereas solid polyniobates such as Na{sub 8}Nb{sub 6}O{sub 19} 13H{sub 2}O(s) appear to predominate at pH > 9. Solubilities of the crystalline B-Nb{sub 2}O{sub 5} were determined in five NaClO{sub 4} solutions (0.1 {le} Im/mol {center_dot} kg{sup -1} {le} 1.0) over a wide pH range at (25.0 {+-} 0.1) C and at 0.1 MPa. A limited number of measurements were also made at Im = 6.0 mol {center_dot} kg{sup -1}, whereas at Im = 1.0 mol {center_dot} kg{sup -1} the full range of pH was also covered at (10, 50 and 70) C. The pH of these solutions was fixed using either HClO{sub 4} (pH {le} 4) or NaOH (pH {ge} 10) and determined by mass balance, whereas the pH on the molality scale was measured in buffer mixtures of acetic acid + acetate (4 {le} pH {le} 6), Bis-Tris (pH {approx} 7), Tris (pH {approx} 8) and boric acid + borate (pH {approx} 9). Treatment of the solubility results indicated the presence of four species, Nb(OH){sub n}{sup 5-n} (where n = 4-7), so that the molal solubility quotients were determined according to: 0.5Nb{sub 2}O{sub 5}(cr) + 0.5(2n-5)H{sub 2}O(l){sup {center_dot}-} Nb(OH){sub n}{sup 5-n} + (n-5)H{sup +} (n = 4-7) and were fitted empirically as a function of ionic strength and temperature, including the appropriate Debye-Hueckel term. A Specific Interaction Theory (SIT) approach was also attempted. The former approach yielded the following values of log 10 K{sub sn} (infinite dilution) at 25 C: -(7.4 {+-} 0.2) for n = 4; -(9.1 {+-} 0.1) for n = 5; -(14.1 {+-} 0.3) for n = 6; and -(23.9 {+-} 0.6) for n = 7. Given the experimental uncertainties (2{sigma}), it is interesting to note that the effect of ionic strength only exceeded the combined uncertainties significantly in the case of log 10 K{sub s6} to I{sub m} = 1.0 mol {center_dot} kg{sup -1}, such that these values may be of use by

  10. Enhancing the basicity of ionic liquids by tuning the cation-anion interaction strength and via the anion-tethered strategy.

    PubMed

    Xu, Dan; Yang, Qiwei; Su, Baogen; Bao, Zongbi; Ren, Qilong; Xing, Huabin

    2014-01-30

    Ionic liquids (ILs) with relatively strong basicity often show impressive performance in chemical processes, so it is important to enhance the basicity of ILs by molecular design. Here, we proposed two effective ways to enhance the basicity of ILs: by weakening the cation-anion interaction strength and by employing the anion-tethered strategy. Notably, two quantum-chemical parameters, the most negative surface electrostatic potential and the lowest surface average local ionization energy, were adopted as powerful tools to demonstrate the electrostatic and covalent aspects of basicity, respectively, at the microscopic level. It was shown that, for the ILs with the same anion (acetate or trifluoroacetate), the basicity of the ILs could be enhanced when the cation-anion interaction strength was weakened. For the acetate anion-based ILs, the hydrogen-bonding basicity scale (β) increased by 29% when the cation changed from 1-butyl-3-methylimidazolium ([Bmim]) to tetrabutylphosphonium ([P4444]), achieving one of the highest reported β values for ILs. Moreover, it was also demonstrated that, when an amine group was tethered to the anion of the IL, its basicity was stronger than when it was tethered to the cation. These results are highly instructive for designing ILs with strong basicity and for improving the efficiency of IL-based processes, such as CO2 capture, SO2 and acetylene absorption, dissolution of cellulose, extraction of bioactive compounds, and so on. PMID:24387657

  11. Experimental and DFT studies on the aggregation behavior of imidazolium-based surface-active ionic liquids with aromatic counterions in aqueous solution.

    PubMed

    Xu, Wenwen; Wang, Tao; Cheng, Ni; Hu, Qiongzheng; Bi, Yanhui; Gong, Yanjun; Yu, Li

    2015-02-01

    Two imidazolium-based surface-active ionic liquids with aromatic counterions, namely, 1-dodecyl-3-methylimidazolium salicylate (C12mimSal) and 1-dodecyl-3-methylimidazolium 3-hydroxy-2-naphthoate (C12mimHNC), were synthesized, and their aggregate behavior in aqueous solutions was systematically explored. Surface tension and conductivity measurements indicate that both C12mimSal and C12mimHNC show superior surface activity compared to the common imidazolium-based SAIL with the same hydrocarbon chain length, 1-dodecyl-3-methylimidazolium bromide (C12mimBr). This result demonstrates that the incorporation of aromatic counterions favors the formation of micelles. C12mimHNC displays a higher surface activity than C12mimSal, resulting from the different hydrophobicities of the counterions. In comparison with C12mimBr, C12mimSal not only can form hexagonal liquid-crystalline phase (H1) in aqueous solution, but also exhibits a broad region of cubic liquid-crystalline phase (V2) at higher concentration. As for the C12mimHNC/H2O system, a lamellar liquid-crystalline (L(α)) phase was observed. These lyotropic liquid crystals (LLCs) were characterized by polarized optical microscopy (POM) and small-angle X-ray scattering (SAXS). Structural parameters calculated from SAXS patterns suggest that a higher concentration of the SAIL leads to a denser arrangement whereas a higher temperature results in the opposite effect. The rheological results manifest that the formed H1 phase in the C12mimSal/H2O system exhibits an impressive viscoelastic behavior, indicated by a modulus (G' and G″) that is 1 order of magnitude higher than that of C12mimBr. Density functional theory (DFT) calculations reveal that C12mimSal has a more negative interaction energy with a water molecule and the Sal(-) counterion presents a stronger electronegativity than the HNC(-) counterion. The specific phase behavior of the C12mimSal/H2O and C12mimHNC/H2O systems can be attributed to the strong synergic

  12. Three strategies to stabilise nearly monodispersed silver nanoparticles in aqueous solution

    PubMed Central

    2012-01-01

    Silver nanoparticles are extensively used due to their chemical and physical properties and promising applications in areas such as medicine and electronics. Controlled synthesis of silver nanoparticles remains a major challenge due to the difficulty in producing long-term stable particles of the same size and shape in aqueous solution. To address this problem, we examine three strategies to stabilise aqueous solutions of 15 nm citrate-reduced silver nanoparticles using organic polymeric capping, bimetallic core-shell and bimetallic alloying. Our results show that these strategies drastically improve nanoparticle stability by distinct mechanisms. Additionally, we report a new role of polymer functionalisation in preventing further uncontrolled nanoparticle growth. For bimetallic nanoparticles, we attribute the presence of a higher valence metal on the surface of the nanoparticle as one of the key factors for improving their long-term stability. Stable silver-based nanoparticles, free of organic solvents, will have great potential for accelerating further environmental and nanotoxicity studies. PACS: 81.07.-b; 81.16.Be; 82.70.Dd. PMID:22356679

  13. Ionic liquid-aqueous solution ultrasonic-assisted extraction of three kinds of alkaloids from Phellodendron amurense Rupr and optimize conditions use response surface.

    PubMed

    Wang, Wenchao; Li, Qingyong; Liu, Yuhui; Chen, Binbin

    2015-05-01

    In this paper, we chose diffident kinds of ionic liquids to optimal selection an optimal one to extract alkaloids from Phellodendron amurense Rupr. Four ionic liquids with diffident carbon chains or anions have been investigated and 1-butyl-3-methylimidazolium bromide with best productivity. Then, selections have been optimized in different conditions, including concentration of ionic liquid, time for ultrasonic treatment, ultrasonic power and solid-liquid ratio. Moreover, three conditions have been comprehensively assessment by response surface methodology, the optimal conditions were determined as follows ultrasonic power 100 W, extraction time 75 min and ratio of solvent to raw material 1:14. Under these conditions, the yield% (MIX) was 106.7% (extracted by heat reflux being defined 100%). Comparing with other methods, the advantages are saving conserving, time saving, high yield% and especially pollution-free. PMID:25443277

  14. Solution-Focused Strategies for Effective Sexual Health Communication among African American Parents and Their Adolescents.

    PubMed

    Johnson, Sharon D; Williams, Sha-Lai

    2015-11-01

    The high rates of sexual risk behaviors, particularly among African American youths who may not be aware of their HIV status, provide indication that, unless prevention efforts are enhanced, this vulnerable group of youths will remain at greater risk for negative health status outcomes. Parents are important in efforts to reduce risk among youths and often have a willingness to be sexuality educators for their children; however, communication barriers often impede their ability to provide preventive sexual health knowledge to their youths. Social workers are often presented with opportunities to help parents develop effective sexual health communication skills in informal settings when formal interventions are not feasible. The present effort considers solution-focused strategies social workers can use to help parents overcome barriers and communicate more positively with their youths about sexual health. PMID:26638502

  15. Structural study of the N,N'-dimethylpropyleneurea solvated lanthanoid(III) ions in solution and solid state with an analysis of the ionic radii of lanthanoid(III) ions.

    PubMed

    Lundberg, Daniel; Persson, Ingmar; Eriksson, Lars; D'Angelo, Paola; De Panfilis, Simone

    2010-05-17

    The structures of the N,N'-dimethylpropyleneurea (dmpu) solvated lanthanoid(III) ions have been studied in dmpu solution (La-Nd, Sm-Lu) and in solid iodide salts (La-Nd, Sm, Gd-Lu) by extended X-ray absorption fine structure (EXAFS), and single crystal X-ray diffraction (La, Pr, Nd, Gd, Tb, Er, Yb, and Lu); the EXAFS studies were performed on both K and L(III) absorption edges. Because of the space-demanding properties of dmpu upon coordination, dmpu solvated metal ions often show coordination numbers lower than those found in corresponding hydrates and solvates of oxygen donor solvents without steric requirements beyond the size of the donor atom. All lanthanoid(III) ions are seven-coordinate in solution, except lutetium(III) which is six-coordinated in regular octahedral fashion, whereas in the solid iodide salts the dmpu solvated lanthanoid(III) ions are all six-coordinate in regular octahedral fashion. A comparison of Ln-O bond lengths in a large number of lanthanoid(III) complexes with neutral oxygen donor ligands and different configurations shows that the metal ion-oxygen distance is specific for each coordination number with a narrow bond distance distribution. This also shows that the radius of the coordinated oxygen atom in these compounds can be assumed to be 1.34 A as proposed for coordinated water, while for ethers such as tetrahydrofuran (thf) it is somewhat larger. Using this atomic radius of oxygen in coordinated water molecules, we have calculated the ionic radii of the lanthanoid(III) ions in four- to nine-coordination and evaluated using the bond lengths reported for homo- and heteroleptic complexes in oxygen donor solvates in solution and solid state. This yields new and revised ionic radii which in some instances are significantly different from the ionic radii normally referenced in the literature, including interpolated values for the elusive promethium(III) ion. PMID:20397652

  16. Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity

    NASA Astrophysics Data System (ADS)

    Small, Leo J.; Wheeler, David R.; Spoerke, Erik D.

    2015-10-01

    Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems.Nanopore size, shape, and surface charge all play

  17. Nanoporous membranes with electrochemically switchable, chemically stabilized ionic selectivity

    NASA Astrophysics Data System (ADS)

    Small, Leo J.; Wheeler, David R.; Spoerke, Erik D.

    2015-10-01

    Nanopore size, shape, and surface charge all play important roles in regulating ionic transport through nanoporous membranes. The ability to control these parameters in situ provides a means to create ion transport systems tunable in real time. Here, we present a new strategy to address this challenge, utilizing three unique electrochemically switchable chemistries to manipulate the terminal functional group and control the resulting surface charge throughout ensembles of gold plated nanopores in ion-tracked polycarbonate membranes 3 cm2 in area. We demonstrate the diazonium mediated surface functionalization with (1) nitrophenyl chemistry, (2) quinone chemistry, and (3) previously unreported trimethyl lock chemistry. Unlike other works, these chemistries are chemically stabilized, eliminating the need for a continuously applied gate voltage to maintain a given state and retain ionic selectivity. The effect of surface functionalization and nanopore geometry on selective ion transport through these functionalized membranes is characterized in aqueous solutions of sodium chloride at pH = 5.7. The nitrophenyl surface allows for ionic selectivity to be irreversibly switched in situ from cation-selective to anion-selective upon reduction to an aminophenyl surface. The quinone-terminated surface enables reversible changes between no ionic selectivity and a slight cationic selectivity. Alternatively, the trimethyl lock allows ionic selectivity to be reversibly switched by up to a factor of 8, approaching ideal selectivity, as a carboxylic acid group is electrochemically revealed or hidden. By varying the pore shape from cylindrical to conical, it is demonstrated that a controllable directionality can be imparted to the ionic selectivity. Combining control of nanopore geometry with stable, switchable chemistries facilitates superior control of molecular transport across the membrane, enabling tunable ion transport systems.Nanopore size, shape, and surface charge all play

  18. Transport and deposition of Suwannee River Humic Acid/Natural Organic Matter formed silver nanoparticles on silica matrices: the influence of solution pH and ionic strength.

    PubMed

    Akaighe, Nelson; Depner, Sean W; Banerjee, Sarbajit; Sohn, Mary

    2013-07-01

    The transport and deposition of silver nanoparticles (AgNPs) formed from Ag(+) reduction by Suwannee River Humic Acid (SRHA) and Suwannee River Natural Organic Matter (SRNOM) utilizing a silica matrix is reported. The morphology and stability of the AgNPs was analyzed by transmission electron microscopy (TEM), dynamic light scattering (DLS) and zeta potential measurements. The percentage conversion of the initial [Ag(+)] to [AgNPs] was determined from a combination of atomic absorption (AAS) and UV-Vis spectroscopy, and centrifugation techniques. The results indicate higher AgNP transport and consequently low deposition in the porous media at basic pH conditions and low ionic strength. However, at low acidic pH and high ionic strength, especially with the divalent metallic cations, the mobility of the AgNPs in the porous media was very low, most likely due to NP aggregation. Overall, the results suggest the potential for AgNP contamination of subsurface soils and groundwater aquifers is mostly dependent on their aggregation state, controlled by the soil water and sediment ionic strength and pH. PMID:23422173

  19. Deposition and release kinetics of nano-TiO2 in saturated porous media: effects of solution ionic strength and surfactants.

    PubMed

    Godinez, Itzel G; Darnault, Christophe J G; Khodadoust, Amid P; Bogdan, Dorin

    2013-03-01

    The aggregation, transport and deposition kinetics (i.e. attachment and release) of TiO(2) nanoparticles (nano-TiO(2)) were investigated as a function of ionic strength and the presence of anionic (sodium dodecylbenzene sulfonate, SDBS) and non-ionic (Triton X-100) surfactants in 100% critical micelle concentration (CMC). The electrolyte concentration of the suspensions dictated the kinetic stability of nano-TiO(2) thus influencing the transport and retention of the nanoaggregates in the saturated porous medium. With increasing ionic strength, the interaction between approaching nano-TiO(2) and nano-TiO(2) already deposited onto collectors surfaces seemed to be more favorable than the interaction between approaching nano-TiO(2) and bare collectors surfaces. The abrupt and gradual reduction in electrolyte concentration during the flushing cycles of the column experiments induced the release of previously deposited nano-TiO(2) suggesting attachment of nano-TiO(2) through secondary energy minimum. PMID:23246754

  20. Better Strategies for Finite Element Solutions of Variable Viscosity Stokes Flow

    NASA Astrophysics Data System (ADS)

    Hasenclever, Jörg; Phipps Morgan, Jason; Shi, Chao

    2010-05-01

    Accurate numerical solution of variable viscosity Stokes Flow is one of the most important issues for better geodynamic understanding of mantle convection and mantle melting. While a good Stokes solver is usually an integral part of a good Navier-Stokes solver, typically Navier-Stokes equations are solved for flow of a fluid with uniform viscosity. The lumped-mass-matrix is an excellent and cheap preconditioner for uniform viscosity Stokes flow (cf. Maday and Patera, 1989), therefore for most applications to Navier-Stokes flow the ‘Stokes' part of the problem is viewed as well-resolved. Unfortunately, the inverse-viscosity-scaled lumped mass matrix does not work nearly as well to precondition Stokes flow in a fluid with strongly varying viscosity. This issue is already central to accurate numerical studies of convection in Earth's silicate-fluid mantle (May and Moresi, 2008; van Geenen et al., 2009; Burstedde et al., 2009) and may become central for researchers investigating Navier-Stokes problems with lateral variations in viscosity. Here we discuss several known computational hurdles to progress, and suggest strategies that offer promise in overcoming them. The choices for solving the discrete pressure equation arising from Stokes flow typically involve several tradeoffs between speed and storage requirements. In exact math, the discrete pressure matrix S is symmetric, so that it should be possible to use a symmetric preconditioned conjugate gradient (CG) Krylov algorithm instead of needing an asymmetric GMRES (cf. Saad, 2003) or GCR (Generalized Conjugate Residual, cf. Van der Vorst, 2003) that would require ~10-50 times more storage of past search directions. However, a CG-like method requires that the action of both S and any pressure preconditioner must be almost perfectly symmetric. This means that we must be very careful about the effects of roundoff in any iterative solver-based pressure preconditioner that may introduce numerically asymmetric operators

  1. pH-Responsive poly(itaconic acid-co-N-vinylpyrrolidone) hydrogels with reduced ionic strength loading solutions offer improved oral delivery potential for high isoelectric point-exhibiting therapeutic proteins.

    PubMed

    Koetting, Michael C; Peppas, Nicholas A

    2014-08-25

    pH-Responsive hydrogels comprised of itaconic acid copolymerized with N-vinylpyrrolidone (P(IA-co-NVP)) were synthesized and tested as carriers for the oral delivery of high isoelectric point (pI) exhibiting therapeutic proteins. Swelling studies show that P(IA-co-NVP) hydrogels exhibit significantly greater and faster pH-responsive swelling than previously studied methacrylic acid-based hydrogels, achieving up to 68% greater equilibrium swelling and 10.4 times greater swelling in time-limited experiments. Using salmon calcitonin as a model high pI protein therapeutic, we show that P(IA-co-NVP) hydrogels exhibit significantly greater delivery potential than methacrylic acid-based hydrogels. Additionally, we show that utilizing a lower ionic strength solution during drug loading significantly improves drug delivery potential for high pI therapeutics. By using a 1.5mM PBS buffer rather than the standard 150 mM PBS buffer during loading, up to 83 times as much calcitonin can be delivered in neutral conditions, with up to a 9.6-fold improvement in percent release. Using P(IA-co-NVP) hydrogel microparticles and a low ionic strength loading solution, up to 48 μg calcitonin/mg hydrogel can be delivered in small intestinal conditions. Based on expected absorption in the small intestine, this is sufficient delivery potential for achieving therapeutic dosage via a single, regularly-sized pill taken daily. PMID:24853463

  2. On-Demand Droplet Fusion: A Strategy for Stimulus-Responsive Biosensing in Solution

    PubMed Central

    2015-01-01

    A novel strategy is reported for biochemically controlled fusion of oil-in-water (O/W) droplets as an in-solution sensor for biological targets. Inspired by the SNARE complex in cells, the emulsions were stabilized by a combination of phospholipids, phospholipid–poly(ethylene glycol) conjugates, and cholesterol-anchored oligonucleotides. Prior to oligonucleotide binding, the droplets were stable in aqueous media, but hybridization of the oligonucleotides in a zipperlike fashion was shown to initiate droplet fusion. Using image analysis of content mixing of dye-loaded droplets, fusion specificity was studied and optimized as a function of interfacial chemistry. Changing the orientation of the anchored oligonucleotides, using long-chain phospholipids (C18 and C22), and binding a complementary oligonucleotide slowed or even halted fusion completely. Based on these studies, a sensor for the biomarker thrombin was designed using competitive binding of aptamer strands, with droplet fusion increasing as a function of thrombin addition in accordance with a simple binding model, with sensitivity down to 100 nM and with results in as little as 15 min. Future efforts will focus on utilizing this mechanism of content mixing to facilitate highly sensitive detection via modalities such as magnetoresistance or chemiluminescence. PMID:25263344

  3. Ionic Liquids Database- (ILThermo)

    National Institute of Standards and Technology Data Gateway

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

  4. Solvent and rotational relaxation of Coumarin-153 in a micellar solution of a room-temperature ionic liquid, 1-butyl-3-methylimidazolium octyl sulfate, in ethylammonium nitrate

    NASA Astrophysics Data System (ADS)

    Rao, Vishal Govind; Ghatak, Chiranjib; Pramanik, Rajib; Sarkar, Souravi; Sarkar, Nilmoni

    2010-10-01

    We have investigated the micelle formation by room-temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium octyl sulfate (bmimOs) with another RTIL, ethyl ammonium nitrate (EAN). In addition, the effect of micelle formation on the solvation and rotational relaxation dynamics have been observed using steady-state and picoseconds time-resolved spectroscopy. Both the solvent and rotational relaxations of Coumarin-153 are retarded in the micelle compared to that of neat EAN. The increase in average solvation time on going from neat EAN to bmimOs-EAN micelle is very small compared to the increase in solvation time on going from pure water to water containing micelle.

  5. Novel strategy for f-HAp/PVP/Ag nanocomposite synthesis from fluoro based ionic liquid assistance: Systematic investigations on its antibacterial and cytotoxicity behaviors.

    PubMed

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

    2016-10-01

    A novel biomimetic f-HAp/PVP/Ag nanocomposite was synthesized under the ionic liquid medium, which was composed of inorganic and organic nanofillers like fluor-hydroxyapatite, silver nanoparticles and polyvinyl pyrrolidone. In composite synthesis, the first time we were used fluorine based ionic liquid for the fluorine contents on the fluor-hydroxyapatite nanoparticles which were resulting in very good crosslinking and interfacial bonding with the PVP and Ag nanoparticles. Ionic liquid has assisted good morphological structure of both inorganic materials. The chemical interaction and crystallinity changes of the nanocomposite were evaluated by FTIR and XRD studies. The surface morphology and composition of the samples were observed by FE-SEM, HR-TEM and EDS analyses. This report reveals that the greener approach for synthesis of fluor-hydroxyapatite nanocomposite and sustained delivery of silver and fluorine ions from the fluor-hydroxyapatite surface to the bacterial surface have been reducing the bacterial growth rate which was evaluated by different pathogenic bacterial strains via different methods and it also favourable cytotoxicity effect with human osteosarcoma (MG-63) cells. PMID:27287093

  6. Ionic Liquid assisted Synthesis of Zeolite-TON

    PubMed Central

    Tian, Yuyang; McPherson, Matthew J; Wheatley, Paul S; Morris, Russell E

    2014-01-01

    An ionic liquid assisted strategy for the synthesis of zeolitic material is reported. This strategy is a solid state synthetic method and the ionic liquid is employed as structure directing agent. A TON-type zeolite, which contains one-dimensional 10-member-ring, is successfully synthesized with the assistance of the ionic liquid, 1-ethyl-3-methylimidazolium bromide. This finding improves our understanding about the challenge of ionothermally synthesizing siliceous and aluminosilicate zeolites. PMID:26213423

  7. Why 'Science + Solutions' Is An Effective & Essential Climate Communications Strategy (Invited)

    NASA Astrophysics Data System (ADS)

    Haines-Stiles, G.; Alley, R. B.; Akuginow, E.

    2013-12-01

    , universities and church groups have used the project in this way. Alley is working with Penn State and Coursera on a MOOC (Massive Open Online Course) focused on energy, economics and the environment and linking to several ETOM YouTube videos. As important as new media, however, is the core message-featured most prominently in the third ETOM program, 'Energy Quest USA'-that regardless of national policies states and cities are moving ahead on clean energy solutions with consequent beneficial impacts on climate change. By cutting demand through conservation and efficiency, Baltimore has avoided a new coal-fired generating plant. Through 30 years of wise urban planning and the support of mass transit, Portland, Oregon, has reduced an average family's transportation costs by some $2,500, while improving health by encouraging cycling and walking. There are proven ways both to adapt to a changing climate and to begin to mitigate its most severe impacts. The ETOM project shows that when presented in a wide and diverse set of media, and in an authoritative and apolitical framework, those messages are received and appreciated by large public audiences. This presentation will report on the success of several of the strategies adopted by the ETOM project, and how they contrast with, or complement, other communications efforts on clean energy and climate change.

  8. Probing the interplay between electrostatic and dispersion interactions in the solvation of nonpolar nonaromatic solute molecules in ionic liquids: An OKE spectroscopic study of CS2/[CnC1im][NTf2] mixtures (n = 1-4)

    NASA Astrophysics Data System (ADS)

    Xue, Lianjie; Tamas, George; Gurung, Eshan; Quitevis, Edward L.

    2014-04-01

    The intermolecular dynamics of dilute solutions of CS2 in 1-alkyl-3-methylimidazolium bis[(trifluoromethane)sulfonyl]amide ([CnC1im][NTf2] for n = 1-4) were studied at 295 K using femtosecond optical Kerr effect (OKE) spectroscopy. The OKE spectra of the CS2/ionic liquid (IL) mixtures were analyzed using an additivity model to obtain the CS2 contribution to the OKE spectrum from which information about the intermolecular modes of CS2 in these mixtures was gleaned. The intermolecular spectrum of CS2 in these mixtures is lower in frequency and narrower than that of neat CS2, as found previously for CS2 in [C5C1im][NTf2]. Moreover, a dependence of the spectra on alkyl chain length is observed that is attributed to the interplay between electrostatic and dispersion interactions. The surprising result in this study is the solubility of CS2 in [C1C1im][NTf2], which involves the interaction of a nonpolar nonaromatic molecular solute and only the charged groups of the IL. We propose that the solubility of CS2 in [C1C1im][NTf2] is determined by three favorable factors - (1) large polarizability of the solute molecule; (2) small size of the solute molecule; and (3) low cohesive energy in the high-charge density regions of the IL.

  9. A new strategy for determination of bisphenol A in the presence of Sudan I using a ZnO/CNTs/ionic liquid paste electrode in food samples.

    PubMed

    Najafi, Maryam; Khalilzadeh, Mohammad A; Karimi-Maleh, Hassan

    2014-09-01

    The electrochemistry of bisphenol A (BPA) was studied by voltammetric methods at a surface of carbon paste electrode modified by a ZnO/CNTs nanocomposite and room-temperature ionic liquid of 1,3-dipropylimidazolium bromide. The ratio of ZnO/CNTs and ionic liquid (IL) on the surface of the electrode has to be controlled carefully because the charging currents. The anodic peaks of BPA and Sudan I in their mixture can be well separated. At pH 7.0 the two peaks are separated ca. 0.47 and 0.70 V, respectively; hence BPA can be determined in the presence of Sudan I and more than 8.7 times current excess of BPA. The peaks current of square wave voltammograms (SWV) of BPA and Sudan I increased linearly with their concentration in the ranges of 0.002-700 μmol L(-1)BPA and 0.2-800 μmol L(-1) Sudan I. The detection limits for BPA and Sudan I were 9.0 nmol L(-1) and 80 nmol L(-1), respectively. The modified electrode has been successfully applied for the assay of BPA in food samples. This study provides a simple and easy approach to selectively detect BPA in the presence of Sudan I. PMID:24731323

  10. Solve the Problem First: Constructive Solution Strategies Can Influence the Accuracy of Retrospective Confidence Judgments

    ERIC Educational Resources Information Center

    Mitchum, Ainsley L.; Kelley, Colleen M.

    2010-01-01

    Two experiments tested whether differences in problem-solving strategies influence the ability of people to monitor their problem-solving effectiveness as measured by confidence judgments. On multiple choice problems, people tend to use either a constructive matching strategy, whereby they attempt to solve a problem before looking at the response…

  11. Statistical Significance of the Contribution of Variables to the PCA Solution: An Alternative Permutation Strategy

    ERIC Educational Resources Information Center

    Linting, Marielle; van Os, Bart Jan; Meulman, Jacqueline J.

    2011-01-01

    In this paper, the statistical significance of the contribution of variables to the principal components in principal components analysis (PCA) is assessed nonparametrically by the use of permutation tests. We compare a new strategy to a strategy used in previous research consisting of permuting the columns (variables) of a data matrix…

  12. Performance evaluation of ant colony optimization-based solution strategies on the mixed-model assembly line balancing problem

    NASA Astrophysics Data System (ADS)

    Akpinar, Sener; Mirac Bayhan, G.

    2014-06-01

    The aim of this article is to compare the performances of iterative ant colony optimization (ACO)-based solution strategies on a mixed-model assembly line balancing problem of type II (MMALBP-II) by addressing some particular features of real-world assembly line balancing problems such as parallel workstations and zoning constraints. To solve the problem, where the objective is to minimize the cycle time (i.e. maximize the production rate) for a predefined number of workstations in an existing assembly line, two ACO-based approaches which differ in the mission assigned to artificial ants are used. Furthermore, each ACO-based approach is conducted with two different pheromone release strategies: global and local pheromone updating rules. The four ACO-based approaches are used for solving 20 representative MMALBP-II to compare their performance in terms of computational time and solution quality. Detailed comparison results are presented.

  13. Structural and Aggregation Study of Protic Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Mattedi, S.; Martin-Pastor, M.; Iglesias, M.

    2011-12-01

    In this work there were studied structural and agreggation aspects of ionic liquids formed by the reaction between ethanolamines with low chain organic acids using NMR techniques. Three ionic liquids composed of pentanoic acid and (mono-, di- and tri-) ethanol amine were studied by 1H, and 13C solution NMR methods. NMR assisted the chemical and quantitative characterization of these three ionic liquids and provided insight in their structural arrangement of their components in the ionic liquid medium. The obtained results could be used to understand the structure and aggregation pattern of these ionic liquids and helps in the development of possible industrial applications.

  14. Acidic Ionic Liquids.

    PubMed

    Amarasekara, Ananda S

    2016-05-25

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

  15. Electrodeposition in Ionic Liquids.

    PubMed

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

    2016-02-01

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

  16. Relationships between undergraduates' argumentation skills, conceptual quality of problem solutions, and problem solving strategies in introductory physics

    NASA Astrophysics Data System (ADS)

    Rebello, Carina M.

    This study explored the effects of alternative forms of argumentation on undergraduates' physics solutions in introductory calculus-based physics. A two-phase concurrent mixed methods design was employed to investigate relationships between undergraduates' written argumentation abilities, conceptual quality of problem solutions, as well as approaches and strategies for solving argumentative physics problems across multiple physics topics. Participants were assigned via stratified sampling to one of three conditions (control, guided construct, or guided evaluate) based on gender and pre-test scores on a conceptual instrument. The guided construct and guided evaluate groups received tasks and prompts drawn from literature to facilitate argument construction or evaluation. Using a multiple case study design, with each condition serving as a case, interviews were conducted consisting of a think-aloud problem solving session paired with a semi-structured interview. The analysis of problem solving strategies was guided by the theoretical framework on epistemic games adapted by Tuminaro and Redish (2007). This study provides empirical evidence that integration of written argumentation into physics problems can potentially improve the conceptual quality of solutions, expand their repertoire of problem solving strategies and show promise for addressing the gender gap in physics. The study suggests further avenues for research in this area and implications for designing and implementing argumentation tasks in introductory college physics.

  17. Structure, microstructure and ionic conductivity of the solid solution LiTi 2- xSn x(PO 4) 3

    NASA Astrophysics Data System (ADS)

    Bounar, Nedjemeddine; Benabbas, Abderrahim; Bouremmad, Farida; Ropa, Patrick; Carru, Jean-Claude

    2012-02-01

    The Nasicon compounds with the composition LiTi 2- xSn x(PO 4) 3 ( x=0-1.8) were synthesised by the solid state reaction. Their structures were determined from X-ray powder diffraction using Rietveld analysis. All the compositions present the space group R-3c. The refinements show that the Ti and Sn cations are statistically distributed over the same position while the Li ones are exclusively located on the M1 site. The lattice constants a and c exhibit linear variation over the whole composition range. The bond lengths are in accordance with those of other Nasicon structures. The SEM micrographs of the samples show relative porous microstructures. The ionic conductivity is about 10 -4-10 -5 S cm -1; for the activation energy, a typical value of 0.32 eV is obtained for x=0.6 composition whereas significant deviation from linearity in the temperature dependence of the dc conductivity, is observed for the Sn-rich ones. This tendency is discussed along with the structural features.

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

    PubMed

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

    2011-11-01

    A simple and cost-effective successive ionic layer adsorption and reaction (SILAR) method was adopted to fabricate hydrophobic ZnO nanostructured surfaces on transparent indium-tin oxide (ITO), glass and polyethylene terephthalate (PET) substrates. ZnO films deposited on different substrates show hierarchical structures like spindle, flower and spherical shape with diameters ranging from 30 to 300 nm. The photo-induced switching behaviors of ZnO film surfaces between hydrophobic and hydrophilic states were examined by water contact angle and X-ray photoelectron spectroscopy (XPS) analysis. ZnO nanostructured films had contact angles of ~140° and 160°±2 on glass and PET substrates, respectively, exhibiting hydrophobic behavior without any surface modification or treatment. Upon exposure to ultraviolet (UV) illumination, the films showed hydrophilic behavior (contact angle: 15°±2), which upon low thermal stimuli revert back to its original hydrophobic nature. Such reversible and repeatable switching behaviors were observed upon cyclical exposure to ultraviolet radiation. These biomimetic ZnO surfaces exhibit good anti-reflective properties with lower reflectance of 9% for PET substrates. Thus, the present work is significant in terms of its potential application in switching devices, solar coatings and self-cleaning smart windows. PMID:21831394

  19. Experimental determination of water activity for binary aqueous cerium(III) ionic solutions: application to an assessment of the predictive capability of the binding mean spherical approximation model.

    PubMed

    Ruas, Alexandre; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe

    2005-12-01

    This work is aimed at a description of the thermodynamic properties of actinide salt solutions at high concentration. The predictive capability of the binding mean spherical approximation (BIMSA) theory to describe the thermodynamic properties of electrolytes is assessed in the case of aqueous solutions of lanthanide(III) nitrate and chloride salts. Osmotic coefficients of cerium(III) nitrate and chloride were calculated from other lanthanide(III) salts properties. In parallel, concentrated binary solutions of cerium nitrate were prepared in order to measure experimentally its water activity and density as a function of concentration, at 25 degrees C. Water activities of several binary solutions of cerium chloride were also measured to check existing data on this salt. Then, the properties of cerium chloride and cerium nitrate solutions were compared within the BIMSA model. Osmotic coefficient values for promethium nitrate and promethium chloride given by this theory are proposed. Finally, water activity measurements were made to examine the fact that the ternary system Ce(NO3)3/HNO3/H2O and the quaternary system Ce(NO3)3/HNO3/N2H5NO3/H2O may be regarded as "simple solutions" (in the sense of Zdanovskii and Mikulin). PMID:16854002

  20. A new strategy to prepare giant vesicles from surface active ionic liquids (SAILs): a study of protein dynamics in a crowded environment using a fluorescence correlation spectroscopic technique.

    PubMed

    Banerjee, Chiranjib; Roy, Arpita; Kundu, Niloy; Banik, Debasis; Sarkar, Nilmoni

    2016-06-01

    A simple procedure for the preparation of giant vesicles using surface active ionic liquids (SAILs) has been provided in this paper. SAILs, used to form vesicles, were synthesized by replacing the cationic part of Aerosol OT (AOT) with cations having alkyl chains of different lengths (ammonium and imidazolium cations). The number of carbons in the alkyl chains of the cations was varied from eight to sixteen. From the observed results, the formation of giant vesicles is found to be dependent on the alkyl chain length as well as the organic moieties of the respective cations. These giant vesicles were characterized using fluorescence lifetime imaging microscopy (FLIM). The conformational dynamics of bovine serum albumin (BSA) inside these giant vesicles was determined using fluorescence correlation spectroscopy (FCS) to get an idea about the protein dynamics in a constrained environment. The interaction of the giant vesicles with the protein was confirmed by the change in the diffusion coefficient and the conformational fluctuation time. PMID:27173474

  1. Cellulose hydrolysis and binding with Trichoderma reesei Cel5A and Cel7A and their core domains in ionic liquid solutions.

    PubMed

    Wahlström, Ronny; Rahikainen, Jenni; Kruus, Kristiina; Suurnäkki, Anna

    2014-04-01

    Ionic liquids (ILs) dissolve lignocellulosic biomass and have a high potential as pretreatment prior to total enzymatic hydrolysis. ILs are, however, known to inactivate cellulases. In this article, enzymatic hydrolysis of microcrystalline cellulose (MCC) and enzyme binding onto the cellulosic substrate were studied in the presence of cellulose-dissolving ILs. Two different ILs, 1,3-dimethylimidazolium dimethylphosphate ([DMIM]DMP) and 1-ethyl-3-methylimidazolium acetate ([EMIM]AcO), and two monocomponent cellulases, Trichoderma reesei cellobiohydrolase Cel7A and endoglucanase Cel5A, were used in the study. The role and IL sensitivity of the carbohydrate-binding module (CBM) were studied by performing hydrolysis and binding experiments with both the intact cellulases, and their respective core domains (CDs). Based on hydrolysis yields and substrate binding experiments for the intact enzymes and their CDs in the presence of ILs, the function of the CBM appeared to be very IL sensitive. Binding data suggested that the CBM was more important for the substrate binding of endoglucanase Cel5A than for the binding of cellobiohydrolase Cel7A. The CD of Cel7A was able to bind well to cellulose even without a CBM, whereas Cel5A CD had very low binding affinity. Hydrolysis also occurred with Cel5A CD even if this protein had very low binding affinity in all the studied matrices. Binding and hydrolysis were less affected by the studied ILs for Cel7A than for Cel5A. To our knowledge, this is the first systematic study of IL effects on cellulase substrate binding. PMID:24258388

  2. Evaluation of strategies for nature-based solutions to drought: a decision support model at the national scale

    NASA Astrophysics Data System (ADS)

    Simpson, Mike; Ives, Matthew; Hall, Jim

    2016-04-01

    There is an increasing body of evidence in support of the use of nature based solutions as a strategy to mitigate drought. Restored or constructed wetlands, grasslands and in some cases forests have been used with success in numerous case studies. Such solutions remain underused in the UK, where they are not considered as part of long-term plans for supply by water companies. An important step is the translation of knowledge on the benefits of nature based solutions at the upland/catchment scale into a model of the impact of these solutions on national water resource planning in terms of financial costs, carbon benefits and robustness to drought. Our project, 'A National Scale Model of Green Infrastructure for Water Resources', addresses this issue through development of a model that can show the costs and benefits associated with a broad roll-out of nature based solutions for water supply. We have developed generalised models of both the hydrological effects of various classes and implementations of nature-based approaches and their economic impacts in terms of construction costs, running costs, time to maturity, land use and carbon benefits. Our next step will be to compare this work with our recent evaluation of conventional water infrastructure, allowing a case to be made in financial terms and in terms of security of water supply. By demonstrating the benefits of nature based solutions under multiple possible climate and population scenarios we aim to demonstrate the potential value of using nature based solutions as a component of future long-term water resource plans. Strategies for decision making regarding the selection of nature based and conventional approaches, developed through discussion with government and industry, will be applied to the final model. Our focus is on keeping our work relevant to the requirements of decision-makers involved in conventional water planning. We propose to present the outcomes of our model for the evaluation of nature

  3. Problem Definition and Solution Strategies in Dental Practice. Final Report, September 19, 1979-October 31, 1980.

    ERIC Educational Resources Information Center

    Dane, J. K.; And Others

    A study was conducted to identify and analyze clinical and nonclinical problems commonly met by dental practitioners, and the strategies and resources used by dentists to resolve these problems. Nearly 50 individuals in dentistry and related areas were organized into a steering committee and four task groups. Data were gathered through meetings of…

  4. Paper-and-Pencil Programming Strategy toward Computational Thinking for Non-Majors: Design Your Solution

    ERIC Educational Resources Information Center

    Kim, Byeongsu; Kim, Taehun; Kim, Jonghoon

    2013-01-01

    The paper-and-pencil programming strategy (PPS) is a way of representing an idea logically by any representation that can be created using paper and pencil. It was developed for non-computer majors to improve their understanding and use of computational thinking and increase interest in learning computer science. A total of 110 non-majors in their…

  5. An Exploration of Strategies Used by Students To Solve Problems with Multiple Ways of Solution.

    ERIC Educational Resources Information Center

    Santos-Trigo, Manuel

    1996-01-01

    Describes a study that provides information about the extent to which students actually use their mathematical resources and strategies to solve problems. Interviews were used to analyze the problem solving abilities of high school students (N=35) as they solved five problems. (DDR)

  6. Noble metal ionic catalysts.

    PubMed

    Hegde, M S; Madras, Giridhar; Patil, K C

    2009-06-16

    Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NO(x), and unburned hydrocarbons-need to be fully converted to CO(2), N(2), and H(2)O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al(2)O(3) or SiO(2) promoted by CeO(2). However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce(1-x)M(x)O(2-delta) and Ce(1-x-y)Ti(y)M(x)O(2-delta) (M = Pt, Pd, Rh; x = 0.01-0.02, delta approximately x, y = 0.15-0.25) oxides in fluorite structure. In these oxide catalysts, Pt(2+), Pd(2+), or Rh(3+) ions are substituted only to the extent of 1-2% of Ce(4+) ion. Lower-valent noble metal ion substitution in CeO(2) creates oxygen vacancies. Reducing molecules (CO, H(2), NH(3)) are adsorbed onto electron-deficient noble metal ions, while oxidizing (O(2), NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NO(x) reduction (with >80% N(2) selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO(2) or Ce(1-x)Ti(x)O(2) were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the

  7. Adjunctive use of the non-ionic surfactant Poloxamer 188 improves fetal dopaminergic cell survival and reinnervation in a neural transplantation strategy for Parkinson's disease.

    PubMed

    Quinn, M; Mukhida, K; Sadi, D; Hong, M; Mendez, I

    2008-01-01

    Although neural transplantation of fetal dopaminergic cells is a promising therapy for Parkinson's disease, poor transplanted cell survival limits its efficacy. In the present study it was hypothesized that the use of Poloxamer 188 (P188), a non-ionic surfactant, during cell preparation and transplantation may protect cells from associated mechanical injury and thus improve transplanted cell survival in a rat model of Parkinson's disease. Fetal rat dopaminergic tissue was dissociated in media with or without P188 and then cultured for 1 week or transplanted into the striatum of rats with unilateral 6-hydroxydopamine lesions of the nigrostriatal dopaminergic pathway. Fetal dopaminergic cell survival and reinnervation of the host brain were examined using tyrosine hydroxylase immunohistochemistry and stereological quantification. The number of surviving tyrosine hydroxylase-immunoreactive cells in vitro and in vivo was significantly increased by 2.2-fold by incubating fetal dopaminergic cells with P188 during tissue dissociation. Furthermore, the striatal reinnervation in parkinsonian rats that received intrastriatal transplants of P188-exposed dopaminergic cells was significantly enhanced (1.8-fold increase) compared with rats that received non-P188-treated cells. In conclusion, P188 protects fetal dopaminergic cells from mechanical injury by increasing cell survival and enhances dopaminergic fibre outgrowth into the transplanted striatum. Use of P188 may thus be an important adjunct to improve the clinical efficacy of neural transplantation for Parkinson's disease. PMID:18093176

  8. Ionic liquid-assisted bidirectional regulation strategy for carbon quantum dots (CQDs)/Bi4O5I2 nanomaterials and enhanced photocatalytic properties.

    PubMed

    Ji, Mengxia; Xia, Jiexiang; Di, Jun; Wang, Bin; Yin, Sheng; Xu, Li; Zhao, Junze; Li, Huaming

    2016-09-15

    In this study, novel visible-light-driven carbon quantum dots (CQDs)/Bi4O5I2 material has been prepared via a reactable ionic liquid 1-hexyl-3-methylimidazolium iodide ([Hmim]I) assisted bidirectional regulation solvothermal method. This is the first time for the preparation of CQDs/Bi4O5I2 material with halogen and CQDs bidirectional regulation at the same time. With CQDs modified on the surface of Bi4O5I2, fast transfer of photogenerated charges and low recombination of photo-induced electron-hole pairs facilitated the enhancement of photodegradation activity. At the same time, the introduction of CQDs made the electrons occupied in high-energy potential on the conduction band of Bi4O5I2 transfer to the reaction center CQDs and the molecular oxygen can be thus activated. The enhanced mechanisms for the active species (holes, hydroxyl and superoxide radicals) during the photocatalytic reaction under visible irradiation were analyzed using DRS analysis, electron spin resonance (ESR) technique and free radicals trapping experiments. PMID:27318012

  9. Ionic liquid-assisted strategy for bismuth-rich bismuth oxybromides nanosheets with superior visible light-driven photocatalytic removal of bisphenol-A.

    PubMed

    Xia, Jiexiang; Ge, Yuping; Di, Jun; Xu, Li; Yin, Sheng; Chen, Zhigang; Liu, Pengjun; Li, Huaming

    2016-07-01

    Novel Bi4O5Br2 photocatalysts were synthesized by a one-pot solvothermal method in the presence of reactable ionic liquid 1-hexadecyl-3-methylimidazolium bromide ([C16mim]Br). X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS) and other characterizations were applied to investigate their structures, morphologies, optical and electronic properties. Bisphenol-A (BPA) was chosen to evaluate the photocatalytic activity of Bi4O5Br2 nanosheets. After the visible light irradiation, about 91.2% of BPA were removed by Bi4O5Br2 after 3.5h with the reaction rate constant of 0.01086, which is much higher than that of the pure BiOBr (24.4%). Liquid chromatography combined with mass spectrometry (LC-MS) technique was used to track the intermediates species, showing the photocatalytic mechanism is related to photogenerated holes instead of hydroxyl radicals. The as-prepared Bi4O5Br2 also exhibited excellent stability as well as reusability, implying a great promising practical application for the photodegradation of organic pollutants. PMID:27061362

  10. Polymer-assisted metal deposition (PAMD): a full-solution strategy for flexible, stretchable, compressible, and wearable metal conductors.

    PubMed

    Yu, You; Yan, Casey; Zheng, Zijian

    2014-08-20

    Metal interconnects, contacts, and electrodes are indispensable elements for most applications of flexible, stretchable, and wearable electronics. Current fabrication methods for these metal conductors are mainly based on conventional microfabrication procedures that have been migrated from Si semiconductor industries, which face significant challenges for organic-based compliant substrates. This Research News highlights a recently developed full-solution processing strategy, polymer-assisted metal deposition (PAMD), which is particularly suitable for the roll-to-roll, low-cost fabrication of high-performance compliant metal conductors (Cu, Ni, Ag, and Au) on a wide variety of organic substrates including plastics, elastomers, papers, and textiles. This paper presents i) the principles of PAMD, and how to use it for making ii) flexible, stretchable, and wearable conductive metal electrodes, iii) patterned metal interconnects, and d) 3D stretchable and compressible metal sponges. A critical perspective on this emerging strategy is also provided. PMID:24458846

  11. Analysis of Residential System Strategies Targeting Least-Cost Solutions Leading to Net Zero Energy Homes: Preprint

    SciTech Connect

    Anderson, R.; Christensen, C.; Horowitz, S.

    2006-04-01

    The U. S. Department of Energy's Building America residential systems research project uses an analysis-based system research approach to identify research priorities, identify technology gaps and opportunities, establish a consistent basis to track research progress, and identify system solutions that are most likely to succeed as the initial targets for residential system research projects. This report describes the analysis approach used by the program to determine the most cost-effective pathways to achieve whole-house energy-savings goals. This report also provides an overview of design/technology strategies leading to net zero energy buildings as the basis for analysis of future residential system performance.

  12. Ultrasensitive sandwich-type electrochemical immunosensor based on a novel signal amplification strategy using highly loaded toluidine blue/gold nanoparticles decorated KIT-6/carboxymethyl chitosan/ionic liquids as signal labels.

    PubMed

    Wang, Yulan; Li, Xiaojian; Cao, Wei; Li, Yueyun; Li, He; Du, Bin; Wei, Qin

    2014-11-15

    An ultrasensitive sandwich-type electrochemical immunosensor for the quantitative detection of carcinoembryonic antigen (CEA) was designed based on a novel signal amplification strategy. Gold nanoparticles decorated mesoporous silica KIT-6 (Au@KIT-6) with large specific surface area and good adsorption properties was used as a label matrix to immobilize both the secondary antibodies (Ab2) and the electron transfer mediator toluidine blue (TB). Ab2 was loaded on KIT-6 due to the presence of gold nanoparticles (Au NPs) and TB was loaded on KIT-6 by physical adsorption. Ionic liquids (ILs) doped carboxymethyl chitosan (CMC) was used to prevent the leak of TB and facilitate the electron transfer. For the immobilization of primary antibodies (Ab1), gold nanoparticles decorated 3-aminopropyltriethoxysilane functionalized graphene sheets (Au@APTES-GS) were used as transducing materials to modify glassy carbon electrodes (GCE). High sensitivity was achieved for the designed immunosensor based on this novel signal amplification strategy. Under optimal conditions, the immunosensor exhibited an extremely low detection limit of 3.3 fg/mL and wide liner range from 10(-5) ng/mL to 10(2) ng/mL for CEA. Moreover, it exhibited good selectivity, acceptable reproducibility and stability, indicating potential application promising in clinical monitoring of tumor biomarkers. PMID:24967751

  13. Innovative Solutions to Sticky Situations: Antiadhesive Strategies for Treating Bacterial Infections.

    PubMed

    Cusumano, Zachary T; Klein, Roger D; Hultgren, Scott J

    2016-04-01

    Bacterial adherence to host tissue is an essential process in pathogenesis, necessary for invasion and colonization and often required for the efficient delivery of toxins and other bacterial effectors. As existing treatment options for common bacterial infections dwindle, we find ourselves rapidly approaching a tipping point in our confrontation with antibiotic-resistant strains and in desperate need of new treatment options. Bacterial strains defective in adherence are typically avirulent and unable to cause infection in animal models. The importance of this initial binding event in the pathogenic cascade highlights its potential as a novel therapeutic target. This article seeks to highlight a variety of strategies being employed to treat and prevent infection by targeting the mechanisms of bacterial adhesion. Advancements in this area include the development of novel antivirulence therapies using small molecules, vaccines, and peptides to target a variety of bacterial infections. These therapies target bacterial adhesion through a number of mechanisms, including inhibition of pathogen receptor biogenesis, competition-based strategies with receptor and adhesin analogs, and the inhibition of binding through neutralizing antibodies. While this article is not an exhaustive description of every advancement in the field, we hope it will highlight several promising examples of the therapeutic potential of antiadhesive strategies. PMID:27227305

  14. Implementation of sustainable sanitation in existing urban areas: long-term strategies for an optimised solution.

    PubMed

    Kaufmann, I; Meyer, T; Kalsch, M; Schmitt, T G; Hamacher, H W

    2007-01-01

    If technologies for decentralised sanitation and reuse (DESAR) and for natural stormwater management should at least partially replace existing systems, then intensive reconstruction work becomes essential. A conversion can only be realised successively over a long period due to high construction and financial expenses and requires new strategies. This paper presents the development and practical implementation of a mathematical tool to find an optimised strategy for the realisation of alternative and more decentralised drainage and sanitation concepts in existing urban areas. The succession of construction measures (e.g. the implementation of decentralised greywater recycling) for the whole period of consideration is determined based upon a mathematical optimisation model on the condition that the favoured future state is known. The model describes the complex interdependencies of the urban water and nutrient cycle and enables the minimisation of both financial efforts and ecological impacts on the way toward the future state. The results of the implementation for a rural area in Germany show that the mathematical optimisation is an adequate instrument to support decision-making processes in finding strategies for the realisation of sustainable urban water management. PMID:17881844

  15. Quantized ionic conductance in nanopores

    SciTech Connect

    Zwolak, Michael; Lagerqvist, Johan; Di Ventra, Massimilliano

    2009-01-01

    Ionic transport in nanopores is a fundamentally and technologically important problem in view of its ubiquitous occurrence in biological processes and its impact on DNA sequencing applications. Using microscopic calculations, we show that ion transport may exhibit strong non-liDearities as a function of the pore radius reminiscent of the conductance quantization steps as a function of the transverse cross section of quantum point contacts. In the present case, however, conductance steps originate from the break up of the hydration layers that form around ions in aqueous solution. Once in the pore, the water molecules form wavelike structures due to multiple scattering at the surface of the pore walls and interference with the radial waves around the ion. We discuss these effects as well as the conditions under which the step-like features in the ionic conductance should be experimentally observable.

  16. Membrane contactor assisted extraction/reaction process employing ionic liquids

    DOEpatents

    Lin, Yupo J.; Snyder, Seth W.

    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.

  17. An alternative local collocation strategy for high-convergence meshless PDE solutions, using radial basis functions

    NASA Astrophysics Data System (ADS)

    Stevens, D.; Power, H.; Meng, C. Y.; Howard, D.; Cliffe, K. A.

    2013-12-01

    This work proposes an alternative decomposition for local scalable meshless RBF collocation. The proposed method operates on a dataset of scattered nodes that are placed within the solution domain and on the solution boundary, forming a small RBF collocation system around each internal node. Unlike other meshless local RBF formulations that are based on a generalised finite difference (RBF-FD) principle, in the proposed "finite collocation" method the solution of the PDE is driven entirely by collocation of PDE governing and boundary operators within the local systems. A sparse global collocation system is obtained not by enforcing the PDE governing operator, but by assembling the value of the field variable in terms of the field value at neighbouring nodes. In analogy to full-domain RBF collocation systems, communication between stencils occurs only over the stencil periphery, allowing the PDE governing operator to be collocated in an uninterrupted manner within the stencil interior. The local collocation of the PDE governing operator allows the method to operate on centred stencils in the presence of strong convective fields; the reconstruction weights assigned to nodes in the stencils being automatically adjusted to represent the flow of information as dictated by the problem physics. This "implicit upwinding" effect mitigates the need for ad-hoc upwinding stencils in convective dominant problems. Boundary conditions are also enforced within the local collocation systems, allowing arbitrary boundary operators to be imposed naturally within the solution construction. The performance of the method is assessed using a large number of numerical examples with two steady PDEs; the convection-diffusion equation, and the Lamé-Navier equations for linear elasticity. The method exhibits high-order convergence in each case tested (greater than sixth order), and the use of centred stencils is demonstrated for convective-dominant problems. In the case of linear elasticity

  18. Technology Solutions Case Study: Innovative Retrofit Foundation Insulation Strategies, Minneapolis, Minnesota

    SciTech Connect

    2015-07-01

    Basements in climates 6 & 7 can account for a fraction of a home's total heat loss when fully conditioned. These foundations are a source of moisture, with convection in open block cavities redistributing water from the wall base, usually when heating. Even when block cavities are capped, the cold foundation concrete can act as a moisture source for wood rim joist components that are in contact with the wall. As below-grade basements are increasingly retrofitted for habitable space, cold foundation walls pose increased challenges for moisture durability, energy use, and occupant comfort. To address this challenge, the NorthernSTAR Building America Partnership evaluated a retrofit insulation strategy for foundations that is designed for use with open-core concrete block foundation walls. The three main goals were to improve moisture control, improve occupant comfort, and reduce heat loss.

  19. Solution of nonlinear finite difference ocean models by optimization methods with sensitivity and observational strategy analysis

    NASA Technical Reports Server (NTRS)

    Schroeter, Jens; Wunsch, Carl

    1986-01-01

    The paper studies with finite difference nonlinear circulation models the uncertainties in interesting flow properties, such as western boundary current transport, potential and kinetic energy, owing to the uncertainty in the driving surface boundary condition. The procedure is based upon nonlinear optimization methods. The same calculations permit quantitative study of the importance of new information as a function of type, region of measurement and accuracy, providing a method to study various observing strategies. Uncertainty in a model parameter, the bottom friction coefficient, is studied in conjunction with uncertain measurements. The model is free to adjust the bottom friction coefficient such that an objective function is minimized while fitting a set of data to within prescribed bounds. The relative importance of the accuracy of the knowledge about the friction coefficient with respect to various kinds of observations is then quantified, and the possible range of the friction coefficients is calculated.

  20. Myocardial protection during minimally invasive mitral valve surgery: strategies and cardioplegic solutions

    PubMed Central

    Davierwala, Piroze; Seeburger, Joerg; Pfannmueller, Bettina; Misfeld, Martin; Borger, Michael A.; Mohr, Friedrich-Wilhelm

    2013-01-01

    Effective myocardial protection and perfusion strategies during minimally invasive mitral valve surgery (Mini-MV) have evolved over the last decade. Our institutional approach for right-sided Mini-MV has been standardized over the last 15 years in more than 4,500 cases. Cardiopulmonary bypass (CPB) is usually instituted by right-sided femoral arterial and venous cannulation with additional cannulation of the right jugular vein in patients with a body weight greater than 75 kg or when a concomitant tricuspid valve (TV) procedure and/or atrial septal defect closure is performed. A single dosage of crystalloid-based cardioplegia [Custodial- histidine-trypthophan-ketoglutarate (Custodial-HTK)] administered via the aortic root in combination with moderate hypothermia (34-35 °C) has become the standard of care for induction and maintenance of myocardial protection at our institution. The present article highlights and discusses the principal techniques of myocardial protection for Mini-MV. PMID:24349985

  1. Molecular simulation of the temperature- and density-dependence of ionic hydration in aqueous SrCl[sub 2] solutions using rigid and flexible water models

    SciTech Connect

    Driesner, T.; Cummings, P.T. )

    1999-09-01

    Molecular dynamics simulations of aqueous SrCl[sub 2] solutions have been performed with two flexible water models [the Bopp[endash]Jancs[acute o][endash]Heinzinger (BJH) and modified Toukan[endash]Rahman simple point charge model (SPC-mTR)] as well as the rigid simple point charge (SPC) model. Recent extended x-ray absorption fine structure spectroscopy (EXAFS) studies of Sr[sup 2+] hydration reported a decrease of the average distance between Sr[sup 2+] and water molecules in the first hydration shell with increasing temperature. The available Sr[sup 2+][endash]water potential for rigid SPC water and its variants is not able to reproduce this hydration shell contraction. Adding intramolecular flexibility in the form of the SPC-mTR potential only slightly improves the performance of the SPC model, while the BJH model performs significantly better. All models predict an expansion of the first hydration shell of the Cl[sup [minus

  2. An investigation of bubble coalescence and post-rupture oscillation in non-ionic surfactant solutions using high-speed cinematography.

    PubMed

    Bournival, G; Ata, S; Karakashev, S I; Jameson, G J

    2014-01-15

    Most processes involving bubbling in a liquid require small bubbles to maximise mass/energy transfer. A common method to prevent bubbles from coalescing is by the addition of surfactants. In order to get an insight into the coalescence process, capillary bubbles were observed using a high speed cinematography. Experiments were performed in solutions of 1-pentanol, 4-methyl-2-pentanol, tri(propylene glycol) methyl ether, and poly(propylene glycol) for which information such as the coalescence time and the deformation of the resultant bubble upon coalescence was extracted. It is shown in this study that the coalescence time increases with surfactant concentration until the appearance of a plateau. The increase in coalescence time with surfactant concentration could not be attributed only to surface elasticity. The oscillation of the resultant bubble was characterised by the damping of the oscillation. The results suggested that a minimum elasticity is required to achieve an increased damping and considerable diffusion has a detrimental effect on the dynamic response of the bubble, thereby reducing the damping. PMID:24231084

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

    SciTech Connect

    Sun, Xiaoqi; Dai, Sheng; Luo, Huimin

    2012-01-01

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

  4. Molecular dynamics simulation study of ionic hydration and ion association in dilute and 1 molal aqueous sodium chloride solutions from ambient to supercritical conditions

    NASA Astrophysics Data System (ADS)

    Driesner, T.; Seward, T. M.; Tironi, I. G.

    1998-09-01

    The increasing demand for accurate equations of state of fluids under extreme conditions and the need for a detailed microscopic picture of aqueous fluids in some areas of geochemistry (e.g., mineral dissolution/precipitation kinetics) potentially make molecular dynamics (MD) simulations a powerful tool for theoretical geochemistry. We present MD simulations of infinitely dilute and 1 molal aqueous NaCl solutions that have been carried out in order to study the systematics of hydration and ion association over a wide range of conditions from ambient to supercritical and compare them to the available experimental data. In the dilute case, the hydration number of the Na + ion remains essentially constant around 5.5 from ambient to supercritical temperatures when the density is kept constant at 1 g cm -3 but decreases to below 5 along the liquid-vapor curve. In both cases, the average ion-first shell water distance decreases by about 0.03 Å from ambient to near critical temperatures. The Cl - ion shows a slight expansion of the first hydration shell by about 0.02 Å from ambient to near critical temperatures. The geometric definition of the first hydration shell becomes ambiguous due to a shift of the position of the first minimum of the Cl-O radial distribution function. In the case of the 1 molal solution, the contraction of the Na + first hydration shell is similar to that in the dilute case whereas the hydration number decreases drastically from 4.9 to 2.8 due to strong ion association. The released waters are replaced on a near 1:1 basis by chloride ions. Polynuclear clusters as predicted by Oelkers and Helgeson (1993b) are observed in the high temperature systems. The hydration shell of the Cl --ion shows significant deviation from the behavior in dilute systems, that is, at near vapor saturated conditions, the expansion of the hydration shell is significantly larger (0.12 Å from ambient to near critical temperatures). Due to a very large shift of the first

  5. Quantized ionic conductance in nanopores.

    PubMed

    Zwolak, Michael; Lagerqvist, Johan; Di Ventra, Massimiliano

    2009-09-18

    Ionic transport in nanopores is a fundamentally and technologically important problem in view of its occurrence in biological processes and its impact on novel DNA sequencing applications. Using molecular dynamics simulations we show that ion transport may exhibit strong nonlinearities as a function of the pore radius reminiscent of the conductance quantization steps as a function of the transverse cross section of quantum point contacts. In the present case, however, conductance steps originate from the break up of the hydration layers that form around ions in aqueous solution. We discuss this phenomenon and the conditions under which it should be experimentally observable. PMID:19792463

  6. Specific ionic effect for simple and rapid colorimetric sensing assays of amino acids using gold nanoparticles modified with task-specific ionic liquid.

    PubMed

    Wu, Datong; Cai, Pengfei; Tao, Zhihao; Pan, Yuanjiang

    2016-01-01

    In this study, a novel task-specific ionic liquid functionalized gold nanoparticle (TSIL-GNP) was successfully prepared and applied in the recognition of amino acids. Particularly, the surface of GNP was modified with the ionic liquid containing carbamido and ester group via thiol, which was characterized by Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The stability of this material in aqueous solution improves apparently and can remain unchanged for more than three months. The effect of pH was also discussed in this study. Attractive ionic interaction would effectively weaken intensity of the covalent coupling between the metal ion and the functional groups of amino acids. Thus, TSIL-GNP was successfully applied to recognizing serine, aspartic acid, lysine, arginine, and histidine in the presence of Cu(2+) through distinctive color changes. Suspension would be generated once a spot of cysteine was added into the GNPs solution. Results indicated that it had a good linear relationship between extinction coefficients and concentration of amino acids in a wide range of 10(-3)-10(-6) M. Moreover, the proposed strategy was successfully used to analyze the histidine in urinary samples. In brief, TSIL-GNP is a suitable substrate for discrimination of five amino acids in a rapid and simple way without sophisticated instruments. PMID:26703268

  7. Reactions of Starch in Ionic Liquids

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  8. Complexation of Microcystins and Nodularin by Cyclodextrins in Aqueous Solution, a Potential Removal Strategy

    PubMed Central

    Chen, Lin; Dionysiou, Dionysios D.; O’Shea, Kevin

    2013-01-01

    Cyanotoxins are potent toxic compounds produced by cyanobacteria during algal blooms, which threaten drinking water supplies. These compounds can poison and kill animals and humans. The host—guest interactions of α-, β-, and γ-cyclodextrins (CD) with problematic cyanotoxins, including microcystins (MCs) and nodularin (NOD), were investigated to demonstrate the potential application of CDs for the removal of these toxins from drinking water or applications related to their separation or purification. MCs and NOD have a hydrophobic Adda chain, which contains diene and benzene functional groups. The complexation of these cyanotoxins with CDs was monitored by nuclear magnetic resonance (NMR). The 1H NMR spectra for MCs are unchanged upon addition of α-CD (smallest host). However, addition of larger hosts, β-CD and γ-CD, leads to significant changes in chemical shifts of the benzene and diene resonances on the 3-amino-9-methoxy-2,6,8-trimethal-10-phenyldeca-4,6-dienoic acid (Adda) chain of MCs and NOD. Solution pH, natural organic matter, and salinity do not appreciably influence the host—guest complexation under our experimental conditions. The experimental binding constants for MCs and NOD with γ-CD are relatively strong, ranging from 1155 to 507 M−1. The observed changes in chemical shifts for specific protons and competitive binding experiments demonstrate a 1:1 inclusion complex between γ-CD and MCs or NOD, with the Adda chains threading through the CD ring, resulting in an inclusion complex. Our results suggest that CD-type substrates are useful hosts for the complexation of MCs and NOD. CDs can be readily attached to a number of polymeric or solid supports and their functionality tailored to strengthen specific host—guest interactions. With further development of such materials, CD host—guest chemistry may find direct application in the removal and/or separation science of these compounds. PMID:21322549

  9. Multi-Target-Directed Ligands and other Therapeutic Strategies in the Search of a Real Solution for Alzheimer's Disease

    PubMed Central

    Agis-Torres, Angel; Sölhuber, Monica; Fernandez, Maria; Sanchez-Montero, J.M.

    2014-01-01

    The lack of an adequate therapy for Alzheimer's Disease (AD) contributes greatly to the continuous growing amount of papers and reviews, reflecting the important efforts made by scientists in this field. It is well known that AD is the most common cause of dementia, and up-to-date there is no prevention therapy and no cure for the disease, which contrasts with the enormous efforts put on the task. On the other hand many aspects of AD are currently debated or even unknown. This review offers a view of the current state of knowledge about AD which includes more relevant findings and processes that take part in the disease; it also shows more relevant past, present and future research on therapeutic drugs taking into account the new paradigm “Multi-Target-Directed Ligands” (MTDLs). In our opinion, this paradigm will lead from now on the research toward the discovery of better therapeutic solutions, not only in the case of AD but also in other complex diseases. This review highlights the strategies followed by now, and focuses other emerging targets that should be taken into account for the future development of new MTDLs. Thus, the path followed in this review goes from the pathology and the processes involved in AD to the strategies to consider in on-going and future researches. PMID:24533013

  10. Highly sensitive label free electrochemical detection of VGEF165 tumor marker based on "signal off" and "signal on" strategies using an anti-VEGF165 aptamer immobilized BSA-gold nanoclusters/ionic liquid/glassy carbon electrode.

    PubMed

    Shamsipur, Mojtaba; Farzin, Leila; Amouzadeh Tabrizi, Mahmoud; Molaabasi, Fatemeh

    2015-12-15

    In this work, a label free electrochemical aptasensor for the detection of ultra-traces of vascular endothelial growth factor (VEGF165) based on "signal off" and "signal on" mechanisms of response was developed. The BSA-gold nanoclusters/ionic liquid (BSA-AuNCs/IL) was used as a suitable nanocomposite platform for immobilization of the aptamer on a glassy carbon electrode. In "signal off" mechanism, the interaction of VEGF165 with its anti-VEGF165 aptamers, resulted in desorption of methylene blue (MB) probe from aptamer and its release into solution. Consequently, the decrease in current intensity of the differential pulse voltammogram of adsorbed MB was monitored and found to be linearly proportional with increasing concentration of VEGF165 in sample solution in the range of 1-120 pM with a limit of detection of 0.32p M. While, in "signal on" mechanism, the interaction of immobilized anti-VEGF165 aptamers on the electrode surface with VEGF165, led to more mass-transfer limiting of the [Fe(CN)6](3-/4-) probe to the electrode surface. Therefore, the charge transfer resistance (Rct) of the probe was increased linearly with increasing concentration of VEGF165 in the range of 2.5-250 pM with a limit of detection of 0.48 pM. The experimental results demonstrated that both of these mechanisms are suitable for determination of low levels of the VEGF165 tumor marker in serum samples. PMID:26162327

  11. Accumulation of γ-aminobutyric acid by Enterococcus avium 9184 in scallop solution in a two-stage fermentation strategy.

    PubMed

    Yang, Haoyue; Xing, Ronge; Hu, Linfeng; Liu, Song; Li, Pengcheng

    2016-07-01

    In this study, a new bacterial strain having a high ability to produce γ-aminobutyric acid (GABA) was isolated from naturally fermented scallop solution and was identified as Enterococcus avium. To the best of our knowledge, this is the first study to prove that E. avium possesses glutamate decarboxylase activity. The strain was then mutagenized with UV radiation and was designated as E. avium 9184. Scallop solution was used as the culture medium to produce GABA. A two-stage fermentation strategy was applied to accumulate GABA. In the first stage, cell growth was regulated. Optimum conditions for cell growth were pH, 6.5; temperature, 37°C; and glucose concentration, 10 g·L(-1) . This produced a maximum dry cell mass of 2.10 g·L(-1) . In the second stage, GABA formation was regulated. GABA concentration reached 3.71 g·L(-1) at 96 h pH 6.0, 37°C and initial l-monosodium glutamate concentration of 10 g·L(-1) . Thus, compared with traditional one-stage fermentation, the two-stage fermentation significantly increased GABA accumulation. These results provide preliminary data to produce GABA using E. avium and also provide a new approach to process and utilize shellfish. PMID:26200650

  12. A Solution Strategy to Include the Opening of the Opercular Slits in Moving-Mesh CFD Models of Suction Feeding.

    PubMed

    Van Wassenbergh, Sam

    2015-07-01

    The gill cover of fish and pre-metamorphic salamanders has a key role in suction feeding by acting as a one-way valve. It initially closes and avoids an inflow of water through the gill slits, after which it opens to allow outflow of the water that was sucked through the mouth into the expanded buccopharyngeal cavity. However, due to the inability of analytical models (relying on the continuity principle) to calculate the flow of fluid through a cavity with two openings and that was changing in shape and size, stringent boundary conditions had to be used in previously developed mathematical models after the moment of the valve's opening. By solving additionally for the conservation of momentum, computational fluid dynamics (CFD) has the capacity to dynamically simulate these flows, but this technique also faces complications in modeling a transition from closed to open valves. Here, I present a relatively simple solution strategy to incorporate the opening of the valves, exemplified in an axisymmetrical model of a suction-feeding sunfish in ANSYS Fluent software. By controlling viscosity of a separately defined fluid entity in the region of the opercular cavity, early inflow can be blocked (high viscosity assigned) and later outflow can be allowed (changing viscosity to that of water). Finally, by analyzing the CFD solution obtained for the sunfish model, a few new insights into the biomechanics of suction feeding are gained. PMID:25936359

  13. Modernization of Physical Appearance and Solution Color Tests Using Quantitative Tristimulus Colorimetry: Advantages, Harmonization, and Validation Strategies.

    PubMed

    Pack, Brian W; Montgomery, Laura L; Hetrick, Evan M

    2015-10-01

    Color measurements, including physical appearance, are important yet often misunderstood and underappreciated aspects of a control strategy for drug substances and drug products. From a patient safety perspective, color can be an important control point for detecting contamination, impurities, and degradation products, with human visual acuity often more sensitive for colored impurities than instrumental techniques such as HPLC. Physical appearance tests and solution color tests can also serve an important role in ensuring that appropriate steps are taken such that clinical trials do not become unblinded when the active material is compared with another product or a placebo. Despite the importance of color tests, compendial visual tests are not harmonized across the major pharmacopoeias, which results in ambiguous specifications of little value, difficult communication of true sample color, and significant extra work required for global registration. Some pharmacopoeias have not yet recognized or adopted technical advances in the instrumental measurement of color and appearance, whereas others begin to acknowledge the advantage of instrumental colorimetry, yet leave implementation of the technology ambiguous. This commentary will highlight the above-mentioned inconsistencies, provide an avenue toward harmonization and modernization, and outline a scientifically sound approach for implementing quantitative technologies for improved measurement, communication, and control of color and appearance for both solutions and solids. Importantly, this manuscript, for the first time, outlines a color method validation approach that is consistent with the International Conference on Harmonization's guidance on the topic of method validation. PMID:26173406

  14. Cellulose regeneration and spinnability from ionic liquids.

    PubMed

    Hauru, Lauri K J; Hummel, Michael; Nieminen, Kaarlo; Michud, Anne; Sixta, Herbert

    2016-02-01

    Ionic liquid solutions of cellulose or dopes can be spun into Lyocell-type textile fibers by dry-jet wet spinning. An extruded dope is drawn over an air gap into water, where the water hydrates the ionic liquid and cellulose is regenerated. Spinnability studies have concentrated on the deformation and failure modes in the air gap and thus the rheology of the unhydrated spinning dope. Herein, a breach in the bath, another failure mode, is discussed. Dopes are prepared from the good spinning solvents NMMO·H2O and [DBNH]OAc and the poor spinning solvents [emim]OAc and [TMGH]OAc. The diffusion constants for water diffusing inwards and for ionic liquid diffusing outwards the emerging filament are measured offline. The resiliences and strengths of cellulose-ionic liquid solutions with different hydration stoichiometries are measured by means of rheometry. By calculating the diffusion dynamics, the resilience distribution of the forming filament is simulated. Gel strength distribution accounts for the tendency of [emim]OAc dopes to undergo a telescope-type breach, whereas the gelatinous solution state of [TMGH]OAc dopes accounts for their poor spinnability. PMID:26660047

  15. 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. PMID:25381609

  16. Applications of ionic liquids.

    PubMed

    Patel, Divia Dinesh; Lee, Jong-Min

    2012-06-01

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

  17. Ionic homeostasis in brain conditioning

    PubMed Central

    Cuomo, Ornella; Vinciguerra, Antonio; Cerullo, Pierpaolo; Anzilotti, Serenella; Brancaccio, Paola; Bilo, Leonilda; Scorziello, Antonella; Molinaro, Pasquale; Di Renzo, Gianfranco; Pignataro, Giuseppe

    2015-01-01

    Most of the current focus on developing neuroprotective therapies is aimed at preventing neuronal death. However, these approaches have not been successful despite many years of clinical trials mainly because the numerous side effects observed in humans and absent in animals used at preclinical level. Recently, the research in this field aims to overcome this problem by developing strategies which induce, mimic, or boost endogenous protective responses and thus do not interfere with physiological neurotransmission. Preconditioning is a protective strategy in which a subliminal stimulus is applied before a subsequent harmful stimulus, thus inducing a state of tolerance in which the injury inflicted by the challenge is mitigated. Tolerance may be observed in ischemia, seizure, and infection. Since it requires protein synthesis, it confers delayed and temporary neuroprotection, taking hours to develop, with a pick at 1–3 days. A new promising approach for neuroprotection derives from post-conditioning, in which neuroprotection is achieved by a modified reperfusion subsequent to a prolonged ischemic episode. Many pathways have been proposed as plausible mechanisms to explain the neuroprotection offered by preconditioning and post-conditioning. Although the mechanisms through which these two endogenous protective strategies exert their effects are not yet fully understood, recent evidence highlights that the maintenance of ionic homeostasis plays a key role in propagating these neuroprotective phenomena. The present article will review the role of protein transporters and ionic channels involved in the control of ionic homeostasis in the neuroprotective effect of ischemic preconditioning and post-conditioning in adult brain, with particular regards to the Na+/Ca2+ exchangers (NCX), the plasma membrane Ca2+-ATPase (PMCA), the Na+/H+ exchange (NHE), the Na+/K+/2Cl− cotransport (NKCC) and the acid-sensing cation channels (ASIC). Ischemic stroke is the third leading

  18. Individual SWCNT based ionic field effect transistor

    NASA Astrophysics Data System (ADS)

    Pang, Pei; He, Jin; Park, Jae Hyun; Krstic, Predrag; Lindsay, Stuart

    2011-03-01

    Here we report that the ionic current through a single-walled carbon nanotube (SWCNT) can be effectively gated by a perpendicular electrical field from a top gate electrode, working as ionic field effect transistor. Both our experiment and simulation confirms that the electroosmotic current (EOF) is the main component in the ionic current through the SWCNT and is responsible for the gating effect. We also studied the gating efficiency as a function of solution concentration and pH and demonstrated that the device can work effectively in the physiological relevant condition. This work opens the door to use CNT based nanofluidics for ion and molecule manipulation. This work was supported by the DNA Sequencing Technology Program of the National Human Genome Research Institute (1RC2HG005625-01, 1R21HG004770-01), Arizona Technology Enterprises and the Biodesign Institute.

  19. Ionic liquids as novel solvents for ionic polymer transducers

    NASA Astrophysics Data System (ADS)

    Bennett, Matthew D.; Leo, Donald J.

    2004-07-01

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

  20. Nonlocal Poisson-Fermi model for ionic solvent

    NASA Astrophysics Data System (ADS)

    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.

  1. 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. PMID:27575084

  2. Absorption and Oxidation of Nitrogen Oxide in Ionic Liquids.

    PubMed

    Kunov-Kruse, Andreas J; Thomassen, Peter L; Riisager, Anders; Mossin, Susanne; Fehrmann, Rasmus

    2016-08-01

    A new strategy for capturing nitrogen oxide, NO, from the gas phase is presented. Dilute NO gas is removed from the gas phase by ionic liquids under ambient conditions. The nitrate anion of the ionic liquid catalyzes the oxidation of NO to nitric acid by atmospheric oxygen in the presence of water. The nitric acid is absorbed in the ionic liquid up to approximately one mole HNO3 per mole of the ionic liquid due to the formation of hydrogen bonds. The nitric acid can be desorbed by heating, thereby regenerating the ionic liquid with excellent reproducibility. Here, time-resolved in-situ spectroscopic investigations of the reaction and products are presented. The procedure reveals a new vision for removing the pollutant NO by absorption into a non-volatile liquid and converting it into a useful bulk chemical, that is, HNO3 . PMID:27384885

  3. Experimental Strategies for Functional Annotation and Metabolism Discovery: Targeted Screening of Solute Binding Proteins and Unbiased Panning of Metabolomes

    PubMed Central

    2015-01-01

    The rate at which genome sequencing data is accruing demands enhanced methods for functional annotation and metabolism discovery. Solute binding proteins (SBPs) facilitate the transport of the first reactant in a metabolic pathway, thereby constraining the regions of chemical space and the chemistries that must be considered for pathway reconstruction. We describe high-throughput protein production and differential scanning fluorimetry platforms, which enabled the screening of 158 SBPs against a 189 component library specifically tailored for this class of proteins. Like all screening efforts, this approach is limited by the practical constraints imposed by construction of the library, i.e., we can study only those metabolites that are known to exist and which can be made in sufficient quantities for experimentation. To move beyond these inherent limitations, we illustrate the promise of crystallographic- and mass spectrometric-based approaches for the unbiased use of entire metabolomes as screening libraries. Together, our approaches identified 40 new SBP ligands, generated experiment-based annotations for 2084 SBPs in 71 isofunctional clusters, and defined numerous metabolic pathways, including novel catabolic pathways for the utilization of ethanolamine as sole nitrogen source and the use of d-Ala-d-Ala as sole carbon source. These efforts begin to define an integrated strategy for realizing the full value of amassing genome sequence data. PMID:25540822

  4. Strategies for Small Volume Resuscitation: Hyperosmotic-Hyperoncotic Solutions, Hemoglobin Based Oxygen Carriers and Closed-Loop Resuscitation

    NASA Technical Reports Server (NTRS)

    Kramer, George C.; Wade, Charles E.; Dubick, Michael A.; Atkins, James L.

    2004-01-01

    Introduction: Logistic constraints on combat casualty care preclude traditional resuscitation strategies which can require volumes and weights 3 fold or greater than hemorrhaged volume. We present a review of quantitative analyses of clinical and animal data on small volume strategies using 1) hypertonic-hyperosmotic solutions (HHS); 2) hemoglobin based oxygen carriers (HBOCs) and 3) closed-loop infusion regimens.Methods and Results: Literature searches and recent queries to industry and academic researchers have allowed us to evaluate the record of 81 human HHS studies (12 trauma trials), 19 human HBOCs studies (3trauma trials) and two clinical studies of closed-loop resuscitation.There are several hundreds animal studies and at least 82 clinical trials and reports evaluating small volume7.2%-7.5% hypertonic saline (HS) most often combined with colloids, e.g., dextran (HSD) or hetastarch(HSS). HSD and HSS data has been published for 1,108 and 392 patients, respectively. Human studies have documented volume sparing and hemodynamic improvements. Meta-analyses suggest improved survival for hypotensive trauma patients treated with HSD with significant reductions in mortality found for patients with blood pressure < 70 mmHg, head trauma, and penetrating injury requiring surgery. HSD and HSS have received regulatory approval in 14 and 3 countries, respectively, with 81,000+ units sold. The primary reported use was head injury and trauma resuscitation. Complications and reported adverse events are surprisingly rare and not significantly different from other solutions.HBOCs are potent volume expanders in addition to oxygen carriers with volume expansion greater than standard colloids. Several investigators have evaluated small volume hyperoncotic HBOCs or HS-HBOC formulations for hypotensive and normotensive resuscitation in animals. A consistent finding in resuscitation with HBOCs is depressed cardiac output. There is some evidence that HBOCs more efficiently unload

  5. An Investigation into the Performance, Solution Strategies and Difficulties in Middle School Students' Calculation of the Volume of a Rectangular Prism

    ERIC Educational Resources Information Center

    Tekin-Sitrava, Reyhan; Isiksal-Bostan, Mine

    2014-01-01

    This qualitative study examined middle school students' performance, solution strategies, difficulties and the underlying reasons for their difficulties in calculating the volume of a rectangular prism. The data was collected from 35 middle school students (6th, 7th and 8th grade students) enrolled in a private school in Istanbul, Turkey. The…

  6. Nonlinear capacitance and electrochemical response of ionic liquid-ionic polymers

    NASA Astrophysics Data System (ADS)

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

    2011-04-01

    In this paper we present a physics-based model for the electrochemical response of ionic liquid-ionic polymer transducers (IPTs) and show how the mobile ionic liquid ions influence the charging characteristics and actuation performance of a device. It is assumed that a certain fraction of the ionic liquid ions exist as "free," making for a total of 3 mobile ions. This leads to predictions of distinctly different charging characteristics for ionic liquid versus water-based IPTs, since for the latter there is only a single mobile ion. The large ionic liquid ions are modeled by including steric effects in a set of modified Nernst-Planck/Poisson equations, and the resulting system of equations is solved using the method of matched asymptotic expansions (MAE). The inclusion of steric effects allows for a realistic description of boundary layer composition near actuator operating voltages (~1 V). Analytical expressions for the charge transferred and differential capacitance are derived as a function of the fraction of free ionic liquid ions, influence of steric effects in formation of the electric double layer, and applied voltage. It is shown that the presence of free ionic liquid ions tends to increase the overall amount of charge transferred, and also leads to a nonmonotonic capacitance-voltage curve. We suggest that these results could be used to experimentally identify the extent of free ionic liquid ion movement and to test the validity of the assumptions made in the underlying theory. A comparison with numerical results shows that while the MAE solution procedure gives valid results for capacitance and charge transferred, it cannot predict the dynamic response due to the presence of multiple time scales in the current decay. This is in contrast to previous results in analyzing water-based IPTs, where the MAE solution is in good agreement with numerical results at all times and applied voltages due to the presence of only a single mobile ion. By examining the

  7. Thermochromism and switchable paramagnetism of cobalt(II) in thiocyanate ionic liquids.

    PubMed

    Osborne, Stephen J; Wellens, Sil; Ward, Chris; Felton, Solveig; Bowman, Robert M; Binnemans, Koen; Swadźba-Kwaśny, Małgorzata; Gunaratne, H Q Nimal; Nockemann, Peter

    2015-07-01

    Temperature-dependent switching of paramagnetism of a cobalt(II) complex is observed in an ionic liquid solution. Paramagnetic and thermochromic switching occur simultaneously due to a reversible change in coordination. This reversible switching is possible in the ionic liquid solution, which enables mobility of thiocyanate anions by remaining mobile at low temperatures and acts as an anion reservoir. PMID:26053484

  8. Electroplating Using Ionic Liquids

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

  9. Role of Ionic Strength in Staphylococcal Cell Aggregation.

    PubMed

    Vanzieleghem, Thomas; Couniot, Numa; Herman-Bausier, Philippe; Flandre, Denis; Dufrêne, Yves F; Mahillon, Jacques

    2016-07-26

    Cell aggregation plays a key role in biofilm formation and pathogenesis of Staphylococcus species. Although the molecular basis of aggregation in Staphylococci has already been extensively investigated, the influence of environmental factors, such as ionic strength, remains poorly understood. In this paper, we report a new type of cellular aggregation of Staphylococci that depends solely on ionic strength. Seven strains out of 14, all belonging to staphylococcal species, formed large cell clusters within minutes in buffers of ionic strength ranging from 1.5 to 50 mM, whereas isolates belonging to other Gram-positive species did not display this phenotype. Atomic force microscopy (AFM) with chemically functionalized tips provided direct evidence that ionic strength modulates cell surface adhesive properties through changes in cell surface charge. The optimal ionic strength for aggregation was found to be strain dependent, but in all cases, bacterial aggregates formed at an ionic strength of 1.5-50 mM were rapidly dispersed in a solution of higher ionic strength, indicating a reversibility of the cell aggregation process. These findings suggest that some staphylococcal isolates can respond to ionic strength as an external stimulus to trigger rapid cell aggregation in a way that has not yet been reported. PMID:27364477

  10. Magnesium Battery Electrolytes in Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Watkins, Tylan Strike

    A lack of adequate energy storage technologies is arguably the greatest hindrance to a modern sustainable energy infrastructure. Chemical energy storage, in the form of batteries, is an obvious solution to the problem. Unfortunately, today's state of the art battery technologies fail to meet the desired metrics for full scale electric grid and/or electric vehicle role out. Considerable effort from scientists and engineers has gone into the pursuit of battery chemistries theoretically capable of far outperforming leading technologies like Li-ion cells. For instance, an anode of the relatively abundant and cheap metal, magnesium, would boost the specific energy by over 4.6 times that of the current Li-ion anode (LiC6). The work presented here explores the compatibility of magnesium electrolytes in TFSI---based ionic liquids with a Mg anode (TFSI = bis(trifluoromethylsulfonyl)imide). Correlations are made between the Mg2+ speciation conditions in bulk solutions (as determined via Raman spectroscopy) and the corresponding electrochemical behavior of the electrolytes. It was found that by creating specific chelating conditions, with an appropriate Mg salt, the desired electrochemical behavior could be obtained, i.e. reversible electrodeposition and dissolution. Removal of TFSI -- contact ion pairs from the Mg2+ solvation shell was found to be essential for reversible electrodeposition. Ionic liquids with polyethylene glycol chains pendent from a parent pyrrolidinium cation were synthesized and used to create the necessary complexes with Mg 2+, from Mg(BH4)2, so that reversible electrodeposition from a purely ionic liquid medium was achieved. The following document discusses findings from several electrochemical experiments on magnesium electrolytes in ionic liquids. Explanations for the failure of many of these systems to produce reversible Mg electrodeposition are provided. The key characteristics of ionic liquid systems that are capable of achieving reversible Mg

  11. Fun with Ionic Compounds

    ERIC Educational Resources Information Center

    Logerwell, Mollianne G.; Sterling, Donna R.

    2007-01-01

    Ionic bonding is a fundamental topic in high school chemistry, yet it continues to be a concept that students struggle to understand. Even if they understand atomic structure and ion formation, it can be difficult for students to visualize how ions fit together to form compounds. This article describes several engaging activities that help…

  12. Synthesis of ionic liquids

    DOEpatents

    Dai, Sheng; Luo, Huimin

    2011-11-01

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

  13. Synthesis of ionic liquids

    DOEpatents

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

    2008-09-09

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

  14. Carbenes from ionic liquids.

    PubMed

    Hollóczki, Oldamur; Nyulászi, László

    2014-01-01

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

  15. 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).

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

    PubMed

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

    2009-06-01

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

  17. Biocatalytic transformations in ionic liquids.

    PubMed

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

    2003-03-01

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

  18. Super ionic conductive glass

    DOEpatents

    Susman, Sherman; Volin, Kenneth J.

    1984-01-01

    An ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A.sub.1+x D.sub.2-x/3 Si.sub.x P.sub.3-x O.sub.12-2x/3, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

  19. Super ionic conductive glass

    DOEpatents

    Susman, S.; Volin, K.J.

    Described is an ionically conducting glass for use as a solid electrolyte in a power or secondary cell containing an alkali metal-containing anode and a cathode separated by an alkali metal ion conducting glass having an ionic transference number of unity and the general formula: A/sub 1 + x/D/sub 2-x/3/Si/sub x/P/sub 3 - x/O/sub 12 - 2x/3/, wherein A is a network modifier for the glass and is an alkali metal of the anode, D is an intermediate for the glass and is selected from the class consisting of Zr, Ti, Ge, Al, Sb, Be, and Zn and X is in the range of from 2.25 to 3.0. Of the alkali metals, Na and Li are preferred and of the intermediate, Zr, Ti and Ge are preferred.

  20. Relationships between Undergraduates' Argumentation Skills, Conceptual Quality of Problem Solutions, and Problem Solving Strategies in Introductory Physics

    ERIC Educational Resources Information Center

    Rebello, Carina M.

    2012-01-01

    This study explored the effects of alternative forms of argumentation on undergraduates' physics solutions in introductory calculus-based physics. A two-phase concurrent mixed methods design was employed to investigate relationships between undergraduates' written argumentation abilities, conceptual quality of problem solutions, as well…

  1. Thermodynamic estimation: Ionic materials

    SciTech Connect

    Glasser, Leslie

    2013-10-15

    Thermodynamics establishes equilibrium relations among thermodynamic parameters (“properties”) and delineates the effects of variation of the thermodynamic functions (typically temperature and pressure) on those parameters. However, classical thermodynamics does not provide values for the necessary thermodynamic properties, which must be established by extra-thermodynamic means such as experiment, theoretical calculation, or empirical estimation. While many values may be found in the numerous collected tables in the literature, these are necessarily incomplete because either the experimental measurements have not been made or the materials may be hypothetical. The current paper presents a number of simple and relible estimation methods for thermodynamic properties, principally for ionic materials. The results may also be used as a check for obvious errors in published values. The estimation methods described are typically based on addition of properties of individual ions, or sums of properties of neutral ion groups (such as “double” salts, in the Simple Salt Approximation), or based upon correlations such as with formula unit volumes (Volume-Based Thermodynamics). - Graphical abstract: Thermodynamic properties of ionic materials may be readily estimated by summation of the properties of individual ions, by summation of the properties of ‘double salts’, and by correlation with formula volume. Such estimates may fill gaps in the literature, and may also be used as checks of published values. This simplicity arises from exploitation of the fact that repulsive energy terms are of short range and very similar across materials, while coulombic interactions provide a very large component of the attractive energy in ionic systems. Display Omitted - Highlights: • Estimation methods for thermodynamic properties of ionic materials are introduced. • Methods are based on summation of single ions, multiple salts, and correlations. • Heat capacity, entropy

  2. 3-Methylpiperidinium ionic liquids.

    PubMed

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

    2015-04-28

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

  3. Cyclic phosphonium ionic liquids

    PubMed Central

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

    2014-01-01

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

  4. Lifetime of Ionic Vacancy Created in Redox Electrode Reaction Measured by Cyclotron MHD Electrode

    PubMed Central

    Sugiyama, Atsushi; Morimoto, Ryoichi; Osaka, Tetsuya; Mogi, Iwao; Asanuma, Miki; Miura, Makoto; Oshikiri, Yoshinobu; Yamauchi, Yusuke; Aogaki, Ryoichi

    2016-01-01

    The lifetimes of ionic vacancies created in ferricyanide-ferrocyanide redox reaction have been first measured by means of cyclotron magnetohydrodynamic electrode, which is composed of coaxial cylinders partly exposed as electrodes and placed vertically in an electrolytic solution under a vertical magnetic field, so that induced Lorentz force makes ionic vacancies circulate together with the solution along the circumferences. At low magnetic fields, due to low velocities, ionic vacancies once created become extinct on the way of returning, whereas at high magnetic fields, in enhanced velocities, they can come back to their initial birthplaces. Detecting the difference between these two states, we can measure the lifetime of ionic vacancy. As a result, the lifetimes of ionic vacancies created in the oxidation and reduction are the same, and the intrinsic lifetime is 1.25 s, and the formation time of nanobubble from the collision of ionic vacancies is 6.5 ms. PMID:26791269

  5. Lifetime of Ionic Vacancy Created in Redox Electrode Reaction Measured by Cyclotron MHD Electrode.

    PubMed

    Sugiyama, Atsushi; Morimoto, Ryoichi; Osaka, Tetsuya; Mogi, Iwao; Asanuma, Miki; Miura, Makoto; Oshikiri, Yoshinobu; Yamauchi, Yusuke; Aogaki, Ryoichi

    2016-01-01

    The lifetimes of ionic vacancies created in ferricyanide-ferrocyanide redox reaction have been first measured by means of cyclotron magnetohydrodynamic electrode, which is composed of coaxial cylinders partly exposed as electrodes and placed vertically in an electrolytic solution under a vertical magnetic field, so that induced Lorentz force makes ionic vacancies circulate together with the solution along the circumferences. At low magnetic fields, due to low velocities, ionic vacancies once created become extinct on the way of returning, whereas at high magnetic fields, in enhanced velocities, they can come back to their initial birthplaces. Detecting the difference between these two states, we can measure the lifetime of ionic vacancy. As a result, the lifetimes of ionic vacancies created in the oxidation and reduction are the same, and the intrinsic lifetime is 1.25 s, and the formation time of nanobubble from the collision of ionic vacancies is 6.5 ms. PMID:26791269

  6. Lifetime of Ionic Vacancy Created in Redox Electrode Reaction Measured by Cyclotron MHD Electrode

    NASA Astrophysics Data System (ADS)

    Sugiyama, Atsushi; Morimoto, Ryoichi; Osaka, Tetsuya; Mogi, Iwao; Asanuma, Miki; Miura, Makoto; Oshikiri, Yoshinobu; Yamauchi, Yusuke; Aogaki, Ryoichi

    2016-01-01

    The lifetimes of ionic vacancies created in ferricyanide-ferrocyanide redox reaction have been first measured by means of cyclotron magnetohydrodynamic electrode, which is composed of coaxial cylinders partly exposed as electrodes and placed vertically in an electrolytic solution under a vertical magnetic field, so that induced Lorentz force makes ionic vacancies circulate together with the solution along the circumferences. At low magnetic fields, due to low velocities, ionic vacancies once created become extinct on the way of returning, whereas at high magnetic fields, in enhanced velocities, they can come back to their initial birthplaces. Detecting the difference between these two states, we can measure the lifetime of ionic vacancy. As a result, the lifetimes of ionic vacancies created in the oxidation and reduction are the same, and the intrinsic lifetime is 1.25 s, and the formation time of nanobubble from the collision of ionic vacancies is 6.5 ms.

  7. Long-range electrostatic screening in ionic liquids.

    PubMed

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

    2015-06-16

    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

  8. 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

  9. Thallium Transfer from Hydrochloric Acid Media into Pure Ionic Liquids.

    PubMed

    Tereshatov, Evgeny E; Boltoeva, Maria Yu; Mazan, Valerie; Volia, Merinda F; Folden, Charles M

    2016-03-10

    Pure hydrophobic ionic liquids are known to extract metallic species from aqueous solutions. In this work we have systematically investigated thallium (Tl) extraction from aqueous hydrochloric acid (HCl) solutions into six pure fluorinated ionic liquids, namely imidazolium- and pyrrolidinium-based ionic liquids with bis(trifluoromethanesulfonyl)imide and bis(fluorosulfonyl)-imide anions. The dependence of the Tl extraction efficiency on the structure and composition of the ionic liquid ions, metal oxidation state, and initial metal and aqueous acid concentrations have been studied. Tl concentrations were on the order of picomolar (analyzed using radioactive tracers) and millimolar (analyzed using inductively coupled plasma mass spectrometry). The extraction of the cationic thallium species Tl(+) is higher for ionic liquids with more hydrophilic cations, while for the TlX(z)(3-z) anionic species (where X = Cl(-) and/or Br(-)), the extraction efficiency is greater for ionic liquids with more hydrophobic cations. The highest distribution value of Tl(III) was approximately 2000. An improved mathematical model based on ion exchange and ion pair formation mechanisms has been developed to describe the coextraction of two different anionic species, and the relative contributions of each mechanism have been determined. PMID:26769597

  10. Employing ionic liquids to deposit cellulose on PET fibers.

    PubMed

    Textor, Torsten; Derksen, Leonie; Gutmann, Jochen S

    2016-08-01

    Several ionic liquids are excellent solvents for cellulose. Starting from that finishing of PET fabrics with cellulose dissolved in ionic liquids like 1-ethyl-3-methyl imidazolium acetate, diethylphosphate and chloride, or the chloride of butyl-methyl imidazolium has been investigated. Finishing has been carried out from solutions of different concentrations, using microcrystalline cellulose or cotton and by employing different cross-linkers. Viscosity of solutions has been investigated for different ionic liquids, concentrations, cellulose sources, linkers and temperatures. Since ionic liquids exhibit no vapor pressure, simple pad-dry-cure processes are excluded. Before drying the ionic liquid has to be removed by a rinsing step. Accordingly rinsing with fresh ionic liquid followed by water or the direct rinsing with water have been tested. The amount of cellulose deposited has been investigated by gravimetry, zinc chloride iodine test as well as reactive dyeing. Results concerning wettability, water up-take, surface resistance, wear-resistance or washing stability are presented. PMID:27112860

  11. The radiation chemistry of ionic liquids: A review

    SciTech Connect

    Mincher, Bruce J.; Wishart, James F.

    2014-07-03

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

  12. The radiation chemistry of ionic liquids: A review

    DOE PAGESBeta

    Mincher, Bruce J.; Wishart, James F.

    2014-07-03

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

  13. Dynamics of Ion Transport in Ionic Liquids.

    PubMed

    Lee, Alpha A; Kondrat, Svyatoslav; Vella, Dominic; Goriely, Alain

    2015-09-01

    A gap in understanding the link between continuum theories of ion transport in ionic liquids and the underlying microscopic dynamics has hindered the development of frameworks for transport phenomena in these concentrated electrolytes. Here, we construct a continuum theory for ion transport in ionic liquids by coarse graining a simple exclusion process of interacting particles on a lattice. The resulting dynamical equations can be written as a gradient flow with a mobility matrix that vanishes at high densities. This form of the mobility matrix gives rise to a charging behavior that is different to the one known for electrolytic solutions, but which agrees qualitatively with the phenomenology observed in experiments and simulations. PMID:26382685

  14. Comparison of bipolar and unipolar ionic diodes

    SciTech Connect

    Vlassiouk, Ivan V

    2010-01-01

    Nanoporous ionic diodes, as well as devices for manipulating ions and molecules in a solution, have attracted a great deal of interest from researchers in various fields from the fundamental point of view. Ionic diodes allow the ions to be transported in one direction and block the transport in the other. There are two types of diodes that have been realized experimentally. A bipolar diode contains a junction between two zones of the pore walls with positive and negative surface charges. A unipolar diode contains a zone that is neutral and a zone that is charged. In this paper we discuss differences in operation of the diodes with a special emphasis on the sensitivity of their performance to the lengths of the charged and neutral zones. We also show that a bipolar diode offers more asymmetric current-voltage curves than a unipolar diode.

  15. Homopolymer Dissolution in a Hydrophilic Ionic Liquid

    NASA Astrophysics Data System (ADS)

    Hoagland, David; Harner, John

    2010-03-01

    Dissolution, structure, and dynamics of both neutral and charged polymers dissolved in a hydrophilic room temperature ionic liquid (IL), ethylmethylimidazolium ethyl sulfate [EMIM][EtSO4], have been studied by classical physicochemical methods (static and dynamic light scattering, intrinsic viscosity, refractometry) to determine differences in solution behavior from conventional aqueous and organic solvents. This IL is water miscible. Many neutral polymers and charged polymer salts molecularly dissolve, although solubility doesn't correlate with polymer hydrophilicity. Model neutral soluble polymers are polyvinylpyrrolidone and hydroroxyethyl cellulose while sodium poly(styrene sulfonate) and the iodo salt of methyl-quaternized poly(vinyl pyridine) fill the same role for charged polymers. The latter display none of the polyelectrolyte effects found in low ionic strength water, consistent with strong electrostatic screening in IL. In virial coefficient and coil size, the IL acts for these neutral and charged polymers as a classical good solvent. (Support: UMass MRSEC)

  16. A new strategy of solution calibration in laser ablation inductively coupled plasma mass spectrometry for multielement trace analysis of geological samples.

    PubMed

    Pickhardt, C; Becker, J S; Dietze, H J

    2000-01-01

    Because multielement trace analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is often limited by the lack of suitable reference materials with a similar matrix composition, a novel quantification strategy using solution calibration was developed. For mass spectrometric multielement determination in geological samples a quadrupole-based LA-ICP-MS is coupled with an ultrasonic nebulizer (USN). In order to arrange matrix matching the standard solutions are nebulized with a USN during solution calibration and simultaneously a blank target (e.g. lithium borate) is ablated with a focused laser beam. The homogeneous geological samples were measured using the same experimental arrangement where a 2% nitric acid is simultaneously nebulized with the USN. Homogeneous targets were prepared from inhomogeneous geological samples by powdering, homogenizing and fusing with a lithium borate mixture in a muffle furnace at 1050 degrees C. Furthermore, a homogeneous geological glass was also investigated. The quantification of analytical results was performed by external calibration using calibration curves measured on standard solutions. In order to compare two different approaches for the quantification of analytical results in LA-ICP-MS, measured concentrations in homogeneous geological targets were also corrected with relative sensitivity coefficients (RSCs) determined using one standard solution only. The analytical results of LA-ICP-MS on various geological samples are in good agreement with the reference values and the results of other trace analytical methods. The relative standard deviation (RSD) for trace element determination (N = 6) is between 2 and 10%. PMID:11220576

  17. Acidic Ionic Liquid/Water Solution as Both Medium and Proton Source for Electrocatalytic H2 Evolution by [Ni(P2N2)2]2+ Complexes

    SciTech Connect

    Pool, Douglas H.; Stewart, Michael P.; O'Hagan, Molly J.; Shaw, Wendy J.; Roberts, John A.; Bullock, R. Morris; DuBois, Daniel L.

    2012-06-08

    The electrocatalytic reduction of protons to H2 by [Ni(PPh2NC6H4-hex2)2](BF4)2 (where PPh2NC6H4-hex2 = 1,5-di(4-n-hexylphenyl)-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) in the highly acidic ionic liquid dibutylformamidium bis(trifluoromethanesulfonyl)amide shows a strong dependence on added water. A turnover frequency of 43,000-53,000 s-1 has been measured for hydrogen production at 25 °C when the mole fraction of water (χH2O) is 0.72. The same catalyst in acetonitrile with added dimethylformamidium trifluoromethanesulfonate and water has a turnover frequency of 720 s-1. Thus the use of an ionic liquid/aqueous solution enhances the observed catalytic rates by more than a factor of 50 compared to acids in traditional organic solvents such as acetonitrile. Complexes [Ni(PPh2NC6H4X2)2](BF4)2 (X = H, OMe, CH2P(O)(OEt)2, Br) are also catalysts in the ionic liquid/water mixture, and the observed catalytic rates correlate with the hydrophobicity of X. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  18. Global Mass Flux Solutions from GRACE: A Comparison of Parameter Estimation Strategies - Mass Concentrations Versus Stokes Coefficients

    NASA Technical Reports Server (NTRS)

    Rowlands, D. D.; Luthcke, S. B.; McCarthy J. J.; Klosko, S. M.; Chinn, D. S.; Lemoine, F. G.; Boy, J.-P.; Sabaka, T. J.

    2010-01-01

    The differences between mass concentration (mas con) parameters and standard Stokes coefficient parameters in the recovery of gravity infonnation from gravity recovery and climate experiment (GRACE) intersatellite K-band range rate data are investigated. First, mascons are decomposed into their Stokes coefficient representations to gauge the range of solutions available using each of the two types of parameters. Next, a direct comparison is made between two time series of unconstrained gravity solutions, one based on a set of global equal area mascon parameters (equivalent to 4deg x 4deg at the equator), and the other based on standard Stokes coefficients with each time series using the same fundamental processing of the GRACE tracking data. It is shown that in unconstrained solutions, the type of gravity parameter being estimated does not qualitatively affect the estimated gravity field. It is also shown that many of the differences in mass flux derivations from GRACE gravity solutions arise from the type of smoothing being used and that the type of smoothing that can be embedded in mas con solutions has distinct advantages over postsolution smoothing. Finally, a 1 year time series based on global 2deg equal area mascons estimated every 10 days is presented.

  19. Using Open-Response Fraction Items to Explore the Relationship between Instructional Modalities and Students' Solution Strategies

    ERIC Educational Resources Information Center

    Shumway, Jessica F.; Moyer-Packenham, Patricia S.; Baker, Joseph M.; Westenskow, Arla; Anderson-Pence, Katie L.; Tucker, Stephen I.; Boyer-Thurgood, Jennifer; Jordan, Kerry E.

    2016-01-01

    The purpose of this study was to explore the relationship between instructional modality used for teaching fractions and third- and fourth-grade students' responses and strategies to open-response fraction items. The participants were 155 third-grade and 200 fourth-grade students from 17 public school classrooms. Students within each class were…

  20. 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…

  1. An efficient iteration strategy for upwind/relaxation solutions to the thin-layer Navier-Stokes equations

    NASA Technical Reports Server (NTRS)

    Newsome, Richard W.; Walters, Robert W.; Thomas, James L.

    1987-01-01

    A previously developed upwind/relaxation algorithm for solving the unsteady, compressible, thin-layer Navier-Stokes equations is presently modified so that the downstream influence of the subsonic part of the boundary layer in an otherwise supersonic flow is suppressed by restricting the streamwise pressure gradient. A 'parabolized' solution is then efficiently obtained by marching downstream and iterating locally in each crossflow plane until achieving convergence. This parabolized solution is an excellent final one for problems without large adverse streamwise pressure gradients.

  2. Ionic surface electrical conductivity in sandstone

    NASA Astrophysics Data System (ADS)

    Glover, Paul W. J.; Meredith, Philip G.; Sammonds, Peter R.; Murrell, Stanley A. F.

    1994-11-01

    Recent analyses of complex conductivity measurements have indicated that high-frequency dispersions encountered in rocks saturated with low-salinity fluids are due to ionic surface conduction and that the form of these dispersions may be dependent upon the nature of the pore and crack surfaces within the rock (Ruffet et al., 1991). Unfortunately, the mechanisms of surface conduction are not well understood, and no model based on rigorous physical principles exists. This paper is split into two parts: an experimental section followed by the development of a theoretical description of adsorption of ions onto mineral surfaces. We have made complex conductivity measurements upon samples of sandstone saturated with a range of different types and concentrations of aqueous solution with a frequency range of 20 Hz to 1 MHz. The frequency dependence of complex conductivity was analyzed using the empirical model of Cole and Cole (1941). The 'fractal' surface models of Le Mehaute and Crepy (1983), Po Zen Wong (1987), the Ruffet el at. (1991) were used to calculate apparent fractal pore surface dimensions for samples saturated with different solution types and concentrations. These showed a pronounced decrease of apparent fractal surface dimension with decreasing electrolyte concentration and a decrease of apparent fractal dimension with increasing relative ionic radius of the dominant cation in solution. A model for ionic surface concentration (ISCOM I) has been developed as the first step in producing a rigorous physicochemical model of surface conduction in quartz-dominated rocks. The results from ISCOM I show that quartz surfaces are overwhelmingly dominated by adsorbed Na(+) when saturated with NaCl solutions of salinities and pH found in actual geological situations. ISCOM I also shows that the concentration threshold for dominance of surface conduction over bulk conduction is aided by depletion of ions from the bulk fluid as a result of their adsorption onto the mineral

  3. Addressing Student Misconceptions Concerning Electron Flow in Aqueous Solutions with Instruction Including Computer Animations and Conceptual Change Strategies.

    ERIC Educational Resources Information Center

    Sanger, Michael J.; Greenbowe, Thomas J.

    2000-01-01

    Investigates the effects of both computer animations of microscopic chemical processes occurring in a galvanic cell and conceptual-change instruction based on chemical demonstrations on students' conceptions of current flow in electrolyte solutions. Finds that conceptual change instruction was effective at dispelling student misconceptions but…

  4. Tuning the Carbon Dioxide Absorption in Amino Acid Ionic Liquids.

    PubMed

    Firaha, Dzmitry S; Kirchner, Barbara

    2016-07-01

    One of the possible solutions to prevent global climate change is the reduction of CO2 emissions, which is highly desired for the sustainable development of our society. In this work, the chemical absorption of carbon dioxide in amino acid ionic liquids was studied through first-principles methods. The use of readily accessible and biodegradable amino acids as building blocks for ionic liquids makes them highly promising replacements for the widely applied hazardous aqueous solutions of amines. A detailed insight into the reaction mechanism of the CO2 absorption was obtained through state-of-the-art theoretical methods. This allowed us to determine the reason for the specific CO2 capacities found experimentally. Moreover, we have also conducted a theoretical design of ionic liquids to provide valuable insights into the precise tuning of the energetic and kinetic parameters of the CO2 absorption. PMID:27214652

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

    PubMed

    Koo, Hyung-Jun; Velev, Orlin D

    2013-01-01

    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. PMID:24404020

  6. The Concept of Ionic Strength Eighty Years after Its Introduction in Chemistry

    NASA Astrophysics Data System (ADS)

    Sastre de Vicente, Manuel E.

    2004-05-01

    Even today, eighty years after its empirical introduction in chemistry, the ionic strength of a solution continues to be regarded as a major variable in examining salt effects in many fields of science. In fact, many studies have examined the effect of, or dependence on, not only T , P , or pH, but also ionic strength. This paper reviews the meaning of ionic strength, including the relationship of ionic strength to macroscopic concepts such as thermodynamic quantities and microscopic ones such as molecule size. See Letter re: this article.

  7. Correlation of thermodynamic data for aqueous electrolyte solutions to very high ionic strength using INSIGHT: Vapor saturated water activity in the system CaCl{sub 2}-H{sub 2}O to 250 C and solid saturation

    SciTech Connect

    Sterner, S.M.; Felmy, A.R.; Oakes, C.S.; Pitzer, K.S.

    1998-05-01

    Osmotic coefficients for the CaCl{sub 2}-H{sub 2}O system between 25 and 250 C and from the dilute region to solid saturation or beyond (i.e., to {approx}12 mCaCl{sub 2} at the lowest temperature and {approx}32 mCaCl{sub 2} at the highest) have been correlated using the following permutations and modifications of the basic Pitzer ion-interaction equation: (1) the basic Pitzer equation, (2) the Pitzer equation augmented by an ionic strength-dependent third virial contribution, (3) the Pitzer equation together with equilibria involving the formation of CaCl{sup +} and CaCl{sub 2}{sup 0}, and (4) the simultaneous combination of all of the above. The effectiveness, accuracy, and practicality of each approach are reviewed.

  8. Understanding SO2 Capture by Ionic Liquids.

    PubMed

    Mondal, Anirban; Balasubramanian, Sundaram

    2016-05-19

    Ionic liquids have generated interest for efficient SO2 absorption due to their low vapor pressure and versatility. In this work, a systematic investigation of the structure, thermodynamics, and dynamics of SO2 absorption by ionic liquids has been carried out through quantum chemical calculations and molecular dynamics (MD) simulations. MP2 level calculations of several ion pairs complexed with SO2 reveal its preferential interaction with the anion. Results of condensed phase MD simulations of SO2-IL mixtures manifested the essential role of both cations and anions in the solvation of SO2, where the solute is surrounded by the "cage" formed by the cations (primarily its alkyl tail) through dispersion interactions. These structural effects of gas absorption are substantiated by calculated Gibbs free energy of solvation; the dissolution is demonstrated to be enthalpy driven. The entropic loss of SO2 absorption in ionic liquids with a larger anion such as [NTf2](-) has been quantified and has been attributed to the conformational restriction of the anion imposed by its interaction with SO2. SO2 loading IL decreases its shear viscosity and enhances the electrical conductivity. This systematic study provides a molecular level understanding which can aid the design of task-specific ILs as electrolytes for efficient SO2 absorption. PMID:27119562

  9. Osmotic Pressure in Ionic Microgel Dispersions

    NASA Astrophysics Data System (ADS)

    Denton, Alan R.; Tang, Qiyun

    2015-03-01

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

  10. Catalytic reactions in ionic liquids.

    PubMed

    Sheldon, R

    2001-12-01

    The chemical industry is under considerable pressure to replace many of the volatile organic compounds (VOCs) that are currently used as solvents in organic synthesis. The toxic and/or hazardous properties of many solvents, notably chlorinated hydrocarbons, combined with serious environmental issues, such as atmospheric emissions and contamination of aqueous effluents is making their use prohibitive. This is an important driving force in the quest for novel reaction media. Curzons and coworkers, for example, recently noted that rigorous management of solvent use is likely to result in the greatest improvement towards greener processes for the manufacture of pharmaceutical intermediates. The current emphasis on novel reaction media is also motivated by the need for efficient methods for recycling homogeneous catalysts. The key to waste minimisation in chemicals manufacture is the widespread substitution of classical 'stoichiometric' syntheses by atom efficient, catalytic alternatives. In the context of homogeneous catalysis, efficient recycling of the catalyst is a conditio sine qua non for economically and environmentally attractive processes. Motivated by one or both of the above issues much attention has been devoted to homogeneous catalysis in aqueous biphasic and fluorous biphasic systems as well as in supercritical carbon dioxide. Similarly, the use of ionic liquids as novel reaction media may offer a convenient solution to both the solvent emission and the catalyst recycling problem. PMID:12239988

  11. Counterion condensation and ionic conductivity

    NASA Astrophysics Data System (ADS)

    Penafiel, L. Miguel; Litovitz, Theodore A.

    1992-02-01

    The occurrence of counterion condensation is demonstrated through measurements of the incremental ionic conductivity of pH buffered Na polyacrylate solutions. pH values were selected to allow variation of the charge density parameter ξ in the range between 0.4 and 2.8, that is, across ξ=1, the theoretical critical level for counterion condensation. The results show two regions where the incremental conductivity, ΔσP, varies differently with ξ. For ξ<1.3, ΔσP remains relatively constant. A sharp drop in ΔσP is observed between ξ=1.3 and ξ=1.7 corresponding to the onset of counterion condensation. It is suggested that this discontinuity reflects a drastic change in the polyion mobility caused by a structural rearrangement of the macromolecule. For ξ≳1.7, ΔσP decreases with approximately constant slope. This latter behavior agrees qualitatively but not quantitatively with the prediction of the counterion condensation model.

  12. Technology Solutions Case Study: Evaluation of Ventilation Strategies in New Construction Multifamily Buildings, New York, New York

    SciTech Connect

    2014-09-01

    In multifamily buildings, particularly in the Northeast, exhaust ventilation strategies are the norm as a means of meeting both local exhaust and whole-unit mechanical ventilation rates. The issue of where the "fresh" air is coming from is gaining significance as air-tightness standards for enclosures become more stringent, and the "normal leakage paths through the building envelope" disappear. Consortium for Advanced Residential Buildings researchers have found that the majority of high performance, new construction, multifamily housing in the Northeast use one of four general strategies for ventilation: continuous exhaust only with no designated supply or make-up air source, continuous exhaust with ducted make-up air to apartments, continuous exhaust with supply through a make-up air device integral to the unit HVAC, and continuous exhaust with supply through a passive inlet device, such as a trickle vent. This research effort included several weeks of building pressure monitoring to validate system performance of the different strategies for providing make-up air to apartments.

  13. Phytoremediation of Ionic and Methyl Mercury Pollution

    SciTech Connect

    Meagher, Richard B.

    2005-06-01

    Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species. Several of these genes have already been shown to enhance mercury phytoremediation. Mercury pollution is a serious, world-wide problem affecting the health of human and wildlife populations. Environmentally, the most serious mercury threat is the production of methylmercury (CH3Hg+) by native bacteria at mercury contaminated wetland sites. Methylmercury is inherently more toxic than metallic (Hg(0)) or ionic (Hg(II)) mercury, and because methylmercury is prolifically biomagnified up the food chain, it poses the most immediate danger to animal populations. We have successfully engineered two model plants, Arabidopsis and tobacco, to use the bacterial merB gene to convert methylmercury to less toxic ionic mercury and to use the bacterial merA gene to further detoxify ionic mercury to the least toxic form of mercury, metallic mercury. Plants expressing both MerA and MerB proteins detoxify methylmercury in two steps to the metallic form. These plants germinate, grow, and set seed at normal growth rates on levels of methylmercury or ionic mercury that are lethal to normal plants. Our newest efforts involve engineering plants with several additional bacterial and plant genes that allow for higher levels of mercury resistance and mercury hyperaccumulation. The potential for these plants to hyperaccumulate mercury was further advanced by developing constitutive, aboveground, and root-specific gene expression systems. Our current strategy is to engineer plants to

  14. Durable Electrooptic Devices Comprising Ionic Liquids

    DOEpatents

    Burrell, Anthony K.; Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark

    2008-11-11

    Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

  15. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Burrell, Anthony K.; Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark

    2009-12-15

    Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes. Some of the electrolyte solutions color to red when devices employing the solutions are powered, leading to red or neutral electrooptic devices.

  16. Enzyme catalysis in ionic liquids.

    PubMed

    Kragl, Udo; Eckstein, Marrit; Kaftzik, Nicole

    2002-12-01

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

  17. Quantum, classical, and hybrid QM/MM calculations in solution: General implementation of the ddCOSMO linear scaling strategy

    SciTech Connect

    Lipparini, Filippo; Scalmani, Giovanni; Frisch, Michael J.; Lagardère, Louis; Stamm, Benjamin; Cancès, Eric; Maday, Yvon; Piquemal, Jean-Philip; Mennucci, Benedetta

    2014-11-14

    We present the general theory and implementation of the Conductor-like Screening Model according to the recently developed ddCOSMO paradigm. The various quantities needed to apply ddCOSMO at different levels of theory, including quantum mechanical descriptions, are discussed in detail, with a particular focus on how to compute the integrals needed to evaluate the ddCOSMO solvation energy and its derivatives. The overall computational cost of a ddCOSMO computation is then analyzed and decomposed in the various steps: the different relative weights of such contributions are then discussed for both ddCOSMO and the fastest available alternative discretization to the COSMO equations. Finally, the scaling of the cost of the various steps with respect to the size of the solute is analyzed and discussed, showing how ddCOSMO opens significantly new possibilities when cheap or hybrid molecular mechanics/quantum mechanics methods are used to describe the solute.

  18. Quantum, classical, and hybrid QM/MM calculations in solution: general implementation of the ddCOSMO linear scaling strategy.

    PubMed

    Lipparini, Filippo; Scalmani, Giovanni; Lagardère, Louis; Stamm, Benjamin; Cancès, Eric; Maday, Yvon; Piquemal, Jean-Philip; Frisch, Michael J; Mennucci, Benedetta

    2014-11-14

    We present the general theory and implementation of the Conductor-like Screening Model according to the recently developed ddCOSMO paradigm. The various quantities needed to apply ddCOSMO at different levels of theory, including quantum mechanical descriptions, are discussed in detail, with a particular focus on how to compute the integrals needed to evaluate the ddCOSMO solvation energy and its derivatives. The overall computational cost of a ddCOSMO computation is then analyzed and decomposed in the various steps: the different relative weights of such contributions are then discussed for both ddCOSMO and the fastest available alternative discretization to the COSMO equations. Finally, the scaling of the cost of the various steps with respect to the size of the solute is analyzed and discussed, showing how ddCOSMO opens significantly new possibilities when cheap or hybrid molecular mechanics/quantum mechanics methods are used to describe the solute. PMID:25399133

  19. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Agrawal, Anoop; Cronin, John P.; Tonazzi, Juan C. L.; Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

    2005-11-01

    Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF3SO3-), bis(trifluoromethylsulfonyl)imide ((CF3SO2)2N-), bis(perfluoroethylsulfonyl)imide ((CF3CF2SO2)2N-) and tris(trifluoromethylsulfonyl)methide ((CF3SO2)3C-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

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

    PubMed

    Chaban, Vitaly V; Prezhdo, Oleg V

    2016-05-26

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

  1. Wettability by Ionic Liquids.

    PubMed

    Liu, Hongliang; Jiang, Lei

    2016-01-01

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

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

    PubMed

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

    2012-08-16

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

  3. New Whole-House Solutions Case Study: HVAC Design Strategy for a Hot-Humid Production Builder, Houston, Texas

    SciTech Connect

    2014-03-01

    Building Science Corporation (BSC) worked directly with the David Weekley Homes - Houston division to develop a cost-effective design for moving the HVAC system into conditioned space. In addition, BSC conducted energy analysis to calculate the most economical strategy for increasing the energy performance of future production houses in preparation for the upcoming code changes in 2015. The following research questions were addressed by this research project: 1. What is the most cost effective, best performing and most easily replicable method of locating ducts inside conditioned space for a hot-humid production home builder that constructs one and two story single family detached residences? 2. What is a cost effective and practical method of achieving 50% source energy savings vs. the 2006 International Energy Conservation Code for a hot-humid production builder? 3. How accurate are the pre-construction whole house cost estimates compared to confirmed post construction actual cost? BSC and the builder developed a duct design strategy that employs a system of dropped ceilings and attic coffers for moving the ductwork from the vented attic to conditioned space. The furnace has been moved to either a mechanical closet in the conditioned living space or a coffered space in the attic.

  4. A thermoresponsive poly(ionic liquid) membrane enables concentration of proteins from aqueous media.

    PubMed

    Kohno, Yuki; Gin, Douglas L; Noble, Richard D; Ohno, Hiroyuki

    2016-06-14

    A new type of poly(ionic liquid) membrane, which shows switchable hydrated states via lower critical solution temperature-type phase behaviour, enables concentration of some water-soluble proteins from aqueous media. PMID:27211060

  5. Phytoremediation of Ionic and Methyl Mercury Pollution

    SciTech Connect

    Meagher, Richard B.

    2005-06-01

    Phytoremediation is defined as the use of plants to extract, resist, detoxify, and/or sequester toxic environmental pollutants. The long-term goal of the proposed research is to develop and test highly productive, field-adapted plant species that have been engineered for the phytoremediation of mercury. A variety of different genes, which should enable plants to clean mercury polluted sites are being tested as tools for mercury phytoremediation, first in model laboratory plants and then in potential field species. Several of these genes have already been shown to enhance mercury phytoremediation. Mercury pollution is a serious, world-wide problem affecting the health of human and wildlife populations. Environmentally, the most serious mercury threat is the production of methylmercury (CH3Hg+) by native bacteria at mercury contaminated wetland sites. Methylmercury is inherently more toxic than metallic (Hg(0)) or ionic (Hg(II)) mercury, and because methylmercury is prolifically biomagnified up the food chain, it poses the most immediate danger to animal populations. We have successfully engineered two model plants, Arabidopsis and tobacco, to use the bacterial merB gene to convert methylmercury to less toxic ionic mercury and to use the bacterial merA gene to further detoxify ionic mercury to the least toxic form of mercury, metallic mercury. Plants expressing both MerA and MerB proteins detoxify methylmercury in two steps to the metallic form. These plants germinate, grow, and set seed at normal growth rates on levels of methylmercury or ionic mercury that are lethal to normal plants. Our newest efforts involve engineering plants with several additional bacterial and plant genes that allow for higher levels of mercury resistance and mercury hyperaccumulation. The potential for these plants to hyperaccumulate mercury was further advanced by developing constitutive, aboveground, and root-specific gene expression systems. Our current strategy is to engineer plants to

  6. Delivery strategies for treatment of age-related ocular diseases: From a biological understanding to biomaterial solutions.

    PubMed

    Delplace, Vianney; Payne, Samantha; Shoichet, Molly

    2015-12-10

    Age-related ocular diseases, such as age-related macular degeneration (AMD), diabetic retinopathy, and glaucoma, result in life-long functional deficits and enormous global health care costs. As the worldwide population ages, vision loss has become a major concern for both economic and human health reasons. Due to recent research into biomaterials and nanotechnology major advances have been gained in the field of ocular delivery. This review provides a summary and discussion of the most recent strategies employed for the delivery of both drugs and cells to the eye to treat a variety of age-related diseases. It emphasizes the current challenges and limitations to ocular delivery and how the use of innovative materials can overcome these issues and ultimately provide treatment for age-related degeneration and regeneration of lost tissues. This review also provides critical considerations and an outlook for future studies in the field of ophthalmic delivery. PMID:26435454

  7. 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.

  8. Ionic liquids: the link to high-temperature molten salts?

    PubMed

    El Abedin, Sherif Zein; Endres, Frank

    2007-11-01

    Due to their wide thermal windows, ionic liquids can be regarded as the missing link between aqueous/organic solutions and high-temperature molten salts. They can be employed efficiently for the coating of other metals with thin layers of tantalum, aluminum, and presumably many others at reasonable temperatures by electrochemical means. The development of ionic liquids, especially air and water stable ones, has opened the door for the electrodeposition of reactive elements such as, for example, Al, Ta, and Si, which in the past were only accessible using high-temperature molten salts or, in part, organic solvents. PMID:17521159

  9. Survival strategies of microorganisms in extreme saline environments

    NASA Astrophysics Data System (ADS)

    Imhoff, J. F.

    Halophilic representatives are found in all main lines of evolutionary descendence of microbes: in archaebacteria, Gram-negative and Gram-positive eubacteria, and also in eucaryotes. In principe all halophilic microorganisms have to adapt their surface and membrane structures to their highly ionic environments. Concerning their intracellular compartment two different strategies have been developed: Inorganic ions are largely excluded in some microorganisms while such ions are actively accumulated in others. In particular the second group of organisms has to adapt the whole metabolic machinery to the highly ionic conditions of several molar salts, whereas in the first group only the outer surface of the cytoplasmic membrane and the extracytoplasmic structures are in contact with high concentrations of inorganic ions. In this latter group, a variety of organic solutes is accumulated in response to increases of the salinity of the environment.

  10. Ionic liquid nanostructure enables alcohol self assembly.

    PubMed

    Murphy, Thomas; Hayes, Robert; Imberti, Silvia; Warr, Gregory G; Atkin, Rob

    2016-05-14

    Weakly structured solutions are formed from mixtures of one or more amphiphiles and a polar solvent (usually water), and often contain additional organic components. They contain solvophobic aggregates or association structures with incomplete segregation of components, which leads to a poorly defined interfacial region and significant contact between the solvent and aggregated hydrocarbon groups. The length scales, polydispersity, complexity and ill-defined structures in weakly structured solutions makes them difficult to probe experimentally, and obscures understanding of their formation and stability. In this work we probe the nanostructure of homogenous binary mixtures of the ionic liquid (IL) propylammonium nitrate (PAN) and octanol as a function of composition using neutron diffraction and atomistic empirical potential structure refinement (EPSR) fits. These experiments reveal why octanol forms weakly structured aggregates in PAN but not in water, the mechanism by which PAN stabilises the octanol assemblies, and how the aggregate morphologies evolve with octanol concentration. This new understanding provides insight into the general stabilisation mechanisms and structural features of weakly structured mixtures, and reveals new pathways for identifying molecular or ionic liquids that are likely to facilitate aggregation of non-traditional amphiphiles. PMID:27102801

  11. Ionic Liquid Crystals: Versatile Materials.

    PubMed

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

    2016-04-27

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

  12. Special Report: Solid Ionic Conductors.

    ERIC Educational Resources Information Center

    Shriver, Duward F.; Farrington, Gregory C.

    1985-01-01

    Solid ionic conductors are unusual materials that may find valuable applications in devices ranging from high-energy density batteries to lasers. The nature of these materials and their potential uses are discussed. (JN)

  13. Nonlinear ionic pulses along microtubules.

    PubMed

    Sekulić, D L; Satarić, B M; Tuszynski, J A; Satarić, M V

    2011-05-01

    Microtubules are cylindrically shaped cytoskeletal biopolymers that are essential for cell motility, cell division and intracellular trafficking. Here, we investigate their polyelectrolyte character that plays a very important role in ionic transport throughout the intra-cellular environment. The model we propose demonstrates an essentially nonlinear behavior of ionic currents which are guided by microtubules. These features are primarily due to the dynamics of tubulin C-terminal tails which are extended out of the surface of the microtubule cylinder. We also demonstrate that the origin of nonlinearity stems from the nonlinear capacitance of each tubulin dimer. This brings about conditions required for the creation and propagation of solitonic ionic waves along the microtubule axis. We conclude that a microtubule plays the role of a biological nonlinear transmission line for ionic currents. These currents might be of particular significance in cell division and possibly also in cognitive processes taking place in nerve cells. PMID:21604102

  14. Novel approaches to ionic chromatography

    SciTech Connect

    Dasgupta, P.K.

    1990-11-01

    Research during this reporting period, continued on ionic chromatography. Major progress has been made towards on-line on-demand generation of ultrapure chemicals by electrochemical means. The concentration of the generated material is governed electrochemically.

  15. Ionic Liquid Epoxy Resin Monomers

    NASA Technical Reports Server (NTRS)

    Paley, Mark S. (Inventor)

    2013-01-01

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

  16. Hydrophobic ionic liquids

    DOEpatents

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

    1998-10-27

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

  17. Hydrophobic ionic liquids

    DOEpatents

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

    1998-01-01

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

  18. MEAN-FIELD THEORY AND COMPUTATION OF ELECTROSTATICS WITH IONIC CONCENTRATION DEPENDENT DIELECTRICS *

    PubMed Central

    LI, BO; WEN, JIAYI; ZHOU, SHENGGAO

    2015-01-01

    We construct a mean-field variational model to study how the dependence of dielectric coefficient (i.e., relative permittivity) on local ionic concentrations affects the electrostatic interaction in an ionic solution near a charged surface. The electrostatic free-energy functional of ionic concentrations, which is the key object in our model, consists mainly of the electrostatic potential energy and the ionic ideal-gas entropy. The electrostatic potential is determined by Poisson’s equation in which the dielectric coefficient depends on the sum of concentrations of individual ionic species. This dependence is assumed to be qualitatively the same as that on the salt concentration for which experimental data are available and analytical forms can be obtained by the data fitting. We derive the first and second variations of the free-energy functional, obtain the generalized Boltzmann distributions, and show that the free-energy functional is in general nonconvex. To validate our mathematical analysis, we numerically minimize our electrostatic free-energy functional for a radially symmetric charged system. Our extensive computations reveal several features that are significantly different from a system modeled with a dielectric coefficient independent of ionic concentration. These include the non-monotonicity of ionic concentrations, the ionic depletion near a charged surface that has been previously predicted by a one-dimensional model, and the enhancement of such depletion due to the increase of surface charges or bulk ionic concentrations. PMID:26877718

  19. Pink noise of ionic conductance through single artificial nanopores revisited.

    PubMed

    Tasserit, C; Koutsioubas, A; Lairez, D; Zalczer, G; Clochard, M-C

    2010-12-31

    We report voltage-clamp measurements through single conical nanopore obtained by chemical etching of a single ion track in polyimide film. Special attention is paid to the pink noise of the ionic current (i.e., 1/f noise) measured with different filling liquids. The relative pink-noise amplitude is almost independent of concentration and pH for KCl solutions, but varies strongly using ionic liquids. In particular, we show that depending on the ionic liquid, the transport of charge carriers is strongly facilitated (low noise and higher conductivity than in the bulk) or jammed. These results show that the origin of the pink noise can be ascribed neither to fluctuations of the pore geometry nor to the pore wall charges, but rather to a cooperative effect on ions motion in confined geometry. PMID:21231637

  20. Ionic versus nonionic MR imaging contrast media: operational definitions.

    PubMed

    Chang, C A; Sieving, P F; Watson, A D; Dewey, T M; Karpishin, T B; Raymond, K N

    1992-01-01

    An experimental rationale is provided to differentiate between the terms ionic and nonionic for magnetic resonance (MR) imaging contrast media such as gadodiamide and gadopentetate dimeglumine. Four independent types of physical measurements (electric conductivity, osmolality, electrophoresis, and ion exchange) were performed on a range of test compounds, including D-glucose, iohexol, gadopentetate dimeglumine, and gadodiamide. Iohexol, D-glucose, and gadodiamide are shown to be nonionic species at physiologic pH (7.4), not measurably dissociating in solution. A range of gadopentetate salts behave as electrolytes, dissociating into constituent charged ions in aqueous media. Operational definitions for the terms ionic and nonionic are provided, and the terms neutral and net zero charge are compared with nonionic for accuracy. The nomenclature nonionic and ionic is deemed appropriate for differentiating MR imaging contrast media. PMID:1623289

  1. Influence of the ionic liquid cation on the solvent extraction of trivalent rare-earth ions by mixtures of Cyanex 923 and ionic liquids.

    PubMed

    Rout, Alok; Binnemans, Koen

    2015-01-21

    Trivalent rare-earth ions were extracted from nitric acid medium by the neutral phosphine oxide extractant Cyanex 923 into ionic liquid phases containing the bis(trifluoromethylsulfonyl)imide anion. Five different cations were considered: 1-butyl-3-methylimidazolium, 1-decyl-3-methylimidazolium, methyltributylammonium, methyltrioctylammonium and trihexyl(tetradecyl)phosphonium. The extraction behavior of neodymium(iii) was investigated as a function of various parameters: pH, extractant concentration, concentration of the neodymium(iii) ion in the aqueous feed and concentration of the salting-out agent. The loading capacity of the ionic liquid phase was studied. The extraction efficiency increased with increasing pH of the aqueous feed solution. The extraction occurred for all ionic liquids via an ion-exchange mechanism and the extraction efficiency could be related to the solubility of the ionic liquid cation in the aqueous phase: high distribution ratios for hydrophilic cations and low ones for hydrophobic cations. Addition of nitrate ions to the aqueous phase resulted in an increase in extraction efficiency for ionic liquids with hydrophobic cations due to extraction of neutral complexes. Neodymium(iii) could be stripped from the ionic liquid phase by 0.5-1.0 M nitric acid solutions and the extracting phase could be reused. The extractability of other rare earths present in the mixture was compared for the five ionic liquids. PMID:25423581

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

    PubMed

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

    2016-01-01

    Consecutive two-dimensional frameworks comprised of molecular or cluster building blocks in large area represent ideal candidates for membranes sieving molecules and nano-objects, but challenges still remain in methodology and practical preparation. Here we exploit a new strategy to build soft single-layer ionic organic-inorganic frameworks via electrostatic interaction without preferential binding direction in water. Upon consideration of steric effect and additional interaction, polyanionic clusters as connection nodes and cationic pseudorotaxanes acting as bridging monomers connect with each other to form a single-layer ionic self-assembled framework with 1.4 nm layer thickness. Such soft supramolecular polymer frameworks possess uniform and adjustable ortho-tetragonal nanoporous structure in pore size of 3.4-4.1 nm and exhibit greatly convenient solution processability. The stable membranes maintaining uniform porous structure demonstrate precisely size-selective separation of semiconductor quantum dots within 0.1 nm of accuracy and may hold promise for practical applications in selective transport, molecular separation and dialysis systems. PMID:26923611

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

    PubMed Central

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

    2016-01-01

    Consecutive two-dimensional frameworks comprised of molecular or cluster building blocks in large area represent ideal candidates for membranes sieving molecules and nano-objects, but challenges still remain in methodology and practical preparation. Here we exploit a new strategy to build soft single-layer ionic organic–inorganic frameworks via electrostatic interaction without preferential binding direction in water. Upon consideration of steric effect and additional interaction, polyanionic clusters as connection nodes and cationic pseudorotaxanes acting as bridging monomers connect with each other to form a single-layer ionic self-assembled framework with 1.4 nm layer thickness. Such soft supramolecular polymer frameworks possess uniform and adjustable ortho-tetragonal nanoporous structure in pore size of 3.4–4.1 nm and exhibit greatly convenient solution processability. The stable membranes maintaining uniform porous structure demonstrate precisely size-selective separation of semiconductor quantum dots within 0.1 nm of accuracy and may hold promise for practical applications in selective transport, molecular separation and dialysis systems. PMID:26923611

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

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

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

  5. Task-specific ionic liquid for solubilizing metal oxides.

    PubMed

    Nockemann, Peter; Thijs, Ben; Pittois, Stijn; Thoen, Jan; Glorieux, Christ; Van Hecke, Kristof; Van Meervelt, Luc; Kirchner, Barbara; Binnemans, Koen

    2006-10-26

    Protonated betaine bis(trifluoromethylsulfonyl)imide is an ionic liquid with the ability to dissolve large quantities of metal oxides. This metal-solubilizing power is selective. Soluble are oxides of the trivalent rare earths, uranium(VI) oxide, zinc(II) oxide, cadmium(II) oxide, mercury(II) oxide, nickel(II) oxide, copper(II) oxide, palladium(II) oxide, lead(II) oxide, manganese(II) oxide, and silver(I) oxide. Insoluble or very poorly soluble are iron(III), manganese(IV), and cobalt oxides, as well as aluminum oxide and silicon dioxide. The metals can be stripped from the ionic liquid by treatment of the ionic liquid with an acidic aqueous solution. After transfer of the metal ions to the aqueous phase, the ionic liquid can be recycled for reuse. Betainium bis(trifluoromethylsulfonyl)imide forms one phase with water at high temperatures, whereas phase separation occurs below 55.5 degrees C (temperature switch behavior). The mixtures of the ionic liquid with water also show a pH-dependent phase behavior: two phases occur at low pH, whereas one phase is present under neutral or alkaline conditions. The structures, the energetics, and the charge distribution of the betaine cation and the bis(trifluoromethylsulfonyl)imide anion, as well as the cation-anion pairs, were studied by density functional theory calculations. PMID:17048916

  6. Decoupling of Ionic Transport from Segmental Relaxation in Polymer Electrolytes

    NASA Astrophysics Data System (ADS)

    Wang, Yangyang; Agapov, Alexander; Fan, Fei; Hong, Kunlun; Yu, Xiang; Mays, Jimmy; Sokolov, Alexei

    2012-02-01

    Polymer electrolytes provide elegant solutions to many difficulties in battery technology. However, their relatively low ionic conductivity has become the bottleneck for developing batteries with higher power density, shorter charging time, and better operations at low temperatures. In this work, we present detailed studies of the relationship between ionic conductivity and segmental relaxation in a set of specially-designed polymer electrolytes with systematic variation in chain rigidity. Our analysis shows that the ionic conductivity indeed can be decoupled from segmental dynamics in rigid polymers and the strength of the decoupling correlates with the fragility, but not with the glass transition temperature. These results call for a revision of the current picture of ionic transport in polymer electrolytes. We relate the observed decoupling phenomenon to frustration in packing of rigid polymers, which also affects their fragility. The principles demonstrated in this study may provide an alternative approach to design of highly conductive materials: by incorporating relatively rigid chain structures, it is possible to develop a new class of solid polymer electrolytes with strongly decoupled ionic conductivity.

  7. Modeling solubility and acid-base properties of some amino acids in aqueous NaCl and (CH3)4NCl aqueous solutions at different ionic strengths and temperatures.

    PubMed

    Bretti, Clemente; Giuffrè, Ottavia; Lando, Gabriele; Sammartano, Silvio

    2016-01-01

    New potentiometric experiments have been performed in NaCl and in (CH3)4NCl media, to determine the protonation constants, the protonation enthalpy changes and the solubility of six natural α-amino acids, namely Glycine (Gly), Alanine (Ala), Valine (Val), Leucine (Leu), Serine (Ser) and Phenylalanine (Phe). The aim of the work is the rationalization of the protonation thermodynamics (log [Formula: see text], solubility and [Formula: see text]) in NaCl, determining recommended, tentative or provisional values in selected experimental conditions and to report, for the first time, data in a weak interacting medium, as (CH3)4NCl. Literature data analysis was performed selecting the most reliable values, analyzed together with new data here reported. Significant trends and similarities were observed in the behavior of the six amino acids, and in some cases it was possible to determine common parameters for the ionic strength and temperature dependence. In general, the first protonation step, relative to the amino group, is significantly exothermic (average value is [Formula: see text] = -44.5 ± 0.4 kJ mol(-1) at infinite dilution and T = 298.15 K), and the second, relative to the carboxylate group, is fairly close to zero ([Formula: see text] = -2.5 ± 1.6, same conditions). In both cases, the main contribution to the proton binding reaction is mainly entropic in nature. For phenylalanine and leucine, solubility measurements at different concentrations of supporting electrolyte allowed to determine total and specific solubility values, then used to obtain the Setschenow and the activity coefficients of all the species involved in the protonation equilibria. The values of the first protonation constant in (CH3)4NCl are lower than the corresponding values in NaCl, due to the weak interaction between the deprotonated amino group and (CH3)4N(+). In this light, differences between the protonation functions in NaCl and (CH3)4NCl were used for the quantification

  8. An investigation on the chemical stability and a novel strategy for long-term stabilization of diphenylalanine nanostructures in aqueous solution

    NASA Astrophysics Data System (ADS)

    Nezammahalleh, H.; Amoabediny, G.; Kashanian, F.; Foroughi Moghaddam, M. H.

    The stability of diphenylalanine (FF) microwires and microtubes in phosphate buffer solution was investigated and a novel strategy was developed for their chemical stabilization. This stability investigation was carried out by optical microscopy and by high performance liquid chromatography (HPLC). These microstructures dissolve in the solution depending upon their degree of FF saturation. The dissolution mechanisms of the structures in kinetically limited processes were found by accurately fitting the experimental dissolution data to a theoretical kinetic equation. The dissolution data were well fitted to the particular Avrami-Erofe'ev kinetic expression (R2 > 0.98). These findings suggest that the structures can be stabilized by a decrease in the hydration of the constituent molecules thorough a chemical conformational induced transition upon heat treatment. The stable microtubes were fabricated in a novel three step procedure consisting of the reduction of silver ions in unstable FF microtubes by a citrate reductant, the stabilization by chemical conformational induced transition upon heat treatment, and the consequent oxidation of the reduced silver by a persulfate oxidant. These materials were characterized by electron microscopy and powder X-ray diffraction techniques. The long-term stability of both structures was also confirmed by optical microscopy and HPLC.

  9. Dual Ionic and Organic Nature of Ionic Liquids

    PubMed Central

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660

  10. Dual Ionic and Organic Nature of Ionic Liquids

    NASA Astrophysics Data System (ADS)

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids—a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs.

  11. Dual Ionic and Organic Nature of Ionic Liquids.

    PubMed

    Shi, Rui; Wang, Yanting

    2016-01-01

    Inherited the advantages of inorganic salts and organic solvents, ionic liquids (ILs) exhibit many superior properties allowing them promising green solvents for the future. Although it has been widely acknowledged that the unique features of ILs originate from their dual ionic and organic nature, its microscopic physical origin still remains blurry. In this work, by comparing the ion/molecule cage structures obtained from molecular dynamics simulations for seven prototypic liquids--a molten inorganic salt, four ILs, a strongly polar organic solvent, and a weakly polar organic solvent, we have revealed that the depth of the cage energy landscape characterizes the ionic nature of ILs, whereas the slope and curvature of its mimimum determine the organic nature of ILs. This finding advances our understanding of ILs and thus will help their efficient utilization as well as the systematic design of novel functionalized ILs. PMID:26782660

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

    PubMed Central

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

    2009-01-01

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

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

    PubMed

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

    2013-10-21

    The ionic liquids 1-hexyl-3-methylimidazolium bis(2-ethylhexyl)phosphate, [C6mim][DEHP], 1-hexyl-1-methylpyrrolidinium bis(2-ethylhexyl)phosphate, [C6mpyr][DEHP], and tetrabutylammonium bis(2-ethylhexyl)phosphate, [N4444][DEHP], were prepared and characterized using (1)H and (13)C NMR spectroscopy. The extraction behavior of neodymium(iii) from nitrate medium by these ionic liquids, diluted with the room temperature ionic liquids 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C6mim][NTf2], 1-hexyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, [C6mpyr][NTf2], and tributylmethylammonium bis(trifluoromethylsulfonyl)imide, [N1444][NTf2], was studied. The distribution ratio of neodymium(iii) was measured as a function of various parameters, such as pH, concentration of the ionic liquid extractant, nature of diluents, concentration of ionic liquid cations and nitrate anions in the aqueous phase. The extraction behavior was compared with that obtained for a solution of the molecular extractant bis(2-ethylhexyl)phosphoric acid (DEHPA) in an ionic liquid diluent. The extraction of neodymium(iii) in the ionic liquids [C6mim][DEHP] and [C6mpyr][DEHP] showed markedly different extraction properties in comparison with that of the quaternary ammonium analogue [N4444][DEHP], especially concerning the pH dependence of the extraction process. These results show that the extraction process can be tuned by the selection of the ionic liquid cation. The extraction experiments also included the trivalent rare-earth ions lanthanum(iii), cerium(iii), praseodymium(iii), ytterbium(iii) and yttrium(iii). Studies of the stripping behavior and the reusability of the ionic liquids were carried out, which indicate that the ionic liquids can be reused with no loss in activity. PMID:23949284

  14. Ionic Graphitization of Ultrathin Films of Ionic Compounds.

    PubMed

    Kvashnin, A G; Pashkin, E Y; Yakobson, B I; Sorokin, P B

    2016-07-21

    On the basis of ab initio density functional calculations, we performed a comprehensive investigation of the general graphitization tendency in rocksalt-type structures. In this paper, we determine the critical slab thickness for a range of ionic cubic crystal systems, below which a spontaneous conversion from a cubic to a layered graphitic-like structure occurs. This conversion is driven by surface energy reduction. Using only fundamental parameters of the compounds such as the Allen electronegativity and ionic radius of the metal atom, we also develop an analytical relation to estimate the critical number of layers. PMID:27333810

  15. On the dissolution of non-metallic solid elements (sulfur, selenium, tellurium and phosphorus) in ionic liquids.

    PubMed

    Boros, Eva; Earle, Martyn J; Gîlea, Manuela A; Metlen, Andreas; Mudring, Anja-Verena; Rieger, Franziska; Robertson, Allan J; Seddon, Kenneth R; Tomaszowska, Alina A; Trusov, Lev; Vyle, Joseph S

    2010-02-01

    Ionic liquids are shown to be good solvents for elemental sulfur, selenium, phosphorus and tellurium, and can be designed to maximise the solubility of these elements. The presence of the [S(3)](*-) radical anion in diluted solutions of sulfur in some ionic liquids has been confirmed, and is the origin of their intense blue colour (cf. lapis lazuli). PMID:20087497

  16. Fluorescence energy transfer efficiency in labeled yeast cytochrome c: a rapid screen for ion biocompatibility in aqueous ionic liquids

    SciTech Connect

    Baker, Sheila N; Zhao, Hua; Pandey, Siddharth; Heller, William T; Bright, Frank; Baker, Gary A

    2011-01-01

    A fluorescence energy transfer de-quenching assay was implemented to follow the equilibrium unfolding behaviour of site-specific tetramethylrhodamine-labelled yeast cytochrome c in aqueous ionic liquid solutions; additionally, this approach offers the prospect of naked eye screening for biocompatible ion combinations in hydrated ionic liquids.

  17. Oxygen Extraction from Regolith Using Ionic Liquids

    NASA Technical Reports Server (NTRS)

    Barrios, Elizabeth A.; Curreri, Peter A.; Karr, Laurel J.

    2011-01-01

    An important concern with long-duration manned space travel is the need to furnish enough materials to the vehicle, as well as the crew, for the duration of the mission. By extracting oxygen from the oxides present in regolith, propellant and life support could be supplied to the vehicle and the crew while in space, thereby limiting the amount of supplies needed prior to lift-off. Using a class of compounds known as ionic liquids, we have been able to lower the electrolysis operating temperature from 1600 C (molten oxide electrolysis) to less than 200 C, making this process much more feasible in terms of energy consumption and materials handling. To make this process ready for deployment into space, we have investigated what steps of the process would be affected by the low-gravity environment in space. In the lab, the solubilization of lunar regolith simulant in ionic liquid produces water vapor that is normally distilled out of solution and subsequently electrolyzed for oxygen production. This distillation is not possible in space, so we have tested a method known as pervaporation and have suggested a way this technique could be incorporated into a reactor design.

  18. Ionic Covalent Organic Frameworks with Spiroborate Linkage.

    PubMed

    Du, Ya; Yang, Haishen; Whiteley, Justin Michael; Wan, Shun; Jin, Yinghua; Lee, Se-Hee; Zhang, Wei

    2016-01-26

    A novel type of ionic covalent organic framework (ICOF), which contains sp(3)  hybridized boron anionic centers and tunable countercations, was constructed by formation of spiroborate linkages. These ICOFs exhibit high BET surface areas up to 1259 m(2)  g(-1) and adsorb a significant amount of H2 (up to 3.11 wt %, 77 K, 1 bar) and CH4 (up to 4.62 wt %, 273 K, 1 bar). Importantly, the materials show good thermal stabilities and excellent resistance to hydrolysis, remaining nearly intact when immersed in water or basic solution for two days. The presence of permanently immobilized ion centers in ICOFs enables the transportation of lithium ions with room-temperature lithium-ion conductivity of 3.05×10(-5)  S cm(-1) and an average Li(+) transference number value of 0.80±0.02. Our approach thus provides a convenient route to highly stable COFs with ionic linkages, which can potentially serve as absorbents for alternative energy sources such as H2, CH4, and also as solid lithium electrolytes/separators for the next-generation lithium batteries. PMID:26696304

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

    PubMed

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

    2016-02-10

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

  20. Lithium ion conducting ionic electrolytes

    DOEpatents

    Angell, C.A.; Xu, K.; Liu, C.

    1996-01-16

    A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100 C or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors. 4 figs.

  1. Lithium ion conducting ionic electrolytes

    DOEpatents

    Angell, C. Austen; Xu, Kang; Liu, Changle

    1996-01-01

    A liquid, predominantly lithium-conducting, ionic electrolyte is described which has exceptionally high conductivity at temperatures of 100.degree. C. or lower, including room temperature. It comprises molten lithium salts or salt mixtures in which a small amount of an anionic polymer lithium salt is dissolved to stabilize the liquid against recrystallization. Further, a liquid ionic electrolyte which has been rubberized by addition of an extra proportion of anionic polymer, and which has good chemical and electrochemical stability, is described. This presents an attractive alternative to conventional salt-in-polymer electrolytes which are not cationic conductors.

  2. Direct UV-spectroscopic measurement of selected ionic-liquid vapors

    SciTech Connect

    Dai, Sheng; Luo, Huimin; Wang, Congmin; Li, Haoran

    2010-01-01

    The hallmark of ionic liquids lies in their negligible vapor pressure. This ultralow vapor pressure makes it difficult to conduct the direct spectroscopic measurement of ionic-liquid vapors. In fact, there have been no electronic spectroscopic data currently available for ionic-liquid vapors. This deficiency significantly hampers the fundamental understanding of the unique molecular structures of ionic liquids. Herein, the UV absorption spectra of eight ionic liquids, such as 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bmim{sup +}] [Tf{sub 2}N{sup -}]) and 1-ethyl-3-methylimidazolium bis(perfluoroethylsulfonyl)imide ([Emim{sup +}][beti{sup -}]) in the vapor phase in a distillation-like environment, were measured through a high-temperature spectroscopic technique to fill this knowledge gap. Two strong absorption peaks of the [Bmim{sup +}][Tf{sub 2}N{sup -}] vapor lie at 202 and 211 nm, slightly different from those of the neat [Bmim{sup +}][Tf{sub 2}N{sup -}] thin film and its solution in water. Based on the quantitative determination of the vapor absorption spectra as a function of temperature, the vaporization enthalpies of these ionic liquids vapors were measured and found to be in good agreement with the corresponding literature values. This in situ method opens up a new avenue to study the nature of ionic-liquid vapors and to determine the vaporization enthalpies of ionic liquids.

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

    NASA Astrophysics Data System (ADS)

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

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

  4. Effect of Ions and Ionic Strength on Surface Plasmon Absorption of Single Gold Nanowires.

    PubMed

    Baral, Susil; Green, Andrew J; Richardson, Hugh H

    2016-06-28

    The local temperature change from a single optically excited gold nanowire, lithographically prepared on Al0.94Ga0.06N embedded with Er(3+) ions, is measured in air, pure water, and various concentrations of aqueous solutions of ionic solutes of NaCl, Na2SO4, and MgSO4. The absorption cross section of the nanowire under pure water (2.25 × 10(-14) m(2)) and different solution ionic strength is measured from the slopes of temperature change versus laser intensity plots. Addition of charges into the solution decreases the amount of heat generated during optical excitation of the gold nanostructures because the absorption cross section of the gold nanowire is attenuated. A Langmuir-type behavior of the absorption cross section with ionic strength is observed that is identified with an increase in the occupancy of screened interfacial charges. The absorption cross section of the nanowire decreases with ionic strength until a saturation value of 9 × 10(-15) m(2), where saturation in the occupancy of screened interfacial charge occurs. Dynamic measurements of temperature for a single gold nanowire immersed in a microchannel flow cell show a sharp and fast temperature drop for the flow of ionic solution compared to the pure (deionized) water, suggesting that the technique can be developed as a sensor probe to detect the presence of ions in solution. PMID:27215955

  5. Solute diffusion in liquid metals

    NASA Technical Reports Server (NTRS)

    Bhat, B. N.

    1973-01-01

    A gas model of diffusion in liquid metals is presented. In this model, ions of liquid metals are assumed to behave like the molecules in a dense gas. Diffusion coefficient of solute is discussed with reference to its mass, ionic size, and pair potential. The model is applied to the case of solute diffusion in liquid silver. An attempt was made to predict diffusion coefficients of solutes with reasonable accuracy.

  6. Ionic wave propagation along actin filaments.

    PubMed

    Tuszyński, J A; Portet, S; Dixon, J M; Luxford, C; Cantiello, H F

    2004-04-01

    We investigate the conditions enabling actin filaments to act as electrical transmission lines for ion flows along their lengths. We propose a model in which each actin monomer is an electric element with a capacitive, inductive, and resistive property due to the molecular structure of the actin filament and viscosity of the solution. Based on Kirchhoff's laws taken in the continuum limit, a nonlinear partial differential equation is derived for the propagation of ionic waves. We solve this equation in two different regimes. In the first, the maximum propagation velocity wave is found in terms of Jacobi elliptic functions. In the general case, we analyze the equation in terms of Fisher-Kolmogoroff modes with both localized and extended wave characteristics. We propose a new signaling mechanism in the cell, especially in neurons. PMID:15041636

  7. Durable electrooptic devices comprising ionic liquids

    DOEpatents

    Warner, Benjamin P.; McCleskey, T. Mark; Burrell, Anthony K.

    2006-10-10

    Electrolyte solutions for electrochromic devices such as rear view mirrors and displays with low leakage currents are prepared using inexpensive, low conductivity conductors. Preferred electrolytes include bifunctional redox dyes and molten salt solvents with enhanced stability toward ultraviolet radiation. The solvents include lithium or quaternary ammonium cations, and perfluorinated sulfonylimide anions selected from trifluoromethylsulfonate (CF.sub.3SO.sub.3.sup.-), bis(trifluoromethylsulfonyl)imide ((CF.sub.3SO.sub.2).sub.2N.sup.-), bis(perfluoroethylsulfonyl)imide ((CF.sub.3CF.sub.2SO.sub.2).sub.2N.sup.-) and tris(trifluoromethylsulfonyl)methide ((CF.sub.3SO.sub.2).sub.3C.sup.-). Electroluminescent, electrochromic and photoelectrochromic devices with nanostructured electrodes include ionic liquids with bifunctional redox dyes.

  8. Self-adaptive Solution Strategies

    NASA Technical Reports Server (NTRS)

    Padovan, J.

    1984-01-01

    The development of enhancements to current generation nonlinear finite element algorithms of the incremental Newton-Raphson type was overviewed. Work was introduced on alternative formulations which lead to improve algorithms that avoid the need for global level updating and inversion. To quantify the enhanced Newton-Raphson scheme and the new alternative algorithm, the results of several benchmarks are presented.

  9. Ionic Liquids as Solvents for Rhodium and Platinum Catalysts Used in Hydrosilylation Reaction.

    PubMed

    Zielinski, Witold; Kukawka, Rafal; Maciejewski, Hieronim; Smiglak, Marcin

    2016-01-01

    A group of imidazolium and pyridinium based ionic liquids has been synthetized, and their ability to dissolve and activate the catalysts used in hydrosilylation reaction of 1-octane and 1,1,1,3,5,5,5-heptamethyltrisiloxane was investigated. An organometallic catalyst as well as inorganic complexes of platinum and rhodium dissolved in ionic liquids were used, forming liquid solutions not miscible with the substrates or with the products of the reaction. The results show that application of such a simple biphasic catalytic system enables reuse of ionic liquid phase with catalysts in multiple reaction cycles reducing the costs and decreasing the amount of catalyst needed per mole of product. PMID:27563869

  10. 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

  11. 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. PMID:23843736

  12. Nanoparticle enhanced ionic liquid heat transfer fluids

    DOEpatents

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

    2014-08-12

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

  13. Ionic transport and electrical relaxation in glass

    NASA Astrophysics Data System (ADS)

    Moynihan, C. T.; Barkatt, A.

    1987-09-01

    The basic purpose of the work described was to achieve extensive and quantitative understanding of ionic transport processes in melts and glasses by means of a combination of experimental measurements and theoretical modeling. Two major subjects of the study were the mechanism of dielectric relaxation in ionically conducting glasses and the large retardation of ionic transport in mixed alkali systems.

  14. The hype with ionic liquids as solvents

    NASA Astrophysics Data System (ADS)

    Kunz, Werner; Häckl, Katharina

    2016-09-01

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

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

    PubMed

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

    2016-04-01

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

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

    SciTech Connect

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

    2013-06-01

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

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

    SciTech Connect

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

    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 microscopy (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.

  18. A general one-pot strategy for the synthesis of high-performance transparent-conducting-oxide nanocrystal inks for all-solution-processed devices.

    PubMed

    Song, Jizhong; Kulinich, Sergei A; Li, Jianhai; Liu, Yanli; Zeng, Haibo

    2015-01-01

    For all-solution-processed (ASP) devices, transparent conducting oxide (TCO) nanocrystal (NC) inks are anticipated as the next-generation electrodes to replace both those synthesized by sputtering techniques and those consisting of rare metals, but a universal and one-pot method to prepare these inks is still lacking. A universal one-pot strategy is now described; through simply heating a mixture of metal-organic precursors a wide range of TCO NC inks, which can be assembled into high-performance electrodes for use in ASP optoelectronics, were synthesized. This method can be used for various oxide NC inks with yields as high as 10 g. The formed NCs are of high crystallinity, uniform morphology, monodispersity, and high ink stability and feature effective doping. Therefore, the inks can be readily assembled into films with a surface roughness of 1.6 nm. Typically, a sheet resistance of 110 Ω sq(-1) can be achieved with a transmittance of 88%, which is the best performance for TCO NC ink-based electrodes described to date. These electrodes can thus drive a polymer light-emitting diode (PLED) with a luminance of 2200 cd m(-2) at 100 mA cm(-2). PMID:25403980

  19. The 29 September 2009 Samoa Islands Tsunami: Simulations Based on the First Focal Mechanism Solutions and Implications on Tsunami Early Warning Strategies

    NASA Astrophysics Data System (ADS)

    Tonini, Roberto; Armigliato, Alberto; Tinti, Stefano

    2011-06-01

    The tsunamigenic earthquake (Mw = 8.1) that occurred on 29 September 2009 at 17:48 UTC offshore of the Samoa archipelago east of the Tonga trench represents an example of the so-called "outer-rise" earthquakes. The areas most affected were the south coasts of Western and American Samoa, where almost 200 people were killed and run-up heights were measured in excess of 5 m at several locations along the coast. Moreover, tide gauge records showed a maximum peak-to-peak height of about 3.5 m near Pago Pago (American Samoa) and of 1.5 m offshore of Apia (Western Samoa). In this work, different fault models based on the focal mechanism solutions proposed by Global CMT and by USGS immediately after the 2009 Samoan earthquake are tested by comparing the near-field recorded signals (three offshore DART buoys and two coastal tide gauges) and the synthetic signals provided by the numerical simulations. The analysis points out that there are lights and shadows, in the sense that none of the computed tsunamis agrees satisfactorily with all the considered signals, although some of them reproduce some of the records quite well. This "partial agreement" and "partial disagreement" are analysed in the perspective of tsunami forecast and of Tsunami Early Warning System strategy.

  20. Rapid isolation of high solute amounts using an online four-dimensional preparative system: normal phase-liquid chromatography coupled to methyl siloxane-ionic liquid-wax phase gas chromatography.

    PubMed

    Sciarrone, Danilo; Pantò, Sebastiano; Tranchida, Peter Quinto; Dugo, Paola; Mondello, Luigi

    2014-05-01

    This study reports the recent evolution of a multidimensional GC-GC-GC preparative system, now combined with an online LC preseparation step, operated under normal phase conditions. It is herein shown that the four-dimensional instrument can collect sample components with a concentration lower than 10%, in a short time period, while maintaining a high level of analyte purity. The LC dimension allows (I) the injection of higher sample amounts, compared to "direct" GC injection; (II) a polarity-based preseparation, leading to the GC injection of simplified subsamples, and thus reducing the possibility of coelutions; (III) to eliminate the essential-oil "matrix", replacing it with the LC mobile phase (the GC system is more protected from potential contamination); (IV) the LC mobile phase is of much lower viscosity with respect to a pure, or highly concentrated essential oil, avoiding difficulties in the syringe sample withdrawal process, prior to GC injection. System optimization was performed by using standard solutions; in addition, a very complex sample, namely, vetiver essential oil, was subjected to the preparative process, with the scope of isolating two low-amount constituents (namely, α-amorphene and β-vetivone). The latter two sesquiterpenoids, which accounted for 1.7 and 4.0% of the sample (considering the volatiles), respectively, were successfully collected at the milligram level, in a one-day work period, with a purity degree in excess of 90%. PMID:24725161

  1. MD Study of Stokes Shifts in Ionic Liquids: Temperature Dependence.

    PubMed

    Wu, Eric C; Kim, Hyung J

    2016-05-26

    Effects of temperature on Stokes shifts, solvation structure, and dynamics in ionic liquids EMI(+)Tf2N(-), EMI(+)PF6(-), and BMI(+)PF6(-) (EMI(+) = 1-ethyl-3-methylimidazolium, BMI(+) = 1-butyl-3-methylimidazolium, Tf2N(-) = bis(trifluoromethylsulfonyl)imide, and PF6(-) = hexafluorophosphate) are investigated via molecular dynamics (MD) computer simulations in the temperature range 350 K ≤ T ≤ 500 K. Two different types of solutes are considered: a simple model diatomic solute and realistic coumarin 153, both of which are characterized by more polar S1 and less polar S0 states. In all three ionic liquids studied, the Stokes shift tends to decrease with increasing temperature. For coumarin 153, as T increases, the Franck-Condon energy for steady-state absorption decreases, whereas that for steady-state emission increases. Our findings indicate that the effective polarity of ionic liquids decreases as T increases. Their solvation dynamics are characterized by an ultrafast initial decay in the subpicosecond time scale, followed by slow dissipative relaxation, regardless of temperature. For both solutes, the solvent frequency that quantifies initial ultrafast dynamics shows little temperature dependence. By contrast, the long-time dissipative dynamics become significantly faster with rising T. Variations of solvation structure with temperature and their connection to Stokes shift and solvation dynamics are briefly examined. PMID:27133895

  2. The solvation structures of cellulose microfibrils in ionic liquids

    SciTech Connect

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

    2011-01-01

    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.

  3. Ionic Conduction Mechanism of Polymer Gel Electrolytes

    NASA Astrophysics Data System (ADS)

    Saito, Yuria; Kataoka, Hiroshi

    2002-12-01

    Carrier migration mechanism of polymer gel electrolyte for lithium secondary batteries was investigated through the dynamic behavior of diffusion coefficient and conductivity. The gel prepared with PEO showed a homogeneous structure with any fraction of the electrolyte solution. The diffusion coefficient of the ionic species decreased with the increase in the polymer fraction in the gel. Cation migration is closely associated with the polymer, showing the reduced activation energy for diffusion with polymer in contrast to the increasing feature of the activation energy of the anion diffusion. The PVDF-gel electrolytes have a solid solubility limit due to the swelling saturation. The excess solution was then trapped in the cavities of the swollen polymer network. As a result, the diffusion showed two components. One is the fast migration of the carriers similar to that in the solution and the other is the relatively slow migration in the swollen region. The latter was influenced by the polymer due to the physical blocking and chemical interactive effects.

  4. Modulating enzyme activity using ionic liquids or surfactants.

    PubMed

    Goldfeder, Mor; Fishman, Ayelet

    2014-01-01

    One of the important strategies for modulating enzyme activity is the use of additives to affect their microenvironment and subsequently make them suitable for use in different industrial processes. Ionic liquids (ILs) have been investigated extensively in recent years as such additives. They are a class of solvents with peculiar properties and a "green" reputation in comparison to classical organic solvents. ILs as co-solvents in aqueous systems have an effect on substrate solubility, enzyme structure and on enzyme-water interactions. These effects can lead to higher reaction yields, improved selectivity, and changes in substrate specificity, and thus there is great potential for IL incorporation in biocatalysis. The use of surfactants, which are usually denaturating agents, as additives in enzymatic reactions is less reviewed in recent years. However, interesting modulations in enzyme activity in their presence have been reported. In the case of surfactants there is a more pronounced effect on the enzyme structure, as can be observed in a number of crystal structures obtained in their presence. For each additive and enzymatic process, a specific optimization process is needed and there is no one-fits-all solution. Combining ILs and surfactants in either mixed micelles or water-in-IL microemulsions for use in enzymatic reaction systems is a promising direction which may further expand the range of enzyme applications in industrial processes. While many reviews exist on the use of ILs in biocatalysis, the present review centers on systems in which ILs or surfactants were able to modulate and improve the natural activity of enzymes in aqueous systems. PMID:24281758

  5. How can a carbene be active in an ionic liquid?

    PubMed

    Thomas, Martin; Brehm, Martin; Hollóczki, Oldamur; Kirchner, Barbara

    2014-02-01

    The solvation of the carbene 1-ethyl-3-methylimidazole-2-ylidene in the ionic liquid 1-ethyl-3-methylimidazolium acetate was investigated by ab initio molecular dynamics simulations in order to reveal the interaction between these two highly important classes of materials: N-heterocyclic carbenes with superb catalytic activity and ionic liquids with advantageous properties as solvents and reaction media. In contrast to previously published data on analogous systems, no hydrogen bond is observed between the hypovalent carbon atom and the most acidic ring hydrogen atoms, as these interaction sites of the imidazolium ring are predominantly occupied by the acetate ions. Keeping the carbene away from the ring hydrogen atoms prevents stabilization of this reactive species, and hence any retarding effect on subsequent reactions, which explains the observed high reactivity of the carbene in acetate-based ionic liquids. Instead, the carbene exhibits a weaker interaction with the methyl group of the imidazolium cation by forming a hitherto unprecedented kind of C⋅⋅⋅H-C hydrogen bond. This unexpected finding not only indicates a novel kind of hydrogen bond for carbenes, but also shows that such interaction sites of the imidazolium cation are not limited to the ring hydrogen atoms. Thus, the results give the solute-solvent interactions within ionic liquids a new perspective, and provide a further, albeit weak, site of interaction to tune in order to achieve the desired environment for any dissolved active ingredient. PMID:24375892

  6. Application of Ionic Liquids in Hydrometallurgy

    PubMed Central

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

    2014-01-01

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

  7. Application of ionic liquids in hydrometallurgy.

    PubMed

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

    2014-01-01

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

  8. Observation of ionic Coulomb blockade in nanopores

    NASA Astrophysics Data System (ADS)

    Feng, Jiandong; Liu, Ke; Graf, Michael; Dumcenco, Dumitru; Kis, Andras; di Ventra, Massimiliano; Radenovic, Aleksandra

    2016-08-01

    Emergent behaviour from electron-transport properties is routinely observed in systems with dimensions approaching the nanoscale. However, analogous mesoscopic behaviour resulting from ionic transport has so far not been observed, most probably because of bottlenecks in the controlled fabrication of subnanometre nanopores for use in nanofluidics. Here, we report measurements of ionic transport through a single subnanometre pore junction, and the observation of ionic Coulomb blockade: the ionic counterpart of the electronic Coulomb blockade observed for quantum dots. Our findings demonstrate that nanoscopic, atomically thin pores allow for the exploration of phenomena in ionic transport, and suggest that nanopores may also further our understanding of transport through biological ion channels.

  9. Phytoremediation of Ionic and Methyl Mercury P

    SciTech Connect

    Meagher, Richard B.

    1999-06-01

    Our long-term goal is to enable highly productive plant species to extract, resist, detoxify, and/or sequester toxic heavy metal pollutants as an environmentally friendly alternative to physical remediation methods. We have focused this phytoremediation research on soil and water-borne ionic and methylmercury. Mercury pollution is a serious world-wide problem affecting the health of human and wild-life populations. Methylmercury, produced by native bacteria at mercury-contaminated wetland sites, is a particularly serious problem due to its extreme toxicity and efficient biomagnification in the food chain. We engineered several plant species (e.g., Arabidopsis, tobacco, canola, yellow poplar, rice) to express the bacterial genes, merB and/or merA, under the control of plant regulatory sequences. These transgenic plants acquired remarkable properties for mercury remediation. (1) Transgenic plants expressing merB (organomercury lyase) extract methylmercury from their growth substrate and degrade it to less toxic ionic mercury. They grow on concentrations of methylmercury that kill normal plants and accumulate low levels of ionic mercury. (2) Transgenic plants expressing merA (mercuric ion reductase) extract and electrochemically reduce toxic, reactive ionic mercury to much less toxic and volatile metallic mercury. This metal transformation is driven by the powerful photosynthetic reducing capacity of higher plants that generates excess NADPH using solar energy. MerA plants grow vigorously on levels of ionic mercury that kill control plants. Plants expressing both merB and merA degrade high levels of methylmercury and volatilize metallic mercury. These properties were shown to be genetically stable for several generations in the two plant species examined. Our work demonstrates that native trees, shrubs, and grasses can be engineered to remediate the most abundant toxic mercury pollutants. Building on these data our working hypothesis for the next grant period is that

  10. Ionic transport properties of template-synthesized gold nanotube membranes

    NASA Astrophysics Data System (ADS)

    Gao, Peng

    Ionic transport in nanotubes exhibits unique properties due to the strong interactions between ions and the nanotube surface. The main objective of my research is to explore and regulate the ionic transport in gold nanotube membranes. Chapter 1 overviews a versatile method of fabricating nanostructured materials, called the template synthesis. Important parameters of the template synthesis are introduced such as templates and deposition methods. The template synthesis method is used to prepare membranes used in this dissertation. Chapter 2 describes a method to increase the ionic conductivity in membranes containing gold nanotubes with small diameter (4 nm). The gold nanotube membrane is prepared by the electroless plating of gold in a commercially available polycarbonate membrane. Voltages are applied to the gold nanotube membrane and fixed charges are injected on the gold nanotube walls. We show that ionic conductivity of the gold nanotube membrane can be enhanced in aqueous potassium chloride (KCl) solution at negative applied voltages. When the most negative voltage (-0.8 V vs. Ag/AgCl) is applied to the membrane, the ionic conductivity of the solution inside the gold nanotube (94 mS.cm-1) is comparable to that of 1 M aqueous KCl, over two orders of magnitude higher than that of the 0.01 M KCl contacting the membrane. Chapter 3 explores another important transport property of the gold nanotube membrane -- ion permselectivity. When the permselective membrane separates two electrolyte solutions at different concentrations, a membrane potential is developed and measured by the potentiometric method. Surface charge density and the ion mobilities are estimated by fitting the experimental data with a pre-existing model. The surface charge density of the gold nanotube membrane in this research is estimated to be 2 muC/cm2. Chapter 4 describes voltage-controlled ionic transport in a gold/polypyrrole membrane doped with sodium dodecylbenzene sulfonate (DBS). Polypyrrole

  11. Wetting in electrolyte solutions.

    PubMed

    Ibagon, Ingrid; Bier, Markus; Dietrich, S

    2013-06-01

    Wetting of a charged substrate by an electrolyte solution is investigated by means of classical density functional theory applied to a lattice model. Within the present model the pure, i.e., salt-free solvent, for which all interactions are of the nearest-neighbor type only, exhibits a second-order wetting transition for all strengths of the substrate-particle and the particle-particle interactions for which the wetting transition temperature is nonzero. The influences of the substrate charge density and of the ionic strength on the wetting transition temperature and on the order of the wetting transition are studied. If the substrate is neutral, the addition of salt to the solvent changes neither the order nor the transition temperature of the wetting transition of the system. If the surface charge is nonzero, upon adding salt this continuous wetting transition changes to first-order within the wide range of substrate surface charge densities and ionic strengths studied here. As the substrate surface charge density is increased, at fixed ionic strength, the wetting transition temperature decreases and the prewetting line associated with the first-order wetting transition becomes longer. This decrease of the wetting transition temperature upon increasing the surface charge density becomes more pronounced by decreasing the ionic strength. PMID:23758391

  12. Doubly thermo-responsive copolymers in ionic liquid.

    PubMed

    Nguyen, H H; El Ezzi, M; Mingotaud, C; Destarac, M; Marty, J-D; Lauth-de Viguerie, N

    2016-04-01

    We report the behaviour of thermoresponsive block copolymers of n-butyl acrylate and N-alkyl acrylamides in [C2mim][NTf2]. Poly(N-isopropylacrylamide) exhibits an upper critical solution temperature in [C2mim][NTf2] whereas poly(n-butyl acrylate) has a lower critical solution temperature. Consequently, these polymers exhibit double thermo-responsiveness correlated with the macromolecular structure. Moreover, a switching from micellar to reverse micellar structures was induced by a change in temperature. This property enables the development of reversible shuttles between ionic liquids and water. PMID:26931173

  13. Accelerated materials design of fast oxygen ionic conductors based on first principles calculations

    NASA Astrophysics Data System (ADS)

    He, Xingfeng; Mo, Yifei

    Over the past decades, significant research efforts have been dedicated to seeking fast oxygen ion conductor materials, which have important technological applications in electrochemical devices such as solid oxide fuel cells, oxygen separation membranes, and sensors. Recently, Na0.5Bi0.5TiO3 (NBT) was reported as a new family of fast oxygen ionic conductor. We will present our first principles computation study aims to understand the O diffusion mechanisms in the NBT material and to design this material with enhanced oxygen ionic conductivity. Using the NBT materials as an example, we demonstrate the computation capability to evaluate the phase stability, chemical stability, and ionic diffusion of the ionic conductor materials. We reveal the effects of local atomistic configurations and dopants on oxygen diffusion and identify the intrinsic limiting factors in increasing the ionic conductivity of the NBT materials. Novel doping strategies were predicted and demonstrated by the first principles calculations. In particular, the K doped NBT compound achieved good phase stability and an order of magnitude increase in oxygen ionic conductivity of up to 0.1 S cm-1 at 900 K compared to the experimental Mg doped compositions. Our results provide new avenues for the future design of the NBT materials and demonstrate the accelerated design of new ionic conductor materials based on first principles techniques. This computation methodology and workflow can be applied to the materials design of any (e.g. Li +, Na +) fast ion-conducting materials.

  14. 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. PMID:662693

  15. Carbons, ionic liquids and quinones for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Diaz, Raul; Doherty, Andrew

    2016-04-01

    Carbons are the main electrode materials used in electrochemical capacitors, which are electrochemical energy storage devices with high power densities and long cycling lifetimes. However, increasing their energy density will improve their potential for commercial implementation. In this regard, the use of high surface area carbons and high voltage electrolytes are well known strategies to increase the attainable energy density, and lately ionic liquids have been explored as promising alternatives to current state of the art acetonitrile-based electrolytes. Also, in terms of safety and sustainability ionic liquids are attractive electrolyte materials for electrochemical capacitors. In addition, it has been shown that the matching of the carbon pore size with the electrolyte ion size further increases the attainable electric double layer (EDL) capacitance and energy density. The use of pseudocapacitive reactions can significantly increase the attainable energy density, and quinonic-based materials offer a potentially sustainable and cost effective research avenue for both the electrode and the electrolyte. This perspective will provide an overview of the current state of the art research on electrochemical capacitors based on combinations of carbons, ionic liquids and quinonic compounds, highlighting performances and challenges and discussing possible future research avenues. In this regard, current interest is mainly focused on strategies which may ultimately lead to commercially competitive sustainable high performance electrochemical capacitors for different applications including those requiring mechanical flexibility and biocompatibility.

  16. Externally Wetted Ionic Liquid Thruster

    NASA Astrophysics Data System (ADS)

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

    2004-10-01

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

  17. Correlation of three-liquid-phase equilibria involving ionic liquids.

    PubMed

    Rodríguez-Escontrela, I; Arce, A; Soto, A; Marcilla, A; Olaya, M M; Reyes-Labarta, J A

    2016-08-01

    The difficulty in achieving a good thermodynamic description of phase equilibria is finding a model that can be extended to a large variety of chemical families and conditions. This problem worsens in the case of systems containing more than two phases or involving complex compounds such as ionic liquids. However, there are interesting applications that involve multiphasic systems, and the promising features of ionic liquids suggest that they will play an important role in many future processes. In this work, for the first time, the simultaneous correlation of liquid-liquid and liquid-liquid-liquid equilibrium data for ternary systems involving ionic liquids has been carried out. To that end, the phase diagram of the water + [P6 6 6 14][DCA] + hexane system has been determined at 298.15 K and 323.15 K and atmospheric pressure. The importance of this system lies in the possibility of using the surface active ionic liquid to improve surfactant enhanced oil recovery methods. With those and previous measurements, thirteen sets of equilibrium data for water + ionic liquid + oil ternary systems have been correlated. The isoactivity equilibrium condition, using the NRTL model, and some pivotal strategies are proposed to correlate these complex systems. Good agreement has been found between experimental and calculated data in all the regions (one triphasic and two biphasic) of the diagrams. The geometric aspects related to the Gibbs energy of mixing function obtained using the model, together with the minor common tangent plane equilibrium condition, are valuable tools to check the consistency of the obtained correlation results. PMID:27427420

  18. Low Temperature Reduction of Alumina Using Fluorine Containing Ionic Liquids

    SciTech Connect

    Reddy, Ramana

    2009-01-31

    EXECUTIVE SUMMARY The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30°C was found to be quasi-reversible, with the charge transfer coefficient

  19. Low Temperature Reduction of Alumina Using Fluorine Containing Ionic Liquids

    SciTech Connect

    Dr. R. G. Reddy

    2007-09-01

    The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30°C was found to be quasi-reversible, with the charge transfer coefficient (0.40). Nucleation

  20. Low Temperature Reduction of Alumina Using Fluorine Containing Ionic Liquids

    SciTech Connect

    Reddy, Ramana G

    2009-01-31

    EXECUTIVE SUMMARY The major objective of the project is to establish the feasibility of using specific ionic liquids capable of sustaining aluminum electrolysis near room temperature at laboratory and batch recirculation scales. It will explore new technologies for aluminum and other valuable metal extraction and process methods. The new technology will overcome many of the limitations associated with high temperatures processes such as high energy consumption and corrosion attack. Furthermore, ionic liquids are non-toxic and could be recycled after purification, thus minimizing extraction reagent losses and environmental pollutant emissions. Ionic liquids are mixture of inorganic and organic salts which are liquid at room temperature and have wide operational temperature range. During the last several years, they were emerging as novel electrolytes for extracting and refining of aluminum metals and/or alloys, which are otherwise impossible using aqueous media. The superior high temperature characteristics and high solvating capabilities of ionic liquids provide a unique solution to high temperature organic solvent problems associated with device internal pressure build-up, corrosion, and thermal stability. However their applications have not yet been fully implemented due to the insufficient understanding of the electrochemical mechanisms involved in processing of aluminum with ionic liquids. Laboratory aluminum electrodeposition in ionic liquids has been investigated in chloride and bis (trifluoromethylsulfonyl) imide based ionic liquids. The electrowinning process yielded current density in the range of 200-500 A/m2, and current efficiency of about 90%. The results indicated that high purity aluminum (>99.99%) can be obtained as cathodic deposits. Cyclic voltammetry and chronoamperometry studies have shown that initial stages of aluminum electrodeposition in ionic liquid electrolyte at 30°C was found to be quasi-reversible, with the charge transfer

  1. Ionic starch-based hydrogels for the prevention of nonspecific protein adsorption.

    PubMed

    Wang, Jinmei; Sun, Hong; Li, Junjie; Dong, Dianyu; Zhang, Yabin; Yao, Fanglian

    2015-03-01

    Non-fouling materials bind water molecules via either hydrogen bonding or ionic solvation to form a hydration layer which is responsible for their resistance to protein adsorption. Three ionic starch-based polymers, namely a cationic starch (C-Starch), an anionic starch (A-Starch) and a zwitterionic starch (Z-Starch), were synthesized via etherification reactions to incorporate both hydrogen bonding and ionic solvation hydration groups into one molecule. Further, C-, A- and Z-Starch hydrogels were prepared via chemical crosslinking. The non-fouling properties of these hydrogels were tested with different proteins in solutions with different ionic strengths. The C-Starch hydrogel had low protein resistance at all ionic strengths; the A-Starch hydrogel resisted protein adsorption at ionic strengths of more than 10mM; and the Z-Starch hydrogel resisted protein adsorption at all ionic strengths. In addition, the A- and Z-Starch hydrogels both resisted cell adhesion. This work provides a new path for developing non-fouling materials using the integration of polysaccharides with anionic or zwitterionic moieties to regulate the protein resistance of materials. PMID:25498650

  2. Direct Capture of Organic Acids From Fermentation Media Using Ionic Liquids

    SciTech Connect

    Klasson, K.T.

    2004-11-03

    Several ionic liquids have been investigated for the extraction of organic acids from fermentation broth. Partitioning of representative organic acids (lactic, acetic, and succinic) between aqueous solution and nine hydrophobic ionic liquids was measured. The extraction efficiencies were strongly dependent on pH of the aqueous phase. Distribution coefficient was very good (approximately 60) at low succinic acid concentrations for one of the ionic liquids (trihexyltetradecylphosphonium methanesulfonate) at neutral pH. However, this ionic liquid had to be diluted with nonanol due to its high viscosity in order to be useful. A diluent (trioctylamine) was also added to this mixture. The results suggest that an extraction system based on ionic liquids may be feasible for succinic acid recovery from fermentation broth and that two ideal extraction stages are needed to reduce the concentration from 33 g/L to 1 g/L of succinic acid. Further studies are needed to evaluate other issues related to practical applications, including ionic liquid loss in the process, toxicity effects of ionic liquids during simultaneous fermentation and extractions.

  3. 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.

  4. Ionic Liquids to Replace Hydrazine

    NASA Technical Reports Server (NTRS)

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

    2011-01-01

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

  5. Revealing ionic motion molecular solids

    NASA Astrophysics Data System (ADS)

    Thurzo, I.; Zahn, D. R. T.

    2006-01-01

    Thin films of mixed valence semiconductor copper-tetracyano-quinodimethane (Cu-TCNQ) and small molecule tris(8-hydroxyquinolinato)aluminum (Alq3) were investigated by current-voltage (I-V) and admittance (C-V,G-V) techniques in single-layer configuration with different combinations of electrodes. The predicted hysteresis of I-V curves and nearly constant loss (NCL) could be observed for both materials. When cycling devices between negative and positive biases, slowly decaying ionic transient currents interfere with steady-state currents and point to unidirectional motions of the ionic species with subsequent redox reaction at one of the electrodes. Plotting the frequency f dependence of the equivalent parallel capacitance at zero bias as log10 C(0) versus log10(f), the dielectric behavior of Cu-TCNQ and Alq3 complies with the effective-medium model for NCL in ionic conductors [J. R. Macdonald J. Appl. Phys. 94, 558 (2003)]. It also holds for a similar plot of the equivalent parallel zero-bias conductance G(0). The nature of the revealed mobile ions is discussed with emphasis on their sources.

  6. Plutonium in Concentrated Solutions

    SciTech Connect

    Clark, Sue B.; Delegard, Calvin H.

    2002-08-01

    Complex, high ionic strength media are used throughout the plutonium cycle, from its processing and purification in nitric acid, to waste storage and processing in alkaline solutions of concentrated electrolytes, to geologic disposal in brines. Plutonium oxidation/reduction, stability, radiolysis, solution and solid phase chemistry have been studied in such systems. In some cases, predictive models for describing Pu chemistry under such non-ideal conditions have been developed, which are usually based on empirical databases describing specific ion interactions. In Chapter 11, Non-Ideal Systems, studies on the behavior of Pu in various complex media and available model descriptions are reviewed.

  7. The Preparation and Characterization of Poly(m-phenyleneisophthalamide) Fibers Using Ionic Liquids

    PubMed Central

    Zhao, Tingting; Wang, Huaping; Zhang, Yumei; Wang, Biao; Jiang, Jianming

    2007-01-01

    A process to produce fibers from Poly(m-phenyleneisophthalamide)(PMIA) solution in an ionic liquid via wet-spinning technology are described. The spinning process was investigated on a small laboratory scale. Ionic liquid spinning solutions were first prepared for PMIA fibers, followed by wet spinning. In the course of this research, the physical properties of the PMIA fibers were estimated. We studied the dependence of the mechanical properties of the obtained PMIA fibers on the composition of the coagulation bath, and on the choice of solvent in spinning solution. The morphology of the fibers from ionic liquid and traditional DMAc solvents via wet-spinning process were observed by scanning electrical microscopy(SEM). The differences of morphologies and properties of the PMIA fibers obtained from two different solvents are discussed.

  8. Environmentally benign methanolysis of polycarbonate to recover bisphenol A and dimethyl carbonate in ionic liquids.

    PubMed

    Liu, Fusheng; Li, Zhuo; Yu, Shitao; Cui, Xiao; Ge, Xiaoping

    2010-02-15

    An environmentally friendly strategy for methanolysis of polycarbonate (PC) to recover bisphenol A (BPA) and dimethyl carbonate (DMC) was developed in which PC could be methanolyzed in an ionic liquid without any acid or base catalyst under moderate conditions. The effects of ionic liquid kinds, temperature, time, and methanol dosage on methanolysis results of PC were examined. It was showed that the methanolysis conversion of PC was almost 100% and the yields of both BPA and DMC were over 95% in presence of ionic liquid 1-n-butyl-3-methylimidazolium chloride ([Bmim][Cl]) and under the conditions of m(PC):m(CH(3)OH):m([Bmim][Cl])=2:3:2, reaction temperature 105 degrees C and time 2.5h. After easily separated from the product, the ionic liquid could be reused 8 times without obvious decrease in the conversion of PC and yields of BPA and DMC. PMID:19773125

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

    PubMed

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

    2013-11-18

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

  10. Electrolytic Conductivity of Four Imidazolium-Based Ionic Liquids

    NASA Astrophysics Data System (ADS)

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

    2013-07-01

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

  11. Radiation Chemistry and Photochemistry of Ionic Liquids

    SciTech Connect

    Wishart, J.F.; Takahaski, K.

    2010-12-01

    As our understanding of ionic liquids and their tunable properties has grown, it is possible to see many opportunities for ionic liquids to contribute to the sustainable use of energy. The potential safety and environmental benefits of ionic liquids, as compared to conventional solvents, have attracted interest in their use as processing media for the nuclear fuel cycle. Therefore, an understanding of the interactions of ionizing radiation and photons with ionic liquids is strongly needed. However, the radiation chemistry of ionic liquids is still a relatively unexplored topic although there has been a significant increase in the number of researchers in the field recently. This article provides a brief introduction to ionic liquids and their interesting properties, and recent advances in the radiation chemistry and photochemistry of ionic liquids. In this article, we will mainly focus on excess electron dynamics and radical reaction dynamics. Because solvation dynamics processes in ionic liquids are much slower than in molecular solvents, one of the distinguishing characteristics is that pre-solvated electrons play an important role in ionic liquid radiolysis. It will be also shown that the reaction dynamics of radical ions is significantly different from that observed in molecular solvents because of the Coulombic screening effects and electrostatic interactions in ionic liquids.

  12. Media ionic strength impacts embryonic responses to engineered nanoparticle exposure

    PubMed Central

    Truong, Lisa; Zaikova, Tatiana; Richman, Erik K.; Hutchison, James E.; Tanguay, Robert L.

    2012-01-01

    Embryonic zebrafish were used to assess the impact of solution ion concentrations on agglomeration and resulting in vivo biological responses of gold nanoparticles (AuNPs). The minimum ion concentration necessary to support embryonic development was determined. Surprisingly, zebrafish exhibit no adverse outcomes when raised in nearly ion-free media. During a rapid throughput screening of AuNPs, 1.2-nm 3-mercaptopropionic acid-functionalized AuNPs (1.2-nm 3-MPA-AuNPs) rapidly agglomerate in exposure solutions. When embryos were exposed to 1.2-nm 3-MPA-AuNPs dispersed in low ionic media, both morbidity and mortality were induced, but when suspended in high ionic media, there was little to no biological response. We demonstrated that the media ionic strength greatly affects agglomeration rates and biological responses. Most importantly, the insensitivity of the zebrafish embryo to external ions indicates that it is possible, and necessary, to adjust the exposure media conditions to optimize NP dispersion prior to assessment. PMID:21809903

  13. Naphthalene-Functionalized, Photoluminescent Room Temperature Ionic Liquids Bearing Small Counterions.

    PubMed

    Zhu, Hongxia; Zhang, Geping; Chen, Mengjun; Zhou, Shengju; Li, Guihua; Wang, Xiaolin; Zhu, Qingzeng; Li, Hongguang; Hao, Jingcheng

    2016-04-25

    Obtaining π-conjugated room temperature ionic liquids (RTILs) is difficult because of the relatively strong π-π interaction among the π-moieties. Existing strategies by using bulky counterions greatly hindered further property optimization and potential applications of these intriguing functional fluids through simple ion exchange. Herein, four naphthalene-functionalized, π-conjugated RTILs with small counterions (Br(-) ) have been facilely synthesized with high yields. Our strategy is to attach branched alkyl chains to the cationic backbone of the target compounds (2 a-d), which effectively tune inter- and intramolecular interactions. Compounds 2 a-d have satisfactory thermal stability (up to 300 °C) and low melting points (<-19 °C). Rheological measurements revealed the fluid character of 2 a-d, whose viscosity decrease with the increase of the alkyl chain length and temperature. The presence of the π-conjugated naphthalene moiety imparts 2 a-d photoluminescent properties in bulk solutions. Moreover, the absence of strong π-π stacking among the naphthalene units in solvent-free states enables them to be used as a new generation of photoluminescent inks. PMID:26929087

  14. Efficient White-Light Generation from Ionically Self-Assembled Triply-Fluorescent Organic Nanoparticles.

    PubMed

    Das, Susmita; Debnath, Tanay; Basu, Amrita; Ghosh, Deepanwita; Das, Abhijit Kumar; Baker, Gary A; Patra, Amitava

    2016-06-20

    Low cost, simple, and environmentally friendly strategies for white-light generation which do not require rare-earth phosphors or other toxic or elementally scare species remain an essentially unmet challenge. Progress in the area of all-organic approaches is highly sought, single molecular systems remaining a particular challenge. Taking inspiration from the designer nature of ionic-liquid chemistry, we now introduce a new strategy toward white-light emission based on the facile generation of nanoparticles comprising three different fluorophores assembled in a well-defined stoichiometry purely through electrostatic interactions. The building blocks consist of the fluorophores aminopyrene, fluorescein, and rhodamine 6G which represent blue, green, and red-emitting species, respectively. Spherical nanoparticles 16(±5) nm in size were prepared which display bright white-light emission with high fluorescence quantum efficiency (26 %) and color coordinate at (0.29, 0.38) which lie in close proximity to pure white light (0.33, 0.33). It is noteworthy that this same fluorophore mixture in free solution yields only blue emission. Density functional theory calculations reveal H-bond and ground-state proton transfer mediated absolute non-parallel orientation of the constituent units which result in frustrated energy transfer, giving rise to emission from the individual centers and concomitant white-light emission. PMID:27219524

  15. Performances and mechanistic investigations of a triphosphine trioxide/ionic liquid system for rare earth extraction.

    PubMed

    Turgis, R; Arrachart, G; Dubois, V; Dourdain, S; Virieux, D; Michel, S; Legeai, S; Lejeune, M; Draye, M; Pellet-Rostaing, S

    2016-01-21

    The extraction of rare earth elements (REEs) from nitric acid solution with a triphosphine trioxide (TPO) is presented. Performances of such a ligand in ionic liquids vs. a classical solvent (benzyl ether) are compared. TPO seems to be 10 to 100 times more efficient when it is dissolved in ionic media whatever the concentration of nitric acid involved. Mechanistic investigations reveal that cation exchange classically observed in ionic liquids is not consistent with the experimental data. Moreover, clear differences in the TPO/Ln complexes between classical and ionic media are highlighted. A stable complex of 1 lanthanide for 3 TPO is formed in an ionic liquid whereas a complex of 1 lanthanide for 6 to 9 TPO is formed in benzyl ether. Back extraction is also studied and good recovery of REEs could be obtained. The TPO/ionic liquid system shows remarkable performances i.e. efficiency and selectivity towards lanthanides in a simulated leaching solution of a Nd/Fe/B/Dy magnet. PMID:26673884

  16. Fabrication of a Multi-Walled Nanotube (MWNT) Ionic Liquid Electrode and Its Application for Sensing Phenolics in Red Wines

    PubMed Central

    Kim, Kyo-Il; Kang, Hee-Young; Lee, Jae-Chan; Choi, Seong-Ho

    2009-01-01

    A multi-walled nanotube (MWNT) ionic liquid was prepared by the immobilization of 1-butylimidazole bromide onto an epoxy group on a poly(glycidyl methacrylate)-grafted MWNT, which was synthesized by radiation-induced graft polymerization of glycidyl methacrylate onto MWNT in an aqueous solution. Subsequently, a MWNT ionic liquid electrode was fabricated by hand-casting MWNT ionic liquid, tyrosinase, and chitosan solution as a binder on indium tin oxide (ITO) glass. The sensing ranges of the MWNT ionic liquid electrode with immobilized tyrosinase was in the range of 0.01-0.08 mM in a phosphate buffer solution. The optimal conditions such as pH, temperature, and effects of different phenolic compounds were determined. The total phenolic compounds of three commercial red wines were also determined on the tyrosinase-immobilized biosensor. PMID:22399973

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

    SciTech Connect

    Robin D. Rogers

    2004-12-09

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

  18. Transfer of complexed and dissociated ionic species at soft interfaces: a voltammetric study of chemical kinetic and diffusional effects.

    PubMed

    Laborda, Eduardo; Olmos, José Manuel; Molina, Ángela

    2016-04-21

    A new transfer mechanism is considered in which two different ionic species of the same charge can be transferred across a soft interface while they interconvert with each other in the original phase through a homogeneous chemical reaction: the aqueous complexation-dissociation coupled to transfer (ACDT) mechanism. This can correspond to a free ion in aqueous solution in the presence of a neutral ligand that complexes it leading to a species that can be more or less lipophilic than the free ion. As a result, the transfer to the organic phase can be facilitated or hindered by the aqueous-phase chemical reaction. Rigorous and approximate explicit analytical solutions are derived for the study of the above mechanism via normal pulse voltammetry, derivative voltammetry and chronoamperometry at macrointerfaces. The solutions enable us to examine the process whatever the species' lipophilicity and diffusivity in each medium and the kinetics and thermodynamics of the chemical reaction in solution. Moreover, when the chemical reaction is at equilibrium, explicit expressions for cyclic voltammetry and square wave voltammetry are obtained. With this set of equations, the influence of different physicochemical phenomena on the voltammetric response is studied as well as the most suitable strategies to characterize them. PMID:27020610

  19. A Triphasic Sorting System: Coordination Cages in Ionic Liquids.

    PubMed

    Grommet, Angela B; Bolliger, Jeanne L; Browne, Colm; Nitschke, Jonathan R

    2015-12-01

    Host-guest chemistry is usually carried out in either water or organic solvents. To investigate the utility of alternative solvents, three different coordination cages were dissolved in neat ionic liquids. By using (19) F NMR spectroscopy to monitor the presence of free and bound guest molecules, all three cages were demonstrated to be stable and capable of encapsulating guests in ionic solution. Different cages were found to preferentially dissolve in different phases, allowing for the design of a triphasic sorting system. Within this system, three coordination cages, namely Fe4 L6 2, Fe8 L12 3, and Fe4 L4 4, each segregated into a distinct layer. Upon the addition of a mixture of three different guests, each cage (in each separate layer) selectively bound its preferred guest. PMID:26494225

  20. Interaction of nonionic surfactant AEO9 with ionic surfactants*

    PubMed Central

    Zhang, Zhi-guo; Yin, Hong

    2005-01-01

    The interaction in two mixtures of a nonionic surfactant AEO9 (C12H25O(CH2CH2O)9H) and different ionic surfactants was investigated. The two mixtures were AEO9/sodium dodecyl sulfate (SDS) and AEO9/cetyltrimethylammonium bromide (CTAB) at molar fraction of AEO9, α AEO9=0.5. The surface properties of the surfactants, critical micelle concentration (CMC), effectiveness of surface tension reduction (γ CMC), maximum surface excess concentration (Γ max) and minimum area per molecule at the air/solution interface (A min) were determined for both individual surfactants and their mixtures. The significant deviations from ideal behavior (attractive interactions) of the nonionic/ionic surfactant mixtures were determined. Mixtures of both AEO9/SDS and AEO9/CTAB exhibited synergism in surface tension reduction efficiency and mixed micelle formation, but neither exhibited synergism in surface tension reduction effectiveness. PMID:15909351

  1. Molecular modeling of diffusion coefficient and ionic conductivity of CO2 in aqueous ionic solutions.

    PubMed

    Garcia-Ratés, Miquel; de Hemptinne, Jean-Charles; Bonet Avalos, Josep; Nieto-Draghi, Carlos

    2012-03-01

    Mass diffusion coefficients of CO(2)/brine mixtures under thermodynamic conditions of deep saline aquifers have been investigated by molecular simulation. The objective of this work is to provide estimates of the diffusion coefficient of CO(2) in salty water to compensate the lack of experimental data on this property. We analyzed the influence of temperature, CO(2) concentration,and salinity on the diffusion coefficient, the rotational diffusion, as well as the electrical conductivity. We observe an increase of the mass diffusion coefficient with the temperature, but no clear dependence is identified with the salinity or with the CO(2) mole fraction, if the system is overall dilute. In this case, we notice an important dispersion on the values of the diffusion coefficient which impairs any conclusive statement about the effect of the gas concentration on the mobility of CO(2) molecules. Rotational relaxation times for water and CO(2) increase by decreasing temperature or increasing the salt concentration. We propose a correlation for the self-diffusion coefficient of CO(2) in terms of the rotational relaxation time which can ultimately be used to estimate the mutual diffusion coefficient of CO(2) in brine. The electrical conductivity of the CO(2)-brine mixtures was also calculated under different thermodynamic conditions. Electrical conductivity tends to increase with the temperature and salt concentration. However, we do not observe any influence of this property with the CO(2) concentration at the studied regimes. Our results give a first evaluation of the variation of the CO(2)-brine mass diffusion coefficient, rotational relaxation times, and electrical conductivity under the thermodynamic conditions typically encountered in deep saline aquifers. PMID:22292779

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

    SciTech Connect

    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 of 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].

  3. Charge transport in confined ionic liquids

    NASA Astrophysics Data System (ADS)

    Sangoro, Joshua; Iacob, Ciprian; Kipnusu, Wycliffe; Kremer, Friedrich

    2011-03-01

    Charge transport and glassy dynamics in neat and polymerized ionic liquids confined in nanoporous silica are investigated in a wide frequency and temperature ranges by a combination of Broadband Dielectric Spectroscopy and Pulsed Field Gradient Nuclear Magnetic Resonance (PFG NMR). By applying the Einstein-Smoluchowski relations to the dielectric spectra, diffusion coefficients are obtained in quantitative agreement with independent PFG NMR. The impact of geometrical confinement as well as the pore wall-ionic liquid interactions on the overall ionic mobility is explored for diverse categories of ionic liquids. The results are discussed within the framework of dynamic glass transition assisted charge transport in ionic liquids. Financial support from the Deutsche Forschungsgemeinschaft under the DFG SPP 1191 Priority Program on Ionic Liquids is gratefully acknowledged.

  4. 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.

  5. Elicitation of the most important structural properties of ionic liquids affecting ecotoxicity in limnic green algae; a QSAR approach.

    PubMed

    Izadiyan, Parisa; Fatemi, M H; Izadiyan, Mahsa

    2013-01-01

    Many ionic liquids are soluble in water and their impact on the aquatic environment has to be evaluated. However, due to the large number of ionic liquids and lack of experimental data, it is necessary to develop estimation procedures in order to reduce the materials and time consumption. In this study using multilayer perceptron neural network (MLP), ant colony optimization (ACO) and multiple linear regression (MLR) strategies, good predictive quantitative structure-activity relationships (QSAR) models were introduced and structural parameters affecting ecotoxicity of ionic liquids in limnic green algae (Scenedesmus vacuolatus) were revealed. Moreover, principal component analysis (PCA) and cluster analysis (CA) approaches were also applied to visualize any possible patterns or relationships among ionic liquids data. It was revealed that selected descriptors of the MLR model are also capable of clustering ionic liquids according to their four level of toxicity. PMID:23107477

  6. Enzyme catalysis with small ionic liquid quantities.

    PubMed

    Fischer, Fabian; Mutschler, Julien; Zufferey, Daniel

    2011-04-01

    Enzyme catalysis with minimal ionic liquid quantities improves reaction rates, stereoselectivity and enables solvent-free processing. In particular the widely used lipases combine well with many ionic liquids. Demonstrated applications are racemate separation, esterification and glycerolysis. Minimal solvent processing is also an alternative to sluggish solvent-free catalysis. The method allows simplified down-stream processing, as only traces of ionic liquids have to be removed. PMID:21107639

  7. Early Events in Ionic Liquid Radiation Chemistry

    SciTech Connect

    Wishart, J.F.; Cook, A.; Rimmer, R.D.; Gohdo, M.

    2010-09-14

    Ionic liquids are interesting and useful materials whose solvation time scales are up to thousands of times longer than in conventional solvents. The extended lifetimes of pre-solvated electrons and other energetic species in ionic liquids has profound consequences for the radiolytic product distributions and reactivity patterns. We use a newly developed, multiplexed variation of pulse-probe spectroscopy to measure the kinetics of the early dynamical and reactive events in ionic liquids.

  8. Analysis of the preliminary results based on the first source solutions for the 29th September 2009 Samoan tsunami: hints for a tsunami early warning system strategy

    NASA Astrophysics Data System (ADS)

    Tinti, Stefano; Armigliato, Alberto; Tonini, Roberto

    2010-05-01

    The 29 September 2009 Samoan tsunami was triggered by a strong earthquake (Mw=8.1) that occurred at 17:48 UTC offshore south of Samoa Islands. This earthquake represents an example of the so-called "outer-rise" earthquakes, that occur in the subducting plate before it enters in the subduction zone and their fault mechanism is normal instead of thrust as expected inside the subduction zone. The areas most affected were the south coasts of Western and American Samoa, where maximum peak-to-peak height of about 3.5 meters and 1.5 meters were recorded by tide-gauge stations respectively at Pago-Pago (American Samoa) and at Apia (Western Samoa). Almost 200 persons were killed and run-up heights were measured in excess of 5 meters on several locations along the coast. This "anomalous" event is considered here "a posteriori" as a good case to test (and to open a discussion on) the today strategies used to forecast tsunami characteristics in the frame of Tsunami Early Warning Systems. In this work different fault models based on the focal mechanism solution proposed by Harvard CMT and USGS immediately after the 2009 Samoan earthquake are considered and tested by comparing some recorded signals (three offshore DART buoys and the two coastal tide gauges located at Apia and Pago-Pago) to the synthetic signals resulting from the numerical simulations provided by the UBO-TSUFD code, that is developed and maintained by the Tsunami Research Team of Bologna University. The analysis found out that all the considered sources lead to some discrepancies between observed and computed signals, though some of them reproduce some of the records quite well. These results suggest some important considerations on the tsunami forecast methods as well as on the difficulty and need of issuing timely and reliable warning in case of complex hazardous situation, which is a task that may require sophisticated decision-making platforms. This work has been conducted in the frame of the European

  9. TOUGHREACT Testing in High Ionic Strength Brine Sandstone Systems

    SciTech Connect

    Xu, Tianfu

    2008-09-01

    Deep saline formations and oil and gas reservoirs often contain concentrated brine solutions of ionic strength greater than 1 (I > 1 M). Geochemical modeling, involving high ionic strength brines, is a challenge. In the original TOUGHREACT code (Xu et al., 2004; Xu et al., 2006), activity coefficients of charged aqueous species are computed using an extended Debye-Huckel (DH) equation and parameters derived by Helgeson et al. (1981). The DH model can deal with ionic strengths from dilute to moderately saline water (up to 6 molal for an NaCl-dominant solution). The equations implemented for the DH model are presented in Appendix A. During the course of the Yucca Mountain project, a Pitzer ion-interaction model was implemented into TOUGHREACT. This allows the application of this simulator to problems involving much more concentrated aqueous solutions, such as those involving geochemical processes in and around high-level nuclear waste repositories where fluid evaporation and/or boiling is expected to occur (Zhang et al., 2007). The Pitzer ion-interaction model, which we refer to as the Pitzer virial approach, and associated ion-interaction parameters have been applied successfully to study non-ideal concentrated aqueous solutions. The formulation of the Pitzer model is presented in Appendix B; detailed information can be founded in Zhang et al. (2007). For CO{sub 2} geological sequestration, the Pitzer ion-interaction model for highly concentrated brines was incorporated into TOUGHREACT/ECO2N, then was tested and compared with a previously implemented extended Debye-Hueckel (DH) ion activity model. The comparison was made through a batch geochemical system using a Gulf Coast sandstone saline formation.

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

    PubMed

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

    2013-01-01

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

  11. Ionic self-assembly affords mesoporous ionic networks by crosslinking linear polyviologens with polyoxometalate clusters.

    PubMed

    Chen, Guojian; Hou, Wei; Li, Jing; Wang, Xiaochen; Zhou, Yu; Wang, Jun

    2016-03-21

    Ionic-bonded mesoporous ionic networks were prepared by the ionic self-assembly of polyoxometalate (POM) clusters with linear cationic polyviologens in water. The POM-enriched PMIN-2(V) possesses a high surface area up to 120 m(2) g(-1), exhibiting superior non-noble metal heterogeneous catalytic performance in the ambient aerobic selective oxidation of 5-hydroxymethylfurfural. PMID:26898883

  12. 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)

  13. Targeting cyst wall is an effective strategy in improving the efficacy of marketed contact lens disinfecting solutions against Acanthamoeba castellanii cysts.

    PubMed

    Abjani, Farhat; Khan, Naveed Ahmed; Yousuf, Farzana Abubakar; Siddiqui, Ruqaiyyah

    2016-06-01

    Acanthamoeba cysts are highly resistant to contact lens disinfecting solutions. Acanthamoeba cyst wall is partially made of 1,4 β-glucan (i.e., cellulose) and other complex polysaccharides making it a hardy shell that protects the resident amoeba. Here, we hypothesize that targeting the cyst wall structure in addition to antiamoebic compound would improve the efficacy of marketed contact lens disinfecting solutions. Using chlorhexidine as an antiamoebic compound and cellulase enzyme to disrupt cyst wall structure, the findings revealed that combination of both agents abolished viability of Acanthamoeba castellanii cysts and trophozoites. When tested alone, none of the agents nor contact lens disinfecting solutions completely destroyed A. castellanii cysts and trophozoites. The absence of cyst wall-degrading enzymes in marketed contact lens disinfecting solutions render them ineffective against Acanthamoeba cysts. It is concluded that the addition of cyst wall degrading molecules in contact lens disinfecting solutions will enhance their efficacy in decreasing the incidence of Acanthamoeba effectively. PMID:26675112

  14. Recovery of sugars from ionic liquid biomass liquor by solvent extraction

    SciTech Connect

    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.

  15. Design of Self-Healing Supramolecular Rubbers by Introducing Ionic Cross-Links into Natural Rubber via a Controlled Vulcanization.

    PubMed

    Xu, Chuanhui; Cao, Liming; Lin, Baofeng; Liang, Xingquan; Chen, Yukun

    2016-07-13

    Introducing ionic associations is one of the most effective approaches to realize a self-healing behavior for rubbers. However, most of commercial rubbers are nonpolar rubbers without now available functional groups to be converted into ionic groups. In this paper, our strategy was based on a controlled peroxide-induced vulcanization to generate massive ionic cross-links via polymerization of zinc dimethacrylate (ZDMA) in natural rubber (NR) and exploited it as a potential self-healable material. We controlled vulcanization process to retard the formation of covalent cross-link network, and successfully generated a reversible supramolecular network mainly constructed by ionic cross-links. Without the restriction of covalent cross-linkings, the NR chains in ionic supramolecular network had good flexibility and mobility. The nature that the ionic cross-links was easily reconstructed and rearranged facilitating the self-healing behavior, thereby enabling a fully cut sample to rejoin and retain to its original properties after a suitable self-healing process at ambient temperature. This study thus demonstrates a feasible approach to impart an ionic association induced self-healing function to commercial rubbers without ionic functional groups. PMID:27337545

  16. Chiral Perylene Materials by Ionic Self-Assembly.

    PubMed

    Echue, Geraldine; Hamley, Ian; Lloyd Jones, Guy C; Faul, Charl F J

    2016-09-01

    Two chiral complexes (1-SDS and 1-SDBS) were prepared via the ionic self-assembly of a chiral perylene diimide tecton with oppositely charged surfactants. The effect of surfactant tail architecture on the self-assembly properties and supramolecular structure was investigated in detail using UV-vis, IR, circular dichroism, light microscopy, X-ray diffraction studies, and electron microscopy. The results obtained revealed the molecular chirality of the parent perylene tecton could be translated into supramolecular helical chirality of the resulting complexes via primary ionic interactions through careful choice of solvent and concentration. Differing solvent-dependent aggregation behavior was observed for these complexes as a result of the different possible noncovalent interactions via the surfactant alkyl tails. The results presented in this study demonstrate that ionic self-assembly (ISA) is a facile strategy for the production of chiral supramolecular materials based on perylene diimides. The structure-function relationship is easily explored here due to the wide selection and easy availability of common surfactants. PMID:27486788

  17. Ionic effects on spindle adaptation

    PubMed Central

    Husmark, I.; Ottoson, D.

    1971-01-01

    1. Effects of changes in ionic environment on the receptor potential were studied in isolated frog spindle. Particular attention was focused on the action of potassium removal on the early adaptive decline of the response. 2. Removal of potassium caused a reduction and final disappearance of the dynamic overshoot of the receptor potential. The static phase of the response was also reduced although to less extent. The repolarization phase of the response following release of phasic or maintained stretch was greatly prolonged. 3. Increased potassium concentration caused a reduction of the response, but did not change its general time course. The amount of reduction was related to the potassium concentration. 4. Removal of sodium caused a marked diminution of the response, the static phase being in general more affected than the dynamic phase. 5. It is suggested that the effects of potassium removal are caused by a delay in sodium inactivation and a partial depolarization of the endings. It is concluded that the greater part of the early adaptation of the spindle proper may be attributed to ionic mechanisms in the transducer membrane. PMID:4256546

  18. Ionic liquid tunes microemulsion curvature.

    PubMed

    Liu, Liping; Bauduin, Pierre; Zemb, Thomas; Eastoe, Julian; Hao, Jingcheng

    2009-02-17

    Middle-phase microemulsions formed from cationic dioctadecyldimethylammonium chloride (DODMAC), anionic sodium dodecylsulfate (SDS), n-butanol, and n-heptane were studied. An ionic liquid (IL), 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), was employed as the electrolyte in the aqueous media instead of inorganic salts usually used in microemulsion formulation. Studies have been carried out as a function of the concentrations of [bmim][BF4], n-butanol, total surfactant (cDODMAC+SDS), and temperature on the phase behavior and the ultralow interfacial tensions in which the anionic component is present in excess in the catanionic film. Ultralow interfacial tension measurements confirmed the formation of middle-phase microemulsions and the necessary conditions for stabilizing middle-phase microemulsions. Electrical conductivity, small-angle X-ray scattering (SAXS), and small-angle neutron scattering (SANS) experiments were also performed, indicating that the typical heptane domain size has an average radius of 360 A and the ionic liquid induces softening of the charged catanionic film. Most interestingly, the IL concentration (cIL) is shown to act as an effective interfacial curvature-control parameter, representing a new approach to tuning the formulation of microemulsions and emulsions. The results expand the potential uses of ILs but also point to the design of new ILs that may achieve superefficient control over interfacial and self-assembly systems. PMID:19161325

  19. The effect of ionic liquid electrolyte concentrations in dye sensitized solar cell using gel electrolyte

    NASA Astrophysics Data System (ADS)

    Pujiarti, H.; Arsyad, W. S.; Wulandari, P.; Hidayat, R.

    2014-09-01

    Dye Sensitized Solar Cells (DSSCs) have received much attention because of some advantages, such as using environment-friendly materials and requiring less high-tech equipment. Commonly DSSCs are built using conventional electrolyte solution, which is prone to electrolyte leakage and low stability. In this paper, we present the characteristics of DSSCs using gel electrolyte, which was made of ionic liquid and hybrid polymer gel, and the effect of ionic liquid concentration on their characteristics. The hybrid composite polymer was composed of siloxane and ethylene glycol polymer networks. Their working performances were investigated by the current-voltage (J-V) characterizations and small ac impedance measurements, which are correlated with the concentrations of ionic liquid electrolyte. The experimental results showed that cell working performance slightly decreased but the solution leakage problem was eliminated.

  20. Use of Ionic Liquid in Fabrication, Characterization, and Processing of Anodic Porous Alumina

    PubMed Central

    2009-01-01

    Two different ionic liquids have been tested in the electrochemical fabrication of anodic porous alumina in an aqueous solution of oxalic acid. It was found that during galvanostatic anodization of the aluminum at a current density of 200 mA/cm2, addition of 0.5% relative volume concentration of 1-butyl-3-methylimidazolium tetrafluoborate resulted in a three-fold increase of the growth rate, as compared to the bare acidic solution with the same acid concentration. This ionic liquid was also used successfully for an assessment of the wettability of the outer surface of the alumina, by means of liquid contact angle measurements. The results have been discussed and interpreted with the aid of atomic force microscopy. The observed wetting property allowed to use the ionic liquid for protection of the pores during a test removal of the oxide barrier layer. PMID:20596395

  1. Mechanistic Study of Electroosmotic Transport Across Hydrated Nail Plates: Effects of pH and Ionic Strength

    PubMed Central

    HAO, JINSONG; LI, S. KEVIN

    2008-01-01

    The objective of this study was to investigate the effects of pH and ionic strength on electroosmotic transport in transungual iontophoresis. Transungual iontophoretic transport of model neutral permeants mannitol (MA) and urea (UR) across fully hydrated human nail plates in phosphate-buffered saline of different pH and ionic strengths were investigated in vitro. Two protocols were involved in the transport experiments with each protocol divided into stages including passive and iontophoresis transport at 0.1 and/or 0.3 mA. Nail plate electrical resistance and water uptake of nail clippings were measured at various pH and ionic strengths. In the pH study, electroosmosis enhanced the anodal transport of MA at pH 9 and cathodal transport at pH 3. The Peclet numbers of MA were more than two times higher than those of UR under these conditions. No significant electroosmosis enhancement was observed for MA and UR at pH 5. In the ionic strength study, a decrease in solution ionic strength from 0.7 to 0.04 M enhanced electroosmotic transport. Nail electrical resistance increased with decreasing the ionic strength of the equilibrating solution, but reached a plateau when the ionic strength was less than approximately 0.07 M. Solution pH and ionic strength had no significant effect on nail hydration. Under the studied pH and ionic strength conditions, the effects of electroosmosis were small compared to the direct-field effects in transungual iontophoretic transport of small to moderate size permeants. PMID:18386836

  2. Tuning the basicity of ionic liquids for efficient synthesis of alkylidene carbonates from CO2 at atmospheric pressure.

    PubMed

    Chen, Kaihong; Shi, Guiling; Dao, Rina; Mei, Ke; Zhou, Xiuyuan; Li, Haoran; Wang, Congmin

    2016-06-14

    A strategy to achieve the efficient synthesis of alkylidene carbonates from CO2 at atmospheric pressure by tuning the basicity of ionic liquids was developed. Excellent yields were obtained due to basic ionic liquids' dual roles both as absorbents and as activators. The reaction mechanism was investigated through a combination of NMR spectroscopy, controlled experiments and quantum calculations, indicating the importance of a moderate basicity. PMID:27241057

  3. Immobilization of ionic liquids to covalent organic frameworks for catalyzing the formylation of amines with CO2 and phenylsilane.

    PubMed

    Dong, Bin; Wang, Liangying; Zhao, Shang; Ge, Rile; Song, Xuedan; Wang, Yu; Gao, Yanan

    2016-06-01

    We presented the immobilization of ionic liquids on the channel walls of COFs using a post-synthetic strategy. The ionic [Et4NBr]50%-Py-COF afforded a high CO2 adsorption capacity of 164.6 mg g(-1) (1 bar, 273 K) and was developed as an effective heterogeneous catalyst for the transformation of CO2 into value-added formamides under ambient conditions. PMID:27152374

  4. An Alternative to the Ionic Model

    ERIC Educational Resources Information Center

    Sanderson, R. T.

    1975-01-01

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

  5. Ionic liquid-in-oil microemulsions.

    PubMed

    Eastoe, Julian; Gold, Sarah; Rogers, Sarah E; Paul, Alison; Welton, Tom; Heenan, Richard K; Grillo, Isabelle

    2005-05-25

    Phase stability and small-angle neutron scattering (SANS) data show that surfactant-stabilized nanodomains of a typical ionic liquid (1-butyl-3-methylimidazolium tetrafluoroborate [bmim][BF4]) may be dispersed by the nonionic surfactant Triton-X100 in cyclohexane. Analyses of these SANS data are consistent with the formation of ionic liquid-in-oil microemulsion droplets. PMID:15898765

  6. Engineered microorganisms having resistance to ionic liquids

    DOEpatents

    Ruegg, Thomas Lawrence; Thelen, Michael P.

    2016-03-22

    The present invention provides for a method of genetically modifying microorganisms to enhance resistance to ionic liquids, host cells genetically modified in accordance with the methods, and methods of using the host cells in a reaction comprising biomass that has been pretreated with ionic liquids.

  7. Ionic switch controls the DNA state in phage λ

    DOE PAGESBeta

    Li, Dong; Liu, Ting; Zuo, Xiaobing; Li, Tao; Qiu, Xiangyun; Evilevitch, Alex

    2015-06-19

    We have recently found that DNA packaged in phage λ undergoes a disordering transition triggered by temperature, which results in increased genome mobility. This solid-to-fluid like DNA transition markedly increases the number of infectious λ particles facilitating infection. However, the structural transition strongly depends on temperature and ionic conditions in the surrounding medium. Using titration microcalorimetry combined with solution X-ray scattering, we mapped both energetic and structural changes associated with transition of the encapsidated λ-DNA. Packaged DNA needs to reach a critical stress level in order for transition to occur. We varied the stress on DNA in the capsid bymore » changing the temperature, packaged DNA length and ionic conditions. We found striking evidence that the intracapsid DNA transition is ‘switched on’ at the ionic conditions mimicking those in vivo and also at the physiologic temperature of infection at 37°C. This ion regulated on-off switch of packaged DNA mobility in turn affects viral replication. The results suggest a remarkable adaptation of phage λ to the environment of its host bacteria in the human gut. The metastable DNA state in the capsid provides a new paradigm for the physical evolution of viruses.« less

  8. Ionic switch controls the DNA state in phage λ

    SciTech Connect

    Li, Dong; Liu, Ting; Zuo, Xiaobing; Li, Tao; Qiu, Xiangyun; Evilevitch, Alex

    2015-06-19

    We have recently found that DNA packaged in phage λ undergoes a disordering transition triggered by temperature, which results in increased genome mobility. This solid-to-fluid like DNA transition markedly increases the number of infectious λ particles facilitating infection. However, the structural transition strongly depends on temperature and ionic conditions in the surrounding medium. Using titration microcalorimetry combined with solution X-ray scattering, we mapped both energetic and structural changes associated with transition of the encapsidated λ-DNA. Packaged DNA needs to reach a critical stress level in order for transition to occur. We varied the stress on DNA in the capsid by changing the temperature, packaged DNA length and ionic conditions. We found striking evidence that the intracapsid DNA transition is ‘switched on’ at the ionic conditions mimicking those in vivo and also at the physiologic temperature of infection at 37°C. This ion regulated on-off switch of packaged DNA mobility in turn affects viral replication. The results suggest a remarkable adaptation of phage λ to the environment of its host bacteria in the human gut. The metastable DNA state in the capsid provides a new paradigm for the physical evolution of viruses.

  9. Pretreatment of Lignocellulosic Biomass with Low-cost Ionic Liquids.

    PubMed

    Gschwend, Florence J V; Brandt, Agnieszka; Chambon, Clementine L; Tu, Wei-Chien; Weigand, Lisa; Hallett, Jason P

    2016-01-01

    A number of ionic liquids (ILs) with economically attractive production costs have recently received growing interest as media for the delignification of a variety of lignocellulosic feedstocks. Here we demonstrate the use of these low-cost protic ILs in the deconstruction of lignocellulosic biomass (Ionosolv pretreatment), yielding cellulose and a purified lignin. In the most generic process, the protic ionic liquid is synthesized by accurate combination of aqueous acid and amine base. The water content is adjusted subsequently. For the delignification, the biomass is placed into a vessel with IL solution at elevated temperatures to dissolve the lignin and hemicellulose, leaving a cellulose-rich pulp ready for saccharification (hydrolysis to fermentable sugars). The lignin is later precipitated from the IL by the addition of water and recovered as a solid. The removal of the added water regenerates the ionic liquid, which can be reused multiple times. This protocol is useful to investigate the significant potential of protic ILs for use in commercial biomass pretreatment/lignin fractionation for producing biofuels or renewable chemicals and materials. PMID:27583830

  10. Ionic switch controls the DNA state in phage λ.

    PubMed

    Li, Dong; Liu, Ting; Zuo, Xiaobing; Li, Tao; Qiu, Xiangyun; Evilevitch, Alex

    2015-07-27

    We have recently found that DNA packaged in phage λ undergoes a disordering transition triggered by temperature, which results in increased genome mobility. This solid-to-fluid like DNA transition markedly increases the number of infectious λ particles facilitating infection. However, the structural transition strongly depends on temperature and ionic conditions in the surrounding medium. Using titration microcalorimetry combined with solution X-ray scattering, we mapped both energetic and structural changes associated with transition of the encapsidated λ-DNA. Packaged DNA needs to reach a critical stress level in order for transition to occur. We varied the stress on DNA in the capsid by changing the temperature, packaged DNA length and ionic conditions. We found striking evidence that the intracapsid DNA transition is 'switched on' at the ionic conditions mimicking those in vivo and also at the physiologic temperature of infection at 37°C. This ion regulated on-off switch of packaged DNA mobility in turn affects viral replication. These results suggest a remarkable adaptation of phage λ to the environment of its host bacteria in the human gut. The metastable DNA state in the capsid provides a new paradigm for the physical evolution of viruses. PMID:26092697

  11. Ionic switch controls the DNA state in phage λ

    PubMed Central

    Li, Dong; Liu, Ting; Zuo, Xiaobing; Li, Tao; Qiu, Xiangyun; Evilevitch, Alex

    2015-01-01

    We have recently found that DNA packaged in phage λ undergoes a disordering transition triggered by temperature, which results in increased genome mobility. This solid-to-fluid like DNA transition markedly increases the number of infectious λ particles facilitating infection. However, the structural transition strongly depends on temperature and ionic conditions in the surrounding medium. Using titration microcalorimetry combined with solution X-ray scattering, we mapped both energetic and structural changes associated with transition of the encapsidated λ-DNA. Packaged DNA needs to reach a critical stress level in order for transition to occur. We varied the stress on DNA in the capsid by changing the temperature, packaged DNA length and ionic conditions. We found striking evidence that the intracapsid DNA transition is ‘switched on’ at the ionic conditions mimicking those in vivo and also at the physiologic temperature of infection at 37°C. This ion regulated on-off switch of packaged DNA mobility in turn affects viral replication. These results suggest a remarkable adaptation of phage λ to the environment of its host bacteria in the human gut. The metastable DNA state in the capsid provides a new paradigm for the physical evolution of viruses. PMID:26092697

  12. Protein Crystallization Using Room Temperature Ionic Fluids

    NASA Technical Reports Server (NTRS)

    Pusey, Marc L.; Paley, Mark Steve; Turner, Megan B.; Rogers, Robin D.

    2006-01-01

    The ionic liquids (ILs) 1-butyl-3-methylimidizolium chloride (C4mim-C1), 1-butyl-3- methylimidizolium diethyleneglycol monomethylethersulfate ([C4mim]DEMGS), and 1-butyl-1 -methylpyrollidinium dihydrogenphosphate ([p1,4]dhp) were tested for their effects on the crystallization of the proteins canavalin, beta-lactoglobulin B, xylanase, and glucose isomerase, using a standard high throughput screen. The crystallization experiments were set up with the ILs added to the protein solutions at 0.2 and 0.4 M final concentrations. Crystallization droplets were set up at three proteixprecipitant ratios (1:1, 2:1, and 4:l), which served to progressively dilute the effects of the screen components while increasing the equilibrium protein and IL concentrations. Crystals were obtained for all four proteins at a number of conditions where they were not obtained from the IL-free control experiment. Over half of the protein-IL combinations tested had more successful outcomes than negative, where the IL-free crystallization was better than the corresponding IL-containing outcome, relative to the control. One of the most common causes of a negative outcome was solubilization of the protein by the IL, resulting in a clear drop. In one instance, we were able to use the IL-induced solubilizing to obtain beta-lactoglobulin B crystals from conditions that gave precipitated protein in the absence of IL. The results suggest that it may be feasible to develop ILs specifically for the task of macromolecule crystallization.

  13. Ultrafiltration modeling of non-ionic microgels.

    PubMed

    Roa, Rafael; Zholkovskiy, Emiliy K; Nägele, Gerhard

    2015-05-28

    Membrane ultrafiltration (UF) is a pressure driven process allowing for the separation and enrichment of protein solutions and dispersions of nanosized microgel particles. The permeate flux and the near-membrane concentration-polarization (CP) layer in this process is determined by advective-diffusive dispersion transport and the interplay of applied and osmotic transmembrane pressure contributions. The UF performance is thus strongly dependent on the membrane properties, the hydrodynamic structure of the Brownian particles, their direct and hydrodynamic interactions, and the boundary conditions. We present a macroscopic description of cross-flow UF of non-ionic microgels modeled as solvent-permeable spheres. Our filtration model involves recently derived semi-analytic expressions for the concentration-dependent collective diffusion coefficient and viscosity of permeable particle dispersions [Riest et al., Soft Matter, 2015, 11, 2821]. These expressions have been well tested against computer simulation and experimental results. We analyze the CP layer properties and the permeate flux at different operating conditions and discuss various filtration process efficiency and cost indicators. Our results show that the proper specification of the concentration-dependent transport coefficients is important for reliable filtration process predictions. We also show that the solvent permeability of microgels is an essential ingredient to the UF modeling. The particle permeability lowers the particle concentration at the membrane surface, thus increasing the permeate flux. PMID:25921331

  14. Variational modeling of ionic polymer plate structures

    NASA Astrophysics Data System (ADS)

    Buechler, Miles A.; Leo, Donald J.

    2006-03-01

    Ionomeric polymers are a promising class of intelligent material which exhibit electromechanical coupling similar to that of piezoelectric bimorphs. Ionomeric polymers are much more compliant than piezoelectric ceramics or polymers and have been shown to produce actuation strain on the order of 5% at operating voltages between 1 V and 5 V. This performance indicates the potential for self-actuating devices manufactured from ionomeric polymers, such as deformable mirrors or low pressure pump diaphragms. This paper presents a variational approach to the dynamic modeling of ionic polymer plates in rectangular coordinates. A linear matrix equation, which relates displacement and charge to applied forces and voltage, is developed to determine the response of the structure to applied forces and applied potentials. The modeling method is based on the incorporation of empirically determined material properties, which have been shown to be highly frequency dependent. The matrices are calculated at discrete frequencies and solved frequency-by-frequency to determine the response of the ionomeric plate structures. A model of a thin rectangular plate is developed and validated experimentally. Simulated frequency response functions are compared to experimental results for several locations on the plate. The response of the plate at certain frequencies is computed and compared to experimentally-determined response shapes. The results demonstrate the validity of the modeling approach in predicting the dynamic response of the ionomeric plate structure. These spatial solutions are also compared to experimentally determined response shapes.

  15. Li(+) solvation in glyme-Li salt solvate ionic liquids.

    PubMed

    Ueno, Kazuhide; Tatara, Ryoichi; Tsuzuki, Seiji; Saito, Soshi; Doi, Hiroyuki; Yoshida, Kazuki; Mandai, Toshihiko; Matsugami, Masaru; Umebayashi, Yasuhiro; Dokko, Kaoru; Watanabe, Masayoshi

    2015-03-28

    Certain molten complexes of Li salts and solvents can be regarded as ionic liquids. In this study, the local structure of Li(+) ions in equimolar mixtures ([Li(glyme)]X) of glymes (G3: triglyme and G4: tetraglyme) and Li salts (LiX: lithium bis(trifluoromethanesulfonyl)amide (Li[TFSA]), lithium bis(pentafluoroethanesulfonyl)amide (Li[BETI]), lithium trifluoromethanesulfonate (Li[OTf]), LiBF4, LiClO4, LiNO3, and lithium trifluoroacetate (Li[TFA])) was investigated to discriminate between solvate ionic liquids and concentrated solutions. Raman spectra and ab initio molecular orbital calculations have shown that the glyme molecules adopt a crown-ether like conformation to form a monomeric [Li(glyme)](+) in the molten state. Further, Raman spectroscopic analysis allowed us to estimate the fraction of the free glyme in [Li(glyme)]X. The amount of free glyme was estimated to be a few percent in [Li(glyme)]X with perfluorosulfonylamide type anions, and thereby could be regarded as solvate ionic liquids. Other equimolar mixtures of [Li(glyme)]X were found to contain a considerable amount of free glyme, and they were categorized as traditional concentrated solutions. The activity of Li(+) in the glyme-Li salt mixtures was also evaluated by measuring the electrode potential of Li/Li(+) as a function of concentration, by using concentration cells against a reference electrode. At a higher concentration of Li salt, the amount of free glyme diminishes and affects the electrode reaction, leading to a drastic increase in the electrode potential. Unlike conventional electrolytes (dilute and concentrated solutions), the significantly high electrode potential found in the solvate ILs indicates that the solvation of Li(+) by the glyme forms stable and discrete solvate ions ([Li(glyme)](+)) in the molten state. This anomalous Li(+) solvation may have a great impact on the electrode reactions in Li batteries. PMID:25733406

  16. Physicochemical Properties of Imidazolium-derived Ionic Liquids with Different C-2 Substitutions

    SciTech Connect

    Liao, Chen; Shao, Nan; Han, Kee Sung; Sun, Xiao-Guang; Jiang, Deen; Hagaman, Edward {Ed} W; Dai, Sheng

    2011-01-01

    Five room temperature ionic liquids based on C-2 substituted imidazolium cations and bis(trifluoromethanesulfonyl)imide (TFSI) anion were synthesized and their physicochemical properties: thermal property, density, viscosity, ionic conductivity, self-diffusion coefficients, and electrochemical stability were systematically investigated. The temperature dependence of both viscosity and ionic conductivities of these ionic liquids can be described by Vogel-Fulcher-Tamman (VFT) equation. Compared with the reference, 1-propyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, the introduction of functional groups at the C-2 position generally increased the viscosity and lowered the ionic conductivity. The introduction of ether group ( CH2OCH2CH2CH2CH3) at the C-2 position not only enhanced the reduction stability of the ionic liquids but also exhibited the lowest solid electrolyte interfacial resistance (RSEI). On the contrary, the introduction of a cyano group ( CN) at the C-2 position not only decreased the reduction stability but also adversely increased the SEI resistance. The effect of the C-2 substitution on the reduction stability was explained by the change of the energy level of the lowest unoccupied molecular orbital. The self-diffusion coefficients (D) of each ion were measured by pulsed field gradient nuclear magnetic resonance (PFG-NMR). The lithium transference number (tLi) of 0.5 M LiTFSI/IL solutions calculated from the self-diffusion coefficients was in the range of 0.04 and 0.09.

  17. Efficient separation of transition metals from rare earths by an undiluted phosphonium thiocyanate ionic liquid.

    PubMed

    Rout, Alok; Binnemans, Koen

    2016-06-21

    The ionic liquid trihexyl(tetradecyl)phosphonium thiocyanate has been used for the extraction of the transition metal ions Co(ii), Ni(ii), Zn(ii), and the rare-earth ions La(iii), Sm(iii) and Eu(iii) from aqueous solutions containing nitrate or chloride salts. The transition metal ions showed a high affinity for the ionic liquid phase and were efficiently extracted, while the extraction efficiency of the rare-earth ions was low. This difference in extraction behavior enabled separation of the pairs Co(ii)/Sm(iii), Ni(ii)/La(iii) and Zn(ii)/Eu(iii). These separations are relevant for the recycling of rare earths and transition metals from samarium cobalt permanent magnets, nickel metal hydride batteries and lamp phosphors, respectively. The extraction of metal ions from a chloride or nitrate solution with a thiocyanate ionic liquid is an example of "split-anion extraction", where different anions are present in the aqueous and ionic liquid phase. Close to 100% loading was possible for Co(ii) and Zn(ii) up to a concentration of 40 g L(-1) of the transition metal salt in the initial aqueous feed solution, whereas the extraction efficiency for Ni(ii) gradually decreased with increase in the initial feed concentration. Stripping of Co(ii), Zn(ii) and Ni(ii) from the loaded ionic liquid phase was possible by a 15 wt% NH3 solution. The ionic liquid could reused after extraction and stripping. PMID:27243450

  18. Lithium-Air and ionic Liquids

    SciTech Connect

    Kellar, Michael

    2015-09-01

    The final portion of this project was accomplished at Sandia National Labs, Livermore, with the overall goal being to optimize lithium-air cells with an ionic liquid electrolyte. Both of these are potential future routes for lithium-ion technology. Lithiumair presents the advantage of higher gravimetric energy density, and ionic liquids present the advantage of greater hydrophobicity and much lower volatility, along with a larger window of electrochemical stability. Ionic liquids however have several drawbacks for the battery industry. Currently they are not as cost effective as many organic solvents. Additionally, because of the added viscosity of ionic interactions compared to the typical dipole interactions of a solvent, the ionic conductivity is lower than for common organic solvents.

  19. Ionic liquid incorporating thiosalicylate for metal removal

    NASA Astrophysics Data System (ADS)

    Wilfred, Cecilia Devi; Mustafa, Fadwa Babiker; Romeli, Fatimah Julia

    2012-09-01

    Ionic liquids are a class of organic molten salts "designer solvents" that are composed totally of anions (inorganic and organic polyatomic) and organic cations. The replacement of volatile organic solvents from a separation process is of utmost importance since the use of a large excess of these solvents is hazardous and creates ecological problem. The new method for metal ion extraction is by using task-specific ionic liquids such as ionic liquids which incorporate thiosalicylate functionality. This paper looks at producing a new cluster of ionic liquids which incorporates thiosalicylate with pyridinium cation. Its thermophysical properties such as density and viscosity in single and binary mixtures are studied. The ionic liquids' capability in metal removal processes is evaluated.

  20. Design Strategy for High-Performance Dendritic Carbazole-Containing Alkynylplatinum(II) Complexes and Their Application in Solution-Processable Organic Light-Emitting Devices.

    PubMed

    Kong, Fred Ka-Wai; Tang, Man-Chung; Wong, Yi-Chun; Chan, Mei-Yee; Yam, Vivian Wing-Wah

    2016-05-18

    A new class of luminescent dendritic carbazole-containing alkynylplatinum(II) complexes has been synthesized, characterized, and applied as phosphorescent dopants in the fabrication of solution-processable organic light-emitting devices (OLEDs). These complexes exhibit high photoluminescence quantum yields of up to 80% in spin-coated thin films. In addition, the incorporation of carbazole dendrons into the platinum(II) center can significantly suppress intermolecular interactions in solid-state thin films, giving rise to emission spectra that are similar to those found in solution irrespective of dopant concentrations. High-performance solution-processable OLEDs have also been fabricated, with a maximum external quantum efficiency of up to 10.4%, which is comparable to that of the vacuum-deposited devices based on the small-molecule counterpart. This is one of the highest ever reported values for solution-processable devices based on platinum(II) complexes with tridentate ligands. PMID:27145466