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Sample records for solute solvent interactions

  1. Solvent - solute interaction

    International Nuclear Information System (INIS)

    Urbanczyk, A.; Kalinowski, M.K.

    1983-01-01

    The electronic absorption spectrum of vanadyl acetylacetonate has been studied in 15 organic solvents. It has been found that wavenumbers and molar absorptivities of the long-wavelength bands (d-d transitions) can be well described by a complementary Lewis acid-base model including Gutmann's donor number [Gutmann V., Wychera E., Inorg. Nucl. Chem. Letters 2, 257 (1966)] and acceptor number [Mayer U., Gutmann V., Gerger W., Monatsh. Chem. 106, 1235 (1975)] of a solvent. This model describes also the solvent effect of the hyperfine splitting constant, Asub(iso)( 51 V), from e.s.r. spectra of VOacac 2 . These observations are discussed in terms of the donor-acceptor concept for solvent-solute interactions. (Author)

  2. Influence of Solvent-Solvent and Solute-Solvent Interaction Properties on Solvent-Mediated Potential

    International Nuclear Information System (INIS)

    Zhou Shiqi

    2005-01-01

    A recently proposed universal calculational recipe for solvent-mediated potential is applied to calculate excess potential of mean force between two large Lennard-Jones (LJ) or hard core attractive Yukawa particles immersed in small LJ solvent bath at supercritical state. Comparison between the present prediction with a hypernetted chain approximation adopted for solute-solute correlation at infinitely dilute limit and existing simulation data shows high accuracy for the region with large separation, and qualitative reliability for the solute particle contact region. The calculational simplicity of the present recipe allows for a detailed investigation on the effect of the solute-solvent and solvent-solvent interaction details on the excess potential of mean force. The resultant conclusion is that gathering of solvent particles near a solute particle leads to repulsive excess PMF, while depletion of solvent particles away from the solute particle leads to attractive excess PMF, and minor change of the solvent-solvent interaction range has large influence on the excess PMF.

  3. Solute-solvent interactions and dynamics probed by THz light

    Science.gov (United States)

    Schwaab, Gerhard; Böhm, Fabian; Ma, Chun-Yu; Havenith, Martina

    The THz range (1-12 THz, 30-400 cm-1) is especially suited to probe changes in the solvent dynamics induced by solutes of different character (hydrophobic, hydrophilic, charged, neutral). In recent years we have investigated a large variety of such solutes and found characteristic spectral fingerprints for ions, but also for uncharged solutes, such as alcohols. We will present a status report on our current understanding of the observed spectral changes and how they relate to physico-chemical parameters like hydration shell size or the lifetime of an excited intermolecular oscillation. In addition, we will show, that in some cases the spectral changes are closely related to the partition function yielding access to a microscopic understanding of macroscopic thermodynamic functions. The authors gratefully acknowledge financial support from the Cluster of Excellence RESOLV (Ruhr-Universität, EXC1069) funded by the Deutsche Forschungsgemeinschaft.

  4. Dynamical interactions between solute and solvent studied by nonlinear infrared spectroscopy

    International Nuclear Information System (INIS)

    Ohta, K.; Tominaga, K.

    2006-01-01

    Interactions between solute and solvent play an important role in chemical reaction dynamics and in many relaxation processes in condensed phases. Recently third-order nonlinear infrared (IR) spectroscopy has shown to be useful to investigate solute-solvent interaction and dynamics of the vibrational transition. These studies provide detailed information on the energy relaxation of the vibrationally excited state, and the time scale and the magnitude of the time correlation functions of the vibrational frequency fluctuations. In this work we have studied vibrational energy relaxation (VER) of solutions and molecular complexes by nonlinear IR spectroscopy, especially IR pump-probe method, to understand the microscopic interactions in liquids. (authors)

  5. Solvent wash solution

    International Nuclear Information System (INIS)

    Neace, J.C.

    1986-01-01

    This patent describes a process for removing diluent degradation products from a solvent extraction solution comprising an admixture of an organic extractant for uranium and plutonium and a non-polar organic liquid diluent, which has been used to recover uranium and plutonium from spent nuclear fuel. Comprising combining a wash solution consisting of: (a) water; and (b) a positive amount up to about, an including, 50 volume percent of at least one highly-polar water-miscible organic solvent, based on the total volume of the water and the highly-polar organic solvent, with the solvent extraction solution after uranium and plutonium values have been stripped from the solvent extraction solution, the diluent degradation products dissolving in the highly-polar organic solvent and the extractant and diluent of the extraction solution not dissolving in the highly-polar organic solvent, and separating the highly-polar organic solvent and the extraction solution to obtain a purified extraction solution

  6. Friction of N-bead macromolecules in solution: Effects of the bead-solvent interaction

    International Nuclear Information System (INIS)

    Uvarov, Alexander; Fritzsche, Stephan

    2006-01-01

    The role of the bead-solvent interaction has been studied for its influence on the dynamics of an N-bead macromolecule which is immersed into a solution. Using a Fokker-Planck equation for the phase-space distribution function of the macromolecule, we show that all the effects of the solution can be treated entirely in terms of the friction tensors which are assigned to each pair of interacting beads in the chain. For the high-density as well as for the critical solvent, the properties of these tensors are discussed in detail and are calculated by using several (realistic) choices of the bead-solvent potential. From the friction tensors, moreover, an expression for the center-of-mass friction coefficient of a (N-bead) chain macromolecule is derived. Numerical data for this coefficient for 'truncated' Lennard-Jones bead-solvent potential are compared with results from molecular dynamic simulations and from the phenomenological theoretical data as found in the literature

  7. 3DRISM-HI-D2MSA: an improved analytic theory to compute solvent structure around hydrophobic solutes with proper treatment of solute–solvent electrostatic interactions

    Science.gov (United States)

    Cao, Siqin; Zhu, Lizhe; Huang, Xuhui

    2018-04-01

    The 3D reference interaction site model (3DRISM) is a powerful tool to study the thermodynamic and structural properties of liquids. However, for hydrophobic solutes, the inhomogeneity of the solvent density around them poses a great challenge to the 3DRISM theory. To address this issue, we have previously introduced the hydrophobic-induced density inhomogeneity theory (HI) for purely hydrophobic solutes. To further consider the complex hydrophobic solutes containing partial charges, here we propose the D2MSA closure to incorporate the short-range and long-range interactions with the D2 closure and the mean spherical approximation, respectively. We demonstrate that our new theory can compute the solvent distributions around real hydrophobic solutes in water and complex organic solvents that agree well with the explicit solvent molecular dynamics simulations.

  8. 3DRISM-HI-D2MSA: an improved analytic theory to compute solvent structure around hydrophobic solutes with proper treatment of solute–solvent electrostatic interactions

    KAUST Repository

    Cao, Siqin

    2017-12-22

    The 3D reference interaction site model (3DRISM) is a powerful tool to study the thermodynamic and structural properties of liquids. However, for hydrophobic solutes, the inhomogeneity of the solvent density around them poses a great challenge to the 3DRISM theory. To address this issue, we have previously introduced the hydrophobic-induced density inhomogeneity theory (HI) for purely hydrophobic solutes. To further consider the complex hydrophobic solutes containing partial charges, here we propose the D2MSA closure to incorporate the short-range and long-range interactions with the D2 closure and the mean spherical approximation, respectively. We demonstrate that our new theory can compute the solvent distributions around real hydrophobic solutes in water and complex organic solvents that agree well with the explicit solvent molecular dynamics simulations.

  9. 3DRISM-HI-D2MSA: an improved analytic theory to compute solvent structure around hydrophobic solutes with proper treatment of solute–solvent electrostatic interactions

    KAUST Repository

    Cao, Siqin; Zhu, Lizhe; Huang, Xuhui

    2017-01-01

    The 3D reference interaction site model (3DRISM) is a powerful tool to study the thermodynamic and structural properties of liquids. However, for hydrophobic solutes, the inhomogeneity of the solvent density around them poses a great challenge to the 3DRISM theory. To address this issue, we have previously introduced the hydrophobic-induced density inhomogeneity theory (HI) for purely hydrophobic solutes. To further consider the complex hydrophobic solutes containing partial charges, here we propose the D2MSA closure to incorporate the short-range and long-range interactions with the D2 closure and the mean spherical approximation, respectively. We demonstrate that our new theory can compute the solvent distributions around real hydrophobic solutes in water and complex organic solvents that agree well with the explicit solvent molecular dynamics simulations.

  10. Wetting behavior of nonpolar nanotubes in simple dipolar liquids for varying nanotube diameter and solute-solvent interactions

    Energy Technology Data Exchange (ETDEWEB)

    Rana, Malay Kumar; Chandra, Amalendu, E-mail: amalen@iitk.ac.in [Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016 (India)

    2015-01-21

    Atomistic simulations of model nonpolar nanotubes in a Stockmayer liquid are carried out for varying nanotube diameter and nanotube-solvent interactions to investigate solvophobic interactions in generic dipolar solvents. We have considered model armchair type single-walled nonpolar nanotubes with increasing radii from (5,5) to (12,12). The interactions between solute and solvent molecules are modeled by the well-known Lennard-Jones and repulsive Weeks-Chandler-Andersen potentials. We have investigated the density profiles and microscopic arrangement of Stockmayer molecules, orientational profiles of their dipole vectors, time dependence of their occupation, and also the translational and rotational motion of solvent molecules in confined environments of the cylindrical nanopores and also in their external peripheral regions. The present results of structural and dynamical properties of Stockmayer molecules inside and near atomistically rough nonpolar surfaces including their wetting and dewetting behavior for varying interactions provide a more generic picture of solvophobic effects experienced by simple dipolar liquids without any specific interactions such as hydrogen bonds.

  11. Interaction between like-charged colloidal particles in aqueous electrolyte solution: Attractive component arising from solvent granularity

    Directory of Open Access Journals (Sweden)

    R.Akiyama

    2007-12-01

    Full Text Available The potential of mean force (PMF between like-charged colloidal particles immersed in aqueous electrolyte solution is studied using the integral equation theory. Solvent molecules are modeled as neutral hard spheres, and ions and colloidal particles are taken to be charged hard spheres. The Coulomb potentials for ion-ion, ion-colloidal particle, and colloidal particle-colloidal particle pairs are divided by the dielectric constant of water. This simple model is employed to account for the effects of solvent granularity neglected in the so-called primitive model. The van der Waals attraction between colloidal particles, which is an essential constituent of conventional DLVO theory, is omitted in the present model. Nevertheless, when the electrolyte concentration is sufficiently high, attractive regions appear in the PMF. In particular, the interaction at small separations is significantly attractive and the contact of colloidal particles is stabilized. This interesting behavior arises from the effects of the translational motion of solvent molecules.

  12. Volumetric, ultrasonic and viscometric studies of solute–solute and solute–solvent interactions of l-threonine in aqueous-sucrose solutions at different temperatures

    International Nuclear Information System (INIS)

    Nain, Anil Kumar; Pal, Renu; Neetu

    2013-01-01

    Highlights: • The study reports density, ultrasonic speed and viscosity data of l-threonine in aqueous-sucrose solutions. • The study elucidates interactions of l-threonine with sucrose in aqueous media. • Provides data to estimate physicochemical properties of proteins in these media. • Correlates physicochemical properties of l-threonine with its behaviour in aqueous-sucrose solutions. -- Abstract: Densities, ρ of solutions of l-threonine in aqueous-sucrose solvents 5%, 10%, 15%, and 20% of sucrose, w/w in water at T = (293.15, 298.15, 303.15, 308.15, 313.15, and 318.15) K; and ultrasonic speeds, u and viscosities, η of these solutions at 298.15, 303.15, 308.15, 313.15, and 318.15 K were measured at atmospheric pressure. From these experimental results, the apparent molar volume, V ϕ , limiting apparent molar volume, V ϕ ∘ and the slope, S v , apparent molar compressibility, K s,ϕ , limiting apparent molar compressibility, K s,ϕ ∘ and the slope, S k , transfer volume, V ϕ,tr ∘ , transfer compressibility, K s,ϕ,tr ∘ , limiting apparent molar expansivity, E ϕ ∘ , Hepler’s constant, (∂ 2 V ϕ ∘ /dT 2 ), Falkenhagen coefficient, A, Jones–Dole coefficient, B and hydration number, n H have been calculated. The results have been interpreted in terms of solute–solvent and solute–solute interactions in these systems. The Gibbs energies of activation of viscous flow per mole of solvent, Δμ 1 ∘number sign and per mole of solute, Δμ 2 ∘number sign were also calculated and discussed in terms of transition state theory. It has been observed that there exist strong solute–solvent interactions in these systems and these interactions increase with increase in sucrose concentration in solution

  13. Reference interaction site model with hydrophobicity induced density inhomogeneity: An analytical theory to compute solvation properties of large hydrophobic solutes in the mixture of polyatomic solvent molecules

    International Nuclear Information System (INIS)

    Cao, Siqin; Sheong, Fu Kit; Huang, Xuhui

    2015-01-01

    Reference interaction site model (RISM) has recently become a popular approach in the study of thermodynamical and structural properties of the solvent around macromolecules. On the other hand, it was widely suggested that there exists water density depletion around large hydrophobic solutes (>1 nm), and this may pose a great challenge to the RISM theory. In this paper, we develop a new analytical theory, the Reference Interaction Site Model with Hydrophobicity induced density Inhomogeneity (RISM-HI), to compute solvent radial distribution function (RDF) around large hydrophobic solute in water as well as its mixture with other polyatomic organic solvents. To achieve this, we have explicitly considered the density inhomogeneity at the solute-solvent interface using the framework of the Yvon-Born-Green hierarchy, and the RISM theory is used to obtain the solute-solvent pair correlation. In order to efficiently solve the relevant equations while maintaining reasonable accuracy, we have also developed a new closure called the D2 closure. With this new theory, the solvent RDFs around a large hydrophobic particle in water and different water-acetonitrile mixtures could be computed, which agree well with the results of the molecular dynamics simulations. Furthermore, we show that our RISM-HI theory can also efficiently compute the solvation free energy of solute with a wide range of hydrophobicity in various water-acetonitrile solvent mixtures with a reasonable accuracy. We anticipate that our theory could be widely applied to compute the thermodynamic and structural properties for the solvation of hydrophobic solute

  14. Solvents interactions with thermochromic print

    Directory of Open Access Journals (Sweden)

    Mirela Rožić

    2017-12-01

    Full Text Available In this study, the interactions between different solvents (benzene, acetone, cyclohexanone, various alcohols and water and thermochromic printing ink were investigated. Thermochromic printing ink was printed on metal surface. Components of thermochromic printing inks are polymeric microcapsules and classic yellow offset printing ink. Below its activation temperature, dye and developer within the microcapsules form a blue coloured complex. Therefore, thermochromic print is green. By heating above the activation temperature, blue colour of the complex turns into the leuco dye colourless state and the green colour of the prints turns into the yellow colour of the classic offset pigment. The results of the interaction with various solvents show that the thermochromic print is stable in all tested solvents except in ethanol, acetone and cyclohexanone. In ethanol, the green colour of the print becomes yellow. SEM analysis shows that microcapsules are dissolved. In acetone and cyclohexanone, the green colour of the print turns into blue, and the microcapsules become significantly more visible. Thus, the yellow pigment interacts with examined ketones. Based on the obtained interactions it can be concluded that the microcapsules have more polar nature than the classical pigment particles. Solvent-thermocromic print interactions were analysed using Hansen solubility parameters that rank the solvents based on their estimated interaction capabilities.

  15. Crystal Nucleation of Tolbutamide in Solution: Relationship to Solvent, Solute Conformation, and Solution Structure.

    Science.gov (United States)

    Zeglinski, Jacek; Kuhs, Manuel; Khamar, Dikshitkumar; Hegarty, Avril C; Devi, Renuka K; Rasmuson, Åke C

    2018-04-03

    The influence of the solvent in nucleation of tolbutamide, a medium-sized, flexible and polymorphic organic molecule, has been explored by measuring nucleation induction times, estimating solvent-solute interaction enthalpies using molecular modelling and calorimetric data, probing interactions and clustering with spectroscopy, and modelling solvent-dependence of molecular conformation in solution. The nucleation driving force required to reach the same induction time is strongly solvent-dependent, increasing in the order: acetonitrilenucleation difficulty is a function of the strength of solvent-solute interaction, with emphasis on the interaction with specific H-bonding polar sites of importance in the crystal structure. A clear exception from this rule is the most difficult nucleation in toluene despite the weakest solvent-solute interactions. However molecular dynamics modelling predicts that tolbutamide assumes an intramolecularly H-bonded conformation in toluene, substantially different from and more stable than the conformation in the crystal structure, and thus presenting an additional barrier to nucleation. This explains why nucleation in toluene is the most difficult and why the relatively higher propensity for aggregation of tolbutamide molecules in toluene solution, as observed with FTIR spectroscopy, does not translate into easier nucleation. Thus, our combined experimental and molecular modelling study suggests that the solvent can influence on the nucleation not only via differences in the desolvation but also through the influence on molecular conformation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. One pot obtention of a tetrabutylammonium hydroxide solution for ironporphyrin-OH- interaction studies in organic solvents

    Directory of Open Access Journals (Sweden)

    Lídia S. Iwamoto

    1999-04-01

    Full Text Available In this work we report the obtention of a tetrabutylammonium hydroxide (TBAOH solution in acetonitrile in a one pot process in order to study the interaction ironporphyrinOH- in non-aqueous systems. All the reactions were carried out under dry argon atmosphere to prevent the contamination of the solution with CO2, which leads to the formation of (TBA2CO3.

  17. Effects of solvent-solute interactions on the stereochemical course in high energy chlorine-38-for chlorine substitution in meso- and rac-1,2-dichloro-1,2-difluoroethane in solution

    International Nuclear Information System (INIS)

    Acciani, T.R.; Su, Y.Y.; Ache, H.J.; Rack, E.P.

    1978-01-01

    The stereochemistry of the chlorine-38-for-chlorine substitution was studied in diastereomeric 1,2-dichloro-1,2-difluoroethanes in solutions. The experimental results are very similar to those previously observed in meso- and d,l-2,4-dichloropentane solutions which by analogy suggest that the stereochemical course of the substitution process is in the present system also predominantly and directly controlled by the properties of the solvent molecules, most likely by the factors which govern the magnitude of intermolecular interaction between reactants and solvents. It appears that strong intermolecular interaction favors substitution via retention of configuration, whereas in solvents having a low dielectric constant the retention/inversion ratio decreases. These results seem further to suggest that if the reaction occurs via the previously postulated caged complex or excited intermediate that the primary attack by the energetic 38 Cl proceeds via both front and backside replacement

  18. The effect of specific solvent-solute interactions on complexation of alkali-metal cations by a lower-rim calix[4]arene amide derivative.

    Science.gov (United States)

    Horvat, Gordan; Stilinović, Vladimir; Kaitner, Branko; Frkanec, Leo; Tomišić, Vladislav

    2013-11-04

    the results of MD simulations, the probability of such orientation of the benzonitrile molecule included in the ligand cone was by far the largest in the case of LiL(+) complex. Because of the favorable PhCN-Li(+) interaction, L was proven to have the highest affinity toward the lithium ion in benzonitrile, which was not the case in the other solvents examined (in acetonitrile, sodium complex was the most stable, whereas in methanol, complexation of lithium was not even observed). That could serve as a remarkable example showing the importance of specific solvent-solute interactions in determining the equilibrium in solution.

  19. Activity coefficients of solutes in binary solvents

    International Nuclear Information System (INIS)

    Gokcen, N.A.

    1982-01-01

    The activity coefficients in dilute ternary systems are discussed in detail by using the Margules equations. Analyses of some relevant data at high temperatures show that the sparingly dissolved solutes in binary solvents follow complex behavior even when the binary solvents are very nearly ideal. It is shown that the activity data on the solute or the binary system cannot permit computation of the remaining activities except for the regular solutions. It is also shown that a fourth-order equation is usually adequate in expressing the activity coefficient of a solute in binary solvents at high temperatures. When the activity data for a binary solvent are difficult to obtain in a certain range of composition, the activity data for a sparingly dissolved solute can be used to supplement determination of the binary activities

  20. Structuring of polymer solutions upon solvent evaporation

    NARCIS (Netherlands)

    Schaefer, C.; van der Schoot, P.|info:eu-repo/dai/nl/102140618; Michels, J. J.

    2015-01-01

    The morphology of solution-cast, phase-separated polymers becomes finer with increasing solvent evaporation rate. We address this observation theoretically for a model polymer where demixing is induced by steady solvent evaporation. In contrast to what is the case for a classical, thermal quench

  1. Ions, solutes and solvents, oh my!

    Energy Technology Data Exchange (ETDEWEB)

    Kemp, Daniel David [Iowa State Univ., Ames, IA (United States)

    2009-08-01

    Modern methods in ab initio quantum mechanics have become efficient and accurate enough to study many gas-phase systems. However, chemists often work in the solution phase. The presence of solvent molecules has been shown to affect reaction mechanisms1, lower reaction energy barriers2, participate in energy transfer with the solute3 and change the physical properties of the solute4. These effects would be overlooked in simple gas phase calculations. Careful study of specific solvents and solutes must be done in order to fully understand the chemistry of the solution phase. Water is a key solvent in chemical and biological applications. The properties of an individual water molecule (a monomer) and the behavior of thousands of molecules (bulk solution) are well known for many solvents. Much is also understood about aqueous microsolvation (small clusters containing ten water molecules or fewer) and the solvation characteristics when bulk water is chosen to solvate a solute. However, much less is known about how these properties behave as the cluster size transitions from the microsolvated cluster size to the bulk. This thesis will focus on species solvated with water clusters that are large enough to exhibit the properties of the bulk but small enough to consist of fewer than one hundred solvent molecules. New methods to study such systems will also be presented.

  2. Solute-solvent interactions in solutions of 2-hydroxy-5-chloro-3-nitroacetophenone isonicotinoylhydrazone in N, N-dimethylformamide at 298-313 K according to ultrasonic and viscometric data

    Science.gov (United States)

    Dikkar, A. B.; Pethe, G. B.; Aswar, A. S.

    2015-12-01

    Density (ρ), speed of sound ( u), and viscosity (η), measurements have been carried on 2-hydroxy- 5-chloro-3-nitroacetophenone isonicotinoylhydrazone (HCNAIH) in N, N-dimethylformamide at 298.15, 303.15, 308.15, and 313.15 K. Adiabatic compressibility (βs), intermolecular free length ( L f), acoustic impedance ( Z), internal pressure ( P int), the apparent molar volume ( V w), limiting apparent molar volume ( V w 0), partial molar expansibility (wE 0), apparent molar adiabatic compressibility ( K w), limiting apparent molar adiabatic compressibility ( K w 0), viscosity B coefficients of Jones-Dole equation have been calculated. The activation free energy (Δμ 2 0 *) for viscous flow in solution have been calculated from B coefficient and partial molar volume data. The calculated parameters are used to interpret the solute-solvent interactions and structure forming/breaking ability of solute in DMF.

  3. Molecular near-field antenna effect in resonance hyper-Raman scattering: Intermolecular vibronic intensity borrowing of solvent from solute through dipole-dipole and dipole-quadrupole interactions

    Energy Technology Data Exchange (ETDEWEB)

    Shimada, Rintaro; Hamaguchi, Hiro-o, E-mail: hhama@nctu.edu.tw [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 University Road, Hsinchu 30010, Taiwan (China)

    2014-05-28

    We quantitatively interpret the recently discovered intriguing phenomenon related to resonance Hyper-Raman (HR) scattering. In resonance HR spectra of all-trans-β-carotene (β-carotene) in solution, vibrations of proximate solvent molecules are observed concomitantly with the solute β-carotene HR bands. It has been shown that these solvent bands are subject to marked intensity enhancements by more than 5 orders of magnitude under the presence of β-carotene. We have called this phenomenon the molecular-near field effect. Resonance HR spectra of β-carotene in benzene, deuterated benzene, cyclohexane, and deuterated cyclohexane have been measured precisely for a quantitative analysis of this effect. The assignments of the observed peaks are made by referring to the infrared, Raman, and HR spectra of neat solvents. It has been revealed that infrared active and some Raman active vibrations are active in the HR molecular near-field effect. The observed spectra in the form of difference spectra (between benzene/deuterated benzene and cyclohexane/deuterated cyclohexane) are quantitatively analyzed on the basis of the extended vibronic theory of resonance HR scattering. The theory incorporates the coupling of excited electronic states of β-carotene with the vibrations of a proximate solvent molecule through solute–solvent dipole–dipole and dipole–quadrupole interactions. It is shown that the infrared active modes arise from the dipole–dipole interaction, whereas Raman active modes from the dipole–quadrupole interaction. It is also shown that vibrations that give strongly polarized Raman bands are weak in the HR molecular near-field effect. The observed solvent HR spectra are simulated with the help of quantum chemical calculations for various orientations and distances of a solvent molecule with respect to the solute. The observed spectra are best simulated with random orientations of the solvent molecule at an intermolecular distance of 10 Å.

  4. Recovery of plutonium from solvent wash solutions

    International Nuclear Information System (INIS)

    Kyser, E.A.

    1992-01-01

    A number of potential alternatives to the acid hydrolysis recovery of Pu were investigated. The most promising alternative for short-term use appears to be an anion exchange process that would eliminate the long boiling times and the multiple-pass concentration steps needed with the solvent extraction process because it separates the Pu from the dibutyl phosphate (DBP) while at the same time concentrating the Pu. However, restart of the Primary Recovery Column (PRC) to process this solution would require significant administrative effort. The original boiling recovery by acid hydrolysis followed by solvent extraction is probably the most expedient way to process the Pu-DBP-carbonate solution currently stored in tank 13.5 even with its long processing times and dilute product concentration. Anion exchange of a heat stabilized acidified solution is a more efficient process, but requires restart of the PRC. Extended-boiling acid hydrolysis or anion exchange of a heat stabilized acidified solution provide two well developed alternatives for recovery of the Pu from the tank 13.5 carbonate. Further work defining additional recovery processes is not planned at this time

  5. Kinetics of hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in binary water-cosolvent mixtures; the role of solvent activity and solute-solute interactions

    NARCIS (Netherlands)

    Rispens, T; Cabaleiro-Lago, C; Engberts, JBFN

    2005-01-01

    Rate constants are reported for the pH-independent hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in aqueous solution as a function of the concentration of added cyanomethane ( acetonitrile), polyethylene glycol ( PEG 400) and tetrahydrofuran ( THF). The concentration of water was varied

  6. Kinetics of hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in binary water-cosolvent mixtures; the role of solvent activity and solute-solute interactions

    NARCIS (Netherlands)

    Rispens, Theo; Cabaleiro-Lago, Celia; Engberts, Jan B. F. N.

    2005-01-01

    Rate constants are reported for the pH-independent hydrolysis of 4-methoxyphenyl-2,2-dichloroethanoate in aqueous solution as a function of the concentration of added cyanomethane (acetonitrile), polyethylene glycol (PEG 400) and tetrahydrofuran (THF). The concentration of water was varied between

  7. STABILITY OF A CYLINDRICAL SOLUTE-SOLVENT INTERFACE: EFFECT OF GEOMETRY, ELECTROSTATICS, AND HYDRODYNAMICS.

    Science.gov (United States)

    Li, B O; Sun, Hui; Zhou, Shenggao

    The solute-solvent interface that separates biological molecules from their surrounding aqueous solvent characterizes the conformation and dynamics of such molecules. In this work, we construct a solvent fluid dielectric boundary model for the solvation of charged molecules and apply it to study the stability of a model cylindrical solute-solvent interface. The motion of the solute-solvent interface is defined to be the same as that of solvent fluid at the interface. The solvent fluid is assumed to be incompressible and is described by the Stokes equation. The solute is modeled simply by the ideal-gas law. All the viscous force, hydrostatic pressure, solute-solvent van der Waals interaction, surface tension, and electrostatic force are balanced at the solute-solvent interface. We model the electrostatics by Poisson's equation in which the solute-solvent interface is treated as a dielectric boundary that separates the low-dielectric solute from the high-dielectric solvent. For a cylindrical geometry, we find multiple cylindrically shaped equilibrium interfaces that describe polymodal (e.g., dry and wet) states of hydration of an underlying molecular system. These steady-state solutions exhibit bifurcation behavior with respect to the charge density. For their linearized systems, we use the projection method to solve the fluid equation and find the dispersion relation. Our asymptotic analysis shows that, for large wavenumbers, the decay rate is proportional to wavenumber with the proportionality half of the ratio of surface tension to solvent viscosity, indicating that the solvent viscosity does affect the stability of a solute-solvent interface. Consequences of our analysis in the context of biomolecular interactions are discussed.

  8. Examination of hydrogen-bonding interactions between dissolved solutes and alkylbenzene solvents based on Abraham model correlations derived from measured enthalpies of solvation

    Energy Technology Data Exchange (ETDEWEB)

    Varfolomeev, Mikhail A.; Rakipov, Ilnaz T. [Chemical Institute, Kazan Federal University, Kremlevskaya 18, Kazan 420008 (Russian Federation); Acree, William E., E-mail: acree@unt.edu [Department of Chemistry, 1155 Union Circle # 305070, University of North Texas, Denton, TX 76203-5017 (United States); Brumfield, Michela [Department of Chemistry, 1155 Union Circle # 305070, University of North Texas, Denton, TX 76203-5017 (United States); Abraham, Michael H. [Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)

    2014-10-20

    Highlights: • Enthalpies of solution measured for 48 solutes dissolved in mesitylene. • Enthalpies of solution measured for 81 solutes dissolved in p-xylene. • Abraham model correlations derived for enthalpies of solvation of solutes in mesitylene. • Abraham model correlations derived for enthalpies of solvation of solutes in p-xylene. • Hydrogen-bonding enthalpies reported for interactions of aromatic hydrocarbons with hydrogen-bond acidic solutes. - Abstract: Enthalpies of solution at infinite dilution of 48 organic solutes in mesitylene and 81 organic solutes in p-xylene were measured using isothermal solution calorimeter. Enthalpies of solvation for 92 organic vapors and gaseous solutes in mesitylene and for 130 gaseous compounds in p-xylene were determined from the experimental and literature data. Abraham model correlations are determined from the experimental enthalpy of solvation data. The derived correlations describe the experimental gas-to-mesitylene and gas-to-p-xylene solvation enthalpies to within average standard deviations of 1.87 kJ mol{sup −1} and 2.08 kJ mol{sup −1}, respectively. Enthalpies of X-H⋯π (X-O, N, and C) hydrogen bond formation of proton donor solutes (alcohols, amines, chlorinated hydrocarbons etc.) with mesitylene and p-xylene were calculated based on the Abraham solvation equation. Obtained values are in good agreement with the results determined using conventional methods.

  9. Solute-solvent interactions in 2,4-dihydroxyacetophenone isonicotinoylhydrazone solutions in N, N-dimethylformamide and dimethyl sulfoxide at 298-313 K on ultrasonic and viscometric data

    Science.gov (United States)

    Dikkar, A. B.; Pethe, G. B.; Aswar, A. S.

    2016-02-01

    The speed of sound ( u), density (ρ), and viscosity (η) of 2,4-dihydroxyacetophenone isonicotinoylhydrazone (DHAIH) have been measured in N, N-dimethyl formamide and dimethyl sulfoxide at equidistance temperatures 298.15, 303.15, 308.15, and 313.15 K. These data were used to calculate some important ultrasonic and thermodynamic parameters such as apparent molar volume ( V ϕ s st ), apparent molar compressibility ( K ϕ), partial molar volume ( V ϕ 0 ) and partial molar compressibility ( K ϕ 0 ), were estimated by using the values of ( V ϕ 0 ) and ( K ϕ), at infinite dilution. Partial molar expansion at infinite dilution, (ϕ E 0 ) has also been calculated from temperature dependence of partial molar volume V ϕ 0 . The viscosity data have been analyzed using the Jones-Dole equation, and the viscosity, B coefficients are calculated. The activation free energy has been calculated from B coefficients and partial molar volume data. The results have been discussed in the term of solute-solvent interaction occurring in solutions and it was found that DHAIH acts as a structure maker in present systems.

  10. The chemistry of nonaqueous solvents v.4 solution phenomena and aprotic solvents

    CERN Document Server

    Lagowski, J J

    1976-01-01

    The Chemistry of Nonaqueous Solvents, Volume IV: Solution Phenomena and Aprotic Solvents focuses on the chemistry of nonaqueous solvents, with emphasis on solution phenomena and aprotic solvents such as tetramethylurea, inorganic acid chlorides, cyclic carbonates, and sulfolane. This book is organized into seven chapters and begins with an overview of the theory of electrical conductivity and elementary experimental considerations, along with some of the interesting research on nonaqueous solvents. It then turns to a discussion on hydrogen bonding phenomena in nonaqueous systems as probed

  11. The influence of ultrasonic waves on molecular structure of high impact polystyrene solutions in different solvents

    International Nuclear Information System (INIS)

    Al-Asaly, S.I.

    1991-01-01

    The aim of the this research is to study some physical properties of polymer solutions of high-impact polystyrene (HIPS) solutions in two different solvents (carbon tetrachloride, xylene) by using ultrasonic technique. Absorption coefficient and velocity of ultrasonic waves through different concentrations of these solutions were measured using ultrasonic pulsed generator at constant frequency (800) KHz. The result implies that there is no chemical interaction between (HIPS) molecules and the solvents. 5 tabs.; 18 figs.; 59 refs

  12. Reformulation of Maxwell's equations to incorporate near-solute solvent structure.

    Science.gov (United States)

    Yang, Pei-Kun; Lim, Carmay

    2008-09-04

    Maxwell's equations, which treat electromagnetic interactions between macroscopic charged objects in materials, have explained many phenomena and contributed to many applications in our lives. Derived in 1861 when no methods were available to determine the atomic structure of macromolecules, Maxwell's equations assume the solvent to be a structureless continuum. However, near-solute solvent molecules are highly structured, unlike far-solute bulk solvent molecules. Current methods cannot treat both the near-solute solvent structure and time-dependent electromagnetic interactions in a macroscopic system. Here, we derive "microscopic" electrodynamics equations that can treat macroscopic time-dependent electromagnetic field problems like Maxwell's equations and reproduce the solvent molecular and dipole density distributions observed in molecular dynamics simulations. These equations greatly reduce computational expense by not having to include explicit solvent molecules, yet they treat the solvent electrostatic and van der Waals effects more accurately than continuum models. They provide a foundation to study electromagnetic interactions between molecules in a macroscopic system that are ubiquitous in biology, bioelectromagnetism, and nanotechnology. The general strategy presented herein to incorporate the near-solute solvent structure would enable studies on how complex cellular protein-ligand interactions are affected by electromagnetic radiation, which could help to prevent harmful electromagnetic spectra or find potential therapeutic applications.

  13. Effect of electrostatic interaction on thermochemical behavior of 12-crown-4 ether in various polar solvents

    International Nuclear Information System (INIS)

    Barannikov, Vladimir P.; Guseynov, Sabir S.; Vyugin, Anatoliy I.

    2010-01-01

    The enthalpies of solution of 12-crown-4 ether have been measured in chloroform, ethyl acetate, acetone, pyridine, acetonitrile and methanol at 298.15 K. The values of enthalpy of solvation and solute-solvent interaction were determined from the obtained results and similar literature data for 12-crown-4 in solvents of various polarities. It was shown that the certain correlation is observed between the enthalpy of solute-solvent interaction and the squared dipole moment of the solvent molecules for solutions in tetrachlormethane, ethyl acetate, pyridine, acetonitrile, DMF, DMSO and propylene carbonate. This means that the electrostatic interaction of 12-crown-4 with polar solvent molecules contributes significantly to the exothermic effect of solvation. The understated negative value was found for the enthalpy of interaction of 12-crown-4 with acetone that can be connected with domination of low polar conformer of the crown ether in acetone medium. The most negative values of enthalpy of solvation are observed for solutions in chloroform and water because of hydrogen bonding between O-atoms of crown ether and molecules of the indicated solvents. This effect is not observed for methanol. The negative coefficient of pairwise solute-solute interaction in methanol indicates that the effects of solvophobic solute-solute interaction and H-bonding of the ether molecule with chain associates of methanol are not evinced in the thermochemical behavior of 12-crown-4.

  14. Effect of solvent and temperature on solution-crystallized terfenadine

    International Nuclear Information System (INIS)

    Leitao, M. Luisa P.; Canotilho, Joao; Ferreira, Simone C.R.; Sousa, Adriano T.; Simoes Redinha, J.

    2004-01-01

    The aim of this work was to understand the crystallization process of terfenadine in solution. Cooling of saturated solutions prepared at 50 deg. C at different temperatures, evaporating the solvent from nearly saturated solutions at a certain temperature, and exposing ethanol solutions of terfenadine to water vapour atmosphere were the techniques used for obtaining terfenadine specimens. The characterization of these specimens was carried out by thermal microscopy, differential thermal analysis, thermogravimetry and powder X-ray diffraction. Crystalline phases, amorphous solids, and solvates were identified. For the solvents used in the present study, the crystallinity degree of terfenadine decreases from ethanol-water to ethanol and from this to methanol. Decreasing the temperature promotes the formation of amorphous solid material; at low temperatures, methanol and ethanol solvates are also formed. Desolvation, following the terfenadine aggregation process in solution accounts for the different behaviour found for the solvents and for the effect of temperature on the structure. The role of the solvent as structure-mediator is explained on the grounds of the values previously published for the enthalpy of solution of terfenadine in the solvents under study

  15. Solute-solvent cavity and bridge functions. I. Varying size of the solute

    International Nuclear Information System (INIS)

    Vyalov, I.; Chuev, G.; Georgi, N.

    2014-01-01

    In this work we present the results of the extensive molecular simulations of solute-solvent cavity and bridge functions. The mixtures of Lennard-Jones solvent with Lennard-Jones solute at infinite dilution are considered for different solute-solvent size ratios—up to 4:1. The Percus-Yevick and hypernetted chain closures deviate substantially from simulation results in the investigated temperature and density ranges. We also find that the behavior of the indirect and cavity correlation functions is non-monotonous within the hard-core region, but the latter can be successfully approximated by mean-field theory if the solute-solvent interaction energy is divided into repulsive and attractive contribution, according to Weeks-Chandler-Andersen theory. Furthermore, in spite of the non-monotonous behavior of logarithm of the cavity function and the indirect correlation function, their difference, i.e., the bridge function remains constant within the hard-core region. Such behavior of the bridge and indirect correlation functions at small distances and for small values of indirect correlation function is well known from the Duh-Haymet plots, where the non-unique relationship results in loops of the bridge function vs. indirect correlation function graphs. We show that the same pathological behavior appears also when distance is small and indirect correlation function is large. We further show that the unique functional behavior of the bridge function can be established when bridge is represented as a function of the renormalized, repulsive indirect correlation function

  16. Quantitative relationship between adsorbed amount of solute and solvent composition

    International Nuclear Information System (INIS)

    Wang Yan; Geng Xindu; Zebolsky, Don M.

    2003-01-01

    A new adsorption isotherm that relates the amount of solute adsorbed to the solvent concentration is proposed. The new equation is derived from Geng and Shi's stoichiometric displacement model for adsorption (SDM-A). The obtained equation may be simplified to an expression containing two parameters. The equation with two parameters, valid for low concentrations of solute, is a logarithmically linear relationship. The intercept contains a thermodynamic equilibrium constant of the solute displacing solvent from the adsorbent. The slope is the negative value of the stoichiometric displacement parameter (Z), the average total number of solvent molecules displaced from an active site on the adsorbent and from the solute. Tests with a homologous series of aromatic alcohols by frontal analysis in reversed phase liquid chromatography demonstrate that experimental results fit the equation well

  17. Carbon Nanotube Dispersion in Solvents and Polymer Solutions: Mechanisms, Assembly, and Preferences.

    Science.gov (United States)

    Pramanik, Chandrani; Gissinger, Jacob R; Kumar, Satish; Heinz, Hendrik

    2017-12-26

    Debundling and dispersion of carbon nanotubes (CNTs) in polymer solutions play a major role in the preparation of carbon nanofibers due to early effects on interfacial ordering and mechanical properties. A roadblock toward ultrastrong fibers is the difficulty to achieve homogeneous dispersions of CNTs in polyacrylonitrile (PAN) and poly(methyl methacrylate) (PMMA) precursor solutions in solvents such as dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAc), and N,N-dimethylformamide (DMF). In this contribution, molecular dynamics simulations with accurate interatomic potentials for graphitic materials that include virtual π electrons are reported to analyze the interaction of pristine single wall CNTs with the solvents and polymer solutions at 25 °C. The results explain the barriers toward dispersion of SWCNTs and quantify CNT-solvent, polymer-solvent, as well as CNT-polymer interactions in atomic detail. Debundling of CNTs is overall endothermic and unfavorable with dispersion energies of +20 to +30 mJ/m 2 in the pure solvents, + 20 to +40 mJ/m 2 in PAN solutions, and +20 to +60 mJ/m 2 in PMMA solutions. Differences arise due to molecular geometry, polar, van der Waals, and CH-π interactions. Among the pure solvents, DMF restricts CNT dispersion less due to the planar geometry and stronger van der Waals interactions. PAN and PMMA interact favorably with the pure solvents with dissolution energies of -0.7 to -1.1 kcal per mole monomer and -1.5 to -2.2 kcal per mole monomer, respectively. Adsorption of PMMA onto CNTs is stronger than that of PAN in all solvents as the molecular geometry enables more van der Waals contacts between alkyl groups and the CNT surface. Polar side groups in both polymers prefer interactions with the polar solvents. Higher polymer concentrations in solution lead to polymer aggregation via alkyl groups and reduce adsorption onto CNTs. PAN and PMMA solutions in DMSO and dilute solutions in DMF support CNT dispersion more than other

  18. Solute-solvent interactions in chloroform solutions of halogenated symmetric double Schiff bases of 1,1'-bis(4-aminophenyl)cyclohexane at 308.15 K according to ultrasonic and viscosity data

    Science.gov (United States)

    Gangani, B. J.; Patel, J. P.; Parsania, P. H.

    2015-12-01

    The density, viscosity and ultrasonic speed (2 MHz) of chloroform solutions of halogenated symmetric double Schiff bases of 1,1'-bis(4-aminophenyl)cyclohexane were investigated at 308.15 K. Various acoustical parameters such as specific acoustical impedance ( Z), adiabatic compressibility ( Ka), Rao's molar sound function ( R m), van der Waals constant ( b), internal pressure (π), free volume ( V f), intermolecular free path length ( L f), classical absorption coefficient (α/ f 2)Cl) and viscous relaxation time (τ) were determine using ultrasonic speed ( U), viscosity (η) and density (ρ) data of Schiff bases solutions and correlated with concentration. Linear increase of Z, b, R, τ, and (α/ f 2)Cl except π (nonlinear) and linear decrease of Ka and L f except V f (nonlinear) with increasing concentration of Schiff bases suggested presence of strong molecular interactions in the solutions. The positive values of solvation number further supported strong molecular interactions in the solutions. The nature and position of halogen substituent also affected the strength of molecular interactions.

  19. Solvent density mode instability in non-polar solutions

    Indian Academy of Sciences (India)

    and excited states of the solute with the compressibility and solvent structure is found to have .... The organization of the rest of the paper is as follows. ...... For the ground state term, as C2 is nearly flat at qσ = q0 = 2π, we can safely ignore.

  20. A solvent/non-solvent system for achieving solution-processed multilayer organic light-emitting devices

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Yue; Wu, Zhaoxin, E-mail: zhaoxinwu@mail.xjtu.edu.cn; He, Lin; Jiao, Bo; Hou, Xun

    2015-08-31

    We developed a solvent/non-solvent system to fabricate the multilayer organic light-emitting devices (OLEDs) based on poly(N-vinylcarbazole) (PVK) by solution-process. This solvent system consists of both the solvent and non-solvent of PVK, in which fluorescent small molecules could be fully dissolved and directly spin-coated on top of the PVK layer; it could effectively avoid the redissolution of PVK during the spin-coating process of small molecules emitting layer. In the further investigation of this system, we also demonstrated the three-component solvent system, and found out that the third component, a less volatile solvent of PVK, was crucial for preparing a smoother interface between PVK and emitting layer. Compared with OLEDs through the vacuum deposition, the devices fabricated by solution-process from the solvent/non-solvent system showed comparable efficiency, which indicate that the solvent/non-solvent system can be used as an alternative process to prepare the polymer and small molecule multilayer devices through all-solution-process. - Highlights: • We fabricate the multilayer OLEDs by solution-process using a novel system. • We develop a solvent/non-solvent system of polymer (PVK) to avoid redissolution. • Small molecules could be fully dissolved and directly spin-coated on PVK layer. • The devices fabricated by the system and vacuum deposition show comparable efficiency.

  1. NMR study of temperature-induced phase separation and polymer-solvent interactions in poly(vinyl methyl ether)/D.sub.2./sub.O/ethanol solutions

    Czech Academy of Sciences Publication Activity Database

    Hanyková, L.; Labuta, J.; Spěváček, Jiří

    2006-01-01

    Roč. 47, č. 17 (2006), s. 6107-6116 ISSN 0032-3861 Grant - others:GA UK 294/2004/B Institutional research plan: CEZ:AV0Z40500505 Keywords : poly(vinyl methyl ether)/D2O/ ethanol solutions * temperature-induced phase separation * 1H and 13C NMR spectroscopy Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.773, year: 2006

  2. Stochastic level-set variational implicit-solvent approach to solute-solvent interfacial fluctuations

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Shenggao, E-mail: sgzhou@suda.edu.cn, E-mail: bli@math.ucsd.edu [Department of Mathematics and Mathematical Center for Interdiscipline Research, Soochow University, 1 Shizi Street, Jiangsu, Suzhou 215006 (China); Sun, Hui; Cheng, Li-Tien [Department of Mathematics, University of California, San Diego, La Jolla, California 92093-0112 (United States); Dzubiella, Joachim [Soft Matter and Functional Materials, Helmholtz-Zentrum Berlin, 14109 Berlin, Germany and Institut für Physik, Humboldt-Universität zu Berlin, 12489 Berlin (Germany); Li, Bo, E-mail: sgzhou@suda.edu.cn, E-mail: bli@math.ucsd.edu [Department of Mathematics and Quantitative Biology Graduate Program, University of California, San Diego, La Jolla, California 92093-0112 (United States); McCammon, J. Andrew [Department of Chemistry and Biochemistry, Department of Pharmacology, Howard Hughes Medical Institute, University of California, San Diego, La Jolla, California 92093-0365 (United States)

    2016-08-07

    Recent years have seen the initial success of a variational implicit-solvent model (VISM), implemented with a robust level-set method, in capturing efficiently different hydration states and providing quantitatively good estimation of solvation free energies of biomolecules. The level-set minimization of the VISM solvation free-energy functional of all possible solute-solvent interfaces or dielectric boundaries predicts an equilibrium biomolecular conformation that is often close to an initial guess. In this work, we develop a theory in the form of Langevin geometrical flow to incorporate solute-solvent interfacial fluctuations into the VISM. Such fluctuations are crucial to biomolecular conformational changes and binding process. We also develop a stochastic level-set method to numerically implement such a theory. We describe the interfacial fluctuation through the “normal velocity” that is the solute-solvent interfacial force, derive the corresponding stochastic level-set equation in the sense of Stratonovich so that the surface representation is independent of the choice of implicit function, and develop numerical techniques for solving such an equation and processing the numerical data. We apply our computational method to study the dewetting transition in the system of two hydrophobic plates and a hydrophobic cavity of a synthetic host molecule cucurbit[7]uril. Numerical simulations demonstrate that our approach can describe an underlying system jumping out of a local minimum of the free-energy functional and can capture dewetting transitions of hydrophobic systems. In the case of two hydrophobic plates, we find that the wavelength of interfacial fluctuations has a strong influence to the dewetting transition. In addition, we find that the estimated energy barrier of the dewetting transition scales quadratically with the inter-plate distance, agreeing well with existing studies of molecular dynamics simulations. Our work is a first step toward the

  3. The Safe and Efficient Evaporation of a Solvent from Solution

    Science.gov (United States)

    Mahon, Andrew R.

    1997-02-01

    The process of evaporating a solvent from a solution can cause problems for many students. By using a water-vacuum aspirator, backflashes of water can flood the sample tube and be detrimental to the experiment. This type of apparatus can also cause problems by drawing the solution it is evaporating back into the vacuum hose, causing the student to lose part or all of the products of their experiment. Macroscale and Microscale Organic Experiments, 2nd edition (1), suggested two techniques to dissolve solvents from a mixture. It suggested blowing a stream of air over the solution from a Pasteur pipet, or attaching a Pasteur pipet to an aspirator and drawing air over the surface of the liquid. Again, the danger of blowing air over the solution leaves the risk of splattering the solution, and drawing air over the surface of the liquid as described further endangers the products of the experiment through the risk of sucking the products up into the pipet aspirator. In an effort to eliminate these problems, a new technique has been developed. By inverting an ordinary 200-mL vacuum flask and pulling a steady current of air from the vacuum apparatus through it, any type of small container can be placed under it, allowing the solvent to be evaporated in a steady, mistake-free manner . By evaporating the solvent from the container that the products will be submitted in, no sample is lost through the process of transferring it from a vacuum flask or beaker to the final container.

  4. Solution thermodynamics of valnemulin hydrogen fumarate in different pure solvents

    International Nuclear Information System (INIS)

    Ouyang, Jinbo; Wang, Jingkang; Huang, Xin; Bao, Ying; Wang, Yongli; Yin, Qiuxiang; Liu, Ailing; Li, Xudong; Hao, Hongxun

    2015-01-01

    Highlights: • The solubility of valnemulin hydrogen fumarate in five pure solvents was experimentally determined. • The solubility data were correlated by Wilson model, NRTL model and UNIQUAC model. • Mixing thermodynamic properties of valnemulin hydrogen fumarate in five pure solvents were calculated. - Abstract: Solubility of valnemulin hydrogen fumarate in five pure solvents was determined within temperature range of (278.15 to 323.15) K by a gravimetric method. The results show that the solubility of valnemulin hydrogen fumarate in tested pure solvents increases with the increasing temperature. The solubility values were correlated by the Wilson model, NRTL model and UNIQUAC model. The UNIQUAC volume parameter, area parameter, and Wilson liquid molar volume parameter of valnemulin hydrogen fumarate were estimated by the group contribution method. It was found that the correlated results are in good agreement with the experimental results. Furthermore, the mixing thermodynamic properties of valnemulin hydrogen fumarate in solutions, including the mixing Gibbs energy, the mixing enthalpy and entropy, were determined by using the Wilson model and the experimental solubility results.

  5. Sequentially solution-processed, nanostructured polymer photovoltaics using selective solvents

    KAUST Repository

    Kim, Do Hwan; Mei, Jianguo; Ayzner, Alexander L.; Schmidt, Kristin; Giri, Gaurav; Appleton, Anthony L.; Toney, Michael F.; Bao, Zhenan

    2014-01-01

    We demonstrate high-performance sequentially solution-processed organic photovoltaics (OPVs) with a power conversion efficiency (PCE) of 5% for blend films using a donor polymer based on the isoindigo-bithiophene repeat unit (PII2T-C10C8) and a fullerene derivative [6,6]-phenyl-C[71]-butyric acid methyl ester (PC71BM). This has been accomplished by systematically controlling the swelling and intermixing processes of the layer with various processing solvents during deposition of the fullerene. We find that among the solvents used for fullerene deposition that primarily swell but do not re-dissolve the polymer underlayer, there were significant microstructural differences between chloro and o-dichlorobenzene solvents (CB and ODCB, respectively). Specifically, we show that the polymer crystallite orientation distribution in films where ODCB was used to cast the fullerene is broad. This indicates that out-of-plane charge transport through a tortuous transport network is relatively efficient due to a large density of inter-grain connections. In contrast, using CB results in primarily edge-on oriented polymer crystallites, which leads to diminished out-of-plane charge transport. We correlate these microstructural differences with photocurrent measurements, which clearly show that casting the fullerene out of ODCB leads to significantly enhanced power conversion efficiencies. Thus, we believe that tuning the processing solvents used to cast the electron acceptor in sequentially-processed devices is a viable way to controllably tune the blend film microstructure. © 2014 The Royal Society of Chemistry.

  6. Interaction of organic solvent with a subbituminous coal below pyrolysis temperature

    Energy Technology Data Exchange (ETDEWEB)

    Lindsey, D.; Grens, E.A.

    1978-06-01

    The interactions of a subbituminous coal with certain binary organic solvent mixtures have been studied at 250/sup 0/C. Mixtures of pyridine, quinoline, piperidine, tetrahydroquinoline, and ethylenediamine with either toluene or tetralin were contacted with coal in a successive batch, stirred reactor, the extractions being carried to near completion. Two distinct behaviors of extraction yield as a function of composition have been identified. In the majority of the solvent mixtures the extraction yield increases linearly with increasing concentration of the more active solvent. When the active solvent is ethylenediamine, however, the extraction yield increases rapidly when small concentrations of ethylenediamine are used but then levels out close to its maximum value in a 50 to 50 mix. This behavior is an indication that, except in the case of ethylenediamine, the activity of solvent mixtures is a function of bulk solution properties.

  7. Enthalpy of solution of α- and β-cyclodextrin in water and in some organic solvents

    International Nuclear Information System (INIS)

    Belica, Sylwia; Sadowska, Monika; Stępniak, Artur; Graca, Anna; Pałecz, Bartłomiej

    2014-01-01

    Highlights: • A great influence of crystalline water on the energetic of dissolving compounds. • The strongest interaction between β-cyclodextrin and DMSO. • The enthalpic pair interaction coefficient, h βCD-EtOH , obtained is positive. • Predominating effects of the partial dehydration of the molecules – βCD-EtOH. -- Abstract: The calorimetric measurements of solution enthalpy of α-cyclodextrin, β-cyclodextrin in water (H 2 O), dimetyloformamid (DMF), dimethyl sulfoxide (DMSO) and aqueous ethanol solutions (H 2 O + EtOH) at 298.15 K were made. The experimental results were used to calculate the enthalpic coefficients of the interactions between cyclodextrin and ethanol molecules in water based on McMillan–Mayer’s model. The results were compared with literature data and with hydrodynamic radii of cyclodextrin in examined solvents and with donor numbers of these solvents. In order to check, if the inclusion complex formation between the solvent with the highest enthalpy of solution and cyclodextrin has happened, the calorimetric isothermal titration measurements were made and the results were interpreted

  8. Effect of Solvent Additives on the Solution Aggregation of Phenyl-C61-Butyl Acid Methyl Ester (PCBM)

    KAUST Repository

    Tummala, Naga Rajesh

    2015-11-24

    High-boiling-point solvent additives, employed during the solution processing of active-layer formulations, impact the efficiency of bulk hetero-junction (BHJ) organic solar cells by influencing the morphological / topological features of the multicomponent thin film. Here, we aim at a better understanding of how these additives change the aggregation landscape in the casting solution prior to film deposition via a multi-scale computational study of the aggregation phenomena of phenyl-C61-butyric-acid methyl ester (PCBM) in various solutions. The energetic landscape of PCBM-solvent / solvent-additive intermolecular interactions is evaluated at the electronic-structure level through symmetry-adapted perturbation theory to determine the nature and strength of non-covalent forces important to aggregation. Molecular dynamics simulations highlight how the choice of solvent and solvent additives control the formation of molecular aggregates. Our results indicate that high-boiling-point solvent additives change the effective interactions among the PCBM and casting-solvent molecules and alter the equilibrium PCBM aggregate sizes in solution.

  9. Molecular microenvironments: Solvent interactions with nucleic acid bases and ions

    Science.gov (United States)

    Macelroy, R. D.; Pohorille, A.

    1986-01-01

    The possibility of reconstructing plausible sequences of events in prebiotic molecular evolution is limited by the lack of fossil remains. However, with hindsight, one goal of molecular evolution was obvious: the development of molecular systems that became constituents of living systems. By understanding the interactions among molecules that are likely to have been present in the prebiotic environment, and that could have served as components in protobiotic molecular systems, plausible evolutionary sequences can be suggested. When stable aggregations of molecules form, a net decrease in free energy is observed in the system. Such changes occur when solvent molecules interact among themselves, as well as when they interact with organic species. A significant decrease in free energy, in systems of solvent and organic molecules, is due to entropy changes in the solvent. Entropy-driven interactioins played a major role in the organization of prebiotic systems, and understanding the energetics of them is essential to understanding molecular evolution.

  10. Solute-solute interactions in intermetallic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Banerjee, Debashis; Murray, Ryan; Collins, Gary S., E-mail: collins@wsu.edu [Washington State University, Department of Physics and Astronomy (United States); Zacate, Matthew O. [Northern Kentucky University, Department of Physics and Geology (United States)

    2017-11-15

    Experiments were carried out on highly ordered GdAl{sub 2} samples containing extremely dilute mole fractions of{sup 111}In/Cd probe-atom solutes (about 10{sup −11}), intrinsic antisite atoms Al{sub Gd} having mole fractions of order 0-10{sup −2}, and doped with Ag solutes at mole fractions of order 10{sup −2}. Three types of defect interactions were investigated. (1) Quadrupole interactions caused by Ag-solute atoms neighboring{sup 111}In/Cd solute probe atoms were detected using the method of perturbed angular correlation of gamma rays (PAC). Three complexes of pairs of In-probes and Ag-solutes occupying neighboring positions on Gd- and Al-sublattices were identified by comparing site fractions in Gd-poor and Gd-rich GdAl{sub 2}(Ag) samples and from the symmetry of the quadrupole interactions. Interaction enthalpies between solute-atom pairs were determined from temperature dependences of observed site fractions. Repulsive interactions were observed for close-neighbor complexes In{sub Gd}+Ag{sub Gd} and In{sub Gd}+Ag{sub Al} pairs, whereas a slightly attractive interaction was observed for In{sub Al}+Ag{sub Al}. Interaction enthalpies were all small, in the range ±0.15 eV. (2) Quadrupole interactions caused by intrinsic antisite atoms Al{sub Gd} neighboring In{sub Gd} probes were also detected and site fractions measured as a function of temperature, as in previous work on samples not doped with Ag-solutes [Temperature- and composition-driven changes in site occupation of solutes in Gd{sub 1+3x}Al{sub 2−3x}, Zacate and Collins (Phys. Rev. B69, 174202 (1))]. However, the effective binding enthalpy between In{sub Gd} probe and Al{sub Gd} antisite was found to change sign from -0.12 eV (attractive interaction) in undoped samples to + 0.24 eV (repulsive) in Ag-doped samples. This may be attributed to an attractive interaction between Al{sub Gd} antisite atoms and Ag-dopants that competes with the attractive interaction between In{sub Gd} and Al{sub Gd

  11. Protein-solvent preferential interactions, protein hydration, and the modulation of biochemical reactions by solvent components.

    Science.gov (United States)

    Timasheff, Serge N

    2002-07-23

    Solvent additives (cosolvents, osmolytes) modulate biochemical reactions if, during the course of the reaction, there is a change in preferential interactions of solvent components with the reacting system. Preferential interactions can be expressed in terms of preferential binding of the cosolvent or its preferential exclusion (preferential hydration). The driving force is the perturbation by the protein of the chemical potential of the cosolvent. It is shown that the measured change of the amount of water in contact with protein during the course of the reaction modulated by an osmolyte is a change in preferential hydration that is strictly a measure of the cosolvent chemical potential perturbation by the protein in the ternary water-protein-cosolvent system. It is not equal to the change in water of hydration, because water of hydration is a reflection strictly of protein-water forces in a binary system. There is no direct relation between water of preferential hydration and water of hydration.

  12. Thermodynamics of solvent interaction with the metal-organic framework MOF-5.

    Science.gov (United States)

    Akimbekov, Zamirbek; Wu, Di; Brozek, Carl K; Dincă, Mircea; Navrotsky, Alexandra

    2016-01-14

    The inclusion of solvent in metal-organic framework (MOF) materials is a highly specific form of guest-host interaction. In this work, the energetics of solvent MOF-5 interactions has been investigated by solution calorimetry in 5 M sodium hydroxide (NaOH) at room temperature. Solution calorimetric measurement of enthalpy of formation (ΔH(f)) of Zn4O(C8H4O4)3·C3H7NO (MOF-5·DMF) and Zn4O(C8H4O4)3·0.60C5H11NO (MOF-5·0.60DEF) from the dense components zinc oxide (ZnO), 1,4-benzenedicarboxylic acid (H2BDC), N,N-dimethylformamide (DMF) and N,N-diethylformamide (DEF) gives values of 16.69 ± 1.21 and 45.90 ± 1.46 kJ (mol Zn4O)(-1), respectively. The enthalpies of interaction (ΔH(int)) for DMF and DEF with MOF-5 are -82.78 ± 4.84 kJ (mol DMF)(-1) and -89.28 ± 3.05 kJ (mol DEF)(-1), respectively. These exothermic interaction energies suggest that, at low guest loading, Lewis base solvents interact more strongly with electron accepting Zn4O clusters in the MOF than at high solvent loading. These data provide a quantitative thermodynamic basis to investigate transmetallation and solvent assisted linker exchange (SALE) methods and to synthesize new MOFs.

  13. Effects of solute--solvent attractive forces on hydrophobic correlations

    International Nuclear Information System (INIS)

    Pratt, L.R.; Chandler, D.

    1980-01-01

    A theory is presented for the effect of slowly varying attractive forces on correlations between nonpolar solutes in dilute aqueous solution. We find that hydrophobic correlations are sensitive to relatively long range slowly varying interactions. Thus, it is possible to make qualitative changes in these correlations by introducing small changes in the attractive forces. Several model calculations are presented to illustrate these facts. The contributions of the Lennard-Jones attractive forces to the computer simulation results of Pangali, Rao, and Berne are calculated. For this case it is found that the potential of mean force between spherical nonpolar solutes is hardly affected by inclusion of attractive forces. However, the osmotic second virial coefficient is dominated by the contributions of the attractive forces. For spherical solutes which provide a reasonable model for the methane molecule, inclusion of attractive forces produces a qualitative change in the methane--methane potential of mean force. The connection between these effects of slowly varying attractive forces and the enthalpic part of Ben-Naim's deltaA/sup H/I is discussed

  14. Measurement and prediction of aromatic solute distribution coefficients for aqueous-organic solvent systems. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J.R.; Luthy, R.G.

    1984-06-01

    Experimental and modeling activities were performed to assess techniques for measurement and prediction of distribution coefficients for aromatic solutes between water and immiscible organic solvents. Experiments were performed to measure distribution coefficients in both clean water and wastewater systems, and to assess treatment of a wastewater by solvent extraction. The theoretical portions of this investigation were directed towards development of techniques for prediction of solute-solvent/water distribution coefficients. Experiments were performed to assess treatment of a phenolic-laden coal conversion wastewater by solvent extraction. The results showed that solvent extraction for recovery of phenolic material offered several wastewater processing advantages. Distribution coefficients were measured in clean water and wastewater systems for aromatic solutes of varying functionality with different solvent types. It was found that distribution coefficients for these compounds in clean water systems were not statistically different from distribution coefficients determined in a complex coal conversion process wastewater. These and other aromatic solute distribution coefficient data were employed for evaluation of modeling techniques for prediction of solute-solvent/water distribution coefficients. Eight solvents were selected in order to represent various chemical classes: toluene and benzene (aromatics), hexane and heptane (alkanes), n-octanol (alcohols), n-butyl acetate (esters), diisopropyl ether (ethers), and methylisobutyl ketone (ketones). The aromatic solutes included: nonpolar compounds such as benzene, toluene and naphthalene, phenolic compounds such as phenol, cresol and catechol, nitrogenous aromatics such as aniline, pyridine and aminonaphthalene, and other aromatic solutes such as naphthol, quinolinol and halogenated compounds. 100 references, 20 figures, 34 tables.

  15. Enthalpies of solution of methylcalix[4]resorcinarene in non-aqueous solvents as a function of concentration and temperature

    Energy Technology Data Exchange (ETDEWEB)

    Riveros, Diana C. [Laboratorio de Termodinamica de Soluciones, Departamento de Quimica, Facultad de Ciencias, Universidad de los Andes, Bogota D.C. (Colombia); Martinez, Fleming [Grupo de Investigaciones Farmaceutico-Fisicoquimicas, Departamento de Farmacia, Facultad de Ciencias, Universidad Nacional de Colombia, Bogota D.C. (Colombia); Vargas, Edgar F., E-mail: edvargas@uniandes.edu.co [Laboratorio de Termodinamica de Soluciones, Departamento de Quimica, Facultad de Ciencias, Universidad de los Andes, Bogota D.C. (Colombia)

    2012-11-20

    Highlights: Black-Right-Pointing-Pointer The solution enthalpies of methylcalix[4]resorcinarene in alcohols have been measured. Black-Right-Pointing-Pointer The solution enthalpies of methylcalix[4]resorcinarene in alcohols are endothermic. Black-Right-Pointing-Pointer Enthalpies of transference are interpreted in terms of proton donor capacity of alcohols. - Abstract: Enthalpies of solution of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxyresorci[4]arene in methanol, ethanol and propanol as a function of molal concentration at (288.15, 298.15 and 308.15) K were measured calorimetrically. The enthalpies of solvation were estimated. Using propanol as the referent solvent, transfer properties to other alcohols were also calculated. In addition, temperature dependence of the enthalpy of solution at infinite dilution was also obtained. The data were interpreted in terms of solute-solvent interactions.

  16. Interaction forces between nanoparticles in Lennard-Jones (L-J) solvents

    International Nuclear Information System (INIS)

    Sinha, Indrajit; Mukherjee, Ashim K

    2014-01-01

    Molecular simulations, such as Monte Carlo (MC) and molecular dynamics (MD) have been recently used for understanding the forces between colloidal nanoparticles that determine the dispersion and stability of nanoparticle suspensions. Herein we review the current status of research in the area of nanoparticles immersed in L-J solvents. The first study by Shinto et al. used large smooth spheres to depict nanoparticles in L-J and soft sphere solvents. The nanoparticles were held fixed at a particular interparticle distance and only the solvents were allowed to equilibrate. Both Van-der-waals and solvation forces were computed at different but fixed interparticle separation. Later Qin and Fitchthorn improved on this model by considering the nanoparticles as collection of molecules, thus taking into the account the effect of surface roughness of nanoparticles. Although the inter particle distance was fixed, the rotation of such nanoparticles with respect to each other was also investigated. Recently, in keeping with the experimental situation, we modified this model by allowing the nanoparticles to move and rotate freely. Solvophilic, neutral and solvophobic interactions between the solvent atoms and those that make up the nanoparticles were modelled. While neutral and solvophobic nanoparticles coalesce even at intermediate distances, solvophilic nanoparticles are more stable in solution due to the formation of a solvent shield

  17. Enthalpies of solution of methylcalix[4]resorcinarene in non-aqueous solvents as a function of concentration and temperature

    International Nuclear Information System (INIS)

    Riveros, Diana C.; Martínez, Fleming; Vargas, Edgar F.

    2012-01-01

    Highlights: ► The solution enthalpies of methylcalix[4]resorcinarene in alcohols have been measured. ► The solution enthalpies of methylcalix[4]resorcinarene in alcohols are endothermic. ► Enthalpies of transference are interpreted in terms of proton donor capacity of alcohols. - Abstract: Enthalpies of solution of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxyresorci[4]arene in methanol, ethanol and propanol as a function of molal concentration at (288.15, 298.15 and 308.15) K were measured calorimetrically. The enthalpies of solvation were estimated. Using propanol as the referent solvent, transfer properties to other alcohols were also calculated. In addition, temperature dependence of the enthalpy of solution at infinite dilution was also obtained. The data were interpreted in terms of solute–solvent interactions.

  18. Solvent extraction of uranium from high acid leach solution

    International Nuclear Information System (INIS)

    Ramadevi, G.; Sreenivas, T.; Navale, A.S.; Padmanabhan, N.P.H.

    2010-01-01

    A significant part of the total uranium reserves all over the world is contributed by refractory uranium minerals. The refractory oxides are highly stable and inert to attack by most of the commonly used acids under normal conditions of acid strength, pressure and temperature. Quantitative dissolution of uranium from such ores containing refractory uranium minerals requires drastic operating conditions during chemical leaching like high acid strength, elevated pressures and temperatures. The leach liquors produced under these conditions normally have high free acidity, which affects the downstream operations like ion exchange and solvent extraction

  19. Electrostatic interactions in aqueous solutions of polyelectrolyte

    International Nuclear Information System (INIS)

    Belloni, Luc

    1982-01-01

    In this study, the structure, equilibrium and transport properties of poly-electrolytes solutions are reported. These dissymmetric systems are studied in the context of a primitive model (Charged hard spheres and rods in a solvent continuum). The first phenomenon studied is the strong electrostatic attractive interaction of counterions on the poly-ion surface. The model used considers the poly-ions on a matrix and the different concentrations are calculated using the P.B. equation. Auto-diffusion coefficients obtained give a good description of experimental slowing down of the counterions. The model allows a correlation between the theoretical limits represented by Bjerrum's and Manning's models and gives a physical significance to the concept of condensation. In the second part, the complete structure is calculated using only slightly restrictive H.N.C. approximation. This theory enables all the pair correlation functions to be calculated as well as thermodynamic data and structure factors. The last part of this study treats transport phenomena. Quasi-elastic light scattering gives information on the autocorrelation function of the scattered light intensity. Analysis using cumulants leads to an effective diffusion coefficient which is theoretically related to the structure factor and the hydrodynamic interactions. A crude approximation of the last contribution allows to fit the experimental data. (author) [fr

  20. Solvent-dependent self-assembly and ordering in slow-drying semi-crystalline conjugated polymer solutions

    KAUST Repository

    Zhao, Kui

    2015-09-07

    The mechanistic understanding of the intrinsic molecular self-assembly of conjugated polymers is of immense importance to controlling the microstructure development in organic semiconducting thin films, with meaningful impact on charge transport and optoelectronic properties. Yet, to date the vast majority of studies have focused on the fast solution process itself, with studies of slower intrinsic molecular self-assembly in formulations lagging behind. Here we have investigated molecular self-assembly during spontaneous organization and uncovered how changes in formulation influence the microstructure, morphology and transport properties of conjugated polymer thin films. Our results suggest that the polymer-solvent interaction is the key factor for the molecular self-assembly and changes in macroscopic charge transport, which is in contrast with most solution processes, such as spin-coating and blade coating, where solvent drying kinetics dominates the aggregation and crystallization processes. Energetically favourable interactions between the polymer and its solvent are shown to cause chain expansion, resulting in a large hydrodynamic volume and few chain entanglements in solution. This provides molecular freedom for self-assembly and is shown to greatly enhance the local and long range order of the polymer, intra-chain backbone planarity and crystallite size. These improvements, in turn, are shown to endow the conjugated polymer with high carrier transport, as demonstrated by organic thin film transistors.

  1. Supramolecular architectures of iron phthalocyanine Langmuir-Blodgett films: The role played by the solution solvents

    Science.gov (United States)

    Rubira, Rafael Jesus Gonçalves; Aoki, Pedro Henrique Benites; Constantino, Carlos José Leopoldo; Alessio, Priscila

    2017-09-01

    The developing of organic-based devices has been widely explored using ultrathin films as the transducer element, whose supramolecular architecture plays a central role in the device performance. Here, Langmuir and Langmuir-Blodgett (LB) ultrathin films were fabricated from iron phthalocyanine (FePc) solutions in chloroform (CHCl3), dichloromethane (CH2Cl2), dimethylformamide (DMF), and tetrahydrofuran (THF) to determine the influence of different solvents on the supramolecular architecture of the ultrathin films. The UV-vis absorption spectroscopy shows a strong dependence of the FePc aggregation on these solvents. As a consequence, the surface pressure vs. mean molecular area (π-A) isotherms and Brewster angle microscopy (BAM) reveal a more homogeneous (surface morphology) Langmuir film at the air/water interface for FePc in DMF. The same morphological pattern observed for the Langmuir films is preserved upon LB deposition onto solid substrates. The Raman and FTIR analyses indicate the DMF-FePc interaction relies on coordination bonds between N atom (from DMF) and Fe atom (from FePc). Besides, the FePc molecular organization was also found to be affected by the DMF-FePc chemical interaction. It is interesting to note that, if the DMF-FePc leads to less aggregated FePc either in solution or ultrathin films (Langmuir and LB), with time (one week) the opposite trend is found. Taking into account the N-Fe interaction, the performance of the FePc ultrathin films with distinct supramolecular architectures composing sensing units was explored as proof-of-principle in the detection of trace amounts of atrazine herbicide in water using impedance spectroscopy. Further statistical and computational analysis reveal not only the role played by FePc supramolecular architecture but also the sensitivity of the system to detect atrazine solutions down to 10-10 mol/L, which is sufficient to monitor the quality of drinking water even according to the most stringent international

  2. Interactions of solvent with the heme region of methemoglobin and fluoro-methemoglobin.

    Science.gov (United States)

    Koenig, S H; Brown, R D; Lindstrom, T R

    1981-06-01

    It is now more than 20 years since Davidson and collaborators (1957, Biochim. Biophys, Acta. 26:370-373; J. Mol. Biol. 1:190-191) applied the theoretical ideas of Bloembergen et al. (1948. Phys. Rev. 73:679-712) on outer sphere magnetic relaxation of solvent protons to studies of solutions of methemoglobin. From then on, there has been debate regarding the relative contributions to paramagnetic solvent proton relaxation by inner sphere (ligand-exchange) effects and by outer sphere (diffusional) effects in methemoglobin solutions. Gupta and Mildvan (1975. J. Biol. Chem 250:146-253) extended the early measurements, attributed the relatively small paramagnetic effects to exchange with solvent of the water ligand of the heme-Fe3+ ion, and interpreted their data to indicate cooperativity and an alkaline Bohr effect in the presence of inositol hexaphosphate. They neglected the earlier discussions entirely, and made no reference to outer sphere effects. We have measured the relaxation rate of solvent protons as a function of magnetic field for solutions of methemoglobin, under a variety of conditions of pH and temperature, and have given careful consideration to the relatively large diamagnetic corrections that are necessary by making analogous measurements on oxyhemoglobin, carbonmonoxyhemoglobin, and cyano- and azide-methemoglobin. (The latter two, because of their short electronic relaxation times, behave as though diamagnetic). We show that the paramagnetic contribution to solvent relaxation can be dominated by outer sphere effects, a result implying that many conclusions, including those of Gupta and Mildvan, require reexamination. Finally, we present data for fluoro-methemoglobin, which relaxes solvent protons an order of magnitude better than does methemoglobin. Here one has a startling breakdown of the dogma that has been the basis for interpreting many ligand-replacement studies; in contrast to the prevailing view that replacement of a water ligand of a protein

  3. Absorption and emission behaviour of trans- p-coumaric acid in aqueous solutions and some organic solvents

    Science.gov (United States)

    Putschögl, M.; Zirak, P.; Penzkofer, A.

    2008-01-01

    The absorption and fluorescence behaviour of trans- p-coumaric acid ( trans-4-hydroxycinnamic acid) is investigated in buffered aqueous solution over a wide range from pH 1 to pH 12, in un-buffered water, and in some organic solvents. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are measured. p-Coumaric acid exists in different ionic forms in aqueous solution depending on the pH. There is an equilibrium between the neutral form ( p-CAH 2) and the single anionic form ( p-CAH -) at low pH (p Kna ≈ 4.9), and between the single anionic and the double anionic form ( p-CA 2-) at high pH (p Kaa ≈ 9.35). In the organic solvents studied trans- p-coumaric acid is dissolved in its neutral form. The fluorescence quantum yield of trans- p-coumaric acid in aqueous solution is ϕF ≈ 1.4 × 10 -4 for the neutral and the single anionic form, while it is ϕF ≈ 1.3 × 10 -3 for the double anionic form. For trans- p-coumaric acid in organic solvents fluorescence quantum yields in the range from 4.8 × 10 -5 (acetonitrile) to 1.5 × 10 -4 (glycerol) were measured. The fluorescence spectra are 7700-10,000 cm -1 Stokes shifted in aqueous solution, and 5400-8200 cm -1 Stokes shifted in the studied organic solvents. Decay paths responsible for the low fluorescence quantum yields are discussed (photo-isomerisation and internal conversion for p-CA 2-, solvent-assisted intra-molecular charge-transfer or ππ ∗ to nπ ∗ transfer and internal conversion for p-CAH 2 and p-CAH -). The solvent dependence of the first ππ ∗ electronic transition frequency and of the fluorescence Stokes shift of p-CAH 2 is discussed in terms of polar solute-solvent interaction effects. Thereby the ground-state and excite-state molecular dipole moments are extracted.

  4. Absorption and emission behaviour of trans-p-coumaric acid in aqueous solutions and some organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Putschoegl, M.; Zirak, P. [Institut II - Experimentelle und Angewandte Physik, Universitaet Regensburg, Universitaetsstrasse 31, D-93053 Regensburg (Germany); Penzkofer, A. [Institut II - Experimentelle und Angewandte Physik, Universitaet Regensburg, Universitaetsstrasse 31, D-93053 Regensburg (Germany)], E-mail: alfons.penzkofer@physik.uni-regensburg.de

    2008-01-22

    The absorption and fluorescence behaviour of trans-p-coumaric acid (trans-4-hydroxycinnamic acid) is investigated in buffered aqueous solution over a wide range from pH 1 to pH 12, in un-buffered water, and in some organic solvents. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are measured. p-Coumaric acid exists in different ionic forms in aqueous solution depending on the pH. There is an equilibrium between the neutral form (p-CAH{sub 2}) and the single anionic form (p-CAH{sup -}) at low pH (pK{sub na} {approx} 4.9), and between the single anionic and the double anionic form (p-CA{sup 2-}) at high pH (pK{sub aa} {approx} 9.35). In the organic solvents studied trans-p-coumaric acid is dissolved in its neutral form. The fluorescence quantum yield of trans-p-coumaric acid in aqueous solution is {phi}{sub F} {approx} 1.4 x 10{sup -4} for the neutral and the single anionic form, while it is {phi}{sub F} {approx} 1.3 x 10{sup -3} for the double anionic form. For trans-p-coumaric acid in organic solvents fluorescence quantum yields in the range from 4.8 x 10{sup -5} (acetonitrile) to 1.5 x 10{sup -4} (glycerol) were measured. The fluorescence spectra are 7700-10,000 cm{sup -1} Stokes shifted in aqueous solution, and 5400-8200 cm{sup -1} Stokes shifted in the studied organic solvents. Decay paths responsible for the low fluorescence quantum yields are discussed (photo-isomerisation and internal conversion for p-CA{sup 2-}, solvent-assisted intra-molecular charge-transfer or {pi}{pi}* to n{pi}* transfer and internal conversion for p-CAH{sub 2} and p-CAH{sup -}). The solvent dependence of the first {pi}{pi}* electronic transition frequency and of the fluorescence Stokes shift of p-CAH{sub 2} is discussed in terms of polar solute-solvent interaction effects. Thereby the ground-state and excite-state molecular dipole moments are extracted.

  5. Absorption and emission behaviour of trans-p-coumaric acid in aqueous solutions and some organic solvents

    International Nuclear Information System (INIS)

    Putschoegl, M.; Zirak, P.; Penzkofer, A.

    2008-01-01

    The absorption and fluorescence behaviour of trans-p-coumaric acid (trans-4-hydroxycinnamic acid) is investigated in buffered aqueous solution over a wide range from pH 1 to pH 12, in un-buffered water, and in some organic solvents. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are measured. p-Coumaric acid exists in different ionic forms in aqueous solution depending on the pH. There is an equilibrium between the neutral form (p-CAH 2 ) and the single anionic form (p-CAH - ) at low pH (pK na ∼ 4.9), and between the single anionic and the double anionic form (p-CA 2- ) at high pH (pK aa ∼ 9.35). In the organic solvents studied trans-p-coumaric acid is dissolved in its neutral form. The fluorescence quantum yield of trans-p-coumaric acid in aqueous solution is φ F ∼ 1.4 x 10 -4 for the neutral and the single anionic form, while it is φ F ∼ 1.3 x 10 -3 for the double anionic form. For trans-p-coumaric acid in organic solvents fluorescence quantum yields in the range from 4.8 x 10 -5 (acetonitrile) to 1.5 x 10 -4 (glycerol) were measured. The fluorescence spectra are 7700-10,000 cm -1 Stokes shifted in aqueous solution, and 5400-8200 cm -1 Stokes shifted in the studied organic solvents. Decay paths responsible for the low fluorescence quantum yields are discussed (photo-isomerisation and internal conversion for p-CA 2- , solvent-assisted intra-molecular charge-transfer or ππ* to nπ* transfer and internal conversion for p-CAH 2 and p-CAH - ). The solvent dependence of the first ππ* electronic transition frequency and of the fluorescence Stokes shift of p-CAH 2 is discussed in terms of polar solute-solvent interaction effects. Thereby the ground-state and excite-state molecular dipole moments are extracted

  6. Human Lactoferricin Is Partially Folded in Aqueous Solution and Is Better Stabilized in a Membrane Mimetic Solvent

    Science.gov (United States)

    Hunter, Howard N.; Demcoe, A. Ross; Jenssen, Håvard; Gutteberg, Tore J.; Vogel, Hans J.

    2005-01-01

    Lactoferricins are highly basic bioactive peptides that are released in the stomach through proteolytic cleavage of various lactoferrin proteins. Here we have determined the solution structure of human lactoferricin (LfcinH) by conventional two-dimensional nuclear magnetic resonance methods in both aqueous solution and a membrane mimetic solvent. Unlike the 25-residue bovine lactoferricin (LfcinB), which adopts a somewhat distorted antiparallel β sheet, the longer LfcinH peptide shows a helical content from Gln14 to Lys29 in the membrane mimetic solvent but a nonexistent β-sheet character in either the N- or C-terminal regions of the peptide. The helical characteristic of the LfcinH peptide resembles the conformation that this region adopts in the crystal structure of the intact protein. The LfcinH structure determined in aqueous solution displays a nascent helix in the form of a coiled conformation in the region from Gln14 to Lys29. Numerous hydrophobic interactions create the basis for the better-defined overall structure observed in the membrane mimetic solvent. The 49-residue LfcinH peptide isolated for these studies was found to be slightly longer than previously reported peptide preparations and was found to have an intact peptide bond between residues Ala11 and Val12. The distinct solution structures of LfcinH and LfcinB represent a novel difference in the physical properties of these two peptides, which contributes to their unique physiological activities. PMID:16048952

  7. Assorted interactions of amino acids prevailing in aqueous vitamin C solutions probed by physicochemical and ab-initio contrivances

    Science.gov (United States)

    Das, Koyeli; Roy, Milan Chandra; Rajbanshi, Biplab; Roy, Mahendra Nath

    2017-11-01

    Qualitative and quantitative analysis of molecular interaction prevailing in tyrosine and tryptophan in aqueous solution of vitamin C have been probed by thermophysical properties. The apparent molar volume (ϕV), viscosity B-coefficient, molal refraction (RM) of tyrosine and tryptophan have been studied in aqueous vitamin C solutions at diverse temperatures via Masson equation which deduced solute-solvent and solute-solute interactions, respectively. Spectroscopic study along with physicochemical and computational techniques provides lots of interesting and highly significant insights of the model biological systems. The overall results established strong solute-solvent interactions between studied amino acids and vitamin C mixture in the ternary solutions.

  8. TBP determination in nitric acid solutions from solvent extraction process

    International Nuclear Information System (INIS)

    Kuada, T.A.; Carvalho, E.I. de; Araujo, I. da C.; Cohen, V.H.

    1988-07-01

    Heavy organic phases have been observed on some occasions during TBP extraction process. These products, described as red oils, were considered as the main cause for process failures, specially in evaporators and concentrators. In view of safety aspects it is necessary to control organic concentration in product and waste solutions. The proposed method involves the organic removal by chloroform as a first step, followed by purification onto a silica gel column. The results are given from analysing TBP and its degradation product (DBP) by gas chromatography. (author) [pt

  9. Elucidating the Solvation Structure and Dynamics of Lithium Polysulfides Resulting from Competitive Salt and Solvent Interactions

    Energy Technology Data Exchange (ETDEWEB)

    Rajput, Nav Nidhi; Murugesan, Vijayakumar; Shin, Yongwoo; Han, Kee Sung; Lau, Kah Chun; Chen, Junzheng; Liu, Jun; Curtiss, Larry A.; Mueller, Karl T.; Persson, Kristin A.

    2017-04-10

    Fundamental molecular level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applica-tions. In particular, exhaustive knowledge of solvation structure, stability and transport properties is critical for developing stable electrolytes for fast charging and high energy density next-generation energy storage systems. Here we report the correlation between solubility, solvation structure and translational dynamics of a lithium salt (Li-TFSI) and polysulfides species using well-benchmarked classical molecular dynamics simulations combined with nuclear magnetic resonance (NMR). It is observed that the polysulfide chain length has a significant effect on the ion-ion and ion-solvent interaction as well as on the diffusion coefficient of the ionic species in solution. In particular, extensive cluster formation is observed in lower order poly-sulfides (Sx2-; x≤4), whereas the longer polysulfides (Sx2-; x>4) show high solubility and slow dynamics in the solu-tion. It is observed that optimal solvent/salt ratio is essen-tial to control the solubility and conductivity as the addi-tion of Li salt increases the solubility but decreases the mo-bility of the ionic species. This work provides a coupled theoretical and experimental study of bulk solvation struc-ture and transport properties of multi-component electro-lyte systems, yielding design metrics for developing optimal electrolytes with improved stability and solubility.

  10. Photo-physical and interactional behavior of two members of group B vitamins in different solvent media

    Science.gov (United States)

    Zakerhamidi, M. S.; Zare Haghighi, L.; Seyed Ahmadian, S. M.

    2017-09-01

    In this paper, absorption and fluorescence spectra of vitamin B12 (cyanocobalamin) and vitamin B6 (pyridoxine) were recorded in solvents with different polarity, at room temperature. These vitamins' photo-physical behavior depends strongly on the solvent's nature along with different attached groups in their structures. In order to investigate the solvent-solute interactions and environmental effect on spectral variations, linear solvation energy relationships concept, suggested by Kamlet and Taft was used. Solvatochromic method was also used for measuring the ground and excited state dipole moments of these vitamins. According to our experimental results, dipole moment of these groups of vitamins in excited state is larger than ground state. Furthermore, obtained photo-physical and interactional properties of used vitamins can give important information on how this group of vitamins behaves in biological systems.

  11. Quantification of interaction and topological parameters of polyisoprene star polymers under good solvent conditions

    KAUST Repository

    Rai, Durgesh K.

    2016-05-05

    Mass fractal scaling, reflected in the mass fractal dimension df, is independently impacted by topology, reflected in the connectivity dimension c, and by tortuosity, reflected in the minimum dimension dmin. The mass fractal dimension is related to these other dimensions by df=cdmin. Branched fractal structures have a higher mass fractal dimension compared to linear structures due to a higher c, and extended structures have a lower dimension compared to convoluted self-avoiding and Gaussian walks due to a lower dmin. It is found, in this work, that macromolecules in thermodynamic equilibrium display a fixed mass fractal dimension df under good solvent conditions, regardless of chain topology. These equilibrium structures accommodate changes in chain topology such as branching c by a decrease in chain tortuosity dmin. Symmetric star polymers are used to understand the structure of complex macromolecular topologies. A recently published hybrid Unified scattering function accounts for interarm correlations in symmetric star polymers along with polymer-solvent interaction for chains of arbitrary scaling dimension. Dilute solutions of linear, three-arm and six-arm polyisoprene stars are studied under good solvent conditions in deuterated p-xylene. Reduced chain tortuosity can be viewed as steric straightening of the arms. Steric effects for star topologies are quantified, and it is found that steric straightening of arms is more significant for lower-molecular-weight arms. The observation of constant df is explained through a modification of Flory-Krigbaum theory for branched polymers.

  12. Quantifying the molecular origins of opposite solvent effects on protein-protein interactions.

    Directory of Open Access Journals (Sweden)

    Vincent Vagenende

    Full Text Available Although the nature of solvent-protein interactions is generally weak and non-specific, addition of cosolvents such as denaturants and osmolytes strengthens protein-protein interactions for some proteins, whereas it weakens protein-protein interactions for others. This is exemplified by the puzzling observation that addition of glycerol oppositely affects the association constants of two antibodies, D1.3 and D44.1, with lysozyme. To resolve this conundrum, we develop a methodology based on the thermodynamic principles of preferential interaction theory and the quantitative characterization of local protein solvation from molecular dynamics simulations. We find that changes of preferential solvent interactions at the protein-protein interface quantitatively account for the opposite effects of glycerol on the antibody-antigen association constants. Detailed characterization of local protein solvation in the free and associated protein states reveals how opposite solvent effects on protein-protein interactions depend on the extent of dewetting of the protein-protein contact region and on structural changes that alter cooperative solvent-protein interactions at the periphery of the protein-protein interface. These results demonstrate the direct relationship between macroscopic solvent effects on protein-protein interactions and atom-scale solvent-protein interactions, and establish a general methodology for predicting and understanding solvent effects on protein-protein interactions in diverse biological environments.

  13. The crystallization of a solid solution in a solvent and the stability of a growth interface

    International Nuclear Information System (INIS)

    Malmejac, Yves

    1971-03-01

    The potential uses of germanium-silicon alloys as thermoelectric generators in hitherto unexploited temperature ranges initiated the present study. Many delicate problems are encountered in the classical methods of preparation. An original technique was sought for crystallization in a metallic solvent. The thermodynamic equilibria between the various phases of the ternary System used were studied in order to justify the method used. The conditions (temperature and composition) were determined in which the cooling of a ternary liquid mixture induces the precipitation of a binary solid solution with the desired composition. If large crystals are to be obtained from the solid solution, metallic solvent precipitation must be replaced by a mono-directional solvent crystallization. The combined effect of a certain number of simple physical phenomena on the stability of a crystal liquid interface was studied: the morphological stability of the crystal growth interface is the first step towards obtaining perfect crystals. (author) [fr

  14. SOLUTION THERMODYNAMICS OF TRICLOSAN AND TRICLOCARBAN IN SOME VOLATILE ORGANIC SOLVENTS

    OpenAIRE

    DELGADO, Daniel R.; R. HOLGUIN, Andres; MARTÍNEZ, Fleming

    2012-01-01

    Thermodynamic functions of Gibbs energy, enthalpy, and entropy for the solution processes of the antimicrobial drugs Triclosan and Triclocarban in five volatile organic solvents were calculated from solubility values at temperatures from 293.15 to 313.15 K. Triclosan and Triclocarban solubility was determined in acetone, acetonitrile (AcCN), ethyl acetate (AcOEt), methanol (MetOH), and cyclohexane (CH). The excess of Gibbs energy and the activity coefficients of the solutes were also calculat...

  15. Evaporation Behavior and Characterization of Eutectic Solvent and Ibuprofen Eutectic Solution.

    Science.gov (United States)

    Phaechamud, Thawatchai; Tuntarawongsa, Sarun; Charoensuksai, Purin

    2016-10-01

    Liquid eutectic system of menthol and camphor has been reported as solvent and co-solvent for some drug delivery systems. However, surprisingly, the phase diagram of menthol-camphor eutectic has not been reported previously. The evaporation behavior, physicochemical, and thermal properties of this liquid eutectic and ibuprofen eutectic solution were characterized in this study. Differential scanning calorimetry (DSC) analysis indicated that a eutectic point of this system was near to 1:1 menthol/camphor and its eutectic temperature was -1°C. The solubility of ibuprofen in this eutectic was 282.11 ± 6.67 mg mL(-1) and increased the drug aqueous solubility fourfold. The shift of wave number from Fourier transform infrared spectroscopy (FTIR) indicated the hydrogen bonding of each compound in eutectic mixture. The weight loss from thermogravimetric analysis of menthol and camphor related to the evaporation and sublimation, respectively. Menthol demonstrated a lower apparent sublimation rate than camphor, and the evaporation rate of eutectic solvent was lower than the sublimation rate of camphor but higher than the evaporation of menthol. The evaporation rate of the ibuprofen eutectic solution was lower than that of the eutectic solvent because ibuprofen did not sublimate. This eutectic solvent prolonged the ibuprofen release with diffusion control. Thus, the beneficial information for thermal behavior and related properties of eutectic solvent comprising menthol-camphor and ibuprofen eutectic solution was attained successfully. The rather low evaporation of eutectic mixture will be beneficial for investigation and tracking the mechanism of transformation from nanoemulsion into nanosuspension in the further study using eutectic as oil phase.

  16. The simple solutions concept: a useful approach to estimate deviation from ideality in solvent extraction

    International Nuclear Information System (INIS)

    Sorel, C.; Pacary, V.

    2010-01-01

    The solvent extraction systems devoted to uranium purification from crude ore to spent fuel involve concentrated solutions in which deviation from ideality can not be neglected. The Simple Solution Concept based on the behaviour of isopiestic solutions has been applied to quantify the activity coefficients of metals and acids in the aqueous phase in equilibrium with the organic phase. This approach has been validated on various solvent extraction systems such as trialkylphosphates, malonamides or acidic extracting agents both on batch experiments and counter-current tests. Moreover, this concept has been successfully used to estimate the aqueous density which is useful to quantify the variation of volume and to assess critical parameters such as the number density of nuclides. (author)

  17. Amino acid salt solutions as solvents in CO2 capture from flue gas

    DEFF Research Database (Denmark)

    Lerche, Benedicte Mai; Thomsen, Kaj; Stenby, Erling Halfdan

    New solvents based on the salts of amino acids have emerged as an alternative to the alkanolamine solutions, for the chemical absorption of CO2 from flue gas. But only few studies on amino acids as CO2 capturing agents have been performed so far. One of the interesting features of amino acid salt...... solutions is their ability to form solid precipitates upon the absorption of CO2. The occurrence of crystallization offers the possibility of increasing the CO2 loading capacity of the solvent. However, precipitation can also have negative effect on the CO2 capture process. The chemical nature of the solid...... of glycine, taurine, and lysine, while in the case of proline, and glutamic acid, the precipitate was found to be bicarbonate. These results give an important contribution to further understanding the potential of amino acid salt solutions in CO2 capture from flue gas....

  18. Quasiparticle Approach to Molecules Interacting with Quantum Solvents.

    Science.gov (United States)

    Lemeshko, Mikhail

    2017-03-03

    Understanding the behavior of molecules interacting with superfluid helium represents a formidable challenge and, in general, requires approaches relying on large-scale numerical simulations. Here, we demonstrate that experimental data collected over the last 20 years provide evidence that molecules immersed in superfluid helium form recently predicted angulon quasiparticles [Phys. Rev. Lett. 114, 203001 (2015)PRLTAO0031-900710.1103/PhysRevLett.114.203001]. Most important, casting the many-body problem in terms of angulons amounts to a drastic simplification and yields effective molecular moments of inertia as straightforward analytic solutions of a simple microscopic Hamiltonian. The outcome of the angulon theory is in good agreement with experiment for a broad range of molecular impurities, from heavy to medium-mass to light species. These results pave the way to understanding molecular rotation in liquid and crystalline phases in terms of the angulon quasiparticle.

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

    Science.gov (United States)

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

    2014-12-01

    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.

  20. The salting-out of molibdoferrats(II from aqueous solutions by the organic solvents

    Directory of Open Access Journals (Sweden)

    Mykola V. Nikolenko

    2016-12-01

    Full Text Available The aim of this work was to develop a method for producing of molybdoferrate(II precipitates by salting-out them from aqueous solutions by means of organic solvents. Dependence of the composition of molybdoferrate(II precipitates on the pH of the reaction solutions was studied. Experiments on salting-out of molybdoferrate(II with various organic solvents were carried out. As a result it was found that the best reagent for the molybdoferrate(II salting-out is acetone. By its use, lowest quantity of the ammonium sulfate impurities was obtained. It is also of importance that by using of acetone the process of regeneration by distillation of the reaction solutions is characterized by the lowest energy consumption. A functional relationship between the solubility of molybdoferrates(II and dielectric constant of the medium was established. By increasing the dielectric constant of the solvent solubility of molybdoferrates(II rapidly increases. The linearized dependence ln(lnS–ln(1/e was proposed to predict the solubility of molybdoferrates(II in various aqueous-organic solutions.

  1. Tuning the Morphology of All-Polymer OPVs through Altering Polymer–Solvent Interactions

    KAUST Repository

    Pavlopoulou, Eleni; Kim, Chang Su; Lee, Stephanie S.; Chen, Zhihua; Facchetti, Antonio; Toney, Michael F.; Loo, Yueh-Lin

    2014-01-01

    © 2014 American Chemical Society. In this work, we investigated the effects of solvent(s)-polymer(s) interactions on the morphology of all-polymer bulk-heterojunction (BHJ) active layers cast from cosolutions. We demonstrate that altering

  2. Dense CO2 as a Solute, Co-Solute or Co-Solvent in Particle Formation Processes: A Review

    Directory of Open Access Journals (Sweden)

    Ana V. M. Nunes

    2011-11-01

    Full Text Available The application of dense gases in particle formation processes has attracted great attention due to documented advantages over conventional technologies. In particular, the use of dense CO2 in the process has been subject of many works and explored in a variety of different techniques. This article presents a review of the current available techniques in use in particle formation processes, focusing exclusively on those employing dense CO2 as a solute, co-solute or co-solvent during the process, such as PGSS (Particles from gas-saturated solutions®, CPF (Concentrated Powder Form®, CPCSP (Continuous Powder Coating Spraying Process, CAN-BD (Carbon dioxide Assisted Nebulization with a Bubble Dryer®, SEA (Supercritical Enhanced Atomization, SAA (Supercritical Fluid-Assisted Atomization, PGSS-Drying and DELOS (Depressurization of an Expanded Liquid Organic Solution. Special emphasis is given to modifications introduced in the different techniques, as well as the limitations that have been overcome.

  3. Process for plutonium rextraction in aqueous solution from an organic solvent, especially for uranium plutonium partition

    International Nuclear Information System (INIS)

    Germain, M.; Gillet, B.; Pasquiou, J.Y.

    1989-01-01

    The organic solvent containing plutonium is contacted with an aqueous solution of a uranous salt, for instance uranous nitrate, and a hydroxylamine salt, for instance the nitrate. In these conditions uranous nitrate is a reducing agent of Pu III and hydroxylamine nitrate stabilizes Pu III and U IV in the aqueous phase. Performances are similar to these of the U IV-hydrazine nitrate without interference of hydrazine nitrate degradation products [fr

  4. Interomolecular interactions in diluted solutions of potassium iodocuprates (1) in dimethyl ether of diethylene glycol

    International Nuclear Information System (INIS)

    Gorodinskaya, Eh.Ya.; Mel'nikova, N.B.; Yurin, K.V.

    1991-01-01

    The role of donor solvent in the formation of potassium mononuclear iodocuprates (1) in the system CuI-KI-dimethyl ether of diethylene glycol has been considerd. The calculated values of enthalpy, free energy and entropy of viscous flow activation in the range of temperatures 298-318 K for the solutions testify to decomposition of the solvent structure. Negative deviations of mole volumes from the additivity rule characterized strong molecular interaction

  5. Predicting the activity coefficients of free-solvent for concentrated globular protein solutions using independently determined physical parameters.

    Directory of Open Access Journals (Sweden)

    Devin W McBride

    Full Text Available The activity coefficient is largely considered an empirical parameter that was traditionally introduced to correct the non-ideality observed in thermodynamic systems such as osmotic pressure. Here, the activity coefficient of free-solvent is related to physically realistic parameters and a mathematical expression is developed to directly predict the activity coefficients of free-solvent, for aqueous protein solutions up to near-saturation concentrations. The model is based on the free-solvent model, which has previously been shown to provide excellent prediction of the osmotic pressure of concentrated and crowded globular proteins in aqueous solutions up to near-saturation concentrations. Thus, this model uses only the independently determined, physically realizable quantities: mole fraction, solvent accessible surface area, and ion binding, in its prediction. Predictions are presented for the activity coefficients of free-solvent for near-saturated protein solutions containing either bovine serum albumin or hemoglobin. As a verification step, the predictability of the model for the activity coefficient of sucrose solutions was evaluated. The predicted activity coefficients of free-solvent are compared to the calculated activity coefficients of free-solvent based on osmotic pressure data. It is observed that the predicted activity coefficients are increasingly dependent on the solute-solvent parameters as the protein concentration increases to near-saturation concentrations.

  6. Solvent Extraction of Tungsten(VI) from Moderate Hydrochloric Acid Solutions with LIX 63

    Energy Technology Data Exchange (ETDEWEB)

    Truong, Hoai Thanh; Lee, Man Seung [Mokpo National University, Jeollanamdo (Korea, Republic of); Kim, Yong Hwan [Incheon Technology Service Centre, Incheon (Korea, Republic of)

    2017-06-15

    The solvent extraction of tungsten(VI) from hydrochloric acid solutions using 5,8-diethyl-7-hydroxydodecan-6-one oxime (LIX 63) was analyzed in solutions having an initial pH range from 2 to 5, by varying the concentration of metal and extractant. In our experimental range, the cationic exchange reaction as well as the solvation reaction occurred simultaneously. The cation exchange reaction was identified by applying a slope analysis method to the extraction data. The existence of cationic tungsten(VI) species was confirmed by ion exchange experiments with Diphonix resin at pH 3. Further study is needed to identify the nature of this tungsten cationic species.

  7. Radiation induced polymerization of MMA in imidazolium ionic liquids and their mixed solutions with organic solvents

    Energy Technology Data Exchange (ETDEWEB)

    Qi Mingying [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100049 (China); Wu Guozhong [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China)], E-mail: wuguozhong@sinap.ac.cn; Sha Maolin; Liu Yusheng [Shanghai Institute of Applied Physics, Chinese Academy of Sciences, P.O. Box 800-204, Shanghai 201800 (China); Graduate University of the Chinese Academy of Sciences, Beijing 100049 (China)

    2008-10-15

    Considerably higher molecular weight (M{sub w}) and multi-modal molecular weight distribution (MWD) of poly(methyl methacrylate) (PMMA) were observed in neat ionic liquids ([bmim][PF{sub 6}] and [bmim][BF{sub 4}]), as well as their mixed solutions with organic solvents, probably due to the high viscosity and inhomogeneity of ionic liquids. FTIR spectra for PMMA showed that a slight amount of ionic liquid remained in the resulting polymer, and DSC measurement indicated the increase of glass transition point of PMMA with increasing of ionic liquid fraction in mixed solutions.

  8. Measurement and Correlation of the Ionic Conductivity of Ionic Liquid-Molecular Solvent Solutions

    Institute of Scientific and Technical Information of China (English)

    LI,Wen-Jing; HAN,Bu-Xing; TAO,Ran-Ting; ZHANG,Zhao-Fu; ZHANG,Jian-Ling

    2007-01-01

    The ionic conductivity of the solutions formed from 1-n-butyl-3-methylimidazolium tetrafluoroborate ([Bmim][BF4]) or 1-n-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF6]) and different molecular solvents (MSs) were measured at 298.15 K. The molar conductivity of the ionic liquids (ILs) increased dramatically with increasing concentration of the MSs. It was found that the molar conductivity of the IL in the solutions studied in this work could be well correlated by the molar conductivity of the neat ILs and the dielectric constant and molar volume of the MSs.

  9. Some studies on the formation of excited states of aromatic solutes in hydrocarbons and other solvents

    Energy Technology Data Exchange (ETDEWEB)

    Salmon, G A [Leeds Univ. (UK). Cookridge High Energy Radiation Research Centre

    1976-01-01

    This paper reviews the work of the author and his co-workers on the radiation-induced formation of excited states of aromatic compounds in solution. The experimental methods used are surveyed and in particular the method of measuring the yields of triplet and singlet excited states of the solute are described. The problems discussed are: (1) the effect of solvent on the yields of excited states, (2) formation of excited states in cyclohexane and other alicyclic hydrocarbons, (3) the formation of excited states in benzene and (4) the identification of T-T absorption spectra.

  10. An adaptive quantum mechanics/molecular mechanics method for the infrared spectrum of water: incorporation of the quantum effect between solute and solvent.

    Science.gov (United States)

    Watanabe, Hiroshi C; Banno, Misa; Sakurai, Minoru

    2016-03-14

    Quantum effects in solute-solvent interactions, such as the many-body effect and the dipole-induced dipole, are known to be critical factors influencing the infrared spectra of species in the liquid phase. For accurate spectrum evaluation, the surrounding solvent molecules, in addition to the solute of interest, should be treated using a quantum mechanical method. However, conventional quantum mechanics/molecular mechanics (QM/MM) methods cannot handle free QM solvent molecules during molecular dynamics (MD) simulation because of the diffusion problem. To deal with this problem, we have previously proposed an adaptive QM/MM "size-consistent multipartitioning (SCMP) method". In the present study, as the first application of the SCMP method, we demonstrate the reproduction of the infrared spectrum of liquid-phase water, and evaluate the quantum effect in comparison with conventional QM/MM simulations.

  11. Effect of organic solvents on dissolution process of mechano-chemically activated molybdenum by inorganic acid solutions

    International Nuclear Information System (INIS)

    Shevtsova, I.Ya.; Chernyak, A.S.; Khal'zov, A.A.

    1992-01-01

    The process of chemical dissolution of mechanochemically activated and nonactivated molybdenite by inorganic acid solutions in certain organic solvents of different nature was considered. It is shown that the highest extraction of molybdenum in solution is achieved in the presence of nitric acid. The dissociation constant of the acid used in the given organic solvent does not affect molybdenite solubility. When dissolving molybdenite by solutions of nitric acid in carbonic acids, alcohols and esters, the solubility of the concentrate depends on the length of hydrocarbon chain of the organic solvent and dispersion degree of mineral source material

  12. Polymer/Solvent and Polymer/Polymer Interaction Studies

    Science.gov (United States)

    1979-08-01

    sealed these solvents (still under nitrogen) in glass tubes. During the first distillation a dark residue remained in the boiler , but no such residue...rN ’ N ýd C’ d 0q 0- H H- H- -1 0j Ob) 0 04i O 󈧭Ji H, 0; C; 0! : H 41-4 4-4 E 4-1 CO H 1-1 ŕ C- C) -- 0p 0 p- v. i> mt %D m >fr 0 4-4 0𔃾-4> HHO

  13. Deep Eutectic Solvent Aqueous Solutions as Efficient Media for the Solubilization of Hardwood Xylans.

    Science.gov (United States)

    Morais, Eduarda S; Mendonça, Patrícia V; Coelho, Jorge F J; Freire, Mara G; Freire, Carmen S R; Coutinho, João A P; Silvestre, Armando J D

    2018-02-22

    This work contributes to the development of integrated lignocellulosic-based biorefineries by the pioneering exploitation of hardwood xylans by solubilization and extraction in deep eutectic solvents (DES). DES formed by choline chloride and urea or acetic acid were initially evaluated as solvents for commercial xylan as a model compound. The effects of temperature, molar ratio, and concentration of the DES aqueous solutions were evaluated and optimized by using a response surface methodology. The results obtained demonstrated the potential of these solvents, with 328.23 g L -1 of xylan solubilization using 66.7 wt % DES in water at 80 °C. Furthermore, xylans could be recovered by precipitation from the DES aqueous media in yields above 90 %. The detailed characterization of the xylans recovered after solubilization in aqueous DES demonstrated that 4-O-methyl groups were eliminated from the 4-O-methylglucuronic acids moieties and uronic acids (15 %) were cleaved from the xylan backbone during this process. The similar M w values of both pristine and recovered xylans confirmed the success of the reported procedure. DES recovery in four additional extraction cycles was also demonstrated. Finally, the successful extraction of xylans from Eucalyptus globulus wood by using aqueous solutions of DES was demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Study of micelle formation in solutions of alkylammonium carboxylates in apolar solvents by positron annihilation techniques

    International Nuclear Information System (INIS)

    Fucugauchi, L.A.; Djermouni, B.; Handel, E.D.; Ache, H.J.

    1979-01-01

    The positron annihilation technique was applied to the study of the self-association process in solutions of alkylammonium carboxylates in apolar solvents, such as cyclohexane and benzene. The results indicate that the positronium formation probability responds very sensitively to changes in the microenvironment in these solutions. A distinct cooperative effect of the solution resulting in abrupt changes in the number of thermal ortho-positronium atoms formed was observed and studied as a function of the length and structure of the hydrocarbon chain in the cationic and anionic parts of the surfactant molecules. While the chain length in the cationic portion of the surfactant seems to have little effect on the positronium formation probability, distinct differences can be observed when the structure of the carboxylate is changed. Furthermore, a profound effect in the physical property of the solutions was recognized when cyclohexane was replaced by benzene as a solvent. The results are discussed in terms of the existing models for self-association. 4 figures

  15. Novel micronisation β-carotene using rapid expansion supercritical solution with co-solvent

    Science.gov (United States)

    Kien, Le Anh

    2017-09-01

    Rapid expansion of supercritical solution (RESS) is the most common approach of pharmaceutical pacticle forming methods using supercritical fluids. The RESS method is a technology producing a small solid product with a very narrow particle size distribution, organic solvent-free particles. This process is also simple and easy to control the operating parameters in comparision with other ways based on supercritical techniques. In this study, β-carotene, a strongly colored red-orange pigment abundant in plants and fruits, has been forming by RESS. In addition, the size and morphology effect of four different RESS parameters including co-solvent, extraction temperature, and extraction pressure and expansion nozzle temperature has surveyed. The particle size distribution has been determined by using laser diffraction experiment. SEM has conducted to analyze the surface structure, DSC and FTIR for thermal and chemical structure analysis.

  16. Solubility and solution thermodynamics of 2-methyl-6-nitroaniline in ten organic solvents at elevated temperatures

    International Nuclear Information System (INIS)

    Cong, Yang; Wang, Jian; Du, Cunbin; Han, Shuo; Zhao, Hongkun

    2016-01-01

    Highlights: • Solubility of 2-methyl-6-nitroaniline in ten solvents were determined. • The solubility were correlated with four thermodynamic models. • Standard dissolution enthalpy and excess enthalpy of the solutions were computed. - Abstract: Knowledge of solubility for 2-methyl-6-nitroaniline in different solvents is essential for its purification and further theoretical studies. In this paper, the solid-liquid equilibrium for 2-methyl-6-nitroaniline in ten pure organic solvents (methanol, ethanol, n-propanol, isopropanol, toluene, ethyl acetate, acetonitrile, acetone, cyclohexane and 1,4-dioxane) was established using the isothermal saturation method at temperatures T = (278.15–313.15) K under pressure of 101.2 kPa, and the solubility of 2-methyl-6-nitroaniline in these solvents were determined by a high-performance liquid chromatography (HPLC). In general, the mole fraction solubility followed the following order from high to low in different solvents: 1,4-dioxane (0.1799–0.3390) > acetone (0.1128–0.3010) > ethyl acetate (0.08414–0.2654) > acetonitrile (0.04179–0.2027) > toluene (0.02367–0.1104) > n-propanol (0.01080–0.04514) > ethanol (0.01020–0.04202) > isopropanol (0.008595–0.03763) > methanol (0.007391–0.03198) > cyclohexane (0.001027–0.005617). The modified Apelblat equation, λh equation, Wilson model and NRTL model were employed to correlate the measured solubility data of 2-methyl-6-nitroaniline in the selected solvents. Results indicated that the largest values of RAD and RMSD acquired by the four models were less than 0.76% and 9.13 × 10"−"4, respectively. The modified Apelblat equation provided better results than the other three models. Furthermore, the standard dissolution enthalpy and excess enthalpy of the solutions were computed from the solubility values. The standard dissolution enthalpies vary within the range from (14.88 to 45.57) kJ·mol"−"1 and are all positive, the dissolution process of 2-methyl-6

  17. Effect of Solvent Additives on the Solution Aggregation of Phenyl-C61-Butyl Acid Methyl Ester (PCBM)

    KAUST Repository

    Tummala, Naga Rajesh; Sutton, Christopher; Aziz, Saadullah G.; Toney, Michael F.; Risko, Chad; Bredas, Jean-Luc

    2015-01-01

    High-boiling-point solvent additives, employed during the solution processing of active-layer formulations, impact the efficiency of bulk hetero-junction (BHJ) organic solar cells by influencing the morphological / topological features

  18. Supported Silver Nanoparticle and Near-Interface Solution Dynamics in a Deep Eutectic Solvent

    Energy Technology Data Exchange (ETDEWEB)

    Hammons, Joshua A.; Ustarroz, Jon; Muselle, Thibault; Torriero, Angel A. J.; Terryn, Herman; Suthar, Kamlesh; Ilavsky, Jan

    2016-01-28

    Type III deep eutectic solvents (DES) have attracted significant interest as both environmentally friendly and functional solvents that are, in some ways, advantageous to traditional aqueous systems. While these solvents continue to produce remarkable thin films and nanoparticle assemblies, their interactions with metallic surfaces are complex and difficult to manipulate. In this study, the near-surface region (2–600 nm) of a carbon surface is investigated immediately following silver nanoparticle nucleation and growth. This is accomplished, in situ, using a novel grazing transmission small-angle X-ray scattering approach with simultaneous voltammetry and electrochemical impedance spectroscopy. With this physical and electrochemical approach, the time evolution of three distinct surface interaction phenomena is observed: aggregation and coalescence of Ag nanoparticles, multilayer perturbations induced by nonaggregated Ag nanoparticles, and a stepwise transport of dissolved Ag species from the carbon surface. The multilayer perturbations contain charge-separated regions of positively charged choline-ethylene and negatively charged Ag and Cl species. Both aggregation-coalescence and the stepwise decrease in Ag precursor near the surface are observed to be very slow (~2 h) processes, as both ion and particle transport are significantly impeded in a DES as compared to aqueous electrolytes. Finally, altogether, this study shows how the unique chemistry of the DES changes near the surface and in the presence of nanoparticles that adsorb the constituent species.

  19. Intermolecular interaction of thiosemicarbazone derivatives to solvents and a potential Aedes aegypti target

    Science.gov (United States)

    da Silva, João Bosco P.; Hallwass, Fernando; da Silva, Aluizio G.; Moreira, Diogo Rodrigo; Ramos, Mozart N.; Espíndola, José Wanderlan P.; de Oliveira, Ana Daura T.; Brondani, Dalci José; Leite, Ana Cristina L.; Merz, Kenneth M.

    2015-08-01

    DFT calculations were used to access information about structure, energy and electronic properties of series of phenyl- and phenoxymethyl-(thio)semicarbazone derivatives with demonstrated activity against the larvae of Aedes aegypti in stage L4. The way as the thiosemicarbazone derivatives can interact with solvents like DMSO and water were analyzed from the comparison between calculated and experimental 1H NMR chemical shifts. The evidences of thiosemicarbazone derivatives making H-bond interaction to solvent have provide us insights on how they can interact with a potential A. aegypti's biological target, the Sterol Carrier Protein-2.

  20. Prediction of thermodynamic instabilities of protein solutions from simple protein–protein interactions

    International Nuclear Information System (INIS)

    D’Agostino, Tommaso; Solana, José Ramón; Emanuele, Antonio

    2013-01-01

    Highlights: ► We propose a model of effective protein–protein interaction embedding solvent effects. ► A previous square-well model is enhanced by giving to the interaction a free energy character. ► The temperature dependence of the interaction is due to entropic effects of the solvent. ► The validity of the original SW model is extended to entropy driven phase transitions. ► We get good fits for lysozyme and haemoglobin spinodal data taken from literature. - Abstract: Statistical thermodynamics of protein solutions is often studied in terms of simple, microscopic models of particles interacting via pairwise potentials. Such modelling can reproduce the short range structure of protein solutions at equilibrium and predict thermodynamics instabilities of these systems. We introduce a square well model of effective protein–protein interaction that embeds the solvent’s action. We modify an existing model [45] by considering a well depth having an explicit dependence on temperature, i.e. an explicit free energy character, thus encompassing the statistically relevant configurations of solvent molecules around proteins. We choose protein solutions exhibiting demixing upon temperature decrease (lysozyme, enthalpy driven) and upon temperature increase (haemoglobin, entropy driven). We obtain satisfactory fits of spinodal curves for both the two proteins without adding any mean field term, thus extending the validity of the original model. Our results underline the solvent role in modulating or stretching the interaction potential

  1. The distribution of n-caprylic acid between organic solvents and aqueous sodium sulfate solution

    International Nuclear Information System (INIS)

    Gloe, K.; Muehl, P.; Kholkin, A.I.; Gindin, L.M.

    1981-01-01

    The distribution of 14 C-labelled n-caprylic acid between n-decane, benzene, isoamyl acetate, diisopropyl ketone, isoamyl alcohol and an aqueous 0.6 molar sodium sulfate solution was studied. The distribution constants and the dimerisation constants were determined for the reactions HRsub((w)) reversible HRsub((org)) and 2 HRsub((org)) reversible (HR)sub(2(org)), respectively. Both the effect of the solvent on the acid distribution and the importance of such studies for the interpretation of liquid-liquid extraction equilibria are discussed. (author)

  2. Cyclohexanone solvent extraction of 99TcO4 from alkaline nuclear waste solutions

    International Nuclear Information System (INIS)

    Schulz, W.W.

    1980-01-01

    Although the 99 Tc cyclohexanone solvent extraction process is still in the bench-scale development stage, the process appears well suited for engineering-scale removal of 99 Tc from alkaline Hanford waste solutions. The most pressing process development need is to resolve the phase disengaging problems encountered during water stripping operations. Stripping tests in pulse columns and/or centrifugal contactors are particularly needed to determine the magnitude of the phase disengaging problem in engineering-scale equipment and to find suitable remedies. 5 figures, 7 tables

  3. The solvent extraction of cerium from sulphate solution - mini plant trials

    International Nuclear Information System (INIS)

    Soldenhoff, K.; Wilkins, D.; Ring, R.

    1998-01-01

    Full text: The Mt. Weld deposit in Western Australia has a complex rare earth mineralisation. The rare earth phosphate minerals, which include monazite, are amenable to conventional caustic cracking followed by hydrochloric acid dissolution of the trivalent rare earths. The presence of the mineral cerianite in the ore, which is unaffected by the alkali attack, results in rejection of a considerable proportion of the cerium to the acid leach residue. The recovery of cerium from a sulphate solution, resulting from the processing of such a residue, is the subject of the current paper. The liquor treated by solvent extraction contained 63 g L -1 rare earths and the cerium to total rare earth ratio was 75%. Other impurities, including Fe and Th, totalled 2000 ppm. A solvent mixture of commercially available extractants in a low aromatic content diluent was used to extract Ce 4+ selectively over the trivalent rare earths. Partial co-extraction of Fe and Th occurred but it was found that these elements were not easily stripped and therefore selective back extraction of cerium was possible. The cerium was stripped from the organic phase by hydrochloric acid and hydrogen peroxide. In continuous counter-current trials two extraction stages and three strip stages were used. In order to produce two grades of strip liquor, stripping was divided into two circuits. The first strip circuit consisting of a single stage, contained proportionally more of the trivalent rare earths. The second strip circuit, consisting of two stages, removed the remaining cerium with proportionally less of the rare earths. A bleed solvent stream was treated for removal of impurities to prevent build-up in the solvent. In the continuous counter current trials, 95% Ce 4+ extraction was achieved and the Ce to total rare earth ratio was upgraded to > 99%

  4. stripping of uranium from DEHPA/TOPO solvent by ammonium carbonate solutions

    International Nuclear Information System (INIS)

    Khorfan, S.; Shino, O.; Wahood, A.; Dahdouh, A.

    2002-01-01

    Uranium is recovered from phosphoric acid by the DEHPA/TOPO process. In this process uranium is stripped from the loaded DEHPA/TOPO solvent in the second cycle by an ammonium carbonate solution. This paper studied stripping of uranium from 0.3 Mol DEHPA/0.075 Mol TOPO in kerosene by different ammonium carbonate solutions. The ammonium carbonate solutions tested were either made locally from ammonia and carbon dioxide gases or commercial and laboratory grades available on the market. A comparison was made between these carbonate solutions in terms of purity, stripping efficiency and phase separation. Both stripping and phase separation were carried out under different conditions of phase ratio and concentrations. The results obtained showed that ammonium carbonate prepared from direct synthesis of ammonia and carbon dioxide gases had a high purity and gave the same stripping yield as the laboratory grade. The phase separation was also slightly improved using a pure synthesized ammonium carbonate solution. the phase separation was found to be best at concentration of 0.5 Mol/L ammonium carbonate solution and at a phase A/O of 1/1 and a temperature of 50 degree centigrade. It was possible to obtain >99% yield by operating 2 stripping stages counter currently under these conditions. (authors)

  5. A study of the solvent effect on the chemical interaction between ortho-positronium and iron(III)-chloride

    International Nuclear Information System (INIS)

    Vertes, A.

    1980-01-01

    The chemical rate constant (k) between ortho-positronium (o-Ps) and iron(III)-chloride was measured in donor solvents as benzene, acetone, pyridine and ethanol. The minimal k was obtained in benzene and the maximal one in acetone. The minimal k value was explained by the low dispersity of FeCl 3 in benzene, and the high rate of the interaction in acetone was considered to be the result of the presence of monomer and dimer iron(III)-species and of the chloride coordination to iron(III). The probability of Ps formation depended only on the character of the solvent and not on the concentration of the FeCl 3 solute. (author)

  6. Extraction of Trivalent Actinides and Lanthanides from Californium Campaign Rework Solution Using TODGA-based Solvent Extraction System

    Energy Technology Data Exchange (ETDEWEB)

    Benker, Dennis [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Delmau, Laetitia Helene [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Dryman, Joshua Cory [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2017-07-01

    This report presents the studies carried out to demonstrate the possibility of quantitatively extracting trivalent actinides and lanthanides from highly acidic solutions using a neutral ligand-based solvent extraction system. These studies stemmed from the perceived advantage of such systems over cationexchange- based solvent extraction systems that require an extensive feed adjustment to make a low-acid feed. The targeted feed solutions are highly acidic aqueous phases obtained after the dissolution of curium targets during a californium (Cf) campaign. Results obtained with actual Cf campaign solutions, but highly diluted to be manageable in a glove box, are presented, followed by results of tests run in the hot cells with Cf campaign rework solutions. It was demonstrated that a solvent extraction system based on the tetraoctyl diglycolamide molecule is capable of quantitatively extracting trivalent actinides from highly acidic solutions. This system was validated using actual feeds from a Cf campaign.

  7. Aqueous solutions/nuclear glasses interactions

    International Nuclear Information System (INIS)

    Delage, F.; Advocat, T.; Vernaz, E.; Crovisier, J.L.

    1991-01-01

    Interactions results of the borosilicate glass used in radioactive wastes confinement and aqueous solutions at various temperature and PH show that for the glass components: - the release rate evolution follows an Arrhenius law, - in acid PH, there is a selective dissolution, - in basic PH, there is a stoechiometric dissolution [fr

  8. Manipulating Single Microdroplets of NaCl Solutions: Solvent Dissolution, Microcrystallization, and Crystal Morphology

    DEFF Research Database (Denmark)

    Utoft, Anders; Kinoshita, Koji; Bitterfield, Deborah

    2018-01-01

    that the same Epstein−Plesset (EP) model, which was originally developed for diffusion-controlled dissolution and uptake of gas, and successfully applied to liquid-in-liquid dissolution, can now also be applied to describe the diffusion-controlled uptake of water from a water-saturated environment using...... of nucleation in the decane system as compared to the octanol system. Thus, the crystal structure is reported to be dendritic for NaCl solution microdroplets dissolving rapidly and nucleating violently in octanol, while they are formed as single cubic crystals in a gentler way for solution-dissolution in decane....... These new techniques and analyses can now also be used for any other system where all relevant parameters are known. An example of this is control of drug/hydrogel/emulsion particle size change due to solvent uptake....

  9. Interactions between wood and coatings with low organic solvent content

    NARCIS (Netherlands)

    Meijer, de M.

    1999-01-01

    The aim of the work described in this thesis is to improve the knowledge on the fundamental interactions between low VOC-coatings and wood, in particular in relation to wood protection in exterior use. To avoid environmental damage and dangerous conditions in the workplace, low-VOC paints

  10. Solvent effects on ion-receptor interactions in the presence of an external electric field.

    Science.gov (United States)

    Novák, Martin; Foroutan-Nejad, Cina; Marek, Radek

    2016-11-09

    In this work we investigated the influence of an external electric field on the arrangement of the solvent shells around ions interacting with a carbon-based receptor. Our survey reveals that the mechanism of interaction between a monoatomic ion and a π-type ion receptor varies by the variation in the solvent polarity, the nature of the ion, and the strength of the external field. The characteristics of the ion-surface interaction in nonpolar solvents are similar to those observed in a vacuum. However, in water, we identified two mechanisms. Soft and polarizable ions preferentially interact with the π-receptor. In contrast, two bonded states were found for hard ions. A fully solvated ion, weakly interacting with the receptor at weak field, and a strong π-complex at the strong-field regime were identified. An abrupt variation in the potential energy surface (PES) associated with the rearrangement of the solvation shell on the surface of the receptor induced by an external field was observed both in implicit and explicit solvent environments. The electric field at which the solvation shell breaks is proportional to the hardness of the ion as has been suggested recently based on experimental observations.

  11. Effects of solute-solute interactions on protein stability studied using various counterions and dendrimers.

    Directory of Open Access Journals (Sweden)

    Curtiss P Schneider

    Full Text Available Much work has been performed on understanding the effects of additives on protein thermodynamics and degradation kinetics, in particular addressing the Hofmeister series and other broad empirical phenomena. Little attention, however, has been paid to the effect of additive-additive interactions on proteins. Our group and others have recently shown that such interactions can actually govern protein events, such as aggregation. Here we use dendrimers, which have the advantage that both size and surface chemical groups can be changed and therein studied independently. Dendrimers are a relatively new and broad class of materials which have been demonstrated useful in biological and therapeutic applications, such as drug delivery, perturbing amyloid formation, etc. Guanidinium modified dendrimers pose an interesting case given that guanidinium can form multiple attractive hydrogen bonds with either a protein surface or other components in solution, such as hydrogen bond accepting counterions. Here we present a study which shows that the behavior of such macromolecule species (modified PAMAM dendrimers is governed by intra-solvent interactions. Attractive guanidinium-anion interactions seem to cause clustering in solution, which inhibits cooperative binding to the protein surface but at the same time, significantly suppresses nonnative aggregation.

  12. A study of fluorescence properties of citrinin in β-cyclodextrin aqueous solution and different solvents

    International Nuclear Information System (INIS)

    Zhou Youxiang; Chen Jianbiao; Dong Lina; Lu Liang; Chen Fusheng; Hu Dingjin; Wang Xiaohong

    2012-01-01

    Citrinin (CIT) is a nephrotoxic mycotoxin initially isolated from filamentous fungus Penicilliu citrinum. It was later isolated from several other species, such as Aspergillus and Monascus. It has a conjugated, planar structure that gives it a natural fluorescence ability, which can be used to develop sensitive methods for detecting CIT in food. In this paper, we used the spectrofluorescence technique to study the effects of pH value, β-cyclodextrin (β-CD) and organic solvents on the CIT fluorescence intensity. The results show that lower pH value, aceitc acid, β-CD and acetonitrile can induce a higher fluorescence intensity of CIT, but methanol or H 2 O has a decreasing effect on the fluorescence intensity of CIT. Findings in this study provide a theoretical basis for development of a high sensitivity fluorescence-based trace analysis for CIT detection. - Highlights: ► The effects of pH, solvents and β-CD on the fluorescence of citrinin are analyzed. ► [H] + , acetic acid, β-CD and acetonitrile can induce CIT fluorescence enhancement. ► Methanol and H 2 O can induce CIT fluorescence reduction. ► The 1:1 inclusion complex of CIT/β-CD can form in acidic phosphate solution.

  13. Theoretical investigation of the weak interaction between graphene and alcohol solvents

    Science.gov (United States)

    Wang, Haining; Chen, Sian; Lu, Shanfu; Xiang, Yan

    2017-05-01

    The dispersion of graphene in five different alcohol solvents was investigated by evaluating the binding energy between graphene and alcohol molecules using DFT-D method. The calculation showed the most stable binding energy appeared at the distance of ∼3.5 Å between graphene and alcohol molecules and increased linearly as changing the alcohol from methanol to 1-pentanol. The weak interaction was further graphically illustrated using the reduced density gradient method. The theoretical study revealed alcohols with more carbon atoms could be a good starting point for screening suitable solvents for graphene dispersion.

  14. Rirang uranium ore processing: continuous solvent extraction of uranium from Rirang ore acid digestion solution

    International Nuclear Information System (INIS)

    Riza, F.; Nuri, H. L.; Waluya, S.; Subijanto, A.; Sarono, B.

    1998-01-01

    Separation of uranium from Rirang ore acid digestion solution by means of continuous solvent extraction using mixer-settlers has been studied and a mixture of 0.3 M D2EHPA and 0.075 M TOPO extracting agent and kerosene diluent is employed to recover and separate uranium from Th, RE, phosphate containing solution. The experiments have been conducted batch-wise and several parameters have been studied including the aqueous to organic phase ratio, A/O, the extraction and the stripping times, and the operation temperature. The optimum conditions for extraction have been found to be A/O = 2 ratio, five minute extraction time per stage at room temperature. The uranium recovery of 99.07% has been achieved at those conditions whilst U can be stripped from the organic phase by 85% H 3 PO 4 solution with an O/A = 1 for 5 minutes stripping time per stage, and in a there stage operation at room temperature yielding a 100% uranium recovery from the stripping process

  15. Solvent-extraction and purification of uranium(VI) and molybdenum(VI) by tertiary amines from acid leach solutions

    International Nuclear Information System (INIS)

    La Gamma, Ana M.G.; Becquart, Elena T.; Chocron, Mauricio

    2008-01-01

    Considering international interest in the yellow-cake price, Argentina is seeking to exploit new uranium ore bodies and processing plants. A study of similar plants would suggest that solvent- extraction with Alamine 336 is considered the best method for the purification and concentration of uranium present in leaching solutions. In order to study the purification of these leach liquors, solvent-extraction tests under different conditions were performed with simulated solutions which containing molybdenum and molybdenum-uranium mixtures. Preliminary extraction tests carried out on mill acid-leaching liquors are also presented. (authors)

  16. Solution Phase Measurement of Both Weak Sigma and C-H---X- Hydrogen Bonding Interactions in Synthetic Anion Receptors

    Energy Technology Data Exchange (ETDEWEB)

    Berryman, Mr. Orion B. [University of Oregon; Sather, Mr. Aaron C [University of Oregon; Hay, Benjamin [ORNL; Meisner, Mr. Jeffrey S. [University of Oregon; Johnson, Prof. Darren W. [University of Oregon

    2008-01-01

    A series of tripodal receptors preorganize electron-deficient aromatic rings to bind halides in organic solvents using weak sigma anion-to-arene interactions or C-H---X- hydrogen bonds. 1H NMR spectroscopy proves to be a powerful technique for quantifying binding in solution, and determining the interaction motifs, even in cases of weak binding.

  17. Chemical Speciation and Bond Lengths of Organic Solutes by Core-Level Spectroscopy: pH and Solvent Influence on p-Aminobenzoic Acid.

    Science.gov (United States)

    Stevens, Joanna S; Gainar, Adrian; Suljoti, Edlira; Xiao, Jie; Golnak, Ronny; Aziz, Emad F; Schroeder, Sven L M

    2015-05-04

    Through X-ray absorption and emission spectroscopies, the chemical, electronic and structural properties of organic species in solution can be observed. Near-edge X-ray absorption fine structure (NEXAFS) and resonant inelastic X-ray scattering (RIXS) measurements at the nitrogen K-edge of para-aminobenzoic acid reveal both pH- and solvent-dependent variations in the ionisation potential (IP), 1s→π* resonances and HOMO-LUMO gap. These changes unequivocally identify the chemical species (neutral, cationic or anionic) present in solution. It is shown how this incisive chemical state sensitivity is further enhanced by the possibility of quantitative bond length determination, based on the analysis of chemical shifts in IPs and σ* shape resonances in the NEXAFS spectra. This provides experimental access to detecting even minor variations in the molecular structure of solutes in solution, thereby providing an avenue to examining computational predictions of solute properties and solute-solvent interactions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Effects of molecular interactions and the existence of different molecular forms of sodium fluoresceinate in solutions

    International Nuclear Information System (INIS)

    Golubeva, N.G.

    1989-01-01

    The results of measurement of fluorescence and absorption spectra of sodium fluoresceinate (FLNa) in different solutions and blood plasma are presented. The influence of solvent nature, its polarity, medium concentration and acidity on frequency, intensity and shape of fluorescence and absorption lines was analyzed. A general medium effect on fluorescence line spectral absorption was calculated from Lippert's equation. The influence of specific interactions has been analyzed on the example of acid-base interactions and hydrogen bonds in two- and multicomponent solutions. Computer processing of the spectra obtained allows to separate some forms of existing fluorophor molecules and to get data on the dynamics of their changes in different solutions. A special attention was given to the analysis of absorption and fluorescence bands of FLNa at its interaction with different proteins and lipids in solutions. From the analysis of data obtained a number of conclusions was drawn on the state of fluophor at its interactions with biological media. (author)

  19. A study of the evaporation of a solvent from a solution--application to writing ink aging.

    Science.gov (United States)

    Cantú, Antonio A

    2012-06-10

    When writing ink is placed on a substrate, a drying process begins. This process is dependent on the composition of the ink and of the substrate. Lociciro et al. provide an equation that describes the drying process based on models developed by earlier investigators. The work given here develops an equation for the drying process that is based on a different and rather simple model. This model considers the evaporation of a solution in an opened vertical container (e.g., a beaker) and consists of a volatile, non-hygroscopic solvent with a non-volatile solute dissolved in it. Three assumptions are made: (a) the rate of evaporation is proportional to the vapor pressure of the solution and to the solution's exposed surface area, (b) this solution vapor pressure is proportional to the solvent vapor pressure with the proportionality constant being the solvent mole fraction (Raoult's law), and (c) a small fraction of the solvent remains trapped in the solute after evaporation ceases. What results is a differential equation, which, when solved, gives the solvent weight W(t) as an implicit function. What emerges naturally from this treatment is the fact that the function W(t) can have a point of maximum acceleration. Prior to this point the drying process is fast and after this point, the drying process is slow. An approximation to W(t) is taken to be the sum of two exponential functions, one describing the fast drying region and the second describing the subsequent slow drying region. Upon including an additive constant, this approximation turns out to be similar to, but not the same as that provided by Lociciro et al. However, their equivalence is shown and then tested using the two inks examined by Lociciro et al. (the drying of a Bic and a Staedtler blue ballpoint ink). The examples of (solvent+solute) systems ("inks") given here consist of the solvent (2-phenoxyethanol) and a solute such as a dye (crystal violet) or a polymer resin such as synthetic resin SK or

  20. Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yanyan; Su, Mao; Yu, Xiaofei; Zhou, Yufan; Wang, Jungang; Cao, Ruiguo; Xu, Wu; Wang, Chongmin; Baer, Donald R.; Borodin, Oleg; Xu, Kang; Wang, Yanting; Wang, Xue-Lin; Xu, Zhijie; Wang, Fuyi; Zhu, Zihua

    2018-02-06

    Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC, which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.

  1. Size effects of solvent molecules on the phase behavior and effective interaction of colloidal systems with the bridging attraction

    International Nuclear Information System (INIS)

    Chen, Jie; Wang, Xuewu; Kline, Steven R; Liu, Yun

    2016-01-01

    There has been much recent research interest towards understanding the phase behavior of colloidal systems interacting with a bridging attraction, where the small solvent particles and large solute colloidal particles can be reversibly associated with each other. These systems show interesting phase behavior compared to the more widely studied depletion attraction systems. Here, we use Baxter’s two-component sticky hard sphere model with a Percus–Yevick closure to solve the Ornstein–Zernike equation and study the size effect on colloidal systems with bridging attractions. The spinodal decomposition regions, percolation transition boundaries and binodal regions are systematically investigated as a function of the relative size of the small solvent and large solute particles as well as the attraction strength between the small and large particles. In the phase space determined by the concentrations of small and large particles, the spinodal and binodal regions form isolated islands. The locations and shapes of the spinodal and binodal regions sensitively depend on the relative size of the small and large particles and the attraction strength between them. The percolation region shrinks by decreasing the size ratio, while the binodal region slightly expands with the decrease of the size ratio. Our results are very important in understanding the phase behavior for a bridging attraction colloidal system, a model system that provides insight into oppositely charged colloidal systems, protein phase behavior, and colloidal gelation mechanisms. (paper)

  2. Size effects of solvent molecules on the phase behavior and effective interaction of colloidal systems with the bridging attraction.

    Science.gov (United States)

    Chen, Jie; Wang, Xuewu; Kline, Steven R; Liu, Yun

    2016-11-16

    There has been much recent research interest towards understanding the phase behavior of colloidal systems interacting with a bridging attraction, where the small solvent particles and large solute colloidal particles can be reversibly associated with each other. These systems show interesting phase behavior compared to the more widely studied depletion attraction systems. Here, we use Baxter's two-component sticky hard sphere model with a Percus-Yevick closure to solve the Ornstein-Zernike equation and study the size effect on colloidal systems with bridging attractions. The spinodal decomposition regions, percolation transition boundaries and binodal regions are systematically investigated as a function of the relative size of the small solvent and large solute particles as well as the attraction strength between the small and large particles. In the phase space determined by the concentrations of small and large particles, the spinodal and binodal regions form isolated islands. The locations and shapes of the spinodal and binodal regions sensitively depend on the relative size of the small and large particles and the attraction strength between them. The percolation region shrinks by decreasing the size ratio, while the binodal region slightly expands with the decrease of the size ratio. Our results are very important in understanding the phase behavior for a bridging attraction colloidal system, a model system that provides insight into oppositely charged colloidal systems, protein phase behavior, and colloidal gelation mechanisms.

  3. Elucidation of the structure of organic solutions in solvent extraction by combining molecular dynamics and X-ray scattering

    International Nuclear Information System (INIS)

    Ferru, G.; Gomes Rodrigues, D.; Berthon, L.; Guilbaud, P.; Diat, O.; Bauduin, P.

    2014-01-01

    Knowledge of the supramolecular structure of the organic phase containing amphiphilic ligand molecules is mandatory for full comprehension of ionic separation during solvent extraction. Existing structural models are based on simple geometric aggregates, but no consensus exists on the interaction potentials. Herein, we show that molecular dynamics crossed with scattering techniques offers key insight into the complex fluid involving weak interactions without any long range ordering. Two systems containing mono- or diamide extractants in heptane and contacted with an aqueous phase were selected as examples to demonstrate the advantages of coupling the two approaches for furthering fundamental studies on solvent extraction. (authors)

  4. Photoluminescence Spectroscopy of Rhodamine 800 Aqueous Solution and Dye-Doped Polymer Thin-Film: Concentration and Solvent Effects

    Science.gov (United States)

    Le, Khai Q.; Dang, Ngo Hai

    2018-05-01

    This paper investigates solvent and concentration effects on photoluminescence (PL) or fluorescence properties of Rhodamine 800 (Rho800) dyes formed in aqueous solution and polymer thin-film. Various commonly used organic solvents including ethanol, methanol and cyclopentanol were studied at a constant dye concentration. There were small changes in the PL spectra for the different solvents in terms of PL intensity and peak wavelength. The highest PL intensity was observed for cyclopentanol and the lowest for ethanol. The longest peak wavelength was found in cyclopentanol (716 nm) and the shortest in methanol (708 nm). Dissolving the dye powder in the methanol solvent and varying the dye concentration in aqueous solution from the high concentrated solution to highly dilute states, the wavelength tunability was observed between about 700 nm in the dilute state and 730 nm at high concentration. Such a large shift may be attributed to the formation of dye aggregates. Rho800 dye-doped polyvinyl alcohol (PVA) polymer thin-film was further investigated. The PL intensity of the dye in the form of thin-film is lower than that of the aqueous solution form whereas the peak wavelength is redshifted due to the presence of PVA. This paper, to our best knowledge, reports the first study of spectroscopic properties of Rho800 dyes in various forms and provides useful guidelines for production of controllable organic luminescence sources.

  5. Influence of the type of solvent on the development of superhydrophobicity from silane-based solution containing nanoparticles

    Science.gov (United States)

    Pantoja, M.; Abenojar, J.; Martinez, M. A.

    2017-03-01

    Superhydrophobic surfaces are very appealing for numerous industrial applications due to their self-cleaning capacity. Although there are different methods to manufacture superhydrophobic surfaces, some of them do not keep the aesthetic appearance of the neat surface. Sol-gel processes are a valid alternative when transparent coatings are desired. The main goal of this research is to study the viability of this method by making superhydrophobic coatings from silane-based solution containing SiO2 nanoparticles. The effect of using different solvents is investigated, as well as the role played by the different components of the solution (silane, nanoparticles and solvent). Solutions of methyltrimethoxisilane (MTS) and tetraethoxysilane (TEOS) and 1% of SiO2 (%wt) were prepared with different solvents (ethanol, ethanol/water and white spirit). The hydrophobicity of the developed coatings is studied using contact angle measurements, while the aesthetic appearance is evaluated with gloss and color measurements. Also, infrared spectroscopy, dynamic light scattering (DSL), and surface tension measurements are used to study the silane solutions. The results show that the capacity of solvents to promote the dispersion of the nanoparticles is crucial to ensuring superhydrophobicity, since these agglomerates provide the micro- and nano- surface roughness required to get a hierarchical structure. However, the combined use of silanes and nanoparticles is key to make a superhydrophobic surface because physical (the surface roughness provided by nanoparticles) and chemical characteristics (hydrophobicity provided by silanes) are coupled.

  6. Homogeneous solutions of hydrophilic enzymes in nonpolar organic solvents. New systems for fundamental studies and biocatalytic transformations.

    Science.gov (United States)

    Mozhaev, V V; Poltevsky, K G; Slepnev, V I; Badun, G A; Levashov, A V

    1991-11-04

    A typical hydrophilic enzyme, CT, can be dissolved in nonpolar organic solvents (n-octane, cyclohexane and toluene) up to microM concentrations. In the homogeneous solution obtained, the enzyme possesses catalytic activity and enormously high thermostability. It does not lose this activity even after several hours refluxing in octane (126 degrees C) or cyclohexane (81 degrees C).

  7. Estimation of the nucleation kinetics for the anti-solvent crystallisation of paracetamol in methanol/water solutions

    Science.gov (United States)

    Ó'Ciardhá, Clifford T.; Frawley, Patrick J.; Mitchell, Niall A.

    2011-08-01

    In this work the primary nucleation kinetics have been estimated for the anti-solvent crystallisation of paracetamol in methanol-water solutions from metastable zone widths (MSZW) and induction times at 25 °C. Laser back-scattering via a focused beam reflectance Measurement (FBRM ®) is utilised to detect the onset of nucleation. The theoretical approach of Kubota was employed to estimate the nucleation kinetics, which accounts for the sensitivity of the nucleation detection technique. This approach is expanded in this work to analyse the induction time for an anti-solvent crystallisation process. Solvent composition is known to have a significant impact on the measured induction times and MSZW. The induction time in this paper was measured from 40% to 70% mass water and the MSZW is measured from 40% to 60% mass water. The primary focus of the paper was to gauge the extent of how solvent composition affects nucleation kinetics so that this effect may be incorporated into a population balance model. Furthermore, the effects of solvent composition on the estimated nucleation rates are investigated. The primary nucleation rates were found to decrease with dynamic solvent composition, with the extent of their reduction linked to the gradient of the solubility curve. Finally, both MSZW and induction time methods have been found to produce similar estimates for the nucleation parameters.

  8. Tuning the Morphology of All-Polymer OPVs through Altering Polymer–Solvent Interactions

    KAUST Repository

    Pavlopoulou, Eleni

    2014-09-09

    © 2014 American Chemical Society. In this work, we investigated the effects of solvent(s)-polymer(s) interactions on the morphology of all-polymer bulk-heterojunction (BHJ) active layers cast from cosolutions. We demonstrate that altering the interactions between the solvent and both the donor and acceptor polymers in the cosolution prior to film-casting induces different solid-state morphological characteristics that subsequently leads to differences in the device performance of organic photovoltaics (OPV). Poly(3-hexylthiophene), P3HT, was codissolved poly[[N,N\\'-bis(2-octyldodecyl)-napthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5 ′-(2,2 ′-bithiophene)], P(NDI2OD-T2), or otherwise known as ActivInk N2200, in dichlorobenzene, chlorobenzene, and xylene. According to the qualitative interaction map we propose, all three solvents exhibit favorable interactions with P3HT. The extent of incompatibility these solvents exhibit with P(NDI2OD-T2), however, varies, with xylene as the worst solvent for P(NDI2OD-T2) among those examined. Polymer-polymer interactions in xylene are, thus, more favorable compared to P(NDI2OD-T2)-xylene interactions. Grazing-incidence wide-angle X-ray scattering measurements on the cast films suggest that this preferential affinity between the two polymers disrupts crystallization in the blends; P(NDI2OD-T2) crystallinity decreases and, concurrently, results in shorter P3HT coherence lengths. Significant mixing of the two polymers is also evidenced. OPVs comprising P3HT and P(NDI2OD-T2) active layers cast from xylene exhibit the best device characteristics compared to OPVs whose active layers are cast from di- or mono-chlorobenzene. We attribute the improved OPV performance for the xylene-cast active layer to the presence of a more intermixed network of nanocrystalline domains of the two polymers, which originates from the affinity of P3HT and P(NDI2OD-T2) in the parent cosolution.

  9. Influence of electrolyte ion-solvent interactions on the performances of supercapacitors porous carbon electrodes

    Science.gov (United States)

    Decaux, C.; Matei Ghimbeu, C.; Dahbi, M.; Anouti, M.; Lemordant, D.; Béguin, F.; Vix-Guterl, C.; Raymundo-Piñero, E.

    2014-10-01

    The development of advanced and safe electrochemical supercapacitors or hybrid supercapacitors combining a battery electrode material such as graphite and a porous carbon electrode implies the use of new electrolytes containing a tetra-alkylammonium or lithium salt dissolved preferentially in a safe and environmentally friendly solvent such as alkylcarbonates. In those systems, the carbon porosity of the activated carbon electrode controls the electrochemical behavior of the whole device. In this work, it is demonstrated that electrolytes containing highly polarizing ions such as Li+ dissolved in polar solvents such as alkylcarbonates do not completely loss their solvation shell at the opposite of what is observed for poorly solvated cations like TEABF4. As a consequence, the optimal carbon pore size for obtaining the largest energy density, while keeping a high power density, is wider when strongly solvated cations, like Li+ are used than for conventional organic electrolytes using acetonitrile as solvent and TEA+ as salt cations. TEA+ cations are easily desolvated and hence are able to penetrate in small pores matching the dimensions of bare ions. The dissimilarity of behavior of alkylcarbonates and acetonitrile based electrolytes highlights the importance of ion-solvent interactions when searching the optimal porous texture for the electrode material.

  10. Solute-matrix and Solute-Solute Interactions during Supercritical Fluid Extraction of Sea Buckthorn Leaves

    Czech Academy of Sciences Publication Activity Database

    Sajfrtová, Marie; Sovová, Helena

    2012-01-01

    Roč. 42, SI (2012), s. 1682-1691 E-ISSN 1877-7058. [International Congress of Chemical and Process Engineering CHISA 2012 and 15th Conference PRES 2012 /20./. Prague, 25.08.2012-29.08.2012] R&D Projects: GA TA ČR TA01010578 Institutional support: RVO:67985858 Keywords : supercritical fluid extraction * sea buckthom leaves * solute-solute interaction Subject RIV: CI - Industrial Chemistry, Chemical Engineering

  11. A Novel Mechanism for Chemical Sensing Based on Solvent-Fluorophore-Substrate Interaction: Highly Selective Alcohol and Water Sensor with Large Fluorescence Signal Contrast.

    Science.gov (United States)

    Chung, Kyeongwoon; Yang, Da Seul; Jung, Jaehun; Seo, Deokwon; Kwon, Min Sang; Kim, Jinsang

    2016-10-06

    Differentiation of solvents having similar physicochemical properties, such as ethanol and methanol, is an important issue of interest. However, without performing chemical analyses, discrimination between methanol and ethanol is highly challenging due to their similarity in chemical structure as well as properties. Here, we present a novel type of alcohol and water sensor based on the subtle differences in interaction among solvent analytes, fluorescent organic molecules, and a mesoporous silica gel substrate. A gradual change in the chemical structure of the fluorescent diketopyrrolopyrrole (DPP) derivatives alters their interaction with the substrate and solvent analyte, which creates a distinct intermolecular aggregation of the DPP derivatives on the silica gel substrate depending on the solvent environment and produces a change in the fluorescence color and intensity as a sensory signal. The devised sensor device, which is fabricated with simple drop-casting of the DPP derivative solutions onto a silica gel substrate, exhibited a completely reversible fluorescence signal change with large fluorescence signal contrast, which allows selective solvent detection by simple optical observation with the naked eye under UV light. Superior selectivity of the alcohol and water sensor system, which can clearly distinguish among ethanol, methanol, ethylene glycol, and water, is demonstrated.

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

    Science.gov (United States)

    de Oliveira, Heitor Fernando Nunes; Rinaldi, Roberto

    2015-05-11

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

  13. Separation of Molybdenum from Acidic High-Phosphorus Tungsten Solution by Solvent Extraction

    Science.gov (United States)

    Li, Yongli; Zhao, Zhongwei

    2017-10-01

    A solvent-extraction process for deep separation of molybdenum from an acidic high-phosphate tungsten solution was developed using tributyl phosphate (TBP) as the extractant and hydrogen peroxide (H2O2) as a complexing agent. The common aqueous complexes of tungsten and molybdenum (PMoxW12-xO40 3-, x = 0-12) are depolymerized to {PO4[Mo(O)2(O-O)]4}3- and {PO4[W(O)2(O-O)]4}3- by H2O2. The former can be preferentially extracted by TBP. The extractant concentration, phase contact time, H2O2 dosage, and H2SO4 concentration were optimized. By employing 80% by volume TBP, O:A = 1:1, 1.0 mol/L H2SO4, 1.0 mol/L H3PO4, a contact time of 2 min, and a molar ratio of H2O2/(W + Mo) equal to 1.5, 60.2% molybdenum was extracted in a single stage, while limiting tungsten co-extraction to 3.2%. An extraction isotherm indicated that the raffinate could be reduced to <0.1 g/L Mo in six stages of continuous counter-current extraction.

  14. Recovery of Cu(II from diluted aqueous solutions by non-dispersive solvent extraction

    Directory of Open Access Journals (Sweden)

    Alguacil, E. J.

    2002-08-01

    Full Text Available The removal of copper from diluted aqueous solutions with ACORGA M5640 extractant using non-dispersive solvent extraction technology was studied. It was possible to remove Cu(II below the international standars from solutions having initially as low concentration as 0,01 g/l under various experimental conditions, i.e aqueous pH 4.0, 10 % v/v ACORGA M5640 in Exxol D100, an organic flow of 100 ml/min, and an aqueous flow 50ml/min. Since the removal occurs by chelating ion exchange between copper from solution and protons from the extractant, the former was stripped by using a 180 g/l sulphuric acid solution which flowed (50 ml/min through the tube side organic was passed (400 ml/min through the shell side of the fibers of the module

    Se estudia la eliminación del cobre presente en disoluciones acuosas diluidas empleando el agente de extracción ACORGA M5640 y la tecnología de extracción con disolventes no dispersiva. Bajo las condiciones experimentales estudiadas, pH de la fase acuosa 4,0 ±0,1, 10 % v/v ACORGA M5640 en Exxsol D100, flujo de la fase orgánica 100 ml/min, flujo de la fase acuosa 50 ml/min, es posible eliminar el Cu(II, por debajo de los límites marcados internacionalmente, en disoluciones con un contenido tan bajo como 0,01 g/1 del metal. Debido a que la extracción transcurre mediante un intercambio catiónico (y formación de un compuesto tipo quelato entre el cobre presente en el medio acuoso y los protones del agente de extracción, el metal se puede reextraer mediante la utilización de una disolución de 180 g/1 de ácido sulfúrico que fluye (50 ml/min a través de la parte interior de las fibras del módulo, mientras que la fase orgánica fluye (400 ml/min por la parte exterior de las mismas fibras.

  15. Thermodynamic activity-based intrinsic enzyme kinetic sheds light on enzyme-solvent interactions.

    Science.gov (United States)

    Grosch, Jan-Hendrik; Wagner, David; Nistelkas, Vasilios; Spieß, Antje C

    2017-01-01

    The reaction medium has major impact on biocatalytic reaction systems and on their economic significance. To allow for tailored medium engineering, thermodynamic phenomena, intrinsic enzyme kinetics, and enzyme-solvent interactions have to be discriminated. To this end, enzyme reaction kinetic modeling was coupled with thermodynamic calculations based on investigations of the alcohol dehydrogenase from Lactobacillus brevis (LbADH) in monophasic water/methyl tert-butyl ether (MTBE) mixtures as a model solvent. Substrate concentrations and substrate thermodynamic activities were varied separately to identify the individual thermodynamic and kinetic effects on the enzyme activity. Microkinetic parameters based on concentration and thermodynamic activity were derived to successfully identify a positive effect of MTBE on the availability of the substrate to the enzyme, but a negative effect on the enzyme performance. In conclusion, thermodynamic activity-based kinetic modeling might be a suitable tool to initially curtail the type of enzyme-solvent interactions and thus, a powerful first step to potentially understand the phenomena that occur in nonconventional media in more detail. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 33:96-103, 2017. © 2016 American Institute of Chemical Engineers.

  16. The structure of the interface in the solvent mediated interaction of dipolar surfaces

    International Nuclear Information System (INIS)

    Dzhavakhidze, P.G.; Levadny, V.G.

    1987-08-01

    Interaction of two dipolar surfaces separated by a polar medium is considered within the framework of nonlocal electrostatics. The dipolar surface layers are modelled as regular lattices with fixed orientation of dipoles which are immersed into the solvent; solvent response is characterized by nonlocal dielectric function. The model is elaborated in order to reveal the role of the dipolar layer discreteness in the electric field produced by one surface and the interaction between two surfaces (which gives rise to the so called ''hydration'' or ''structural'' force acting between mineral surfaces and phospholipid bilayers). The discreteness effects are present only for commensurate lattices. Their special mutual arrangement then may lead to considerable reduction of structural forces, viz. the usual repulsion regime may change at short distances to attraction. Conditions are considered when repulsion is entirely replaced by attraction, i.e. the ''hydration barrier'' disappears. In appended note we discuss the role of solvation of surface dipolar groups. We propose an explanation of why two modes of decay (one with oscillative fine structure) may be present in the dependence of the force upon distance if the surface dipolar groups are immersed deep enough in the solvent and how the long-range oscillative mode disappears when the surface is but weakly solvated. (author). 35 refs, 5 figs

  17. The structure of the interface in the solvent-mediated interaction of dipolar surfaces

    International Nuclear Information System (INIS)

    Dzhavakhidze, P.G.; Kornyshev, A.A.; Levadny, V.G.

    1988-01-01

    Interaction of two dipolar surfaces separated by a polar medium is considered within the framework of nonlocal electrostatics. The dipolar-surface layers are modelled as regular lattices with fixed orientation of dipoles which are immersed into the solvent; solvent response is characterized by nonlocal dielectric function. The model is elaborated in order to reveal the role of the dypolar-layer discreteness in the electric field produced by one surface and the interaction between two surfaces (which gives rise to the so-called ''hydration'' or ''structural'' force acting between mineral surfaces and phospholipid bilayers). The discreteness effects are present only for commensurate lattices. Their special mutual arrangement then may lead to considerable reduction of structural forces, viz. the usual repulsion regime may change at short distances to attraction. Conditions are considered when repulsion is entirely replaced by attraction, i.e. the ''hydration barrier'' disappears. In appended note it is discussed the role of solvation of surface dipolar groups. It is proposed an explanation of why two modes of decay (one with oscillative fine structure) may be present in the dependence of the force upon distance, if the surface dipolar groups are immersed deep enough in the solvent, and how the long-range oscillative mode disappears when the surface is but weakly solvated

  18. Control of Chemical Equilibrium by Solvent: A Basis for Teaching Physical Chemistry of Solutions

    Science.gov (United States)

    Prezhdo, Oleg V.; Craig, Colleen F.; Fialkov, Yuriy; Prezhdo, Victor V.

    2007-01-01

    The study demonstrates that the solvent present in a system can highly alter and control the chemical equilibrium of a system. The results show that the dipole moment and polarizibility of a system can be highly altered by using different mixed solvents.

  19. Photostability of solutions of rare earth chelates in organic solvents and polymers

    International Nuclear Information System (INIS)

    Karasev, V.E.; Mirochnik, A.G.; Lysun, T.V.; Vovna, V.I.

    1990-01-01

    Consideration is given to results of comparative study of photochemical properties of rare erath chelate complexes (adducts of rare earth β-diketonates with triphenylphosphine oxide, hexamethylphosphotriamide, phenanthroline) in organic solvents and polymers. Effect of excitation conditions, composition, solvent, nature of ligand and rare earth ion on photolysis rate was investigated. 9 refs.; 2 figs.; 4 tabs

  20. Dependence of Interaction Free Energy between Solutes on an External Electrostatic Field

    Directory of Open Access Journals (Sweden)

    Pei-Kun Yang

    2013-07-01

    Full Text Available To explore the athermal effect of an external electrostatic field on the stabilities of protein conformations and the binding affinities of protein-protein/ligand interactions, the dependences of the polar and hydrophobic interactions on the external electrostatic field, −Eext, were studied using molecular dynamics (MD simulations. By decomposing Eext into, along, and perpendicular to the direction formed by the two solutes, the effect of Eext on the interactions between these two solutes can be estimated based on the effects from these two components. Eext was applied along the direction of the electric dipole formed by two solutes with opposite charges. The attractive interaction free energy between these two solutes decreased for solutes treated as point charges. In contrast, the attractive interaction free energy between these two solutes increased, as observed by MD simulations, for Eext = 40 or 60 MV/cm. Eext was applied perpendicular to the direction of the electric dipole formed by these two solutes. The attractive interaction free energy was increased for Eext = 100 MV/cm as a result of dielectric saturation. The force on the solutes along the direction of Eext computed from MD simulations was greater than that estimated from a continuum solvent in which the solutes were treated as point charges. To explore the hydrophobic interactions, Eext was applied to a water cluster containing two neutral solutes. The repulsive force between these solutes was decreased/increased for Eext along/perpendicular to the direction of the electric dipole formed by these two solutes.

  1. Quantifying the thermodynamic interactions of polyhedral boranes in solution to guide nanocomposite fabrication

    Energy Technology Data Exchange (ETDEWEB)

    Mutz, M. [University of Tennessee, Department of Chemistry (United States); Eastwood, Eric [Honeywell Kansas City Plant (United States); Lee, Mark E. [University of Missouri (United States); Bowen, Daniel E. [Honeywell Kansas City Plant (United States); Dadmun, M. D., E-mail: dad@utk.edu [University of Tennessee, Department of Chemistry (United States)

    2012-11-15

    The solubility of boron containing nanoparticles in a variety of solvents is quantified using static light scattering in conjunction with refractometry. Four polyhedral boranes were tested in this work, using refractometry to obtain dn/dc, while static light scattering quantifies A{sub 2}. A{sub 2} obtained from these measurements was then used to calculate {chi}, the solute-solvent interaction parameter, and the Hildebrand solubility parameter, {delta}, which provides a quantifiable method to identify good solvents. Of the nanoparticles studied, 1,3-di-o-carboranylpropane is thermodynamically stable in toluene, with a {chi} less than 0.5, a solubility limit of 2.47 mg/mL, and all solutions remaining clear with no visible particle settling. For all of the particles tested, there was good correlation between the physical observations of the solutions, {chi}, and {delta}. For instance, lower values of {chi} correspond to a smaller radius of gyration (R{sub g}). A list of suitable solvents based on {delta} is also presented.

  2. Development of a novel solvent for the simultaneous separation of strontium and cesium from dissolved Spent Nuclear Fuel solutions

    International Nuclear Information System (INIS)

    Catherine L. Riddle; John D. Baker; Jack D. Law; Christopher A. McGrath; David H. Meikrantz; Bruce J. Mincher; Dean R. Peterman; Terry A. Todd

    2004-01-01

    The recovery of Cs and Sr from acidic solutions by solvent extraction has been investigated. The goal of this project was to develop an extraction process to remove Cs and Sr from high-level waste in an effort to reduce the heat loading in storage. Solvents for the extraction of Cs and Sr separately have been used on both caustic and acidic spent nuclear fuel waste in the past. The objective of this research was to find a suitable solvent for the extraction of both Cs and Sr simultaneously from acidic nitrate media. The solvents selected for this research possess good stability and extraction behavior when mixed together. The extraction experiments were performed with 4,4,(5)-Di-(tbutyldicyclohexano)-18-crown-6 (DtBuCH18C6), Calix[4]arene-bis-(tert-octylbenzocrown-6) (BOBCalixC6) and 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol (Cs-7SB modifier) in a branched aliphatic kerosene (Isopar L). The BOBCalixC6 and Cs-7SB modifier were developed at Oak Ridge National Laboratory (ORNL) by Bonnesen et al. [1]. The values obtained from the SREX solvent for DSr in 1 M nitric acid ranged from 0.7 to 2.2 at 25 C and 10 C respectively. The values for DCs in 1 M nitric acid with the CSSX solvent ranged from 8.0 to 46.0 at 25 C and 10 C respectively. A new mixed solvent, developed at the Idaho National Engineering and Environmental Laboratory (INEEL) by Riddle et al. [2], showed distributions for Sr ranging from 8.8 to 17.4 in 1 M nitric acid at 25 C and 10 C respectively. The DCs for the mixed solvent ranged from 7.7 to 20.2 in 1 M nitric acid at 25 C to 10 C respectively. The unexpectedly high distributions for Sr at both 25 C and 10 C show a synergy in the mixed solvent. The DCs, although lower than with CSSX solvent, still showed good extraction behavior

  3. The effect of various solvents on the back channel of solution-processed In-Ga-Zn-O thin-film transistors intended for biosensor applications

    International Nuclear Information System (INIS)

    Kim, Si Joon; Jung, Joohye; Yoon, Doo Hyun; Kim, Hyun Jae

    2013-01-01

    This study investigated the effects of exposing solution-processed In-Ga-Zn-O (IGZO) thin-film transistors (TFTs), intended for biosensor applications, to various solvents. Various solvents, such as the nonpolar solvent chlorobenzene and the polar solvents ethanol and deionized (DI) water, were dropped and adsorbed on exposed IGZO channel surfaces. All IGZO TFT devices exhibited a negative threshold voltage shift and a sub-threshold swing degradation, without an accompanying degradation in field-effect mobility. These variations depended on the dielectric constant of the solvents; with the exception of the IGZO TFT device exposed to DI water, they all gradually returned to their initial states.

  4. Modeling Groundwater-Surface Water Interaction and Contaminant Transport of Chlorinated Solvent Contaminated Site

    Science.gov (United States)

    Yimer Ebrahim, Girma; Jonoski, Andreja; van Griensven, Ann; Dujardin, Juliette; Baetelaan, Okke; Bronders, Jan

    2010-05-01

    Chlorinated-solvent form one of the largest groups of environmental chemicals. Their use and misuse in industry have lead to a large entry of these chemicals into the environment, resulting in widespread dissemination and oftentimes environmental contamination. Chlorinated solvent contamination of groundwater resources has been widely reported. For instance, there has been much interest in the assessment of these contaminant levels and their evolutions with time in the groundwater body below the Vilvoorde-Machelen industrial area (Belgium). The long industrial history of the area has lead to complex patterns of pollution from multiple sources and the site has been polluted to the extent that individual plumes are not definable any more. Understanding of groundwater/surface water interaction is a critical component for determining the fate of contaminant both in streams and ground water due to the fact that groundwater and surface water are in continuous dynamic interaction in the hydrologic cycle. The interaction has practical consequences in the quantity and quality of water in either system in the sense that depletion and/or contamination of one of the system will eventually affect the other one. The transition zone between a stream and its adjacent aquifer referred to as the hyporheic zone plays a critical role in governing contaminant exchange and transformation during water exchange between the two water bodies. The hyporheic zone of Zenne River ( the main receptor ) is further complicated due to the fact that the river banks are artificially trained with sheet piles along its reach extending some 12 m below the surface. This study demonstrates the use of MODFLOW, a widely used modular three-dimensional block-centred finite difference, saturated flow model for simulating the flow and direction of movement of groundwater through aquifer and stream-aquifer interaction and the use of transport model RT3D, a three-dimensional multi-species reactive transport model

  5. ``Living polymers'' in organic solvents : stress relaxation in bicopper tetracarboxylate/tert-butyl cyclohexane solutions

    Science.gov (United States)

    Terech, P.; Maldivi, P.; Dammer, C.

    1994-10-01

    Viscoelastic solutions of a bicopper tetracarboxylate complex in tert-butylcyclohexane have been studied by dynamic rheology in a wide range of concentrations (0.5-1.5 % volume fraction). The zero shear viscosity, the elastic modulus, the terminal stress relaxation time and the height of the high-frequency dip, in a Cole-Cole representation of the complex elastic modulus, follow scaling laws. The related exponents are discussed in the context of the physics of “living polymers” : a term used to describe worm-like species undergoing scission/recombination reactions competing mainly with the reptation motions of the chains. The current system, made up of molecular threads (17.5 Å diameter) of Cu2(O2C-CH(C2H5)C4H9)4 in the apolar solvent, is representative of a “living polymer” where, instead of mechanisms involving transient star polymeric crosslinks, a reversible scission mechanism prevails. The dynamics in the high-frequency range evolves from a regime where reptation is the dominant relaxation mechanism to a cross-over regime where “breathing” fluctuations and Rouse motions become important. Large modifications of the stress relaxation function occur for more concentrated systems. The binary system is the first example of a “living polymer” in an organic solvent and exhibits elastic moduli (G ≈ ca. 120 Pa à φ = 1 %) which are at least 20 times larger than those found for the aqueous “living polymer” systems. Les solutions viscoélastiques d'un tétracarboxylate binucléaire de cuivre dans le tert-butylcyclohexane sont étudiées par rhéologie en mode dynamique dans une gamme étendue de concentrations (0,5 %-15,5 %). La viscosité à gradient nul, le module élastique, le temps terminal de relaxation et la hauteur du puits à haute fréquence, dans une représentation Cole-Cole du module élastique complexe, suivent des lois d'échelles. Les exposants correspondants sont discutés dans le contexte de la physique des “polymères vivants

  6. Selective nonspecific solvation under dielectric saturation and fluorescence spectra of dye solutions in binary solvents.

    Science.gov (United States)

    Bakhshiev, N G; Kiselev, M B

    1991-09-01

    The influence of selective nonspecific solvation on the fluorescence spectra of three substitutedN-methylphthalimides in a binary solvent system consisting of a nonpolar (n-heptane) and a polar (pyridine) component has been studied under conditions close to dielectric saturation. The substantially nonlinearity of the effect is confirmation that the spectral shifts of fluorescence bands depend on the number of polar solvent molecules involved in solvating the dye molecule. The measured fluorescence spectral shifts determined by substituting one nonpolar solvent molecula with a polar one in the proximity of the dye molecule agree quantitatively with the forecasts of the previously proposed semiempirical theory which describes this nonlinear solvation phenomenon.

  7. Recovery by solvent extraction of vanadium from spent catalysts leaching solutions using Primene 81R

    Directory of Open Access Journals (Sweden)

    Lozano, L. J.

    2001-10-01

    Full Text Available Recovery of vanadium contained in solutions coming from spent catalysts leaching process by means of solvent extraction techniques using primary amine Primene 81R, has been studied in this work, resulting in an industrial multistage process for the treatment of these effluents. Results obtained allows to propose an extraction mechanism for vanadium(V with this amine in acidic media, verifying the great influence of pH on the process and fix adequate ranges for variables: O/A ratio, organic phase composition, pH, stirring speed and phase separation speed. These values were simulated in industrial conditions. Vanadium is finally recovered by means of precipitation as ammonium metavanadate and later calcination to obtain vanadium pentoxide of commercial grade.

    En el presente trabajo se ha estudiado la recuperación del vanadio contenido en soluciones procedentes del proceso de lixiviación de catalizadores agotados, por medio de la técnica de extracción con disolventes, empleando la amina primaria PRIMENE 81R, planteando un proceso industrial multietapa para el tratamiento de estos efluentes. Los resultados obtenidos permiten proponer un mecanismo de extracción para el vanadio(V, con esta amina en medio ácido, verificando la gran influencia del pH en el proceso y Ajando los rangos adecuados para las siguientes variables: relación O/A, composición de la fase orgánica, pH, velocidad de agitación y velocidad de separación de fases. Esos valores se simularon en condiciones industriales. El vanadio se recupera finalmente precipitándolo como metavanadato amónico y posterior calcinación para obtener pentóxido de vanadio de calidad comercial.

  8. A study of photon interaction parameters in some commonly used solvents

    International Nuclear Information System (INIS)

    Singh, Tejbir; Kaur, Paramjeet; Singh, Parjit S

    2007-01-01

    Various parameters of dosimetric interest such as mass attenuation coefficients, effective atomic numbers and electron densities of some commonly used solvents such as acetonitrile (C 4 H 3 N), butanol (C 4 H 9 OH), chlorobenzene (C 6 H 5 Cl), diethylether (C 4 H 10 O), ethanol (C 2 H 5 OH), methanol (CH 3 OH), propanol (C 3 H 7 OH) and water (H 2 O) were computed in the wide energy range of 10 keV-100 GeV. A comparative study of two different methods used to compute effective atomic numbers has been done. It is observed that in the intermediate energy region (0.1-5 MeV), the mass attenuation coefficient values becomes almost the same for all the solvents, and the effective atomic number and electron density show almost constant values, whereas significant variation is observed in both lower (10-100 keV) and higher (5 MeV-100 GeV) energy regions for all the solvents, which may be due to the dominance of different partial interaction processes in different energy regions

  9. Molecular interactions in the betaine monohydrate-polyol deep eutectic solvents: Experimental and computational studies

    Science.gov (United States)

    Zahrina, Ida; Mulia, Kamarza; Yanuar, Arry; Nasikin, Mohammad

    2018-04-01

    DES (deep eutectic solvents) are a new class of ionic liquids that have excellent properties. The strength of interaction between molecules in the DES affects their properties and applications. In this work, the strength of molecular interactions between components in the betaine monohydrate salt and polyol (glycerol or/and propylene glycol) eutectic mixtures was studied by experimental and computational studies. The melting point and fusion enthalpy of the mixtures were measured using STA (Simultaneous Thermal Analyzer). The nature and strength of intermolecular interactions were observed by FT-IR and NMR spectroscopy. The molecular dynamics simulation was used to determine the number of H-bonds, percent occupancy, and radial distribution functions in the eutectic mixtures. The interaction between betaine monohydrate and polyol is following order: betaine monohydrate-glycerol-propylene glycol > betaine monohydrate-glycerol > betaine monohydrate-propylene glycol, where the latter is the eutectic mixture with the lowest stability, strength and extent of the hydrogen bonding interactions between component molecules. The presence of intra-molecular hydrogen bonding interactions, the inter-molecular hydrogen bonding interactions between betaine molecule and polyol, and also interactions between polyol and H2O of betaine monohydrate in the eutectic mixtures.

  10. Effect of solvent composition on the limiting current of anodic dissolution of tungsten in aqueous-ethanol solutions of alkali

    International Nuclear Information System (INIS)

    Konoplyantseva, N.A.; L'vova, L.A.; Davydov, A.D.; AN SSSR, Moscow. Inst. Ehlektrokhimii)

    1987-01-01

    The effect of quantitative composition of solvent on tungsten anodic dissolution in aqueous-ethanol solutions of KOH is studied. It is shown that with an increase in ethanol content in aqueous-ethanol solutions of alkali the limiting current of tungsten anodic dissolution decreases. An increase in KOH concentration in certain limits (in ethanol solutions it is the range between 0.75 and 1.0 M KOH) results in the increase of the limiting current; with further increase in solution concentration the limiting current decreases, which can be related to the change of the limiting stage. An assumption is made that total reaction of tungsten anodic dissolution and the main reasons for the limiting current appearance do not change from aqueous to aqueous-ethanol and ethanol solutions of alkali

  11. Recovery of Vanadium from H2SO4-HF Acidic Leaching Solution of Black Shale by Solvent Extraction and Precipitation

    Directory of Open Access Journals (Sweden)

    Xingbin Li

    2016-03-01

    Full Text Available The recovery of vanadium from sulfuric and hydrofluoric mixed acid solutions generated by the direct leaching of black shale was investigated using solvent extraction and precipitation methods. The process consisted of reduction, solvent extraction, and stripping, followed by precipitation and calcination to yield vanadium pentoxide. The influence of various operating parameters on the extraction and recovery of vanadium was studied. Vanadium (IV was selectively extracted using a mixture of 10% (v/v di(2-ethylhexylphosphoric acid and 5% (v/v tri-n-butylphosphate in sulfonated kerosene. Using six extraction and five stripping stages, the extraction efficiency for vanadium was 96.7% and the stripping efficiency was 99.7%. V2O5 with a purity of 99.52% was obtained by oxidation of the loaded strip solution and precipitation of ammonium polyvanadate at pH 1.8 to 2.2, followed by calcination of the dried precipitate at 550 °C for 2 h. It was concluded that the combination of solvent extraction and precipitation is an efficient method for the recovery of vanadium from a multi-element leach solution generated from black shale.

  12. Quantifying the thermodynamic interactions of polyhedral boranes in solution to guide nanocomposite fabrication

    International Nuclear Information System (INIS)

    Mutz, M.; Eastwood, Eric; Lee, Mark E.; Bowen, Daniel E.; Dadmun, M. D.

    2012-01-01

    The solubility of boron containing nanoparticles in a variety of solvents is quantified using static light scattering in conjunction with refractometry. Four polyhedral boranes were tested in this work, using refractometry to obtain dn/dc, while static light scattering quantifies A 2 . A 2 obtained from these measurements was then used to calculate χ, the solute–solvent interaction parameter, and the Hildebrand solubility parameter, δ, which provides a quantifiable method to identify good solvents. Of the nanoparticles studied, 1,3-di-o-carboranylpropane is thermodynamically stable in toluene, with a χ less than 0.5, a solubility limit of 2.47 mg/mL, and all solutions remaining clear with no visible particle settling. For all of the particles tested, there was good correlation between the physical observations of the solutions, χ, and δ. For instance, lower values of χ correspond to a smaller radius of gyration (R g ). A list of suitable solvents based on δ is also presented.

  13. Incorporating information on predicted solvent accessibility to the co-evolution-based study of protein interactions.

    Science.gov (United States)

    Ochoa, David; García-Gutiérrez, Ponciano; Juan, David; Valencia, Alfonso; Pazos, Florencio

    2013-01-27

    A widespread family of methods for studying and predicting protein interactions using sequence information is based on co-evolution, quantified as similarity of phylogenetic trees. Part of the co-evolution observed between interacting proteins could be due to co-adaptation caused by inter-protein contacts. In this case, the co-evolution is expected to be more evident when evaluated on the surface of the proteins or the internal layers close to it. In this work we study the effect of incorporating information on predicted solvent accessibility to three methods for predicting protein interactions based on similarity of phylogenetic trees. We evaluate the performance of these methods in predicting different types of protein associations when trees based on positions with different characteristics of predicted accessibility are used as input. We found that predicted accessibility improves the results of two recent versions of the mirrortree methodology in predicting direct binary physical interactions, while it neither improves these methods, nor the original mirrortree method, in predicting other types of interactions. That improvement comes at no cost in terms of applicability since accessibility can be predicted for any sequence. We also found that predictions of protein-protein interactions are improved when multiple sequence alignments with a richer representation of sequences (including paralogs) are incorporated in the accessibility prediction.

  14. A novel method for determining the solubility of small molecules in aqueous media and polymer solvent systems using solution calorimetry.

    Science.gov (United States)

    Fadda, Hala M; Chen, Xin; Aburub, Aktham; Mishra, Dinesh; Pinal, Rodolfo

    2014-07-01

    To explore the application of solution calorimetry for measuring drug solubility in experimentally challenging situations while providing additional information on the physical properties of the solute material. A semi-adiabatic solution calorimeter was used to measure the heat of dissolution of prednisolone and chlorpropamide in aqueous solvents and of griseofulvin and ritonavir in viscous solutions containing polyvinylpyrrolidone and N-ethylpyrrolidone. Dissolution end point was clearly ascertained when heat generation stopped. The heat of solution was a linear function of dissolved mass for all drugs (solution of 9.8 ± 0.8, 28.8 ± 0.6, 45.7 ± 1.6 and 159.8 ± 20.1 J/g were obtained for griseofulvin, ritonavir, prednisolone and chlorpropamide, respectively. Saturation was identifiable by a plateau in the heat signal and the crossing of the two linear segments corresponds to the solubility limit. The solubilities of prednisolone and chlopropamide in water by the calorimetric method were 0.23 and 0.158 mg/mL, respectively, in agreement with the shake-flask/HPLC-UV determined values of 0.212 ± 0.013 and 0.169 ± 0.015 mg/mL, respectively. For the higher solubility and high viscosity systems of griseofulvin and ritonavir in NEP/PVP mixtures, respectively, solubility values of 65 and 594 mg/g, respectively, were obtained. Solution calorimetry offers a reliable method for measuring drug solubility in organic and aqueous solvents. The approach is complementary to the traditional shake-flask method, providing information on the solid properties of the solute. For highly viscous solutions, the calorimetric approach is advantageous.

  15. Photoreactivity of biologically active compounds. XVII. Influence of solvent interactions on spectroscopic properties and photostability of primaquine.

    Science.gov (United States)

    Kristensen, S

    2005-06-01

    The influence of solvent interactions on absorption properties, fluorescence properties (emission spectra and quantum yields) and relative photochemical degradation rates of primaquine has been investigated, in order to evaluate photochemical reaction mechanisms and chemical properties of the compound. The first absorption band (n - pi*) of primaquine is only slightly dependent on properties of the solvent, which can be ascribed to a strong, intramolecular hydrogen bond between the quinoline N and amine group in the ground state (S0). Amphiprotic solvents with predominant acidic properties (water and methanol) will to some extent stabilize the molecule and initiate hypsochromic shifts of the absorption band by protic interactions, while the other solvents (amphiprotic, basic and neutral) influence the absorption spectrum by general solvent effects only. The excited singlet (S1*) state of primaquine interacts more efficiently with the surrounding solvents than the S0 state, as evaluated by the Stokes shifts. The pKa value of the quinoline N is likely to increase in the S1* state, which is important for the observed protic interactions with amphiprotic solvents of predominant acidity. Specific solvent effects are highly important for the efficiency of the fluorescence (fluorescence quantum yields; phi f). The fluorescence is quenched by amphiprotic solvents, likely due to a rupture of the intramolecular bond and protonation of the quinolone N, and enhanced by polar, non-protic (basic) solvents, probably by stabilization of the delta intramolecular hydrogen bond. The observed photochemical degradation rates of primaquine in amphiprotic media are positively correlated with phi f, indicating that the photochemical degradation of primaquine is dependent on intramolecular hydrogen bonding and non protonated lone-pair electrons at the quinoline N. The intramolecular ring-formation with a subsequent increased lipophilic character and (lack of) interactions with the

  16. Solvent extraction of silver(I) from dilute cyanide solutions with 2,4-dihydroxyacetophenone thiosemicarbazone

    International Nuclear Information System (INIS)

    Reddy, A.V.; Reddy, Y.K.; Reddy, G.S.

    1986-01-01

    The solvent extraction of silver(I) was carried out in 0.5M nitric acid in the presence of cyanide by 2,4-dihydroxyacetophenone thiosemicarbazone (DATS). Ethyl acetate was used as a solvent and quantitative recovery was possible with 12.5-fold excess of the reagent in a single extraction. In this medium silver(I) forms a 2:2 complex (metal:ligand) with DATS. The effect of diverse ions on the extraction of silver(I) was investigated. (author)

  17. 1D and 2D NMR Spectroscopy of Bonding Interactions within Stable and Phase-Separating Organic Electrolyte-Cellulose Solutions.

    Science.gov (United States)

    Clough, Matthew T; Farès, Christophe; Rinaldi, Roberto

    2017-09-11

    Organic electrolyte solutions (i.e. mixtures containing an ionic liquid and a polar, molecular co-solvent) are highly versatile solvents for cellulose. However, the underlying solvent-solvent and solvent-solute interactions are not yet fully understood. Herein, mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate, the co-solvent 1,3-dimethyl-2-imidazolidinone, and cellulose are investigated using 1D and 2D NMR spectroscopy. The use of a triply- 13 C-labelled ionic liquid enhances the signal-to-noise ratio for 13 C NMR spectroscopy, enabling changes in bonding interactions to be accurately pinpointed. Current observations reveal an additional degree of complexity regarding the distinct roles of cation, anion, and co-solvent toward maintaining cellulose solubility and phase stability. Unexpectedly, the interactions between the dialkylimidazolium ring C 2 -H substituent and cellulose become more pronounced at high temperatures, counteracted by a net weakening of acetate-cellulose interactions. Moreover, for mixtures that exhibit critical solution behavior, phase separation is accompanied by the apparent recombination of cation-anion pairs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Determination and correlation of solubility and solution thermodynamics of oxiracetam in three (alcohol + water) binary solvents

    International Nuclear Information System (INIS)

    Li, Kangli; Du, Shichao; Wu, Songgu; Cai, Dongchen; Wang, Jinxu; Zhang, Dejiang; Zhao, Kaifei; Yang, Peng; Yu, Bo; Guo, Baisong; Li, Daixi; Gong, Junbo

    2016-01-01

    Highlights: • The solubility of racemic oxiracetam in three binary solvents were determined. • The experimental solubility of racemic oxiracetam were correlated by four models. • The dissolution thermodynamic properties of racemic oxiracetam were calculated. - Abstract: In this paper, we proposed a static analysis method to experimentally determine the (solid + liquid) equilibrium of racemic oxiracetam in (methanol + water), (ethanol + water) and (isopropanol + water) binary solvents with alcohol mole fraction ranging from 0.30 to 0.90 at atmosphere pressure (p = 0.1 MPa). For the experiments, the temperatures range from (283.15 to 308.15) K. The results showed that the solubility of oxiracetam increased with the increasing temperature, while decreased with the increasing organic solvent fraction in all three tested binary solvent systems. The modified Apelblat model, the CNIBS/Redlich–Kister model, the combined version of Jouyban–Acree model and the NRTL model were employed to correlate the measured solubility values, respectively. Additionally, some of the thermodynamic properties which can help to evaluate its dissolution behavior were obtained based on the NRTL model.

  19. Solvent Extraction of Co, Ni and Mn from NCM Sulfate Leaching Solution of Li(NCMO2 Secondary Battery Scraps

    Directory of Open Access Journals (Sweden)

    Hong Hyun Seon

    2017-06-01

    Full Text Available As a part of the study on recycling Li(NCMO2 lithium-ion battery scraps, solvent extraction experiments were performed using different extraction agents such as PC88A, Cyanex272 and D2EHPA to separate Co, Ni and Mn from the leaching solution. When the ratio of Mn to Ni was about 0.4 in the leaching solution, the separation factor for Co and Mn was found to be less than 10 so that the separation of Co and Ni was insufficient. When solvent extraction was done using the solution with the lower Mn/Ni ratio of 0.05 where Mn was removed by potassium permanganate and chlorine dioxide, more than 99% of Mn could be extracted through five courses of extraction using 30vol% D2EHPA while the extraction rates of Co and Ni were around 17% and 11%, respectively. In the case that Mn was removed from the solution, the extraction rate of Co was higher than 99% whereas less than 7% Ni was extracted using Cyanex272 suggesting that Co and Ni elements were effectively separated.

  20. Substitution of chlorinated and fluorinated solvents by biodegradable detergent solution in components cleaning of nuclear fuel elements

    International Nuclear Information System (INIS)

    Vieira, Andre Luiz Pinto da Silva

    2000-01-01

    As the auxiliary oils used in machining evolved from integral into aqueous emulsion, and later on into aqueous-solution synthetic oils, the components cleaning process with organic solvents, originally adopted at the Fuel Element Factory (FEC), Industrias Nucleares do Brasil S.A. (INB) began to present problems in removing oil residues from machined components, due to the incompatibility between aqueous and organic media. In order to eliminate such incompatibility and adapt the process to the environmental laws restricting production and use of chlorinated or fluorinated solvents as a measure for preserving the atmosphere's ozone layer, in 1995 INB initiated the development of a components cleaning process using biodegradable aqueous detergent. The effort was completed in 2000 with the construction of a machine in keeping with the specific geometry of the fuel-assembly components and the operating conditions required for working with the new process. (author)

  1. Communication Solutions by Improving Interactive Art Projects

    Directory of Open Access Journals (Sweden)

    Gintarė Vainalavičiūtė

    2016-03-01

    Full Text Available The article examines the emergence of new forms of expression in modern society such as technology, which makes the traditional art active and the users are drawn into the processes of creation and dissemination. Interactive art technology gradually integrates more and more people to be interested on it because of its innovative and interesting concept and idea. Interactive art removes traditional boundaries between the artist and “public”. Appearance of the new modern technologies in the art provoked the development of the interactive art which later evolved into some other forms of art as cinema, interactive dance, music and etc. The article is based on Lithuanian and foreign academic works, interactive art definition is provided the theoretical aspect of an interactive art projects is highlighted. The modern theories of marketing communications are defined. To solve examined issues marketing communication model with highlighted key elements is proposed.

  2. A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum-classical approximation. II. Proton transfer reaction in non-polar solvent

    Science.gov (United States)

    Kojima, H.; Yamada, A.; Okazaki, S.

    2015-05-01

    The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum-classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute-solvent interactions.

  3. Controlling solution-phase polymer aggregation with molecular weight and solvent additives to optimize polymer-fullerene bulk heterojunction solar cells

    KAUST Repository

    Bartelt, Jonathan A.; Douglas, Jessica D.; Mateker, William R.; El Labban, Abdulrahman; Tassone, Christopher J.; Toney, Michael F.; Fré chet, Jean Mj J; Beaujuge, Pierre; McGehee, Michael D.

    2014-01-01

    The bulk heterojunction (BHJ) solar cell performance of many polymers depends on the polymer molecular weight (M n) and the solvent additive(s) used for solution processing. However, the mechanism that causes these dependencies is not well

  4. Solvent and solute isotope effects in the aqueous solution of gases. Progress report, July 1, 1978-October 31, 1979

    International Nuclear Information System (INIS)

    Benson, B.B.; Krause, D. Jr.

    1979-10-01

    After developing a 3 He/ 4 He dual beam collection system for the mass spectrometer, the isotopic fractionation factor was determined for helium dissolved in H 2 O, D 2 O, seawater and ethanol. In all solvents the temperature dependence of the fractionation is different from that for a simple isotope vapor pressure effect. Addition of salt to H 2 O increases the fractionation, and the relative salting-out coefficient changes with temperature. A double isotopic effect occurs - the fractionations in D 2 O and H 2 O differ. In ethanol the fractionation is 25% less than in H 2 O

  5. Solvent Extraction and Separation of Chromium(III) and (V I) in Aqueous Solutions with Trioctylphosphine Oxide

    International Nuclear Information System (INIS)

    Sekine, T.; Yamada, M.

    1999-01-01

    The solvent extraction of chromium(III) and (V I) in aqueous solutions with a solvating type extractant, trioctylphosphine oxide(TOPO), in hexane is studied. Kinetically inert Cr 3+ is extracted from 1 mol dm -3 sodium perchlorate solution very quickly and quantitatively as Cr(H 2 O · TOPO) 6 3+ (CIO 4 -) 3 . Chromium(V I) in hydrochloric acid is extracted effectively as the H 2 CrO $ (H CI) n centre dot TOPO m species ( m = 2 or 3, n = 0 to 2) and the distribution ratio increased by an increase in the acid concentration. From these, a procedure is proposed for the extraction of both chromium(V I) and chromium(III) in aqueous solution separately with 0.1 mol dm -3 TOPO in hexane

  6. Ion-solvent interactions and the complex behaviour of U(IV) and U(VI) with chloro-ligands in ethanol-water mixtures

    International Nuclear Information System (INIS)

    Kim, J.I.; Duschner, H.; Hashimoto, T.; Born, H.J.

    1975-01-01

    The complex chemical behaviour of U(IV) and U(VI) in amphiprotic solutions, especially in mixtures of solvents, was investigated using ion exchange and solvent extraction methods. The experimental data was used, on the one hand, in order to obtain complexing constants in dependence of ligands and their concentration as well as of the agent and to classify these in a universal scale of ion activities with water as reference point, and on the other hand, to explain the interactions between central atom, ligand and solvating molecule. One aim of these investigations is to understand the basic mechanisms in adjusting the equilibrium between two different phases in the separation chemistry of these elements. (orig./LH) [de

  7. The stability of high-Tc BSCCO/Ag superconducting microcomposites in water, some inorganic solutions and organic solvents

    International Nuclear Information System (INIS)

    Gao, W.; Chen, J.; Yang, C.O.; McNabb, D.; Sande, J. vander

    1992-01-01

    Bi(Pb)-Sr-Ca-Cu-O/Ag (BSCCO/Ag) superconducting microcomposites with zero-resistance temperatures from 102 to 108 K and critical current densities of ∝600 A/cm 2 at 77 K were produced by oxidation and annealling of metallic precursor alloys. The stabilities and degradation behavior of BSCCO/Ag specimens in various environments were studied by a combination of mass loss measurement, electrical transport measurement and microstructural observation. The environmental conditions used in the present work were moist air, distilled water, aqueous solutions of NaCl, NaOH and acetic acid, and organic solvents methanol and acetone. Although there is a general tendency toward a decrease in critical current density after a long exposure to most of the testing conditions, the specimens containing a high percent of Ag (≥70 wt.%) showed very little decrease in Tc and J c up to 200 days of exposure in moist air and distilled water, and up to 20 days in NaCl solution, methanol and acetone. It was found that the superconducting ''2223'' phase is stable in water, neutral solutions and the organic solvents, reacts very slowly with basic solutions, and dissolves rapidly in acidic solutions. Some non-superconducting Ca-rich oxides dissolve in water and neutral and basic solutions and therefore damage the connection of the superconducting grains in low-Ag containing specimens. The excellent stability of the BSCCO/Ag superconducting microcomposites containing high Ag provides an important advantage for their potential industrial application. (orig.)

  8. Electrochemical reactions of uranyl(VI) complexes in aqueous solution, non-aqueous solvents, and ionic liquids

    International Nuclear Information System (INIS)

    Ikeda, Yasuhisa

    2006-01-01

    Author's recent experimental results on the chemistry of U(V) in aqueous solution, non-aqueous solvents, and ionic solvents by cyclic voltametry are described. The U(V) was produced by electrochemical reduction of uranyl U(VI) ions or complexes such as carbonates, DMF(N, N-dimethylformamide), DMSO(dimethylsulfoxide), acetylacetonato, and other organic polydental ligands. The produced U(V) complexes were studied by spectrophotometry using optical-transmission thin-layer electrode. The U(V) complexes in non-aqueous solvents were found to be rather stable, they undergo ligand-dissociation reaction but not disproportionation reaction. The structure and electronic spectra as well as IR spectra of the complexes were studied. The present method was further developed to study the behavior of U(V) complexes in ionic liquids as molten salts, e.g., alkaline metals chlorides. Thus, the present research contributes to understanding the chemistry of 5fl system. Application to such nuclear technology as spent fuel reprocessing is discussed. (S. Ohno)

  9. Influence of solvent polarization and non-uniform ion size on electrostatic properties between charged surfaces in an electrolyte solution

    Science.gov (United States)

    Sin, Jun-Sik

    2017-12-01

    In this paper, we study electrostatic properties between two similar or oppositely charged surfaces immersed in an electrolyte solution by using the mean-field approach accounting for solvent polarization and non-uniform size effects. Applying a free energy formalism accounting for unequal ion sizes and orientational ordering of water dipoles, we derive coupled and self-consistent equations to calculate electrostatic properties between charged surfaces. Electrostatic properties for similarly charged surfaces depend on the counterion size but not on the coion size. Moreover, electrostatic potential and osmotic pressure between similarly charged surfaces are found to be increased with increasing counterion size. On the other hand, the corresponding ones between oppositely charged surfaces are related to both sizes of positive and negative ions. For oppositely charged surfaces, the electrostatic potential, number density of solvent molecules, and relative permittivity of an electrolyte having unequal ion sizes are not symmetric about the centerline between the charged surfaces. For either case, the consideration of solvent polarization results in a decrease in the electrostatic potential and the osmotic pressure compared to the case without the effect.

  10. Process optimization for inkjet printing of triisopropylsilylethynyl pentacene with single-solvent solutions

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xianghua, E-mail: xhwang@hfut.edu.cn [Key Lab of Special Display Technology, Ministry of Education, National Engineering Lab of Special Display Technology, National Key Lab of Advanced Display Technology, Academy of Opto-Electronic Technology, Hefei University of Technology, Hefei 230009 (China); Yuan, Miao [Key Lab of Special Display Technology, Ministry of Education, National Engineering Lab of Special Display Technology, National Key Lab of Advanced Display Technology, Academy of Opto-Electronic Technology, Hefei University of Technology, Hefei 230009 (China); School of Electronic Science & Applied Physics, Hefei University of Technology, Hefei 230009 (China); Xiong, Xianfeng; Chen, Mengjie [Key Lab of Special Display Technology, Ministry of Education, National Engineering Lab of Special Display Technology, National Key Lab of Advanced Display Technology, Academy of Opto-Electronic Technology, Hefei University of Technology, Hefei 230009 (China); Qin, Mengzhi [Key Lab of Special Display Technology, Ministry of Education, National Engineering Lab of Special Display Technology, National Key Lab of Advanced Display Technology, Academy of Opto-Electronic Technology, Hefei University of Technology, Hefei 230009 (China); School of Electronic Science & Applied Physics, Hefei University of Technology, Hefei 230009 (China); Qiu, Longzhen; Lu, Hongbo; Zhang, Guobing; Lv, Guoqiang [Key Lab of Special Display Technology, Ministry of Education, National Engineering Lab of Special Display Technology, National Key Lab of Advanced Display Technology, Academy of Opto-Electronic Technology, Hefei University of Technology, Hefei 230009 (China); Choi, Anthony H.W. [Department of Electrical and Electronic Engineering, The University of Hong Kong, Hong Kong (China)

    2015-03-02

    Inkjet printing of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-PEN), a small molecule organic semiconductor, is performed on two types of substrates. Hydrophilic SiO{sub 2} substrates prepared by a combination of surface treatments lead to either a smaller size or a coffee-ring profile of the single-drop film. A hydrophobic surface with dominant dispersive component of surface energy such as that of a spin-coated poly(4-vinylphenol) film favors profile formation with uniform thickness of the printed semiconductor owing to the strong dispersion force between the semiconductor molecules and the hydrophobic surface of the substrate. With a hydrophobic dielectric as the substrate and via a properly selected solvent, high quality TIPS-PEN films were printed at a very low substrate temperature of 35 °C. Saturated field-effect mobility measured with top-contact thin-film transistor structure shows a narrow distribution and a maximum of 0.78 cm{sup 2}V{sup −1} s{sup −1}, which confirmed the film growth on the hydrophobic substrate with increased crystal coverage and continuity under the optimized process condition. - Highlights: • Hydrophobic substrates were employed to inhibit the coffee-ring effect. • Contact-line pinning is primarily controlled by the dispersion force. • Solvent selection is critical to crystal coverage of the printed film. • High performance and uniformity are achieved by process optimization.

  11. Separation of Ce and La from Synthetic Chloride Leach Solution of Monazite Sand by Precipitation and Solvent Extraction

    Science.gov (United States)

    Banda, Raju; Jeon, Ho Seok; Lee, Man Seung

    2014-12-01

    Precipitation and solvent extraction experiments have been performed to recover light rare earths from simulated monazite sand chloride leach solutions. Precipitation conditions were obtained to recover Ce by adding NaClO as an oxidant. Among some cationic extractants (PC 88A, D2EHPA, Cyanex 272, LIX 63), PC 88A showed the best performance to separate La from the resulting chloride solution. Furthermore, the mixture of PC 88A with other solvating (TBP, TOPO) and amine extractants (Alamine 336, Aliquat 336) was tested to increase the separation factor of La from Pr and Nd. The use of mixed extractants greatly enhanced the separation of La from the two other metals. McCabe-Thiele diagrams for the extraction of Pr and Nd with the PC 88A/Alamine 336 mixture were constructed.

  12. Indium recovery from acidic aqueous solutions by solvent extraction with D2EHPA: a statistical approach to the experimental design

    Directory of Open Access Journals (Sweden)

    Fortes M.C.B.

    2003-01-01

    Full Text Available This experimental work presents the optimization results of obtaining a high indium concentration solution and minimum iron poisoning by solvent extraction with D2EHPA solubilized in isoparaffin and exxsol. The variables studied in the extraction step were D2EHPA concentration, acidity of the aqueous phase and time of contact between phases. Different hydrochloric and sulfuric acid concentrations were studied for the stripping step. The optimum experimental conditions resulted in a solution with 99% indium extraction and less than 4% iron. The construction of a McCabe-Thiele diagram indicated two theoretical countercurrent stages for indium extraction and at least six stages for indium stripping. Finally, the influence of associated metals found in typical sulfate leach liquors from zinc plants was studied. Under the experimental conditions for maximum indium extraction, 96% indium extraction was obtained, iron extraction was about 4% and no Ga, Cu and Zn were co-extracted.

  13. Quantum mechanical study of solvent effects in a prototype SN2 reaction in solution: Cl- attack on CH3Cl.

    Science.gov (United States)

    Kuechler, Erich R; York, Darrin M

    2014-02-07

    The nucleophilic attack of a chloride ion on methyl chloride is an important prototype SN2 reaction in organic chemistry that is known to be sensitive to the effects of the surrounding solvent. Herein, we develop a highly accurate Specific Reaction Parameter (SRP) model based on the Austin Model 1 Hamiltonian for chlorine to study the effects of solvation into an aqueous environment on the reaction mechanism. To accomplish this task, we apply high-level quantum mechanical calculations to study the reaction in the gas phase and combined quantum mechanical/molecular mechanical simulations with TIP3P and TIP4P-ew water models and the resulting free energy profiles are compared with those determined from simulations using other fast semi-empirical quantum models. Both gas phase and solution results with the SRP model agree very well with experiment and provide insight into the specific role of solvent on the reaction coordinate. Overall, the newly parameterized SRP Hamiltonian is able to reproduce both the gas phase and solution phase barriers, suggesting it is an accurate and robust model for simulations in the aqueous phase at greatly reduced computational cost relative to comparably accurate ab initio and density functional models.

  14. Interaction of photons with some solutions

    International Nuclear Information System (INIS)

    Singh, Kulwant; Gagandeep; Lark, B.S.; Sahota, H.S.

    2000-01-01

    With the advancement and applicability of gamma attenuation coefficients in a variety of applications, accurate data on narrow beam attenuation coefficients are required. In order to make use of the fact that scattering and absorption of gamma radiations are related to the density and effective atomic number of the material, a knowledge of the mass attenuation coefficients, μ/ρ is of prime importance. Hubbell and Seltzer have compiled the mass attenuation coefficients for a large number of compounds and mixtures of dosimetric and biological importance. The previous studies for the determination of attenuation coefficients have been concerned with crystalline samples in the solid form. In the pioneer work, Teli et al. have determined the gamma ray attenuation coefficients in dilute solutions of some salts. Gerward determined linear and mass attenuation coefficients in the general case as well as in the limit of extreme dilution. Recently Singh et al., measured attenuation coefficients of some solutes in water at different concentrations. The present study covers the study of attenuation coefficients of 1:1 and 1:2 electrolytes of some chlorides and sulphates in energy regions in which the influence of all photon processes can be seen and the investigation is expected to yield valuable information. (author)

  15. Solvent Dependency of the UV-Vis Spectrum of Indenoisoquinolines: Role of Keto-Oxygens as Polarity Interaction Probes

    Science.gov (United States)

    Coletta, Andrea; Castelli, Silvia; Chillemi, Giovanni; Sanna, Nico; Cushman, Mark; Pommier, Yves; Desideri, Alessandro

    2013-01-01

    Indenoisoquinolines are the most promising non-campthotecins topoisomerase IB inhibitors. We present an integrated experimental/computational investigation of the UV-Vis spectra of the IQNs parental compound (NSC314622) and two of its derivatives (NSC724998 and NSC725776) currently undergoing Phase I clinical trials. In all the three compounds a similar dependence of the relative absorption intensities at 270 nm and 290 nm on solvent polarity is found. The keto-oxygens in positions 5 and 11 of the molecular scaffold of the molecule are the principal chromophores involved in this dependence. Protic interactions on these sites are also found to give rise to absorptions at wavelength <250 nm observed in water solution, due to the stabilization of highly polarized tautomers of the molecule. These results suggest that the keto-oxygens are important polarizable groups that can act as useful interactors with the molecular receptor, providing at the same time an useful fingerprint for the monitoring of the drug binding to topoisomerase IB. PMID:24086299

  16. Exfoliating and Dispersing Few-Layered Graphene in Low-Boiling-Point Organic Solvents towards Solution-Processed Optoelectronic Device Applications.

    Science.gov (United States)

    Zhang, Lu; Miao, Zhongshuo; Hao, Zhen; Liu, Jun

    2016-05-06

    With normal organic surfactants, graphene can only be dispersed in water and cannot be dispersed in low-boiling-point organic solvents, which hampers its application in solution-processed organic optoelectronic devices. Herein, we report the exfoliation of graphite into graphene in low-boiling-point organic solvents, for example, methanol and acetone, by using edge-carboxylated graphene quantum dots (ECGQD) as the surfactant. The great capability of ECGQD for graphene dispersion is due to its ultralarge π-conjugated unit that allows tight adhesion on the graphene surface through strong π-π interactions, its edge-carboxylated structure that diminishes the steric effects of the oxygen-containing functional groups on the basal plane of ECGQD, and its abundance of carboxylic acid groups for solubility. The graphene dispersion in methanol enables the application of graphene:ECGQD as a cathode interlayer in polymer solar cells (PSCs). Moreover, the PSC device performance of graphene:ECGQD is better than that of Ca, the state-of-the-art cathode interlayer material. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Cosmological solutions in string theory with dilaton self interaction potential

    International Nuclear Information System (INIS)

    Mora, C.; Pimentel, L.O.

    2003-01-01

    In this work we present homogeneous and isotropic cosmological solutions for the low energy limit of string theory with a self interacting potential for the scalar field. For a potential that is a linear combination of two exponential, a family of exact solutions are found for the different spatial curvatures. Among this family a non singular accelerating solution for positive curvature is singled out and the violation of the energy conditions for that solution is studied, and also its astrophysical consequences. The string coupling for this solution is finite. (Author)

  18. Principles of interactions in non-aqueous electrolyte solutions

    NARCIS (Netherlands)

    Lyklema, J.

    2013-01-01

    In this paper a review is presented on the molecular interactions in non-aqueous media of low dielectric permittivity. Qualitative and quantitative distinctions with aqueous solutions are emphasized. The reviewed themes include dispersion forces, dissociation and association equilibria,

  19. Solutions to raptor-wind farm interactions

    Energy Technology Data Exchange (ETDEWEB)

    Madders, M.; Walker, D.G. [CRE Energy Ltd., Scottish Power, Glasgow (United Kingdom)

    2000-07-01

    Wind energy developments in the uplands have the potential to adversely impact upon a number of raptor species by lowering survival and reproductive rates. In many cases, wind farms are proposed in areas where raptors are already under pressure from existing land uses, notably sheep grazing and forestry. This paper summarises the approach used to assess the impact of a 30MW wind farm on a pair of golden eagles in the Kintyre peninsula, Scotland. We outline the method being used to manage habitats for the benefit of the eagles and their prey. By adopting management practices that are both wide-scale and long-term, we aim to reduce the impact to the wind farm to levels considered acceptable by the conservation agencies, and improve breeding productivity of the eagles using the wind farm. The implications of this innovative approach for future raptor--wind farm interactions are discussed. (Author)

  20. On condensation driven by electrostatic interactions in macroionic solutions

    International Nuclear Information System (INIS)

    Badirkhan, Z.; Tosi, M.P.

    1989-04-01

    Liquid-vapour phase separation, as it normally follows from attractive interactions, is demonstrated under pure Coulomb interactions for the primitive model of macroionic solutions in the mean spherical approximation and related to observations on dilute solutions of highly charged latex particles. It is stressed that the corresponding effective pair potential between macro-ions is of the DLVO repulsive type. (author). 14 refs, 2 figs

  1. Recovery of salicylic acid from aqueous solution by solvent extraction and supported liquid membrane using TOMAC as carrier

    International Nuclear Information System (INIS)

    Kouki, Noura; Tayeb, Rafik; Dhahbi, Mahmoud

    2009-01-01

    Conventional sewage treatment plants do not fully degrade residues of pharmaceuticals, so that they are introduced into the aquatic environment. On this basis, the demand for the development of efficient systems for removing these compounds from water has assumed a great research interest. Membrane operations are increasingly employed in many industrial sectors as important alternative technologies to the classical processes of separation. Among membrane-based separation processes, the use of supported liquid membranes (SLMs) has received growing attention during recent years. In our work we had tried to recover a pharmaceutical product, salicylic acid (S.A), from an aqueous solution by solvent extraction and supported liquid membrane using an ionic liquid: the tri octylmethylammonium chloride (TOMAC) as carrier. Ionic liquids has been revealed as interesting clean alternatives to classical solvents and their use as a liquid phase results in the stabilization of the SLMs duo to their negligible vapour pressure, the possibility of minimising their solubility in the surrounding phases by adequate selection of the cation and anion, and the greater capillary force associated with their high viscosity. For this reason we had studied the influence of different parameters which could affect the efficiency of the transport: pH of the feed phase, the nature of the strippant, the concentration of the strippant, the nature of the support and the initial concentration of the salicylic acid in the feed phase. We had noticed that the pH of the feed solution had no effect of the percentage extraction and after 24 hours we can extract completely our solute. TOMAC seemed to be a good extractant but we found difficult to strip salicylic acid from the TOMAC phase and this could be related to the formation of water micro environments in the ionic liquid membrane.

  2. Polyimide Dielectric Layer on Filaments for Organic Field Effect Transistors: Choice of Solvent, Solution Composition and Dip-Coating Speed

    Directory of Open Access Journals (Sweden)

    Rambausek Lina

    2014-09-01

    Full Text Available In today’s research, smart textiles is an established topic in both electronics and the textile fields. The concept of producing microelectronics directly on a textile substrate is not a mere idea anymore and several research institutes are working on its realisation. Microelectronics like organic field effect transistor (OFET can be manufactured with a layered architecture. The production techniques used for this purpose can also be applied on textile substrates. Besides gate, active and contact layers, the isolating or dielectric layer is of high importance in the OFET architecture. Therefore, generating a high quality dielectric layer that is of low roughness and insulating at the same time is one of the fundamental requirements in building microelectronics on textile surfaces. To evaluate its potential, we have studied polyimide as a dielectric layer, dip-coated onto copper-coated polyester filaments. Accordingly, the copper-coated polyester filament was dip-coated from a polyimide solution with two different solvents, 1-methyl-2-pyrrolidone (NMP and dimethylformaldehyde. A variety of dip-coating speeds, solution concentrations and solvent-solute combinations have been tested. Their effect on the quality of the layer was analysed through microscopy, leak current measurements and atomic force microscopy (AFM. Polyimide dip-coating with polyimide resin dissolved in NMP at a concentration of 15w% in combination with a dip-coating speed of 50 mm/min led to the best results in electrical insulation and roughness. By optimising the dielectric layer’s properties, the way is paved for applying the subsequent semi-conductive layer. In further research, we will be working with the organic semiconductor material TIPS-Pentacene

  3. Preparation of Highly Pure Vanadyl Sulfate from Sulfate Solutions Containing Impurities of Iron and Aluminum by Solvent Extraction Using EHEHPA

    Directory of Open Access Journals (Sweden)

    Dan Li

    2017-03-01

    Full Text Available The preparation of highly pure vanadyl sulfate from sulfate solutions containing impurities of iron and aluminumwas investigated by solvent extraction with 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (EHEHPA and tri-n-butyl phosphate (TBP as the phase modifier. The extraction and stripping conditions of vanadium (IV and its separation from iron and aluminum were optimized. Under the optimal extraction conditions, the extraction of vanadium (IV and iron were 68% and 53%, respectively, while only 2% aluminum was extracted in a single contact, suggesting good separation of vanadium (IV from aluminum. Sulfuric acid solution was used for the stripping. Nearly 100% vanadium (IV and 95% aluminum were stripped, while only 10% iron was stripped under the optimal stripping conditions in a single contact, suggesting good separation of vanadium (IV from iron. After five stages of extraction and stripping, highly pure vanadyl sulfate containing 76.5 g/L V (IV with the impurities of 12 mg/L Fe and 10 mg/L Al was obtained, which is suitable for the electrolyte of a vanadium redox flow battery. Organic solution was well regenerated after stripping by oxalic acid solution to remove the remaining iron. The mechanism of vanadium (IV extraction using EHEHPA was also discussed based on the Fourier transform infrared spectroscopy (FT-IR analysis.

  4. Thermodynamics of hydrogen bonding and van der Waals interactions of organic solutes in solutions of imidazolium based ionic liquids: “Structure-property” relationships

    Energy Technology Data Exchange (ETDEWEB)

    Varfolomeev, Mikhail A., E-mail: vma.ksu@gmail.com; Khachatrian, Artashes A.; Akhmadeev, Bulat S.; Solomonov, Boris N.

    2016-06-10

    Highlights: • Solution enthalpies of organic solutes in imidazolium based ionic liquids were measured. • van der Waals interactions scale of imidazolium based ionic liquids was proposed. • Enthalpies of solvation of organic solutes in ionic liquids were determined. • Hydrogen bond enthalpies of organic solutes with ionic liquids were calculated. • Relationships between structure of ionic liquids and thermochemical data were obtained. - Abstract: In the present work thermochemistry of intermolecular interactions of organic compounds in solutions of imidazolium based ionic liquids (ILs) has been studied using solution calorimetry method. Enthalpies of solution at infinite dilution of non-polar (alkanes, aromatic hydrocarbons) and polar (alcohols, amides, and etc.) organic solutes in two ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium trifluoromethanesulfonate were measured at 298.15 K. The scale of van der Waals interactions of imidazolium based ILs has been proposed on the basis of solution enthalpies of n-alkanes in their media. The effect of the cation and anion structure of ILs on the enthalpies of solvation was analyzed. Enthalpies of hydrogen bonding of organic solutes with imidazolium based ILs were determined. It has been shown that these values are close to zero for proton acceptor solutes. At the same time, enthalpies of hydrogen bonding of proton donor solutes with ionic liquids are increased depending the anion: tetrafluoroborate ≈ bis(trifluoromethylsulfonyl)imide < 2-(2-methoxyethoxy)ethyl sulfate < trifluoromethanesulfonate. Enthalpies of van der Waals interactions and hydrogen bonding in the solutions of imidazolium based ionic liquids were compared with the same data for molecular solvents.

  5. Thermodynamics of hydrogen bonding and van der Waals interactions of organic solutes in solutions of imidazolium based ionic liquids: “Structure-property” relationships

    International Nuclear Information System (INIS)

    Varfolomeev, Mikhail A.; Khachatrian, Artashes A.; Akhmadeev, Bulat S.; Solomonov, Boris N.

    2016-01-01

    Highlights: • Solution enthalpies of organic solutes in imidazolium based ionic liquids were measured. • van der Waals interactions scale of imidazolium based ionic liquids was proposed. • Enthalpies of solvation of organic solutes in ionic liquids were determined. • Hydrogen bond enthalpies of organic solutes with ionic liquids were calculated. • Relationships between structure of ionic liquids and thermochemical data were obtained. - Abstract: In the present work thermochemistry of intermolecular interactions of organic compounds in solutions of imidazolium based ionic liquids (ILs) has been studied using solution calorimetry method. Enthalpies of solution at infinite dilution of non-polar (alkanes, aromatic hydrocarbons) and polar (alcohols, amides, and etc.) organic solutes in two ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium trifluoromethanesulfonate were measured at 298.15 K. The scale of van der Waals interactions of imidazolium based ILs has been proposed on the basis of solution enthalpies of n-alkanes in their media. The effect of the cation and anion structure of ILs on the enthalpies of solvation was analyzed. Enthalpies of hydrogen bonding of organic solutes with imidazolium based ILs were determined. It has been shown that these values are close to zero for proton acceptor solutes. At the same time, enthalpies of hydrogen bonding of proton donor solutes with ionic liquids are increased depending the anion: tetrafluoroborate ≈ bis(trifluoromethylsulfonyl)imide < 2-(2-methoxyethoxy)ethyl sulfate < trifluoromethanesulfonate. Enthalpies of van der Waals interactions and hydrogen bonding in the solutions of imidazolium based ionic liquids were compared with the same data for molecular solvents.

  6. Structural elucidation, molecular representation and solvent interactions of vitrinite-rich and inertinite-rich South African coals

    Science.gov (United States)

    van Niekerk, Daniel

    the kinetic parameters and it was found that the swelling was governed by relaxation of the coal structure (super-Case II swelling). X-ray computed tomography was conducted confirming anisotropic swelling. The petrographic transitions (maceral-group composition and reflectance) with solvent swelling and extraction were quantified. No changes in the maceral compositions were found, but changes in some coal particles were observed. Random reflectance analysis showed that, for both vitrinite and inertinite, there is a decrease in reflectance values with solvent treatment. Vitrinite reflectograms showed a shift from the dominant reflecting V-types to lower V-types. The inertinite reflectograms exhibited an increase in number of I-types (broadening of reflectrograms). Molecular simulation and visualization approaches to solvent swelling and extraction were performed on the proposed molecular models of vitrinite-rich and inertinite-rich coals. A theoretical extraction yield was determined using solubility parameters and showed agreement with experimental extraction yield trends. Statistical Associating Fluid Theory (SAFT) modeling was explored to test whether this method could predict swelling extent. The predicted swelling trends of SAFT were comparable to that of the experimental swelling results. SAFT was found to be a promising tool for solvent-coal interaction predictions. Partially solvent swollen structures were constructed by the addition of solvent molecules to the original coal molecules using a amorphous building approach. This method showed that coal-coal non-bonding interaction changed with the introduction of solvent. A disruption in the van der Waals interaction energies and a change in hydrogen bond distributions were observed in the swollen coal models and quantified. It was concluded that small changes in coal structure translates to significant changes in solvent interaction behavior. These changes were successfully visualized and simulated using

  7. Abundant Interaction Solutions of Sine-Gordon Equation

    Directory of Open Access Journals (Sweden)

    DaZhao Lü

    2012-01-01

    Full Text Available With the help of computer symbolic computation software (e.g., Maple, abundant interaction solutions of sine-Gordon equation are obtained by means of a constructed Wronskian form expansion method. The method is based upon the forms and structures of Wronskian solutions of sine-Gordon equation, and the functions used in the Wronskian determinants do not satisfy linear partial differential equations. Such interaction solutions are difficultly obtained via other methods. And the method can be automatically carried out in computer.

  8. Solute–Solute Interaction In α IRON: The Status QUO

    Directory of Open Access Journals (Sweden)

    Numakura H.

    2015-09-01

    Full Text Available An overview is presented on the interaction of substitutional solutes with carbon and nitrogen in α iron, which is an important factor in controlling the properties of steels. Starting from a simple model of trapping of the interstitial solute atoms by substitutional solute atoms, the principles of experimental methods for quantitative studies are described, focussing on the Snoek relaxation and solubility measurements, and the knowledge acquired by such experiments is reviewed. An account of recent theoretical approaches to the interaction is also given.

  9. Approximate Solutions of Interactive Dynamic Influence Diagrams Using Model Clustering

    DEFF Research Database (Denmark)

    Zeng, Yifeng; Doshi, Prashant; Qiongyu, Cheng

    2007-01-01

    Interactive dynamic influence diagrams (I-DIDs) offer a transparent and semantically clear representation for the sequential decision-making problem over multiple time steps in the presence of other interacting agents. Solving I-DIDs exactly involves knowing the solutions of possible models...

  10. Interacting with the biomolecular solvent accessible surface via a haptic feedback device

    Directory of Open Access Journals (Sweden)

    Hayward Steven

    2009-10-01

    Full Text Available Abstract Background From the 1950s computer based renderings of molecules have been produced to aid researchers in their understanding of biomolecular structure and function. A major consideration for any molecular graphics software is the ability to visualise the three dimensional structure of the molecule. Traditionally, this was accomplished via stereoscopic pairs of images and later realised with three dimensional display technologies. Using a haptic feedback device in combination with molecular graphics has the potential to enhance three dimensional visualisation. Although haptic feedback devices have been used to feel the interaction forces during molecular docking they have not been used explicitly as an aid to visualisation. Results A haptic rendering application for biomolecular visualisation has been developed that allows the user to gain three-dimensional awareness of the shape of a biomolecule. By using a water molecule as the probe, modelled as an oxygen atom having hard-sphere interactions with the biomolecule, the process of exploration has the further benefit of being able to determine regions on the molecular surface that are accessible to the solvent. This gives insight into how awkward it is for a water molecule to gain access to or escape from channels and cavities, indicating possible entropic bottlenecks. In the case of liver alcohol dehydrogenase bound to the inhibitor SAD, it was found that there is a channel just wide enough for a single water molecule to pass through. Placing the probe coincident with crystallographic water molecules suggests that they are sometimes located within small pockets that provide a sterically stable environment irrespective of hydrogen bonding considerations. Conclusion By using the software, named HaptiMol ISAS (available from http://www.haptimol.co.uk, one can explore the accessible surface of biomolecules using a three-dimensional input device to gain insights into the shape and water

  11. The effects of a co-solvent on fabrication of cellulose acetate membranes from solutions in 1-ethyl-3-methylimidazolium acetate

    KAUST Repository

    Kim, Dooli

    2016-08-15

    Ionic liquids have been considered green solvents for membrane fabrication. However, the high viscosity of their polymer solutions hinders the formation of membranes with strong mechanical properties. In this study, acetone was explored as a co-solvent with the ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) to dissolve cellulose acetate. The effects of acetone on the thermodynamic and kinetic aspects of the polymer solutions were studied and the physicochemical properties and separation capability of their resultant membranes were analyzed. The Hansen solubility parameters of [EMIM]OAc were measured by the software HSPiP and these data demonstrated that acetone was a suitable co-solvent to increase the solubility of cellulose acetate. The Gibbs free energy of mixing ΔGm was estimated to determine the proper composition of the polymer solution with better solubility. The study of the kinetics of phase separation showed that the demixing rate of the CA polymer solution in acetone and [EMIM]OAc was higher than that for solutions in [EMIM]OAc only. The membranes prepared from the former solution had higher water permeance and better mechanical stability than those prepared from the later solution. Adding acetone as a co-solvent opened the opportunity of fabricating membranes with higher polymer concentrations for higher separation capability and better mechanical properties. © 2016

  12. The effects of a co-solvent on fabrication of cellulose acetate membranes from solutions in 1-ethyl-3-methylimidazolium acetate

    KAUST Repository

    Kim, Dooli; Le, Ngoc Lieu; Nunes, Suzana Pereira

    2016-01-01

    Ionic liquids have been considered green solvents for membrane fabrication. However, the high viscosity of their polymer solutions hinders the formation of membranes with strong mechanical properties. In this study, acetone was explored as a co-solvent with the ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) to dissolve cellulose acetate. The effects of acetone on the thermodynamic and kinetic aspects of the polymer solutions were studied and the physicochemical properties and separation capability of their resultant membranes were analyzed. The Hansen solubility parameters of [EMIM]OAc were measured by the software HSPiP and these data demonstrated that acetone was a suitable co-solvent to increase the solubility of cellulose acetate. The Gibbs free energy of mixing ΔGm was estimated to determine the proper composition of the polymer solution with better solubility. The study of the kinetics of phase separation showed that the demixing rate of the CA polymer solution in acetone and [EMIM]OAc was higher than that for solutions in [EMIM]OAc only. The membranes prepared from the former solution had higher water permeance and better mechanical stability than those prepared from the later solution. Adding acetone as a co-solvent opened the opportunity of fabricating membranes with higher polymer concentrations for higher separation capability and better mechanical properties. © 2016

  13. Self-assembly of poly(vinylidene fluoride–polystyrene block copolymers in solution: Effects of the length of polystyrene block and solvent compositions

    Directory of Open Access Journals (Sweden)

    Yao Wu

    2017-09-01

    Full Text Available We report the first preliminary and extensive study on the solution self-assembly behaviors of poly(vinylidene fluoride–b-polystyrene (PVDF–PS block copolymers. The two PVDF–PS polymers we examined have the same length of PVDF block with number averaged repeating unit of 180, but distinctly different lengths of PS block with number averaged repeating unit of 125 and 1202. The self-assembly experiments were carried out in a series of mixture solutions containing a good solvent N,N-dimethylformamide and a selective solvent with different ratios. Our results showed that the self-assembly process was greatly affected by the two factors we examined, i.e. the length of the PS block and the solvent composition. We hope that our study could stimulate more research on the self-assembly of PVDF-containing polymers in solution.

  14. Simulated x-ray scattering of protein solutions using explicit-solvent models

    International Nuclear Information System (INIS)

    Park, Sanghyun; Bardhan, Jaydeep P.; Makowski, Lee; Roux, Benoit

    2009-01-01

    X-ray solution scattering shows new promise for the study of protein structures, complementing crystallography and nuclear magnetic resonance. In order to realize the full potential of solution scattering, it is necessary to not only improve experimental techniques but also develop accurate and efficient computational schemes to relate atomistic models to measurements. Previous computational methods, based on continuum models of water, have been unable to calculate scattering patterns accurately, especially in the wide-angle regime which contains most of the information on the secondary, tertiary, and quaternary structures. Here we present a novel formulation based on the atomistic description of water, in which scattering patterns are calculated from atomic coordinates of protein and water. Without any empirical adjustments, this method produces scattering patterns of unprecedented accuracy in the length scale between 5 and 100 A, as we demonstrate by comparing simulated and observed scattering patterns for myoglobin and lysozyme.

  15. Multipolar Force Fields and Their Effects on Solvent Dynamics around Simple Solutes

    DEFF Research Database (Denmark)

    Jakobsen, Sofie; Bereau, Tristan; Meuwly, Markus

    2015-01-01

    The performance of multipole (MTP) and point charge (PC) force fields in classical molecular dynamics (MD) simulations of condensed-phase systems for both equilibrium and dynamical quantities is compared. MTP electrostatics provides an improved description of the anisotropic electrostatic potential......, which is especially important to describe key, challenging interactions, such as lone pairs, π-interactions, and hydrogen bonds. These chemical environments are probed by focusing on the hydration properties of two molecules: N-methylacetamide and phenyl bromide. Both, equilibrium and dynamical...

  16. Solution processing of chalcogenide materials using thiol-amine "alkahest" solvent systems.

    Science.gov (United States)

    McCarthy, Carrie L; Brutchey, Richard L

    2017-05-02

    Macroelectronics is a major focus in electronics research and is driven by large area applications such as flat panel displays and thin film solar cells. Innovations for these technologies, such as flexible substrates and mass production, will require efficient and affordable semiconductor processing. Low-temperature solution processing offers mild deposition methods, inexpensive processing equipment, and the possibility of high-throughput processing. In recent years, the discovery that binary "alkahest" mixtures of ethylenediamine and short chain thiols possess the ability to dissolve bulk inorganic materials to yield molecular inks has lead to the wide study of such systems and the straightforward recovery of phase pure crystalline chalcogenide thin films upon solution processing and mild annealing of the inks. In this review, we recount the work that has been done toward elucidating the scope of this method for the solution processing of inorganic materials for use in applications such as photovoltaic devices, electrocatalysts, photodetectors, thermoelectrics, and nanocrystal ligand exchange. We also take stock of the wide range of bulk materials that can be used as soluble precursors, and discuss the work that has been done to reveal the nature of the dissolved species. This method has provided a vast toolbox of over 65 bulk precursors, which can be utilized to develop new routes to functional chalcogenide materials. Future studies in this area should work toward a better understanding of the mechanisms involved in the dissolution and recovery of bulk materials, as well as broadening the scope of soluble precursors and recoverable functional materials for innovative applications.

  17. Non-equilibrium reaction and relaxation dynamics in a strongly interacting explicit solvent: F + CD{sub 3}CN treated with a parallel multi-state EVB model

    Energy Technology Data Exchange (ETDEWEB)

    Glowacki, David R., E-mail: drglowacki@gmail.com [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Department of Computer Science, University of Bristol, Bristol BS8 1UB (United Kingdom); PULSE Institute and Department of Chemistry, Stanford University, Stanford, California 94305 (United States); SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States); Orr-Ewing, Andrew J. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Harvey, Jeremy N. [Department of Chemistry, KU Leuven, Celestijnenlaan 200F, B-3001 Heverlee (Belgium)

    2015-07-28

    We describe a parallelized linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM and TINKER. Forces are obtained using the Hellmann-Feynman relationship, giving continuous gradients, and good energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to explicitly correlated coupled cluster theory, we built a 64-state MS-EVB model designed to study the F + CD{sub 3}CN → DF + CD{sub 2}CN reaction in CD{sub 3}CN solvent (recently reported in Dunning et al. [Science 347(6221), 530 (2015)]). This approach allows us to build a reactive potential energy surface whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We ran molecular dynamics simulations to examine a range of observables which follow in the wake of the reactive event: energy deposition in the nascent reaction products, vibrational relaxation rates of excited DF in CD{sub 3}CN solvent, equilibrium power spectra of DF in CD{sub 3}CN, and time dependent spectral shifts associated with relaxation of the nascent DF. Many of our results are in good agreement with time-resolved experimental observations, providing evidence for the accuracy of our MS-EVB framework in treating both the solute and solute/solvent interactions. The simulations provide additional insight into the dynamics at sub-picosecond time scales that are difficult to resolve experimentally. In particular, the simulations show that (immediately following deuterium abstraction) the nascent DF finds itself in a non-equilibrium regime in two different respects: (1) it is highly vibrationally excited, with ∼23 kcal mol{sup −1} localized in the stretch and (2) its post-reaction solvation environment, in which it is not yet hydrogen-bonded to CD{sub 3}CN solvent molecules, is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational

  18. Non-equilibrium reaction and relaxation dynamics in a strongly interacting explicit solvent: F + CD3CN treated with a parallel multi-state EVB model.

    Science.gov (United States)

    Glowacki, David R; Orr-Ewing, Andrew J; Harvey, Jeremy N

    2015-07-28

    We describe a parallelized linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM and TINKER. Forces are obtained using the Hellmann-Feynman relationship, giving continuous gradients, and good energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to explicitly correlated coupled cluster theory, we built a 64-state MS-EVB model designed to study the F + CD3CN → DF + CD2CN reaction in CD3CN solvent (recently reported in Dunning et al. [Science 347(6221), 530 (2015)]). This approach allows us to build a reactive potential energy surface whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We ran molecular dynamics simulations to examine a range of observables which follow in the wake of the reactive event: energy deposition in the nascent reaction products, vibrational relaxation rates of excited DF in CD3CN solvent, equilibrium power spectra of DF in CD3CN, and time dependent spectral shifts associated with relaxation of the nascent DF. Many of our results are in good agreement with time-resolved experimental observations, providing evidence for the accuracy of our MS-EVB framework in treating both the solute and solute/solvent interactions. The simulations provide additional insight into the dynamics at sub-picosecond time scales that are difficult to resolve experimentally. In particular, the simulations show that (immediately following deuterium abstraction) the nascent DF finds itself in a non-equilibrium regime in two different respects: (1) it is highly vibrationally excited, with ∼23 kcal mol(-1) localized in the stretch and (2) its post-reaction solvation environment, in which it is not yet hydrogen-bonded to CD3CN solvent molecules, is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational relaxation of the nascent DF results in a spectral

  19. Determination of Stoichiometry of Solutes in Molten Salt Solvents by Correlations of Relative Raman Band Intensities

    DEFF Research Database (Denmark)

    Boghosian, Soghomon; Berg, Rolf W.

    1999-01-01

    ); (2) Nb2O5 + nS(2)O(7)(2-) (1) --> Y2n- (1); (3) MoO3 + nS(2)O(7)(2-) (1) --> Z(2n)- (1). It is shown that the solute complex species formed in the studied reactions have, respectively, the following stoichiometries: (1) n = 2, (VO)(2)O(SO4)(4)(4-); (2) n = 3, NbO(SO4)(3)(3-); (3) n = 1, MoO(SO4)(2)(2-)....

  20. Selective and Efficient Solvent Extraction of Copper(II Ions from Chloride Solutions by Oxime Extractants

    Directory of Open Access Journals (Sweden)

    Zahra Kaboli Tanha

    2016-06-01

    Full Text Available Oxime extractants 3-tert-butyl-2-hydroxy-5-methyl benzaldehyde oxime (HL1 and 3-tert-butyl-2-hydroxy-5-methoxy benzaldehyde oxime (HL2 were synthesized and characterized by conventional spectroscopic methods. Suitable lipophilic nature of the prepared extractants allowed examining the ability of these molecules for extraction-separation of copper from its mixture with normally associated metal ions by performing competitive extraction experiments of Cu(II, Co(II, Ni(II, Zn(II, Cd(II and Pb(II ions from chloride solutions. Both ligands transfer selectively the copper ions into dichloromethane by a cation exchange mechanism. Conventional log-log analysis and isotherm curves showed that Cu(II ions are extracted as the complexes with 1:2 metal to ligand ratio by both extractants. Verification of the effect of the organic diluent used in the extraction of copper ions by HL1 and HL2 demonstrated that the extraction efficiency varies as: dichloromethane ~ dichloroethane > toluene > xylene > ethylacetate. Time dependency investigation of the extraction processes revealed that the kinetics of the extraction of copper by HL2 is more rapid than that of HL1. The application of the ligands for extraction-separation of copper ions from leach solutions of cobalt and nickel-cadmium filter-cakes of a zinc production plants was evaluated.

  1. Conductivity enhancement of silver nanowire networks via simple electrolyte solution treatment and solvent washing

    Science.gov (United States)

    Gu, Jiahui; Wang, Xuelin; Chen, Hongtao; Yang, Shihua; Feng, Huanhuan; Ma, Xing; Ji, Hongjun; Wei, Jun; Li, Mingyu

    2018-06-01

    As a promising replacement material for indium tin oxide in flexible electronics, silver nanowires (AgNWs) usually need complicated post-treatment to reduce the high contact resistance across the intersections when used as transparent conductive films. In this work, a widely applicable nano-joining method for improving the overall conductivity of AgNW networks with different kinds of electrolyte solutions is presented. By treatment with an electrolyte solution with appropriate ionic strengths, the insulating surfactant layer (polyvinylpyrrolidone, PVP) on the AgNWs could be desorbed, and the AgNW network could be densified. The sheet resistance of the AgNW film on a glass slide is reduced by 60.9% (from 67.5 to 26.4 Ohm sq‑1) with a transmittance of 92.5%. High-resolution transmission electron microscopy analysis indicates that atomic diffusion occurs at the intersection of two AgNWs. Thus, metallurgical bonding on the nanometer scale is achieved across the junctions of the AgNWs, leading to a significant enhancement in the conductivity of the AgNW network.

  2. A Mesoscopic Model for Protein-Protein Interactions in Solution

    OpenAIRE

    Lund, Mikael; Jönsson, Bo

    2003-01-01

    Protein self-association may be detrimental in biological systems, but can be utilized in a controlled fashion for protein crystallization. It is hence of considerable interest to understand how factors like solution conditions prevent or promote aggregation. Here we present a computational model describing interactions between protein molecules in solution. The calculations are based on a molecular description capturing the detailed structure of the protein molecule using x-ray or nuclear ma...

  3. Measuring the enthalpies of interaction between glycine, L-cysteine, glycylglycine, and sodium dodecyl sulfate in aqueous solutions

    Science.gov (United States)

    Badelin, V. G.; Mezhevoi, I. N.; Tyunina, E. Yu.

    2017-03-01

    Calorimetric measurements of enthalpies of solution Δsol H m for glycine, L-cysteine, and glycylglycine in aqueous solutions of sodium dodecyl sulfate (SDS) with concentrations of up to 0.05 mol kg-1 are made. Standard enthalpy of solution Δsol H 0 and enthalpy of transfer Δtr H 0 of the dipeptide from water into mixed solvent are calculated. The calculated enthalpy coefficients of paired interactions of amino acids and dipeptide with SDS prove to be positive. Hydrophobic interactions between the biomolecules and SDS are found to have a major impact on the enthalpies of interaction in the three-component systems under study, within the indicated range of concentrations.

  4. GC-MS analysis of ethanol solution with D2O as solvent implanted by low energy N+

    International Nuclear Information System (INIS)

    Shi Huaibin; Shao Chunlin; Yu Zengliang

    2001-10-01

    Low energy ions were produced by N 2 glow-discharge. The positive ones were accelerated into ethanol solution with D 2 O as solvent to induce chemical reactions. GC-MS analysis showed that DCH 2 CH 2 OH, HOCH 2 CH 2 OD were produced by such kind of implantation. Thus, it was proved that the reaction was mainly caused by radicals generated by decomposition of water molecules, D . and . OD played an important role in the process. Meanwhile, CH 3 COOD and HOCH 2 CH 2 ND 2 were also found in the products, so it was concluded that the reaction was carried out under an oxidative atmosphere, which was thought to be probably related to . OD radicals, too. The capture of D from D 2 O by N + to form . ND 2 radicals was not only an initial step to produce HOCH 2 CH 2 ND 2 but also served as a probable pattern for 'nitrogen deposition'. All these were helpful to reveal the mechanism of the reaction induced by low energy N + implanting into solution samples

  5. Selective separation of furfural and hydroxymethylfurfural from an aqueous solution using a supported hydrophobic deep eutectic solvent liquid membrane.

    Science.gov (United States)

    Dietz, Carin H J T; Kroon, Maaike C; Di Stefano, Michela; van Sint Annaland, Martin; Gallucci, Fausto

    2017-12-14

    For the first time, 12 different supported deep eutectic solvent (DES) liquid membranes were prepared and characterized. These membranes consist of a polymeric support impregnated with a hydrophobic DES. First, the different membranes were characterized and their stability in water and air was determined. Subsequently, the supported DES liquid membranes were applied for the recovery of furfural (FF) and hydroxymethylfurfural (HMF) from aqueous solutions. The effects of substrate properties (e.g. pore size), DES properties (e.g. viscosity) and concentrations of FF and HMF in the feed phase on the observed diffusivities and permeabilities were assessed. It was found that the addition of DES enhances the transport of FF and HMF through the polymeric membrane support. In particular, the use of the DES consisting of thymol + lidocaine (in the molar ratio 2 : 1) impregnated in a polyethylene support resulted in enhanced transport for both FF and HMF, and is most interesting for (in situ) isolation of FF and HMF from aqueous solutions, e.g. in biorefinery processes.

  6. Ions in solution basic principles of chemical interactions

    CERN Document Server

    Burgess, J

    1999-01-01

    This outline of the principles and chemical interactions in inorganic solution chemistry delivers a course module in an area of considerable complexity. Problems with solutions and tutorial hints to test comprehension have been added as a feature to check readers' understanding and assist self-study. Exercises and projects are also provided to help readers deepen and extend their knowledge and understanding. Inorganic solution chemistry is treated thoroughly Emphasis is placed upon NMR, UV-VIS, IR Raman spectroscopy, X-ray diffraction, and such topics as acid-base behaviour, stability constants and kinetics.

  7. Interactions of dipeptides with Triton X-100 in aqueous solution: A volumetric and spectroscopic study

    International Nuclear Information System (INIS)

    Yan, Zhenning; Wu, Shuangyan; Pan, Qi; Geng, Rui; Gu, Bixin; Wang, Jianji

    2014-01-01

    Highlights: • The values of V 2,ϕ o and Δ t V° are positive. • Interactions of Triton X-100 with charged and polar groups of dipeptides dominate. • Addition of dipeptide in water decreases the c cmc and the aggregation number of Triton X-100. • The affinity between dipeptide and Triton X-100 micelle increases with the increase in the length of alkyl chain of peptides. • Triton X-100 interacts with dipeptides more weakly than SDS. -- Abstract: The interactions of dipeptides with Triton X-100 in aqueous solution have been investigated by means of density, fluorescence spectroscopy and UV–vis spectroscopy. The standard partial molar volume (V 2,ϕ o ), standard partial molar volume of transfer for dipeptide from water to aqueous Triton X-100 solution (Δ t V o ) and partial molar expansibility (E ϕ o ) have been calculated from density data. Fluorescence spectroscopy was used to estimate the critical micellar concentration (c cmc ) and micelle aggregation number of Triton X-100 in aqueous dipeptide solutions. Effects of temperature and hydrocarbon chain length of dipeptides on the volumetric properties of dipeptide and critical micelle concentration (c cmc ) of Triton X-100 were examined. The pyrene fluorescence spectra were also used to study the change of micropolarity produced by the interactions of Triton X-100 with dipeptides. From the results of UV–vis absorption spectra, the binding constant between dipeptide and Triton X-100 above the c cmc was determined. The results have been interpreted in terms of solute–solvent interactions and structural changes in the mixed solutions

  8. Opalescence in monoclonal antibody solutions and its correlation with intermolecular interactions in dilute and concentrated solutions.

    Science.gov (United States)

    Raut, Ashlesha S; Kalonia, Devendra S

    2015-04-01

    Opalescence indicates physical instability of a formulation because of the presence of aggregates or liquid-liquid phase separation in solution and has been reported for monoclonal antibody (mAb) formulations. Increased solution opalescence can be attributed to attractive protein-protein interactions (PPIs). Techniques including light scattering, AUC, or membrane osmometry are routinely employed to measure PPIs in dilute solutions, whereas opalescence is seen at relatively higher concentrations, where both long- and short-range forces contribute to overall PPIs. The mAb molecule studied here shows a unique property of high opalescence because of liquid-liquid phase separation. In this study, opalescence measurements are correlated to PPIs measured in diluted and concentrated solutions using light scattering (kD ) and high-frequency rheology (G'), respectively. Charges on the molecules were calculated using zeta potential measurements. Results indicate that high opalescence and phase separation are a result of the attractive interactions in solution; however, the presence of attractive interactions do not always imply phase separation. Temperature dependence of opalescence suggests that thermodynamic contribution to opalescence is significant and Tcloud can be utilized as a potential tool to assess attractive interactions in solution. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

  9. Nonadiabatic dynamics of electron transfer in solution: Explicit and implicit solvent treatments that include multiple relaxation time scales

    International Nuclear Information System (INIS)

    Schwerdtfeger, Christine A.; Soudackov, Alexander V.; Hammes-Schiffer, Sharon

    2014-01-01

    The development of efficient theoretical methods for describing electron transfer (ET) reactions in condensed phases is important for a variety of chemical and biological applications. Previously, dynamical dielectric continuum theory was used to derive Langevin equations for a single collective solvent coordinate describing ET in a polar solvent. In this theory, the parameters are directly related to the physical properties of the system and can be determined from experimental data or explicit molecular dynamics simulations. Herein, we combine these Langevin equations with surface hopping nonadiabatic dynamics methods to calculate the rate constants for thermal ET reactions in polar solvents for a wide range of electronic couplings and reaction free energies. Comparison of explicit and implicit solvent calculations illustrates that the mapping from explicit to implicit solvent models is valid even for solvents exhibiting complex relaxation behavior with multiple relaxation time scales and a short-time inertial response. The rate constants calculated for implicit solvent models with a single solvent relaxation time scale corresponding to water, acetonitrile, and methanol agree well with analytical theories in the Golden rule and solvent-controlled regimes, as well as in the intermediate regime. The implicit solvent models with two relaxation time scales are in qualitative agreement with the analytical theories but quantitatively overestimate the rate constants compared to these theories. Analysis of these simulations elucidates the importance of multiple relaxation time scales and the inertial component of the solvent response, as well as potential shortcomings of the analytical theories based on single time scale solvent relaxation models. This implicit solvent approach will enable the simulation of a wide range of ET reactions via the stochastic dynamics of a single collective solvent coordinate with parameters that are relevant to experimentally accessible

  10. Modelling copper solvent extraction from acidic sulphate solutions using MOC 45

    Directory of Open Access Journals (Sweden)

    Alguacil, F. J.

    1998-05-01

    Full Text Available A mathematical model to predict the extraction has been developed for the Cu-MOC 45 system. The model consists of sets of nonlinear mass action and mass balance equations where the dimerization of the oxime was also considered. The predictive model calculated the equilibrium concentrations from the total oxime concentration, total copper concentration, initial pH value and the O/A volume phase ratio. The model suggests that the extraction of copper can be defined by the existence of two species into the organic solution: CuR2 (kext = 4.2 and Cu(HR22 (kext = 10.000- The initial oxime concentration defines the predominancy in the organic solution of both species. The model can be used to predict copper extraction isotherm as well as copper stripping with sulphuric acid.

    Se desarrolla un modelo matemático para predecir el proceso de extracción en el sistema Cu-MOC 45. El modelo consiste en un conjunto de ecuaciones en el que se considera la dimerización de la oxima. El modelo permite predecir la extracción a partir de las concentraciones totales de la oxima y del cobre, del pH inicial y de la relación de fases O/A. La extracción de cobre responde a la existencia de dos especies en la fase orgánica: CuR2 (kext = 4,2 y Cu(HR22 (kext = 10.000. La predominancia de una u otra especie en esta fase depende de la concentración inicial de la oxima. El modelo también puede predecir las isotermas de extracción y la reextracción de cobre mediante ácido sulfúrico.

  11. Associative Interactions in Crowded Solutions of Biopolymers Counteract Depletion Effects.

    Science.gov (United States)

    Groen, Joost; Foschepoth, David; te Brinke, Esra; Boersma, Arnold J; Imamura, Hiromi; Rivas, Germán; Heus, Hans A; Huck, Wilhelm T S

    2015-10-14

    The cytosol of Escherichia coli is an extremely crowded environment, containing high concentrations of biopolymers which occupy 20-30% of the available volume. Such conditions are expected to yield depletion forces, which strongly promote macromolecular complexation. However, crowded macromolecule solutions, like the cytosol, are very prone to nonspecific associative interactions that can potentially counteract depletion. It remains unclear how the cytosol balances these opposing interactions. We used a FRET-based probe to systematically study depletion in vitro in different crowded environments, including a cytosolic mimic, E. coli lysate. We also studied bundle formation of FtsZ protofilaments under identical crowded conditions as a probe for depletion interactions at much larger overlap volumes of the probe molecule. The FRET probe showed a more compact conformation in synthetic crowding agents, suggesting strong depletion interactions. However, depletion was completely negated in cell lysate and other protein crowding agents, where the FRET probe even occupied slightly more volume. In contrast, bundle formation of FtsZ protofilaments proceeded as readily in E. coli lysate and other protein solutions as in synthetic crowding agents. Our experimental results and model suggest that, in crowded biopolymer solutions, associative interactions counterbalance depletion forces for small macromolecules. Furthermore, the net effects of macromolecular crowding will be dependent on both the size of the macromolecule and its associative interactions with the crowded background.

  12. Structural and thermal characterization of hemicelluloses isolated by organic solvents and alkaline solutions from Tamarix austromongolica.

    Science.gov (United States)

    Sun, Yong-Chang; Wen, Jia-Long; Xu, Feng; Sun, Run-Cang

    2011-05-01

    Three organosolv and three alkaline hemicellulosic fractions were prepared from lignocellulosic biomass of the fast-growing shrub Tamarix austromongolica (Tamarix Linn.). Sugar analysis revealed that the organosolv-soluble fractions contained a higher content of glucose (33.7-6.5%) and arabinose (14.8-5.6%), and a lower content of xylose (62.2-54.8%) than the hemicellulosic fractions isolated with aqueous alkali solutions. A relatively high concentration of alkali resulted in a decreasing trend of the xylose/4-O-methyl-D-glucuronic acid ratio in the alkali-soluble fractions. The results of NMR analysis supported a major substituted structure based on a linear polymer of β-(1→4)-linked d-xylopyranosyl residues, having ramifications of α-L-arabinofuranose and 4-O-methyl-D-glucuronic acid residues monosubstituted at O-3 and O-2, respectively. Thermogravimetric analysis revealed that one step of major mass loss occurred between 200-400°C, as hemicelluloses devolatilized with total volatile yield of about 55%. It was found that organosolv-soluble fractions are more highly ramified, and showed a higher thermal stability than the alkali-soluble fractions. Copyright © 2011 Elsevier Ltd. All rights reserved.

  13. Solvent extraction of Th(IV) from aqueous solution with methylimidazole in ionic liquid

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wenkui; Lv, Hui; Liu, Ziyi; Wu, Jianrong; Li, Shun; Shen, Yinglin [Lanzhou Univ. (China). Radiochemistry Lab.; Yang, Shenghua [State Key Laboratory of Applied Organic Chemistry, Lanzhou (China)

    2016-07-01

    An extraction of Th(IV) was performed using 1-methylimidazole (1-MIM) or 2-methylimidazole (2-MIM) as the extractant in imidazolium type ionic liquids (ILs) or n-pentanol. The extractability for Th{sup 4+} in ILs was by far higher than that obtained in n-pentanol. The extraction mechanism was determined by slope analysis and ESI-MS. The transfer of Th{sup 4+} with MIM into ILs proceeded through both a cationic exchange and a neutral solvation mechanism, whereas the partitioning of Th{sup 4+} with MIM into n-pentanol only underwent a neutral solvation mechanism. The thermodynamic parameters values (ΔH, ΔS and ΔG) for extraction of Th{sup 4+} with 1-MIM in IL were calculated and the results indicated the extraction reaction was spontaneous and went through endothermic process. Separation of Th{sup 4+} from the solution of lanthanides (III) and uranium was also carried out by 1-MIM in ILs and n-pentanol.

  14. Introducing a standard method for experimental determination of the solvent response in laser pump, x-ray probe time-resolved wide-angle x-ray scattering experiments on systems in solution

    DEFF Research Database (Denmark)

    Kjær, Kasper Skov; Brandt van Driel, Tim; Kehres, Jan

    2013-01-01

    In time-resolved laser pump, X-ray probe wide-angle X-ray scattering experiments on systems in solution the structural response of the system is accompanied by a solvent response. The solvent response is caused by reorganization of the bulk solvent following the laser pump event, and in order...... response-the solvent term-experimentally when applying laser pump, X-ray probe time-resolved wide-angle X-ray scattering. The solvent term describes difference scattering arising from the structural response of the solvent to changes in the hydrodynamic parameters: pressure, temperature and density. We...... is demonstrated to exhibit first order behaviour with respect to the amount of energy deposited in the solution. We introduce a standardized method for recording solvent responses in laser pump, X-ray probe time-resolved X-ray wide-angle scattering experiments by using dye mediated solvent heating. Furthermore...

  15. STUDY OF SOLVENT AND CATALYST INTERACTIONS IN DIRECT COAL LIQUEFACTION; FINAL

    International Nuclear Information System (INIS)

    Michael T. Klein; William H. Calkins; Jasna Tomic

    2000-01-01

    To provide a better understanding of the roles of a solid catalyst and the solvent in Direct Coal Liquefaction, a small reactor was equipped with a porous-walled basket which was permeable to the solvent but was not permeable to the coal or solid catalyst. With this equipment and a high volatile bituminous coal it was found that direct contact between the catalyst in the basket and the coal outside the basket is not required for catalyzed coal liquefaction. The character of the solvent in this system makes a significant difference in the conversion of the coal, the better solvents being strong donor solvents. Because of the extensive use of thermogravimetric analysis in this laboratory, it was noted that the peak temperature for volatiles evolution from coal was a reliable measure of coal rank. Because of this observation, a variety of coals of a range of ranks was investigated. It was shown in this work that measuring the peak temperature for volatiles evolution was a quite precise indicator of rank and correlated closely with the rank value obtained by measuring vitrinite reflectance, a more difficult measurement to make. This prompted the desire to know the composition of the volatile material evolved as a function of coal rank. This was then measured by coupling a TGA to a mass spectrometer using laser activation and photoionization detection TG-PI-MS. The predominant species in volatiles of low rank coal turned out to be phenols with some alkenes. As the rank increases, the relative amounts of alkene and aromatic hydrocarbons increases and the oxygenated species decrease. It was shown that these volatiles were actually pyrolytic products and not volatilization products of the coal. Solvent extraction experiments coupled with Thermogravimetric-photoionization-mass spectrometry (TG-PI-MS) indicated that the low boiling and more extractable material are essentially similar in chemical types to the non-extractable portions but apparently higher molecular weight

  16. Study of uranium(VI) speciation in phosphoric acid solutions and of its recovery by solvent extraction

    International Nuclear Information System (INIS)

    Dartiguelongue, Adrien

    2014-01-01

    Because small amounts of uranium are present in phosphate rocks, wet phosphoric acids may contain up to 300 ppm of uranium(VI). Therefore, such acids are a cost-effective unconventional source of this metal. Its recovery is a challenge for metallurgical firms which must develop reliable and selective solvent extraction processes. Such processes need to know the chemical equilibria involved in the extraction process, the speciation of uranium and its thermodynamics in solution. These two last points have been investigated in this work. Firstly, the most probable species of uranium(VI) in phosphoric acid solutions have been selected thanks to a detailed review of the literature. Then, a thermodynamic model founded on an equation of state for electrolytes has been built according these hypotheses. It has been validated with speciation data coming from original ATR-IR spectroscopy measurements. Finally, the composition of the aqueous phosphoric acid solutions and the activity coefficients obtained have been combined with a chemical model of uranium(VI) extraction into an organic phase containing a synergistic mixture of bis(2-ethylhexyl)phosphoric acid (D2EHPA) and tri-n-octylphosphine oxide (TOPO) in order to represent the variation of the distribution coefficient of uranium(VI) with H 3 PO 4 concentration. This model had been previously developed at Chimie ParisTech at a given concentration of H 3 PO 4 (i.e., 5,3 mol/L), but in the present study we have tested its validity in an extended range of phosphoric acid concentrations (i.e., 1-7 mol/L) and improved it. (author)

  17. SOLVENT EFFECT ON PROTONATION OF TPPS IN WATER-DMF ...

    African Journals Online (AJOL)

    2016 Chemical Society of Ethiopia ... Department of Chemistry, Jouybar branch, Islamic Azad University, Jouybar, Iran ... hydrogen bonding interactions between solute and solvent components are mainly responsible for the change in.

  18. The solvent extraction of zinc, iron, and indium from chloride solutions by neutral organophosphorus compounds

    International Nuclear Information System (INIS)

    Preston, J.S.; Du Preez, A.C.

    1985-01-01

    The preparation of several neutral organophosphorus compounds and their evaluation as selective extractants for zinc in chloride media are described. The compounds belong to the series trialkyl phosphates (RO) 3 PO, dialkyl alkylphosphonates R'PO(OR) 2 , alkyl dialkylphosphinates R 2 'PO(OR), and trialkyl-phosphine oxides R 3 'PO. They were characterized by measurement of their physical properties (melting and boiling points, refractive indices, and densities), and their purities were confirmed by osmometric determination of their molecular masses; by carbon and hydrogen microanalysis; by the titrimetric determination of acidic impurities; and, for liquid products, by comparison of their experimental molar refractivities with empirical values. Metal-distribution equilibria were determined for solutions of the extractants in xylene and aqueous phase containing 0,5 to 5,0 M sodium chloride. Moderately good selectivities were shown for zinc(II) over iron(III), and excellent selectivities were shown for zinc(II) over iron(II), copper(II), lead(II), and cadmium(II). The extraction of indium(III) was similar to that of zinc(II). The extraction of zinc(III), iron(III), and indium(III) increased markedly through the series. (RO) 3 PO 2 2 'PO(OR) 3 'PO. The incorporation of phenyl groups into the compounds led to weaker extraction. The extracted complexes of zinc(II), iron(III), and indium(III) have the stoichiometries ZnCl 2 L 2 ,FeCl 3 L 2 (H 2 O), and InCl 3 L 2 (H 2 O) respectively, where L represents the neutral organophosphorus compound

  19. Weak solutions for Euler systems with non-local interactions

    Czech Academy of Sciences Publication Activity Database

    Carrillo, J. A.; Feireisl, Eduard; Gwiazda, P.; Swierczewska-Gwiazda, A.

    2017-01-01

    Roč. 95, č. 3 (2017), s. 705-724 ISSN 0024-6107 EU Projects: European Commission(XE) 320078 - MATHEF Institutional support: RVO:67985840 Keywords : Euler system * dissipative solutions * Newtonian interaction Subject RIV: BA - General Mathematics OBOR OECD: Pure mathematics Impact factor: 0.895, year: 2016 http://onlinelibrary.wiley.com/doi/10.1112/jlms.12027/abstract

  20. A Solvent Switch for the Stabilization of Multiple Hemiacetals on an Inorganic Platform: Role of Supramolecular Interactions.

    Science.gov (United States)

    Kalita, Alok Ch; Gupta, Sandeep K; Murugavel, Ramaswamy

    2016-05-10

    Reaction of Zn(OAc)2 ⋅2 H2 O with 2,6-diisopropylphenyl phosphate (dippH2 ) in the presence of pyridine-4-carboxaldehyde (Py-4-CHO) in methanol resulted in the isolation of a tetrameric zinc phosphate cluster [Zn(dipp)(Py-4-CH(OH)(OMe))]4 ⋅4 MeOH (1) with four hemiacetal moieties stabilized on the double-4-ring inorganic cubane cluster. The change of solvent from methanol to acetonitrile leads to the formation of [Zn(dipp)(Py-4-CHO)]4 (2), in which the coordinated Py-4-CHO retains its aldehydic form. Dissolution of 1 in CD3 CN readily converts it to the aldehydic form and yields 2. Similarly 2, which exists in the aldehyde form in CD3 CN, readily converts to the hemiacetal form in CD3 OD/CH3 OH. Compound 1 is an unprecedented example in which four hemiacetals have been stabilized on a single molecule in the solid state retaining its stability in solution as revealed by its (1) H NMR spectrum in CD3 OD. The solution stability of 1 and 2 has further been confirmed by ESI-MS studies. To generalize the stabilization of multiple hemiacetals on a single double-four-ring platform, pyridine-2-carboxaldehyde (Py-2-CHO) was used as the auxiliary ligand in the reaction between zinc acetate and dippH2 , leading to isolation of [Zn(dipp)(Py-2-CH(OH)(OMe))]4 (3). Understandably, recrystallization of 3 from acetonitrile yields the parent aldehydic form, [Zn(dipp)(Py-2-CHO)]4 (4). Single-crystal X-ray diffraction studies reveal that supramolecular bonding, aided by hydrogen-bonding interactions involving the hemiacetal functionalities (C-OH, C-OMe, and C-H), are responsible for the observed stabilization. The hemiacetal/aldehyde groups in 1 and 2 readily react with p-toluidine, 2,6-dimethylaniline, and 4-bromoaniline to yield the corresponding tetra-Schiff base ligands, [Zn(dipp)(L)]4 (L=4-methyl-N-(pyridin-4-ylmethylidene)aniline (5), 2,6-dimethyl-N-(pyridin-4-ylmethylene)-aniline (6), and 4-bromo-N-(pyridin-4-ylmethylene)aniline (7)). Isolation of 5-7 opens up further

  1. Solvent density inhomogeneities and solvation free energies in supercritical diatomic fluids: a density functional approach.

    Science.gov (United States)

    Husowitz, B; Talanquer, V

    2007-02-07

    Density functional theory is used to explore the solvation properties of a spherical solute immersed in a supercritical diatomic fluid. The solute is modeled as a hard core Yukawa particle surrounded by a diatomic Lennard-Jones fluid represented by two fused tangent spheres using an interaction site approximation. The authors' approach is particularly suitable for thoroughly exploring the effect of different interaction parameters, such as solute-solvent interaction strength and range, solvent-solvent long-range interactions, and particle size, on the local solvent structure and the solvation free energy under supercritical conditions. Their results indicate that the behavior of the local coordination number in homonuclear diatomic fluids follows trends similar to those reported in previous studies for monatomic fluids. The local density augmentation is particularly sensitive to changes in solute size and is affected to a lesser degree by variations in the solute-solvent interaction strength and range. The associated solvation free energies exhibit a nonmonotonous behavior as a function of density for systems with weak solute-solvent interactions. The authors' results suggest that solute-solvent interaction anisotropies have a major influence on the nature and extent of local solvent density inhomogeneities and on the value of the solvation free energies in supercritical solutions of heteronuclear molecules.

  2. Bulk viscosity, interaction and the viability of phantom solutions

    Energy Technology Data Exchange (ETDEWEB)

    Leyva, Yoelsy; Sepulveda, Mirko [Universidad de Tarapaca, Departamento de Fisica, Facultad de Ciencias, Arica (Chile)

    2017-06-15

    We study the dynamics of a bulk viscosity model in the Eckart approach for a spatially flat Friedmann-Robertson-Walker (FRW) Universe. We have included radiation and dark energy, assumed as perfect fluids, and dark matter treated as an imperfect fluid having bulk viscosity. We also introduce an interaction term between the dark matter and dark energy components. Considering that the bulk viscosity is proportional to the dark matter energy density and imposing a complete cosmological dynamics, we find bounds on the bulk viscosity in order to reproduce a matter-dominated era (MDE). This constraint is independent of the interaction term. Some late time phantom solutions are mathematically possible. However, the constraint imposed by a MDE restricts the interaction parameter, in the phantom solutions, to a region consistent with a null value, eliminating the possibility of late time stable solutions with w < -1. From the different cases that we study, the only possible scenario, with bulk viscosity and interaction term, belongs to the quintessence region. In the latter case, we find bounds on the interaction parameter compatible with latest observational data. (orig.)

  3. Ion-ion and ion-solvent interactions in lithium imidazolide electrolytes studied by Raman spectroscopy and DFT models.

    Science.gov (United States)

    Scheers, Johan; Niedzicki, Leszek; Zukowska, Grażyna Z; Johansson, Patrik; Wieczorek, Władysław; Jacobsson, Per

    2011-06-21

    Molecular level interactions are of crucial importance for the transport properties and overall performance of ion conducting electrolytes. In this work we explore ion-ion and ion-solvent interactions in liquid and solid polymer electrolytes of lithium 4,5-dicyano-(2-trifluoromethyl)imidazolide (LiTDI)-a promising salt for lithium battery applications-using Raman spectroscopy and density functional theory calculations. High concentrations of ion associates are found in LiTDI:acetonitrile electrolytes, the vibrational signatures of which are transferable to PEO-based LiTDI electrolytes. The origins of the spectroscopic changes are interpreted by comparing experimental spectra with simulated Raman spectra of model structures. Simple ion pair models in vacuum identify the imidazole nitrogen atom of the TDI anion to be the most important coordination site for Li(+), however, including implicit or explicit solvent effects lead to qualitative changes in the coordination geometry and improved correlation of experimental and simulated Raman spectra. To model larger aggregates, solvent effects are found to be crucial, and we finally suggest possible triplet and dimer ionic structures in the investigated electrolytes. In addition, the effects of introducing water into the electrolytes-via a hydrate form of LiTDI-are discussed.

  4. Electric Dipole Transition Moments and Solvent-Dependent Interactions of Fluorescent Boron-Nitrogen Substituted Indole Derivatives.

    Science.gov (United States)

    Saif, Mari; Widom, Julia R; Xu, Senmiao; Abbey, Eric R; Liu, Shih-Yuan; Marcus, Andrew H

    2015-06-25

    Fluorescent analogues of the indole side chain of tryptophan can be useful spectroscopic probes of protein-protein and protein-DNA interactions. Here we present linear dichroism and solvent-dependent spectroscopic studies of two fluorescent analogues of indole, in which the organic C═C unit is substituted with the isosteric inorganic B-N unit. We studied the so-called "external" BN indole, which has C2v symmetry, and the "fused" BN indole with Cs symmetry. We performed a combination of absorption and fluorescence spectroscopy, ultraviolet linear dichroism (UV-LD) in stretched poly(ethylene) (PE) films, and quantum chemical calculations on both BN indole compounds. Our measurements allowed us to characterize the degree of alignment for both molecules in stretched PE films. We thus determined the orientations and magnitudes of the two lowest energy electric dipole transition moments (EDTMs) for external BN indole, and the two lowest energy EDTMs for fused BN indole within the 30 000-45 000 cm(-1) spectral range. We compared our experimental results to those of quantum chemical calculations using standard density functional theory (DFT). Our theoretical predictions for the low-energy EDTMs are in good agreement with our experimental data. The absorption and fluorescence spectra of the external and the fused BN indoles are sensitive to solvent polarity. Our results indicate that the fused BN indole experiences much greater solvation interactions with polar solvents than does the external BN indole.

  5. Comparison of interaction of aromatic solvents in hybrid and textile biocomposites

    CSIR Research Space (South Africa)

    Jacob John, Maya

    2009-11-01

    Full Text Available the sorption uptake of organic solvents in hybrid and woven biocomposites. EXPERIMENTAL Sisal fiber was obtained from Sheeba Fibers, Poovancode, Tamil Nadu. Oil palm fiber was obtained from Oil Palm India Limited. Natural rubber used for the study...

  6. Ascorbic Acid and BSA Protein in Solution and Films: Interaction and Surface Morphological Structure

    Directory of Open Access Journals (Sweden)

    Rafael R. G. Maciel

    2013-01-01

    Full Text Available This paper reports on the study of the interactions between ascorbic acid (AA and bovine serum albumin (BSA in aqueous solution as well as in films (BSA/AA films prepared by the layer-by-layer technique. Regarding to solution studies, a hyperchromism (in the range of ultraviolet was found as a function of AA concentration, which suggested the formation of aggregates from AA and BSA. Binding constant, , determined for aggregates from BSA and AA was found to be about 102 M−1, which indicated low affinity of AA with BSA. For the BSA/AA films, it was also noted that the AA adsorption process and surface morphological structures depended on AA concentration. By changing the contact time between the AA and BSA, a hypochromism was revealed, which was associated to decrease of accessibility of solvent to tryptophan due to formation of aggregates. Furthermore, different morphological structures of aggregates were observed, which were attributed to the diffusion-limited aggregation. Since most of studies of interactions of drugs and proteins are performed in solution, the analysis of these processes by using films can be very valuable because this kind of system is able to employ several techniques of investigation in solid state.

  7. STUDY OF SOLVENT AND CATALYST INTERACTIONS IN DIRECT COAL LIQUEFACTION; SEMIANNUAL

    International Nuclear Information System (INIS)

    Michael T. Klein

    2000-01-01

    There are several aspects of the Direct Coal Liquefaction process which are not fully understood and which if better understood might lead to improved yields and conversions. Among these questions are the roles of the catalyst and the solvent. While the solvent is known to act by transfer of hydrogen atoms to the free radicals formed by thermal breakdown of the coal in an uncatalyzed system, in the presence of a solid catalyst as is now currently practiced, the yields and conversions are higher than in an uncatalyzed system. The role of the catalyst in this case is not completely understood. DOE has funded many projects to produce ultrafine and more active catalysts in the expectation that better contact between catalyst and coal might result. This approach has met with limited success probably because mass transfer between two solids in a fluid medium i.e. the catalyst and the coal, is very poor. It is to develop an understanding of the role of the catalyst and solvent in Direct Liquefaction that this project was initiated. Specifically it was of interest to know whether direct contact between the coal and the catalyst was important. By separating the solid catalyst in a stainless steel basket permeable to the solvent but not the coal in the liquefaction reactor, it was shown that the catalyst still maintains a catalytic effect on the liquefaction process. There is apparently transfer of hydrogen atoms from the catalyst through the basket wall to the coal via the solvent. Strong hydrogen donor solvents appear to be more effective in this respect than weak hydrogen donors. It therefore appears that intimate contact between catalyst and coal is not a requirement, and that the role of the catalyst may be to restore the hydrogen donor strength to the solvent as the reaction proceeds. A range of solvents of varying hydrogen donor strength was investigated. Because of the extensive use of thermogravimetric analysis in this laboratory in was noted that the peak

  8. Electronic excitation of molecules in solution calculated using the symmetry-adapted cluster–configuration interaction method in the polarizable continuum model

    International Nuclear Information System (INIS)

    Fukuda, Ryoichi; Ehara, Masahiro

    2015-01-01

    The effects from solvent environment are specific to the electronic states; therefore, a computational scheme for solvent effects consistent with the electronic states is necessary to discuss electronic excitation of molecules in solution. The PCM (polarizable continuum model) SAC (symmetry-adapted cluster) and SAC-CI (configuration interaction) methods are developed for such purposes. The PCM SAC-CI adopts the state-specific (SS) solvation scheme where solvent effects are self-consistently considered for every ground and excited states. For efficient computations of many excited states, we develop a perturbative approximation for the PCM SAC-CI method, which is called corrected linear response (cLR) scheme. Our test calculations show that the cLR PCM SAC-CI is a very good approximation of the SS PCM SAC-CI method for polar and nonpolar solvents

  9. Scalar, electromagnetic, and gravitational fields interaction: Particlelike solutions

    International Nuclear Information System (INIS)

    Bronnikov, K.A.; Melnikov, V.N.; Shikin, G.N.; Staniukovich, K.P.

    1979-01-01

    Particlelike static spherically symmetric solutions to massless scalar and electromagnetic field equations combined with gravitational field equations are considered. Two criteria for particlelike solutions are formulated: the strong one (solutions are required to be singularity free) and the weak one (singularities are admitted but the total energy and material field energy should be finite). Exact solutions for the following physical systems are considered with their own gravitational field: (i) linear scalar (minimally coupled or conformal) plus electromagnetic field; (ii) the same fields with a bare mass source in the form of charged incoherent matter distributions; (iii) nonlinear electromagnetic field with an abritrary dependence on the invariant F/sub alphabeta/F/sup alphabeta/; and (iv) directly interacting scalar and electromagnetic fields. Case (i) solutions are not particlelike (except those with horizons, in which static regions formally satisfy the weak criterion). For systems (ii), examples of nonsingular models are constructed, in particular, a model for a particle--antiparticle pair of a Wheeler-handle type, without scalar field and explict electric charges. Besides, a number of limitations upon nonsingular model parameters is indicated. Systems (iii) are proved to violate the strong criterion for any type of nonlinearity but can satisfy the weak criterion (e.g., the Born--Infeld nonlinearity). For systems (iv) some particlelike solutions by the weak criterion are constructed and a regularizing role of gravitation is demonstrated. Finally, an example of a field system satisfying the strong criterion is given

  10. Br2(X) microsolvation in helium clusters: effect of the interaction on the quantum solvent density distribution.

    Science.gov (United States)

    Di Paola, Cono; Gianturco, Franco A; López-Durán, David; de Lara-Castells, Maria Pilar; Delgado-Barrio, Gerardo; Villarreal, Pablo; Jellinek, Julius

    2005-07-11

    The Born-Oppenheimer potential energy surface for the Br2(X) molecule interacting with a varying number of 4He bosons is constructed following two different schemes which employ either a full ab initio evaluation of the Br2-He interaction forces or an estimate of the latter through an empirical model. Both descriptions are employed by carrying out diffusion Monte Carlo (DMC) calculations of the ground-state energies and quantum wavefunctions for Br2-(He)n clusters with n up to 24. The results clearly indicate, for both interactions, the occurrence of the full solvation of the molecular dopant within the quantum bosonic "solvent" but also show differences between the two models in terms of the expected density distributions of the surrounding particles within the shorter-range region that makes up the clusters with smaller n values. Our calculations also show that such differences become insignificant for the larger 4He clusters surrounding the Br2 molecule, where density profiles and bulk behaviour are chiefly driven by the solvent structure, once n values reach the region of 15-20 adatoms.

  11. Viscometric studies of interactions between ionic liquid 1-octyl-3-methyl-imidazolium bromide and polyvinyl pyrrolidone in aqueous solutions

    International Nuclear Information System (INIS)

    Mehrdad, Abbas; Shekaari, Hemayat; Niknam, Zahra

    2014-01-01

    Highlights: • Viscosities of PVP in aqueous solution of IL are measured. • The flow activation energies are calculated. • The flow activation energies are correlated in terms of polymer concentration. • Intrinsic viscosity of PVP is decreased by increasing temperature. - Abstract: Ionic liquids are investigated as solvents for polymerization processes, as plasticizers of various kinds of polymers and as components of the polymeric matrixes. In this research, viscosity of polyvinyl pyrrolidone in aqueous solution of ionic liquid, 1-octyl-3-methyl imidazolium bromide are measured at various temperatures. The flow activation energies are calculated and correlated in terms of polymer concentration. From sign of the initial slope of the activation energy versus polymer concentration at zero concentration, it is concluded that thermodynamic quality of ionic liquid aqueous solutions are reduced by increasing temperature. The value of the intrinsic viscosity of polyvinyl pyrrolidone was determined using Huggins equation and thermodynamic parameters of this polymer were calculated on the basis of intrinsic viscosity. Also the effect of ionic liquid, 1-octyl-3-methyl imidazolium bromide on the thermodynamic parameters of dilute aqueous polyvinyl pyrrolidone solutions, such as (polymer + solvent) interaction parameter, theta temperature, the heat of dilution parameter and the entropy of dilution parameter was investigated. Results suggest that the thermodynamic quality of water was increased slightly by the addition of ionic liquid in aqueous solution of polyvinyl pyrrolidone

  12. Extensional Rheology of Entangled Polystyrene Solutions Suggests Importance of Nematic Interactions

    DEFF Research Database (Denmark)

    Huang, Qian; Javier Alvarez, Nicolas; Matsumiya, Yumi

    2013-01-01

    We compare the linear and nonlinear rheological response of three entangled polystyrene solutions with the same concentration of polymer, but diluted using different solvents. The three solutions have exactly the same physical tube model parameters when normalized to the same time scale. Although...

  13. Phase separation phenomena in solutions of poly(2,6-dimethyl-1,4-phenylene oxide). IV. Thermodynamic parameters for solutions in a series of homologous solvents: Toluene to hexylbenzene

    NARCIS (Netherlands)

    Koenhen, D.M.; Bakker, A.; Broens, L.; van den Berg, J.W.A.; Smolders, C.A.

    1984-01-01

    Melting-point curves for solutions of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) in a series of homologous solvents (toluene to n-hexylbenzene) have been obtained from visual and differential scanning calorimetry measurements. The measured melting points were used to calculate thermodynamic

  14. Flavor release and perception in hard candy: influence of flavor compound-flavor solvent interactions.

    Science.gov (United States)

    Schober, Amanda L; Peterson, Devin G

    2004-05-05

    The release kinetics of l-menthol dissolved in propylene glycol (PG), Miglyol, or 1,8-cineole (two common odorless flavor solvents differing in polarity and a hydrophobic flavor compound) were monitored from a model aqueous system via atmospheric pressure chemical ionization mass spectrometry (APCI-MS). Breath analysis was also conducted via APCI-MS to monitor release of l-menthol from hard candy that used PG and Miglyol for l-menthol incorporation. The quantities of l-menthol released when dissolved in PG or Miglyol from the model aqueous system were found to be similar and overall significantly greater in comparison to when dissolved in 1,8-cineole. Analogous results were reported by the breath analysis of hard candy. The release kinetics of l-menthol from PG or Miglyol versus from 1,8-cineole were notably more rapid and higher in quantity. Results from the sensory time-intensity study also indicated that there was no perceived difference in the overall cooling intensity between the two flavor solvent delivery systems (PG and Miglyol).

  15. Molar volumes of LiI in H{sub 2}O and D{sub 2}O solutions; Structural hydration interactions

    Energy Technology Data Exchange (ETDEWEB)

    Jakli, Gy. [KFKI Atomic Energy Research Institute, P.O. Box 49, H-1525 Budapest (Hungary)], E-mail: jakli@aeki.kfki.hu

    2009-01-15

    According to a recent study of the H{sub 2}O and D{sub 2}O molar volume isotope effect (MVIE) of the alkali metal chloride solutions, neither the standard nor the excess MVIE of the LiCl corresponds to the usual hydrophilic hydration characteristics of the inorganic ions above room temperatures. This phenomenon can not be rationalized by electrostriction, with the collapse of the 'loose' tetrahedral ('ice-like') water structure due to the electrostatic (ion + dipole) interaction. It seemed possible that this unique hydration behaviour of the Li{sup +} would be stronger and could reveal further structural information with a less hydrophilic anion than the chloride. Therefore we have determined the MVIE of the LiI as a function of temperature and concentration. The densities of normal and heavy water solutions of LiI have been measured with six-figure precision at T = (288.15, 298.15, and 308.15) K from (0.03 to 4) molal, m, using a vibrating-tube densitometer. The solvent isotope effect on the apparent molar volume, as well as on the solute and solvent partial molar volumes, was evaluated. As expected, with the rationalization of the MVIE of LiI instead of the geometric structural differences of the isotopic solvents, the energetic contributions have to be considered at all the temperatures investigated. At infinite dilution, a high degree of compensation between the reversed influences of the Li{sup +} and I{sup -} on the activities of the isotopic solvents determines the MVIE. By increasing concentration, the highly asymmetric energetic interactions of the Li{sup +} and the I{sup -} with the solvent apparently result in a 'mutual salting-out' effect. At a concentration {approx}0.7m, a uniquely abrupt structural rearrangement results in a 'solvent-separated ion-pair' solution structure.

  16. Interaction of gypsum with lead in aqueous solutions

    International Nuclear Information System (INIS)

    Astilleros, J.M.; Godelitsas, A.; Rodriguez-Blanco, J.D.; Fernandez-Diaz, L.; Prieto, M.; Lagoyannis, A.; Harissopulos, S.

    2010-01-01

    Sorption processes on mineral surfaces are a critical factor in controlling the distribution and accumulation of potentially harmful metals in the environment. This work investigates the effectiveness of gypsum (CaSO 4 .2H 2 O) to sequester Pb. The interaction of gypsum fragments with Pb-bearing solutions (10, 100 and 1000 mg/L) was monitored by performing macroscopic batch-type experiments conducted at room temperature. The aqueous phase composition was periodically determined by Atomic Absorption Spectrometry (AAS), Ion Chromatography (IC) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Regardless of the [Pb aq ] initial , a [Pb aq ] final aq ] initial ≥ 100 mg/L and significantly slower (t > 1 week) for [Pb aq ] initial = 10 mg/L. Speciation calculations revealed that after a long time of interaction (1 month), all the solutions reached equilibrium with respect to both gypsum and anglesite. For [Pb aq ] initial ≥ 100 mg/L, sorption takes place mainly via the rapid dissolution of gypsum and the simultaneous formation of anglesite both on the gypsum surface and in the bulk solution. In the case of [Pb aq ] initial = 10 mg/L, no anglesite precipitation was observed, but surface spectroscopy (proton Rutherford Backscattering Spectroscopy, p-RBS) confirmed the formation of Pb-bearing surface layers on the (0 1 0) gypsum surface in this case also. This study shows that the surface of gypsum can play an important role in the attenuation of Pb in contaminated waters.

  17. Interactions of acidic solutions with sediments: a case study

    International Nuclear Information System (INIS)

    Peterson, S.R.; Serne, R.J.; Felmy, A.R.; Erikson, R.L.; Krupka, K.M.; Gee, G.W.

    1984-01-01

    A methodology is presented for investigating the chemical interactions of acidic solutions with sediments. The MINTEQ geochemical computer code was used to predict solid-phase reactions that might occur when acidic solutions contact neutral sediments which, in turn, may control the concentrations of certain dissolved components. Results of X-ray diffraction analysis of laboratory samples of sediments that have been contacted with acidic uranium mill tailings solutions suggest gypsum and jarosite precipitated. These same mineralogical changes were identified in sediment samples collected from a drained uranium mill evaporation pond (Lucky Mc mine in Wyoming) with a 10-year history of acid attack. Geochemical modeling predicted that these same phases and several amorphous solids not identifiable by X-ray diffraction should have precipitated in the contacted sediments. An equilibrium conceptual model consisting of an assemblage of minerals and amorphous solid phases was then developed to represent a sediment column through which uranium mill tailings solutions were percolated. The MINTEQ code was used to predict effluent solution concentrations resulting from the reactions of the tailings solution with the assemblage of solid phases in the conceptual model. The conceptual model successfully predicted the concentrations of several of the macro-constituents (e.g., Ca, SO 4 , Al, Fe, and Mn), but was not successful in modeling the concentrations of trace elements. The lack of success in predicting the observed trace metal concentrations suggests that other mechanisms, such as adsorption, must be included in future models. The geochemical modeling methodology coupled with the laboratory and field studies should be applicable to a variety of waste disposal problems

  18. Late time solution for interacting scalar in accelerating spaces

    Energy Technology Data Exchange (ETDEWEB)

    Prokopec, Tomislav, E-mail: t.prokopec@uu.nl [Institute for Theoretical Physics, Spinoza Institute and EMME$\\Phi$, Utrecht University, Postbus 80.195, Utrecht, 3508 TD The Netherlands (Netherlands)

    2015-11-01

    We consider stochastic inflation in an interacting scalar field in spatially homogeneous accelerating space-times with a constant principal slow roll parameter ε. We show that, if the scalar potential is scale invariant (which is the case when scalar contains quartic self-interaction and couples non-minimally to gravity), the late-time solution on accelerating FLRW spaces can be described by a probability distribution function (PDF) ρ which is a function of φ/H only, where φ=φ( x-vector ) is the scalar field and H=H(t) denotes the Hubble parameter. We give explicit late-time solutions for ρarrow ρ{sub ∞}(φ/H), and thereby find the order ε corrections to the Starobinsky-Yokoyama result. This PDF can then be used to calculate e.g. various n-point functions of the (self-interacting) scalar field, which are valid at late times in arbitrary accelerating space-times with ε= constant.

  19. Enthalpic interactions of N-glycylglycine with xylitol in aqueous sodium chloride and potassium chloride solutions at T = 298.15 K

    International Nuclear Information System (INIS)

    Liu Min; Wang Lili; Zhu Lanying; Li Hui; Sun Dezhi; Di Youying; Li Linwei

    2010-01-01

    The mixing enthalpies of N-glycylglycine with xylitol and their respective enthalpies of dilution in aqueous sodium chloride and potassium chloride solutions have been determined by using flow-mix isothermal microcalorimetry at the temperature of 298.15 K. These experimental results have been used to determine the heterotactic enthalpic interaction coefficients (h xy , h xxy , and h xyy ) according to the McMillan-Mayer theory. It has been found that the heterotactic enthalpic pairwise interaction coefficients h xy between N-glycylglycine and xylitol in aqueous sodium chloride and potassium chloride solutions are negative and become less negative with an increase in the molality of sodium chloride or potassium chloride. The results are discussed in terms of solute-solute and solute-solvent interactions.

  20. Enthalpic interactions of N-glycylglycine with xylitol in aqueous sodium chloride and potassium chloride solutions at T = 298.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Liu Min, E-mail: panpanliumin@163.co [College of Chemistry and Chemical Engineering, Liao Cheng University, Liaocheng, Shandong 252059 (China); Wang Lili [College of Chemistry and Chemical Engineering, Liao Cheng University, Liaocheng, Shandong 252059 (China); Zhu Lanying [College of Life Science and Bioengineering, Liao Cheng University, Liaocheng, Shandong 252059 (China); Li Hui; Sun Dezhi; Di Youying; Li Linwei [College of Chemistry and Chemical Engineering, Liao Cheng University, Liaocheng, Shandong 252059 (China)

    2010-07-15

    The mixing enthalpies of N-glycylglycine with xylitol and their respective enthalpies of dilution in aqueous sodium chloride and potassium chloride solutions have been determined by using flow-mix isothermal microcalorimetry at the temperature of 298.15 K. These experimental results have been used to determine the heterotactic enthalpic interaction coefficients (h{sub xy}, h{sub xxy}, and h{sub xyy}) according to the McMillan-Mayer theory. It has been found that the heterotactic enthalpic pairwise interaction coefficients h{sub xy} between N-glycylglycine and xylitol in aqueous sodium chloride and potassium chloride solutions are negative and become less negative with an increase in the molality of sodium chloride or potassium chloride. The results are discussed in terms of solute-solute and solute-solvent interactions.

  1. Investigation on molecular interaction of amino acids in aqueous disodium hydrogen phosphate solutions with reference to volumetric and compressibility measurements

    International Nuclear Information System (INIS)

    Kumar, Harsh; Singla, Meenu; Jindal, Rajeev

    2014-01-01

    Highlights: • Densities and speeds of sound of amino acids in aqueous disodium hydrogen phosphate. • Partial molar volumes and compressibility of transfer. • Positive values of transfer volume indicates interactions between ions of amino acids and TSC. • Ion–hydrophilic and hydrophilic–hydrophilic interactions are present. • Pair-wise interactions are dominant in the mixtures. -- Abstract: The interactions of amino acids glycine (Gly), L-alanine (Ala), and L-valine (Val) with disodium hydrogen phosphate (DSHP) as a function of temperature have been investigated by combination of volumetric and acoustic measurements. Densities (ρ) and speeds of sound (u) of amino acids in aqueous solutions of disodium hydrogen phosphate have been measured at T = (288.15, 293.15, 298.15, 303.15 and 308.15) K and atmospheric pressure. The apparent molar volume (V ϕ ), the partial molar volume (V ϕ 0 ) and standard partial molar volumes of transfer (ΔV ϕ 0 ) for amino acids from water to aqueous disodium hydrogen phosphate solutions have been calculated from density data. Partial molar adiabatic compressibility (κ ϕ,s ) and partial molar adiabatic compressibility of transfer (Δκ ϕ,S 0 ) have been calculated from speed of sound data. The pair (V AB , κ AB ) and triplet (V ABB , κ ABB ) interaction coefficient have been calculated from both the properties. The results have been explained based on competing patterns of interactions of co-solvents and the solute

  2. Segment-segment interactions of poly(N-isopropylacrylamide) in aqueous methanol solutions by using small-angle scattering

    CERN Document Server

    Shimizu, S; Furusaka, M

    2002-01-01

    Small-angle neutron and X-ray scattering from semidilute solutions of poly(N-isopropylacrylamide) in D sub 2 O, methanol and methanol-water mixtures has been measured in the poor solvent regime. The binary and the ternary cluster integrals of polymer segments were determined from the concentration dependence of the correlation length at several temperatures just below the lower critical solution temperature. Then, contributions of segment-segment interactions to the entropy and the enthalpy have been calculated from the temperature dependence of interaction parameters and it has been found that both values are positive in the D sub 2 O and the methanol-water systems at a small content of methanol, while both values are negative in the other system. (orig.)

  3. Segment-segment interactions of poly(N-isopropylacrylamide) in aqueous methanol solutions by using small-angle scattering

    International Nuclear Information System (INIS)

    Shimizu, S.; Kurita, K.; Furusaka, M.

    2002-01-01

    Small-angle neutron and X-ray scattering from semidilute solutions of poly(N-isopropylacrylamide) in D 2 O, methanol and methanol-water mixtures has been measured in the poor solvent regime. The binary and the ternary cluster integrals of polymer segments were determined from the concentration dependence of the correlation length at several temperatures just below the lower critical solution temperature. Then, contributions of segment-segment interactions to the entropy and the enthalpy have been calculated from the temperature dependence of interaction parameters and it has been found that both values are positive in the D 2 O and the methanol-water systems at a small content of methanol, while both values are negative in the other system. (orig.)

  4. Interaction of indium trichloride with calcium carbonate in aqueous solutions

    International Nuclear Information System (INIS)

    Kochetkova, N.V.; Toptygina, G.M.; Soklakova, O.V.; Evdokimov, V.I.

    1991-01-01

    Interaction of indium trichloride with calcium carbonate in aqueous solutions was studied, using methods of potentiometry, isothermal solubility and physicochemical computer simulating. The Gibb's energy value for crystal indium trihydroxide formation was calculated on the basis of experimental data on In(OH) 3 solubility. The value obtained was used for estimating equilibrium composition of InCl 3 -HCl-CaCO 3 -CO 2 -H 2 O system at a temperature of 25 deg C and carbon dioxide partial pressure of 0.05 to 1 at

  5. Interaction of natural borates with potassium hydroxide solution

    International Nuclear Information System (INIS)

    Azarova, L.A.; Vinogradov, E.E.; Kudinov, I.B.; Panasyuk, G.P.; Danilov, V.P.

    2000-01-01

    Interaction of natural borates - inyoite, ulexite and hydroboracite MgCa[B 3 O 4 (OH) 3 ] 2 ·3H 2 O with KOH solution is studied at 50 Deg C by the methods of chemical, x- ray phase, differential thermal analyses and IR spectroscopy. IR spectra points out on island character of forming borates and confirms the data of x-ray phase and chemical analyses about presence of asharite and calcium hydrous borate in resulting products. Hydroboracite (chain structure) under the action of potassium hydroxide passes into borates of magnesium and calcium with island structure and in this case boron transforms partially into liquid phase. When potassium hydroxide interacts with inyoite and ulexite calcium hydroxide and roentgenoamorphous boron-containing product precipitate [ru

  6. Effect of solvent on the structure of a protein (H3.1) with a coarse-grained model with knowledge-based interactions

    Science.gov (United States)

    Pandey, Ras; Farmer, Barry

    2013-03-01

    Quality of solvent plays a critical role in modulating the structure of a protein along with the temperature. Using a coarse-grained Monte Carlo simulation based on three knowledge-based contact potentials (MJ, BT, BFKV) we examine the structure and dynamics of a histone (H3.1). The empty lattice sites constitute the effective solvent medium in which the protein is embedded. Residue-solvent characteristic interaction is based on the hydropathy index while the residue-residue interaction is used from the knowledge-based contact matrices derived from ensembles of protein structures in the protein data bank. Large scale simulations are performed to analyze the structure of protein for a range of residue-solvent interaction strength, a measure of the solvent quality with each potential. Unlike the monotonic thermal response, the radius of gyration of the protein exhibits non-monotonic dependence of the solvent strength. Quantitative comparison of the structure and dynamics emerging from three knowledge-based potentials will be presented in this talk. This work is supported by Air Force Research Laboratory.

  7. Interaction of gypsum with lead in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Astilleros, J.M., E-mail: jmastill@geo.ucm.es [Dpto. Cristalografia y Mineralogia, Universidad Complutense de Madrid, Jose Antonio Novais, 2, E-28040 Madrid (Spain); Godelitsas, A. [Department of Mineralogy and Petrology, Faculty of Geology and Geoenvironment, University of Athens, Panepistimioupoli Zographou, 15784 Athens (Greece); Rodriguez-Blanco, J.D. [School of Earth and Environments, Faculty of Environment, University of Leeds, Leeds LS2 9JT (United Kingdom); Fernandez-Diaz, L. [Dpto. Cristalografia y Mineralogia, Universidad Complutense de Madrid, Jose Antonio Novais, 2, E-28040 Madrid (Spain); Prieto, M. [Dpto. de Geologia, Universidad de Oviedo, E-30005 Oviedo (Spain); Lagoyannis, A.; Harissopulos, S. [Tandem Accelerator Laboratory, Institute of Nuclear Physics, NCSR ' Demokritos' , GR-15310 Attiki (Greece)

    2010-07-15

    Sorption processes on mineral surfaces are a critical factor in controlling the distribution and accumulation of potentially harmful metals in the environment. This work investigates the effectiveness of gypsum (CaSO{sub 4}.2H{sub 2}O) to sequester Pb. The interaction of gypsum fragments with Pb-bearing solutions (10, 100 and 1000 mg/L) was monitored by performing macroscopic batch-type experiments conducted at room temperature. The aqueous phase composition was periodically determined by Atomic Absorption Spectrometry (AAS), Ion Chromatography (IC) and Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). Regardless of the [Pb{sub aq}]{sub initial}, a [Pb{sub aq}]{sub final} < 4 mg/L was always reached. The uptake process was fast (t < 1 h) for [Pb{sub aq}]{sub initial} {>=} 100 mg/L and significantly slower (t > 1 week) for [Pb{sub aq}]{sub initial} = 10 mg/L. Speciation calculations revealed that after a long time of interaction (1 month), all the solutions reached equilibrium with respect to both gypsum and anglesite. For [Pb{sub aq}]{sub initial} {>=} 100 mg/L, sorption takes place mainly via the rapid dissolution of gypsum and the simultaneous formation of anglesite both on the gypsum surface and in the bulk solution. In the case of [Pb{sub aq}]{sub initial} = 10 mg/L, no anglesite precipitation was observed, but surface spectroscopy (proton Rutherford Backscattering Spectroscopy, p-RBS) confirmed the formation of Pb-bearing surface layers on the (0 1 0) gypsum surface in this case also. This study shows that the surface of gypsum can play an important role in the attenuation of Pb in contaminated waters.

  8. Vapour–Liquid Equilibria in the Polymer + Solvent System Containing Lower Concentrations of Solute at Normal or Reduced Pressures

    Czech Academy of Sciences Publication Activity Database

    Pavlíček, Jan; Bogdanić, Grozdana; Wichterle, Ivan

    2013-01-01

    Roč. 358, 25 NOV (2013), s. 301-303 ISSN 0378-3812 Institutional support: RVO:67985858 Keywords : vapour–liquid equilibrium * experimental data * polymer-solvent system Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.241, year: 2013

  9. Interactive Tutoring in Blended Studies: Hindrances and Solutions

    Directory of Open Access Journals (Sweden)

    Asim Ismail Ilyas (Al-Titinchy

    2016-01-01

    Full Text Available This paper distinguishes between traditional teaching known as lecturing (the teacher centered approach; and tutoring (the contemporary technology-oriented interactive teaching/learning approach. It is based on the implementation of tutoring strategies of ‘blended studies’  at the Arab Open University. It investigates the application of modern interactive teaching/learning strategies, specifying some hindering factors in the AOU-Jordan Branch context. The factors include four variables: tutors, students, course material and assessment. The paper is based on qualitative research in terms of a real teaching/leaning context, using both observation and conversation with learners, besides the use of some quantitative data retrieved from a questionnaire in which learners’ views are sought regarding a number of relevant matters. A number of suggested solutions related to each of the hindering factors are presented, which if applied, may secure shifting the balance of the teaching/learning process to a more interactive technology-based tutoring level, which in turn will enhance learners’ opportunities for the attainment of better academic standards, and secure a higher degree of achievement of the shared educational goals of learners and the educational institution they study in.

  10. Spectroscopic and DFT study of solvent effects on the electronic absorption spectra of sulfamethoxazole in neat and binary solvent mixtures

    Science.gov (United States)

    Almandoz, M. C.; Sancho, M. I.; Blanco, S. E.

    2014-01-01

    The solvatochromic behavior of sulfamethoxazole (SMX) was investigated using UV-vis spectroscopy and DFT methods in neat and binary solvent mixtures. The spectral shifts of this solute were correlated with the Kamlet and Taft parameters (α, β and π*). Multiple lineal regression analysis indicates that both specific hydrogen-bond interaction and non specific dipolar interaction play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra using TD-DFT methods were in good agreement with the experimental ones. Binary mixtures consist of cyclohexane (Cy)-ethanol (EtOH), acetonitrile (ACN)-dimethylsulfoxide (DMSO), ACN-dimethylformamide (DMF), and aqueous mixtures containing as co-solvents DMSO, ACN, EtOH and MeOH. Index of preferential solvation was calculated as a function of solvent composition and non-ideal characteristics are observed in all binary mixtures. In ACN-DMSO and ACN-DMF mixtures, the results show that the solvents with higher polarity and hydrogen bond donor ability interact preferentially with the solute. In binary mixtures containing water, the SMX molecules are solvated by the organic co-solvent (DMSO or EtOH) over the whole composition range. Synergistic effect is observed in the case of ACN-H2O and MeOH-H2O, indicating that at certain concentrations solvents interact to form association complexes, which should be more polar than the individual solvents of the mixture.

  11. Depleted depletion drives polymer swelling in poor solvent mixtures.

    Science.gov (United States)

    Mukherji, Debashish; Marques, Carlos M; Stuehn, Torsten; Kremer, Kurt

    2017-11-09

    Establishing a link between macromolecular conformation and microscopic interaction is a key to understand properties of polymer solutions and for designing technologically relevant "smart" polymers. Here, polymer solvation in solvent mixtures strike as paradoxical phenomena. For example, when adding polymers to a solvent, such that all particle interactions are repulsive, polymer chains can collapse due to increased monomer-solvent repulsion. This depletion induced monomer-monomer attraction is well known from colloidal stability. A typical example is poly(methyl methacrylate) (PMMA) in water or small alcohols. While polymer collapse in a single poor solvent is well understood, the observed polymer swelling in mixtures of two repulsive solvents is surprising. By combining simulations and theoretical concepts known from polymer physics and colloidal science, we unveil the microscopic, generic origin of this collapse-swelling-collapse behavior. We show that this phenomenon naturally emerges at constant pressure when an appropriate balance of entropically driven depletion interactions is achieved.

  12. Order of wetting transitions in electrolyte solutions.

    Science.gov (United States)

    Ibagon, Ingrid; Bier, Markus; Dietrich, S

    2014-05-07

    For wetting films in dilute electrolyte solutions close to charged walls we present analytic expressions for their effective interface potentials. The analysis of these expressions renders the conditions under which corresponding wetting transitions can be first- or second-order. Within mean field theory we consider two models, one with short- and one with long-ranged solvent-solvent and solvent-wall interactions. The analytic results reveal in a transparent way that wetting transitions in electrolyte solutions, which occur far away from their critical point (i.e., the bulk correlation length is less than half of the Debye length) are always first-order if the solvent-solvent and solvent-wall interactions are short-ranged. In contrast, wetting transitions close to the bulk critical point of the solvent (i.e., the bulk correlation length is larger than the Debye length) exhibit the same wetting behavior as the pure, i.e., salt-free, solvent. If the salt-free solvent is governed by long-ranged solvent-solvent as well as long-ranged solvent-wall interactions and exhibits critical wetting, adding salt can cause the occurrence of an ion-induced first-order thin-thick transition which precedes the subsequent continuous wetting as for the salt-free solvent.

  13. Alkali metal cation complexation and solvent interactions by robust chromium(III) fluoride complexes

    DEFF Research Database (Denmark)

    Birk, T.; Magnussen, M.J.; Piligkos, Stergios

    2010-01-01

    )] have been synthesized from mer-[CrF3(py)(3)] and shown to precipitate sodium salts from solution, of which 3[CrF3(Me(3-)tacn)]center dot 2Na(Bph(4)).solv and 6[CrF3(terpy)]center dot 4Na(Bph(4)).solv have been crystallographically characterized. In these clusters, the neutral fluoride complexes bring...

  14. Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

    Science.gov (United States)

    Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

    2011-12-01

    The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.

  15. Controlling solution-phase polymer aggregation with molecular weight and solvent additives to optimize polymer-fullerene bulk heterojunction solar cells

    KAUST Repository

    Bartelt, Jonathan A.

    2014-03-20

    The bulk heterojunction (BHJ) solar cell performance of many polymers depends on the polymer molecular weight (M n) and the solvent additive(s) used for solution processing. However, the mechanism that causes these dependencies is not well understood. This work determines how M n and solvent additives affect the performance of BHJ solar cells made with the polymer poly(di(2-ethylhexyloxy)benzo[1,2-b:4,5-b\\']dithiophene-co- octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD). Low M n PBDTTPD devices have exceedingly large fullerene-rich domains, which cause extensive charge-carrier recombination. Increasing the M n of PBDTTPD decreases the size of these domains and significantly improves device performance. PBDTTPD aggregation in solution affects the size of the fullerene-rich domains and this effect is linked to the dependency of PBDTTPD solubility on M n. Due to its poor solubility high M n PBDTTPD quickly forms a fibrillar polymer network during spin-casting and this network acts as a template that prevents large-scale phase separation. Furthermore, processing low M n PBDTTPD devices with a solvent additive improves device performance by inducing polymer aggregation in solution and preventing large fullerene-rich domains from forming. These findings highlight that polymer aggregation in solution plays a significant role in determining the morphology and performance of BHJ solar cells. The performance of poly(di(2-ethylhexyloxy) benzo[1,2-b:4,5-b\\']dithiophene-co-octylthieno[3,4-c]pyrrole-4,6-dione) (PBDTTPD) bulk heterojunction solar cells strongly depends on the polymer molecular weight, and processing these bulk heterojunctions with a solvent additive preferentially improves the performance of low molecular weight devices. It is demonstrated that polymer aggregation in solution significantly impacts the thin-film bulk heterojunction morphology and is vital for high device performance. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. A calorimetric study of the interactions in the aqueous solutions of lysozyme in the presence of denaturing cosolvents

    International Nuclear Information System (INIS)

    Castronuovo, Giuseppina; Niccoli, Marcella

    2012-01-01

    Highlights: ► A thermodynamic method is reported to monitor the chemical denaturation of lysozyme. ► The enthalpic interaction coefficients are very useful parameters to gain information about the mechanism through which two hydrated molecules interact in solution. ► Hypotheses are proposed about the mechanism underlying the denaturation of lysozyme induced by high concentrations of urea or ethanol. - Abstract: A thermodynamic method is reported to monitor the chemical denaturation of lysozyme. Heats of dilution of the protein in concentrated aqueous solutions of urea or ethanol have been determined at 298.15 K by flow microcalorimetry. The pairwise enthalpic interaction coefficients of the protein in the different solvent media are derived. These parameters allow to gain information about the influence of the cosolvents on the interactions acting between two interacting hydrated molecules of lysozyme, hence on the denaturation process. At increasing urea concentration, up to about 6 mol kg −1 , the values of the interaction coefficients are large and negative and remain almost unaltered. The invariance of the coefficients underlines that, even in highly concentrated urea, the hydration shell of the protein is such to maintain essentially unaltered the native conformation. At higher urea concentrations, a sudden change in the sign of the coefficients monitors the variation in the interactions between two hydrated denatured protein molecules. The same trend is found when ethanol is the cosolvent. At increasing concentration of the cosolvent, coefficients are, at first, almost invariant. After that, denaturation occurs, detected as a jump toward much more negative values. The results obtained are rationalized on the basis of those previously found for small model molecules in concentrated solutions of urea or ethanol. The thermodynamic framework allows useful comments to be made on the possible mode of action of the two cosolvents on the stability of proteins

  17. A calorimetric study of the interactions in the aqueous solutions of lysozyme in the presence of denaturing cosolvents

    Energy Technology Data Exchange (ETDEWEB)

    Castronuovo, Giuseppina, E-mail: giuseppina.castronuovo@unina.it [Department of Chemistry, University Federico II of Naples, Complesso Universitario Monte S. Angelo, via Cintia, 80126 Naples (Italy); Niccoli, Marcella [Department of Chemistry, University Federico II of Naples, Complesso Universitario Monte S. Angelo, via Cintia, 80126 Naples (Italy)

    2012-09-10

    Highlights: Black-Right-Pointing-Pointer A thermodynamic method is reported to monitor the chemical denaturation of lysozyme. Black-Right-Pointing-Pointer The enthalpic interaction coefficients are very useful parameters to gain information about the mechanism through which two hydrated molecules interact in solution. Black-Right-Pointing-Pointer Hypotheses are proposed about the mechanism underlying the denaturation of lysozyme induced by high concentrations of urea or ethanol. - Abstract: A thermodynamic method is reported to monitor the chemical denaturation of lysozyme. Heats of dilution of the protein in concentrated aqueous solutions of urea or ethanol have been determined at 298.15 K by flow microcalorimetry. The pairwise enthalpic interaction coefficients of the protein in the different solvent media are derived. These parameters allow to gain information about the influence of the cosolvents on the interactions acting between two interacting hydrated molecules of lysozyme, hence on the denaturation process. At increasing urea concentration, up to about 6 mol kg{sup -1}, the values of the interaction coefficients are large and negative and remain almost unaltered. The invariance of the coefficients underlines that, even in highly concentrated urea, the hydration shell of the protein is such to maintain essentially unaltered the native conformation. At higher urea concentrations, a sudden change in the sign of the coefficients monitors the variation in the interactions between two hydrated denatured protein molecules. The same trend is found when ethanol is the cosolvent. At increasing concentration of the cosolvent, coefficients are, at first, almost invariant. After that, denaturation occurs, detected as a jump toward much more negative values. The results obtained are rationalized on the basis of those previously found for small model molecules in concentrated solutions of urea or ethanol. The thermodynamic framework allows useful comments to be made on

  18. Water as a solute in aprotic dipolar solvents. 2. D2O-H2O solute isotope effects on the enthalpy of water dissolution in nitromethane, acetonitrile and propylene carbonate at 298.15 K

    International Nuclear Information System (INIS)

    Ivanov, Evgeniy V.; Smirnov, Valeriy I.

    2010-01-01

    The enthalpies of solution of ordinary (H 2 O) and heavy (D 2 O) water in nitromethane (NM), acetonitrile (ACN) and propylene carbonate (PC) were measured calorimetrically at 298.15 K. Standard (at the infinite dilution) enthalpies of solution and solvation, along with D 2 O-H 2 O solute isotope effects on the quantities in question, were calculated. The enthalpies of solution of water H/D isotopologues were found to be positive by sign and substantially increasing in magnitude on going from ACN and PC to NM, whereas the corresponding positive solute H/D isotope effect changes in a consequence: NM > ACN > PC. The qualitative interrelations between the enthalpy-isotopic effect of dissolution (solvation) of water and the electron-accepting/donating ability of aprotic dipolar solvent (within a series considered) were found.

  19. Effects of solvent additive on “s-shaped” curves in solution-processed small molecule solar cells

    Directory of Open Access Journals (Sweden)

    John A. Love

    2016-11-01

    Full Text Available A novel molecular chromophore, p-SIDT(FBTThCA82, is introduced as an electron-donor material for bulk heterojunction (BHJ solar cells with broad absorption and near ideal energy levels for the use in combination with common acceptor materials. It is found that films cast from chlorobenzene yield devices with strongly s-shaped current–voltage curves, drastically limiting performance. We find that addition of the common solvent additive diiodooctane, in addition to facilitating crystallization, leads to improved vertical phase separation. This yields much better performing devices, with improved curve shape, demonstrating the importance of morphology control in BHJ devices and improving the understanding of the role of solvent additives.

  20. The Interaction of Sorbitol with Caffeine in Aqueous Solution.

    Science.gov (United States)

    Tavagnacco, Letizia; Brady, John W; Cesàro, Attilio

    2013-09-01

    Molecular dynamics simulations were carried out on a system of caffeine interacting with the sugar alcohol sorbitol. The system examined had a caffeine concentration 0.083 m and a sugar concentration 1.08 m. The trajectories of all molecules in the system were collected over a period of 80 ns and analyzed to determine whether there is any tendency for sorbitol to bind to caffeine, and if so, by what mechanism. The results show that the sorbitol molecules have an affinity for the caffeine molecules and that the binding occurred by the interaction of the aliphatic hydrophobic protons of the sugar with the caffeine face. This intermolecular association via face-to-face stacking, as suggested by simulation studies, is similar to that found for sucrose and for D-glucose, which overwhelmingly exists in the pyranose ring chair form in aqueous solution, as well as for caffeine-caffeine association. The sorbitol molecules, however, exist as relatively extended chains and are, therefore, topologically quite different from the sugars sucrose and glucose. The comparison of the average conformation of sorbitol molecules bound to caffeine with that of molecules in the free state shows a substantial similarity.

  1. Single-Chain Conformation for Interacting Poly(N-isopropylacrylamide in Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Boualem Hammouda

    2015-04-01

    Full Text Available The demixing phase behavior of Poly(N-isopropylacrylamide (PNIPAM aqueous solution is investigated using small-angle neutron scattering. This polymer phase separates upon heating and demixes around 32 °C. The pre-transition temperature range is characterized by two scattering modes; a low-Q (large-scale signal and a high-Q dissolved chains signal. In order to get insight into this pre-transition region, especially the origin of the low-Q (large-scale structure, the zero average contrast method is used in order to isolate single-chain conformations even in the demixing polymers transition region. This method consists of measuring deuterated and non-deuterated polymers dissolved in mixtures of deuterated and non-deuterated water for which the polymer scattering length density matches the solvent scattering length density. A fixed 4% polymer mass fraction is used in a contrast variation series where the d-water/h-water fraction is varied in order to determine the match point. The zero average contrast (match point sample displays pure single-chain scattering with no interchain contributions. Our measurements prove that the large scale structure in this polymer solution is due to a transient polymer network formed through hydrophobic segment-segment interactions. Scattering intensity increases when the temperature gets close to the phase boundary. While the apparent radius of gyration increases substantially at the Lower Critical Solution Temperature (LCST transition due to strong interchain correlation, the single-chain true radius of gyration has been found to decrease slightly with temperature when approaching the transition.

  2. Modulation of intra- and inter-sheet interactions in short peptide self-assembly by acetonitrile in aqueous solution

    International Nuclear Information System (INIS)

    Deng Li; Zhao Yurong; Zhou Peng; Xu Hai; Wang Yanting

    2016-01-01

    Besides our previous experimental discovery (Zhao Y R, et al . 2015 Langmuir , 31, 12975) that acetonitrile (ACN) can tune the morphological features of nanostructures self-assembled by short peptides KIIIIK (KI4K) in aqueous solution, further experiments reported in this work demonstrate that ACN can also tune the mass of the self-assembled nanostructures. To understand the microscopic mechanism how ACN molecules interfere peptide self-assembly process, we conducted a series of molecular dynamics simulations on a monomer, a cross- β sheet structure, and a proto-fibril of KI4K in pure water, pure ACN, and ACN-water mixtures, respectively. The simulation results indicate that ACN enhances the intra-sheet interaction dominated by the hydrogen bonding (H-bonding) interactions between peptide backbones, but weakens the inter-sheet interaction dominated by the interactions between hydrophobic side chains. Through analyzing the correlations between different groups of solvent and peptides and the solvent behaviors around the proto-fibril, we have found that both the polar and nonpolar groups of ACN play significant roles in causing the opposite effects on intermolecular interactions among peptides. The weaker correlation of the polar group of ACN than water molecule with the peptide backbone enhances H-bonding interactions between peptides in the proto-fibril. The stronger correlation of the nonpolar group of ACN than water molecule with the peptide side chain leads to the accumulation of ACN molecules around the proto-fibril with their hydrophilic groups exposed to water, which in turn allows more water molecules close to the proto-fibril surface and weakens the inter-sheet interactions. The two opposite effects caused by ACN form a microscopic mechanism clearly explaining our experimental observations. (paper)

  3. Radiometric determination of 90Sr in the dissolver solution of the spent PHWR fuel after its separation with solvent extraction and extraction chromatography

    International Nuclear Information System (INIS)

    Kulkarni, P.G.; Gupta, K.K.; Pant, D.K.; Bhalerao, B.A.; Gurba, P.B.; Janardan, P.; Changrani, R.D.; Dey, P.K.; Pathak, P.N.; Mohapatra, P.K.; Manchanda, V.K.

    2010-01-01

    A simple radiometric method for 90 Sr determination in the dissolver solution of the PHWR spent fuel has been developed.The method involves the quantitative separation of Sr from the associated actinides and other fission products by solvent extraction with 30% trialkylphosphine oxide (TRPO) -n-dodecane followed by extraction chromatography with XAD-7-Di-butylcyclohexano-18-crown-6 resin. The separation scheme yields quantitative recovery of 90 Sr and the separated 90 Sr was found to be radiochemically pure. 90 Sr was estimated by β-radiometry and the precision of the method at 5 mCi/mL level was 2% (RSD). (author)

  4. Multipoint attachment to a support protects enzyme from inactivation by organic solvents: alpha-Chymotrypsin in aqueous solutions of alcohols and diols.

    Science.gov (United States)

    Mozhaev, V V; Sergeeva, M V; Belova, A B; Khmelnitsky, Y L

    1990-03-25

    Inactivation of alpha-chymotrypsin in aqueous solutions of alcohols and diols proceeds both reversibly and irreversibly. Reversible loss of the specific enzyme activity results from conformational changes (unfolding) of the enzyme detected by fluorescence spectroscopy. Multipoint covalent attachment to the matrix of polyacryl-amide gel by copolymerization method stabilizes alpha-chymotrypsin from denaturation by alcohols, the stabilizing effect increasing with the number of bonds between the protein and the support. Immobilization protects the enzyme also from irreversible inactivation by organic solvents resulting from bimolecular aggregation and autolysis.

  5. Solution thermodynamics of creatine monohydrate in binary (water + ethanol) solvent systems at T = (278.15 to 328.15) K

    International Nuclear Information System (INIS)

    Song, Liangcheng; Wei, Lihua; Si, Tao; Guo, Huai; Yang, Chunhui

    2016-01-01

    Highlights: • The solubilities of creatine monohydrate in (ethanol + water) mixtures were investigated. • The solubility data were well correlated by Jouyban–Acree model. • Solution thermodynamic properties were calculated. • The dissolving process of creatine monohydrate in was endothermic and entropy-driven. - Abstract: In order to optimize the crystallization process of creatine monohydrate, the solubility of creatine monohydrate in the binary (water + ethanol) mixture was measured at temperatures ranging from 278.15 K to 328.15 K using the laser monitoring technique. The solubility increased with both the temperature and the mole fraction of water in the solvent mixture. The experimental solubility was well correlated by the Jouyban–Acree model, which generated a sensitive solubility surface for creatine monohydrate. Furthermore, the thermodynamic parameters of this dissolution process were also estimated. The results showed that the dissolution process of creatine monohydrate in each solvent mixture was endothermic and entropy-driven, and that the dissolution of creatine monohydrate became much easier when the mole fraction of water in the solvent mixture increased.

  6. Supercritical fluid extraction: spectroscopic study of interactions comparison to solvent extraction

    International Nuclear Information System (INIS)

    Rustenholtz Farawila, A.

    2005-06-01

    Supercritical fluid carbon dioxide (SF-CO 2 ) was chosen to study Supercritical Fluid Extraction (SFE) of cesium and uranium. At first, crown ethers were considered as chelating agents for the SFE of cesium. The role of water and its interaction with crown ethers were especially studied using Fourier-Transform Infra-Red (FT-IR) spectroscopy in SF-CO 2 . A sandwich configuration between two crown ethers and a water molecule was observed in the SF-CO 2 phase for the first time. The equilibrium between the single and the bridge configurations was defined. The enthalpy of the hydrogen bond formation was also calculated. These results were then compared to the one in different mixtures of chloroform and carbon tetra-chloride using Nuclear Magnetic Resonance (NMR). To conclude this first part and in order to understand the whole picture of the recovery of cesium, I studied the role of water in the equilibrium between the cesium and the di-cyclo-hexano18-crown-6.In a second part, the supercritical fluid extraction of uranium was studied in SF-CO 2 . For this purpose, different complexes of Tributyl Phosphate (TBP), nitric acid and water were used as chelating and oxidizing agents. I first used FT-IR to study the TBP-water interaction in SF-CO 2 . These results were then compared to the one obtained with NMR in chloroform. NMR spectroscopy was also used to understand the TBP-nitric acid-water interaction first alone and then in chloroform. To conclude my research work, I succeeded to improve the efficiency of uranium extraction and stripping into water for a pilot-plant where enriched uranium is extracted from incinerated waste coming from nuclear fuel fabrication. TBP-nitric acid complexes were used in SF-CO 2 for the extraction of uranium from ash. (author)

  7. Supercritical fluid extraction: spectroscopic study of interactions comparison to solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Rustenholtz Farawila, A

    2005-06-15

    Supercritical fluid carbon dioxide (SF-CO{sub 2}) was chosen to study Supercritical Fluid Extraction (SFE) of cesium and uranium. At first, crown ethers were considered as chelating agents for the SFE of cesium. The role of water and its interaction with crown ethers were especially studied using Fourier-Transform Infra-Red (FT-IR) spectroscopy in SF-CO{sub 2}. A sandwich configuration between two crown ethers and a water molecule was observed in the SF-CO{sub 2} phase for the first time. The equilibrium between the single and the bridge configurations was defined. The enthalpy of the hydrogen bond formation was also calculated. These results were then compared to the one in different mixtures of chloroform and carbon tetra-chloride using Nuclear Magnetic Resonance (NMR). To conclude this first part and in order to understand the whole picture of the recovery of cesium, I studied the role of water in the equilibrium between the cesium and the di-cyclo-hexano18-crown-6.In a second part, the supercritical fluid extraction of uranium was studied in SF-CO{sub 2}. For this purpose, different complexes of Tributyl Phosphate (TBP), nitric acid and water were used as chelating and oxidizing agents. I first used FT-IR to study the TBP-water interaction in SF-CO{sub 2}. These results were then compared to the one obtained with NMR in chloroform. NMR spectroscopy was also used to understand the TBP-nitric acid-water interaction first alone and then in chloroform. To conclude my research work, I succeeded to improve the efficiency of uranium extraction and stripping into water for a pilot-plant where enriched uranium is extracted from incinerated waste coming from nuclear fuel fabrication. TBP-nitric acid complexes were used in SF-CO{sub 2} for the extraction of uranium from ash. (author)

  8. Biomolecular-solvent stereodynamic coupling probed by deuteration

    International Nuclear Information System (INIS)

    Fornili, S.L.; Leone, M.; Madonia, F.; Migliore, M.; Palma-Vittorelli, M.B.; Palma, M.U.; San Biagio, P.L.

    1983-01-01

    Thermodynamic interpretation of experiments with isotopically perturbed solvent supports the view that solvent stereodynamics is directly relevant to thermodynamic stability of biomolecules. According with the current understanding of the structure of the aqueous solvent, in any stereodynamic configuration of the latter, connectivity pathways are identifiable for their topologic and order properties. Perturbing the solvent by isotopic substitution or, e.g., by addition of co-solvents, can therefore be viewed as reinforcing or otherwise perturbing these topologic structures. This microscopic model readily visualizes thermodynamic interpretation. In conclusion, the topologic stereodynamic structures of connectivity pathways in the solvent, as modified by interaction with solutes, acquire a specific thermodynamic and biological significance, and the problem of thermodynamic and functional stability of biomolecules is seen in its full pertinent phase space

  9. Statistical and computer analysis for the solvent effect on the elctronis adsorption spectra of monoethanolamine complexes

    International Nuclear Information System (INIS)

    Masoud, M.S.; Motaweh, H.A.; Ali, A.E.

    1999-01-01

    Full text.the electronic absorption spectra of the octahedral complexes containing monoethanolamine were recorded in different solvents (dioxine, chlororm, ethanol, dimethylformamide, dimethylsulfoxide and water). The data analyzed based on multiple linear regression technique using the equation: ya (a is the regression intercept) are various empirical solvent polarytiparameters; constants are calculated using micro statistic program on pc computer. The solvent spectral data of the complexes are compared to that of nugot, the solvent assists the spectral data to be red shifts. In case of Mn (MEA) CL complex, numerous bands are appeared in presence of CHCI DMF and DMSO solvents probably due to the numerous oxidation states. The solvent parameters: E (solvent-solute hydrogen bond and dipolar interaction); (dipolar interaction related to the dielectric constant); M (solute permanent dipole-solvent induced ipole) and N (solute permanent dipole-solvent permanent dipole) are correlated with the structure of the complexes, in hydrogen bonding solvents (Band in case of complexes as the dielectric constant increases, blue shift occurs in due to conjugation with high stability, the data in DMF and DMSO solvents are nearly the same probably due to their similarity

  10. Corrosion phenomena in sodium-potassium coolant resulting from solute interaction in multicomponent solution

    Science.gov (United States)

    Krasin, V. P.; Soyustova, S. I.

    2018-03-01

    The solubility of Fe, Cr, Ni, V, Mn and Mo in sodium-potassium melt has been calculated using the mathematical framework of pseudo-regular solution model. The calculation results are compared with available published experimental data on mass transfer of components of austenitic stainless steel in sodium-potassium loop under non-isothermal conditions. It is shown that the parameters of pair interaction of oxygen with transition metal can be used to predict the corrosion behavior of structural materials in sodium-potassium melt in the presence of oxygen impurity. The results of calculation of threshold concentration of oxygen of ternary oxide formation of sodium with transitional metals (Fe, Cr, Ni, V, Mn, Mo) are given in conditions when pure solid metal comes in contact with sodium-potassium melt.

  11. A Visualization Technique for Accessing Solution Pool in Interactive Methods of Multiobjective Optimization

    OpenAIRE

    Filatovas, Ernestas; Podkopaev, Dmitry; Kurasova, Olga

    2015-01-01

    Interactive methods of multiobjective optimization repetitively derive Pareto optimal solutions based on decision maker’s preference information and present the obtained solutions for his/her consideration. Some interactive methods save the obtained solutions into a solution pool and, at each iteration, allow the decision maker considering any of solutions obtained earlier. This feature contributes to the flexibility of exploring the Pareto optimal set and learning about the op...

  12. Influence of ionic liquids on actinides extraction by diphenyl(dibutyl)carbamoylmethylphosphine oxide in different solvents from nitric acid solution

    International Nuclear Information System (INIS)

    Pribylova, G.A.

    2011-01-01

    Influence of ionic liquids (ILs) addition (1-50 wt%) on extraction efficiency of actinides by diphenyl(dibutyl)carbamoylmethylphosphine oxide (Ph 2 Bu 2 ) from 3 M HNO 3 has been studied. Am(III) distribution ratios in two-phase systems 0.1 M Ph 2 Bu 2 in either DCE or CHCl 3 -3 M HNO 3 depending on the nature of additional ionic liquids: imidazolium-based ILs: [C 4 mim][PF 6 ], [C 4 mim][BF 4 ] and phosphonium-based ILs: PPF 6 , PBF 4 and PCl were determined. The highest value of Am(III) extraction ratio change (1040) was found on addition of PPF 6 to Ph 2 Bu 2 in CHCl 3 . Extraction of Pu(IV) and U(VI) by 0.001 M Ph 2 Bu 2 in the presence of [C 4 mim][PF 6 ] in DCE, CHCl 3 or meta-nitrobenzotrifluoride (NBTF) have been investigated. The greatest enhancement of extraction efficiency was observed using CHCl 3 , the least polar studied solvent. Using a mixture of conventional solvent and ionic liquid as a solvent for extractant enables one to increase distribution ratios and reduce viscosity of organic phase as compared with ionic liquid viscosity. The marked increase of Am(III), Pu(IV) and U(VI) extraction extent by Ph 2 Bu 2 on addition of ionic liquids to the extent of 10 wt% permit one essentially to diminish amounts considerably more expensive carbamoylmethylphosphine oxide(the general name is CMPO) used in TRUEX process. (author)

  13. Donor-acceptor interaction between non-aqueous solvents and I{sub 2} to generate I{sup -}{sub 3}, and its implication in dye sensitized solar cells

    Energy Technology Data Exchange (ETDEWEB)

    Kebede, Zerihun [Department of Chemistry, Kotebe College of Teacher Education, P.O. Box 31248, Addis Ababa (Ethiopia); Lindquist, Sten-Eric [Department of Physical Chemistry, Uppsala University, P.O. Box 532, S-751 21 Uppsala (Sweden)

    1999-03-16

    The spectrophotometric properties of I{sup -}, I{sub 2} and the I{sup -}/I{sub 2} mixture were studied in 1,2-dichloroethane (DCE), acetone (AC), acetonitrile (ACN), ethanol (EtOH), methanol (MeOH), tertiary-butanol (t-BuOH), dimethylformamide (DMF), propylenecarbonate (PC), 3-methoxypropionitrile (MePN), dimethylsulfoxide (DMSO), dioxane (DIO) and pyridine (PY) solutions. From the investigation it has been realized that in DCE, I{sup -}, I{sub 2} and I{sup -}/I{sub 2} mixture have the same absorption peak at 500 nm. I{sup -} gives rise to the absorption spectra at about 220, 290 and 360 nm in t-BuOH and in PY solutions. However, in all other solvents the I{sup -} generates peaks only around 220 nm. Similarly I{sub 2} and the I{sup -}/I{sub 2} mixture in all solvents except DCE have indicated similar absorption peaks around 220, 290 and 360 nm. On the other hand, except in PC and DMF, I{sub 2} shows the additional peaks in the range of 380-500 nm which are assigned to the formation of a I{sub 2}-solvent complex. The peaks around 290 and 360 nm indicate the presence of I{sup -}{sub 3} and around 220 nm is the peak of I{sup -}. The spectral shift of the I{sub 2} solutions in the visible region is interesting and is the core of this report. It points to the importance of donor-acceptor interaction between solvents and iodine. The data obtained in these solvents were well correlated to the donor number (DN) of the solvents. From this correlation the DN of MePN was estimated to 14.6. The absorption peak of I{sub 2} in DCE(DN=0.0) is 500 nm and in PY(DN=33.1) is 378 nm. This peak shift due to solvent effects corresponds to an energy difference close to 0.8 eV. The absorption peak shift due to addition of the 0.0080 vol%. PY(1 mM) in 1 mM I{sub 2}-ACN solutions corresponds to ca. 0.6 eV. The blue shift of I{sub 2} absorption in basic solvents indicates the tendency to form a complex. The increase of the efficiency of the dye-sensitized solar cell by addition of PY to I

  14. Continuous-flow Heck synthesis of 4-methoxybiphenyl and methyl 4-methoxycinnamate in supercritical carbon dioxide expanded solvent solutions

    Directory of Open Access Journals (Sweden)

    Phei Li Lau

    2013-12-01

    Full Text Available The palladium metal catalysed Heck reaction of 4-iodoanisole with styrene or methyl acrylate has been studied in a continuous plug flow reactor (PFR using supercritical carbon dioxide (scCO2 as the solvent, with THF and methanol as modifiers. The catalyst was 2% palladium on silica and the base was diisopropylethylamine due to its solubility in the reaction solvent. No phosphine co-catalysts were used so the work-up procedure was simplified and the green credentials of the reaction were enhanced. The reactions were studied as a function of temperature, pressure and flow rate and in the case of the reaction with styrene compared against a standard, stirred autoclave reaction. Conversion was determined and, in the case of the reaction with styrene, the isomeric product distribution was monitored by GC. In the case of the reaction with methyl acrylate the reactor was scaled from a 1.0 mm to 3.9 mm internal diameter and the conversion and turnover frequency determined. The results show that the Heck reaction can be effectively performed in scCO2 under continuous flow conditions with a palladium metal, phosphine-free catalyst, but care must be taken when selecting the reaction temperature in order to ensure the appropriate isomer distribution is achieved. Higher reaction temperatures were found to enhance formation of the branched terminal alkene isomer as opposed to the linear trans-isomer.

  15. Variation and decomposition of the partial molar volume of small gas molecules in different organic solvents derived from molecular dynamics simulations.

    Science.gov (United States)

    Klähn, Marco; Martin, Alistair; Cheong, Daniel W; Garland, Marc V

    2013-12-28

    The partial molar volumes, V(i), of the gas solutes H2, CO, and CO2, solvated in acetone, methanol, heptane, and diethylether are determined computationally in the limit of infinite dilution and standard conditions. Solutions are described with molecular dynamics simulations in combination with the OPLS-aa force field for solvents and customized force field for solutes. V(i) is determined with the direct method, while the composition of V(i) is studied with Kirkwood-Buff integrals (KBIs). Subsequently, the amount of unoccupied space and size of pre-formed cavities in pure solvents is determined. Additionally, the shape of individual solvent cages is analyzed. Calculated V(i) deviate only 3.4 cm(3) mol(-1) (7.1%) from experimental literature values. Experimental V(i) variations across solutions are reproduced qualitatively and also quantitatively in most cases. The KBI analysis identifies differences in solute induced solvent reorganization in the immediate vicinity of H2 (<0.7 nm) and solvent reorganization up to the third solvation shell of CO and CO2 (<1.6 nm) as the origin of V(i) variations. In all solutions, larger V(i) are found in solvents that exhibit weak internal interactions, low cohesive energy density and large compressibility. Weak internal interactions facilitate solvent displacement by thermal solute movement, which enhances the size of solvent cages and thus V(i). Additionally, attractive electrostatic interactions of CO2 and the solvents, which do not depend on internal solvent interactions only, partially reversed the V(i) trends observed in H2 and CO solutions where electrostatic interactions with the solvents are absent. More empty space and larger pre-formed cavities are found in solvents with weak internal interactions, however, no evidence is found that solutes in any considered solvent are accommodated in pre-formed cavities. Individual solvent cages are found to be elongated in the negative direction of solute movement. This wake behind

  16. Variation and decomposition of the partial molar volume of small gas molecules in different organic solvents derived from molecular dynamics simulations

    Science.gov (United States)

    Klähn, Marco; Martin, Alistair; Cheong, Daniel W.; Garland, Marc V.

    2013-12-01

    The partial molar volumes, bar V_i, of the gas solutes H2, CO, and CO2, solvated in acetone, methanol, heptane, and diethylether are determined computationally in the limit of infinite dilution and standard conditions. Solutions are described with molecular dynamics simulations in combination with the OPLS-aa force field for solvents and customized force field for solutes. bar V_i is determined with the direct method, while the composition of bar V_i is studied with Kirkwood-Buff integrals (KBIs). Subsequently, the amount of unoccupied space and size of pre-formed cavities in pure solvents is determined. Additionally, the shape of individual solvent cages is analyzed. Calculated bar V_i deviate only 3.4 cm3 mol-1 (7.1%) from experimental literature values. Experimental bar V_i variations across solutions are reproduced qualitatively and also quantitatively in most cases. The KBI analysis identifies differences in solute induced solvent reorganization in the immediate vicinity of H2 (<0.7 nm) and solvent reorganization up to the third solvation shell of CO and CO2 (<1.6 nm) as the origin of bar V_i variations. In all solutions, larger bar V_i are found in solvents that exhibit weak internal interactions, low cohesive energy density and large compressibility. Weak internal interactions facilitate solvent displacement by thermal solute movement, which enhances the size of solvent cages and thus bar V_i. Additionally, attractive electrostatic interactions of CO2 and the solvents, which do not depend on internal solvent interactions only, partially reversed the bar V_i trends observed in H2 and CO solutions where electrostatic interactions with the solvents are absent. More empty space and larger pre-formed cavities are found in solvents with weak internal interactions, however, no evidence is found that solutes in any considered solvent are accommodated in pre-formed cavities. Individual solvent cages are found to be elongated in the negative direction of solute

  17. Interaction enthalpies of solid human serum albumin with water-dioxane mixtures: comparison with water and organic solvent vapor sorption

    International Nuclear Information System (INIS)

    Sirotkin, Vladimir A.; Faizullin, Djihanguir A.

    2004-01-01

    Enthalpy changes (ΔH tot ) on the immersion of dehydrated human serum albumin (HSA) into water-dioxane mixtures have been measured using a Setaram BT-2.15 calorimeter at 298 K. Thermodynamic activity of water was varied from 0 to 1. Calorimetric results are discussed together with the FTIR-spectroscopic data on water and organic solvent vapor adsorption/desorption isotherms on solid HSA. Dioxane sorption exhibits a pronounced hysteresis. Calorimetric and dioxane desorption dependencies consist of two parts. No dioxane sorption was observed in low water activity region (a w tot values are close to zero. At water activity about 0.5 the sharp exothermic drop of the interaction enthalpy values was observed. This exothermic drop is accompanied by the sharp increase in the amount of sorbed dioxane and additional water sorption (compared with that for pure water). Dioxane adsorption branch resembles a smooth curve. In this case, solid HSA binds more than 300 mol dioxane/mol HSA at low water activities. By using a water activity-based comparison we distinguished between dioxane-assisted and dioxane-competitive effect on water sorption. The obtained results demonstrate that the hydration 'history' of solid protein is an important factor that controls as the state of protein macromolecule as well as the sorption of low-molecular organic molecules

  18. Study of interaction in systems of MoCl/sub 5/-MeCl/sub 2/ (Me - Sn, Zn, Cd, Hg) - a solvent

    Energy Technology Data Exchange (ETDEWEB)

    Golub, A M; Trachevskii, V V; Ul' ko, N V [Kievskij Gosudarstvennyj Univ. (Ukrainian SSR)

    1978-04-01

    Interaction of Mo(5) with dichlorides of tin, zinc, cadmium and mercury in organic solvents was studied by preparative methods, by electron, epr, infrared spectrometry and by conductometry. A polynuclear diamagnetic compound with Mo(5):Sn(2) ratio of 2:1 formed in acetone. A coordination polynuclear compound of (MoOCl/sub 3/)/sub 2/xSnCl/sub 2/x2CH/sub 3/CN was isolated from acetonitrile. It is shown that formation of solvate-chloride and solvate complexes of Mo(5) in solvents depends both on the solvating capacity of the solvent and on stability of the MeCl/sup -3/ (Me is Sn, Zn, Cd, Hg) chloride complex, which grows in the Zn < Sn < Cd < Hg series.

  19. Polar and low polar solvents media effect on dipole moments of some diazo Sudan dyes

    Science.gov (United States)

    Zakerhamidi, M. S.; Golghasemi Sorkhabi, Sh.; Shamkhali, A. N.

    2014-06-01

    Absorption and fluorescence spectra of three Sudan dyes (SudanIII, SudanIV and Sudan black B) were recorded in various solvents with different polarity in the range of 300-800 nm, at room temperature. The solvatochromic method was used to investigate dipole moments of these dyes in ground and excited states, in different media. The solvatochromic behavior of these substances and their solvent-solute interactions were analyzed via solvent polarity parameters. Obtained results express the effects of solvation on tautomerism and molecular configuration (geometry) of Sudan dyes in solvent media with different polarity. Furthermore, analyze of solvent-solute interactions and value of ground and excited states dipole moments suggests different forms of resonance structures for Sudan dyes in polar and low-polar solvents.

  20. One-pot synthesis of stable colloidal solutions of MFe2O4 nanoparticles using oleylamine as solvent and stabilizer

    International Nuclear Information System (INIS)

    Pérez-Mirabet, Leonardo; Solano, Eduardo; Martínez-Julián, Fernando; Guzmán, Roger; Arbiol, Jordi; Puig, Teresa; Obradors, Xavier; Pomar, Alberto; Yáñez, Ramón; Ros, Josep; Ricart, Susagna

    2013-01-01

    Highlights: ► One-pot synthesis of ferrite magnetic nanoparticles ( 3 and M(acac) 2 (M = Co, Mn, Cu and Zn) in oleylamine, which also acts as a capping ligand, by producing stable colloidal dispersions of nanoparticles in non-polar solvents. The properties of the nanoparticles have been studied via different techniques, such as transmission electron microscopy, which shows that nanoparticles are monocrystallines and a narrow dispersion in size; magnetic analyses have demonstrated that the resulting ferrite nanoparticles show high saturation values and superparamagnetic behavior at room temperature; X-ray diffraction has also been performed, and it confirms that the synthesized nanoparticles have a spinel structure. Complementarily, ligand exchange has been also carried out in order to produce dispersions of the synthesized nanoparticles in polar media

  1. Solute-solvent complex switching dynamics of chloroform between acetone and dimethylsulfoxide-two-dimensional IR chemical exchange spectroscopy.

    Science.gov (United States)

    Kwak, Kyungwon; Rosenfeld, Daniel E; Chung, Jean K; Fayer, Michael D

    2008-11-06

    Hydrogen bonds formed between C-H and various hydrogen bond acceptors play important roles in the structure of proteins and organic crystals, and the mechanisms of C-H bond cleavage reactions. Chloroform, a C-H hydrogen bond donor, can form weak hydrogen-bonded complexes with acetone and with dimethylsulfoxide (DMSO). When chloroform is dissolved in a mixed solvent consisting of acetone and DMSO, both types of hydrogen-bonded complexes exist. The two complexes, chloroform-acetone and chloroform-DMSO, are in equilibrium, and they rapidly interconvert by chloroform exchanging hydrogen bond acceptors. This fast hydrogen bond acceptor substitution reaction is probed using ultrafast two-dimensional infrared (2D-IR) vibrational echo chemical exchange spectroscopy. Deuterated chloroform is used in the experiments, and the 2D-IR spectrum of the C-D stretching mode is measured. The chemical exchange of the chloroform hydrogen bonding partners is tracked by observing the time-dependent growth of off-diagonal peaks in the 2D-IR spectra. The measured substitution rate is 1/30 ps for an acetone molecule to replace a DMSO molecule in a chloroform-DMSO complex and 1/45 ps for a DMSO molecule to replace an acetone molecule in a chloroform-acetone complex. Free chloroform exists in the mixed solvent, and it acts as a reactive intermediate in the substitution reaction, analogous to a SN1 type reaction. From the measured rates and the equilibrium concentrations of acetone and DMSO, the dissociation rates for the chloroform-DMSO and chloroform-acetone complexes are found to be 1/24 ps and 1/5.5 ps, respectively. The difference between the measured rate for the complete substitution reaction and the rate for complex dissociation corresponds to the diffusion limited rate. The estimated diffusion limited rate agrees well with the result from a Smoluchowski treatment of diffusive reactions.

  2. Interactions of glutamine dipeptides with sodium dodecyl sulfate in aqueous solution measured by volume, conductivity, and fluorescence spectra

    Energy Technology Data Exchange (ETDEWEB)

    Yan Zhenning, E-mail: yanzzn@zzu.edu.cn [Department of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001 (China); Sun Ximeng; Li Weiwei; Li Yu [Department of Chemistry, Zhengzhou University, Zhengzhou, Henan 450001 (China); Wang Jianji [Department of Chemistry, Henan Normal University, Xinxiang, Henan 453007 (China)

    2011-10-15

    Highlights: > Ion-ion and ion-polar group interactions are dominant interactions. > The SDS addition and temperature increase cause a dehydration effect on dipeptides. > The addition of dipeptide in water decreases the c{sub cmc} of SDS. > Enthalpy-entropy compensation takes place during micellization. > Micelle aggregation number was decreased by addition of glutamine dipeptides. - Abstract: Densities, conductivities, and fluorescence spectra of {l_brace}sodium dodecyl sulfate (SDS) + glutamine dipeptide + water{r_brace} mixtures were measured as a function of temperature. The density data have been utilized to calculate apparent molar volumes, standard partial molar volumes (V{sub 2,{phi}}{sup o}), standard partial molar volumes of transfer from water to aqueous SDS solutions ({Delta}{sub t}V{sup o}), the hydration number, partial molar expansibility (E{sub {phi}}{sup o}), and Hepler's constant of glutamine dipeptides. The critical micellar concentration (c{sub cmc}) and the degree of counterion dissociation of SDS micelles obtained from electrical conductivity data have been estimated at various concentrations of glutamine dipeptide. Thermodynamic parameters of micellization of SDS in aqueous dipeptide solutions have been determined from c{sub cmc} values and an enthalpy-entropy compensation effect was observed for the ternary systems. The pyrene fluorescence spectra were used to study the change of micropolarity produced by the interaction of SDS with glutamine dipeptide, and the aggregation behavior of SDS. The results have been interpreted in terms of solute-solvent interactions and structural changes in the mixed solutions.

  3. Calorimetric study of interaction of barium hydroxide with diluted solutions of hydrofluoric acid

    International Nuclear Information System (INIS)

    Kurbanov, A.R.; Sharipov, D.Sh.

    1993-01-01

    Present article is devoted to calorimetric study of interaction of barium hydroxide with diluted solutions of hydrofluoric acid. The calorimetric study of interaction of barium hydroxide with diluted solutions of hydrofluoric acid was carried out in order to determine the thermal effects of reactions. The results of interaction of Ba(OH) 4 ·8H 2 O with 5, 10, and 20% solution of hydrofluoric acid were considered.

  4. Study of solvent-conjugated polymer interactions by polarized spectroscopy: MEH-PPV and Poly(9,9'-dioctylfluorene-2,7-diyl)

    International Nuclear Information System (INIS)

    Cossiello, Rafael F.; Susman, Mariano D.; Aramendia, Pedro F.; Atvars, Teresa D.Z.

    2010-01-01

    Absorption, emission, and anisotropy measurements were performed on poly-[2-methoxy-5(2'-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and poly-(9,9'-dioctylfluorene-2,7-diyl) (PF) solutions of various solvents, and in thin films deposited from them. The good correlation of MEH-PPV absorption and emission energy with Hildebrandt's dispersive parameter indicate that dispersive forces regulate the effective extent of the luminophore. The excitation and the emission spectra of α and β chains can be distinguished in PF solutions using the steady-state anisotropy. PF films show greater memory effect from the solutions from which they were spun than MEH-PPV. Anisotropy of MEH-PPV is very low, both in solutions and in films reflecting efficient energy migration. Anisotropy of PF in solutions and films demonstrates great differences in energy transfer efficiency within the α and β phases, while there is no energy transfer between these chain conformations.

  5. From the depletion attraction to the bridging attraction: the effect of solvent molecules on the effective colloidal interactions.

    Science.gov (United States)

    Chen, Jie; Kline, Steven R; Liu, Yun

    2015-02-28

    Depletion attraction induced by non-adsorbing polymers or small particles in colloidal solutions has been widely used as a model colloidal interaction to understand aggregation behavior and phase diagrams, such as glass transitions and gelation. However, much less attention has been paid to study the effective colloidal interaction when small particles/molecules can be reversibly attracted to large colloidal particles. At the strong attraction limit, small particles can introduce bridging attraction as it can simultaneously attach to neighbouring large colloidal particles. We use Baxter's multi-component method for sticky hard sphere systems with the Percus-Yevick approximation to study the bridging attraction and its consequence to phase diagrams, which are controlled by the concentration of small particles and their interaction with large particles. When the concentration of small particles is very low, the bridging attraction strength increases very fast with the increase of small particle concentration. The attraction strength eventually reaches a maximum bridging attraction (MBA). Adding more small particles after the MBA concentration keeps decreasing the attraction strength until reaching a concentration above which the net effect of small particles only introduces an effective repulsion between large colloidal particles. These behaviors are qualitatively different from the concentration dependence of the depletion attraction on small particles and make phase diagrams very rich for bridging attraction systems. We calculate the spinodal and binodal regions, the percolation lines, the MBA lines, and the equivalent hard sphere interaction line for bridging attraction systems and have proposed a simple analytic solution to calculate the effective attraction strength using the concentrations of large and small particles. Our theoretical results are found to be consistent with experimental results reported recently.

  6. How do glycerol and dimethyl sulphoxide affect local tetrahedral structure of water around a nonpolar solute at low temperature? Importance of preferential interaction

    Science.gov (United States)

    Daschakraborty, Snehasis

    2018-04-01

    Glycerol and dimethyl sulphoxide (DMSO) have vital roles in cryoprotection of living cells, tissues, etc. The above action has been directly linked with disruption of hydrogen (H-) bond structure and dynamics of water by these cosolvents at bulk region and around various complex units, such as peptide, amino acid, protein, and lipid membrane. However, the disruption of the local structure of the water solvent around a purely hydrophobic solute is still not studied extensively. The latter is also important in the context of stabilization of protein from cold denaturation. Through all-atom molecular dynamics simulation, we have investigated the comparative effect of glycerol and DMSO on the orientational order of water around a nonpolar solute at -5 °C. A steady reduction of the tetrahedral order of water is observed at bulk (>10 Å distance from the solute) and solute interface (structure of the interfacial water more than that of the bulk water, glycerol affects the water structure almost uniformly at all regions around the solute. Furthermore, while glycerol helps to retain water molecules at the interface, DMSO significantly reduces the water content in that region. We have put forward a plausible mechanism for these contrasting roles of these cosolvents. The solute-cosolvent hydrophobic-interaction-induced orientational alignment of an interfacial cosolvent molecule determines whether the involvement of the cosolvent molecules in H-bonding with solvent water in the interface is akin to the bulk region or not.

  7. Spectrophotometric and electrochemical studies of the interaction of cryptand 222 with DDQ and I2 in ethanol solution

    Directory of Open Access Journals (Sweden)

    Abolfazl Semnani

    2006-12-01

    Full Text Available Spectrophotometric and electrochemical studies concerning the interaction of cryptand 222 with DDQ and I2 have been performed in ethanol solution. In the case of DDQ, the results are indicative of the formation of C222¬+ and DDQ- through an equilibrium reaction. The results of I2 indicate the formation of I2-ethanol complex and I3- in the absence of C222. In the presence of C222, the formation of C222I¬+ and I3- through a non-equilibrium reaction is confirmed. The equilibrium constant of the redox reaction between DDQ and C222 has been calculated from the absorbance mole ratio data, using the nonlinear least square program “KINFIT”. The electrochemical reversibility of I-/I2 couple and irreversibility of DDQ/DDQ- is indicated by amperometry. The behavior of DDQ and I2 has been compared. A comparison with aprotic solvents has also been made.

  8. Effect of the isotopic composition of the solvent (water) in the absolute turbidity of polietilen-glicols solutions

    International Nuclear Information System (INIS)

    Molinari, M.A.; Videla, G.J.

    1975-11-01

    Variation in the absolute turbidity of solutions of carbowax 20 M (about 17%) and carbowax 4000 (about 39%) were observed when the relation D 2 O/H 2 O was changed from 0 to 100%, for incident wavelength of 546 and 436 nm. (author) [es

  9. Does an electronic continuum correction improve effective short-range ion-ion interactions in aqueous solution?

    Science.gov (United States)

    Bruce, Ellen E.; van der Vegt, Nico F. A.

    2018-06-01

    Non-polarizable force fields for hydrated ions not always accurately describe short-range ion-ion interactions, frequently leading to artificial ion clustering in bulk aqueous solutions. This can be avoided by adjusting the nonbonded anion-cation or cation-water Lennard-Jones parameters. This approach has been successfully applied to different systems, but the parameterization is demanding owing to the necessity of separate investigations of each ion pair. Alternatively, polarization effects may effectively be accounted for using the electronic continuum correction (ECC) of Leontyev et al. [J. Chem. Phys. 119, 8024 (2003)], which involves scaling the ionic charges with the inverse square-root of the water high-frequency dielectric permittivity. ECC has proven to perform well for monovalent salts as well as for divalent salts in water. Its performance, however, for multivalent salts with higher valency remains unexplored. The present work illustrates the applicability of the ECC model to trivalent K3PO4 and divalent K2HPO4 in water. We demonstrate that the ECC models, without additional tuning of force field parameters, provide an accurate description of water-mediated interactions between salt ions. This results in predictions of the osmotic coefficients of aqueous K3PO4 and K2HPO4 solutions in good agreement with experimental data. Analysis of ion pairing thermodynamics in terms of contact ion pair (CIP), solvent-separated ion pair, and double solvent-separated ion pair contributions shows that potassium-phosphate CIP formation is stronger with trivalent than with divalent phosphate ions.

  10. Solvent extraction

    Energy Technology Data Exchange (ETDEWEB)

    Coombs, D.M.; Latimer, E.G.

    1988-01-05

    It is an object of this invention to provide for the demetallization and general upgrading of heavy oil via a solvent extracton process, and to improve the efficiency of solvent extraction operations. The yield and demetallization of product oil form heavy high-metal content oil is maximized by solvent extractions which employ either or all of the following techniques: premixing of a minor amount of the solvent with feed and using countercurrent flow for the remaining solvent; use of certain solvent/free ratios; use of segmental baffle tray extraction column internals and the proper extraction column residence time. The solvent premix/countercurrent flow feature of the invention substantially improves extractions where temperatures and pressures above the critical point of the solvent are used. By using this technique, a greater yield of extract oil can be obtained at the same metals content or a lower metals-containing extract oil product can be obtained at the same yield. Furthermore, the premixing of part of the solvent with the feed before countercurrent extraction gives high extract oil yields and high quality demetallization. The solvent/feed ratio features of the invention substanially lower the captial and operating costs for such processes while not suffering a loss in selectivity for metals rejection. The column internals and rsidence time features of the invention further improve the extractor metals rejection at a constant yield or allow for an increase in extract oil yield at a constant extract oil metals content. 13 figs., 3 tabs.

  11. Novel Regenerated Solvent Extraction Processes for the Recovery of Carboxylic Acids or Ammonia from Aqueous Solutions Part I. Regeneration of Amine-Carboxylic Acid Extracts

    Energy Technology Data Exchange (ETDEWEB)

    Poole, Loree Joanne [Univ. of California, Berkeley, CA (United States); King, C. Judson [Univ. of California, Berkeley, CA (United States)

    1990-03-01

    Two novel regenerated solvent extraction processes are examined. The first process has the potential to reduce the energy costs inherent in the recovery of low-volatility carboxylic acids from dilute aqueous solutions. The second process has the potential for reducing the energy costs required for separate recovery of ammonia and acid gases (e.g. CO2 and H2S) from industrial sour waters. The recovery of carboxylic acids from dilute aqueous solution can be achieved by extraction with tertiary amines. An approach for regeneration and product recovery from such extracts is to back-extract the carboxylic acid with a water-soluble, volatile tertiary amine, such as trimethylamine. The resulting trimethylammonium carboxylate solution can be concentrated and thermally decomposed, yielding the product acid and the volatile amine for recycle. Experimental work was performed with lactic acid, succinic acid, and fumaric acid. Equilibrium data show near-stoichiometric recovery of the carboxylic acids from an organic solution of Alamine 336 into aqueous solutions of trimethylamine. For fumaric and succinic acids, partial evaporation of the aqueous back extract decomposes the carboxylate and yields the acid product in crystalline form. The decomposition of aqueous solutions of trimethylammonium lactates was not carried out to completion, due to the high water solubility of lactic acid and the tendency of the acid to self-associate. The separate recovery of ammonia and acid gases from sour waters can be achieved by combining steam-stripping of the acid gases with simultaneous removal of ammonia by extraction with a liquid cation exchanger. The use of di-2,4,4-trimethylpentyl phosphinic acid as the liquid cation exchanger is explored in this work. Batch extraction experiments were carried out to measure the equilibrium distribution ratio of ammonia between an aqueous buffer solution and an organic solution of the phosphinic acid (0.2N) in Norpar 12. The

  12. Partition coefficients of organics between water and carbon dioxide revisited: Correlation with solute molecular descriptors and solvent cohesive properties

    Czech Academy of Sciences Publication Activity Database

    Roth, Michal

    2016-01-01

    Roč. 50, č. 23 (2016), s. 12857-12863 ISSN 0013-936X R&D Projects: GA ČR(CZ) GA16-03749S Institutional support: RVO:68081715 Keywords : partitioning between water and supercritical CO2 * organic solutes * K-factor modeling * linear solvation energy relationship Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 6.198, year: 2016

  13. Electrochemical sensing of concanavalin A and ovalbumin interaction in solution

    Czech Academy of Sciences Publication Activity Database

    Vargová, Veronika; Helma, Robert; Paleček, Emil; Ostatná, Veronika

    2016-01-01

    Roč. 935, SEP2016 (2016), s. 97-103 ISSN 0003-2670 R&D Projects: GA ČR(CZ) GA13-00956S Institutional support: RVO:68081707 Keywords : Protein-protein interactions * Lectin-glycoprotein interactions * Ovalbumin Subject RIV: BO - Biophysics Impact factor: 4.950, year: 2016

  14. Caffeine-water-polypeptide interaction in aqueous solution

    Science.gov (United States)

    Ghabi, Habib; Dhahbi, Mahmoud

    1999-04-01

    The interaction of caffeine monomer with the synthetic polypeptides polyasparagine (pAg) and polyaspartic acid (pAsp) was studied by UV spectrophotometry. The results show that different types of interactions are possible depending on the nature of polypeptide. The form of the complex was discussed.

  15. Interactions of flavanoids with bradykinin in aqueous solution

    Science.gov (United States)

    B. Berke; F.L. Tobiason; T. Hatano; C Cheze; J. Vercauteren; Richard W. Hemingway

    1999-01-01

    Complexation with proteins is central to much of the biological and industrial significance of plant polyphenols. Definition of the interaction of these two classes of biopolymers has, therefore, been studied for decades. The most important mechanism seems to involve hydrophobic interactions and also hydrogen bonding, but to a smaller extent. Study of specific...

  16. Magnetic effects on the solvent properties investigated by molecular dynamics simulation

    Energy Technology Data Exchange (ETDEWEB)

    Moosavi, Fatemeh, E-mail: moosavibaigi@um.ac.ir; Gholizadeh, Mostafa

    2014-03-15

    This paper investigates how an external constant magnetic field in the Z-direction affects the performance of a solvent. The molecular dynamics simulation comprised common inorganic and organic solvents including water, acetone, acetonitrile, toluene, and n-hexane at the ambient temperature and pressure. A static magnetic field applied in the simulation process is able to reduce the solvent mobility in the solution in order to enhance the solvent–solute reaction. Simulation results show that the diffusivity decreases because of increasing the effective interactions. Besides, magnetic field reduces the volume of the solvent and increases the strength of the hydrogen bonds by maximizing attractive electrostatic and vdW interactions caused by changes in the radial distribution function of the solvents. Hydrogen-bonding characteristics of solvents investigated by molecular dynamics simulations were evidence for the hydrogen bonding strength of O···H that is a more efficient intermolecular hydrogen-bonding in comparison with N···H. - Highlights: • Molecular dynamics simulation technique investigates the effect of magnetic field on transport dynamics inside the solvent bulk. • External constant magnetic field influences on intermolecular interactions, thermophysics, and transport properties of the solvents. • Applying magnetic field strengthened hydrogen bond maximizes attractive electrostatic interactions, charge distribution becomes stronger, and the molecule mobility is demoted. • The low diffusivity of the solvents in the solutions increases the performance of the interactions and promotes the interactions. • On introducing a magnetic field of flux density parallel to the Z-direction, solvent acts as an obstacle to diffusion of solutes.

  17. Enthalpic characteristics of interactions occurring between an ascorbic acid and some saccharides in aqueous solutions

    International Nuclear Information System (INIS)

    Terekhova, Irina V.; Kulikov, Oleg V.; Titova, Elena S.

    2004-01-01

    The enthalpies of solution of mono- and disaccharides were measured in water and aqueous ascorbic acid solutions at 298.15 K using a calorimeter of solution. Enthalpies of transfer of saccharides from water to aqueous ascorbic acid solutions were derived, and enthalpic coefficients of pair interaction h xy were calculated according to MacMillan-Mayer theory. Interactions of ascorbic acid with D-fructose and sucrose are energetically favorable and characterized by negative h xy coefficients while h xy for the interactions occurring between ascorbic acid and α-D glucose, D-galactose and maltose are positive. The obtained results are interpreted in terms of the influence of structure and solvation of solutes on the thermodynamic parameters of their interaction in solutions

  18. Solvent extraction of Cu, Mo, V, and U from leach solutions of copper ore and flotation tailings

    International Nuclear Information System (INIS)

    Smolinski, Tomasz; Wawszczak, Danuta; Deptula, Andrzej; Lada, Wieslawa; Olczak, Tadeusz; Rogowski, Marcin; Pyszynska, Marta; Chmielewski, Andrzej Grzegorz

    2017-01-01

    Flotation tailings from copper production are deposits of copper and other valuable metals, such as Mo, V and U. New hydrometallurgical technologies are more economical and open up new possibilities for metal recovery. This work presents results of the study on the extraction of copper by mixed extractant consisting p-toluidine dissolved in toluene. The possibility of simultaneous liquid-liquid extraction of molybdenum and vanadium was examined. D2EHPA solutions was used as extractant, and recovery of individual elements compared for the representative samples of ore and copper flotation tailings. Radiometric methods were applied for process optimization. (author)

  19. Solvent extraction of Cu, Mo, V, and U from leach solutions of copper ore and flotation tailings.

    Science.gov (United States)

    Smolinski, Tomasz; Wawszczak, Danuta; Deptula, Andrzej; Lada, Wieslawa; Olczak, Tadeusz; Rogowski, Marcin; Pyszynska, Marta; Chmielewski, Andrzej Grzegorz

    2017-01-01

    Flotation tailings from copper production are deposits of copper and other valuable metals, such as Mo, V and U. New hydrometallurgical technologies are more economical and open up new possibilities for metal recovery. This work presents results of the study on the extraction of copper by mixed extractant consisting p -toluidine dissolved in toluene. The possibility of simultaneous liquid-liquid extraction of molybdenum and vanadium was examined. D2EHPA solutions was used as extractant, and recovery of individual elements compared for the representative samples of ore and copper flotation tailings. Radiometric methods were applied for process optimization.

  20. Solutions to the Problem of Diminished Social Interaction

    OpenAIRE

    Peter K. Jonason; Gregory D. Webster; A. Elizabeth Lindsey

    2008-01-01

    Social animals, like humans, need to interact with others, but this is not always possible. When genuine social interaction is lacking, individuals may seek out or use sources of interaction that co-opt agency detection mechanisms vis-à-vis the human voice and images of people, called social snacking. Study 1 (N = 240) found that ratings of how alone participants felt were correlated with frequency of talking to themselves and using the TV for company. Study 2 (N = 66) was a daily diary study...

  1. Separation by solvent extraction

    International Nuclear Information System (INIS)

    Holt, C.H. Jr.

    1976-01-01

    In a process for separating fission product values from U and Pu values contained in an aqueous solution, an oxidizing agent is added to the solution to secure U and Pu in their hexavalent state. The aqueous solution is contacted with a substantially water-immiscible organic solvent with agitation while the temperature is maintained at from -1 to -2 0 C until the major part of the water present is frozen. The solid ice phase is continuously separated as it is formed and a remaining aqueous liquid phase containing fission product values and a solvent phase containing Pu and U values are separated from each other. The last obtained part of the ice phase is melted and added to the separated liquid phase. The resulting liquid is treated with a new supply of solvent whereby it is practically depleted of U and Pu

  2. Solvent effects in ionic liquids: empirical linear energy-density relationships.

    Science.gov (United States)

    Cerda-Monje, A; Aizman, A; Tapia, R A; Chiappe, C; Contreras, R

    2012-07-28

    Multiparameter linear energy-density relationships to model solvent effects in room temperature ionic liquids (RTILs) are introduced and tested. The model incorporates two solvent dependent and two specific solute-solvent parameters represented by a set of electronic indexes derived from the conceptual density functional theory. The specific solute-solvent interactions are described in terms of the electronic chemical potential for proton migration between the anion or cation and the transition state structure of a specific reaction. These indexes provide a quantitative estimation of the hydrogen bond (HB) acceptor basicity and the hydrogen bond donor acidity of the ionic solvent, respectively. A sound quantitative scale of HB strength is thereby obtained. The solvent dependent contributions are described by the global electrophilicity of the cation and nucleophilicity of the anion forming the ionic liquid. The model is illustrated for the kinetics of cycloaddition of cyclopentadiene towards acrolein. In general, cation HB acidity outweighs the remaining parameters for this reaction.

  3. Aggregation in charged nanoparticles solutions induced by different interactions

    Energy Technology Data Exchange (ETDEWEB)

    Abbas, S.; Kumar, Sugam; Aswal, V. K., E-mail: vkaswal@barc.gov.in [Solid State Physics Division, Bhabha Atomic Research Centre, Mumbai 400 085 (India); Kohlbrecher, J. [Laboratory for Neutron Scattering, Paul Scherrer Institut, CH-5232 PSI Villigen (Switzerland)

    2016-05-23

    Small-angle neutron scattering (SANS) has been used to study the aggregation of anionic silica nanoparticles as induced through different interactions. The nanoparticle aggregation is induced by addition of salt (NaCl), cationic protein (lysozyme) and non-ionic surfactant (C12E10) employing different kind of interactions. The results show that the interaction in presence of salt can be explained using DLVO theory whereas non-DLVO forces play important role for interaction of nanoparticles with protein and surfactant. The presence of salt screens the repulsion between charged nanoparticles giving rise to a net attraction in the DLVO potential. On the other hand, strong electrostatic attraction between nanoparticle and oppositely charged protein leads to protein-mediated nanoparticle aggregation. In case of non-ionic surfactant, the relatively long-range attractive depletion interaction is found to be responsible for the particle aggregation. Interestingly, the completely different interactions lead to similar kind of aggregate morphology. The nanoparticle aggregates formed are found to have mass fractal nature having a fractal dimension (~2.5) consistent with diffusion limited type of fractal morphology in all three cases.

  4. Stabilizing the border steady-state solution of two interacting ...

    African Journals Online (AJOL)

    In this paper, we have successfully developed a feedback control which has been used to stabilize an unstable steady-state solution (0, 3.3534). This convergence has occurred when the values of the final time are 190, 200, 210 and 220 which corresponds to the scenario when the value of the step length of our simulation ...

  5. Density Changes in the Optimized CSSX Solvent System

    Energy Technology Data Exchange (ETDEWEB)

    Lee, D.D.

    2002-11-25

    Density increases in caustic-side solvent extraction (CSSX) solvent have been observed in separate experimental programs performed by different groups of researchers. Such changes indicate a change in chemical composition. Increased density adversely affects separation of solvent from denser aqueous solutions present in the CSSX process. Identification and control of factors affecting solvent density are essential for design and operation of the centrifugal contactors. The goals of this research were to identify the factors affecting solvent density (composition) and to develop correlations between easily measured solvent properties (density and viscosity) and the chemical composition of the solvent, which will permit real-time determination and adjustment of the solvent composition. In evaporation experiments, virgin solvent was subjected to evaporation under quiescent conditions at 25, 35, and 45 C with continuously flowing dry air passing over the surface of the solvent. Density and viscosity were measured periodically, and chemical analysis was performed on the solvent samples. Chemical interaction tests were completed to determine if any chemical reaction takes place over extended contact time that changes the composition and/or physical properties. Solvent and simulant, solvent and strip solution, and solvent and wash solution were contacted continuously in agitated flasks. They were periodically sampled and the density measured (viscosity was also measured on some samples) and then submitted to the Chemical Sciences Division of Oak Ridge National Laboratory for analysis by nuclear magnetic resonance (NMR) spectrometry and high-performance liquid chromatography (HPLC) using the virgin solvent as the baseline. Chemical interaction tests showed that solvent densities and viscosities did not change appreciably during contact with simulant, strip, or wash solution. No effects on density and viscosity and no chemical changes in the solvent were noted within

  6. Ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate, an efficient solvent for extraction of acetone from aqueous solutions

    International Nuclear Information System (INIS)

    Saien, Javad; Badieh, Marjan Mohammadi Sarab; Norouzi, Mahdi; Salehzadeh, Sadegh

    2015-01-01

    Highlights: • The use of HMIMPF_6 as a green ionic was feasible in the extraction of acetone from water. • The binodal curves were determined by cloud point measurement method. • High level separation factor of acetone between the ionic liquid and water were achieved. • The thermodynamic properties of HMIMPF_6 were obtained by the Density Functional Theory calculations. • The NRTL and UNIQUAC models were applied satisfactorily to correlate the equilibrium data. - Abstract: (Liquid + liquid) equilibrium (LLE) of the chemical system of {water + acetone + 1-Hexyl-3-methylimidazolium hexafluorophosphate (HMIMPF_6) ionic liquid} was studied at different temperatures of (293.2, 298.2 and 303.2) K and under atmospheric pressure of 81.5 kPa. The results show that HMIMPF_6 provides the acetone distribution coefficient and separation factor values within (0.8813 to 1.2351) and (3.0 to 54.4), respectively; indicating the high capability of the ionic liquid for extraction of acetone from aqueous solutions. In most cases, acetone solubility in the ionic liquid is higher than in water, especially at higher solute concentrations. Meanwhile, higher separation factor is relevant to the lower temperature due to lower (water + ionic liquid) miscibility. The consistency of tie line data, at each temperature, was examined with Othmer–Tobias correlation. The values were nicely reproduced with the well-known NRTL and UNIQUAC models. Accordingly, the required thermodynamic properties of HMIMPF_6 were obtained by the Density Functional Theory (DFT) calculations, carried out at the M06/6-311++G"∗"∗ level of theory. The root mean square deviations (RMSD) between experimental and model concentration values were 0.0192 and 0.0255, respectively; indicating close agreement of the both models.

  7. Morphologies and separation characteristics of polyphenyl sulfone-based solvent resistant nanofiltration membranes: Effect of polymer concentration in casting solution and membrane pretreatment condition

    International Nuclear Information System (INIS)

    Sani, Nur Aimie Abdullah; Lau, Woei Jye; Ismail, Ahmad Fauzi

    2015-01-01

    The performance of polyphenylsulfone (PPSU) solvent resistant nanofiltration (SRNF)-based flat sheet membranes prepared from phase inversion method was investigated by varying the concentration of polymer in the dope solution and condition of membrane pretreatment process. The membrane properties were characterized by SEM, FTIR, AFM and contact angle goniometer, while their performance was evaluated by measuring methanol flux and rejection of different molecular weight of dyes (ranging from 269 to 1,470 g/mol) in methanol. The experimental results showed that the polymer concentration has great impact not only on the final membrane morphology but also its separation characteristics. Increasing polymer concentration from 17 to 25wt% tended to suppress finger-like structure and more pear-like pores were developed, causing methanol flux to decrease. This can be explained by the decrease in molecular weight cut off (MWCO) of the membrane prepared at high polymer concentration. With respect to the effect of membrane pretreatment conditions, the rejection of membrane was negatively affected with longer immersion period in methanol solution prior to filtration experiment. The variation in membrane rejection can be attributed to the rearrangement of the polymer chain, which results in membrane swelling and/or change of membrane surface hydrophilicity

  8. Morphologies and separation characteristics of polyphenyl sulfone-based solvent resistant nanofiltration membranes: Effect of polymer concentration in casting solution and membrane pretreatment condition

    Energy Technology Data Exchange (ETDEWEB)

    Sani, Nur Aimie Abdullah; Lau, Woei Jye; Ismail, Ahmad Fauzi [Universiti Teknologi Malaysia, Skudai (Malaysia)

    2015-04-15

    The performance of polyphenylsulfone (PPSU) solvent resistant nanofiltration (SRNF)-based flat sheet membranes prepared from phase inversion method was investigated by varying the concentration of polymer in the dope solution and condition of membrane pretreatment process. The membrane properties were characterized by SEM, FTIR, AFM and contact angle goniometer, while their performance was evaluated by measuring methanol flux and rejection of different molecular weight of dyes (ranging from 269 to 1,470 g/mol) in methanol. The experimental results showed that the polymer concentration has great impact not only on the final membrane morphology but also its separation characteristics. Increasing polymer concentration from 17 to 25wt% tended to suppress finger-like structure and more pear-like pores were developed, causing methanol flux to decrease. This can be explained by the decrease in molecular weight cut off (MWCO) of the membrane prepared at high polymer concentration. With respect to the effect of membrane pretreatment conditions, the rejection of membrane was negatively affected with longer immersion period in methanol solution prior to filtration experiment. The variation in membrane rejection can be attributed to the rearrangement of the polymer chain, which results in membrane swelling and/or change of membrane surface hydrophilicity.

  9. Densities, refractive indices, and viscosities of N,N-diethylethanol ammonium chloride–glycerol or –ethylene glycol deep eutectic solvents and their aqueous solutions

    International Nuclear Information System (INIS)

    Siongco, Kathrina R.; Leron, Rhoda B.; Li, Meng-Hui

    2013-01-01

    Highlights: • The densities, refractive indices, and viscosities of aqueous DES solutions were measured. • DES are made from N,N-diethylethanol ammonium chloride + glycerol or ethylene glycol. • The temperature studied was (298.15 to 343.15) K. • The measured data were reported as functions of temperature and composition. • The measured data were represented satisfactorily by the applied correlations. -- Abstract: In this work, we report new experimental data on density, ρ, refractive index, n D, and viscosity, η, of two deep eutectic solvents, N,N-diethylethanol ammonium chloride–glycerol (DEACG) and N,N-diethylethanol ammonium chloride–ethylene glycol (DEACEG), and their aqueous solutions, over the complete composition range, at temperatures from (298.15 to 343.15) K. Densities and viscosities were measured using the vibrating tube and the falling ball techniques, respectively, while the refractive index at the sodium D line was measured using an automatic refractometer. We aimed to represent the measured properties as a function of temperature and composition, and correlated them using the Redlich–Kister-type equation, for density, a polynomial function, for refractive index, and the Vogel–Fulcher–Tammann (VFT) equation, for viscosity

  10. Analytical solutions of hypersonic type IV shock - shock interactions

    Science.gov (United States)

    Frame, Michael John

    An analytical model has been developed to predict the effects of a type IV shock interaction at high Mach numbers. This interaction occurs when an impinging oblique shock wave intersects the most normal portion of a detached bow shock. The flowfield which develops is complicated and contains an embedded jet of supersonic flow, which may be unsteady. The jet impinges on the blunt body surface causing very high pressure and heating loads. Understanding this type of interaction is vital to the designers of cowl lips and leading edges on air- breathing hypersonic vehicles. This analytical model represents the first known attempt at predicting the geometry of the interaction explicitly, without knowing beforehand the jet dimensions, including the length of the transmitted shock where the jet originates. The model uses a hyperbolic equation for the bow shock and by matching mass continuity, flow directions and pressure throughout the flowfield, a prediction of the interaction geometry can be derived. The model has been shown to agree well with the flowfield patterns and properties of experiments and CFD, but the prediction for where the peak pressure is located, and its value, can be significantly in error due to a lack of sophistication in the model of the jet fluid stagnation region. Therefore it is recommended that this region of the flowfield be modeled in more detail and more accurate experimental and CFD measurements be used for validation. However, the analytical model has been shown to be a fast and economic prediction tool, suitable for preliminary design, or for understanding the interactions effects, including the basic physics of the interaction, such as the jet unsteadiness. The model has been used to examine a wide parametric space of possible interactions, including different Mach number, impinging shock strength and location, and cylinder radius. It has also been used to examine the interaction on power-law shaped blunt bodies, a possible candidate for

  11. Ellipsometry-based combination of isothermal sorption-desorption measurement and temperature programmed desorption technique: A probe for interaction of thin polymer films with solvent vapor

    Science.gov (United States)

    Efremov, Mikhail Yu.; Nealey, Paul F.

    2018-05-01

    An environmental chamber equipped with an in situ spectroscopic ellipsometer, programmatic vapor pressure control, and variable temperature substrate holder has been designed for studying polymer coating behavior during an exposure to a solvent vapor and also for probing the residual solvent in the film afterwards. Both sorption-desorption cycle at a constant temperature and temperature programmed desorption (TPD) of the residual solvent manifest themselves as a change of the film thickness. Monitoring of ellipsometric angles of the coating allows us to determine the thickness as a function of the vapor pressure or sample temperature. The solvent vapor pressure is precisely regulated by a computer-controlled pneumatics. TPD spectra are recorded during heating of the film in an oil-free vacuum. The vapor pressure control system is described in detail. The system has been tested on 6-170 nm thick polystyrene, poly(methyl methacrylate), and poly(2-vinyl pyridine) films deposited on silicon substrates. Liquid toluene, water, ethanol, isopropanol, cyclohexane, 1,2-dichloroethane, and chlorobenzene were used to create a vapor atmosphere. Typical sorption-desorption and TPD curves are shown. The instrument achieves sub-monolayer sensitivity for adsorption studies on flat surfaces. Polymer-solvent vapor systems with strong interaction demonstrate characteristic absorption-desorption hysteresis spanning from vacuum to the glass transition pressure. Features on the TPD curves can be classified as either glass transition related film contraction or low temperature broad contraction peak. Typical absorption-desorption and TPD dependencies recorded for the 6 nm thick polystyrene film demonstrate the possibility to apply the presented technique for probing size effects in extremely thin coatings.

  12. Lump solutions with interaction phenomena in the (2+1)-dimensional Ito equation

    Science.gov (United States)

    Zou, Li; Yu, Zong-Bing; Tian, Shou-Fu; Feng, Lian-Li; Li, Jin

    2018-03-01

    In this paper, we consider the (2+1)-dimensional Ito equation, which was introduced by Ito. By considering the Hirota’s bilinear method, and using the positive quadratic function, we obtain some lump solutions of the Ito equation. In order to ensure rational localization and analyticity of these lump solutions, some sufficient and necessary conditions are provided on the parameters that appeared in the solutions. Furthermore, the interaction solutions between lump solutions and the stripe solitons are discussed by combining positive quadratic function with exponential function. Finally, the dynamic properties of these solutions are shown via the way of graphical analysis by selecting appropriate values of the parameters.

  13. Deasphalting solvents

    International Nuclear Information System (INIS)

    Carrillo, J. A; Caceres, J; Vela, G; Bueno, H

    1996-01-01

    This paper describes how the deasphalted oil (DMO) or demetalized oil (DMO) quality (CCR, Ni, V end asphaltenes contents) changes with: DAO or DMO yield, solvent/feed ratio, type of vacuum reside (from paraffinic to blends with vis breaking bottoms), extraction temperature and extraction solvent (propane, propylene, n-butane and I butane)

  14. Controlling coverage of solution cast materials with unfavourable surface interactions

    KAUST Repository

    Burlakov, V. M.; Eperon, G. E.; Snaith, H. J.; Chapman, S. J.; Goriely, A.

    2014-01-01

    Creating uniform coatings of a solution-cast material is of central importance to a broad range of applications. Here, a robust and generic theoretical framework for calculating surface coverage by a solid film of material de-wetting a substrate is presented. Using experimental data from semiconductor thin films as an example, we calculate surface coverage for a wide range of annealing temperatures and film thicknesses. The model generally predicts that for each value of the annealing temperature there is a range of film thicknesses leading to poor surface coverage. The model accurately reproduces solution-cast thin film coverage for organometal halide perovskites, key modern photovoltaic materials, and identifies processing windows for both high and low levels of surface coverage. © 2014 AIP Publishing LLC.

  15. Controlling coverage of solution cast materials with unfavourable surface interactions

    KAUST Repository

    Burlakov, V. M.

    2014-03-03

    Creating uniform coatings of a solution-cast material is of central importance to a broad range of applications. Here, a robust and generic theoretical framework for calculating surface coverage by a solid film of material de-wetting a substrate is presented. Using experimental data from semiconductor thin films as an example, we calculate surface coverage for a wide range of annealing temperatures and film thicknesses. The model generally predicts that for each value of the annealing temperature there is a range of film thicknesses leading to poor surface coverage. The model accurately reproduces solution-cast thin film coverage for organometal halide perovskites, key modern photovoltaic materials, and identifies processing windows for both high and low levels of surface coverage. © 2014 AIP Publishing LLC.

  16. Anion-π aromatic neutral tweezers complexes: are they stable in polar solvents?

    Science.gov (United States)

    Sánchez-Lozano, Marta; Otero, Nicolás; Hermida-Ramón, Jose M; Estévez, Carlos M; Mandado, Marcos

    2011-03-17

    The impact of the solvent environment on the stabilization of the complexes formed by fluorine (T-F) and cyanide (T-CN) substituted tweezers with halide anions has been investigated theoretically. The study was carried out using computational methodologies based on density functional theory (DFT) and symmetry adapted perturbation theory (SAPT). Interaction energies were obtained at the M05-2X/6-31+G* level. The obtained results show a large stability of the complexes in solvents with large dielectric constant and prove the suitability of these molecular tweezers as potential hosts for anion recognition in solution. A detailed analysis of the effects of the solvent on the electron withdrawing ability of the substituents and its influence on the complex stability has been performed. In particular, the interaction energy in solution was split up into intermonomer and solvent-complex terms. In turn, the intermonomer interaction energy was partitioned into electrostatic, exchange, and polarization terms. Polar resonance structures in T-CN complexes are favored by polar solvents, giving rise to a stabilization of the intermonomer interaction, the opposite is found for T-F complexes. The solvent-complex energy increases with the polarity of the solvent in T-CN complexes, nonetheless the energy reaches a maximum and then decreases slowly in T-F complexes. An electron density analysis was also performed before and after complexation, providing an explanation to the trends followed by the interaction energies and their different components in solution.

  17. Nonautonomous discrete bright soliton solutions and interaction management for the Ablowitz-Ladik equation.

    Science.gov (United States)

    Yu, Fajun

    2015-03-01

    We present the nonautonomous discrete bright soliton solutions and their interactions in the discrete Ablowitz-Ladik (DAL) equation with variable coefficients, which possesses complicated wave propagation in time and differs from the usual bright soliton waves. The differential-difference similarity transformation allows us to relate the discrete bright soliton solutions of the inhomogeneous DAL equation to the solutions of the homogeneous DAL equation. Propagation and interaction behaviors of the nonautonomous discrete solitons are analyzed through the one- and two-soliton solutions. We study the discrete snaking behaviors, parabolic behaviors, and interaction behaviors of the discrete solitons. In addition, the interaction management with free functions and dynamic behaviors of these solutions is investigated analytically, which have certain applications in electrical and optical systems.

  18. Modeling of solvent extraction equilibrium of Cu(II from sulphuric Acid solution with MOC-55TD

    Directory of Open Access Journals (Sweden)

    Alguacil, F. J.

    1999-06-01

    Full Text Available The extraction of Cu(II from acidic sulphate aqueous solutions using the commercial MOC-55TD extractant is studied. A predictive model, which consists in a set of non-linear mass action and mass balance equations is proposed. The model was solved using a tailor-made equation-solving program. The extraction of copper can be described by the formation of CuR2 species (log Kext= 0.717 ± 0.03 in the organic phase. The copper equilibrium isotherm was also obtained at 20°C.

    Se estudia la extracción de Cu(II de disoluciones acuosas acidas, en medio sulfato, mediante la oxima comercial MOC-55TD. Se propone un modelo para predecir la extracción del metal; este modelo consiste en una serie de ecuaciones no lineales de acción de masas y balance de masas. El modelo se resolvió empleando un programa de ordenador específicamente definido para este tipo de equilibrios. La extracción de cobre se describe por la formación de la especie CuR2 (log Kext= 0,717 ± 0,03 en la fase orgánica. Se ha obtenido la isoterma de extracción de cobre a 20 °C.

  19. Solution processable mixed-solvent exfoliated MoS2 nanosheets for efficient and robust organic light-emitting diodes

    Science.gov (United States)

    Liu, Chia-Wei; Wang, Chia; Liao, Chia-Wei; Golder, Jan; Tsai, Ming-Chih; Young, Hong-Tsu; Chen, Chin-Ti; Wu, Chih-I.

    2018-04-01

    We demonstrate the use of solution-processed molybdenum trioxide (MoO3) nanoparticle-decorated molybdenum disulfide (MoS2) nanosheets (MoS2/MoO3) as hole injection layer (HIL) in organic lighting diodes (OLEDs). The device performance is shown to be significantly improved by the introduction of such MoS2/MoO3 HIL without any post-ultraviolet-ozone treatment, and is shown to better the performance of devices fabricated using conventional poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) and MoO3 nanoparticle HILs. The MoS2/MoO3 nanosheets form a compact film, as smooth as PEDOT:PSS films and smoother than MoO3 nanoparticle films, when simply spin-coated on indium tin oxide substrates. The improvement in device efficiency can be attributed to the smooth surface of the nanostructured MoS2/MoO3 HIL and the excellent conductivity characteristics of the two-dimensional (2D) layered material (MoS2), which facilitate carrier transport in the device and reduce the sheet resistance. Moreover, the long-term stability of OLED devices that use such MoS2/MoO3 layers is shown to be improved dramatically compared with hygroscopic and acidic PEDOT:PSS-based devices.

  20. Solution processable mixed-solvent exfoliated MoS2 nanosheets for efficient and robust organic light-emitting diodes

    Directory of Open Access Journals (Sweden)

    Chia-Wei Liu

    2018-04-01

    Full Text Available We demonstrate the use of solution-processed molybdenum trioxide (MoO3 nanoparticle-decorated molybdenum disulfide (MoS2 nanosheets (MoS2/MoO3 as hole injection layer (HIL in organic lighting diodes (OLEDs. The device performance is shown to be significantly improved by the introduction of such MoS2/MoO3 HIL without any post-ultraviolet-ozone treatment, and is shown to better the performance of devices fabricated using conventional poly(3,4-ethylenedioxythiophene-poly(styrenesulfonate (PEDOT:PSS and MoO3 nanoparticle HILs. The MoS2/MoO3 nanosheets form a compact film, as smooth as PEDOT:PSS films and smoother than MoO3 nanoparticle films, when simply spin-coated on indium tin oxide substrates. The improvement in device efficiency can be attributed to the smooth surface of the nanostructured MoS2/MoO3 HIL and the excellent conductivity characteristics of the two-dimensional (2D layered material (MoS2, which facilitate carrier transport in the device and reduce the sheet resistance. Moreover, the long-term stability of OLED devices that use such MoS2/MoO3 layers is shown to be improved dramatically compared with hygroscopic and acidic PEDOT:PSS-based devices.

  1. Bringing Interactivity to the Web: The JAVA Solution.

    Science.gov (United States)

    Knee, Richard H.; Cafolla, Ralph

    Java is an object-oriented programming language of the Internet. It's popularity lies in its ability to create interactive Web sites across platforms. The most common Java programs are applications and applets, which adhere to a set of conventions that lets them run within a Java-compatible browser. Java is becoming an essential subject matter and…

  2. Vibrational spectroscopy on intermolecular interactions in solutions and at interfaces

    NARCIS (Netherlands)

    Nissink, Johannes Wilhelmus Maria

    1999-01-01

    In recent years, considerable progress has been made in the areas of molecular recognition and surface analysis. These fields meet in the field of sensor development, where the interaction between molecules and a suitably modified surface is of utmost importance. Vibrational spectroscopy is quite

  3. Coulomb plus strong interaction bound states - momentum space numerical solutions

    International Nuclear Information System (INIS)

    Heddle, D.P.; Tabakin, F.

    1985-01-01

    The levels and widths of hadronic atoms are calculated in momentum space using an inverse algorithm for the eigenvalue problem. The Coulomb singularity is handled by the Lande substraction method. Relativistic, nonlocal, complex hadron-nucleus interactions are incorporated as well as vacuum polarization and finite size effects. Coordinate space wavefunctions are obtained by employing a Fourier Bessel transformation. (orig.)

  4. Elastic interaction of partially debonded circular inclusions. I. Theoretical solution

    DEFF Research Database (Denmark)

    Kushch, V.I.; Shmegera, S.V.; Mishnaevsky, Leon

    2010-01-01

    and provides a simple and rapidly convergent iterative algorithm. The presented numerical data show an accuracy and numerical efficiency of the proposed method and discover the way and extent to which the elastic interaction between the partially debonded inclusions affects the local fields, stress intensity...... factors and the energy release rate at the interface crack tips....

  5. Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents.

    Science.gov (United States)

    Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng; Ma, Jing

    2018-03-01

    Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o -cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o -cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o -cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260-280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o -cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o -cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively.

  6. Intermolecular Interactions and Cooperative Effects from Electronic Structure Calculations: An Effective Means for Developing Interaction Potentials for Condensed Phase Simulations

    Energy Technology Data Exchange (ETDEWEB)

    Xantheas, Sotiris S.

    2004-05-01

    The modeling of the macroscopic properties of homogeneous and inhomogeneous systems via atomistic simulations such as molecular dynamics (MD) or Monte Carlo (MC) techniques is based on the accurate description of the relevant solvent-solute and solvent-solvent intermolecular interactions. The total energy (U) of an n-body molecular system can be formally written as [1,2,3

  7. Visualization of protein interaction networks: problems and solutions

    Directory of Open Access Journals (Sweden)

    Agapito Giuseppe

    2013-01-01

    Full Text Available Abstract Background Visualization concerns the representation of data visually and is an important task in scientific research. Protein-protein interactions (PPI are discovered using either wet lab techniques, such mass spectrometry, or in silico predictions tools, resulting in large collections of interactions stored in specialized databases. The set of all interactions of an organism forms a protein-protein interaction network (PIN and is an important tool for studying the behaviour of the cell machinery. Since graphic representation of PINs may highlight important substructures, e.g. protein complexes, visualization is more and more used to study the underlying graph structure of PINs. Although graphs are well known data structures, there are different open problems regarding PINs visualization: the high number of nodes and connections, the heterogeneity of nodes (proteins and edges (interactions, the possibility to annotate proteins and interactions with biological information extracted by ontologies (e.g. Gene Ontology that enriches the PINs with semantic information, but complicates their visualization. Methods In these last years many software tools for the visualization of PINs have been developed. Initially thought for visualization only, some of them have been successively enriched with new functions for PPI data management and PIN analysis. The paper analyzes the main software tools for PINs visualization considering four main criteria: (i technology, i.e. availability/license of the software and supported OS (Operating System platforms; (ii interoperability, i.e. ability to import/export networks in various formats, ability to export data in a graphic format, extensibility of the system, e.g. through plug-ins; (iii visualization, i.e. supported layout and rendering algorithms and availability of parallel implementation; (iv analysis, i.e. availability of network analysis functions, such as clustering or mining of the graph, and the

  8. Soil solution interactions may limit Pb remediation using P ...

    Science.gov (United States)

    Lead (Pb) contaminated soils are a potential exposure hazard to the public. Amending soils with phosphorus (P) may reduce Pb soil hazards. Soil from Cleveland, OH containing 726 ± 14 mg Pb kg-1 was amended in a laboratory study with bone meal and triple super phosphate (TSP) at 5:1 P:Pb molar ratios. Soil was acidified, neturalized and re-acidified to encourage Pb phosphate formation. PRSTM-probes were used to evaluate changes in soil solution chemistry. Soil acidification did not decrease in vitro bioaccessible (IVBA) Pb using either a pH 1.5, 0.4 M glycine solution or a pH 2.5 solution with organic acids. PRSTM-probe data found soluble Pb increased 10-fold in acidic conditions compared to circumnetural pH conditions. In acidic conditions (p = 3-4), TSP treated soils increased detected P 10-fold over untreated soils. Bone meal application did not increase PRSTM-probe detected P, indicating there may have been insufficient P to react with Pb. X-ray absorption spectroscopy suggested a 10% increase in pyromorphite formation for the TSP treated soil only. Treatments increased soil electrical conductivity above 16 mS cm-1, potentially causing a new salinity hazard. This study used a novel approach by combining the human ingestion endpoint, PRSTM-probes, and X-ray absorption spectroscopy to evaluate treatment efficacy. PRSTM-probe data indicated potentially excess Ca relative to P across incubation steps that could have competed with Pb for soluble P. Mor

  9. Activity and conformation of lysozyme in molecular solvents, protic ionic liquids (PILs) and salt-water systems.

    Science.gov (United States)

    Wijaya, Emmy C; Separovic, Frances; Drummond, Calum J; Greaves, Tamar L

    2016-09-21

    Improving protein stabilisation is important for the further development of many applications in the pharmaceutical, specialty chemical, consumer product and agricultural sectors. However, protein stabilization is highly dependent on the solvent environment and, hence, it is very complex to tailor protein-solvent combinations for stable protein maintenance. Understanding solvent features that govern protein stabilization will enable selection or design of suitable media with favourable solution environments to retain protein native conformation. In this work the structural conformation and activity of lysozyme in 29 solvent systems were investigated to determine the role of various solvent features on the stability of the enzyme. The solvent systems consisted of 19 low molecular weight polar solvents and 4 protic ionic liquids (PILs), both at different water content levels, and 6 aqueous salt solutions. Small angle X-ray scattering, Fourier transform infrared spectroscopy and UV-vis spectroscopy were used to investigate the tertiary and secondary structure of lysozyme along with the corresponding activity in various solvation systems. At low non-aqueous solvent concentrations (high water content), the presence of solvents and salts generally maintained lysozyme in its native structure and enhanced its activity. Due to the presence of a net surface charge on lysozyme, electrostatic interactions in PIL-water systems and salt solutions enhanced lysozyme activity more than the specific hydrogen-bond interactions present in non-ionic molecular solvents. At higher solvent concentrations (lower water content), solvents with a propensity to exhibit the solvophobic effect, analogous to the hydrophobic effect in water, retained lysozyme native conformation and activity. This solvophobic effect was observed particularly for solvents which contained hydroxyl moieties. Preferential solvophobic effects along with bulky chemical structures were postulated to result in less

  10. Method for Predicting Solubilities of Solids in Mixed Solvents

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela; Abildskov, Jens; O'Connell, J. P.

    2009-01-01

    A method is presented for predicting solubilities of solid solutes in mixed solvents, based on excess Henry's law constants. The basis is statistical mechanical fluctuation solution theory for composition derivatives of solute/solvent infinite dilution activity coefficients. Suitable approximatio...

  11. Solvent substitution

    International Nuclear Information System (INIS)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general ''Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated

  12. Solvent substitution

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The DOE Environmental Restoration and Waste Management Office of Technology Development and the Air Force Engineering and Services Center convened the First Annual International Workshop on Solvent Substitution on December 4--7, 1990. The primary objectives of this joint effort were to share information and ideas among attendees in order to enhance the development and implementation of required new technologies for the elimination of pollutants associated with industrial use of hazardous and toxic solvents; and to aid in accelerating collaborative efforts and technology transfer between government and industry for solvent substitution. There were workshop sessions focusing on Alternative Technologies, Alternative Solvents, Recovery/Recycling, Low VOC Materials and Treatment for Environmentally Safe Disposal. The 35 invited papers presented covered a wide range of solvent substitution activities including: hardware and weapons production and maintenance, paint stripping, coating applications, printed circuit boards, metal cleaning, metal finishing, manufacturing, compliance monitoring and process control monitoring. This publication includes the majority of these presentations. In addition, in order to further facilitate information exchange and technology transfer, the US Air Force and DOE solicited additional papers under a general Call for Papers.'' These papers, which underwent review and final selection by a peer review committee, are also included in this combined Proceedings/Compendium. For those involved in handling, using or managing hazardous and toxic solvents, this document should prove to be a valuable resource, providing the most up-to-date information on current technologies and practices in solvent substitution. Individual papers are abstracted separated.

  13. Android design patterns interaction design solutions for developers

    CERN Document Server

    Nudelman, Greg

    2013-01-01

    Master the challenges of Android user interface development with these sample patterns With Android 4, Google brings the full power of its Android OS to both smartphone and tablet computing. Designing effective user interfaces that work on multiple Android devices is extremely challenging. This book provides more than 75 patterns that you can use to create versatile user interfaces for both smartphones and tablets, saving countless hours of development time. Patterns cover the most common and yet difficult types of user interactions, and each is supported with richly illustrate

  14. The Interaction of Sorbitol with Caffeine in Aqueous Solution

    OpenAIRE

    Tavagnacco, Letizia; Brady, John W.; Cesàro, Attilio

    2013-01-01

    Molecular dynamics simulations were carried out on a system of caffeine interacting with the sugar alcohol sorbitol. The system examined had a caffeine concentration 0.083 m and a sugar concentration 1.08 m. The trajectories of all molecules in the system were collected over a period of 80 ns and analyzed to determine whether there is any tendency for sorbitol to bind to caffeine, and if so, by what mechanism. The results show that the sorbitol molecules have an affinity for the caffeine mole...

  15. Studies on the retention mechanism of solutes in hydrophilic interaction chromatography using stoichiometric displacement theory I. The linear relationship of lgk' vs. lg[H2O].

    Science.gov (United States)

    Wang, Fei; Yang, Fan; Tian, Yang; Liu, Jiawei; Shen, Jiwei; Bai, Quan

    2018-01-01

    A stoichiometric displacement model for retention (SDM-R) of small solutes and proteins based on hydrophilic interaction chromatography (HILIC) was presented. A linear equation that related the logarithm of the capacity factor of the solute to the logarithm of the concentration of water in the mobile phase was derived. The stoichiometric displacement parameters, Z (the number of water molecules required to displace a solute from ligands) and lgI (containing a number of constants that relate to the affinity of solute to the ligands) could be obtained from the slope and the intercept of the linear plots of lgk' vs. lg[H 2 O]. The retention behaviors and retention mechanism of 15 kinds of small solutes and 6 kinds of proteins on 5 kinds HILIC columns with different ligands were investigated with SDM-R in typical range of water concentration in mobile phase. A good linear relationship between lgk' and lg[H 2 O] demonstrated that the most rational retention mechanism of solute in HILIC was a stoichiometric displacement process between solute and solvent molecules with water as displacing agents, which was not only valid for small solutes, but also could be used to explain the retention mechanism of biopolymers in HILIC. Comparing with the partition and adsorption models in HILIC, SDM-R was superior to them. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. Effect of solvents on relation of intensities of bands of luminescence spectra of terbium and dysprosium ions in solutions of their complexes with acetoacetic ester

    International Nuclear Information System (INIS)

    Kononenko, L.I.; Bel'tyukova, S.V.; Meshkova, S.B.; Kravchenko, T.B.; Poluehktov, N.S.

    1978-01-01

    An investigation is made of the effect of different solvents on the ratio of the intensity of luminescence spectrum bands of terbium and dysprosium ions, corresponding and not corresponding to ''supersensitive'' transitions in complex compounds with acetoacetic ether. A dependence is established between these values and the dielectric constant of the solvent, and also parallels in their changes, which indicate the similar manifestation of the effect of solvents in both elements. A correlation is observed between ratios of the intensity of luminescence spectrum bands and values of forces of neodymium complex absorption band oscillators in different solvents

  17. A Quantum Dot with Spin-Orbit Interaction--Analytical Solution

    Science.gov (United States)

    Basu, B.; Roy, B.

    2009-01-01

    The practical applicability of a semiconductor quantum dot with spin-orbit interaction gives an impetus to study analytical solutions to one- and two-electron quantum dots with or without a magnetic field.

  18. Language, interactivity and solution probing: repetition without repetition

    DEFF Research Database (Denmark)

    Cowley, Stephen; Nash, Luarina

    2013-01-01

    Recognition of the importance of autopoiesis to biological systems was crucial in building an alternative to the classic view of cognitive science. However, concepts like structural coupling and autonomy are not strong enough to throw light on language and human problem solving. The argument...... is presented though a case study where a person solves a problem and, in so doing relies on non-local aspects of the ecology as well as his observer's mental domain. Like Anthony Chemero we make links with ecological psychology to emphasize how embodiment draws on cultural resources as people concert thinking......, action and perception. We trace this to human interactivity or sense-saturated coordination that renders possible language and human forms of cognition: it links human sense-making to historical experience. People play roles with natural and cultural artifacts as they act, animate groups and live through...

  19. Interaction between two parallel plates covered with a polyelectrolyte brush layer in an electrolyte solution.

    Science.gov (United States)

    Ohshima, Hiroyuki

    An approximate analytic expression is derived for the interaction energy between two parallel plates covered with a polyelectrolyte brush layer in an electrolyte solution. The interaction energy has three components: electrostatic interaction energy between two brush layers before and after their contact, steric interaction energy between two brush layers after their contact, and the van der Waals interaction energy between the cores of the plates. It is shown that these three components are of the same order of magnitude and contribute equally to the total interaction energy between two polyelectrolyte-coated plates in an electrolyte solution. On the basis of Derjaguin's approximation, an approximate expression for the interaction energy between two spherical particles covered with polyelectrolyte brush layers is also derived.

  20. Solubility determination and thermodynamic modelling of allisartan isoproxil in different binary solvent mixtures from T = (278.15 to 313.15) K and mixing properties of solutions

    International Nuclear Information System (INIS)

    Yang, Yaoyao; Yang, Peng; Du, Shichao; Li, Kangli; Zhao, Kaifei; Xu, Shijie; Hou, Baohong; Gong, Junbo

    2016-01-01

    Highlights: • The solubility of allisartan isoproxil in binary solvent mixtures were determined. • Apelblat, CNIBS/R-K and Jouyban-Acree models were used to correlate the solubility. • Solubility parameter theory was used to explain the co-solvency phenomenon. • Regular mixing rules were used to calculate solubility parameter of binary solvents. • The mixing thermodynamics were calculated and discussed based on NRTL model. - Abstract: In this work, the solubility of allisartan isoproxil in binary solvent mixtures, including (acetone + water), (acetonitrile + water) and (methanol + water), was determined by a gravimetric method with the temperature ranging from (278.15 to 313.15) K at atmospheric pressure (p = 0.1 MPa). The solubility of allisartan isoproxil in three binary solvent mixtures all increased with the rising of temperature at a constant solvent composition. For the binary solvent mixtures of (methanol + water), the solubility increased with the increasing of methanol fraction, while it appeared maximum value at a certain solvent composition in the other two binary solvent mixtures (acetone + water and acetonitrile + water). Based on the theory of solubility parameter, Fedors method and two mixing rules were employed to calculate the solubility parameters, by which the proximity of solubility parameters between allisartan isoproxil and binary solvent mixtures explained the co-solvent phenomenon. Additionally, the modified Apelblat equation, CNIBS/R-K model and Jouyban-Acree model were used to correlate the solubility data in binary solvent mixtures, and it turned out that all the three correlation models could give a satisfactory result. Furthermore, the mixing thermodynamic properties were calculated based on NRTL model, which indicated that the mixing process was spontaneous and exothermic.

  1. Enthalpies of dilution of aqueous Li{sub 2}B{sub 4}O{sub 7} solutions at 298.15K and application of ion-interaction model

    Energy Technology Data Exchange (ETDEWEB)

    Yin Guoyin [Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Yao Yan [Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008 (China) and Graduate School of Chinese Academy of Sciences, Beijing 100039 (China)]. E-mail: yaoy@isl.ac.cn; Jiao Baojuan [Department of Chemistry, Northwest University, Xi' an 710069 (China); Chen Sanping [Department of Chemistry, Northwest University, Xi' an 710069 (China); Gao Shengli [Department of Chemistry, Northwest University, Xi' an 710069 (China)

    2005-09-15

    The enthalpies of dilution have been measured for aqueous Li{sub 2}B{sub 4}O{sub 7} solutions from 0.0212 to 2.1530molkg{sup -1} at 298.15K. The relative apparent molar enthalpies, L{sub {phi}}, and relative partial molar enthalpies of the solvent and solute, L-bar{sub 1} and L-bar{sub 2} were calculated. The thermodynamic properties of the complex aqueous solutions were represented with a modified Pitzer ion-interaction model.

  2. Pfaffian Solutions and Resonant Interaction Properties of a Coupled BKP Lattice

    International Nuclear Information System (INIS)

    Zhao Hai-Qiong; Yu Guo-Fu

    2014-01-01

    In this paper, we give a coupled lattice equation with the help of Hirota operators, which comes from a special BKP lattice. Two-soliton and three-soliton solutions to the coupled system are constructed. Furthermore, resonant interaction of the two-soliton solution is analyzed in detail. Under some special resonant condition, it is shown that low soliton can propagate faster than high one. Finally, the N-soliton solution is presented in the Pfaffian form. (general)

  3. High throughput research and evaporation rate modeling for solvent screening for ethylcellulose barrier membranes in pharmaceutical applications.

    Science.gov (United States)

    Schoener, Cody A; Curtis-Fisk, Jaime L; Rogers, True L; Tate, Michael P

    2016-10-01

    Ethylcellulose is commonly dissolved in a solvent or formed into an aqueous dispersion and sprayed onto various dosage forms to form a barrier membrane to provide controlled release in pharmaceutical formulations. Due to the variety of solvents utilized in the pharmaceutical industry and the importance solvent can play on film formation and film strength it is critical to understand how solvent can influence these parameters. To systematically study a variety of solvent blends and how these solvent blends influence ethylcellulose film formation, physical and mechanical film properties and solution properties such as clarity and viscosity. Using high throughput capabilities and evaporation rate modeling, thirty-one different solvent blends composed of ethanol, isopropanol, acetone, methanol, and/or water were formulated, analyzed for viscosity and clarity, and narrowed down to four solvent blends. Brookfield viscosity, film casting, mechanical film testing and water permeation were also completed. High throughput analysis identified isopropanol/water, ethanol, ethanol/water and methanol/acetone/water as solvent blends with unique clarity and viscosity values. Evaporation rate modeling further rank ordered these candidates from excellent to poor interaction with ethylcellulose. Isopropanol/water was identified as the most suitable solvent blend for ethylcellulose due to azeotrope formation during evaporation, which resulted in a solvent-rich phase allowing the ethylcellulose polymer chains to remain maximally extended during film formation. Consequently, the highest clarity and most ductile films were formed. Employing high throughput capabilities paired with evaporation rate modeling allowed strong predictions between solvent interaction with ethylcellulose and mechanical film properties.

  4. Determination of the interaction parameter and topological scaling features of symmetric star polymers in dilute solution

    KAUST Repository

    Rai, Durgesh K.; Beaucage, Gregory; Ratkanthwar, Kedar; Beaucage, Peter; Ramachandran, Ramnath; Hadjichristidis, Nikolaos

    2015-01-01

    Star polymers provide model architectures to understand the dynamic and rheological effects of chain confinement for a range of complex topological structures like branched polymers, colloids, and micelles. It is important to describe the structure of such macromolecular topologies using small-angle neutron and x-ray scattering to facilitate understanding of their structure-property relationships. Modeling of scattering from linear, Gaussian polymers, such as in the melt, has applied the random phase approximation using the Debye polymer scattering function. The Flory-Huggins interaction parameter can be obtained using neutron scattering by this method. Gaussian scaling no longer applies for more complicated chain topologies or when chains are in good solvents. For symmetric star polymers, chain scaling can differ from ν=0.5(df=2) due to excluded volume, steric interaction between arms, and enhanced density due to branching. Further, correlation between arms in a symmetric star leads to an interference term in the scattering function first described by Benoit for Gaussian chains. In this work, a scattering function is derived which accounts for interarm correlations in symmetric star polymers as well as the polymer-solvent interaction parameter for chains of arbitrary scaling dimension using a hybrid Unified scattering function. The approach is demonstrated for linear, four-arm and eight-arm polyisoprene stars in deuterated p-xylene.

  5. Determination of the interaction parameter and topological scaling features of symmetric star polymers in dilute solution

    KAUST Repository

    Rai, Durgesh K.

    2015-07-15

    Star polymers provide model architectures to understand the dynamic and rheological effects of chain confinement for a range of complex topological structures like branched polymers, colloids, and micelles. It is important to describe the structure of such macromolecular topologies using small-angle neutron and x-ray scattering to facilitate understanding of their structure-property relationships. Modeling of scattering from linear, Gaussian polymers, such as in the melt, has applied the random phase approximation using the Debye polymer scattering function. The Flory-Huggins interaction parameter can be obtained using neutron scattering by this method. Gaussian scaling no longer applies for more complicated chain topologies or when chains are in good solvents. For symmetric star polymers, chain scaling can differ from ν=0.5(df=2) due to excluded volume, steric interaction between arms, and enhanced density due to branching. Further, correlation between arms in a symmetric star leads to an interference term in the scattering function first described by Benoit for Gaussian chains. In this work, a scattering function is derived which accounts for interarm correlations in symmetric star polymers as well as the polymer-solvent interaction parameter for chains of arbitrary scaling dimension using a hybrid Unified scattering function. The approach is demonstrated for linear, four-arm and eight-arm polyisoprene stars in deuterated p-xylene.

  6. Interaction of derived polymers from pyrrole with biocompatible solutions

    International Nuclear Information System (INIS)

    Lopez G, O. G.

    2010-01-01

    This work presents a study about the synthesis by plasma, the electric properties and superficial interaction of polymers derived from pyrrole doped with Iodine with potential use as bio material. Poly-pyrrole is a semiconductor and biocompatible polymer with potential application in the development of artificial muscles and implants where the electric interaction between cells and material is an important variable. The syntheses were made at 13.5 MHz in a glass tubular reactor of 1500 cm 3 with electrodes of 6.5 cm diameter and stainless steel flanges. An electrode was connected to the RF terminal of the power supply that is combined with a matching coupling resistance. The monomer and dopant used in this work were pyrrole and Iodine respectively, in closed containers. They were vaporized and injected separately into the reactor at room temperature and 0.1 mbar. The vapors of the reagents mixed freely in the reactor. The synthesis time was 240 min at 40, 60, 80 and 100 W. The polymers were obtained as thin films adhered to the reactor walls. The films were washed and swollen with distilled water and removed from the reactor walls with a small spatula. The polymers were irradiated with gamma rays at 18 and 22 KGy. Due to the fact that the doses are cumulative, the final dose applied was 40 KGy. The polymers characterization was carried out by Fourier Transform Infrared Spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy, contact angle, electrical conductivity and X-ray diffraction. The analyses indicates that the polymers have very similar structure in almost the entire power range, showing C-O, C=C, C-H, O-H, N-H bonds with a predominantly amorphous structure. The TGA analyses showed that the material has 4 or 5 loses of material. The first one starts after that 115 C except for the material irradiated at 40 KGy, this one begins in 87 C, the second one is in the interval of 196 and 295 C, the third one between 311 and 500 C, and the last

  7. Interaction between tetracycline and smectite in aqueous solution.

    Science.gov (United States)

    Li, Zhaohui; Chang, Po-Hsiang; Jean, Jiin-Shuh; Jiang, Wei-Teh; Wang, Chih-Jen

    2010-01-15

    The fate and transport of commonly used antibiotics in soil and groundwater have attracted renewed studies due to increased sensitivities of analytical instruments and thus frequent detections of these compounds even in treated wastewater. Smectite, an important soil component, has large surface area and high cation exchange capacity, while tetracycline (TC) can exist in different forms and charges under different pH conditions. Thus, the interaction between smectite and TC in aqueous systems is of great importance. This research focused on elucidating the mechanisms of TC uptake by smectite, in terms of TC adsorption, cation desorption, and pH changes associated with TC adsorption by smectite and intercalation in smectite. TC adsorption onto smectite was a relatively fast process even though most of the adsorption sites were in the interlayer position involved in intercalation as confirmed by the expansion of d(001) spacing. The TC adsorption capacity was equivalent to 0.74-1.11 times the cation exchange capacity for three of the four smectite minerals studied. Accompanying TC adsorption was simultaneous adsorption of H(+), resulting in protonation of TC on the dimethylamine group. At higher TC input concentrations further adsorption of H(+) resulted in the ratio of H(+) adsorbed to TC adsorbed greater than one, suggesting that additionally adsorbed H(+) could serve as counterions to partially offset the negative charges on the tricarbonyl or phenolic diketone functional groups. The positive correlations between cations desorbed and TC adsorbed, as well as TC adsorbed and H(+) adsorbed, provided a first time evidence to confirm cation exchange as the main mechanism of TC uptake, even under neutral pH conditions.

  8. Behaviour of ruthenium (3) bromocomplexes in nonaqueous solvents

    International Nuclear Information System (INIS)

    Rudnitskaya, O.V.; Miroshnichenko, I.V.; Pichkov, V.N.

    1989-01-01

    Behaviour of K 3 [RuBr 6 ] · H 2 O and K 3 [Ru 2 Br 9 ] in solutions of dimethylsulfoxide and dimethylformamide is investigated by absorption and ESR spectroscopy. Complexes are shown to be labile in solutions, interact easily with solvents. Formation of ruthenium (3) and (2) bromide-dimethylsulfoxide complexes occurs gradually in DMSO, final product is trans-[Ru(DMSO) 4 Br 2

  9. Ultrafast spontaneous emission modulation of graphene quantum dots interacting with Ag nanoparticles in solution

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Jianwei [Department of Physics, Shanghai University, Shanghai 200444 (China); Research Center of Quantum Macro-Phenomenon and Application, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (China); Lu, Jian, E-mail: luj@sari.ac.cn; Wang, Zhongyang, E-mail: wangzy@sari.ac.cn [Research Center of Quantum Macro-Phenomenon and Application, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (China); Wang, Liang [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Institute of Nanochemistry and Nanobiology, Shanghai University, Shanghai 200444 (China); Tian, Linfan [Research Center of Quantum Macro-Phenomenon and Application, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (China); School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210 (China); Deng, Xingxia [Research Center of Quantum Macro-Phenomenon and Application, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210 (China); School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Tian, Lijun [Department of Physics, Shanghai University, Shanghai 200444 (China); Pan, Dengyu [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China)

    2016-07-11

    We investigated the strong interaction between graphene quantum dots and silver nanoparticles in solution using time-resolved photoluminescence techniques. In solution, the silver nanoparticles are surrounded by graphene quantum dots and interacted with graphene quantum dots through exciton-plasmon coupling. An ultrafast spontaneous emission process (lifetime 27 ps) was observed in such a mixed solution. This ultrafast lifetime corresponds to the emission rate exceeding 35 GHz, with the purcell enhancement by a factor of ∼12. These experiment results pave the way for the realization of future high speed light sources applications.

  10. Hydrophobic interactions between polymethacrylic acid and sodium laureth sulfate in aqueous solutions

    Science.gov (United States)

    Yaremko, Z. M.; Fedushinskaya, L. B.; Burka, O. A.; Soltys, M. N.

    2014-09-01

    The role of hydrophobic interaction in the development of associative processes is demonstrated, based on the concentration dependences of the viscosity and pH of binary solutions of polymethacrylic acid as an anionic polyelectrolyte and sodium laureth sulfate as an anionic surfactant. It is found that the inflection point on the dependence of the difference between the pH values of binary solutions of polymethacrylic acid and sodium laureth sulfate on the polyelectrolyte concentration is a criterion for determining the predominant contribution from hydrophobic interaction, as is the inflection point on the dependence of pH of individual solutions of polymethacrylic acid on the polyelectrolyte concentration.

  11. Towards a Model of Human Resource Solutions for Achieving Intergenerational Interaction in Organisations

    Science.gov (United States)

    McGuire, David; By, Rune Todnem; Hutchings, Kate

    2007-01-01

    Purpose: Achieving intergenerational interaction and avoiding conflict is becoming increasingly difficult in a workplace populated by three generations--Baby Boomers, Generation X-ers and Generation Y-ers. This paper presents a model and proposes HR solutions towards achieving co-operative generational interaction. Design/methodology/approach:…

  12. Interaction between bacteriophage and pyrophyllite clay in aqueous solution

    Science.gov (United States)

    Park, Jeong-Ann; Kim, Jae-Hyun; Kang, Jin-Kyu; Son, Jeong-Woo; Yi, In-Geol; Kim, Song-Bae

    2014-05-01

    Viral contamination results in a degradation in drinking water quality and a threat to public health. Toprovide safe drinking water, water treatment alternatives using various adsorbents and filter media such as activated carbon, bituminous coal, quartz sand and clay have been considered. Pyrophyllite is a 2:1 clay mineral having dioctahedral layer structure with octahedrally coordinated Al ion sheets between two sheets of SiO4 tetrahedra. It is a hydrous aluminosilicate clay with the chemical composition AlSi2O5(OH). Pyrophyllite has recently been investigated as a potential low-cost and environmental friendly adsorbent for removing various contaminants. The aim of this study was to investigate the removal of the bacteriophage MS2 from aqueous solution using pyrophyllite. Batch experiments were conducted to examine the MS2 sorption to pyrophyllite. The influence of fluoride, a groundwater contaminant, on the removal of MS2 was also observed. Batch results demonstrated that pyrophyllite was effective in MS2 removal. The percent removal increased from 5.26% to 99.99% (= 4.0 log removal) as the pyrophyllite concentrations increased from 0.2 to 20 g/L. More than 99% of MS2 could be removed with a pyrophyllite concentration of ≥ 4 g/L. The sorption of MS2 to pyrophyllite was rapid. Within 15 min, approximately 99.98% (= 3.7 log removal) of MS2 was attained. More than 4.0 log removal was achieved after 180 min. The experimental data were analyzed with the pseudo first-order and pseudo second-order kinetic models. The correlation coefficient showed that pseudo second-order model was better than pseudo first-order model at describing the kinetic data. The amount of MS2 removed at equilibrium was determined to be 1.43 × 108 pfu/g from the pseudo second-order model. The experimental data were also analyzed with the Freundlich and Langmuir isotherm models. The correlation coefficients showed that the Langmuir model was more suitable than the Freundlich model for MS2

  13. Note: Nonpolar solute partial molar volume response to attractive interactions with water.

    Science.gov (United States)

    Williams, Steven M; Ashbaugh, Henry S

    2014-01-07

    The impact of attractive interactions on the partial molar volumes of methane-like solutes in water is characterized using molecular simulations. Attractions account for a significant 20% volume drop between a repulsive Weeks-Chandler-Andersen and full Lennard-Jones description of methane interactions. The response of the volume to interaction perturbations is characterized by linear fits to our simulations and a rigorous statistical thermodynamic expression for the derivative of the volume to increasing attractions. While a weak non-linear response is observed, an average effective slope accurately captures the volume decrease. This response, however, is anticipated to become more non-linear with increasing solute size.

  14. Note: Nonpolar solute partial molar volume response to attractive interactions with water

    Energy Technology Data Exchange (ETDEWEB)

    Williams, Steven M.; Ashbaugh, Henry S., E-mail: hanka@tulane.edu [Department of Chemical and Biomolecular Engineering, Tulane University, New Orleans, Louisiana 70118 (United States)

    2014-01-07

    The impact of attractive interactions on the partial molar volumes of methane-like solutes in water is characterized using molecular simulations. Attractions account for a significant 20% volume drop between a repulsive Weeks-Chandler-Andersen and full Lennard-Jones description of methane interactions. The response of the volume to interaction perturbations is characterized by linear fits to our simulations and a rigorous statistical thermodynamic expression for the derivative of the volume to increasing attractions. While a weak non-linear response is observed, an average effective slope accurately captures the volume decrease. This response, however, is anticipated to become more non-linear with increasing solute size.

  15. Studies on the interactions of diglycine and triglycine with polyethylene glycol 400 in aqueous solutions by density and ultrasound speed measurements

    International Nuclear Information System (INIS)

    Sahin, Melike; Ayranci, Erol

    2013-01-01

    Highlights: ► Di- and tri-glycine in aqueous PEG400 solutions were investigated thermodynamically. ► Density and ultrasound speed of glycine oligomer-PEG400-water systems were measured. ► Apparent molar volumes and isentropic compressions were calculated. ► Apparent molar isobaric expansions were derived. ► Results were interpreted in terms of water–glycine oligomer-PEG400 interactions. -- Abstract: Density and ultrasound speed were measured accurately for diglycine + water, triglycine + water, diglycine + water-polyethylene glycol 400 (PEG400) and triglycine + water-PEG400 solutions at T = (293.15, 298.15, 303.15 and 308.15) K. The results were used in evaluating thermodynamic properties as apparent molar volumes (V Ø ) and apparent molar isentropic compressions (K SΦ ) of diglycine and triglycine in water and in PEG400 solutions. Infinite dilution values of these parameters, V o Ø , and K o SΦ , were obtained from their plots as a function of molality by extrapolation and have been utilized in obtaining transfer volumes and transfer compressions at infinite dilution. All transfer volumes and transfer compressions were found to increase with increasing molality of PEG400. Apparent molar isobaric expansions were derived from the temperature dependence of V Ø values at infinite dilution and at finite concentrations. All the results were interpreted in terms of solute (diglycine or triglycine) and co-solute (PEG400) and solvent (H 2 O) interactions

  16. Study of the solvent effects on the molecular structure and Cdbnd O stretching vibrations of flurbiprofen

    Science.gov (United States)

    Tekin, Nalan; Pir, Hacer; Sagdinc, Seda

    2012-12-01

    The effects of 15 solvents on the C=O stretching vibrational frequency of flurbiprofen (FBF) were determined to investigate solvent-solute interactions. Solvent effects on the geometry and C=O stretching vibrational frequency, ν(C=O), of FBF were studied theoretically at the DFT/B3LYP and HF level in combination with the polarizable continuum model and experimentally using attenuated total reflection infrared spectroscopy (ATR-IR). The calculated C=O stretching frequencies in the liquid phase are in agreement with experimental values. Moreover, the wavenumbers of ν(C=O) of FBF in different solvents have been obtained and correlated with the Kirkwood-Bauer-Magat equation (KBM), the solvent acceptor numbers (ANs), and the linear solvation energy relationships (LSERs). The solvent-induced stretching vibrational frequency shifts displayed a better correlation with the LSERs than with the ANs and KBM.

  17. Molecular-scale hydrophobic interactions between hard-sphere reference solutes are attractive and endothermic.

    Science.gov (United States)

    Chaudhari, Mangesh I; Holleran, Sinead A; Ashbaugh, Henry S; Pratt, Lawrence R

    2013-12-17

    The osmotic second virial coefficients, B2, for atomic-sized hard spheres in water are attractive (B2 attractive with increasing temperature (ΔB2/ΔT attractive and endothermic at moderate temperatures. Hydrophobic interactions between atomic-sized hard spheres in water are more attractive than predicted by the available statistical mechanical theory. These results constitute an initial step toward detailed molecular theory of additional intermolecular interaction features, specifically, attractive interactions associated with hydrophobic solutes.

  18. Massive bosons interacting with gravity: No standard solutions in Robertson-Walker space-time

    International Nuclear Information System (INIS)

    Zecca, A.

    2009-01-01

    The problem of the interaction of boson and gravitational field is formulated in the Robertson-Walker space-time. It consist the simultaneous solution of the boson and of the Einstein field equation whose source is the energy momentum tensor of the boson field. By direct verification it is shown that the problem does not admit solutions in the class of massive standard solutions, previously determined, of the boson field equation. Also there cannot be solutions, in case of massive interacting boson, that are superpositions of standard solutions. The case of massless boson field is left open. The result is essentially due to the very special form of the Einstein tensor in Robertson-Walker metric.

  19. Caffeine and Sugars Interact in Aqueous Solutions: A Simulation and NMR Study

    OpenAIRE

    Tavagnacco, Letizia; Engström, Olof; Schnupf, Udo; Saboungi, Marie-Louise; Himmel, Michael; Widmalm, Göran; Cesàro, Attilio; Brady, John W.

    2012-01-01

    Molecular dynamics simulations were carried out on several systems of caffeine interacting with simple sugars. These included a single caffeine molecule in a 3 molal solution of α-D-glucopyranose, at a caffeine concentration of 0.083 molal; a single caffeine in a 3 molal solution of β-D-glucopyranose, and a single caffeine molecule in a 1.08 molal solution of sucrose (table sugar). Parallel Nuclear Magnetic Resonance titration experiments were carried out on the same solutions under similar c...

  20. Solvent substitutes

    International Nuclear Information System (INIS)

    Evanoff, S.P.

    1995-01-01

    The environmental and industrial hygiene regulations promulgated since 1980, most notably the Superfund Amendments and Reauthorization Act (SARA), the Hazardous and Solid Waste Amendments to the Resources Conservation and Recovery Act (RCRA), and the Clean Air Act Amendments of 1990, have brought about an increased emphasis on user exposure, hazardous waste generation, and air emissions. As a result, industry is performing a fundamental reassessment of cleaning solvents, processes, and procedures. The more progressive organizations have made their goal the elimination of solvents that may pose significant potential human health and environmental hazards. This chapter discusses solvent cleaning in metal-finishing, metal-manufacturing, and industrial maintenance applications; precision cleaning; and electronics manufacturing. Nonmetallic cleaning, adhesives, coatings, inks, and aerosols also will be addressed, but in a more cursory manner

  1. Solution and gas phase evidence of anion binding through the secondary bonding interactions of a bidentate bis-antimony(iii) anion receptor.

    Science.gov (United States)

    Qiu, J; Song, B; Li, X; Cozzolino, A F

    2017-12-20

    The solution and gas phase halide binding to a bis-antimony(iii) anion receptor was studied. This new class of anion receptors utilizes the strong Sb-centered secondary bonding interactions (SBIs) that are formed opposite to the polar Sb-O primary bond. 1 H NMR titration data were fitted statistically to binding models and solution-phase binding energetics were extracted, while the formation of anion-to-receptor complexes was observed using ESI-MS. Density functional theory calculations suggest that their affinity towards binding halide anions is mitigated by the strong explicit solvation effect in DMSO, which gives insights into future designs that circumvent direct solvent binding and are anticipated to yield tighter and perhaps more selectivity in anion binding.

  2. Acetone-based cellulose solvent.

    Science.gov (United States)

    Kostag, Marc; Liebert, Tim; Heinze, Thomas

    2014-08-01

    Acetone containing tetraalkylammonium chloride is found to be an efficient solvent for cellulose. The addition of an amount of 10 mol% (based on acetone) of well-soluble salt triethyloctylammonium chloride (Et3 OctN Cl) adjusts the solvent's properties (increases the polarity) to promote cellulose dissolution. Cellulose solutions in acetone/Et3 OctN Cl have the lowest viscosity reported for comparable aprotic solutions making it a promising system for shaping processes and homogeneous chemical modification of the biopolymer. Recovery of the polymer and recycling of the solvent components can be easily achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The local phase transitions of the solvent in the neighborhood of a solvophobic polymer at high pressures

    Energy Technology Data Exchange (ETDEWEB)

    Budkov, Yu. A., E-mail: urabudkov@rambler.ru [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation); National Research University Higher School of Economics, Moscow (Russian Federation); Department of Chemistry, Lomonosov Moscow State University, Moscow (Russian Federation); Vyalov, I. I. [Istituto Italiano di Tecnologia, via Morego 30, Genova 16163 (Italy); Kolesnikov, A. L. [Ivanovo State University, Ivanovo (Russian Federation); Institut für Nichtklassische Chemie e.V., Universitat Leipzig, Leipzig (Germany); Georgi, N., E-mail: bancocker@mail.ru [Max Planck Institute for Mathematics in the Sciences, Leipzig (Germany); Chuev, G. N. [Max Planck Institute for the Physics of Complex Systems, Dresden (Germany); Institute of Theoretical and Experimental Biophysics, Russian Academy of Science, Pushchino, Moscow Region (Russian Federation); Kiselev, M. G. [G.A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation); Department of Chemistry, Lomonosov Moscow State University, Moscow (Russian Federation)

    2014-11-28

    We investigate local phase transitions of the solvent in the neighborhood of a solvophobic polymer chain which is induced by a change of the polymer-solvent repulsion and the solvent pressure in the bulk solution. We describe the polymer in solution by the Edwards model, where the conditional partition function of the polymer chain at a fixed radius of gyration is described by a mean-field theory. The contributions of the polymer-solvent and the solvent-solvent interactions to the total free energy are described within the mean-field approximation. We obtain the total free energy of the solution as a function of the radius of gyration and the average solvent number density within the gyration volume. The resulting system of coupled equations is solved varying the polymer-solvent repulsion strength at high solvent pressure in the bulk. We show that the coil-globule (globule-coil) transition occurs accompanied by a local solvent evaporation (condensation) within the gyration volume.

  4. Influence of hydroxypropylmethyl cellulose-sodium laurylsulfate interaction on rheological properties of the solution

    Directory of Open Access Journals (Sweden)

    Šaletić Jelena V.

    2004-01-01

    Full Text Available Interactions between the polymers and surfactants in solution have widely been investigated because of their scientific and technological importance. These interactions can be utilized to modify the physicochemical properties of system in many food products, pharmaceutical formulations, personal care products, paints, pesticides, etc. Interaction between nonionic polymer - hydroxypropylmethyl cellulose (HPMC and anionic surfactant - sodium laurylsulfate (SDS in solution has been investigated in this paper by rheological measurements. Rheological measurements are performed by rotational viscometer at 20°C and changes of rheological characteristics of HPMC solutions (0.5-1.5% with increasing SDS concentrations (0-4.0% were determined. The results of these investigations showed that viscosity of the solution is dependant on HPMC-SDS interaction. At particular SDS concentration viscosity increases, reach maximum and after that decreases until reach constant value. From the viscosity changes the characteristic concentrations of SDS, critical aggregation concentration (cac and polymer saturation point (psp, were determined. These concentrations are in linear relationships with HPMC concentrations. Rheological properties of the solution are strong influenced by HPMC-SDS interaction and exhibits more or less pronounced pseudoplastic behavior, which changes to Newtonian one after the psp has been reached.

  5. Validation of a UV Spectrometric Method for the Assay of Tolfenamic Acid in Organic Solvents

    Directory of Open Access Journals (Sweden)

    Sofia Ahmed

    2015-01-01

    Full Text Available The present study has been carried out to validate a UV spectrometric method for the assay of tolfenamic acid (TA in organic solvents. TA is insoluble in water; therefore, a total of thirteen commonly used organic solvents have been selected in which the drug is soluble. Fresh stock solutions of TA in each solvent in a concentration of 1 × 10−4 M (2.62 mg% were prepared for the assay. The method has been validated according to the guideline of International Conference on Harmonization and parameters like linearity, range, accuracy, precision, sensitivity, and robustness have been studied. Although the method was found to be efficient for the determination of TA in all solvents on the basis of statistical data 1-octanol, followed by ethanol and methanol, was found to be comparatively better than the other studied solvents. No change in the stock solution stability of TA has been observed in each solvent for 24 hours stored either at room (25±1°C or at refrigerated temperature (2–8°C. A shift in the absorption maxima has been observed for TA in various solvents indicating drug-solvent interactions. The studied method is simple, rapid, economical, accurate, and precise for the assay of TA in different organic solvents.

  6. Meeting on Solute/Solvent Interactions Held in Aberdeen Proving Ground, Maryland on May 29-30, 1991

    Science.gov (United States)

    1992-01-01

    the magnitudes of the nuclear charges and therefore cannot be assumed to indicate relative reactivities toward nucleophiles. There is accordingly no...APPENDIX 3 ORGANIZATIONS OF AUTHORS IN THESE PROCEEDINGS Central Michigan University 49 Instituto de Quimica Fisica 33 La Sierra University, Riverside 71...Aberdeen Proving Gd, MD Joxe-Luis Abbud Christopher Cramer Instituto de Quimica Fisica SMCCR-RSP-C "Rocasolano" U.S. Army Chemical RD&E Center Conajo

  7. Thermodynamic functions for solubility of 3-nitro-o-toluic acid in nine organic solvents from T = (283.15 to 318.15) K and apparent thermodynamic properties of solutions

    International Nuclear Information System (INIS)

    Li, Xinbao; Wang, Mingju; Du, Cunbin; Cong, Yang; Zhao, Hongkun

    2017-01-01

    Highlights: • Solubilities of 3-nitro-o-toluic acid in nine organic solvents were determined. • The solubilities were correlated by using four thermodynamic models. • The mixing properties of solution were computed based on Wilson model. - Abstract: Separation of 3-nitro-o-toluic acid from its isomeric mixtures has essential significance in industry. In this work, by using isothermal saturation method, the solid-liquid equilibrium for 3-nitro-o-toluic acid in nine organic solvents (acetonitrile, methanol, ethanol, n-propanol, isopropanol, ethyl acetate, acetone, 1,4-dioxane and 2-butanone) were obtained experimentally within a temperature range from (283.15 to 318.15) K under atmosphere pressure of 101.2 kPa, and the solubility values of 3-nitro-o-toluic acid in these solvents were determined by a high-performance liquid chromatography. Within the studied temperature range, the mole fraction solubility of 3-nitro-o-toluic acid in selected organic solvents increased with increasing temperature. Except for ethyl acetate, the descending order of the mole fraction solubility values were as follow: 1,4-dioxane > acetone > 2-butanone > methanol > ethanol > isopropanol > n-propanol > acetonitrile. The solubility values determined for 3-nitro-o-toluic acid in the selected solvents were correlated and back calculated with the modified Apelblat equation, λh equation, Wilson model and NRTL model. The largest values of RAD and RMSD obtained with the four models were 0.67% and 4.02 × 10 −4 , respectively. In general, the four thermodynamic models were all acceptable for describing the solubility behaviour of 3-nitro-o-toluic acid in these solvents. In addition, the apparent mixing Gibbs energy, mixing enthalpy, mixing entropy, activity coefficient at infinitesimal concentration and reduced excess enthalpy were calculated. The acquired solubility data and thermodynamic studies would be very important in optimizing the separation process of 3-nitro-o-toluic acid from

  8. On the solubility of nicotinic acid and isonicotinic acid in water and organic solvents

    International Nuclear Information System (INIS)

    Abraham, Michael H.; Acree, William E.

    2013-01-01

    Highlights: ► Solubilities of nicotinic acid and isonicotinic acids in organicsolvents have been determined. ► Solubilities are used to calculate Abraham descriptors for the two acids. ► These descriptors then yield water-solvent and gas-solvent partitions into numerous solvents. ► The solubility of the neutral acids in water is obtained. ► The method is straightforward and can be applied to any set of compound solubilities. -- Abstract: We have determined the solubility of nicotinic acid in four solvents and the solubility of isonicotinic acid in another four solvents. These results, together with literature data on the solubility of nicotinic acid in five other organic solvents and isonicotinic acid in four other organic solvents, have been analyzed through two linear Gibbs energy relationships in order to extract compound properties, or descriptors, that encode various solute–solvent interactions. The descriptors for nicotinic acid and isonicotinic acid can then be used in known equations for partition of solutes between water and organic solvents to predict partition coefficients and then further solubility in a host of organic solvents, as well as to predict a number of other physicochemical properties

  9. Organic solvents improve hydrocarbon desorption and biodegradation in highly contaminated weathered soils

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Rivero, M. [Tecnologico de Estudios Superiores de Ecatepec, Mexico City (Mexico); Saucedo-Casteneda, G.; Gutierrez-Rojas, M. [Autonoma Metropolitan Univ., Mexico City (Mexico). Dept. of Biotechnology

    2007-07-15

    A toluene-based microbial slurry phase system was used to remediate hydrocarbons (HC) in highly contaminated soil samples collected from a site next to a working refinery in Mexico. Initial HC concentrations of the samples were 237.2 {+-} 16,6 g kg{sup -1} in dry soil. The microbial consortium consisted of 10 different strains in a mineral solution. Non-polar solvents used in the phase system included hexane, benzene, and toluene. Polar solvents included n-butanol, acetone, and methanol. The bioavailability of the HCs was increased using both polar and nonpolar solvents in order to promote desorption from the soil and to enhance overall HC biodegradation. HC desorption was analyzed in an abiotic system. Respiration and residual HCs were examined after a period of 30 days in order to compare the effects of the 2 solvents. The biodegradation extracts were then fractionated in a silica gel column to determine if the solvents actually enhanced the biodegradation of specific HC fractions. The study showed that induced dipole interactions forces resulted when nonpolar molecules were dissolved into a nonpolar solvent. Results for desorption and solubility varied among the 6 solvents. Higher dielectric constants resulted in higher solubility and desorption of HCs for nonpolar solvents, while the opposite effect was observed for polar solvents. It was concluded that toluene produced better biodegradation results than any of the milder solvents. 34 refs., 4 tabs., 1 fig.

  10. Interaction mode and nanoparticle formation of bovine serum albumin and anthocyanin in three buffer solutions

    International Nuclear Information System (INIS)

    Zhou, Rui; Dong, Xueyan; Song, Lanlan; Jing, Hao

    2014-01-01

    Investigation of interaction mode of bovine serum albumin (BSA) and anthocyanin (ACN) in different solutions will help us understand the interaction mechanism and functional change of bioactive small molecule and biomacromolecule. This study investigated the binding mode, including binding constant, number of binding sites, binding force of BSA and ACN interaction in three buffer solutions of phosphate (PBS), sodium chloride (NaCl), and PBS-NaCl, using fluorescence spectroscopy and synchronous fluorescence spectroscopy. Formation and characteristics of BSA–ACN complex were also investigated using dynamic light scattering (DLS) and transmission electron microscopy (TEM). The results showed that ACN could interact with BSA at both tyrosine (Tyr) and tryptophan (Trp) residues through both hydrogen bonds and van der Waals force, and the same binding mode was seen in dH 2 O and three buffer solutions. The value of binding constant K was decreased as the temperature increased from 298 K to 308 K, and the decreasing degree was in the order of dH 2 O (9.0×10 4 )>NaCl (2.64×10 4 )/PBS (2.37×10 4 )>PBS-NaCl (0.88×10 4 ), which was inversely correlated with the ionic strength of the buffer solutions of PBS-NaCl>NaCl>PBS. It indicated that stability of BSA–ACN complex was affected most in dH 2 O than in three buffer solutions. The BSA and ACN interaction led to formation of BSA–ACN nanoparticles. The sizes of BSA–ACN nanoparticles in dH 2 O were smaller than that in three buffer solutions, which correlated with stronger binding force between BSA and ACN in dH 2 O than in three buffer solutions at room temperature (25 °C, 298 K). - Highlights: • We report the influences of four solutions on the BSA–ACN interaction. • We report the relationship between BSA–ACN interaction and particle size of complex. • The stability of BSA–ACN complex was affected most in dH 2 O than in buffer solutions

  11. Molecular Theory and the Effects of Solute Attractive Forces on Hydrophobic Interactions.

    Science.gov (United States)

    Chaudhari, Mangesh I; Rempe, Susan B; Asthagiri, D; Tan, L; Pratt, L R

    2016-03-03

    The role of solute attractive forces on hydrophobic interactions is studied by coordinated development of theory and simulation results for Ar atoms in water. We present a concise derivation of the local molecular field (LMF) theory for the effects of solute attractive forces on hydrophobic interactions, a derivation that clarifies the close relation of LMF theory to the EXP approximation applied to this problem long ago. The simulation results show that change from purely repulsive atomic solute interactions to include realistic attractive interactions diminishes the strength of hydrophobic bonds. For the Ar-Ar rdfs considered pointwise, the numerical results for the effects of solute attractive forces on hydrophobic interactions are opposite in sign and larger in magnitude than predicted by LMF theory. That comparison is discussed from the point of view of quasichemical theory, and it is suggested that the first reason for this difference is the incomplete evaluation within LMF theory of the hydration energy of the Ar pair. With a recent suggestion for the system-size extrapolation of the required correlation function integrals, the Ar-Ar rdfs permit evaluation of osmotic second virial coefficients B2. Those B2's also show that incorporation of attractive interactions leads to more positive (repulsive) values. With attractive interactions in play, B2 can change from positive to negative values with increasing temperatures. This is consistent with the puzzling suggestions of decades ago that B2 ≈ 0 for intermediate cases of temperature or solute size. In all cases here, B2 becomes more attractive with increasing temperature.

  12. Interaction of Fe(II) with Polyacrylic Acid as a Simplification of Humic Acid: Comparison of Ion Exchange and Solvent Extraction Methods

    International Nuclear Information System (INIS)

    Budi Setiawan

    2007-01-01

    To estimate the safety assessment around the disposal facility, the interaction behavior of radionuclides/metal ions into organic material (such as humic acids) exist in natural water becomes an important study. To avoid the effect of heterogeneous composition of humic acid, polyacrylic acids (abbrev. APA) was used as are representative of homogeneous polymeric weak acid. The experiments have been carried out by solvent extraction and ion exchange methods to find out the suitable method for the study of complex formation of Fe(II) with humic acid(AH) and APA. The solvent extraction experiment has been done by using diphenylthiocarbazone (dithizone) in CCl 4 and C Fe(II) were 10 -8 M to 10 -5 M, pH around 5 and I=0.1M NaCI. In ionic exchange experiment, C Fe(II) were 10 -8 to 10 -4 M, pH from 4.8 to 5.5 in I=0.1M NaCl. The apparent complex formation constant is defined as β α = [ML]/([M][R]), where [M] and [ML] are concentration of free and bound of Fe(II) and [R] is the concentration of dissociated carboxylic group in macromolecules of PAA. The results shown that, for solvent extraction experiments, variable concentration of Fe(II) had no appreciable influence on the distribution ratio of Fe(II)-polyacrylate at the tracer concentration with the log D to be 1.32 ± 0.03 (pcH 5.25). At macro concentration, the distribution ratio of Fe(II) becomes smaller due to oxidation and obtained log D value to be 1.04 ± 0.07 (pcH 5.34). An interest kind was observed at higher PAA concentration, the distribution ratio curve becomes higher presumably due to the problem on redox sensitive characteristic of Fe(II) and/or coagulation of Fe(II)-polyacrylate at the interface of aqueous-organic phases. In case of ionic exchange method, the plot of I/Kd versus [R] gives a straight line result indicating this method is appropriate and more superior compare than solvent extraction method to determine the complex formation constant. (author)

  13. Interaction of cadmium and indium nitrate mixture with sodium tungstate in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Belousova, E E; Krivobok, V I; Gruba, A I [Donetskij Gosudarstvennyj Univ. (Ukrainian SSR)

    1982-01-01

    The interaction of the mixture of cadmium and indium nitrates with sodium tungstate in aqueous solution is studied using the methods of ''residual concentrations'', pH potentiometry and conductometry. Independent of the ratio of components in the initial solution a mixture of coprecipitated normal tungstates of cadmium and indium is formed in the system. Heat treatment of the precipitates at 800 deg C for 50 hrs with subsequent hardening results in the formation of solid solutions on the basis of normal cadmium and indium tungstates.

  14. Study of the chemical interactions of actinide cations in solution at macroscopic concentrations

    International Nuclear Information System (INIS)

    Maurice, C.

    1983-01-01

    The aim of this work was to study the interactions of pentavalent neptunium in dodecane-diluted tributyl phosphate with other metallic cations, especially uranium VI and ruthenium present in reprocessing solutions. Pentavalent neptunium on its own was shown to exist in several forms complexed by water and TBP and also to dimerise. In the complex it forms with uranium VI the interaction via the neptunyl oxygen is considerably enhanced in organic solution. Dibutyl phosphoric acid strengthens the interaction between neptunium and uranium. The Np V-ruthenium interaction reveals the existence of a new cation-cation complex; the process takes place in two successive stage and leads to the formation, reinforced and accelerated by HDBP, of a highly to the formation, reinforced and accelerated by HDBP, of a highly stable complex. These results contribute towards a better knowledge of the behaviour of neptunium in the reprocessing operation [fr

  15. From micelle supramolecular assemblies in selective solvents to isoporous membranes

    KAUST Repository

    Nunes, Suzana Pereira

    2011-08-16

    The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. © 2011 American Chemical Society.

  16. From micelle supramolecular assemblies in selective solvents to isoporous membranes

    KAUST Repository

    Nunes, Suzana Pereira; Karunakaran, Madhavan; Neelakanda, Pradeep; Behzad, Ali Reza; Hooghan, Bobby; Sougrat, Rachid; He, Haoze; Peinemann, Klaus-Viktor

    2011-01-01

    The supramolecular assembly of PS-b-P4VP copolymer micelles induced by selective solvent mixtures was used to manufacture isoporous membranes. Micelle order in solution was confirmed by cryo-scanning electron microscopy in casting solutions, leading to ordered pore morphology. When dioxane, a solvent that interacts poorly with the micelle corona, was added to the solution, polymer-polymer segment contact was preferential, increasing the intermicelle contact. Immersion in water gave rise to asymmetric porous membranes with exceptional pore uniformity and high porosity. The introduction of a small number of carbon nanotubes to the casting solution improved the membrane stability and the reversibility of the gate response in the presence of different pH values. © 2011 American Chemical Society.

  17. An exact solution of two friendly interacting directed walks near a sticky wall

    International Nuclear Information System (INIS)

    Tabbara, R; Owczarek, A L; Rechnitzer, A

    2014-01-01

    We find the exact solution of two interacting friendly directed walks (modelling polymers) on the square lattice. These walks are confined to the quarter plane by a horizontal attractive surface, to capture the effects of DNA-denaturation and adsorption. We find the solution to the model’s corresponding generating function by means of the obstinate kernel method. Specifically, we apply this technique in two different instances to establish partial solutions for two simplified generating functions of the same underlying model that ignore either surface or shared contacts. We then subsequently combine our two partial solutions to find the solution for the full generating function in terms of the two simpler variants. This expression guides our analysis of the model, where we find the system exhibits four phases, and proceed to delineate the full phase diagram, showing that all observed phase transitions are second-order. (paper)

  18. Chemical composition separation of a propylene-ethylene random copolymer by high temperature solvent gradient interaction chromatography.

    Science.gov (United States)

    Liu, Yonggang; Phiri, Mohau Justice; Ndiripo, Anthony; Pasch, Harald

    2017-11-03

    A propylene-ethylene random copolymer was fractionated by preparative temperature rising elution fractionation (TREF). The structural heterogeneity of the bulk sample and its TREF fractions was studied by high temperature liquid chromatography with a solvent gradient elution from 1-decanol to 1,2,4-trichlorobenzene. HPLC alone cannot resolve those propylene-ethylene copolymers with high ethylene content in the bulk sample, due to their low weight fractions in the bulk sample and a small response factor of these components in the ELSD detector, as well as their broad chemical composition distribution. These components can only be detected after being separated and enriched by TREF followed by HPLC analysis. Chemical composition separations were achieved for TREF fractions with average ethylene contents between 2.1 and 22.0mol%, showing that copolymers with higher ethylene contents were adsorbed stronger in the Hypercarb column and eluted later. All TREF fractions, except the 40°C fraction, were relatively homogeneous in both molar mass and chemical composition. The 40°C fraction was rather broad in both molar mass and chemical composition distributions. 2D HPLC showed that the molar masses of the components containing more ethylene units were getting lower for the 40°C fraction. HPLC revealed and confirmed that co-crystallization influences the separation in TREF of the studied propylene-ethylene copolymer. Copyright © 2017 Elsevier B.V. All rights reserved.

  19. Deposition dynamics of multi-solvent bioinks

    Science.gov (United States)

    Kaneelil, Paul; Pack, Min; Cui, Chunxiao; Han, Li-Hsin; Sun, Ying

    2017-11-01

    Inkjet printing cellular scaffolds using bioinks is gaining popularity due to the advancement of printing technology as well as the growing demands of regenerative medicine. Numerous studies have been conducted on printing scaffolds of biomimetic structures that support the cell production of human tissues. However, the underlying physics of the deposition dynamics of bioinks remains elusive. Of particular interest is the unclear deposition dynamics of multi-solvent bioinks, which is often used to tune the micro-architecture formation. Here we systematically studied the effects of jetting frequency, solvent properties, substrate wettability, and temperature on the three-dimensional deposition patterns of bioinks made of Methacrylated Gelatin and Carboxylated Gelatin. The microflows inside the inkjet-printed picolitre drops were visualized using fluorescence tracer particles to decipher the complex processes of multi-solvent evaporation and solute self-assembly. The evolution of droplet shape was observed using interferometry. With the integrated techniques, the interplay of solvent evaporation, biopolymer deposition, and multi-drop interactions were directly observed for various ink and substrate properties, and printing conditions. Such knowledge enables the design and fabrication of a variety of tissue engineering scaffolds for potential use in regenerative medicine.

  20. Stress, strain, and structural dynamics an interactive handbook of formulas, solutions, and Matlab toolboxes

    CERN Document Server

    Yang, Bingen

    2005-01-01

    Stress, Strain, and Structural Dynamics is a comprehensive and definitive reference to statics and dynamics of solids and structures, including mechanics of materials, structural mechanics, elasticity, rigid-body dynamics, vibrations, structural dynamics, and structural controls. This text integrates the development of fundamental theories, formulas and mathematical models with user-friendly interactive computer programs, written in the powerful and popular MATLAB. This unique merger of technical referencing and interactive computing allows instant solution of a variety of engineering problems

  1. Effect of the composition of a solution on the enthalpies of solvation of piperidine in methanol-acetonitrile and dimethylsulfoxide-acetonitrile mixed solvents

    Science.gov (United States)

    Kuz'mina, I. A.; Volkova, M. A.; Sitnikova, K. A.; Sharnin, V. A.

    2014-01-01

    Heat effects of dissolution of piperidine (ppd) are measured by calorimetry at 298.15 K over the range of composition of acetonitrile-methanol (AN-MeOH) mixed solvents. Based on the Δsol H ○(ppd)AN-MeOH values obtained using the literature data on Δsol H ○ (ppd) in acetonitrile-dimethylsulfoxide (AN-DMSO) mixed solvents and the vaporization enthalpy of ppd, the enthalpies of solvation of amine in AN-MeOH and AN-DMSO binary mixtures are calculated. A rise in the exothermicity of solvation of piperidine is observed upon the transition from AN to DMSO and MeOH, due mainly to the enhanced solvation of the amino group of ppd as a result of changes in the acid-base properties of the mixed solvent.

  2. Investigation of processes of interaction relativistic electrons with the solutions of organic dyes

    International Nuclear Information System (INIS)

    Buki, A.Yu.; Gokov, S.P.; Kazarinov, Yu.G.; Kalenik, S.A.; Kasilov, V.I.; Kochetov, S.S.; Makhnenko, P.L.; Mel'nitskiy, I.V.; Tverdohvalov, A.V.; Tsyatsko, V.V.; Shopen, O.A.

    2014-01-01

    Investigation of the processes of interaction of ionizing radiation with complex organic objects can solve a number of fundamental and applied problems in radiation physics, chemistry and biology. In this work we investigated the dose dependence (dose range 1...5MRad) optical density relative concentrations of water, alcohol and glycerine solution following organic dyes: methylene blue - C 16 H 18 N 3 SCl and methyl orange - C 14 H 14 N 3 O 3 SNa, irradiated with an electron beam with an energy of 16MeV. In the analysis of absorption spectra, it was found that water solutions of dyes have less resistance to radiation as compared with the alcohol and glycerol. Also, all solutions of methyl orange less radiation resistant than the methylene blue solution. Analysis of the spectra showed that these relationships are close to linear in the range of doses. To understand the physical and chemical processes occurring in the interaction of relativistic electrons with the studied organic objects were performed the computer simulations of the energy spectra of ions formed due to breaking the chemical bonds of molecules of dye solutions using the program SRIM-2010. The analysis showed that radiation - stimulated chemical processes play a major role in the destruction of the source of organic dye molecules. The remaining processes (interaction of electrons and nuclei, the cascade processes) accounts for about 10% of all molecular breaks.

  3. Exact solution of an Ising model with competing interactions on a Cayley tree

    CERN Document Server

    Ganikhodjaev, N N; Wahiddin, M R B

    2003-01-01

    The exact solution of an Ising model with competing restricted interactions on the Cayley tree, and in the absence of an external field is presented. A critical curve is defined where it is possible to get phase transitions above it, and a single Gibbs state is obtained elsewhere.

  4. Direct interaction between linear electron transfer chains and solute transport systems in bacteria

    NARCIS (Netherlands)

    Elferink, Marieke G.L.; Hellingwerf, Klaas J.; Belkum, Marco J. van; Poolman, Bert; Konings, Wil N.

    1984-01-01

    In studies on alanine and lactose transport in Rhodopseudomonas sphaeroides we have demonstrated that the rate of solute uptake in this phototrophic bacterium is regulated by the rate of light-induced cyclic electron transfer. In the present paper the interaction between linear electron transfer

  5. Exploring a multi-scale method for molecular simulation in continuum solvent model: Explicit simulation of continuum solvent as an incompressible fluid.

    Science.gov (United States)

    Xiao, Li; Luo, Ray

    2017-12-07

    We explored a multi-scale algorithm for the Poisson-Boltzmann continuum solvent model for more robust simulations of biomolecules. In this method, the continuum solvent/solute interface is explicitly simulated with a numerical fluid dynamics procedure, which is tightly coupled to the solute molecular dynamics simulation. There are multiple benefits to adopt such a strategy as presented below. At this stage of the development, only nonelectrostatic interactions, i.e., van der Waals and hydrophobic interactions, are included in the algorithm to assess the quality of the solvent-solute interface generated by the new method. Nevertheless, numerical challenges exist in accurately interpolating the highly nonlinear van der Waals term when solving the finite-difference fluid dynamics equations. We were able to bypass the challenge rigorously by merging the van der Waals potential and pressure together when solving the fluid dynamics equations and by considering its contribution in the free-boundary condition analytically. The multi-scale simulation method was first validated by reproducing the solute-solvent interface of a single atom with analytical solution. Next, we performed the relaxation simulation of a restrained symmetrical monomer and observed a symmetrical solvent interface at equilibrium with detailed surface features resembling those found on the solvent excluded surface. Four typical small molecular complexes were then tested, both volume and force balancing analyses showing that these simple complexes can reach equilibrium within the simulation time window. Finally, we studied the quality of the multi-scale solute-solvent interfaces for the four tested dimer complexes and found that they agree well with the boundaries as sampled in the explicit water simulations.

  6. Preferential solvation of fluorenone and 4-hydroxyfluorenone in binary solvent mixtures

    International Nuclear Information System (INIS)

    Jozefowicz, Marek; Heldt, Janina R.

    2003-01-01

    Preferential solvation of fluorenone and 4-hydroxyfluorenone in binary solvent mixtures has been studied using steady-state spectroscopic measurements. This study concerns the solvent-induced shift of the absorption and fluorescence spectra of both molecules in two solvent mixtures, i.e., cyclohexane-tetrahydrofuran and cyclohexane-ethanol. The first system contains polar solute molecules, fluorenone and 4-hydroxyfluorenone, in a mixture of polar aprotic (tetrahydrofuran) and non-polar (cyclohexane) solvents. In the second solvents mixture, hydrogen bonding with solute molecules (ethanol) may occur. The results of spectroscopic measurements are analysed using theoretical models of Bakshiev, Mazurenko and Suppan which describe preferential solvation phenomena. In the case of cyclohexane-tetrahydrofuran mixtures, the deviation from linearity in the absorption and fluorescence solvatochromic shifts vs. the solution polarity is due to non-specific dipolar solvent-solute interactions. For cyclohexane-ethanol binary mixtures, both non-specific and specific (hydrogen bond and proton-relay tautomerization) interactions contribute to the observed solvatochromism

  7. Interactions between halloysite nanotubes and poly(styrene sulfonate) in solution

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jae Heon; Ryu, Jung Ju; Shin, Joo Huei; Lee, Hoik; Sohn, Dae Won [Dept. of Chemistry and Research Institute for Convergence of Basic Science, Hanyang University, Seoul (Korea, Republic of); Kim, Ick Soo [Nano Fusion Technology Research Lab, Division of Frontier Fibers, Institute for Fiber Engineering (IFES), Interdisciplinary Cluster for Cutting Edge Research (ICCER), Shinshu University, Nagano (Japan)

    2017-01-15

    The interaction between halloysite nanotubes (HNT) and poly(styrene sulfonate) (PSS) in aqueous solution was investigated by dynamic light scattering. Dynamic behavior of HNT/PSS was observed with different salt, HNT, and PSS concentrations. The HNT colloids were stabilized by PSS over a wide range of HNT concentrations, and HNT suspension in dilute solution formed stable HNT/PSS particles. On the other hand, HNT particles aggregated as sediments at higher concentrations due to strong attraction among HNT rods, and HNT aggregates were stabilized by additional PSS. The interactions between HNT and PSS are described by the van der Waals–London force (VDWL). The stabilization process of HNT/PSS particles in salt solution was proposed by comparing the hydrodynamic radii and apparent intensities of samples. The results demonstrate that electrostatic, steric, and depletion stabilization processes are responsible for the stable dispersion of HNT even at high concentration.

  8. Interaction between copper and radiocesium in Indian mustard and sunflower grown in the hydroponic solution

    International Nuclear Information System (INIS)

    Shirong Tang; Xiaochang Wang

    2002-01-01

    Both Indian mustard and sunflower were grown in a hydroponic solution treated with different concentration activities of 134 Cs or with different amounts of copper or with both in order to investigate the interaction between copper and radiocesium. It was found that 134 Cs activity concentration applied in the nutrient solution exerted more influence on the uptake and translocation of copper by Indian mustard than by sunflower. Indian mustard grown in hydroponic solution containing certain levels of copper and being treated with higher 134 Cs activity concentration showed higher uptake of copper than sunflower. However, in the case of root copper concentrations, sunflower showed significantly higher copper immobilization by roots than Indian mustard. It was also found that the presence of copper the the hydroponic solution did modify radiocesium uptake by both species. The application of 1 mg/l in the growth medium could greatly increase the uptake of 134 Cs by both species. With 3 mg/l concentration of copper amended to the solution, the accumulation of 134 Cs by both species was decreased compared to the 1 mg/l copper treatment. These lines of evidence show that there is stronger interaction between copper and radiocesium in Indian mustard than in sunflower during the root uptake through nutrient solution. (author)

  9. Theoretical study of solvent effects on the coil-globule transition

    Science.gov (United States)

    Polson, James M.; Opps, Sheldon B.; Abou Risk, Nicholas

    2009-06-01

    The coil-globule transition of a polymer in a solvent has been studied using Monte Carlo simulations of a single chain subject to intramolecular interactions as well as a solvent-mediated effective potential. This solvation potential was calculated using several different theoretical approaches for two simple polymer/solvent models, each employing hard-sphere chains and hard-sphere solvent particles as well as attractive square-well potentials between some interaction sites. For each model, collapse is driven by variation in a parameter which changes the energy mismatch between monomers and solvent particles. The solvation potentials were calculated using two fundamentally different methodologies, each designed to predict the conformational behavior of polymers in solution: (1) the polymer reference interaction site model (PRISM) theory and (2) a many-body solvation potential (MBSP) based on scaled particle theory introduced by Grayce [J. Chem. Phys. 106, 5171 (1997)]. For the PRISM calculations, two well-studied solvation monomer-monomer pair potentials were employed, each distinguished by the closure relation used in its derivation: (i) a hypernetted-chain (HNC)-type potential and (ii) a Percus-Yevick (PY)-type potential. The theoretical predictions were each compared to results obtained from explicit-solvent discontinuous molecular dynamics simulations on the same polymer/solvent model systems [J. Chem. Phys. 125, 194904 (2006)]. In each case, the variation in the coil-globule transition properties with solvent density is mostly qualitatively correct, though the quantitative agreement between the theory and prediction is typically poor. The HNC-type potential yields results that are more qualitatively consistent with simulation. The conformational behavior of the polymer upon collapse predicted by the MBSP approach is quantitatively correct for low and moderate solvent densities but is increasingly less accurate for higher densities. At high solvent densities

  10. The solvation of L-serine in mixtures of water with some aprotic solvents at 298.15 K

    Science.gov (United States)

    Mezhevoi, I. N.; Badelin, V. G.

    2009-03-01

    The integral enthalpies of solution Δsol H m of L-serine in mixtures of water with acetonitrile, 1,4-dioxane, dimethylsulfoxide (DMSO), and acetone were measured by solution calorimetry at organic component concentrations up to 0.31 mole fractions. The standard enthalpies of solution (Δsol H°), transfer (Δtr H°), and solvation (Δsolv H°) of L-serine from water into mixed solvents were calculated. The dependences of Δsol H°, Δsolv H°, and Δtr H° on the composition of aqueous-organic solvents contained extrema. The calculated enthalpy coefficients of pair interactions of the amino acid with cosolvent molecules were positive and increased in the series acetonitrile, 1,4-dioxane, DMSO, acetone. The results obtained were interpreted from the point of view of various types of interactions in solutions and the influence of the nature of organic solvents on the thermochemical characteristics of solutions.

  11. Computer Aided Solvent Selection and Design Framework

    DEFF Research Database (Denmark)

    Mitrofanov, Igor; Conte, Elisa; Abildskov, Jens

    and computer-aided tools and methods for property prediction and computer-aided molecular design (CAMD) principles. This framework is applicable for solvent selection and design in product design as well as process design. The first module of the framework is dedicated to the solvent selection and design...... in terms of: physical and chemical properties (solvent-pure properties); Environment, Health and Safety (EHS) characteristic (solvent-EHS properties); operational properties (solvent–solute properties). 3. Performing the search. The search step consists of two stages. The first is a generation and property...... identification of solvent candidates using special software ProCAMD and ProPred, which are the implementations of computer-aided molecular techniques. The second consists of assigning the RS-indices following the reaction–solvent and then consulting the known solvent database and identifying the set of solvents...

  12. Validation of a stability-indicating hydrophilic interaction liquid chromatographic method for the quantitative determination of vitamin k3 (menadione sodium bisulfite) in injectable solution formulation.

    Science.gov (United States)

    Ghanem, Mashhour M; Abu-Lafi, Saleh A; Hallak, Hussein O

    2013-01-01

    A simple, specific, accurate, and stability-indicating method was developed and validated for the quantitative determination of menadione sodium bisulfite in the injectable solution formulation. The method is based on zwitterionic hydrophilic interaction liquid chromatography (ZIC-HILIC) coupled with a photodiode array detector. The desired separation was achieved on the ZIC-HILIC column (250 mm × 4.6 mm, 5 μm) at 25°C temperature. The optimized mobile phase consisted of an isocratic solvent mixture of 200mM ammonium acetate (NH4AC) solution and acetonitrile (ACN) (20:80; v/v) pH-adjusted to 5.7 by glacial acetic acid. The mobile phase was fixed at 0.5 ml/min and the analytes were monitored at 261 nm using a photodiode array detector. The effects of the chromatographic conditions on the peak retention, peak USP tailing factor, and column efficiency were systematically optimized. Forced degradation experiments were carried out by exposing menadione sodium bisulfite standard and the injectable solution formulation to thermal, photolytic, oxidative, and acid-base hydrolytic stress conditions. The degradation products were well-resolved from the main peak and the excipients, thus proving that the method is a reliable, stability-indicating tool. The method was validated as per ICH and USP guidelines (USP34/NF29) and found to be adequate for the routine quantitative estimation of menadione sodium bisulfite in commercially available menadione sodium bisulfite injectable solution dosage forms.

  13. Friction and Wear Management Using Solvent Partitioning of Hydrophilic-Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

    Science.gov (United States)

    Richmond, Robert Chaffee (Inventor); Schramm, Jr., Harry F. (Inventor); Defalco, Francis G. (Inventor)

    2015-01-01

    Lubrication additives of the current invention require formation of emulsions in base lubricants, created with an aqueous salt solution plus a single-phase compound such that partitioning within the resulting emulsion provides thermodynamically targeted compounds for boundary layer organization thus establishing anti-friction and/or anti-wear. The single-phase compound is termed "boundary layer organizer", abbreviated BLO. These emulsion-contained compounds energetically favor association with tribologic surfaces in accord with the Second Law of Thermodynamics, and will organize boundary layers on those surfaces in ways specific to the chemistry of the salt and BLO additives. In this way friction modifications may be provided by BLOs targeted to boundary layers via emulsions within lubricating fluids, wherein those lubricating fluids may be water-based or oil-based.

  14. Virtual in Real. Interactive Solutions for Learning and Communication in the National Archaeological Museum of Marche

    Science.gov (United States)

    Clini, P.; Nespeca, R.; Ruggeri, L.

    2017-05-01

    Today the ICTs are favourable additions to museum exhibitions. This work aims to realize an innovative system of digital exploitation of artefacts in the National Archaeological Museum of Marche (MANaM), in order to create a shared museum that will improve the knowledge of cultural contents through the paradigm "learning by interacting" and "edutainment". The main novelty is the implementation of stand-alone multimedia installations for digital artefacts that combine real and virtual scenarios in order to enrich the experience, the knowledge and the multi-sensory perception. A Digital Library (DL) is created using Close Range Photogrammetry (CRP) techniques applied to 21 archaeological artefacts belonging to different categories. Enriched with other data (texts, images, multimedia), all 3D models flow into the cloud data server from which are recalled in the individual exhibitions. In particular, we have chosen three types of technological solutions: VISUAL, TACTILE, SPATIAL. All the solutions take into account the possibility of group interaction, allowing the participation of the interaction to an appropriate number of users. Sharing the experience enables greater involvement, generating communicative effectiveness much higher than it would get from a lonely visit. From the "Museum Visitors Behaviour Analysis" we obtain a survey about users' needs and efficiency of the interactive solutions. The main result of this work is the educational impact in terms of increase in visitors, specially students, learning increase of historical and cultural content, greater user involvement during the visit to the museum.

  15. Understanding Solvent Manipulation of Morphology in Bulk-Heterojunction Organic Solar Cells.

    Science.gov (United States)

    Chen, Yuxia; Zhan, Chuanlang; Yao, Jiannian

    2016-10-06

    Film morphology greatly influences the performance of bulk-heterojunction (BHJ)-structure-based solar cells. It is known that an interpenetrating bicontinuous network with nanoscale-separated donor and acceptor phases for charge transfer, an ordered molecular packing for exciton diffusion and charge transport, and a vertical compositionally graded structure for charge collection are prerequisites for achieving highly efficient BHJ organic solar cells (OSCs). Therefore, control of the morphology to obtain an ideal structure is a key problem. For this solution-processing BHJ system, the solvent participates fully in film processing. Its involvement is critical in modifying the nanostructure of BHJ films. In this review, we discuss the effects of solvent-related methods on the morphology of BHJ films, including selection of the casting solvent, solvent mixture, solvent vapor annealing, and solvent soaking. On the basis of a discussion on interaction strength and time between solvent and active materials, we believe that the solvent-morphology-performance relationship will be clearer and that solvent selection as a means to manipulate the morphology of BHJ films will be more rational. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Investigation into interaction of mixture of zinc and neodymium nitrates with sodium tungstates in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Rozantsev, G M; Krivobok, V I [Donetskij Gosudarstvennyj Univ. (Ukrainian SSR)

    1978-09-01

    The methods of residual concentrations, pH-potentiometry, and conductometry have been used for studying interaction between the mixture of zinc and neodymium nitrates with sodium tungstate in aqueous solutions. It has been established that independent of the ratio between the components the reaction product is a mixture of simultaneously precipitated zinc and neodymium orthotungstates. Thermal treatment of such mixtures at 650-700 deg C for 40 h and subsequent hardening yields solid solution of the structure ..cap alpha..-Eu/sub 2/(WO/sub 4/)/sub 3/ within the concentration range 85-100 mol % of Nd/sub 2/(WO/sub 4/)/sub 3/.

  17. An exact solution of three interacting friendly walks in the bulk

    International Nuclear Information System (INIS)

    Tabbara, R; Owczarek, A L; Rechnitzer, A

    2016-01-01

    We find the exact solution of three interacting friendly directed walks on the square lattice in the bulk, modelling a system of homopolymers that can undergo a multiple polymer fusion or zipping transition by introducing two distinct interaction parameters that differentiate between the zipping of only two or all three walks. We establish functional equations for the model’s corresponding generating function that are subsequently solved exactly by means of the obstinate kernel method. We then proceed to analyse our model, first considering the case where triple-walk interaction effects are ignored, finding that our model exhibits two phases which we classify as free and gelated (or zipped) regions, with the system exhibiting a second-order phase transition. We then analyse the full model where both interaction parameters are incorporated, presenting the full phase diagram and highlighting the additional existence of a first-order gelation (zipping) boundary. (paper)

  18. Organic solvents in electromembrane extraction: recent insights

    DEFF Research Database (Denmark)

    Huang, Chuixiu; Gjelstad, Astrid; Pedersen-Bjergaard, Stig

    2016-01-01

    the introduction. Under the influence of an electrical field, EME is based on electrokinetic migration of the analytes through a supported liquid membrane (SLM), which is an organic solvent immobilized in the pores of the polymeric membrane, and into the acceptor solution. Up to date, close to 150 research...... articles with focus on EME have been published. The current review summarizes the performance of EME with different organic solvents and discusses several criteria for efficient solvents in EME. In addition, the authors highlight their personal perspective about the most promising organic solvents for EME...... and have indicated that more fundamental work is required to investigate and discover new organic solvents for EME....

  19. Cesium Concentration in MCU Solvent

    International Nuclear Information System (INIS)

    Walker, D

    2006-01-01

    During Modular Caustic-Side Solvent Extraction (CSSX) Unit (MCU) operations, Cs-137 concentrations in product streams will vary depending on the location in the process and on the recent process conditions. Calculations of cesium concentrations under a variety of operating conditions reveal the following: (1) Under nominal operations with salt solution feed containing 1.1 Ci Cs-137 per gallon, the maximum Cs-137 concentration in the process will occur in the strip effluent (SE) and equal 15-16.5 Ci/gal. (2) Under these conditions, the majority of the solvent will contain 0.005 to 0.01 Ci/gal, with a limited portion of the solvent in the contactor stages containing ∼4 Ci/gal. (3) When operating conditions yield product near 0.1 Ci Cs-137/gal in the decontaminated salt solution (DSS), the SE cesium concentration will be the same or lower than in nominal operations, but majority of the stripped solvent will increase to ∼2-3 Ci/gal. (4) Deviations in strip and waste stream flow rates cause the largest variations in cesium content: (a) If strip flow rates deviate by -30% of nominal, the SE will contain ∼23 Ci/gal, although the cesium content of the solvent will increase to only 0.03 Ci/gal; (b) If strip flow rate deviates by -77% (i.e., 23% of nominal), the SE will contain 54 Ci/gal and solvent will contain 1.65 Ci/gal. At this point, the product DSS will just reach the limit of 0.1 Ci/gal, causing the DSS gamma monitors to alarm; and (c) Moderate (+10 to +30%) deviations in waste flow rate cause approximately proportional increases in the SE and solvent cesium concentrations. Recovery from a process failure due to poor cesium stripping can achieve any low cesium concentration required. Passing the solvent back through the contactors while recycling DSS product will produce a ∼70% reduction during one pass through the contactors (assuming the stripping D value is no worse than 0.36). If the solvent is returned to the solvent hold tank (containing additional

  20. Interactions of U(VI), Nd, and Th(IV) at the Calcite-solution interface

    International Nuclear Information System (INIS)

    Carroll, S.A.; Dran, J.C.

    1992-01-01

    The interactions of U(VI), Nd, and Th(IV) at the calcite-solution interface at controlled pCO 2 (g) have been investigated by Rutherford backscattering (RBS), scanning electron microscopy (SEM) and energy dispersive (EDS) analyses of reacted calcite. Uranium precipitation at the calcite-solution interface was observed only for those experiments in which the initial [U(VI)] was greater than the solubility of rutherfordine, UO 2 CO 3 (s). At pH 8.0, flat radial uranium and calcium zoned precipitates form at the mineral-solution interface. At pH 4.3, uranium forms an anastomosing precipitate throughout the calcite surface. RBS analyses confirmed the SEM analyses showing that uranium forms a solid phase within the calcite surface, but formation of an uranium-calcium solid solution at depth is limited. In sharp contrast to U(VI), Nd is concentrated in the solid phase as individual neodymium-calcium carbonate crystals. Calcite and pure orthorhombic neodymium carbonate crystals dissolve at the expense of the formation of a more stable neodymium-calcium solid solution. In the presence of calcite, a thorium-calcium solid solution forms by exchanging Th for Ca in the calcite structure. Thorium precipitates in two linear trends which intersect each other at approximately 105deg C and 75deg C, parallel to calcite rhombohedral cleavage faces. (orig.)

  1. Energetics of the molecular interactions of L-alanine and L-serine with xylitol, D-sorbitol, and D-mannitol in aqueous solutions at 298.15 K

    Science.gov (United States)

    Mezhevoi, I. N.; Badelin, V. G.

    2013-04-01

    Integral enthalpies of dissolution Δsol H m of L-alanine and L-serine are measured via the calorimetry of dissolution in aqueous solutions of xylitol, D-sorbitol, and D-mannitol. Standard enthalpies of dissolution (Δsol H ○) and the transfer (Δtr H ○) of amino acids from water to binary solvent are calculated from the experimental data. Using the McMillan-Mayer theory, enthalpy coefficients of pairwise interactions h xy of amino acids with molecules of polyols are calculated that are negative. The obtained results are discussed within the theory of the prevalence of different types of interactions in mixed solutions and the effect of the structural features of interacting biomolecules on the thermochemical parameters of dissolution of amino acids.

  2. Measure solutions for non-local interaction PDEs with two species

    Energy Technology Data Exchange (ETDEWEB)

    Francesco, Marco Di [Department of Mathematical and Statistical Sciences, University of Bath, Claverton Down, Bath, BA2 7AY (United Kingdom); Fagioli, Simone [DISIM—Department of Information Engineering, Computer Science and Mathematics, University of L' Aquila, Via Vetoio 1 (Coppito) 67100 L' Aquila (AQ) (Italy)

    2013-10-01

    This paper presents a systematic existence and uniqueness theory of weak measure solutions for systems of non-local interaction PDEs with two species, which are the PDE counterpart of systems of deterministic interacting particles with two species. The main motivations behind those models arise in cell biology, pedestrian movements, and opinion formation. In case of symmetrizable systems (i.e. with cross-interaction potentials one multiple of the other), we provide a complete existence and uniqueness theory within (a suitable generalization of) the Wasserstein gradient flow theory in Ambrosio et al (2008 Gradient Flows in Metric Spaces and in the Space of Probability Measures (Lectures in Mathematics ETH Zürich) 2nd edn (Basel: Birkhäuser)) and Carrillo et al (2011 Duke Math. J. 156 229–71), which allows the consideration of interaction potentials with a discontinuous gradient at the origin. In the general case of non-symmetrizable systems, we provide an existence result for measure solutions which uses a semi-implicit version of the Jordan–Kinderlehrer–Otto (JKO) scheme (Jordan et al 1998 SIAM J. Math. Anal. 29 1–17), which holds in a reasonable non-smooth setting for the interaction potentials. Uniqueness in the non-symmetrizable case is proven for C{sup 2} potentials using a variant of the method of characteristics. (paper)

  3. Measure solutions for non-local interaction PDEs with two species

    International Nuclear Information System (INIS)

    Francesco, Marco Di; Fagioli, Simone

    2013-01-01

    This paper presents a systematic existence and uniqueness theory of weak measure solutions for systems of non-local interaction PDEs with two species, which are the PDE counterpart of systems of deterministic interacting particles with two species. The main motivations behind those models arise in cell biology, pedestrian movements, and opinion formation. In case of symmetrizable systems (i.e. with cross-interaction potentials one multiple of the other), we provide a complete existence and uniqueness theory within (a suitable generalization of) the Wasserstein gradient flow theory in Ambrosio et al (2008 Gradient Flows in Metric Spaces and in the Space of Probability Measures (Lectures in Mathematics ETH Zürich) 2nd edn (Basel: Birkhäuser)) and Carrillo et al (2011 Duke Math. J. 156 229–71), which allows the consideration of interaction potentials with a discontinuous gradient at the origin. In the general case of non-symmetrizable systems, we provide an existence result for measure solutions which uses a semi-implicit version of the Jordan–Kinderlehrer–Otto (JKO) scheme (Jordan et al 1998 SIAM J. Math. Anal. 29 1–17), which holds in a reasonable non-smooth setting for the interaction potentials. Uniqueness in the non-symmetrizable case is proven for C 2 potentials using a variant of the method of characteristics. (paper)

  4. Free-solution, label-free molecular interactions studied by back-scattering interferometry

    DEFF Research Database (Denmark)

    Bornhop, D.J.; Latham, J.C.; Kussrow, A.

    2007-01-01

    Free-solution, label-free molecular interactions were investigated with back-scattering interferometry in a simple optical train composed of a helium-neon laser, a microfluidic channel, and a position sensor. Molecular binding interactions between proteins, ions and protein, and small molecules...... and protein, were determined with high dynamic range dissociation constants (K-d spanning six decades) and unmatched sensitivity (picomolar K-d's and detection limits of 10,000s of molecules). With this technique, equilibrium dissociation constants were quantified for protein A and immunoglobulin G...

  5. Acceleration of criticality analysis solution convergence by matrix eigenvector for a system with weak neutron interaction

    Energy Technology Data Exchange (ETDEWEB)

    Nomura, Yasushi; Takada, Tomoyuki; Kuroishi, Takeshi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Kadotani, Hiroyuki [Shizuoka Sangyo Univ., Iwata, Shizuoka (Japan)

    2003-03-01

    In the case of Monte Carlo calculation to obtain a neutron multiplication factor for a system of weak neutron interaction, there might be some problems concerning convergence of the solution. Concerning this difficulty in the computer code calculations, theoretical derivation was made from the general neutron transport equation and consideration was given for acceleration of solution convergence by using the matrix eigenvector in this report. Accordingly, matrix eigenvector calculation scheme was incorporated together with procedure to make acceleration of convergence into the continuous energy Monte Carlo code MCNP. Furthermore, effectiveness of acceleration of solution convergence by matrix eigenvector was ascertained with the results obtained by applying to the two OECD/NEA criticality analysis benchmark problems. (author)

  6. Interaction of Celestine Concentrate and Reagent Grade SrSO4 with Oxalate Solutions

    Directory of Open Access Journals (Sweden)

    Abdullah Obut

    2012-12-01

    Full Text Available The interaction of reagent grade strontium sulphate and celestine concentrate with aqueous solutions of oxalic acid, sodiumoxalate and ammonium oxalate for the production of strontium carbonate were investigated for different oxalate compound:SrSO4 moleratios and reaction times using x-ray diffraction analysis and dissolution tests. Under the same experimental conditions, it was foundthat aqueous oxalic acid and sodium oxalate solutions had no or little effect on reagent grade strontium sulphate or celestineconcentrate, but aqueous ammonium oxalate solution converted them into strontium oxalate hydrate. Strontium carbonate was obtainedat conversion ratios of 74.7% for the celestine concentrate and 84.6 % for the reagent grade strontium sulphate by the decompositionof the obtained strontium oxalate hydrate at 600 °C under air atmosphere.

  7. Interaction of titanium and zirconium hydroxides with aqueous solutions of lead(2) salts

    International Nuclear Information System (INIS)

    Savenko, V.G.; Sakharov, V.V.; Nurgalieva, A.A.; Petrov, K.I.

    1980-01-01

    The mixed phases, characterized by the Pb : Zr 4 ratio are synthesized during the process of geterophase interaction of zirconium hydroxide with solutions of lead nitrate and acetate. The process of the mixed phases thermolysis on the base of amorphous zirconium hydroxides is investigated by the methods of DTA, X-ray phase analysis and IR spectroscopy. The metastable phases are formed during the thermolysis process

  8. Interaction of silicon nanoparticles with the molecules of bovine serum albumin in aqueous solutions

    International Nuclear Information System (INIS)

    Anenkova, K A; Sergeeva, I A; Petrova, G P; Fedorova, K V; Osminkina, L A; Timoshenko, Viktor Yu

    2011-01-01

    Using the method of photon-correlation spectroscopy, the coefficient of translational diffusion D t and the hydrodynamic radius R of the particles in aqueous solutions of the bovine serum albumin, containing silicon nanoparticles, are determined. The character of the dependence of these parameters on the concentration of the protein indicates the absence of interaction between the studied particles in the chosen range of albumin concentrations 0.2 - 1.0 mg mL -1 . (optical technologies in biophysics and medicine)

  9. Effect of ternary solute interaction on interfacial segregation and grain boundary embrittlement

    Czech Academy of Sciences Publication Activity Database

    Lejček, Pavel

    2013-01-01

    Roč. 48, č. 14 (2013), 4965-4972 ISSN 0022-2461 R&D Projects: GA MŠk(CZ) LM2011026; GA ČR GAP108/12/0144 Institutional research plan: CEZ:AV0Z10100520 Keywords : interfacial segregation * intergranular embrittlement * solute interaction * modeling * thermodynamics Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.305, year: 2013

  10. Electron paramagnetic resonance response and magnetic interactions in ordered solid solutions of lithium nickel oxides

    Energy Technology Data Exchange (ETDEWEB)

    Azzoni, C.B. [Istituto Nazionale di Fisica della Materia, Dipartimento di Fisica ' Alessandro Volta' , Universita di Pavia, Pavia (Italy); Paleari, A. [Istituto Nazionale di Fisica della Materia, Dipartimento di Fisica, Universita di Milano, Milan (Italy); Massarotti, V.; Capsoni, D. [Dipartimento di Chimica-Fisica, Universita di Pavia, Pavia (Italy)

    1996-09-23

    EPR data of ordered solid solutions of lithium nickel oxides are reported as a function of the lithium content. The features of the signal and the EPR centre density are analysed by a model of dynamical trapping of holes in [(Ni{sup 2+}-O-Ni{sup 2+})-h{sup +}] complexes. The possible origin of the interactions responsible for the magnetic ordering and some features of the transport properties are also discussed. (author)

  11. Molecular Thermodynamic Modeling of Mixed Solvent Solubility

    DEFF Research Database (Denmark)

    Ellegaard, Martin Dela; Abildskov, Jens; O’Connell, John P.

    2010-01-01

    A method based on statistical mechanical fluctuation solution theory for composition derivatives of activity coefficients is employed for estimating dilute solubilities of 11 solid pharmaceutical solutes in nearly 70 mixed aqueous and nonaqueous solvent systems. The solvent mixtures range from...... nearly ideal to strongly nonideal. The database covers a temperature range from 293 to 323 K. Comparisons with available data and other existing solubility methods show that the method successfully describes a variety of observed mixed solvent solubility behaviors using solute−solvent parameters from...

  12. Application of Differential Colorimetry To Evaluate Anthocyanin-Flavonol-Flavanol Ternary Copigmentation Interactions in Model Solutions.

    Science.gov (United States)

    Gordillo, Belén; Rodríguez-Pulido, Francisco J; González-Miret, M Lourdes; Quijada-Morín, Natalia; Rivas-Gonzalo, Julián C; García-Estévez, Ignacio; Heredia, Francisco J; Escribano-Bailón, M Teresa

    2015-09-09

    The combined effect of anthocyanin-flavanol-flavonol ternary interactions on the colorimetric and chemical stability of malvidin-3-glucoside has been studied. Model solutions with fixed malvidin-3-glucoside/(+)-catechin ratio (MC) and variable quercetin-3-β-d-glucoside concentration (MC+Q) and solutions with fixed malvidin-3-glucoside/quercetin-3-β-d-glucoside ratio (MQ) and variable (+)-catechin concentration (MQ+C) were tested at levels closer to those existing in wines. Color variations during storage were evaluated by differential colorimetry. Changes in the anthocyanin concentration were monitored by HPLC-DAD. CIELAB color-difference formulas were demonstrated to be of practical interest to assess the stronger and more stable interaction of quercetin-3-β-d-glucoside with MC binary mixture than (+)-catechin with MQ mixture. The results imply that MC+Q ternary solutions kept their intensity and bluish tonalities for a longer time in comparison to MQ+C solutions. The stability of malvidin-3-glucoside improves when the concentration of quercetin-3-β-d-glucoside increases in MC+Q mixtures, whereas the addition of (+)-catechin in MQ+C mixtures resulted in an opposite effect.

  13. Prediction of the solubility in lipidic solvent mixture: Investigation of the modeling approach and thermodynamic analysis of solubility.

    Science.gov (United States)

    Patel, Shruti V; Patel, Sarsvatkumar

    2015-09-18

    Self-micro emulsifying drug delivery system (SMEDDS) is one of the methods to improve solubility and bioavailability of poorly soluble drug(s). The knowledge of the solubility of pharmaceuticals in pure lipidic solvents and solvent mixtures is crucial for designing the SMEDDS of poorly soluble drug substances. Since, experiments are very time consuming, a model, which allows for solubility predictions in solvent mixtures based on less experimental data is desirable for efficiency. Solvents employed were Labrafil® M1944CS and Labrasol® as lipidic solvents; Capryol-90®, Capryol-PGMC® and Tween®-80 as surfactants; Transcutol® and PEG-400 as co-solvents. Solubilities of both drugs were determined in single solvent systems at temperature (T) range of 283-333K. In present study, we investigated the applicability of the thermodynamic model to understand the solubility behavior of drugs in the lipiodic solvents. By using the Van't Hoff and general solubility theory, the thermodynamic functions like Gibbs free energy, enthalpy and entropy of solution, mixing and solvation for drug in single and mixed solvents were understood. The thermodynamic parameters were understood in the framework of drug-solvent interaction based on their chemical similarity and dissimilarity. Clotrimazole and Fluconazole were used as active ingredients whose solubility was measured in single solvent as a function of temperature and the data obtained were used to derive mathematical models which can predict solubility in multi-component solvent mixtures. Model dependent parameters for each drug were calculated at each temperature. The experimental solubility data of solute in mixed solvent system were measured experimentally and further correlated with the calculates values obtained from exponent model and log-linear model of Yalkowsky. The good correlation was observed between experimental solubility and predicted solubility. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. Hydration interactions and stability of soluble microbial products in aqueous solutions.

    Science.gov (United States)

    Wang, Ling-Ling; Wang, Long-Fei; Ye, Xiao-Dong; Yu, Han-Qing

    2013-10-01

    Soluble microbial products (SMP) are organic compounds excreted by microorganisms in their metabolism and decay and the main constituents in effluent from biological wastewater treatment systems. They also have an important contribution to the dissolved organic matters in natural aqueous systems. So far the interactions between SMP colloids have not been well explored. In this work, the interactions between SMP colloids in water and salt solutions were studied by using a combination of static and dynamic light scattering, Fourier transform infrared spectra, Zeta potential and acid-base titration techniques. The second osmotic virial coefficient had a larger value in a 750-mM salt solution than that in a 50-mM solution, indicating that repulsion between SMP colloids increased with an increase in salt concentration, which is contrary with the classic Derjaguin, Landau, Verwey, and Overbeek (DLVO) theory. Such a repulsion was attributed to water structuring and enhanced by the accumulation of hydrophilic counter ions around SMP colloids and the formed hydration force. The repulsion and hydration effect led to the dispersing and deeper draining structure, accompanied by a decreased hydrodynamic radius and increased diffusion coefficient. This hydration force was related to so-called ion specific effect, and electrolyte sodium chloride had a more substantial effect on hydration force than KCl, CsCl, NaBr and NaI. Our results provide an experimental approach to explore the SMP structures, inter-colloid interactions and confirm the non-DLVO forces. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. International Symposium on Solute-Solute-Solvent Interactions (7th) Held at Reading, United Kingdom on 15-19 July 1985.

    Science.gov (United States)

    1985-07-19

    between conceptually opposed models, such as mass artion law binding and Poisson- Roltzmann condensation; and the few experimental cr teria available for a...Phys. 60, 1545 (19714). 2. R. Sonnenschein and K. Heinzinger, Chem. Phys. Lett. 102, 550 (1983). . 3. Gy. I. Szasz , K. Heinzinger and W.O. Riede, Z...between the gas and the aqueous phases is given by the Henry’s law constant, Ii, defined as H = HgX(g)J[IHgX(solv)] .1 The magnitude H is ~;trongly

  16. UV laser interaction with a fluorescent dye solution studied using pulsed digital holography.

    Science.gov (United States)

    Amer, Eynas; Gren, Per; Sjödahl, Mikael

    2013-10-21

    A frequency tripled Q-switched Nd-YAG laser (wavelength 355 nm, pulse duration 12 ns) has been used to pump Coumarin 153 dye solved in ethanol. Simultaneously, a frequency doubled pulse (532 nm) from the same laser is used to probe the solvent perpendicularly resulting in a gain through stimulated laser induced fluorescence (LIF) emission. The resulting gain of the probe beam is recorded using digital holography by blending it with a reference beam on the detector. Two digital holograms without and with the pump beam were recorded. Intensity maps were calculated from the recorded digital holograms and used to calculate the gain of the probe beam due to the stimulated LIF. In addition numerical data of the local temperature rise was calculated from the corresponding phase maps using Radon inversion. It was concluded that about 15% of the pump beam energy is transferred to the dye solution as heat while the rest is consumed in the radiative process. The results show that pulsed digital holography is a promising technique for quantitative study of fluorescent species.

  17. Temperature-based on-column solute focusing in capillary liquid chromatography reduces peak broadening from pre-column dispersion and volume overload when used alone or with solvent-based focusing.

    Science.gov (United States)

    Groskreutz, Stephen R; Horner, Anthony R; Weber, Stephen G

    2015-07-31

    On-column focusing is essential for satisfactory performance using capillary scale columns. On-column focusing results from generating transient conditions at the head of the column that lead to high solute retention. Solvent-based on-column focusing is a well-known approach to achieve this. Temperature-assisted on-column focusing (TASF) can also be effective. TASF improves focusing by cooling a short segment of the column inlet to a temperature that is lower than the column temperature during the injection and then rapidly heating the focusing segment to the match the column temperature. A troublesome feature of an earlier implementation of TASF was the need to leave the capillary column unpacked in that portion of the column inside the fitting connecting it to the injection valve. We have overcome that problem in this work by packing the head of the column with solid silica spheres. In addition, technical improvements to the TASF instrumentation include: selection of a more powerful thermo-electric cooler to create faster temperature changes and electronic control for easy incorporation into conventional capillary instruments. Used in conjunction with solvent-based focusing and with isocratic elution, volumes of paraben samples (esters of p-hydroxybenzoic acid) up to 4.5-times the column liquid volume can be injected without significant bandspreading due to volume overload. Interestingly, the shapes of the peaks from the lowest volume injections that we can make, 30nL, are improved when using TASF. TASF is very effective at reducing the detrimental effects of pre-column dispersion using isocratic elution. Finally, we show that TASF can be used to focus the neuropeptide galanin in a sample solvent with elution strength stronger than the mobile phase. Here, the stronger solvent is necessitated by the need to prevent peptide adsorption prior to and during analysis. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Temperature-based on-column solute focusing in capillary liquid chromatography reduces peak broadening from precolumn dispersion and volume overload when used alone or with solvent-based focusing

    Science.gov (United States)

    Groskreutz, Stephen R.; Horner, Anthony R.; Weber, Stephen G.

    2015-01-01

    On-column focusing is essential for satisfactory performance using capillary scale columns. On-column focusing results from generating transient conditions at the head of the column that lead to high solute retention. Solvent-based on-column focusing is a well-known approach to achieve this. Temperature-assisted on-column focusing (TASF) can also be effective. TASF improves focusing by cooling a short segment of the column inlet to a temperature that is lower than the column temperature during the injection and then rapidly heating the focusing segment to the match the column temperature. A troublesome feature of an earlier implementation of TASF was the need to leave the capillary column unpacked in that portion of the column inside the fitting connecting it to the injection valve. We have overcome that problem in this work by packing the head of the column with solid silica spheres. In addition, technical improvements to the TASF instrumentation include: selection of a more powerful thermo-electric cooler to create faster temperature changes and electronic control for easy incorporation into conventional capillary instruments. Used in conjunction with solvent-based focusing and with isocratic elution, volumes of paraben samples (esters of p-hydroxybenzoic acid) up to 4.5-times the column liquid volume can be injected without significant bandspreading due to volume overload. Interestingly, the shapes of the peaks from the lowest volume injections that we can make, 30 nL, are improved when using TASF. TASF is very effective at reducing the detrimental effects of precolumn dispersion using isocratic elution. Finally, we show that TASF can be used to focus the neuropeptide galanin in a sample solvent with elution strength stronger than the mobile phase. Here, the stronger solvent is necessitated by the need to prevent peptide adsorption prior to and during analysis. PMID:26091787

  19. The spectral properties of (--epigallocatechin 3-O-gallate (EGCG fluorescence in different solvents: dependence on solvent polarity.

    Directory of Open Access Journals (Sweden)

    Vladislav Snitsarev

    Full Text Available (--Epigallocatechin 3-O-gallate (EGCG a molecule found in green tea and known for a plethora of bioactive properties is an inhibitor of heat shock protein 90 (HSP90, a protein of interest as a target for cancer and neuroprotection. Determination of the spectral properties of EGCG fluorescence in environments similar to those of binding sites found in proteins provides an important tool to directly study protein-EGCG interactions. The goal of this study is to examine the spectral properties of EGCG fluorescence in an aqueous buffer (AB at pH=7.0, acetonitrile (AN (a polar aprotic solvent, dimethylsulfoxide (DMSO (a polar aprotic solvent, and ethanol (EtOH (a polar protic solvent. We demonstrate that EGCG is a highly fluorescent molecule when excited at approximately 275 nm with emission maxima between 350 and 400 nm depending on solvent. Another smaller excitation peak was found when EGCG is excited at approximately 235 nm with maximum emission between 340 and 400 nm. We found that the fluorescence intensity (FI of EGCG in AB at pH=7.0 is significantly quenched, and that it is about 85 times higher in an aprotic solvent DMSO. The Stokes shifts of EGCG fluorescence were determined by solvent polarity. In addition, while the emission maxima of EGCG fluorescence in AB, DMSO, and EtOH follow the Lippert-Mataga equation, its fluorescence in AN points to non-specific solvent effects on EGCG fluorescence. We conclude that significant solvent-dependent changes in both fluorescence intensity and fluorescence emission shifts can be effectively used to distinguish EGCG in aqueous solutions from EGCG in environments of different polarity, and, thus, can be used to study specific EGCG binding to protein binding sites where the environment is often different from aqueous in terms of polarity.

  20. Modeling the growth and interaction of stylolite networks, using the discrete element method for pressure solution

    Science.gov (United States)

    Makedonska, N.; Sparks, D. W.; Aharonov, E.

    2012-12-01

    Pressure solution (also termed chemical compaction) is considered the most important ductile deformation mechanism operating in the Earth's upper crust. This mechanism is a major player in a variety of geological processes, including evolution of sedimentary basins, hydrocarbon reservoirs, aquifers, earthquake recurrence cycles, and fault healing. Pressure solution in massive rocks often localizes into solution seams or stylolites. Field observations of stylolites often show elastic/brittle interactions in regions between pressure solution features, including and shear fractures, veins and pull-apart features. To understand these interactions, we use a grain-scale model based on the Discrete Element Method that allows granular dissolution at stressed contacts between grains. The new model captures both the slow chemical compaction process and the more abrupt brittle fracturing and sliding between grains. We simulate a sample of rock as a collection of particles, each representing either a grain or a unit of rock, bonded to each other with breakable cement. We apply external stresses to this sample, and calculate elastic and frictional interactions between the grains. Dissolution is modeled by an irreversible penetration of contacting grains into each other at a rate that depends on the contact stress and an adjustable rate constant. Experiments have shown that dissolution rates at grain contacts are greatly enhanced when there is a mineralogical contrast. Therefore, we dissolution rate constant can be increased to account for an amount of impurities (e.g. clay in a quartz or calcite sandstone) that can accumulate on dissolving contacts. This approach allows large compaction and shear strains within the rock, while allowing examination of local grain-scale heterogeneity. For example, we will describe the effect of pressure solution on the distribution of contact forces magnitudes and orientations. Contact forces in elastic granular packings are inherently

  1. Thermodynamic properties of solutions of sodium di-hydrogen phosphate in (1-propanol + water) mixed-solvent media over the temperature range of (283.15 to 303.15) K

    International Nuclear Information System (INIS)

    Sadeghi, Rahmat; Parhizkar, Hana

    2008-01-01

    The apparent molar volume and apparent molar isentropic compressibility of solutions of sodium di-hydrogen phosphate (NaH 2 PO 4 ) in (1-propanol + water) mixed-solvent media with alcohol mass fractions of 0.00, 0.05, 0.10, and 0.15 are reported over the range of temperature (283.15 to 303.15) K at 5 K intervals. The results were fitted to a Redlich-Mayer type equation from which the apparent molar volume and apparent molar isentropic compressibility of the solutions at the infinite dilution were also calculated at the working temperature. The results show a positive transfer volume of NaH 2 PO 4 from an aqueous solution to an aqueous 1-propanol solution. The apparent molar isentropic compressibility of NaH 2 PO 4 in aqueous 1-propanol solutions is negative and it increases with increasing the concentration of NaH 2 PO 4 , 1-propanol, and temperature. Electrical conductivity and refractive index of the solutions are also studied at T = 298.15 K. The effects of the electrolyte concentration and relative permittivity of the medium on the molar conductivity were also investigated

  2. Insecticide solvents: interference with insecticidal action.

    Science.gov (United States)

    Brattsten, L B; Wilkinson, C F

    1977-06-10

    Several commercial solvent mixtures commonly used as insecticide carriers in spray formulations increase by more than threefold the microsomal N-demethylation of p-chloro N-methylaniline in midgut preparations of southern army-worm (Spodoptera eridania) larvae exposed orally to the test solvents. Under laboratory conditions, the same solvent mixtures exhibit a protective action against the in vivo toxicity of the insecticide carbaryl to the larvae. The data are discussed with respect to possible solvent-insecticide interactions occurring under field conditions and, more broadly, to potential toxicological hazards of these solvents to humans.

  3. Restoring solvent for nuclear separation processes

    International Nuclear Information System (INIS)

    Reif, D.J.

    1987-01-01

    Solvent extraction separation processes are used to recover usable nuclear materials from spent fuels. These processes involve the use of an extractant/diluent (solvent) for separation of the reusable actinides from unwanted fission products. The most widely used processes employ tributyl phosphate as an extractant diluted with a normal-paraffin hydrocarbon. During use, the solvent is altered due to hydrolysis and radiolysis, forming materials that influence product losses, product decontamination, and separation efficiencies. In most processes, the solvent is recycled after cleaning. Solvent cleaning generally involves scrubbing with a sodium carbonate solution. Studies at the Savannah River Laboratory have shown that carbonate washing, although removing residual solvent activity, does not remove more solvent-soluble binding ligands (formed by solvent degradation), which hold fission products in the solvent. Treatment of the solvent with a solid adsorbent after carbonate washing removes binding ligands and significantly improves recycled solvent performance. Laboratory work to establish the advantage of adsorbent cleaning and the development of a full-scale adsorption process is described. The application of this process for cleaning the first cycle solvent of a Savannah River Plant production process is discussed

  4. Interactions between Surfactants in Solution and Electrospun Protein Fibers: Effects on Release Behavior and Fiber Properties

    DEFF Research Database (Denmark)

    Boutrup Stephansen, Karen; García-Díaz, María; Jessen, Flemming

    2016-01-01

    , and drug delivery. In the present study, we present a systematic investigation of how surfactants and proteins, as physiologically relevant components, interact with insulin-loaded fish sarcoplasmic protein (FSP) electrospun fibers (FSP-Ins fibers) in solution and thereby affect fiber properties...... such as accessible surface hydrophilicity, physical stability, and release characteristics of an encapsulated drug. Interactions between insulin-loaded protein fibers and five anionic surfactants (sodium taurocholate, sodium taurodeoxycholate, sodium glycocholate, sodium glycodeoxycholate, and sodium dodecyl sulfate......Intermolecular interaction phenomena occurring between endogenous compounds, such as proteins and bile salts, and electrospun compounds are so far unreported, despite the exposure of fibers to such biorelevant compounds when applied for biomedical purposes, e.g., tissue engineering, wound healing...

  5. Spectroscopic characterization of Greek dolomitic marble surface interacted with uranium and thorium in aqueous solutions

    International Nuclear Information System (INIS)

    Godelitsas, A.; Kokkoris, M.; Chatzitheodoridis, E.; Misaelides, P.

    2008-01-01

    The surface of a typical Greek (Thassian) dolomitic marble was studied after interaction with U- and Th-containing aqueous solutions (1000 mg/L, free-drift experiments for 1 week at atmospheric P CO 2 ), using 12 C-RBS and Laser μ-Raman spectroscopy. Powder-XRD and SEM-EDS were also applied to investigate the phases deposited on the surface of the interacted samples. The obtained results indicated a considerable removal of U from the aqueous medium mainly due to massive surface precipitation of amorphous UO 2 -hydroxide phases forming a relatively thick (μm-sized) coating on the carbonate substrate. The interaction of Th with dolomitic marble surface is also intense leading to a formation of an amorphous Th-hydroxide layer of similar thickness but of significantly lower elemental atomic proportion

  6. Spectroscopic characterization of Greek dolomitic marble surface interacted with uranium and thorium in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Godelitsas, A. [Faculty of Geology and Geoenvironment, University of Athens, 15784 Zographou, Athens (Greece)], E-mail: agodel@geol.uoa.gr; Kokkoris, M. [School of Applied Mathematics and Physics, National Technical University of Athens, 15780 Zographou, Athens (Greece); Chatzitheodoridis, E. [School of Mining and Metallurgical Engineering, National Technical University of Athens, 15780 Zographou, Athens (Greece); Misaelides, P. [Faculty of Chemistry, Aristotle University of Thessaloniki, 54124 Thessaloniki (Greece)

    2008-05-15

    The surface of a typical Greek (Thassian) dolomitic marble was studied after interaction with U- and Th-containing aqueous solutions (1000 mg/L, free-drift experiments for 1 week at atmospheric P{sub CO{sub 2}}), using {sup 12}C-RBS and Laser {mu}-Raman spectroscopy. Powder-XRD and SEM-EDS were also applied to investigate the phases deposited on the surface of the interacted samples. The obtained results indicated a considerable removal of U from the aqueous medium mainly due to massive surface precipitation of amorphous UO{sub 2}-hydroxide phases forming a relatively thick ({mu}m-sized) coating on the carbonate substrate. The interaction of Th with dolomitic marble surface is also intense leading to a formation of an amorphous Th-hydroxide layer of similar thickness but of significantly lower elemental atomic proportion.

  7. Spectroscopic characterization of Greek dolomitic marble surface interacted with uranium and thorium in aqueous solutions

    Science.gov (United States)

    Godelitsas, A.; Kokkoris, M.; Chatzitheodoridis, E.; Misaelides, P.

    2008-05-01

    The surface of a typical Greek (Thassian) dolomitic marble was studied after interaction with U- and Th-containing aqueous solutions (1000 mg/L, free-drift experiments for 1 week at atmospheric PCO2), using 12C-RBS and Laser μ-Raman spectroscopy. Powder-XRD and SEM-EDS were also applied to investigate the phases deposited on the surface of the interacted samples. The obtained results indicated a considerable removal of U from the aqueous medium mainly due to massive surface precipitation of amorphous UO2-hydroxide phases forming a relatively thick (μm-sized) coating on the carbonate substrate. The interaction of Th with dolomitic marble surface is also intense leading to a formation of an amorphous Th-hydroxide layer of similar thickness but of significantly lower elemental atomic proportion.

  8. Thermodynamics of the interaction between antihistamines with native and hydroxypropyl-cyclodextrin derivatives in aqueous solutions

    International Nuclear Information System (INIS)

    Alvarez-Lopez, Enrique; Perez-Casas, Silvia

    2013-01-01

    Highlights: • The complexes formation between cyclodextrins and pheniramines were studied by ITC. • In all the cases, the process is enthalpy driven. • The interactions between cyclodextrins and pheniramines are discussed. -- Abstract: The interactions of native and hydroxypropyl-cyclodextrin derivatives with pheniramine, (±)-brompheniramine, (+)-brompheniramine, (±)-chlorpheniramine, (+)-chlorpheniramine, carbinoxamine maleate salts and doxylamine succinate salt have been studied by isothermal titration calorimetry at T = 298.15 K in aqueous solution. The enthalpies and association constants for the complex formation were obtained, from which the Gibbs energy and entropy changes were derived. The thermodynamic parameters corresponding to the transfer process of the guest from the native to the modified CD are also calculated. The results show that the hydrophobic interactions are important in this process, but the size of the guest and the nature of the substituent are also of some importance

  9. Attractive interactions between reverse aggregates and phase separation in concentrated malonamide extractant solutions

    International Nuclear Information System (INIS)

    Erlinger, C.; Belloni, L.; Zemb, T.; Madic, C.

    1999-01-01

    Using small angle X-ray scattering, conductivity, and phase behavior determination, the authors show that concentrated solutions of malonamide extractants, dimethyldibutyltetradecylmalonamide (DMDBTDMA), are organized in reverse oligomeric aggregates which have many features in common with reverse micelles. The aggregation numbers of these reverse globular aggregates as well as their interaction potential are determined from absolute scattering curves. An attractive interaction is responsible for the demixing of the oil phase when in equilibrium with excess oil. Prediction of conductivity as well as the formation conditions for the third phase is possible using standard liquid theory applied to the extractant aggregates. The interactions, modeled with the sticky sphere model proposed by Baster, are shown to be due to steric interactions resulting from the hydrophobic tails of the extractant molecule and van der Waals forces between the highly polarizable water core of the reverse micelles. The attractive interaction in the oil phase, equilibrated with water, is determined as a function of temperature, extractant molecule concentration, and proton and neodynium(III) cation concentration. It is shown that van der Waals interactions, with an effective Hamaker constant of 3kT, quantitatively explain the behavior of DMDBTDMA in n-dodecane in terms of scattering as well as phase stability limits

  10. Molecular interactions and redox effects of carvacrol and thymol on myofibrillar proteins using a non-destructive and solvent-free methodological approach.

    Science.gov (United States)

    Lahmar, Aida; Akcan, Tolga; Chekir-Ghedira, Leila; Estévez, Mario

    2018-04-01

    The present study provides molecular insight into the effect of thymol and carvacrol on the oxidative damage caused to myofibrillar proteins by a hydroxyl-radical generating system (HRGS). An innovative model system was designed, in which gels, prepared with increasing levels of myofibrillar proteins, were oxidized by a HRGS (Fe 3+ /H 2 O 2 , 60 °C and 7 days) in the presence of lipids. The molecular affinity between myofibrillar proteins and both terpenes, as well as their effect on the oxidative stability of the gel systems, were studied using a non-destructive and solvent-free procedure based on fluorescence spectroscopy. Carvacrol displayed more affinity than thymol for establishing chemical interactions with protein residues. Both terpenes exhibited a significant antioxidant potential against the generation of lipid-derived volatile carbonyls and against the formation of protein crosslinking. This procedure may be applied to meat products to assess the effectiveness of a given antioxidant additive without size reduction or sample processing. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. Interaction of sodium monoborate and boric acid with some mono- and disaccharides in aqueous solutions (from data on isomolar solutions method)

    International Nuclear Information System (INIS)

    Shvarts, E.M.; Ignash, R.T.; Belousova, R.G.

    2000-01-01

    Interaction of sodium monoborate Na[B(OH) 4 ] and boric acid with D-glucose, D-fructose, D-saccharose and D-lactose in aqueous solution depending on the solution total concentration is studied through the method of isomolar solutions with application of conductometry and polarimetry. It is shown by the D-glucose and D-fructose examples that the method of isomolar solutions leads to results compatible with the data obtained by other methods and it may be applied to other saccharides [ru

  12. Solution interactions of diclofenac sodium and meclofenamic acid sodium with hydroxypropyl methylcellulose (HPMC).

    Science.gov (United States)

    Pygall, Samuel R; Griffiths, Peter C; Wolf, Bettina; Timmins, Peter; Melia, Colin D

    2011-02-28

    Many pharmaceutical agents require formulation in order to facilitate their efficacious delivery. However, the interaction between the active species and the formulation additives has the potential to significantly influence the pharmocokinetics of the active. In this study, the solution interactions between hydroxypropyl methylcellulose (HPMC) with two non-steroidal anti-inflammatories - the sodium salts of diclofenac and meclofenamate - were investigated using tensiometric, rheological, NMR, neutron scattering and turbidimetric techniques. The two drugs behaved very differently-meclofenamate addition to HPMC solutions led to substantial increases in viscosity, a depression of the gel point and a marked reduction in the self-diffusion coefficient of the drug, whereas diclofenac did not induce these changes. Collectively, these observations are evidence of meclofenamate forming self-assembled aggregates on the HPMC, a phenomenon not observed with diclofenac Na. Any process that leads to aggregation on a nonionic polymer will not be strongly favoured when the aggregating species is charged. Thus, it is hypothesised that the distinction between the two drugs arises as a consequence of the tautomerism present in meclofenamate that builds electron density on the carbonyl group that is further stabilised by hydrogen bonding to the HPMC. This mechanism is absent in the diclofenac case and thus no interaction is observed. These studies propose for the first time a molecular basis for the observed often-unexpected, concentration-dependant changes in HPMC solution properties when co-formulated with different NSAIDs, and underline the importance of characterising such fundamental interactions that have the potential to influence drug release in solid HPMC-based dosage forms. Copyright © 2010 Elsevier B.V. All rights reserved.

  13. Integrating R and Java for Enhancing Interactivity of Algorithmic Data Analysis Software Solutions

    Directory of Open Access Journals (Sweden)

    Titus Felix FURTUNĂ

    2016-06-01

    Full Text Available Conceiving software solutions for statistical processing and algorithmic data analysis involves handling diverse data, fetched from various sources and in different formats, and presenting the results in a suggestive, tailorable manner. Our ongoing research aims to design programming technics for integrating R developing environment with Java programming language for interoperability at a source code level. The goal is to combine the intensive data processing capabilities of R programing language, along with the multitude of statistical function libraries, with the flexibility offered by Java programming language and platform, in terms of graphical user interface and mathematical function libraries. Both developing environments are multiplatform oriented, and can complement each other through interoperability. R is a comprehensive and concise programming language, benefiting from a continuously expanding and evolving set of packages for statistical analysis, developed by the open source community. While is a very efficient environment for statistical data processing, R platform lacks support for developing user friendly, interactive, graphical user interfaces (GUIs. Java on the other hand, is a high level object oriented programming language, which supports designing and developing performant and interactive frameworks for general purpose software solutions, through Java Foundation Classes, JavaFX and various graphical libraries. In this paper we treat both aspects of integration and interoperability that refer to integrating Java code into R applications, and bringing R processing sequences into Java driven software solutions. Our research has been conducted focusing on case studies concerning pattern recognition and cluster analysis.

  14. Self-interacting inelastic dark matter: a viable solution to the small scale structure problems

    Energy Technology Data Exchange (ETDEWEB)

    Blennow, Mattias; Clementz, Stefan; Herrero-Garcia, Juan, E-mail: emb@kth.se, E-mail: scl@kth.se, E-mail: juan.herrero-garcia@adelaide.edu.au [Department of Physics, School of Engineering Sciences, KTH Royal Institute of Technology, AlbaNova University Center, 106 91 Stockholm (Sweden)

    2017-03-01

    Self-interacting dark matter has been proposed as a solution to the small-scale structure problems, such as the observed flat cores in dwarf and low surface brightness galaxies. If scattering takes place through light mediators, the scattering cross section relevant to solve these problems may fall into the non-perturbative regime leading to a non-trivial velocity dependence, which allows compatibility with limits stemming from cluster-size objects. However, these models are strongly constrained by different observations, in particular from the requirements that the decay of the light mediator is sufficiently rapid (before Big Bang Nucleosynthesis) and from direct detection. A natural solution to reconcile both requirements are inelastic endothermic interactions, such that scatterings in direct detection experiments are suppressed or even kinematically forbidden if the mass splitting between the two-states is sufficiently large. Using an exact solution when numerically solving the Schrödinger equation, we study such scenarios and find regions in the parameter space of dark matter and mediator masses, and the mass splitting of the states, where the small scale structure problems can be solved, the dark matter has the correct relic abundance and direct detection limits can be evaded.

  15. Interactions between fluorinated cationic guar gum and surfactants in the dilute and semi-dilute solutions.

    Science.gov (United States)

    Wang, Chen; Li, Xiaorui; Li, Peizhi; Niu, Yuhua

    2014-01-01

    The interactions between the fluorinated cationic guar gum (FCGG) and ionic surfactants including cetyl trimethyl ammonium bromide (CTAB) and sodium lauryl sulfate (SDS) were studied by light scattering, fluorescence spectroscopy, UV-spectrophotometer, (19)F NMR and dynamic rheometer, respectively. The FCGG is prepared with cationic guar gum, isophorone diisocyanate and 2,2,3,4,4,4-hexafluoro-1-butanol. The results show that, with the addition of the surfactants, the stretching degree of the FCGG chains is increased in the FCGG/CTAB solutions, while the dramatical shrinking of FCGG chain, the phase separation and the re-stretched macromolecules appear successively because of the electricity neutralization reaction in the FCGG/SDS system. The mixed hydrophobic domains in all solutions will be reinforced and then dismantled. The solution elasticity shows up the maximum value accordingly. The surfactants can be embedded in the micro-domains and then hinder the fluorinated segmental motions. The interactions between FCGG and SDS are much stronger than those between FCGG and CTAB. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Solvent sorting in (mixed solvent electrolyte) systems: Time-resolved ...

    Indian Academy of Sciences (India)

    lar solvents as an effective single component dipo- lar liquid that is characterized ... and time (t) dependent solvation energy of mobile dipo- lar solute with density ..... Even though this way for modification of C is purely ad- hoc, the observation ...

  17. Indium recovery by solvent extraction

    International Nuclear Information System (INIS)

    Fortes, Marilia Camargos Botelho

    1999-04-01

    Indium has been recovered as a byproduct from residues generated from the sulfuric acid leaching circuits in mineral plants for zinc recovery. Once its recovery comes from the slags of other metals recovery, it is necessary to separate it from the other elements which usually are present in high concentrations. Many works have been approaching this separation and indicate the solvent extraction process as the main technique used. In Brazilian case, indium recovery depends on the knowledge of this technique and its development. This paper describes the solvent extraction knowledge for the indium recovery from aqueous solutions generated in mineral plants. The results for determination of the best experimental conditions to obtain a high indium concentration solution and minimum iron poisoning by solvent extraction with di (2-ethylhexyl)-phosphoric acid (D2EHPA) solubilized in isoparafin and exxsol has been presented. (author)

  18. Structure and dynamics of solutions

    CERN Document Server

    Ohtaki, H

    2013-01-01

    Recent advances in the study of structural and dynamic properties of solutions have provided a molecular picture of solute-solvent interactions. Although the study of thermodynamic as well as electronic properties of solutions have played a role in the development of research on the rate and mechanism of chemical reactions, such macroscopic and microscopic properties are insufficient for a deeper understanding of fast chemical and biological reactions. In order to fill the gap between the two extremes, it is necessary to know how molecules are arranged in solution and how they change their pos

  19. Proliferating cell nuclear antigen (PCNA interactions in solution studied by NMR.

    Directory of Open Access Journals (Sweden)

    Alfredo De Biasio

    Full Text Available PCNA is an essential factor for DNA replication and repair. It forms a ring shaped structure of 86 kDa by the symmetric association of three identical protomers. The ring encircles the DNA and acts as a docking platform for other proteins, most of them containing the PCNA Interaction Protein sequence (PIP-box. We have used NMR to characterize the interactions of PCNA with several other proteins and fragments in solution. The binding of the PIP-box peptide of the cell cycle inhibitor p21 to PCNA is consistent with the crystal structure of the complex. A shorter p21 peptide binds with reduced affinity but retains most of the molecular recognition determinants. However the binding of the corresponding peptide of the tumor suppressor ING1 is extremely weak, indicating that slight deviations from the consensus PIP-box sequence dramatically reduce the affinity for PCNA, in contrast with a proposed less stringent PIP-box sequence requirement. We could not detect any binding between PCNA and the MCL-1 or the CDK2 protein, reported to interact with PCNA in biochemical assays. This suggests that they do not bind directly to PCNA, or they do but very weakly, with additional unidentified factors stabilizing the interactions in the cell. Backbone dynamics measurements show three PCNA regions with high relative flexibility, including the interdomain connector loop (IDCL and the C-terminus, both of them involved in the interaction with the PIP-box. Our work provides the basis for high resolution studies of direct ligand binding to PCNA in solution.

  20. Effective interactions in lysozyme aqueous solutions: a small-angle neutron scattering and computer simulation study.

    Science.gov (United States)

    Abramo, M C; Caccamo, C; Costa, D; Pellicane, G; Ruberto, R; Wanderlingh, U

    2012-01-21

    We report protein-protein structure factors of aqueous lysozyme solutions at different pH and ionic strengths, as determined by small-angle neutron scattering experiments. The observed upturn of the structure factor at small wavevectors, as the pH increases, marks a crossover between two different regimes, one dominated by repulsive forces, and another one where attractive interactions become prominent, with the ensuing development of enhanced density fluctuations. In order to rationalize such experimental outcome from a microscopic viewpoint, we have carried out extensive simulations of different coarse-grained models. We have first studied a model in which macromolecules are described as soft spheres interacting through an attractive r(-6) potential, plus embedded pH-dependent discrete charges; we show that the uprise undergone by the structure factor is qualitatively predicted. We have then studied a Derjaguin-Landau-Verwey-Overbeek (DLVO) model, in which only central interactions are advocated; we demonstrate that this model leads to a protein-rich/protein-poor coexistence curve that agrees quite well with the experimental counterpart; experimental correlations are instead reproduced only at low pH and ionic strengths. We have finally investigated a third, "mixed" model in which the central attractive term of the DLVO potential is imported within the distributed-charge approach; it turns out that the different balance of interactions, with a much shorter-range attractive contribution, leads in this latter case to an improved agreement with the experimental crossover. We discuss the relationship between experimental correlations, phase coexistence, and features of effective interactions, as well as possible paths toward a quantitative prediction of structural properties of real lysozyme solutions. © 2012 American Institute of Physics

  1. Electronic-property dependent interactions between tetracycline and graphene nanomaterials in aqueous solution.

    Science.gov (United States)

    He, Lin; Liu, Fei-Fei; Zhao, Mengyao; Qi, Zhen; Sun, Xuefei; Afzal, Muhammad Zaheer; Sun, Xiaomin; Li, Yanhui; Hao, Jingcheng; Wang, Shuguang

    2018-04-01

    Understanding the interactions between graphene nanomaterials (GNMs) and antibiotics in aqueous solution is critical to both the engineering applications of GNMs and the assessment of their potential impact on the fate and transport of antibiotics in the aquatic environment. In this study, adsorption of one common antibiotic, tetracycline, by graphene oxide (GO) and reduced graphene oxide (RGO) was examined with multi-walled carbon nanotubes (MWCNTs) and graphite as comparison. The results showed that the tetracycline adsorption capacity by the four selected carbonaceous materials on the unit mass basis followed an order of GO>RGO>MWCNTs>graphite. Upon normalization by surface area, graphite, RGO and MWCNTs had almost the same high tetracycline adsorption affinity while GO exhibited the lowest. We proposed π-electron-property dependent interaction mechanisms to explain the observed different adsorption behaviors. Density functional theory (DFT) calculations suggested that the oxygen-containing functional groups on GO surface reduced its π-electron-donating ability, and thus decreased the π-based interactions between tetracycline and GO surface. Comparison of adsorption efficiency at different pH indicated that electrostatic interaction also played an important role in tetracycline-GO interactions. Site energy analysis confirmed a highly heterogeneous distribution of the binding sites and strong tetracycline binding affinity of GO surface. Copyright © 2017. Published by Elsevier B.V.

  2. On the role of specific interactions in the diffusion of nanoparticles in aqueous polymer solutions.

    Science.gov (United States)

    Mun, Ellina A; Hannell, Claire; Rogers, Sarah E; Hole, Patrick; Williams, Adrian C; Khutoryanskiy, Vitaliy V

    2014-01-14

    Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(N-vinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions.

  3. Interaction Between Cyanine Dye IR-783 and Polystyrene Nanoparticles in Solution.

    Science.gov (United States)

    Zhang, Yunzhi; Xu, Hui; Casabianca, Leah B

    2018-05-17

    The interactions between small molecule drugs or dyes and nanoparticles are important to the use of nanoparticles in medicine. Noncovalent adsorption of dyes on nanoparticle surfaces is also important to the development of nanoparticle dual-use imaging contrast agents. In the present work, solution-state NMR is used to examine the noncovalent interaction between a near-infrared cyanine dye and the surface of polystyrene nanoparticles in solution. Using 1D proton NMR, we can approximate the number of dye molecules that associate with each nanoparticle for different sized nanoparticles. Saturation-Transfer Difference (STD)-NMR was also used to show that protons near the positively-charged nitrogen in the dye are more strongly associated with the negatively-charged nanoparticle surface than protons near the negatively-charged sulfate groups of the dye. The methods described here can be used to study similar drug or dye molecules interacting with the surface of organic nanoparticles. This article is protected by copyright. All rights reserved.

  4. Caffeine and sugars interact in aqueous solutions: a simulation and NMR study.

    Science.gov (United States)

    Tavagnacco, Letizia; Engström, Olof; Schnupf, Udo; Saboungi, Marie-Louise; Himmel, Michael; Widmalm, Göran; Cesàro, Attilio; Brady, John W

    2012-09-27

    Molecular dynamics simulations were carried out on several systems of caffeine interacting with simple sugars. These included a single caffeine molecule in a 3 m solution of α-D-glucopyranose, at a caffeine concentration of 0.083 m, a single caffeine in a 3 m solution of β-D-glucopyranose, and a single caffeine molecule in a 1.08 m solution of sucrose (table sugar). Parallel nuclear magnetic resonance titration experiments were carried out on the same solutions under similar conditions. Consistent with previous thermodynamic experiments, the sugars were found to have an affinity for the caffeine molecules in both the simulations and experiments, and the binding in these complexes occurs by face-to-face stacking of the hydrophobic triad of protons of the pyranose rings against the caffeine face, rather than by hydrogen bonding. For the disaccharide, the binding occurs via stacking of the glucose ring against the caffeine, with a lesser affinity for the fructose observed. These findings are consistent with the association being driven by hydrophobic hydration and are similar to the previously observed binding of glucose rings to various other planar molecules, including indole, serotonin, and phenol.

  5. Neoclassical Solution of Transient Interaction of Plane Acoustic Waves with a Spherical Elastic Shell

    Directory of Open Access Journals (Sweden)

    Hanson Huang

    1996-01-01

    Full Text Available A detailed solution to the transient interaction of plane acoustic waves with a spherical elastic shell was obtained more than a quarter of a century ago based on the classical separation of variables, series expansion, and Laplace transform techniques. An eight-term summation of the time history series was sufficient for the convergence of the shell deflection and strain, and to a lesser degree, the shell velocity. Since then, the results have been used routinely for validation of solution techniques and computer methods for the evaluation of underwater explosion response of submerged structures. By utilizing modern algorithms and exploiting recent advances of computer capacities and floating point mathematics, sufficient terms of the inverse Laplace transform series solution can now be accurately computed. Together with the application of the Cesaro summation using up to 70 terms of the series, two primary deficiencies of the previous solution are now remedied: meaningful time histories of higher time derivative data such as acceleration and pressure are now generated using a sufficient number of terms in the series; and uniform convergence around the discontinuous step wave front is now obtained, completely eradicating spurious oscillations due to the Gibbs' phenomenon. New results of time histories of response items of interest are presented.

  6. Discrimination of solvent from protein regions in native Fouriers as a means of evaluating heavy-atom solutions in the MIR and MAD methods

    International Nuclear Information System (INIS)

    Terwilliger, Thomas C.; Berendzen, Joel

    1999-01-01

    The presence of distinct regions of high and low density variation in electron-density maps is found to be a good indicator of the correctness of a heavy-atom solution in the MIR and MAD methods. An automated examination of the native Fourier is tested as a means of evaluation of a heavy-atom solution in MAD and MIR methods for macromolecular crystallography. It is found that the presence of distinct regions of high and low density variation in electron-density maps is a good indicator of the correctness of a heavy-atom solution in the MIR and MAD methods. The method can be used to evaluate heavy-atom solutions during MAD and MIR structure solutions and to determine the handedness of the structure if anomalous data have been measured

  7. Interaction Mechanisms between Air Bubble and Molybdenite Surface: Impact of Solution Salinity and Polymer Adsorption.

    Science.gov (United States)

    Xie, Lei; Wang, Jingyi; Yuan, Duowei; Shi, Chen; Cui, Xin; Zhang, Hao; Liu, Qi; Liu, Qingxia; Zeng, Hongbo

    2017-03-07

    The surface characteristics of molybdenite (MoS 2 ) such as wettability and surface interactions have attracted much research interest in a wide range of engineering applications, such as froth flotation. In this work, a bubble probe atomic force microscope (AFM) technique was employed to directly measure the interaction forces between an air bubble and molybdenite mineral surface before/after polymer (i.e., guar gum) adsorption treatment. The AFM imaging showed that the polymer coverage on the surface of molybdenite could achieve ∼5.6, ∼44.5, and ∼100% after conditioning in 1, 5, and 10 ppm polymer solution, respectively, which coincided with the polymer coverage results based on contact angle measurements. The electrolyte concentration and surface treatment by polymer adsorption were found to significantly affect bubble-mineral interaction and attachment. The experimental force results on bubble-molybdenite (without polymer treatment) agreed well with the calculations using a theoretical model based on the Reynolds lubrication theory and augmented Young-Laplace equation including the effect of disjoining pressure. The overall surface repulsion was enhanced when the NaCl concentration decreased from 100 to 1 mM, which inhibited the bubble-molybdenite attachment. After conditioning the molybdenite surface in 1 ppm polymer solution, it was more difficult for air bubbles to attach to the molybdenite surface due to the weakened hydrophobic interaction with a shorter decay length. Increasing the polymer concentration to 5 ppm effectively inhibited bubble attachment on mineral surface, which was mainly due to the much reduced hydrophobic interaction as well as the additional steric repulsion between the extended polymer chains and bubble surface. The results provide quantitative information on the interaction mechanism between air bubbles and molybdenite mineral surfaces on the nanoscale, with useful implications for the development of effective polymer

  8. Interactive telemedicine solution based on a secure mHealth application.

    Science.gov (United States)

    Eldeib, Ayman M

    2014-01-01

    In dynamic healthcare environments, caregivers and patients are constantly moving. To increase the healthcare quality when it is necessary, caregivers need the ability to reach each other and securely access medical information and services from wherever they happened to be. This paper presents an Interactive Telemedicine Solution (ITS) to facilitate and automate the communication within a healthcare facility via Voice over Internet Protocol (VOIP), regular mobile phones, and Wi-Fi connectivity. Our system has the capability to exchange/provide securely healthcare information/services across geographic barriers through 3G/4G wireless communication network. Our system assumes the availability of an Electronic Health Record (EHR) system locally in the healthcare organization and/or on the cloud network such as a nation-wide EHR system. This paper demonstrate the potential of our system to provide effectively and securely remote healthcare solution.

  9. On the solution of the equations for nonlinear interaction of three damped waves

    International Nuclear Information System (INIS)

    1976-01-01

    Three-wave interactions are analyzed in a coherent wave description assuming different linear damping (or growth) of the individual waves. It is demonstrated that when two of the coefficients of dissipation are equal, the set of equations can be reduced to a single equivalent equation, which in the nonlinearly unstable case, where one wave is undamped, asymptotically takes the form of an equation defining the third Painleve transcendent. It is then possible to find an asymptotic expansion near the time of explosion. This solution is of principal interest since it indicates that the solution of the general three-wave system, where the waves undergo different individual dissipations, belongs to a higher class of functions, which reduces to Jacobian elliptic functions only in the case where all waves suffer the same damping [fr

  10. A family of solutions with radiation reaction and retarded interactions for two charges in classical electrodynamics

    International Nuclear Information System (INIS)

    Rivera, R.; Villarroel, D.

    2002-01-01

    A family of solutions of the Lorentz-Dirac equation is constructed. It consists in the motion of two charges e 1 and e 2 of masses m 1 and m 2 in two coplanar and concentric circles of radii a and b. The charges rotate with constant angular velocity, and have an angular separation ψ. The radiation reaction forces and the retarded interactions between the charges are taken into account. The external electromagnetic field that allows the motion consists of a tangential time-independent electric field that takes a fixed value on each orbit, and a homogeneous time-independent magnetic field perpendicular to the plane of the motion. For all the solutions energy conservation is rigorously demonstrated by evaluating the energy radiated, with independence of the equation of motion, through the calculation of the instantaneous energy flux across a sphere of an infinitely large radius

  11. Interaction between lactose and cadmium chloride in aqueous solutions as seen by diffusion coefficients measurements

    International Nuclear Information System (INIS)

    Verissimo, Luis M.P.; Gomes, Joselaine C.S.; Romero, Carmen; Esteso, Miguel A.; Sobral, Abilio J.F.N.; Ribeiro, Ana C.F.

    2013-01-01

    Highlights: ► Diffusion coefficients of aqueous systems containing lactose and cadmium chloride. ► Influence of the lactose on the diffusion of cadmium chloride. ► Interactions between Cd 2+ and lactose. -- Abstract: Diffusion coefficients of an aqueous system containing cadmium chloride 0.100 mol · dm −3 and lactose at different concentrations at 25 °C have been measured, using a conductimetric cell and an automatic apparatus to follow diffusion. The cell relies on an open-ended capillary method and a conductimetric technique is used to follow the diffusion process by measuring the resistance of a solution inside the capillaries, at recorded times. From these results and by ab initio calculations, it was possible to obtain a better understanding of the effect of lactose on transport of cadmium chloride in aqueous solutions

  12. Interactions of hydrazine, ferrous sulfamate, sodium nitrite, and nitric acid in nuclear fuel processing solutions

    International Nuclear Information System (INIS)

    Gray, L.W.

    1977-03-01

    Hydrazine and ferrous sulfamate are used as reductants in a variety of nuclear fuel processing solutions. An oxidant, normally sodium nitrite, must frequently be added to these nitric acid solutions before additional processing can proceed. The interactions of these four chemicals have been studied under a wide variety of conditions using a 2/sup p/ factorial experimental design to determine relative reaction rates for desired reactions and side reactions. Evidence for a hydrazine-stabilized, sulfamic acid--nitrous acid intermediate was obtained; this intermediate can hydrolyze to ammonia or decompose to nitrogen. The oxidation of Fe 2+ by NO 2 - was shown to proceed at about the same rate as the scavenging of NO 2 - by sulfamic acid. Various side reactions are discussed

  13. Results and preliminary analysis of critical experiments with interacting slab solution tanks

    International Nuclear Information System (INIS)

    Gurin, Victor N.; Ryazanov, Boris G.; Sviridov, Victor I.

    2003-01-01

    The paper presents the main results of several sets of critical experiments with two interacting similar slab tanks filled with aqueous solution of uranyl nitrate with uranium of 90% enrichment. These experiments were carried out at the RF-GS facility, Obninsk, Russia. Tanks with the thickness of 15 cm, width of 100 cm and height of 120 cm were used in these experiments. The experiments were conducted with partitions made of concrete, brick, polyethylene, cadmium, borated polyethylene. Consideration was given to the dependence of critical volume in each tank on the distance between the tanks and on the partition thickness. The tanks were filled with solutions of highly enriched uranium with its concentrations of 75 g/L and 250 g/L. Critical experiments were analysed with the MCNP 4A code based on the Monte-Carlo method and with the ENDF/B-V library. (author)

  14. Effect of the Solvent Temperatures on Dynamics of Serine Protease Proteinase K

    Directory of Open Access Journals (Sweden)

    Peng Sang

    2016-02-01

    Full Text Available To obtain detailed information about the effect of the solvent temperatures on protein dynamics, multiple long molecular dynamics (MD simulations of serine protease proteinase K with the solute and solvent coupled to different temperatures (either 300 or 180 K have been performed. Comparative analyses demonstrate that the internal flexibility and mobility of proteinase K are strongly dependent on the solvent temperatures but weakly on the protein temperatures. The constructed free energy landscapes (FELs at the high solvent temperatures exhibit a more rugged surface, broader spanning range, and higher minimum free energy level than do those at the low solvent temperatures. Comparison between the dynamic hydrogen bond (HB numbers reveals that the high solvent temperatures intensify the competitive HB interactions between water molecules and protein surface atoms, and this in turn exacerbates the competitive HB interactions between protein internal atoms, thus enhancing the conformational flexibility and facilitating the collective motions of the protein. A refined FEL model was proposed to explain the role of the solvent mobility in facilitating the cascade amplification of microscopic motions of atoms and atomic groups into the global collective motions of the protein.

  15. Weakly hydrated surfaces and the binding interactions of small biological solutes.

    Science.gov (United States)

    Brady, John W; Tavagnacco, Letizia; Ehrlich, Laurent; Chen, Mo; Schnupf, Udo; Himmel, Michael E; Saboungi, Marie-Louise; Cesàro, Attilio

    2012-04-01

    Extended planar hydrophobic surfaces, such as are found in the side chains of the amino acids histidine, phenylalanine, tyrosine, and tryptophan, exhibit an affinity for the weakly hydrated faces of glucopyranose. In addition, molecular species such as these, including indole, caffeine, and imidazole, exhibit a weak tendency to pair together by hydrophobic stacking in aqueous solution. These interactions can be partially understood in terms of recent models for the hydration of extended hydrophobic faces and should provide insight into the architecture of sugar-binding sites in proteins.

  16. Covariant interactions of two spinless particles: all local solutions of the angular condition

    International Nuclear Information System (INIS)

    Leutwyler, H.; Stern, J.

    1977-06-01

    The solutions of the algebraic problem posed by covariant Hamiltonian quantum mechanics are discussed. If, in the transverse relative coordinates, the mass and spin operators are differential operators of at most second order, the system is shown to be described by a manifestly covariant wave equation supplemented with a covariant constraint. If, in addition, one requires the wave equation and the constraint to be local in the coordinates of both particles, the freedom left in the interaction reduces to four constants. The resulting class of systems represents a generalization of the relativistic oscillator of Feynman, Kislinger and Ravndal

  17. Interactions between Surfactants in Solution and Electrospun Protein Fibers: Effects on Release Behavior and Fiber Properties

    DEFF Research Database (Denmark)

    Boutrup Stephansen, Karen; García-Díaz, María; Jessen, Flemming

    2016-01-01

    , and drug delivery. In the present study, we present a systematic investigation of how surfactants and proteins, as physiologically relevant components, interact with insulin-loaded fish sarcoplasmic protein (FSP) electrospun fibers (FSP-Ins fibers) in solution and thereby affect fiber properties...... such as accessible surface hydrophilicity, physical stability, and release characteristics of an encapsulated drug. Interactions between insulin-loaded protein fibers and five anionic surfactants (sodium taurocholate, sodium taurodeoxycholate, sodium glycocholate, sodium glycodeoxycholate, and sodium dodecyl sulfate......), a cationic surfactant (benzalkonium chloride), and a neutral surfactant (Triton X-100) were studied. The anionic surfactants increased the insulin release in a concentration-dependent manner, whereas the neutral surfactant had no significant effect on the release. Interestingly, only minute amounts...

  18. Study of interaction of bismuth, strontium, calcium copper, lead nitrates solutions with sodium oxalate solution with the aim of HTSC synthesis

    International Nuclear Information System (INIS)

    Danilov, V.P.; Krasnobaeva, O.N.; Nosova, T.A.

    1993-01-01

    With the aim of developing a new technique for HTSC oxides synthesis on the base of combined sedimentation of hydroxy salts and their heat treatment is studied interaction of bismuth, strontium, calcium, copper and lead nitrates with alkali solution of sodium oxalate. Conditions for total sedimentation of all five metals from the solution are found. The phase composition of interaction products is determined. It is established that they are high-dispersed homogeneous mixture of three phases of variable composition: twin hydroxalate of copper-bismuth, lead hydroxalate and twin oxalate of strontium-calcium. After heat treatment of the phases are obtained the HTSC oxides

  19. Vector boson star solutions with a quartic order self-interaction

    Science.gov (United States)

    Minamitsuji, Masato

    2018-05-01

    We investigate boson star (BS) solutions in the Einstein-Proca theory with the quartic order self-interaction of the vector field λ (AμA¯ μ)2/4 and the mass term μ A¯ μAμ/2 , where Aμ is the complex vector field and A¯μ is the complex conjugate of Aμ, and λ and μ are the coupling constant and the mass of the vector field, respectively. The vector BSs are characterized by the two conserved quantities, the Arnowitt-Deser-Misner (ADM) mass and the Noether charge associated with the global U (1 ) symmetry. We show that in comparison with the case without the self-interaction λ =0 , the maximal ADM mass and Noether charge increase for λ >0 and decrease for λ vector field above which there is no vector BS solution, and for λ >0 it can be expressed by the simple analytic expression. For a sufficiently large positive coupling Λ ≔Mpl2λ /(8 π μ2)≫1 , the maximal ADM mass and Noether charge of the vector BSs are obtained from the critical central amplitude and of O [√{λ }Mpl3/μ2ln (λ Mpl2/μ2)] , which is different from that of the scalar BSs, O (√{λϕ }Mpl3/μϕ2) , where λϕ and μϕ are the coupling constant and the mass of the complex scalar field.

  20. Electrochemical methods to study hydrogen production during interaction of copper with deoxygenated aqueous solution

    International Nuclear Information System (INIS)

    Lilja, Christina; Betova, Iva; Bojinov, Martin

    2016-01-01

    In some countries, spent nuclear fuel is planned to be encapsulated in canisters with a copper shell for corrosion protection, for further disposal in geologic repositories. The possibilities for corrosion after oxygen depletion must be evaluated, even if copper is considered to be immune in oxygen-free water. To follow the interaction of copper with deoxygenated aqueous solution, open-circuit potentiometric and electrochemical impedance measurements have been coupled to in-situ detection of cupric ion, dissolved molecular hydrogen and oxygen concentrations using electrochemical sensors. A kinetic model that considers the production of hydrogen as a catalytic process, the rate of which is proportional to the surface coverage of an intermediate species formed during interaction between copper and the solution is used to interpret the results. Kinetic parameters are estimated by a simultaneous fit of the experimental impedance spectra, the open circuit potential and cupric ion concentration as depending on temperature (22–70 °C) and exposure time (up to 720 h) to the model equations. Using the obtained values and a balance equation of hydrogen production on copper and its diffusion out of the cell through its walls, the kinetic parameters of this process are estimated by fitting dissolved molecular hydrogen concentration vs. time data at the three temperatures.

  1. Interaction between blood-brain barrier and glymphatic system in solute clearance.

    Science.gov (United States)

    Verheggen, I C M; Van Boxtel, M P J; Verhey, F R J; Jansen, J F A; Backes, W H

    2018-03-30

    Neurovascular pathology concurs with protein accumulation, as the brain vasculature is important for waste clearance. Interstitial solutes, such as amyloid-β, were previously thought to be primarily cleared from the brain by blood-brain barrier transport. Recently, the glymphatic system was discovered, in which cerebrospinal fluid is exchanged with interstitial fluid, facilitated by the aquaporin-4 water channels on the astroglial endfeet. Glymphatic flow can clear solutes from the interstitial space. Blood-brain barrier transport and glymphatic clearance likely serve complementary roles with partially overlapping mechanisms providing a well-conditioned neuronal environment. Disruption of these mechanisms can lead to protein accumulation and may initiate neurodegenerative disorders, for instance amyloid-β accumulation and Alzheimer's disease. Although both mechanisms seem to have a similar purpose, their interaction has not been clearly discussed previously. This review focusses on this interaction in healthy and pathological conditions. Future health initiatives improving waste clearance might delay or even prevent onset of neurodegenerative disorders. Defining glymphatic flow kinetics using imaging may become an alternative way to identify those at risk of Alzheimer's disease. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

  2. Solution NMR study of the yeast cytochrome c peroxidase: cytochrome c interaction

    Energy Technology Data Exchange (ETDEWEB)

    Volkov, Alexander N., E-mail: ovolkov@vub.ac.be; Nuland, Nico A. J. van [Vrije Universiteit Brussel, Jean Jeener NMR Centre, Structural Biology Brussels (Belgium)

    2013-07-15

    Here we present a solution NMR study of the complex between yeast cytochrome c (Cc) and cytochrome c peroxidase (CcP), a paradigm for understanding the biological electron transfer. Performed for the first time, the CcP-observed heteronuclear NMR experiments were used to probe the Cc binding in solution. Combining the Cc- and CcP-detected experiments, the binding interface on both proteins was mapped out, confirming that the X-ray structure of the complex is maintained in solution. Using NMR titrations and chemical shift perturbation analysis, we show that the interaction is independent of the CcP spin-state and is only weakly affected by the Cc redox state. Based on these findings, we argue that the complex of the ferrous Cc and the cyanide-bound CcP is a good mimic of the catalytically-active Cc-CcP compound I species. Finally, no chemical shift perturbations due to the Cc binding at the low-affinity CcP site were observed at low ionic strength. We discuss possible reasons for the absence of the effects and outline future research directions.

  3. Interactions between colloidal silver and photosynthetic pigments located in cyanobacteria fragments and in solution.

    Science.gov (United States)

    Siejak, Przemysław; Frackowiak, Danuta

    2007-09-25

    Changes in the yield of the fluorescence emitted by pigments of photosynthetic organisms could be used for the establishment of the presence of some toxic substances. The presence of colloidal metals can be indicated by enhancement of pigments' emission as a result of plasmons generation. The spectra of the pigments of cyanobacterium Synechocystis located in the bacterium fragments and in solutions with and without colloidal silver additions have been measured. The quantum yield of the pigments' fluorescence in solution has been observed to increase at some wavelength of excitation, while the fluorescence of the pigments in the bacteria fragments has been only quenched as a consequence of interactions with colloidal silver particles. Close contact between pigment molecules located in bacteria fragments and silver particles is probably not possible. We plan in future to investigate the influence of other, more typical metal pollutants of water, using similar spectral methods and several other photosynthetic bacteria pigments, in solution, in cell fragments and in the whole bacteria organisms.

  4. 90Y and 90Sr separation from hydrochloric acid solutions using TODGA as the extractant by solvent extraction and SLM methods

    International Nuclear Information System (INIS)

    Dutta, S.; Raut, D.R.; Mohapatra, P.K.; Manchanda, V.K.

    2010-01-01

    Yttrium-90 is an important radionuclide known for its therapeutic application in nuclear medicine. It is a pure β-emitter with no associated gamma rays and decays to stable daughter 90 Zr. Suitability of this isotope is because of its short half-life (t 1/2 = 64.2 hrs) and high β emissions (E max = 2.28 MeV. An important source of 90 Y is through the decay of 90 Sr, which produces carrier free isotope. 90 Sr (t 1/2 28 yrs) attains secular equilibrium with 90 Y in a short period and can serve as a long term source for the latter isotope because of relatively long half-life of the parent isotope. Solvent extraction studies with N,N,N',N'-tetra-octyldiglycolamide (TODGA) has shown that Y(III) is well extracted in 6 M HCI while at the same time, extraction of Sr(II) is very low leading to a separation factor (D Y /D Sr = 60,000). This property of TODGA can be exploited for the separation of Y from Sr. In the present work, Supported Liquid Membrane (SLM) based separation of Y and Sr has been explored using TODGA as the carrier

  5. One-pot synthesis of stable colloidal solutions of MFe{sub 2}O{sub 4} nanoparticles using oleylamine as solvent and stabilizer

    Energy Technology Data Exchange (ETDEWEB)

    Pérez-Mirabet, Leonardo [Departament de Química, Universitat Autònoma de Barcelona, Campus de la UAB, 08193 Bellaterra (Spain); Solano, Eduardo, E-mail: eduardo.solano@uab.cat [Departament de Química, Universitat Autònoma de Barcelona, Campus de la UAB, 08193 Bellaterra (Spain); Martínez-Julián, Fernando; Guzmán, Roger [Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra (Spain); Arbiol, Jordi [Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra (Spain); Institució Catalana de Recerca i Estudis Avançats (ICREA), 08019 Barcelona (Spain); Puig, Teresa; Obradors, Xavier; Pomar, Alberto [Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra (Spain); Yáñez, Ramón; Ros, Josep [Departament de Química, Universitat Autònoma de Barcelona, Campus de la UAB, 08193 Bellaterra (Spain); Ricart, Susagna [Institut de Ciència de Materials de Barcelona, ICMAB-CSIC, Campus de la UAB, 08193 Bellaterra (Spain)

    2013-03-15

    Highlights: ► One-pot synthesis of ferrite magnetic nanoparticles (<10 nm) in non-polar media. ► Nanoparticles present high monocrystal quality and monodispersion. ► Superparamagnetic behavior at room temperature. ► Nanoparticles transfer to polar media via ligand exchange. - Abstract: An easy, efficient, reproducible and scalable one-pot synthetic methodology to obtain magnetic spinel ferrite nanoparticles has been developed. This approach is based on one-pot thermal decomposition of Fe(acac){sub 3} and M(acac){sub 2} (M = Co, Mn, Cu and Zn) in oleylamine, which also acts as a capping ligand, by producing stable colloidal dispersions of nanoparticles in non-polar solvents. The properties of the nanoparticles have been studied via different techniques, such as transmission electron microscopy, which shows that nanoparticles are monocrystallines and a narrow dispersion in size; magnetic analyses have demonstrated that the resulting ferrite nanoparticles show high saturation values and superparamagnetic behavior at room temperature; X-ray diffraction has also been performed, and it confirms that the synthesized nanoparticles have a spinel structure. Complementarily, ligand exchange has been also carried out in order to produce dispersions of the synthesized nanoparticles in polar media.

  6. Interaction of radiation-generated radicals with myoglobin in aqueous solution

    International Nuclear Information System (INIS)

    Whitburn, K.D.; Hoffman, M.Z.

    1984-01-01

    The interaction of radiation-generated OH/H with oxymyoglobin (MbO 2 ) has been studied in the presence of catalase at pH 7.3 over the range of 5 to 510 μM O 2 . The conversion of MbO 2 to heme-modified products has been examined under conditions where depletion of O 2 in irradiated solutions both can and cannot be compensated by O 2 -transfer across the solution phase boundary. In the theoretical limit of [O 2 ] -> 0 in bulk solution, MbO 2 is converted stoichiometrically to ferri- and ferromyoglobin with G(-MbO 2 ) approx.= 6.0, G(ferroMb) approx.3.0, and G(ferriMb) approx.= 3.0. An increase in [O 2 ] in bulk solution beyond the zero-limit progressively suppresses the conversion of MbO 2 to the heme-modified derivatives. At [O 2 ] >300 μM, an O 2 -independent path of ferriMb formation with G approx.= 0.6 is evident. Two sources of ferriMb induced by OH/H are proposed: an O 2 -independent path involving direct oxidative attack of OH at the oxyferroheme, and O 2 -dependent paths of production of ferriMb and ferroMb involving the mediation of O 2 -scavengeable secondary hemeprotein radicals. It is suggested that the modifications of the heme group in the absence of O 2 are accompanied by redox modifications on the globin moiety. (author)

  7. Solvent extraction of lanthanide ions with 1-Phenyl-3-Methyl-4-Benzoyl-Pyrazolone-5 (HPMBP), 2. Extraction of Erbium(III), Ytterbium(III) and Lutetium(III) by HPMBP from aqueous-methanol solutions

    International Nuclear Information System (INIS)

    Czakis-Sulikowska, D.M.; Kuznik, B.; Malinowska, A.

    1990-01-01

    The solvent extraction of lanthanides(III)(Ln = Er, Yb, Lu) by 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HL) in carbon tetrachloride from aqueous-methanol phase was investigated. The equilibrium constants for the extraction from aqueous-50 % (ν/ν) methanol phase (K ex ), two-phase stability constants of the complexes LnL 3 (β 3 * ) and stability constants of complexes LnL 2+ , LnL 2 + , LnL 3 (β n )(Ln = Yb, Lu) were calculated. It was confirmed that the addition of methanol to the aqueous phase causes a synergistic effect. The influence of methanol on the dissociation constant of HPMBP (K a ) and the distribution constant of HPMBP (p HL ) between carbon tetrachloride and water-methanol solutions was investigated. (Authors)

  8. Method of decomposing radioactive organic solvent wastes

    International Nuclear Information System (INIS)

    Uki, Kazuo; Ichihashi, Toshio; Hasegawa, Akira; Sato, Tatsuaki

    1986-01-01

    Purpose: To decompose radioactive organic solvent wastes or radioactive hydrocarbon solvents separated therefrom into organic materials under moderate conditions, as well as greatly decrease the amount of secondary wastes generated. Method: Radioactive organic solvent wastes comprising an organic phosphoric acid ester ingredient and a hydrocarbon ingredient as a diluent therefor, or radioactive hydrocarbon solvents separated therefrom are oxidatively decomposed by hydrogen peroxide in an aqueous phosphoric acid solution of phosphoric acid metal salts finally into organic materials to perform decomposing treatment for the radioactive organic solvent wastes. The decomposing reaction is carried out under relatively moderate conditions and cause less burden to facilities or the likes. Further, since the decomposed liquid after the treatment can be reused for the decomposing reaction as a catalyst solution secondary wastes can significantly be decreased. (Yoshihara, H.)

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

    Science.gov (United States)

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

    2018-05-09

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

  10. Phenomenology of polymer solution dynamics

    National Research Council Canada - National Science Library

    Phillies, George D. J

    2011-01-01

    ... solutions, not dilute solutions or polymer melts. From centrifugation and solvent dynamics to viscosity and diffusion, experimental measurements and their quantitative representations are the core of the discussion...

  11. Radiochromic liquid solution

    International Nuclear Information System (INIS)

    Noakes, J.E.; Culp, R.A.

    1983-01-01

    A radiochromic solution which is sensitive to small dosages of ionizing and ultraviolet radiation is described. It consists of a solution of a leucocyanide dye in a clear polar solvent with enough organic acid added to make the solution at least slightly acidic and responds to radiation by permanently changing color. Up to one half of the solution by weight can be replaced by a second solution of an aromatic solvent and an organic fluor. Another modification of the invention is a solution of a leucocyanide dye in a clear polar solvent having an aromatic group, an organic fluor, and enough organic acid to make the solution at least slightly acidic. (author)

  12. Solvent extraction of zirconium

    International Nuclear Information System (INIS)

    Kim, S.S.; Yoon, J.H.

    1981-01-01

    The extraction of zirconium(VI) from an aqueous solution of constant ionic strength with versatic acid-10 dissolved in benzen was studied as a function of pH and the concentration of zirconium(VI) and organic acid. The effects of sulphate and chlorine ions on the extraction of the zirconium(VI) were briefly examined. It was revealed that (ZrOR 2 .2RH) is the predominant species of extracted zirconium(VI) in the versatic acid-10. The chemical equation and the apparent equilibrium constants thereof have been determined as follows. (ZrOsup(2+))aq+ 2(R 2 H 2 )sub(org) = (ZrOR 2 .2RH)sub(org)+2(H + )aq Ksub(Zr) = (ZrOR 2 .2RH)sub(org)(H + ) 2 /(ZrOsup(2+))sub(aq)(R 2 H 2 )sup(2)sub(org) = 3.3 x 10 -7 . The synergistic effects of TBP and D2EHPA were also studied. In the mixed solvent with 0.1M TBP, the synergistic effect was observed, while the mixed solvent with D2EHPA showed the antisynergistic effect. (Author)

  13. A Boundary Element Solution to the Problem of Interacting AC Fields in Parallel Conductors

    Directory of Open Access Journals (Sweden)

    Einar M. Rønquist

    1984-04-01

    Full Text Available The ac fields in electrically insulated conductors will interact through the surrounding electromagnetic fields. The pertinent field equations reduce to the Helmholtz equation inside each conductor (interior problem, and to the Laplace equation outside the conductors (exterior problem. These equations are transformed to integral equations, with the magnetic vector potential and its normal derivative on the boundaries as unknowns. The integral equations are then approximated by sets of algebraic equations. The interior problem involves only unknowns on the boundary of each conductor, while the exterior problem couples unknowns from several conductors. The interior and the exterior problem are coupled through the field continuity conditions. The full set of equations is solved by standard Gaussian elimination. We also show how the total current and the dissipated power within each conductor can be expressed as boundary integrals. Finally, computational results for a sample problem are compared with a finite difference solution.

  14. Exact solution of two interacting run-and-tumble random walkers with finite tumble duration

    International Nuclear Information System (INIS)

    Slowman, A B; Evans, M R; Blythe, R A

    2017-01-01

    We study a model of interacting run-and-tumble random walkers operating under mutual hardcore exclusion on a one-dimensional lattice with periodic boundary conditions. We incorporate a finite, poisson-distributed, tumble duration so that a particle remains stationary whilst tumbling, thus generalising the persistent random walker model. We present the exact solution for the nonequilibrium stationary state of this system in the case of two random walkers. We find this to be characterised by two lengthscales, one arising from the jamming of approaching particles, and the other from one particle moving when the other is tumbling. The first of these lengthscales vanishes in a scaling limit where the continuous-space dynamics is recovered whilst the second remains finite. Thus the nonequilibrium stationary state reveals a rich structure of attractive, jammed and extended pieces. (paper)

  15. Adaptive solution of some steady-state fluid-structure interaction problems

    International Nuclear Information System (INIS)

    Etienne, S.; Pelletier, D.

    2003-01-01

    This paper presents a general integrated and coupled formulation for modeling the steady-state interaction of a viscous incompressible flow with an elastic structure undergoing large displacements (geometric non-linearities). This constitutes an initial step towards developing a sensitivity analysis formulation for this class of problems. The formulation uses velocity and pressures as unknowns in a flow domain and displacements in the structural components. An interface formulation is presented that leads to clear and simple finite element implementation of the equilibrium conditions at the fluid-solid interface. Issues of error estimation and mesh adaptation are discussed. The adaptive formulation is verified on a problem with a closed form solution. It is then applied to a sample case for which the structure undergoes large displacements induced by the flow. (author)

  16. Geochemical and numerical modelling of interactions between solid solutions and an aqueous solution. Extension of a reactive transport computer code called Archimede and application to reservoirs diagenesis; Modelisation geochimique et numerique des interactions entre des solutions solides et une solution aqueuse: extension du logiciel de reaction-transport archimede et application a la diagenese des reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Nourtier-Mazauric, E.

    2003-03-15

    This thesis presents a thermodynamic and kinetic model of interactions between a fluid and ideal solid solutions represented by several end-members. The reaction between a solid solution and the aqueous solution results from the competition between the stoichiometric dissolution of the initial solid solution and the co-precipitation of the least soluble solid solution in the fluid at considered time. This model was implemented in ARCHIMEDE, a computer code of reactive transport in porous media, then applied to various examples. In the case of binary solid solutions, a graphical method allowed to determine the compositions of the precipitating solid solutions, with the aid of the end-member chemical potentials. The obtained program could be used to notably model the diagenesis of clayey or carbonated oil reservoirs, or the ground pollutant dispersion. (author)

  17. "Pseudo" Faraday cage: a solution for telemetry link interaction between a left ventricular assist device and an implantable cardioverter defibrillator.

    Science.gov (United States)

    Jacob, Sony; Cherian, Prasad K; Ghumman, Waqas S; Das, Mithilesh K

    2010-09-01

    Patients implanted with left ventricular assist devices (LVAD) may have implantable cardioverter defibrillators (ICD) implanted for sudden cardiac death prevention. This opens the possibility of device-device communication interactions and thus interferences. We present a case of such interaction that led to ICD communication failure following the activation of an LVAD. In this paper, we describe a practical solution to circumvent the communication interference and review the communication links of ICDs and possible mechanisms of ICD-LVAD interactions.

  18. Interaction of radiation-generated radicals with myoglobin in aqueous solution

    International Nuclear Information System (INIS)

    Whitburn, K.D.; Hoffman, M.Z.

    1985-01-01

    The γ-radiolysis of aqueous solutions of ferrimyoglobin in the presence of N 2 O at pH 7.3 has been examined as a function of added catalase and oxygen. Changes in the nature of the heme group have been monitored by visible absorption spectrophotometry and analysed quantitatively by a multiple wavelength method based on Beer's Law. Simple chemical analyses have been used to confirm qualitative identification of the product derivatives. As observed previously, the ferriheme is reduced by indirect globin-mediated action initiated by radical OH/H radical. The yield of reduced product decreases as [O 2 ] derived from irradiated water and from protein-mediated processes in oxygenated solution, is eliminated by the presence of catalase. Formation of a hemichrome form of ferrimyoglobin is apparent at higher doses in the presence of O 2 . These results demonstrate that oxygen plays an important role in controlling the nature and extent of redox that manifests ultimately on the heme group of ferrimyoglobin as a result of the initial interaction of radical OH/H radical. (author)

  19. Effects of processing method and solute interactions on pepsin digestibility of cooked proso millet flour.

    Science.gov (United States)

    Gulati, Paridhi; Sabillón, Luis; Rose, Devin J

    2018-07-01

    Previous studies have reported a substantial decline in in vitro digestibility of proso millet protein upon cooking. In this study, several processing techniques and cooking solutions were tested with the objective of preventing the loss in pepsin digestibility. Proso millet flour was subjected to the following processing techniques: high pressure processing (200 and 600 MPa for 5 and 20 min); germination (96 h); fermentation (48 h); roasting (dry heating); autoclaving (121 °C, 3 h), and treatment with transglutaminase (160 mg/g protein, 37 °C, 2 h). To study the interaction of millet proteins with solutes, millet flour was heated with sucrose (3-7 M); NaCl (2-6 M); and CaCl 2 (0.5-3 M). All processing treatments failed to prevent the loss in pepsin digestibility except germination and treatment with transglutaminase, which resulted in 23 and 39% increases in digestibility upon cooking, respectively, when compared with unprocessed cooked flours. Heating in concentrated solutions of sucrose and NaCl were effective in preventing the loss in pepsin digestibility, an effect that was attributed to a reduction in water activity (a w ). CaCl 2 was also successful in preventing the loss in digestibility but its action was similar to chaotrops like urea. Thus, a combination of enzymatic modification and cooking of millet flour with either naturally low a w substances or edible sources of chaotropic ions may be useful in processing of proso millet for development of novel foods without loss in digestibility. However, more research is required to determine optimum processing conditions. Copyright © 2018 Elsevier Ltd. All rights reserved.

  20. Influence of solvent composition on the miscibility and physical stability of naproxen/PVP K 25 solid dispersions prepared by cosolvent spray-drying.

    Science.gov (United States)

    Paudel, Amrit; Van den Mooter, Guy

    2012-01-01

    To investigate the influence of solvent properties on the phase behavior and physical stability of spray-dried solid dispersions containing naproxen and PVP K 25 prepared from binary cosolvent systems containing methanol, acetone and dichloromethane. The viscosity, polymer globular size and evaporation rate of the spray-drying feed solutions were characterized. The solid dispersions were prepared by spray-drying drug-polymer solutions in binary solvent blends containing different proportions of each solvent. The phase behavior was investigated with mDSC, pXRD, FT-IR and TGA. Further, physical stability of solid dispersions was assessed by analyzing after storage at 75% RH. The solid dispersions prepared from solvent/anti-solvent mixture showed better miscibility and physical stability over those prepared from the mixtures of good solvents. Thus, solid dispersions prepared from dichloromethane-acetone exhibited the best physicochemical attributes followed by those prepared from methanol-acetone. FT-IR analysis revealed differential drug-polymer interaction in solid dispersions prepared from various solvent blends, upon the exposure to elevated humidity. Spray-drying from a cocktail of good solvent and anti-solvent with narrower volatility difference produces solid dispersions with better miscibility and physical stability resulting from the simultaneous effect on the polymer conformation and better dispersivity of drug.

  1. Solvents and solvent effects in organic chemistry

    National Research Council Canada - National Science Library

    Reichardt, C; Welton, T

    2011-01-01

    .../guest complexation equilibria and reactions in biphasic solvent systems and neoteric solvents, respectively. More than 900 new references have been added, giving preference to review articles, and many older ones have been deleted. New references either replace older ones or are added to the end of the respective reference list of each chapter. Th...

  2. State-dependent electron delocalization dynamics at the solute-solvent interface: soft-x-ray absorption spectroscopy and ab initio calculations.

    Science.gov (United States)

    Bokarev, Sergey I; Dantz, Marcus; Suljoti, Edlira; Kühn, Oliver; Aziz, Emad F

    2013-08-23

    Nonradiative decay channels in the L-edge fluorescence yield spectra from transition-metal-aqueous solutions give rise to spectral distortions with respect to x-ray transmission spectra. Their origin is unraveled here using partial and inverse partial fluorescence yields on the microjet combined with multireference ab initio electronic structure calculations. Comparing Fe2+, Fe3+, and Co2+ systems we demonstrate and quantify unequivocally the state-dependent electron delocalization within the manifold of d orbitals as one origin of this observation.

  3. Initiating fibro-proliferation through interfacial interactions of myoglobin colloids with collagen in solution.

    Science.gov (United States)

    Dhanasekaran, Madhumitha; Dhathathreyan, Aruna

    2017-08-01

    This work examines fibro-proliferation through interaction of myoglobin (Mb), a globular protein with collagen, an extracellular matrix fibrous protein. Designed colloids of Mb at pH 4.5 and 7.5 have been mixed with collagen solution at pH 7.5 and 4.5 in different concentrations altering their surface charges. For the Mb colloids, 100-200nm sizes have been measured from Transmission electron micrographs and zeta sizer. CD spectra shows a shift to beta sheet like structure for the protein in the colloids. Interaction at Mb/Collagen interface studied using Dilational rheology, Quartz crystal microbalance with dissipation and Differential Scanning calorimetry show that the perturbation is not only by the charge compensation arising from the difference in pH of the colloids and collagen, but also by the organized assembly of collagen at that particular pH. Results demonstrate that positive Mb colloids at pH 4.5, having more% of entrained water stabilize the collagen fibrils (pH 7.5) around them. Ensuing dehydration leads to effective cross-linking and inherently anisotropic growth of fibrils/fibres of collagen. In the case of Mb colloids at pH 7.5, the fibril formation seems to supersede the clustering of Mb suggesting that the fibro-proliferation is both pH and hydrophilic-hydrophobic balance dependent at the interface. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. An online interactive geometric database including exact solutions of Einstein's field equations

    International Nuclear Information System (INIS)

    Ishak, Mustapha; Lake, Kayll

    2002-01-01

    We describe a new interactive database (GRDB) of geometric objects in the general area of differential geometry. Database objects include, but are not restricted to, exact solutions of Einstein's field equations. GRDB is designed for researchers (and teachers) in applied mathematics, physics and related fields. The flexible search environment allows the database to be useful over a wide spectrum of interests, for example, from practical considerations of neutron star models in astrophysics to abstract space-time classification schemes. The database is built using a modular and object-oriented design and uses several Java technologies (e.g. Applets, Servlets, JDBC). These are platform-independent and well adapted for applications developed for the World Wide Web. GRDB is accompanied by a virtual calculator (GRTensorJ), a graphical user interface to the computer algebra system GRTensorII, used to perform online coordinate, tetrad or basis calculations. The highly interactive nature of GRDB allows systematic internal self-checking and minimization of the required internal records. This new database is now available online at http://grdb.org

  5. Adsorption of Antibiotics on Graphene and Biochar in Aqueous Solutions Induced by π-π Interactions

    Science.gov (United States)

    Peng, Bingquan; Chen, Liang; Que, Chenjing; Yang, Ke; Deng, Fei; Deng, Xiaoyong; Shi, Guosheng; Xu, Gang; Wu, Minghong

    2016-08-01

    The use of carbon based materials on the removal of antibiotics with high concentrations has been well studied, however the effect of this removal method is not clear on the actual concentration of environments, such as the hospital wastewater, sewage treatment plants and aquaculture wastewater. In this study, experimental studies on the adsorption of 7 antibiotics in environmental concentration of aqueous solutions by carbon based materials have been observed. Three kinds of carbon materials have shown very fast adsorption to antibiotics by liquid chromatography-tandem mass spectrometry (LC-MS-MS) detection, and the highest removal efficiency of antibiotics could reach to 100% within the range of detection limit. Surprisedly, the adsorption rate of graphene with small specific surface area was stronger than other two biochar, and adsorption rate of the two biochar which have approximate specific surface and different carbonization degree, was significantly different. The key point to the present observation were the π-π interactions between aromatic rings on adsorbed substance and carbon based materials by confocal laser scanning microscope observation. Moreover, adsorption energy markedly increased with increasing number of the π rings by using the density functional theory (DFT), showing the particular importance of π-π interactions in the adsorption process.

  6. Solution Structure and Membrane Interaction of the Cytoplasmic Tail of HIV-1 gp41 Protein.

    Science.gov (United States)

    Murphy, R Elliot; Samal, Alexandra B; Vlach, Jiri; Saad, Jamil S

    2017-11-07

    The cytoplasmic tail of gp41 (gp41CT) remains the last HIV-1 domain with an unknown structure. It plays important roles in HIV-1 replication such as mediating envelope (Env) intracellular trafficking and incorporation into assembling virions, mechanisms of which are poorly understood. Here, we present the solution structure of gp41CT in a micellar environment and characterize its interaction with the membrane. We show that the N-terminal 45 residues are unstructured and not associated with the membrane. However, the C-terminal 105 residues form three membrane-bound amphipathic α helices with distinctive structural features such as variable degree of membrane penetration, hydrophobic and basic surfaces, clusters of aromatic residues, and a network of cation-π interactions. This work fills a major gap by providing the structure of the last segment of HIV-1 Env, which will provide insights into the mechanisms of Gag-mediated Env incorporation as well as the overall Env mobility and conformation on the virion surface. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. A linear complementarity method for the solution of vertical vehicle-track interaction

    Science.gov (United States)

    Zhang, Jian; Gao, Qiang; Wu, Feng; Zhong, Wan-Xie

    2018-02-01

    A new method is proposed for the solution of the vertical vehicle-track interaction including a separation between wheel and rail. The vehicle is modelled as a multi-body system using rigid bodies, and the track is treated as a three-layer beam model in which the rail is considered as an Euler-Bernoulli beam and both the sleepers and the ballast are represented by lumped masses. A linear complementarity formulation is directly established using a combination of the wheel-rail normal contact condition and the generalised-α method. This linear complementarity problem is solved using the Lemke algorithm, and the wheel-rail contact force can be obtained. Then the dynamic responses of the vehicle and the track are solved without iteration based on the generalised-α method. The same equations of motion for the vehicle and track are adopted at the different wheel-rail contact situations. This method can remove some restrictions, that is, time-dependent mass, damping and stiffness matrices of the coupled system, multiple equations of motion for the different contact situations and the effect of the contact stiffness. Numerical results demonstrate that the proposed method is effective for simulating the vehicle-track interaction including a separation between wheel and rail.

  8. Chromatographic study of the conformational behavior of graft copolymers with a broad distribution of grafting densities in dilute solutions in selective solvents for grafts

    Czech Academy of Sciences Publication Activity Database

    Netopilík, Miloš; Janata, Miroslav; Svitáková, Romana; Trhlíková, Olga; Berek, D.; Macova, E.; Limpouchová, Z.; Procházka, K.

    2016-01-01

    Roč. 39, č. 1 (2016), s. 50-58 ISSN 1082-6076 R&D Projects: GA ČR(CZ) GA13-02938S Grant - others:OPPK(XE) CZ.2.16/3.1.00/24504 Institutional support: RVO:61389013 Keywords : interaction chromatography * size exclusion chromatography * poly(4-methylstyrene)-graft-poly(2-vinylpyridine) Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.697, year: 2016

  9. Measurements and correlation of viscosities and conductivities for the mixtures of ethylammonium nitrate with organic solvents

    International Nuclear Information System (INIS)

    Litaeim, Yousra; Zarrougi, Ramzi; Dhahbi, Mahmoud

    2009-01-01

    Room temperature ionic liquids (IL) as a new class of organic molten salts have been considered as an alternative of traditional organic solvents (OS). The physico-chemical transport properties of mixtures IL/OS were investigated and described by ion-ion, ion solvent and solvent-solvent interactions. Ethylammonium nitrate (EAN) was studied in presence of two types of organic solvents: the dimethyl carbonate (DMC) and the formamide (FA). The variation of the viscosity with salt concentration and temperature shows that EAN ions behave as a structure breaker for the DMC. However, no effect was recorded in the case of FA. Concentrated electrolyte solutions behave as very structured media and checked a theory of pseudo-lattice. The existence of a conductivity maximum indicates two competing effects; the increasing number of charge carriers and the higher viscosity of the electrolyte as the salt concentration was raised. The use of the Walden product to investigate ionic interactions of EAN with both solvents was discussed. A study of the effect of temperature on the conductivity and viscosity reveals that both systems (EAN/DMC and EAN/FA) obey an Arrhenius low. The activation energies for the tow transport process (Ea,L and Ea,h) as a function of the salt concentration were evaluated.

  10. Effects of intermolecular interactions on the stability of carbon nanotube–gold nanoparticle conjugates in solution

    Directory of Open Access Journals (Sweden)

    Konczak L

    2016-11-01

    Full Text Available Lukasz Konczak,1 Jolanta Narkiewicz-Michalek,2 Giorgia Pastorin,3 Tomasz Panczyk1 1Institute of Catalysis and Surface Chemistry, Polish Academy of Sciences, Cracow, 2Department of Chemistry, Maria Curie-Sklodowska University, Lublin, Poland; 3Department of Pharmacy, National University of Singapore, Singapore Abstract: This work deals with the role of intermolecular interactions in the stability of a carbon nanotube (CNT capped by functionalized gold nanoparticles (AuNPs. The importance of such a system is due to its potential application as a pH-controlled drug carrier. Our preliminary experimental studies showed that fabrication of such a nanobottle/nanocontainer is feasible and it is possible to encapsulate the anticancer drug cisplatin inside the inner space of a CNT and seal its ends by functionalized AuNPs. The expected behavior, that is, detachment of AuNPs at acidic pH and the release of cisplatin, was, however, not observed. On the other hand, our theoretical studies of chemically identical system led to the conclusion that the release of cisplatin at acidic pH should be observed. Therefore, in this work, a deeper theoretical analysis of various factors that could be responsible for the disagreement between experimental and theoretical results were performed. The study found that the major factor is a large dispersion interaction component acting between CNT and AuNP in solution in the case of the experimental system. This factor can be controlled to some extent by tuning the system size or the ratio between AuNP diameter and CNT diameter. Thus, such kind of a pH-sensitive drug carrier is still of great interest, but its structural parameters need to be properly adjusted. Keywords: hydrazone bond, drug delivery, dispersion interactions, cisplatin, acidic pH

  11. Interactive dualism as a partial solution to the mind-brain problem for psychiatry.

    Science.gov (United States)

    McLaren, N

    2006-01-01

    With the collapse of the psychoanalytic and the behaviorist models, and the failure of reductive biologism to account for mental life, psychiatry has been searching for a broad, integrative theory on which to base daily practice. The most recent attempt at such a model, Engel's 'biopsychosocial model', has been shown to be devoid of any scientific content, meaning that psychiatry, alone among the medical disciplines, has no recognised scientific basis. It is no coincidence that psychiatry is constantly under attack from all quarters. In order to develop, the discipline requires an integrative and interactive model which can take account of both the mental and the physical dimensions of human life, yet still remain within the materialist scientific ethos. This paper proposes an entirely new model of mind based in Chalmers' 'interactive dualism' which satisfies those needs. It attributes the causation of all behaviour to mental life, but proposes a split in the nature of mentality such that mind becomes a composite function with two, profoundly different aspects. Causation is assigned to a fast, inaccessible cognitive realm operating within the brain machinery while conscious experience is seen as the outcome of a higher order level of brain processing. The particular value of this model is that it immediately offers a practical solution to the mind-brain problem in that, while all information-processing takes place in the mental realm, it is not in the same order of abstraction as perception. This leads to a model of rational interaction which acknowledges both psyche and soma. It can fill the gap left by the demise of Engel's empty 'biopsychosocial model'.

  12. Investigations to explore interactions in (polyhydroxy solute + L-ascorbic acid + H2O) solutions at different temperatures: Calorimetric and viscometric approach

    International Nuclear Information System (INIS)

    Banipal, Parampaul K.; Sharma, Mousmee; Aggarwal, Neha; Banipal, Tarlok S.

    2016-01-01

    Highlights: • The hydrophilic-hydrophilic interactions predominate at low temperatures. • Enthalpy change for polyol is less exothermic than its parent saccharide. • Δ dil C o p,2,m values suggest structural increase in presence of L-ascorbic acid. • Solutes act as kosmotropes in L-ascorbic acid (aq) solutions as indicated by dB/dT. - Abstract: Isothermal titration micro-calorimeter has been used to measure the enthalpy change (q) of polyhydroxy solutes [(+)-D-xylose, xylitol, (+)-D-glucose, 2-deoxy-D-glucose, (+)-methyl-α-D-glucopyranoside, and (+)-maltose monohydrate] in water and in (0.05, 0.15, and 0.25) mol·kg −1 L-ascorbic acid (aq) solutions at (288.15, 298.15, 308.15, and 318.15) K. Limiting enthalpies of dilution (Δ dil H°) of these solutes were calculated from heat evolved/absorbed during calorimetric experiments. Further thermodynamic quantities such as limiting enthalpies of dilution of transfer (Δ tr Δ dil H°), change in heat capacity (Δ dil C o p,2,m ), and pair (h AB ) and triplet (h ABB ) enthalpic interaction coefficients were also calculated and used to explore the nature of interactions of solutes with cosolute (L-ascorbic acid). The Jones-Dole viscosity B-coefficients for (+)-D-xylose, xylitol, (+)-D-galactose, galactitol, (+)-D-glucose, 2-deoxy-D-glucose, (+)-methyl-α-D-glucopyranoside, and (+)-maltose monohydrate in water and in (0.05, 0.15, 0.25, and 0.35) mol·kg −1 L-ascorbic acid (aq) solutions have been determined from viscosity (η) data measured over temperature range (288.15–318.15) K and at pressure, P = 101.3 kPa. The temperature dependence of B-coefficients (dB/dT), and viscosity B-coefficients of transfer (Δ tr B) of solutes from water to cosolute have also been estimated. These parameters have been discussed in terms of structure-making (kosmotropic) or -breaking (chaotropic) behavior of solutes.

  13. On the theory of electric double layer with explicit account of a polarizable co-solvent

    Energy Technology Data Exchange (ETDEWEB)

    Budkov, Yu. A., E-mail: urabudkov@rambler.ru [Laboratory of NMR Spectroscopy and Numerical Investigations of Liquids, G. A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation); Department of Applied Mathematics, National Research University Higher School of Economics, Moscow (Russian Federation); Kolesnikov, A. L. [Institut für Nichtklassische Chemie e.V., Universität Leipzig, Leipzig (Germany); Kiselev, M. G. [Laboratory of NMR Spectroscopy and Numerical Investigations of Liquids, G. A. Krestov Institute of Solution Chemistry of the Russian Academy of Sciences, Ivanovo (Russian Federation)

    2016-05-14

    We present a continuation of our theoretical research into the influence of co-solvent polarizability on a differential capacitance of the electric double layer. We formulate a modified Poisson-Boltzmann theory, using the formalism of density functional approach on the level of local density approximation taking into account the electrostatic interactions of ions and co-solvent molecules as well as their excluded volume. We derive the modified Poisson-Boltzmann equation, considering the three-component symmetric lattice gas model as a reference system and minimizing the grand thermodynamic potential with respect to the electrostatic potential. We apply present modified Poisson-Boltzmann equation to the electric double layer theory, showing that accounting for the excluded volume of co-solvent molecules and ions slightly changes the main result of our previous simplified theory. Namely, in the case of small co-solvent polarizability with its increase under the enough small surface potentials of electrode, the differential capacitance undergoes the significant growth. Oppositely, when the surface potential exceeds some threshold value (which is slightly smaller than the saturation potential), the increase in the co-solvent polarizability results in a differential capacitance decrease. However, when the co-solvent polarizability exceeds some threshold value, its increase generates a considerable enhancement of the differential capacitance in a wide range of surface potentials. We demonstrate that two qualitatively different behaviors of the differential capacitance are related to the depletion and adsorption of co-solvent molecules at the charged electrode. We show that an additive of the strongly polarizable co-solvent to an electrolyte solution can shift significantly the saturation potential in two qualitatively different manners. Namely, a small additive of strongly polarizable co-solvent results in a shift of saturation potential to hig