Molecular simulations and experimental studies of solubility and diffusivity for pure and mixed gases of H2, CO2, and Ar absorbed in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]).

PubMed

Shi, Wei; Sorescu, Dan C; Luebke, David R; Keller, Murphy J; Wickramanayake, Shan

2010-05-20

Classical molecular dynamics and Monte Carlo simulations are used to calculate the self-diffusivity and solubility of pure and mixed CO(2), H(2), and Ar gases absorbed in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf(2)N]). Overall, the computed absorption isotherms, Henry's law constants, and partial molar enthalpies for pure H(2) agree well with the experimental data obtained by Maurer et al. [J. Chem. Eng. Data 2006, 51, 1364] and the experimental values determined in this work. However, the agreement is poor between the simulations and the experimental data by Noble et al. [Ind. Eng. Chem. Res. 2008, 47, 3453] and Costa Gomes [J. Chem. Eng. Data 2007, 52, 472] at high temperatures. The computed H(2) permeability values are in good agreement with the experimental data at 313 K obtained by Luebke et al. [J. Membr. Sci. 2007, 298, 41; ibid, 2008, 322, 28], but about three times larger than the experimental value at 573 K from the same group. Our computed H(2) solubilities using different H(2) potential models have similar values and solute polarizations were found to have a negligible effect on the predicted gas solubilities for both the H(2) and Ar. The interaction between H(2) and the ionic liquid is weak, about three times smaller than between the ionic liquid and Ar and six times smaller than that of CO(2) with the ionic liquid, results that are consistent with a decreasing solubility from CO(2) to Ar and to H(2). The molar volume of the ionic liquid was found to be the determining factor for the H(2) solubility. For mixed H(2) and Ar gases, the solubilities for both solutes decrease compared to the respective pure gas solubilities. For mixed gases of CO(2) and H(2), the solubility selectivity of CO(2) over H(2) decreases from about 30 at 313 K to about 3 at 573 K. For the permeability, the simulated values for CO(2) in [hmim][Tf(2)N] are about 20-60% different than the experimental data by Luebke et al. [J. Membr. Sci. 2008, 322, 28].

Partial molar volume of n-alcohols at infinite dilution in water calculated by means of scaled particle theory.

PubMed

Graziano, Giuseppe

2006-04-07

The partial molar volume of n-alcohols at infinite dilution in water is smaller than the molar volume in the neat liquid phase. It is shown that the formula for the partial molar volume at infinite dilution obtained from the scaled particle theory equation of state for binary hard sphere mixtures is able to reproduce in a satisfactory manner the experimental data over a large temperature range. This finding implies that the packing effects play the fundamental role in determining the partial molar volume at infinite dilution in water also for solutes, such as n-alcohols, forming H bonds with water molecules. Since the packing effects in water are largely related to the small size of its molecules, the latter feature is the ultimate cause of the decrease in partial molar volume associated with the hydrophobic effect.

Direct mapping of ion diffusion times on LiCoO2 surfaces with nanometer resolution

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

Guo, Senli; Jesse, Stephen; Kalnaus, Sergiy

2011-01-01

The strong coupling between the molar volume and mobile ion concentration in ionically-conductive solids is used for spatially-resolved studies of ionic transport on the polycrystalline LiCoO2 surface by time-resolved spectroscopy. Strong variability between ionic transport at the grain boundaries and within the grains is observed, and the relationship between relaxation and hysteresis loop formation is established. The use of the strain measurements allows ionic transport be probed on the nanoscale, and suggests enormous potential for probing ionic materials and devices.

What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents.

PubMed

Mazzini, Virginia; Craig, Vincent S J

2017-10-01

The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity.

Partial molar volumes of proteins: amino acid side-chain contributions derived from the partial molar volumes of some tripeptides over the temperature range 10-90 degrees C.

PubMed

Häckel, M; Hinz, H J; Hedwig, G R

1999-11-15

The partial molar volumes of tripeptides of sequence glycyl-X-glycine, where X is one of the amino acids alanine, leucine, threonine, glutamine, phenylalanine, histidine, cysteine, proline, glutamic acid, and arginine, have been determined in aqueous solution over the temperature range 10-90 degrees C using differential scanning densitometry . These data, together with those reported previously, have been used to derive the partial molar volumes of the side-chains of all 20 amino acids. The side-chain volumes are critically compared with literature values derived using partial molar volumes for alternative model compounds. The new amino acid side-chain volumes, along with that for the backbone glycyl group, were used to calculate the partial specific volumes of several proteins in aqueous solution. The results obtained are compared with those observed experimentally. The new side-chain volumes have also been used to re-determine residue volume changes upon protein folding.

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

NASA Astrophysics Data System (ADS)

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.

Study of thermodynamic and acoustic behaviour of nicotinic acid in binary aqueous mixtures of D-lactose

NASA Astrophysics Data System (ADS)

Sharma, Ravi; Thakur, R. C.

2017-07-01

In the present study, the thermodynamic properties such as partial molar volumes, partial molar expansibilities, partial molar compressibilities, partial molar heat capacities and isobaric thermal expansion coefficient of different solutions of nicotinic acid in binary aqueous mixtures of D-lactose have been determined at different temperatures (298.15, 303.15, 308.15, 313.15) K. Masson's equation is used to interpret the data in terms of solute-solute and solute-solvent interactions. In the present study it has been found that nicotinic acid behaves as structure maker in aqueous and binary aqueous mixtures of D-lactose.

Unfolding and refolding details of lysozyme in the presence of β-casein micelles.

PubMed

Wu, Fu-Gen; Luo, Jun-Jie; Yu, Zhi-Wu

2011-02-28

In this work, we selected a small globular protein, lysozyme, to study how it unfolds and refolds in the presence of micelles composed of the unstructured β-casein proteins by using microcalorimetry and circular dichroism spectroscopy. It was found that a partially unfolded structure of lysozyme starts to form when the β-casein/lysozyme molar ratio is above 0.7, and the structure forms exclusively when the β-casein/lysozyme molar ratio is above 1.6. This partially unfolded state of lysozyme loses most of its tertiary structure and after heating, the denatured lysozyme molecules are trapped in the charged coatings of β-casein micelles and cannot refold upon cooling. The thus obtained protein complex can be viewed as a kind of special polyelectrolyte complex micelle. The net charge ratios of the two proteins and the ionic strength of the dispersions can significantly modulate the electrostatic and hydrophobic interactions between the two proteins. Our present work may have implications for the nanoparticle protein engineering therapy in the biomedicine field and may provide a better understanding of the principles governing the protein-protein interactions. Besides, the heating-cooling-reheating procedure employed in this work can also be used to study the unfolding and refolding details of the target protein in other protein-protein, protein-polymer and protein-small solute systems.

Association between the presence of a partially erupted mandibular third molar and the existence of caries in the distal of the second molars.

PubMed

Falci, S G M; de Castro, C R; Santos, R C; de Souza Lima, L D; Ramos-Jorge, M L; Botelho, A M; Dos Santos, C R R

2012-10-01

The objective of this study was to verify, using periapical radiographs, whether a partially erupted mandibular third molar is a factor in the presence of dental caries on the distal surface of the adjacent second molar. Two-forty six high quality periapical radiographs were selected, each showing a partially erupted mandibular third molar. The variables analyzed were: tooth number; gender; age; radiographic presence of caries on the distal surface of the adjacent molar; Pell and Gregory classification; Winter classification; angulation and distance between the second and mandibular third molar. The examiners were previously calibrated to collect data (kappa statistics from 0.87 to 1.0). The prevalence rate of caries on the distal surface of the second molar was 13.4%. In the logistical multivariate regression analysis, the angulation (OR=8.5; IC95%: 1.7-43.8; p=0.011) and the gender (OR=3.3; IC95%: 1.4-7.7; p=0.005) remained statistically significant after an age adjustment was made. The results indicate that the presence of a partially erupted mandibular third molar with an angulation of 31 degrees or more, is a risk factor for caries on the distal surface of the mandibular second molars. Copyright © 2012 International Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.

The Component Slope Linear Model for Calculating Intensive Partial Molar Properties: Application to Waste Glasses

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

Reynolds, Jacob G.

2013-01-11

Partial molar properties are the changes occurring when the fraction of one component is varied while the fractions of all other component mole fractions change proportionally. They have many practical and theoretical applications in chemical thermodynamics. Partial molar properties of chemical mixtures are difficult to measure because the component mole fractions must sum to one, so a change in fraction of one component must be offset with a change in one or more other components. Given that more than one component fraction is changing at a time, it is difficult to assign a change in measured response to a changemore » in a single component. In this study, the Component Slope Linear Model (CSLM), a model previously published in the statistics literature, is shown to have coefficients that correspond to the intensive partial molar properties. If a measured property is plotted against the mole fraction of a component while keeping the proportions of all other components constant, the slope at any given point on a graph of this curve is the partial molar property for that constituent. Actually plotting this graph has been used to determine partial molar properties for many years. The CSLM directly includes this slope in a model that predicts properties as a function of the component mole fractions. This model is demonstrated by applying it to the constant pressure heat capacity data from the NaOH-NaAl(OH{sub 4}H{sub 2}O system, a system that simplifies Hanford nuclear waste. The partial molar properties of H{sub 2}O, NaOH, and NaAl(OH){sub 4} are determined. The equivalence of the CSLM and the graphical method is verified by comparing results detennined by the two methods. The CSLM model has been previously used to predict the liquidus temperature of spinel crystals precipitated from Hanford waste glass. Those model coefficients are re-interpreted here as the partial molar spinel liquidus temperature of the glass components.« less

Compositional dependent partial molar volume and compressibility of CO2 in rhyolite, phonolite and basalt glasses

NASA Astrophysics Data System (ADS)

Lerch, P.; Seifert, R.; Malfait, W. J.; Sanchez-Valle, C.

2012-12-01

Carbon dioxide is the second most abundant volatile in magmatic systems and plays an important role in many magmatic processes, e.g. partial melting, volatile saturation, outgassing. Despite this relevance, the volumetric properties of carbon-bearing silicates at relevant pressure and temperature conditions remain largely unknown because of considerable experimental difficulties associated with in situ measurements. Density and elasticity measurements on quenched glasses can provide an alternative source of information. For dissolved water, such measurements indicate that the partial molar volume is independent of compositions at ambient pressure [1], but the partial molar compressibility is not [2, 3]. Thus the partial molar volume of water may depend on melt composition at elevated pressure. For dissolved CO2, no such data is available. In order to constrain the effect of magma composition on the partial molar volume and compressibility of dissolved carbon, we determined the density and elasticity for three series of carbon-bearing basalt, phonolite and rhyolite glasses, quenched from 3.5 GPa and relaxed at ambient pressure. The CO2 content varies between 0 to 3.90 wt% depending on the glass composition. Glass densities were determined using the sink/float method in a diiodomethane (CH2I2) - acetone mixture. Brillouin measurements were conducted on relaxed and unrelaxed silicate glasses in platelet geometry to determine the compressional (VP) and shear (VS) wave velocities and elastic moduli. The partial molar volume of CO2 in rhyolite, phonolite and basalt glasses is 25.4 ± 0.9, 22.1 ± 0.6 and 26.6 ±1.8 cm3/mol, respectively. Thus, unlike for dissolved water, the partial molar volume of CO2 displays a resolvable compositional effect. Although the composition and CO2/carbonate speciation of the phonolite glasses is intermediate between that of the rhyolite and basalt glasses, the molar volume is not. Similar to dissolved water, the partial molar bulk modulus of CO2 displays a strong compositional effect. If these compositional dependencies persist in the analogue melts, the partial molar volume of dissolved CO2 will depend on melt composition, both at low and elevated pressure. Thus, for CO2-bearing melts, a full quantitative understanding of density dependent magmatic processes, such as crystal fractionation, magma mixing and melt extraction will require in situ measurements for a range of melt compositions. [1] Richet, P. et al., 2000, Contrib Mineral Petrol, 138, 337-347. [2] Malfait et al. 2011, Am. Mineral. 96, 1402-1409. [3] Whittington et al., 2012, Am. Mineral. 97, 455-467.

Relationship Between Third Mandibular Molar Angulation and Distal Cervical Caries in the Second Molar.

PubMed

Claudia, Andreescu; Barbu, Horia Mihail; Adi, Lorean; Gultekin, Alper; Reiser, Vadim; Gultekin, Pinar; Mijiritsky, Eitan

2018-03-16

Third lower molar partially erupted is commonly encountered in dental practice. This situation challenges clinicians with the dilemma whether to remove or to monitor it, because this molar can cause pathology of the adjacent second molar. The aim of this retrospective study is to evaluate the relationship between third mandibular molar and distal cervical caries in second molar. This retrospective study analyzed 55 digital orthopantograms of adult patients and a total number of 95 mandibular third molars were assessed for eruption status, angulation, radiographic evidence of caries or restoration in the mandibular third molar, and radiographic evidence of caries or restoration in the distal surface of the mandibular second molar. The distal cervical caries in second molar is associated with fully erupted and partially erupted wisdom molar in horizontal, mesioangular and vertical position and less with presence of caries in third molar. There are caries lesions in distal second molars in mesioangular position when adjacent third molar is caries free.

Parsing partial molar volumes of small molecules: a molecular dynamics study.

PubMed

Patel, Nisha; Dubins, David N; Pomès, Régis; Chalikian, Tigran V

2011-04-28

We used molecular dynamics (MD) simulations in conjunction with the Kirkwood-Buff theory to compute the partial molar volumes for a number of small solutes of various chemical natures. We repeated our computations using modified pair potentials, first, in the absence of the Coulombic term and, second, in the absence of the Coulombic and the attractive Lennard-Jones terms. Comparison of our results with experimental data and the volumetric results of Monte Carlo simulation with hard sphere potentials and scaled particle theory-based computations led us to conclude that, for small solutes, the partial molar volume computed with the Lennard-Jones potential in the absence of the Coulombic term nearly coincides with the cavity volume. On the other hand, MD simulations carried out with the pair interaction potentials containing only the repulsive Lennard-Jones term produce unrealistically large partial molar volumes of solutes that are close to their excluded volumes. Our simulation results are in good agreement with the reported schemes for parsing partial molar volume data on small solutes. In particular, our determined interaction volumes() and the thickness of the thermal volume for individual compounds are in good agreement with empirical estimates. This work is the first computational study that supports and lends credence to the practical algorithms of parsing partial molar volume data that are currently in use for molecular interpretations of volumetric data.

The component slope linear model for calculating intensive partial molar properties /application to waste glasses and aluminate solutions

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

Reynolds, Jacob G.

2013-01-11

Partial molar properties are the changes occurring when the fraction of one component is varied while the fractions of all other component mole fractions change proportionally. They have many practical and theoretical applications in chemical thermodynamics. Partial molar properties of chemical mixtures are difficult to measure because the component mole fractions must sum to one, so a change in fraction of one component must be offset with a change in one or more other components. Given that more than one component fraction is changing at a time, it is difficult to assign a change in measured response to a changemore » in a single component. In this study, the Component Slope Linear Model (CSLM), a model previously published in the statistics literature, is shown to have coefficients that correspond to the intensive partial molar properties. If a measured property is plotted against the mole fraction of a component while keeping the proportions of all other components constant, the slope at any given point on a graph of this curve is the partial molar property for that constituent. Actually plotting this graph has been used to determine partial molar properties for many years. The CSLM directly includes this slope in a model that predicts properties as a function of the component mole fractions. This model is demonstrated by applying it to the constant pressure heat capacity data from the NaOH-NaAl(OH){sub 4}-H{sub 2}O system, a system that simplifies Hanford nuclear waste. The partial molar properties of H{sub 2}O, NaOH, and NaAl(OH){sub 4} are determined. The equivalence of the CSLM and the graphical method is verified by comparing results determined by the two methods. The CSLM model has been previously used to predict the liquidus temperature of spinel crystals precipitated from Hanford waste glass. Those model coefficients are re-interpreted here as the partial molar spinel liquidus temperature of the glass components.« less

The Component Slope Linear Model for Calculating Intensive Partial Molar Properties: Application to Waste Glasses and Aluminate Solutions - 13099

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

Reynolds, Jacob G.

2013-07-01

Partial molar properties are the changes occurring when the fraction of one component is varied while the fractions of all other component mole fractions change proportionally. They have many practical and theoretical applications in chemical thermodynamics. Partial molar properties of chemical mixtures are difficult to measure because the component mole fractions must sum to one, so a change in fraction of one component must be offset with a change in one or more other components. Given that more than one component fraction is changing at a time, it is difficult to assign a change in measured response to a changemore » in a single component. In this study, the Component Slope Linear Model (CSLM), a model previously published in the statistics literature, is shown to have coefficients that correspond to the intensive partial molar properties. If a measured property is plotted against the mole fraction of a component while keeping the proportions of all other components constant, the slope at any given point on a graph of this curve is the partial molar property for that constituent. Actually plotting this graph has been used to determine partial molar properties for many years. The CSLM directly includes this slope in a model that predicts properties as a function of the component mole fractions. This model is demonstrated by applying it to the constant pressure heat capacity data from the NaOHNaAl(OH){sub 4}-H{sub 2}O system, a system that simplifies Hanford nuclear waste. The partial molar properties of H{sub 2}O, NaOH, and NaAl(OH){sub 4} are determined. The equivalence of the CSLM and the graphical method is verified by comparing results determined by the two methods. The CSLM model has been previously used to predict the liquidus temperature of spinel crystals precipitated from Hanford waste glass. Those model coefficients are re-interpreted here as the partial molar spinel liquidus temperature of the glass components. (authors)« less

Ionic Liquid Crystals: Versatile Materials.

PubMed

Goossens, Karel; Lava, Kathleen; Bielawski, Christopher W; Binnemans, Koen

2016-04-27

This Review covers the recent developments (2005-2015) in the design, synthesis, characterization, and application of thermotropic ionic liquid crystals. It was designed to give a comprehensive overview of the "state-of-the-art" in the field. The discussion is focused on low molar mass and dendrimeric thermotropic ionic mesogens, as well as selected metal-containing compounds (metallomesogens), but some references to polymeric and/or lyotropic ionic liquid crystals and particularly to ionic liquids will also be provided. Although zwitterionic and mesoionic mesogens are also treated to some extent, emphasis will be directed toward liquid-crystalline materials consisting of organic cations and organic/inorganic anions that are not covalently bound but interact via electrostatic and other noncovalent interactions.

What is the fundamental ion-specific series for anions and cations? Ion specificity in standard partial molar volumes of electrolytes and electrostriction in water and non-aqueous solvents† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc02691a Click here for additional data file.

PubMed Central

Mazzini, Virginia

2017-01-01

The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity. PMID:29147533

Characterisation of cationic potato starch by asymmetrical flow field-flow fractionation. Influence of ionic strength and degree of substitution.

PubMed

Santacruz, Stalin

2014-06-15

The properties of a paper sheet depend on the absorption together with the physico-chemical properties of additives used in the paper processing. The effect of ionic strength and degree of substitution of cationic potato starch on the elution pattern of asymmetrical flow field-flow fractionation was analysed. The effect of starch derivatisation, in either dry or wet phase, was also investigated. Average molar mass showed no difference between the starches obtained from the two derivatisation processes. Apparent densities showed that dry cationic starch had higher density than wet cationic starch for a hydrodynamic radius between 50 and 100 nm. Elution times of native and three cationic starches increased when the ionic strength increased from 50 to 100mM. No differences in the molar mass among cationic starches with different degree of substitution suggested no degradation due to a derivatisation process. Large sample loads can be used at 100mM without overloading. Copyright © 2014 Elsevier Ltd. All rights reserved.

Two-Stage Conversion of High Free Fatty Acid Jatropha curcas Oil to Biodiesel Using Brønsted Acidic Ionic Liquid and KOH as Catalysts

PubMed Central

Das, Subrata; Thakur, Ashim Jyoti; Deka, Dhanapati

2014-01-01

Biodiesel was produced from high free fatty acid (FFA) Jatropha curcas oil (JCO) by two-stage process in which esterification was performed by Brønsted acidic ionic liquid 1-(1-butylsulfonic)-3-methylimidazolium chloride ([BSMIM]Cl) followed by KOH catalyzed transesterification. Maximum FFA conversion of 93.9% was achieved and it reduced from 8.15 wt% to 0.49 wt% under the optimum reaction conditions of methanol oil molar ratio 12 : 1 and 10 wt% of ionic liquid catalyst at 70°C in 6 h. The ionic liquid catalyst was reusable up to four times of consecutive runs under the optimum reaction conditions. At the second stage, the esterified JCO was transesterified by using 1.3 wt% KOH and methanol oil molar ratio of 6 : 1 in 20 min at 64°C. The yield of the final biodiesel was found to be 98.6% as analyzed by NMR spectroscopy. Chemical composition of the final biodiesel was also determined by GC-MS analysis. PMID:24987726

Synthesis and characterization of new class of ionic liquids containing phenolate anion

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

Lethesh, Kallidanthiyil Chellappan, E-mail: lethesh.chellappan@petronas.com.my; Wilfred, Cecilia Devi; Taha, M. F.

2014-10-24

In these manuscript novel ionic liquids containing a new class of 'phenolate' anions was synthesized and characterized. 1-methylmidazole with different alkyl chains such as butyl, hexyl and octyl groups was used as the cationic part. All the ionic liquids were obtained as liquids at room temperature. The synthesized ionic liquids were characterized using {sup 1}H NMR and {sup 13}C NMR spectroscopy. The thermal stability of the ionic liquids was studied using thermo gravimetric analysis (TGA). The effect of temperature on the density and viscosity of the ionic liquids were studied over a temperature range from 293.15 K to 373.15K atmore » atmospheric pressure. From the experimental values of density, the molecular volume, standard molar entropy and the lattice energy of the ionic liquids were calculated.« less

Fast sodium ionic conduction in Na2B10H10-Na2B12H12 pseudo-binary complex hydride and application to a bulk-type all-solid-state battery

NASA Astrophysics Data System (ADS)

Yoshida, Koji; Sato, Toyoto; Unemoto, Atsushi; Matsuo, Motoaki; Ikeshoji, Tamio; Udovic, Terrence J.; Orimo, Shin-ichi

2017-03-01

In the present work, we developed highly sodium-ion conductive Na2B10H10-Na2B12H12 pseudo-binary complex hydride via mechanically ball-milling admixtures of the pure Na2B10H10 and Na2B12H12 components. Both of these components show a monoclinic phase at room temperature, but ball-milled mixtures partially stabilized highly ion-conductive, disordered cubic phases, whose fraction and favored structural symmetry (body-centered cubic or face-centered cubic) depended on the conditions of mechanical ball-milling and molar ratio of the component compounds. First-principles molecular-dynamics simulations demonstrated that the total energy of the closo-borane mixtures and pure materials is quite close, helping to explain the observed stabilization of the mixed compounds. The ionic conductivity of the closo-borane mixtures appeared to be correlated with the fraction of the body-centered-cubic phase, exhibiting a maximum at a molar ratio of Na2B10H10:Na2B12H12 = 1:3. A conductivity as high as log(σ/S cm-1) = -3.5 was observed for the above ratio at 303 K, being approximately 2-3 orders of magnitude higher than that of either pure material. A bulk-type all-solid-state sodium-ion battery with a closo-borane-mixture electrolyte, sodium-metal negative-electrode, and TiS2 positive-electrode demonstrated a high specific capacity, close to the theoretical value of NaTiS2 formation and a stable discharge/charge cycling for at least eleven cycles, with a high discharge capacity retention ratio above 91% from the second cycle.

Experimental investigation of thermodynamic properties of binary mixture of acetic acid + n-butanol and acetic acid + water at temperature from 293.15 K to 343.15 K

NASA Astrophysics Data System (ADS)

Paul, M. Danish John; Shruthi, N.; Anantharaj, R.

2018-04-01

The derived thermodynamic properties like excess molar volume, partial molar volume, excess partial molar volume and apparent volume of binary mixture of acetic acid + n-butanolandacetic acid + water has been investigated using measured density of mixtures at temperatures from 293.15 K to 343.15.

Densities, Ultrasonic Speeds, and Excess Properties of Binary Mixtures of Diethylene Glycol with 1-Butanol, 2-Butanol, and 1,4-Butanediol at Different Temperatures

NASA Astrophysics Data System (ADS)

Ali, Anwar; Ansari, Sana; Uzair, Sahar; Tasneem, Shadma; Nabi, Firdosa

2015-11-01

Densities ρ and ultrasonic speeds u for pure diethylene glycol, 1-butanol, 2-butanol, and 1,4-butanediol and for their binary mixtures over the entire composition range were measured at 298.15 K, 303.15 K, 308.15 K, and 313.15 K. Using these data, the excess molar volumes, VE_m, deviations in isentropic compressibilities, {\\varDelta }ks, apparent molar volumes, V_{φi} , partial molar volumes, overline{V}_{m,i} , and excess partial molar volumes, overline{V}_{m,i}^E , have been calculated over the entire composition range, and also the excess partial molar volumes of the components at infinite dilution, overline{V}_{m,i}^{E,infty } have been calculated. The excess functions have been correlated using the Redlich-Kister equation at different temperatures. The variations of these derived parameters with composition and temperature are presented graphically.

Partial molar volumes and viscosities of aqueous hippuric acid solutions containing LiCl and MnCl2 · 4H2O at 303.15 K

NASA Astrophysics Data System (ADS)

Deosarkar, S. D.; Tawde, P. D.; Zinjade, A. B.; Shaikh, A. I.

2015-09-01

Density (ρ) and viscosity (η) of aqueous hippuric acid (HA) solutions containing LiCl and MnCl2 · 4H2O have been studied at 303.15 K in order to understand volumetric and viscometric behavior of these systems. Apparent molar volume (φv) of salts were calculated from density data and fitted to Massons relation and partial molar volumes (φ{v/0}) at infinite dilution were determined. Relative viscosity data has been used to determine viscosity A and B coefficients using Jones-Dole relation. Partial molar volume and viscosity coefficients have been discussed in terms of ion-solvent interactions and overall structural fittings in solution.

Calculation of Derivative Thermodynamic Hydration and Aqueous Partial Molar Properties of Ions Based on Atomistic Simulations.

PubMed

Dahlgren, Björn; Reif, Maria M; Hünenberger, Philippe H; Hansen, Niels

2012-10-09

The raw ionic solvation free energies calculated on the basis of atomistic (explicit-solvent) simulations are extremely sensitive to the boundary conditions and treatment of electrostatic interactions used during these simulations. However, as shown recently [Kastenholz, M. A.; Hünenberger, P. H. J. Chem. Phys.2006, 124, 224501 and Reif, M. M.; Hünenberger, P. H. J. Chem. Phys.2011, 134, 144104], the application of an appropriate correction scheme allows for a conversion of the methodology-dependent raw data into methodology-independent results. In this work, methodology-independent derivative thermodynamic hydration and aqueous partial molar properties are calculated for the Na(+) and Cl(-) ions at P° = 1 bar and T(-) = 298.15 K, based on the SPC water model and on ion-solvent Lennard-Jones interaction coefficients previously reoptimized against experimental hydration free energies. The hydration parameters considered are the hydration free energy and enthalpy. The aqueous partial molar parameters considered are the partial molar entropy, volume, heat capacity, volume-compressibility, and volume-expansivity. Two alternative calculation methods are employed to access these properties. Method I relies on the difference in average volume and energy between two aqueous systems involving the same number of water molecules, either in the absence or in the presence of the ion, along with variations of these differences corresponding to finite pressure or/and temperature changes. Method II relies on the calculation of the hydration free energy of the ion, along with variations of this free energy corresponding to finite pressure or/and temperature changes. Both methods are used considering two distinct variants in the application of the correction scheme. In variant A, the raw values from the simulations are corrected after the application of finite difference in pressure or/and temperature, based on correction terms specifically designed for derivative parameters at P° and T(-). In variant B, these raw values are corrected prior to differentiation, based on corresponding correction terms appropriate for the different simulation pressures P and temperatures T. The results corresponding to the different calculation schemes show that, except for the hydration free energy itself, accurate methodological independence and quantitative agreement with even the most reliable experimental parameters (ion-pair properties) are not yet reached. Nevertheless, approximate internal consistency and qualitative agreement with experimental results can be achieved, but only when an appropriate correction scheme is applied, along with a careful consideration of standard-state issues. In this sense, the main merit of the present study is to set a clear framework for these types of calculations and to point toward directions for future improvements, with the ultimate goal of reaching a consistent and quantitative description of single-ion hydration thermodynamics in molecular dynamics simulations.

Hydration of alcohol clusters in 1-propanol-water mixture studied by quasielastic neutron scattering and an interpretation of anomalous excess partial molar volume.

PubMed

Misawa, M; Inamura, Y; Hosaka, D; Yamamuro, O

2006-08-21

Quasielastic neutron scattering measurements have been made for 1-propanol-water mixtures in a range of alcohol concentration from 0.0 to 0.167 in mole fraction at 25 degrees C. Fraction alpha of water molecules hydrated to fractal surface of alcohol clusters in 1-propanol-water mixture was obtained as a function of alcohol concentration. Average hydration number N(ws) of 1-propanol molecule is derived from the value of alpha as a function of alcohol concentration. By extrapolating N(ws) to infinite dilution, we obtain values of 12-13 as hydration number of isolated 1-propanol molecule. A simple interpretation of structural origin of anomalous excess partial molar volume of water is proposed and as a result a simple equation for the excess partial molar volume is deduced in terms of alpha. Calculated values of the excess partial molar volumes of water and 1-propanol and the excess molar volume of the mixture are in good agreement with experimental values.

An empirical relation between the limiting ionic molar conductivities and self-diffusion coefficients of pure solvents

NASA Astrophysics Data System (ADS)

Matsuyama, Hisashi; Motoyoshi, Kota

2018-05-01

The limiting ionic molar conductivity (λ∞) of an electrolyte solution depends on the self-diffusion coefficient (Ds) of the pure solvent when the temperature (T) changes. To study the Ds-dependence of λ∞, we proposed a new empirical relation λ∞ ∝(Ds / T) t , with a parameter t. The relation is applied to the λ∞ and Ds of alkali, tetra-alkyl ammonium, and halogen ions in water or methanol. All ions except for tetra-alkyl ammonium ions in water exhibit excellent linear relationships in their λ∞ ∝(Ds / T) t plots, with t in the range from 0.88 to 1.26. This is the first report showing an affirmative linear correlation between λ∞ and Ds.

Properties of L-ascorbic acid in water and binary aqueous mixtures of D-glucose and D-fructose at different temperatures

NASA Astrophysics Data System (ADS)

Sharma, Ravi; Thakur, R. C.; Sani, Balwinder; Kumar, Harsh

2017-12-01

Using density and sound velocity partial molar volumes, partial molar adiabatic compressibilities, partial molar expansibilities and structure of L-ascorbic acid have been determined in water and aqueous mixtures of D-glucose and D-fructose at different concentrations and temperatures. Masson's equation was used to analyze the measured data. The obtained parameters have been interpreted in terms of solute-solute and solute-solvent interactions. It is found that the L-ascorbic acid acts as structure breaker in water as well in binary studied mixtures.

[Orthodontic partial disimpaction of mandibular third molars prior to surgical extraction].

PubMed

Derton, Nicolà; Perini, Alessandro; Giordanetto, José; Biondi, Giovanni; Siciliani, Giuseppe

2009-06-01

Odontodysplasia of the third molars is a relatively common anomaly. The frequent complications associated with this disorder very often constitute an indication for extraction of the third molar. This surgical treatment can damage the lower alveolar nerve and/or trigger distal bone loss of the second molar, thus jeopardizing the future status of the periodontium. The author presents two case studies treated exclusively with miniscrews with no dental anchorage in order to achieve partial eruption of the third molar moving it away from the lower alveolar nerve and to avoid unwanted impact on other teeth. Following this procedure, the third molar was extracted without complications. In conclusion, this approach can offer an alternative to surgical treatment alone in cases where the proximity of tooth and nerve poses a significant risk.

A simple way to intrude overerupted upper second molars with miniscrews.

PubMed

Cao, Yang; Liu, Chufeng; Wang, Chunxian; Yang, Xiaoyu; Duan, Peijia; Xu, Chenrong

2013-12-01

Various methods of using skeletal anchorage for the intrusion of overerupted maxillary molars have been reported; however, it is difficult to intrude the overerupted upper second molars because of the low bone density in the region of the tuberosity. This article illustrates a new treatment method using partial fixed edgewise appliances and miniscrews to intrude the overerupted upper second molars. The miniscrews were applied to reinforce the anchorage of the upper first molar. The intrusive force was generated by the Ni-Ti wire. The clinical results showed a significant intrusion effect without root resorption or periodontal problems. This report demonstrates that the combination of partial conventional fixed appliances with miniscrews is a simple and effective treatment option to intrude overerupted upper second molars, especially in situations where miniscrews cannot be inserted directly next to the second molar. © 2013 by the American College of Prosthodontists.

Preparation of Some Novel Copper(I) Complexes and their Molar Conductances in Organic Solvents

NASA Astrophysics Data System (ADS)

Gill, Dip Singh; Rana, Dilbag

2009-04-01

Attempts have been made to prepare some novel copper(I) nitrate, sulfate, and perchlorate complexes. Molar conductances of these complexes have been measured in organic solvents like acetonitrile (AN), acetone (AC), methanol (MeOH), N,N-dimethylformamide (DMF), N,Ndimethylacetamide (DMA), and dimethylsulfoxide (DMSO) at 298 K. The molar conductance data have been analyzed to obtain limiting molar conductances (λ0) and ion association constants (KA) of the electrolytes. The results showed that all these complexes are strong electrolytes in all organic solvents. The limiting ionic molar conductances (λo± ) for various ions have been calculated using Bu4NBPh4 as reference electrolyte. The actual radii for copper(I) complex ions are very large and different in different solvents and indicate some solvation effects in each solvent system

Live-born diploid fetus complicated with partial molar pregnancy presenting with pre-eclampsia, maternal anemia, and seemingly huge placenta: A rare case of confined placental mosaicism and literature review.

PubMed

Kawasaki, Kaoru; Kondoh, Eiji; Minamiguchi, Sachiko; Matsuda, Fumihiko; Higasa, Koichiro; Fujita, Kohei; Mogami, Haruta; Chigusa, Yoshitsugu; Konishi, Ikuo

2016-08-01

A partial molar pregnancy almost always ends in miscarriage due to a triploid fetus. We describe a rare case of a singleton, partial molar pregnancy with a seemingly huge placenta, which continued to delivery of a live-born diploid baby. A 27-year-old primigravida suffered from severe pre-eclampsia and progressive anemia. The uterus was enormously enlarged for the gestational age. A cesarean section was performed because of deterioration of maternal status at 25 weeks' gestation, when more than 3000 mL blood spouted concurrently with the delivery of the placenta. The histological examination showed congestion in the decidua, which indicated disturbance of maternal venous return from the intervillous space. The chromosome complement of the placenta and the neonate were 69,XXX and 46,XX, respectively. We also reviewed all published cases of a singleton, partial molar pregnancy. A literature search yielded 18 cases of a singleton, diploid fetus with partial molar pregnancy. The mean gestational age at delivery was 24.5 ± 6.2 weeks, and fetuses survived outside the uterus in only four cases (22.2%). Intriguingly, previous reports numbered 10 cases with diploid placenta as well as five cases with no karyotyping of the placenta, indicating that they may have included a complete mole in a twin pregnancy or placental mesenchymal dysplasia. In conclusion, this was the first case of placentomegaly that presented manifestations of excessive abdominal distension and maternal severe anemia, and the second case of a singleton, partial molar pregnancy confirmed by chromosome analysis resulting in a diploid living baby. © 2016 Japan Society of Obstetrics and Gynecology.

Static and transport properties of alkyltrimethylammonium cation-based room-temperature ionic liquids.

PubMed

Seki, Shiro; Tsuzuki, Seiji; Hayamizu, Kikuko; Serizawa, Nobuyuki; Ono, Shimpei; Takei, Katsuhito; Doi, Hiroyuki; Umebayashi, Yasuhiro

2014-05-01

We have measured physicochemical properties of five alkyltrimethylammonium cation-based room-temperature ionic liquids and compared them with those obtained from computational methods. We have found that static properties (density and refractive index) and transport properties (ionic conductivity, self-diffusion coefficient, and viscosity) of these ionic liquids show close relations with the length of the alkyl chain. In particular, static properties obtained by experimental methods exhibit a trend complementary to that by computational methods (refractive index ∝ [polarizability/molar volume]). Moreover, the self-diffusion coefficient obtained by molecular dynamics (MD) simulation was consistent with the data obtained by the pulsed-gradient spin-echo nuclear magnetic resonance technique, which suggests that computational methods can be supplemental tools to predict physicochemical properties of room-temperature ionic liquids.

Alkaline ionic liquids applied in supported ionic liquid catalyst for selective hydrogenation of citral to citronellal

PubMed Central

Salminen, Eero; Virtanen, Pasi; Mikkola, Jyri-Pekka

2014-01-01

The challenge in preparation of ionic liquids containing a strong alkaline anion is to identify a suitable cation which can tolerate the harsh conditions induced by the anion. In this study, a commercial quaternary ammonium compound (quat) benzalkonium [ADBA] (alkyldimethylbenzylammonium) was used as a cation in the synthesis of different alkaline ionic liquids. In fact, the precursor, benzalkonium chloride, is a mixture of alkyldimethylbenzylammonium chlorides of various alkyl chain lengths and is commonly used in the formulation of various antiseptic products. The prepared ionic liquids were utilized as Supported Ionic Liquid Catalysts (SILCAs). Typically, a SILCA contains metal nanoparticles, enzymes, or metal complexes in an ionic liquid layer which is immobilized on a solid carrier material such as an active carbon cloth (ACC). The catalysts were applied in the selective hydrogenation of citral to citronellal which is an important perfumery chemical. Interestingly, 70% molar yield toward citronellal was achieved over a catalyst containing the alkaline ionic liquid benzalkonium methoxide. PMID:24790972

The gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide from combustion calorimetry, vapor pressure measurements, and ab initio calculations.

PubMed

Emel'yanenko, Vladimir N; Verevkin, Sergey P; Heintz, Andreas

2007-04-04

Ionic liquids are attracting growing interest as alternatives to conventional molecular solvents. Experimental values of vapor pressure, enthalpy of vaporization, and enthalpy of formation of ionic liquids are the key thermodynamic quantities, which are required for the validation and development of the molecular modeling and ab initio methods toward this new class of solvents. In this work, the molar enthalpy of formation of the liquid 1-butyl-3-methylimidazolium dicyanamide, 206.2 +/- 2.5 kJ.mol-1, was measured by means of combustion calorimetry. The molar enthalpy of vaporization of 1-butyl-3-methylimidazolium dicyanamide, 157.2 +/- 1.1 kJ.mol-1, was obtained from the temperature dependence of the vapor pressure measured using the transpiration method. The latter method has been checked with measurements of 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide, where data are available from the effusion technique. The first experimental determination of the gaseous enthalpy of formation of the ionic liquid 1-butyl-3-methylimidazolium dicyanamide, 363.4 +/- 2.7 kJ.mol-1, from thermochemical measurements (combustion and transpiration) is presented. Ab initio calculations of the enthalpy of formation in the gaseous phase have been performed for 1-butyl-3-methylimidazolium dicyanamide using the G3MP2 theory. Excellent agreement with experimental results has been observed. The method developed opens a new way to obtain thermodynamic properties of ionic liquids which have not been available so far.

Partial Molar Volumes of Aqua Ions from First Principles.

PubMed

Wiktor, Julia; Bruneval, Fabien; Pasquarello, Alfredo

2017-08-08

Partial molar volumes of ions in water solution are calculated through pressures obtained from ab initio molecular dynamics simulations. The correct definition of pressure in charged systems subject to periodic boundary conditions requires access to the variation of the electrostatic potential upon a change of volume. We develop a scheme for calculating such a variation in liquid systems by setting up an interface between regions of different density. This also allows us to determine the absolute deformation potentials for the band edges of liquid water. With the properly defined pressures, we obtain partial molar volumes of a series of aqua ions in very good agreement with experimental values.

Determination of thermodynamic properties of poly (cyclohexyl methacrylate) by inverse gas chromatography.

PubMed

Kaya, Ismet; Pala, Cigdem Yigit

2014-07-01

In this work, some thermodynamic properties of poly (cyclohexyl methacrylate) were studied by inverse gas chromatography (IGC). For this purpose, the polymeric substance was coated on Chromosorb W and which was filled into a glass column. The retention times (t(r)) of the probes were determined from the interactions of poly (cyclohexyl methacrylate) with n-pentane, n-hexane, n-heptane, n-octane, n-decane, methanol, ethanol, 2-propanol, butanol, acetone, ethyl methyl ketone, benzene, toluene and o-xylene by IGC technique. Then, the specific volume (Vg(0)) was determined for each probe molecule. By using (1/T; lnVg(0)) graphics, the glass transition temperature of poly (cyclohexyl methacrylate) was found to be 373 K. The adsorption heat under the glass transition temperature (deltaH(a)), and partial molar heat of sorption above the glass transition (deltaH1(S)), partial molar free energy of sorption (deltaG1(S)) and partial molar entropy of sorption (deltaS1(S)) belonging to sorption for every probe were calculated. The partial molar heat of mixing at infinite dilution (deltaH1(infinity)), partial molar free energy of mixing at infinite dilution (deltaG1(infinity)), Flory-Huggins interaction parameter (chi12(infinity)) and weight fraction activity coefficient (a1/w1)(infinity) values of polymer-solute systems were calculated at different column temperatures. The solubility parameters (delta2) of the polymer were obtained by IGC technique.

Prevalence of missing and impacted third molars in adults aged 25 years and above

PubMed Central

Jung, Yun-Hoa

2013-01-01

Purpose The purpose of this study was to determine the prevalence of missing and impacted third molars in people aged 25 years and above. Materials and Methods The study sample of 3,799 patients was chosen randomly from patients who visited Pusan National University Dental Hospital and had panoramic radiographs taken. The data collected included presence and impaction state, angulation, and depth of impaction of third molars, and radiographically detected lesions of third molars and adjacent second molars. Results A greater percentage of men than women retained at least one third molar. The incidence of third molars decreased with increasing age. The incidence of partially impacted third molars greatly declined after the age of 30. Vertically impacted maxillary third molars and horizontally impacted mandibular third molars were most frequent in all age groups. Among the maxillary third molars, those impacted below the cervical line of the second molar were most frequent in all age groups, and among the mandibular third molars, deeply impacted third molars were most frequent in those aged over 40. Dental caries was the most common radiographic lesion of the third molars. Mesioangularly impacted third molars showed radiographic lesions in 13 (9.5%) adjacent maxillary second molars and 117 (27.4%) mandibular second molars. Conclusion The number of remaining third molars decreased and the percentage of Class C depth increased with age. Caries was the most frequent lesion in third molars. Partially impacted mesioangular third molars showed a high incidence of caries or periodontal bone loss of the adjacent second molar. Regular oral examination will be essential to keep asymptomatic third molars in good health. PMID:24380060

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

NASA Astrophysics Data System (ADS)

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.

Study on the temperature-dependent coupling among viscosity, conductivity and structural relaxation of ionic liquids.

PubMed

Yamaguchi, Tsuyoshi; Yonezawa, Takuya; Koda, Shinobu

2015-07-15

The frequency-dependent viscosity and conductivity of three imidazolium-based ionic liquids were measured at several temperatures in the MHz region, and the results are compared with the intermediate scattering functions determined by neutron spin echo spectroscopy. The relaxations of both the conductivity and the viscosity agree with that of the intermediate scattering function at the ionic correlation when the relaxation time is short. As the relaxation time increases, the relaxations of the two transport properties deviate to lower frequencies than that of the ionic structure. The deviation begins at a shorter relaxation time for viscosity than for conductivity, which explains the fractional Walden rule between the zero-frequency values of the shear viscosity and the molar conductivity.

Infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide.

PubMed

Kong, Chang Yi; Siratori, Tomoya; Funazukuri, Toshitaka; Wang, Guosheng

2014-10-03

The effects of temperature and density on retention of platinum(II) 2,4-pentanedionate in supercritical fluid chromatography were investigated at temperatures of 308.15-343.15K and pressure range from 8 to 40MPa by the chromatographic impulse response method with curve fitting. The retention factors were utilized to derive the infinite dilution partial molar volumes of platinum(II) 2,4-pentanedionate in supercritical carbon dioxide. The determined partial molar volumes were small and positive at high pressures but exhibited very large and negative values in the highly compressible near critical region of carbon dioxide. Copyright © 2014 Elsevier B.V. All rights reserved.

The apparent solubility of aluminum (III) in Hanford high-level waste.

PubMed

Reynolds, Jacob G

2012-01-01

The solubility of aluminum in Hanford nuclear waste impacts on the processability of the waste by a number of proposed treatment options. For many years, Hanford staff has anecdotally noted that aluminum appears to be considerably more soluble in Hanford waste than the simpler electrolyte solutions used as analogues. There has been minimal scientific study to confirm these anecdotal observations, however. The present study determines the apparent solubility product for gibbsite in 50 tank samples. The ratio of hydroxide to aluminum in the liquid phase for the samples is calculated and plotted as a function of total sodium molarity. Total sodium molarity is used as a surrogate for ionic strength, because the relative ratios of mono-, di- and trivalent anions are not available for all of the samples. These results were compared to the simple NaOH-NaAl(OH)(4)-H(2)O system, and the NaOH-NaAl(OH)(4)-NaCl-H(2)O system data retrieved from the literature. The results show that gibbsite is apparently more soluble in the samples than in the simple systems whenever the sodium molarity is greater than 2M. This apparent enhanced solubility cannot be explained solely by differences in ionic strength. The change in solubility with ionic strength in simple systems is small compared to the difference between aluminum solubility in Hanford waste and the simple systems. The reason for the apparent enhanced solubility is unknown, but could include kinetic or thermodynamic factors that are not present in the simple electrolyte systems. Any kinetic explanation would have to explain why the samples are always supersaturated whenever the sodium molarity is above 2M. Real waste characterization data should not be used to validate thermodynamic solubility models until it can be confirmed that the apparent enhanced gibbsite solubility is a thermodynamic effect and not a kinetic effect.

The apparent solubility of aluminum (III) in Hanford high-level waste

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

Reynolds, Jacob G.

2012-12-01

The solubility of aluminum in Hanford nuclear waste impacts on the process ability of the waste by a number of proposed treatment options. For many years, Hanford staff has anecdotally noted that aluminum appears to be considerably more soluble in Hanford waste than the simpler electrolyte solutions used as analogues. There has been minimal scientific study to confirm these anecdotal observations, however. The present study determines the apparent solubility product for gibbsite in 50 tank samples. The ratio of hydroxide to aluminum in the liquid phase for the samples is calculated and plotted as a function of total sodium molarity.more » Total sodium molarity is used as a surrogate for ionic strength, because the relative ratios of mono, di and trivalent anions are not available for all of the samples. These results were compared to the simple NaOH-NaAl(OH{sub 4})H{sub 2}O system, and the NaOH-NaAl(OH{sub 4})NaCl-H{sub 2}O system data retrieved from the literature. The results show that gibbsite is apparently more soluble in the samples than in the simple systems whenever the sodium molarity is greater than two. This apparent enhanced solubility cannot be explained solely by differences in ionic strength. The change in solubility with ionic strength in simple systems is small compared to the difference between aluminum solubility in Hanford waste and the simple systems. The reason for the apparent enhanced solubility is unknown, but could include. kinetic or thermodynamic factors that are not present in the simple electrolyte systems. Any kinetic explanation would have to explain why the samples are always supersaturated whenever the sodium molarity is above two. Real waste characterization data should not be used to validate thermodynamic solubility models until it can be confirmed that the apparent enhanced gibbsite solubility is a thermodynamic effect and not a kinetic effect.« less

How Does the Addition of a Third Ion Affect the Molecular Interactions and the Thermodynamic Properties of Acetate-Based Ionic Liquids?

PubMed

Otero, I; Lepre, L F; Dequidt, A; Husson, P; Costa Gomes, M F

2017-10-19

The effect of the addition of a third ion to the ionic liquid 1-butyl-3-methylimidazolium acetate [C 4 C 1 Im][OAc] was studied through the measurement of the enthalpy of mixing and of the excess molar volume of its mixtures with 1-butyl-3-methylimidazolium trifluoroacetate [C 4 C 1 Im][CF 3 CO 2 ], 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [C 4 C 1 Im][NTf 2 ], and tetrabutylphosphonium acetate [P 4444 ][OAc]. Negative enthalpies of mixing (Δ mix H < 0) and positive excess molar volumes (V E > 0) were observed in all cases. The infrared and NMR studies of the pure ionic liquids and their mixtures show that the presence of a third ion with a weaker affinity with the common counterion contributes to prevailing the more favorable hydrogen-bond, herein always between the imidazolium cation and the acetate anion. Both radial and spatial distribution functions calculated by molecular simulation confirm this behavior. The remarkable enhancement of the viscosities of the [C 4 C 1 Im][OAc] + [P 4444 ][OAc] mixtures could be discussed in light of the calculated friction coefficients.

Partial Molar Volumes of 15-Crown-5 Ether in Mixtures of N,N-Dimethylformamide with Water.

PubMed

Tyczyńska, Magdalena; Jóźwiak, Małgorzata

2014-01-01

The density of 15-crown-5 ether (15C5) solutions in the mixtures of N,N -dimethylformamide (DMF) and water (H 2 O) was measured within the temperature range 293.15-308.15 K using an Anton Paar oscillatory U-tube densimeter. The results were used to calculate the apparent molar volumes ( V Φ ) of 15C5 in the mixtures of DMF + H 2 O over the whole concentration range. Using the apparent molar volumes and Redlich and Mayer equation, the standard partial molar volumes of 15-crown-5 were calculated at infinite dilution ([Formula: see text]). The limiting apparent molar expansibilities ( α ) were also calculated. The data are discussed from the point of view of the effect of concentration changes on interactions in solution.

A finite element analysis of the stress distribution to the mandible from impact forces with various orientations of third molars*

PubMed Central

Liu, Yun-feng; Wang, Russell; Baur, Dale A.; Jiang, Xian-feng

2018-01-01

Objective: To investigate the stress distribution to the mandible, with and without impacted third molars (IM3s) at various orientations, resulting from a 2000-Newton impact force either from the anterior midline or from the body of the mandible. Materials and methods: A 3D mandibular virtual model from a healthy dentate patient was created and the mechanical properties of the mandible were categorized to 9 levels based on the Hounsfield unit measured from computed tomography (CT) images. Von Mises stress distributions to the mandibular angle and condylar areas from static impact forces (Load I-front blow and Load II left blow) were evaluated using finite element analysis (FEA). Six groups with IM3 were included: full horizontal bony, full vertical bony, full 450 mesioangular bony, partial horizontal bony, partial vertical, and partial 450 mesioangular bony impaction, and a baseline group with no third molars. Results: Von Mises stresses in the condyle and angle areas were higher for partially than for fully impacted third molars under both loading conditions, with partial horizontal IM3 showing the highest fracture risk. Stresses were higher on the contralateral than on the ipsilateral side. Under Load II, the angle area had the highest stress for various orientations of IM3s. The condylar region had the highest stress when IM3s were absent. Conclusions: High-impact forces are more likely to cause condylar rather than angular fracture when IM3s are missing. The risk of mandibular fracture is higher for partially than fully impacted third molars, with the angulation of impaction having little effect on facture risk. PMID:29308606

Signal Amplification in Field Effect-Based Sandwich Enzyme-Linked Immunosensing by Tuned Buffer Concentration with Ionic Strength Adjuster.

PubMed

Kumar, Satyendra; Kumar, Narendra; Panda, Siddhartha

2016-04-01

Miniaturization of the sandwich enzyme-based immunosensor has several advantages but could result in lower signal strength due to lower enzyme loading. Hence, technologies for amplification of the signal are needed. Signal amplification in a field effect-based electrochemical immunosensor utilizing chip-based ELISA is presented in this work. First, the molarities of phosphate buffer saline (PBS) and concentrations of KCl as ionic strength adjuster were optimized to maximize the GOx glucose-based enzymatic reactions in a beaker for signal amplification measured by change in the voltage shift with an EIS device (using 20 μl of solution) and validated with a commercial pH meter (using 3 ml of solution). The PBS molarity of 100 μM with 25 mM KCl provided the maximum voltage shift. These optimized buffer conditions were further verified for GOx immobilized on silicon chips, and similar trends with decreased PBS molarity were obtained; however, the voltage shift values obtained on chip reaction were lower as compared to the reactions occurring in the beaker. The decreased voltage shift with immobilized enzyme on chip could be attributed to the increased Km (Michaelis-Menten constant) values in the immobilized GOx. Finally, a more than sixfold signal enhancement (from 8 to 47 mV) for the chip-based sandwich immunoassay was obtained by altering the PBS molarity from 10 to 100 μM with 25 mM KCl.

Studies of Partial Molar Volumes of Some Narcotic-Analgesic Drugs in Aqueous-Alcoholic Mixtures at 25°C

NASA Astrophysics Data System (ADS)

Sharma, Poonam; Chauhan, S.; Syal, V. K.; Chauhan, M. S.

2008-04-01

Partial molar volumes of the drugs Parvon Spas, Parvon Forte, Tramacip, and Parvodex in aqueous mixtures of methanol (MeOH), ethanol (EtOH), and propan-1-ol (1-PrOH) have been determined. The data have been evaluated using the Masson equation. The parameters, apparent molar volumes {(φ_v)}, partial molar volumes {(φ_v0)}, and S v values (experimental slopes) have been interpreted in terms of solute solvent interactions. In addition, these studies have also been extended to determine the effect of these drugs on the solvation behavior of an electrolyte (sodium chloride), a surfactant (sodium dodecyl sulfate), and a non-electrolyte (sucrose). It can be inferred from these studies that all drug cations can be regarded as structure makers/promoters due to hydrophobic hydration. Furthermore, the results are correlated to understand the solution behavior of drugs in aqueous-alcoholic systems, as a function of the nature of the alcohol and solutes.

Towards a universal method for calculating hydration free energies: a 3D reference interaction site model with partial molar volume correction.

PubMed

Palmer, David S; Frolov, Andrey I; Ratkova, Ekaterina L; Fedorov, Maxim V

2010-12-15

We report a simple universal method to systematically improve the accuracy of hydration free energies calculated using an integral equation theory of molecular liquids, the 3D reference interaction site model. A strong linear correlation is observed between the difference of the experimental and (uncorrected) calculated hydration free energies and the calculated partial molar volume for a data set of 185 neutral organic molecules from different chemical classes. By using the partial molar volume as a linear empirical correction to the calculated hydration free energy, we obtain predictions of hydration free energies in excellent agreement with experiment (R = 0.94, σ = 0.99 kcal mol (- 1) for a test set of 120 organic molecules).

Standard partial molar volumes of some aqueous alkanolamines and alkoxyamines at temperatures up to 325 degrees C: functional group additivity in polar organic solutes under hydrothermal conditions.

PubMed

Bulemela, E; Tremaine, Peter R

2008-05-08

Apparent molar volumes of dilute aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), N,N-dimethylethanolamine (DMEA), ethylethanolamine (EAE), 2-diethylethanolamine (2-DEEA), and 3-methoxypropylamine (3-MPA) and their salts were measured at temperatures from 150 to 325 degrees C and pressures as high as 15 MPa. The results were corrected for the ionization and used to obtain the standard partial molar volumes, Vo2. A three-parameter equation of state was used to describe the temperature and pressure dependence of the standard partial molar volumes. The fitting parameters were successfully divided into functional group contributions at all temperatures to obtain the standard partial molar volume contributions. Including literature results for alcohols, carboxylic acids, and hydroxycarboxylic acids yielded the standard partial molar volume contributions of the functional groups >CH-, >CH2, -CH3, -OH, -COOH, -O-, -->N, >NH, -NH2, -COO-Na+, -NH3+Cl-, >NH2+Cl-, and -->NH+Cl- over the range (150 degrees C

Evidence against the involvement of ionically bound cell wall proteins in pea epicotyl growth

NASA Technical Reports Server (NTRS)

Melan, M. A.; Cosgrove, D. J.

1988-01-01

Ionically bound cell wall proteins were extracted from 7 day old etiolated pea (Pisum sativum L. cv Alaska) epicotyls with 3 molar LiCl. Polyclonal antiserum was raised in rabbits against the cell wall proteins. Growth assays showed that treatment of growing region segments (5-7 millimeters) of peas with either dialyzed serum, serum globulin fraction, affinity purified immunoglobulin, or papain-cleaved antibody fragments had no effect on growth. Immunofluorescence microscopy confirmed antibody binding to cell walls and penetration of the antibodies into the tissues. Western blot analysis, immunoassay results, and affinity chromatography utilizing Sepharose-bound antibodies confirmed recognition of the protein preparation by the antibodies. Experiments employing in vitro extension as a screening measure indicated no effect upon extension by antibodies, by 50 millimolar LiCl perfusion of the apoplast or by 3 molar LiCl extraction. Addition of cell wall protein to protease pretreated segments did not restore extension nor did addition of cell wall protein to untreated segments increase extension. It is concluded that, although evidence suggests that protein is responsible for the process of extension, the class(es) of proteins which are extracted from pea cell walls with 3 molar LiCl are probably not involved in this process.

Hydrogen bond basicity of ionic liquids and molar entropy of hydration of salts as major descriptors in the formation of aqueous biphasic systems.

PubMed

Passos, Helena; Dinis, Teresa B V; Cláudio, Ana Filipa M; Freire, Mara G; Coutinho, João A P

2018-05-23

Aqueous biphasic systems (ABS) composed of ionic liquids (ILs) and conventional salts have been largely investigated and successfully used in separation processes, for which the determination of the corresponding ternary phase diagrams is a prerequisite. However, due the large number of ILs that can be prepared and their high structural versatility, it is impossible to experimentally cover and characterize all possible combinations of ILs and salts that may form ABS. The development of tools for the prediction and design of IL-based ABS is thus a crucial requirement. Based on a large compilation of experimental data, a correlation describing the formation of IL-based ABS is shown here, based on the hydrogen-bonding interaction energies of ILs (EHB) obtained by the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) and the molar entropy of hydration of the salt ions. The ability of the proposed model to predict the formation of novel IL-based ABS is further ascertained.

Role of reduced precursor and solvolytic reagent molar ratio on preparation and properties of ionogel

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

Gupta, Abhishek Kumar; Verma, Yogendra Lal; Singh, Manish Pratap

In the present study, ionogels have been synthesized by immobilizing IL (1-ethyl-3-methylimidazolium tetrafluoroborate) in silica gel matrices using non-aqueous route. In this process, tetraethyl orho-silane (TEOS) as a precursor to silicon dioxide and formic acid as a solvolytic gelating reagent in reduced molar ratio 1:4 were used. We find that reduced molar concentration of formic acid results the formation of ionogels having less number of closed pores (totally isolated from their neighbours), larger density and stable monolithic form. TEM and SEM measurements are used to visualize the morphology of sample and closed pores present in the sample. N{sub 2}-sorption measurementmore » is used to measure the pore parameters of the silica matrices which shows the mesoporous structure. DSC and TGA results show the change in phase transition temperature and thermal stability of IL upon confinement in silica matrices. Moreover, ionic conductivity of bulk and confined IL is measured using impedance spectroscopy and it has been found that it increases with increasing the temperature as well as concentration of IL in ionogels. Apart from these characterization techniques, ionogels have been characterized using FTIR and fluorescence spectroscopy which exhibit the change in vibrational frequencies and fluorescence behaviour of confined IL. - Highlights: • Synthesis of stable ionogel using non-hydrolytic route with reduced precursor and solvolytic reagent molar ratio. • Ionogels are free from entrapped residual reaction product. • The ionogels synthesized with higher amount of ionic liquids show bulk liquid like electrical behaviour.« less

Determination of partial molar volumes from free energy perturbation theory†

PubMed Central

Vilseck, Jonah Z.; Tirado-Rives, Julian

2016-01-01

Partial molar volume is an important thermodynamic property that gives insights into molecular size and intermolecular interactions in solution. Theoretical frameworks for determining the partial molar volume (V°) of a solvated molecule generally apply Scaled Particle Theory or Kirkwood–Buff theory. With the current abilities to perform long molecular dynamics and Monte Carlo simulations, more direct methods are gaining popularity, such as computing V° directly as the difference in computed volume from two simulations, one with a solute present and another without. Thermodynamically, V° can also be determined as the pressure derivative of the free energy of solvation in the limit of infinite dilution. Both approaches are considered herein with the use of free energy perturbation (FEP) calculations to compute the necessary free energies of solvation at elevated pressures. Absolute and relative partial molar volumes are computed for benzene and benzene derivatives using the OPLS-AA force field. The mean unsigned error for all molecules is 2.8 cm3 mol−1. The present methodology should find use in many contexts such as the development and testing of force fields for use in computer simulations of organic and biomolecular systems, as a complement to related experimental studies, and to develop a deeper understanding of solute–solvent interactions. PMID:25589343

Determination of partial molar volumes from free energy perturbation theory.

PubMed

Vilseck, Jonah Z; Tirado-Rives, Julian; Jorgensen, William L

2015-04-07

Partial molar volume is an important thermodynamic property that gives insights into molecular size and intermolecular interactions in solution. Theoretical frameworks for determining the partial molar volume (V°) of a solvated molecule generally apply Scaled Particle Theory or Kirkwood-Buff theory. With the current abilities to perform long molecular dynamics and Monte Carlo simulations, more direct methods are gaining popularity, such as computing V° directly as the difference in computed volume from two simulations, one with a solute present and another without. Thermodynamically, V° can also be determined as the pressure derivative of the free energy of solvation in the limit of infinite dilution. Both approaches are considered herein with the use of free energy perturbation (FEP) calculations to compute the necessary free energies of solvation at elevated pressures. Absolute and relative partial molar volumes are computed for benzene and benzene derivatives using the OPLS-AA force field. The mean unsigned error for all molecules is 2.8 cm(3) mol(-1). The present methodology should find use in many contexts such as the development and testing of force fields for use in computer simulations of organic and biomolecular systems, as a complement to related experimental studies, and to develop a deeper understanding of solute-solvent interactions.

Surface effects on ionic Coulomb blockade in nanometer-size pores

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

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

PubMed

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

2018-01-12

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

Solvation of apolar compounds in protic ionic liquids: the non-synergistic effect of electrostatic interactions and hydrogen bonds.

PubMed

Sedov, I A; Magsumov, T I; Salikov, T M; Solomonov, B N

2017-09-27

The solvation properties of protic ionic liquids such as alkylammonium salts are still virtually uncharacterized. Both electrostatic interactions between charged particles and hydrogen bond networks in a solvent are known to hinder the solubility of apolar species. Protic ionic liquids can be a priori expected to dissolve hydrocarbons worse than aprotic ionic liquids which do not form hydrogen bonds between the ions. We measured the limiting activity coefficients of several alkanes and alkylbenzenes in propylammonium and butylammonium nitrates at 298 K. Surprisingly, we observed the tendency of higher solubility than for the same compounds in aprotic ionic liquids with a similar molar volume. The calculations of the excess Gibbs free energies using test particle insertions into the snapshots of molecular dynamics trajectories reproduced lower values in protic rather than in aprotic ionic liquids for both methane molecules and hard sphere solutes. This can be explained by the favorable solvation of apolar species in the apolar domain of nanostructured PILs. For the first time, we point out at the essential difference between the solvation properties of two types of ionic liquids and prove that it arises from the cavity formation term.

The retention of pit and fissure sealants placed in primary school children by Dental Health Services, Victoria.

PubMed

Messer, L B; Calache, H; Morgan, M V

1997-08-01

The benefit of a public sector sealant programme for children in Australia is yet to be established. This study evaluated sealants placed by therapists of the School Dental Service in Victoria, between 1989 and 1994, on permanent teeth of children in 15 primary schools in Melbourne. Seven hundred and seventy four children aged 6-12 years were examined in school dental clinics by six calibrated examiners. A total of 5363 sealants placed on 2875 permanent teeth (including 2616 first molars, 91 per cent of sample) up to four and a half years previously was examined. Values for complete and partial sealant retention were highest for premolars (86 per cent, 9 per cent respectively, total 95 per cent); similar for occlusal surfaces of maxillary and mandibular first molars (63 per cent, 30 per cent; 62 per cent, 32 per cent respectively) and buccal pits of mandibular molars (66 per cent); and low for pits/fissures of Carabelli's cusps of maxillary molars (44 per cent). Cross-sectional examination up to 24 months for both maxillary and mandibular first molars indicated average values of 67 per cent complete retention, 27 per cent partial retention, 6 per cent missing; thereafter complete retention decreased and partial retention increased. Sealant failures in the six months post-placement were attributed to technique failure. Regardless of sealant retention, caries experience was low under partially retained or missing sealants (4.5 per cent) and completely retained sealants (0.4 per cent). It is concluded that the SDS sealant programme is a sound preventive dental public health approach.

Dilatometric measurement of the partial molar volume of water sorbed to durum wheat flour.

PubMed

Hasegawa, Ayako; Ogawa, Takenobu; Adachi, Shuji

2013-01-01

Moisture sorption isotherms were measured at 25 °C for untreated, dry-heated and pre-gelatinized durum wheat flour samples. The isotherms could be expressed by the Guggenheim-Anderson-de Boer equation. The amount of water sorbed to the untreated flour was highest for low water activity, with water sorbed to the pre-gelatinized and dry-heated flour samples following. The dry-heated and pregelatinized flour samples exhibited the same dependence of the moisture content on the partial molar volume of water at 25 °C as the untreated flour. The partial molar volume of water was ca. 9 cm(3)/mol at a moisture content of 0.03 kg-H2O/kg-d.m. The volume increased with increasing moisture content, and reached a constant value of ca. 17.5 cm(3)/mol at a moisture content of 0.2 kg-H2O/kg-d.m. or higher.

On archaebacterial ATPase from Halobacterium saccharovorum

NASA Technical Reports Server (NTRS)

Kristjansson, H.; Ponnamperuma, C.; Hochstein, L.; Altekar, W.

1984-01-01

The energy transducing ATPase from Halobacterium saccharovorum was studied in order to define the origin of energy transducing systems. The ATPase required high salt concentration (4M NaCl) for activity; activity was rapidly lost when NaCl was below 1 Molar. At low salt concentration, the membrane bound ATPase activity could be stabilized in presence of spermine. However, following solubilization spermine was ineffective. Furthermore, F1 ATPase activity was stabilized by ammonium sulfate even when the NaCl concentration was less than 1 Molar. These studies suggest that stabilization by hydrophobic interactions preceded ionic ones in the evolution of the energy transducing ATPases.

Protraction of mandibular second and third molars assisted by partial corticision and miniscrew anchorage.

PubMed

Mimura, Hiroshi

2013-08-01

A woman, aged 47 years 6 months, with an anterior open bite and a left-shifted mandible was treated with a mandibular right first molar extraction and without orthognathic surgery. However, her mandibular second molar did not move mesially during treatment because of the dense lamina dura; therefore, corticision was applied only on the mesial aspect of the mandibular second molar, and a miniscrew was inserted simultaneously. Corticision was introduced as a supplemental dentoalveolar surgery in orthodontic therapy to achieve accelerated tooth movement with minimal surgical intervention. In this technique, a reinforced scalpel was used as a thin chisel to separate the interproximal cortices transmucosally without a flap. This technique was applied not to accelerate tooth movement, but to protract the mandibular molars. One miniscrew was inserted on the mesiobuccal side of the mandibular right molar for protraction and intrusion. In addition, 2 miniscrews were inserted in the buccal sides of the maxillary first and second molars and the palatal side of the maxillary first molar to intrude them for correction of the mandibular shift and the cant of the occlusal plane. Excellent occlusion and correction of the anterior open bite were achieved without surgery. At the 2-year follow-up examination, the patient had a good occlusion and showed good stability with no opening of the extraction space. A partial corticision is an effective option for facilitating movement of mandibular molars. Copyright © 2013 American Association of Orthodontists. Published by Mosby, Inc. All rights reserved.

Densities of L-Glutamic Acid HCl Drug in Aqueous NaCl and KCl Solutions at Different Temperatures

NASA Astrophysics Data System (ADS)

Ryshetti, Suresh; Raghuram, Noothi; Rani, Emmadi Jayanthi; Tangeda, Savitha Jyostna

2016-04-01

Densities (ρ ) of (0.01 to 0.07) {mol}{\\cdot } {kg}^{-1} L-Glutamic acid HCl (L-HCl) drug in water, and in aqueous NaCl and KCl (0.5 and 1.0) {mol}{\\cdot } {kg}^{-1} solutions have been reported as a function of temperature at T = (298.15, 303.15, 308.15, and 313.15) K and atmospheric pressure. The accurate density (ρ ) values are used to estimate the various parameters such as the apparent molar volume (V_{2,{\\upphi }}), the partial molar volume (V2^{∞}), the isobaric thermal expansion coefficient (α 2), the partial molar expansion (E2^{∞}), and Hepler's constant (partial 2V2^{∞}/partial T2)P. The Cosphere overlap model is used to understand the solute-solvent interactions in a ternary mixture (L-HCl drug + NaCl or KCl + water). Hepler's constant (partial 2V2^{∞}/partial T2)_P is utilized to interpret the structure-making or -breaking ability of L-HCl drug in aqueous NaCl and KCl solutions, and the results are inferred that L-HCl drug acts as a structure maker, i.e., kosmotrope in aqueous NaCl solutions and performs as a structure breaker, i.e., chaotrope in aqueous KCl solutions.

Thermodynamic properties of hyperbranched polymer, Boltorn U3000, using inverse gas chromatography.

PubMed

Domańska, Urszula; Zołek-Tryznowska, Zuzanna

2009-11-19

Mass-fraction activity coefficients at infinite dilution (Omega13(infinity)) of alkanes (C5-C10), cycloalkanes (C5-C8), alkenes (C5-C8), alkynes (C5-C8), aromatic hydrocarbons (benzene, toluene, ethylbenzene, o-, m-, p-xylene, thiophene), alcohols (C1-C5), water, ethers (tetrahydrofuran (THF), methyl-tert-butylether (MTBE), diethyl-, di-n-propyl-, di-n-butyl ether), and ketones (propanone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, cyclopentanone) in the hyperbranched polymer, Boltorn U3000 (B-U3000), have been determined by inverse gas chromatography (IGC) using the polymer as the stationary phase. The measurements were carried out at different temperatures between 308.15 and 348.15 K. The density and thermophysical properties of polymer were described. The specific retention volume (V(g)), the Flory-Huggins interaction parameter (chi13(infinity)), the molar enthalpy of sorption (the partial molar enthalpies of solute dissolution) (Delta(s)H), the partial molar excess enthalpy at infinite dilution of the solute and polymer (DeltaH1(E,infinity)), the partial molar Gibbs excess energy at infinite dilution (DeltaG1(E,infinity)), and the solubility parameter (delta3) were calculated.

Biodiesel from Citrullus colocynthis Oil: Sulfonic-Ionic Liquid-Catalyzed Esterification of a Two-Step Process

PubMed Central

Ali Elsheikh, Yasir; Hassan Akhtar, Faheem

2014-01-01

Biodiesel was prepared from Citrullus colocynthis oil (CCO) via a two-step process. The first esterification step was explored in two ionic liquids (ILs) with 1,3-disulfonic acid imidazolium hydrogen sulfate (DSIMHSO4) and 3-methyl-1-sulfonic acid imidazolium hydrogen sulfate (MSIMHSO4). Both ILs appeared to be good candidates to replace hazardous acidic catalyst due to their exceptional properties. However, the two sulfonic chains existing in DSIMHSO4 were found to increase the acidity to the IL than the single sulfonic chain in MSIMHSO4. Based on the results, 3.6 wt% of DSIMHSO4, methanol/CCO molar ratio of 12 : 1, and 150°C offered a final FFA conversion of 95.4% within 105 min. A 98.2% was produced via second KOH-catalyzed step in 1.0%, 6 : 1 molar ratio, 600 rpm, and 60°C for 50 min. This new two-step catalyzed process could solve the corrosion and environmental problems associated with the current acidic catalysts. PMID:24987736

Physicochemical properties of betaine monohydrate-carboxylic acid mixtures

NASA Astrophysics Data System (ADS)

Zahrina, I.; Nasikin, M.; Mulia, K.

2018-05-01

Green solvents are widely used to minimize environmental problems associated with the use of volatile organic solvents in many industries. DES are new green solvents in recent. The physicochemical properties of DES can be varied by properly combining of salts with different hydrogen bond donors. The objective of this work is to investigate the effect of varying molar ratios on the physicochemical properties of betaine monohydrate-carboxylic acid (i.e,. propionic or acetic acid) mixtures. Properties of mixtures were measured at 40°C. The viscosity, polarity scale (ENR), density, pH, and water content tend to decrease with the decrease in a molar ratio of betaine monohydrate to acid. Conversely, the ionic conductivity was increased. The physicochemical properties of these mixtures depend on the hydrogen bonding interactions between betaine, water and acid molecules. Betaine monohydratecarboxylic acid mixtures have wide range of polarity, low viscosity, high ionic conductivity, and density higher than 1 g·cm-3 that make them fit for numerous various applications. Additionally, due to these mixtures have acidic pH, it should be properly selected of metal type to minimize corrosion problems in industrial application.

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

NASA Technical Reports Server (NTRS)

Sumida, John

2002-01-01

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

Covalent Incorporation of Ionic Liquid into Ion-Conductive Networks via Thiol-Ene Photopolymerization.

PubMed

Tibbits, Andrew C; Yan, Yushan S; Kloxin, Christopher J

2017-07-01

Ene-functionalized ionic liquids with a range of different cationic groups and counteranions react stoichiometrically within a tetrathiol-divinyl ether formulation within 20 minutes to form thiol-ene polymers with measurable ionic conductivities via a photoinitiated polymerization and crosslinking reaction. Dynamic mechanical analysis indicates that these networks are more spatially heterogeneous and possess higher glass transition temperatures (T g ) compared with thiol-ene formulations without charge. While tuning the molar content of ionic liquid monomer is one method for adjusting the crosslink and charge densities of the thiol-ene polymeric ionic liquid networks, the presence of cation-anion interactions also plays a critical role in dictating the thermomechanical and conductive properties. Particularly, while cationic structure effects are not significant on the polymer properties, the use of a weakly coordinating hydrophobic anion (bistriflimide) instead of bromide-based networks results in an apparent decrease in hydrated ion conductivity (7.4 to 1.5 mS cm -1 ) and T g (-9.6 to -17.8 °C). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rapid analysis of ultraviolet filters using dispersive liquid-liquid microextraction coupled to headspace gas chromatography and mass spectrometry.

PubMed

Pierson, Stephen A; Trujillo-Rodríguez, María J; Anderson, Jared L

2018-05-29

An ionic-liquid-based in situ dispersive liquid-liquid microextraction method coupled to headspace gas chromatography and mass spectrometry was developed for the rapid analysis of ultraviolet filters. The chemical structures of five ionic liquids were specifically designed to incorporate various functional groups for the favorable extraction of the target analytes. Extraction parameters including ionic liquid mass, molar ratio of ionic liquid to metathesis reagent, vortex time, ionic strength, pH, and total sample volume were studied and optimized. The effect of the headspace temperature and volume during the headspace sampling step was also evaluated to increase the sensitivity of the method. The optimized procedure is fast as it only required ∼7-10 min per extraction and allowed for multiple extractions to be performed simultaneously. In addition, the method exhibited high precision, good linearity, and low limits of detection for six ultraviolet filters in aqueous samples. The developed method was applied to both pool and lake water samples attaining acceptable relative recovery values. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid-liquid equilibria of binary mixtures of a lipidic ionic liquid with hydrocarbons.

PubMed

Green, Blane D; Badini, Alexander J; O'Brien, Richard A; Davis, James H; West, Kevin N

2016-01-28

Although structurally diverse, many ionic liquids (ILs) are polar in nature due to the strong coulombic forces inherent in ionic compounds. However, the overall polarity of the IL can be tuned by incorporating significant nonpolar content into one or more of the constituent ions. In this work, the binary liquid-liquid equilibria of one such IL, 1-methyl-3-(Z-octadec-9-enyl)imidazolium bistriflimide, with several hydrocarbons (n-hexane, n-octane, n-decane, cyclohexane, methylcyclohexane, 1-octene) is measured over the temperature range 0-70 °C at ambient pressure using a combination of cloud point and gravimetric techniques. The phase behavior of the systems are similar in that they exhibit two phases: one that is 60-90 mole% hydrocarbon and a second phase that is nearly pure hydrocarbon. Each phase exhibits a weak dependence of composition on temperature (steep curve) above ∼10 °C, likely due to swelling and restructuring of the nonpolar nano-domains of the IL being limited by energetically unfavorable restructuring in the polar nano-domains. The solubility of the n-alkanes decreases with increasing size (molar volume), a trend that continues for the cyclic alkanes, for which upper critical solution temperatures are observed below 70 °C. 1-Octene is found to be more soluble than n-octane, attributable to a combination of its lower molar volume and slightly higher polarity. The COSMO-RS model is used to predict the T-x'-x'' diagrams and gives good qualitative agreement of the observed trends. This work presents the highest known solubility of n-alkanes in an IL to date and tuning the structure of the ionic liquid to maximize the size/shape trends observed may provide the basis for enhanced separations of nonpolar species.

The effect of various quantum mechanically derived partial atomic charges on the bulk properties of chloride-based ionic liquids

NASA Astrophysics Data System (ADS)

Zolghadr, Amin Reza; Ghatee, Mohammad Hadi; Moosavi, Fatemeh

2016-08-01

Partial atomic charges using various quantum mechanical calculations for [Cnmim]Cl (n = 1, 4) ionic liquids (ILs) are obtained and used for development of molecular dynamics simulation (MD) force fields. The isolated ion pairs are optimized using HF, B3LYP, and MP2 methods for electronic structure with 6-311++G(d,p) basis set. Partial atomic charges are assigned to the atomic center with CHELPG and NBO methods. The effect of these sets of partial charges on the static and dynamic properties of ILs is evaluated by performing a series of MD simulations and comparing the essential thermodynamic properties with the available experimental data and available molecular dynamics simulation results. In contrast to the general trends reported for ionic liquids with BF4, PF6, and iodide anions (in which restrained electrostatic potential (RESP) charges are preferred), partial charges derived by B3LYP-NBO method are relatively good in prediction of the structural, dynamical, and thermodynamic energetic properties of the chloride based ILs.

Effect of additives on eremomycin sorbent selectivity in separation of salbutamol enantiomers using supercritical fluid chromatography

NASA Astrophysics Data System (ADS)

Pokrovskiy, O. I.; Kayda, A. S.; Usovich, O. I.; Parenago, O. O.; Lunin, V. V.

2017-11-01

A regime is found in which chiral stationary phase based on macrocyclic glycopeptide eremomycin allows separation of salbutamol sulfate enantiomers in supercritical fluid chromatography. Enantioseparation occurs only when two dynamic modifiers are used simultaneously: isopropylamin + trifluoroacetic acid or isopropylamin + ammonium acetate. Amine molar concentration in mobile phase has to be higher than acid molar concentration, otherwise enantiomers coelute. We suppose that with amine excess a mechanism of enantiorecognition is realized which involves ionic sorbent-sorbate interactions. Such mechanism is well-known for glycopeptide chiral selectors in liquid chromatography, but for supercritical fluid chromatography it is reported for the first time.

Quadrupole terms in the Maxwell equations: Born energy, partial molar volume, and entropy of ions.

PubMed

Slavchov, Radomir I; Ivanov, Tzanko I

2014-02-21

A new equation of state relating the macroscopic quadrupole moment density Q to the gradient of the field ∇E in an isotropic fluid is derived: Q = αQ(∇E - U∇·E/3), where the quadrupolarizability αQ is proportional to the squared molecular quadrupole moment. Using this equation of state, a generalized expression for the Born energy of an ion dissolved in quadrupolar solvent is obtained. It turns out that the potential and the energy of a point charge in a quadrupolar medium are finite. From the obtained Born energy, the partial molar volume and the partial molar entropy of a dissolved ion follow. Both are compared to experimental data for a large number of simple ions in aqueous solutions. From the comparison the value of the quadrupolar length LQ is determined, LQ = (αQ/3ɛ)(1/2) = 1-4 Å. Data for ion transfer from aqueous to polar oil solution are analyzed, which allowed for the determination of the quadrupolarizability of nitrobenzene.

On a relationship between molecular polarizability and partial molar volume in water.

PubMed

Ratkova, Ekaterina L; Fedorov, Maxim V

2011-12-28

We reveal a universal relationship between molecular polarizability (a single-molecule property) and partial molar volume in water that is an ensemble property characterizing solute-solvent systems. Since both of these quantities are of the key importance to describe solvation behavior of dissolved molecular species in aqueous solutions, the obtained relationship should have a high impact in chemistry, pharmaceutical, and life sciences as well as in environments. We demonstrated that the obtained relationship between the partial molar volume in water and the molecular polarizability has in general a non-homogeneous character. We performed a detailed analysis of this relationship on a set of ~200 organic molecules from various chemical classes and revealed its fine well-organized structure. We found that this structure strongly depends on the chemical nature of the solutes and can be rationalized in terms of specific solute-solvent interactions. Efficiency and universality of the proposed approach was demonstrated on an external test set containing several dozens of polyfunctional and druglike molecules.

Partial molar volume of proteins studied by the three-dimensional reference interaction site model theory.

PubMed

Imai, Takashi; Kovalenko, Andriy; Hirata, Fumio

2005-04-14

The three-dimensional reference interaction site model (3D-RISM) theory is applied to the analysis of hydration effects on the partial molar volume of proteins. For the native structure of some proteins, the partial molar volume is decomposed into geometric and hydration contributions using the 3D-RISM theory combined with the geometric volume calculation. The hydration contributions are correlated with the surface properties of the protein. The thermal volume, which is the volume of voids around the protein induced by the thermal fluctuation of water molecules, is directly proportional to the accessible surface area of the protein. The interaction volume, which is the contribution of electrostatic interactions between the protein and water molecules, is apparently governed by the charged atomic groups on the protein surface. The polar atomic groups do not make any contribution to the interaction volume. The volume differences between low- and high-pressure structures of lysozyme are also analyzed by the present method.

Infinitely dilute partial molar properties of proteins from computer simulation.

PubMed

Ploetz, Elizabeth A; Smith, Paul E

2014-11-13

A detailed understanding of temperature and pressure effects on an infinitely dilute protein's conformational equilibrium requires knowledge of the corresponding infinitely dilute partial molar properties. Established molecular dynamics methodologies generally have not provided a way to calculate these properties without either a loss of thermodynamic rigor, the introduction of nonunique parameters, or a loss of information about which solute conformations specifically contributed to the output values. Here we implement a simple method that is thermodynamically rigorous and possesses none of the above disadvantages, and we report on the method's feasibility and computational demands. We calculate infinitely dilute partial molar properties for two proteins and attempt to distinguish the thermodynamic differences between a native and a denatured conformation of a designed miniprotein. We conclude that simple ensemble average properties can be calculated with very reasonable amounts of computational power. In contrast, properties corresponding to fluctuating quantities are computationally demanding to calculate precisely, although they can be obtained more easily by following the temperature and/or pressure dependence of the corresponding ensemble averages.

Physical properties of ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various anions and the bis(trifluoromethylsulfonyl)imide anion with various cations.

PubMed

Jin, Hui; O'Hare, Bernie; Dong, Jing; Arzhantsev, Sergei; Baker, Gary A; Wishart, James F; Benesi, Alan J; Maroncelli, Mark

2008-01-10

Physical properties of 4 room-temperature ionic liquids consisting of the 1-butyl-3-methylimidazolium cation with various perfluorinated anions and the bis(trifluoromethylsulfonyl)imide (Tf2N-) anion with 12 pyrrolidinium-, ammonium-, and hydroxyl-containing cations are reported. Electronic structure methods are used to calculate properties related to the size, shape, and dipole moment of individual ions. Experimental measurements of phase-transition temperatures, densities, refractive indices, surface tensions, solvatochromic polarities based on absorption of Nile Red, 19F chemical shifts of the Tf2N- anion, temperature-dependent viscosities, conductivities, and cation diffusion coefficients are reported. Correlations among the measured quantities as well as the use of surface tension and molar volume for estimating Hildebrand solubility parameters of ionic liquids are also discussed.

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

DTIC Science & Technology

2008-08-01

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

Global expression for representing cohesive-energy curves. II

NASA Technical Reports Server (NTRS)

Schlosser, Herbert; Ferrante, John

1993-01-01

Schlosser et al. (1991) showed that the R dependence of the cohesive energy of partially ionic solids may be characterized by a two-term energy relationship consisting of a Coulomb term arising from the charge transfer, delta-Z, and a scaled universal energy function, E*(a *), which accounts for the partially covalent character of the bond and for repulsion between the atomic cores for small R; a* is a scaled length. In the paper by Schlosser et al., the normalized cohesive-energy curves of NaCl-structure alkali-halide crystals were generated with this expression. In this paper we generate the cohesive-energy curves of several families of partially ionic solids with different crystal structures and differing degrees of ionicity. These include the CsCl-structure Cs halides, and the Tl and Ag halides, which have weaker ionic bonding than the alkali halides, and which have the CsCl and NaCl structures, respectively. The cohesive-energy-curve parameters are then used to generate theoretical isothermal compression curves for the Li, Na, K, Cs, and Ag halides. We find good agreement with the available experimental compression data.

Utility of p57 immunohistochemistry in differentiating between complete mole, partial mole & non-molar or hydropic abortus.

PubMed

Samadder, Abhimanyu; Kar, Rakhee

2017-01-01

There is considerable inter-observer variability in the diagnosis of molar pregnancies by histomorphological examination of products of conception (POC). The p57KIP2 gene is paternally imprinted and expressed from the maternal allele. On immunohistochemistry (IHC) with p57, complete mole (CM) shows absent staining whereas hydropic abortus (HA) and partial mole (PM) show positive staining. This study was undertaken to evaluate the role of p57 IHC along with histomorphology in differentiating between CM, PM and non-molar or HA. This was a cross-sectional study over a period of three and a half years on archival material. Detailed histomorphological review along with p57 IHC was carried out in 28 diagnosed cases (23 CM, 4 PM and 1 molar pregnancy not categorized) and 25 controls of four normal placentas and 21 POC (8 non-hydropic and 13 HA). In 14.8 per cent (4/27) cases, there was discordance in accurate subtyping of molar pregnancy. One case of CM showed inconsistent IHC pattern. In 15.4 per cent (2/13) HA, molar pregnancy was final diagnosis. After final review, there were 25 CM, five PM, 22 non-molar controls including 10 HA and one not assigned (PM/HA). IHC with p57 was negative in 96 per cent CM and positive in 100 and 95 per cent PM and non-molar controls, respectively. This study showed that negative p57KIP2 immunostaining reliably identified CM and could be used in association with the histological findings to distinguish CM from its mimics.

The influence of surface state and saturation state on the dissolution kinetics of biogenic aragonite in seawater

USGS Publications Warehouse

Acker, James G.; Byrne, R.H.

1989-01-01

Uses several realistic partial molar volume changes (??V) for aragonite dissolution in seawater. Indicates that the molar volume change for aragonite dissolution is within the bounds -37 cm 3/mole ?????V ??? -39.5 cm3/mole. -from Authors

Standard Partial Molar Heat Capacities and Volumes of Barium and Cadmium Ions in Dimethylsulfoxide at 298.15 K

NASA Astrophysics Data System (ADS)

Novikov, A. N.; Doronin, Ya. I.; Rakhmanova, P. A.

2018-07-01

The heat capacities and volumes of dimethylsulfoxide (DMSO) solutions of barium and cadmium iodides at 298.15 K were measured by calorimetry and densimetry. The standard partial molar heat capacities \\bar C_{p,2}^° and volumes \\bar V2^° of BaI2 and CdI2 in DMSO were calculated. The standard heat capacities \\bar C_{p,i}^° and volumes \\bar {V}i^° of barium and cadmium ions in DMSO at 298.15 K were determined.

Distal cervical caries in the mandibular second molar: an indication for the prophylactic removal of third molar teeth? Update.

PubMed

McArdle, Louis W; McDonald, Fraser; Jones, Judith

2014-02-01

In 2005 we reported the clinical findings of 100 patients who had mandibular third molars removed because of distal cervical caries in the mandibular second molar. The aim of this follow-up study was to find out whether the findings in a new group of patients corroborate those of our previous study. We report on the clinical features of 239 patients (mean (SD) age 32.1 (7.85) years, range 20-65) who had 288 mandibular third molars removed because of distal cervical caries in the second molar. Patients had better dental health than average, and 67% had a DMF (decayed, missing, or filled) score of 5 or less. In 89% of third molars the mesial angulation was between 40° and 80°. Distal cervical caries in second molars is a late complication of third molar retention. The prophylactic removal of a partially erupted mesioangular third molar will prevent distal cervical caries forming in the second molar tooth. Copyright © 2013 The British Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.

Phycobilisomes from blue-green and red algae: isolation criteria and dissociation characteristics

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

Gantt, E.; Lipschultz, C.A.; Grabowski, J.

1979-04-01

A general procedure for the isolation of functionally intact phycobilisomes was devised, based on modifications of previously used procedures. It has been successful with numerous species of red and blue-green algae (Anabaena variabilis, Anacystis nidulans, Agmenellum quadruplicatum, Fremyella diplosiphon, Glaucosphaera vacuolata, Griffithsia pacifica, Nemalion multifidum, Nostoc sp., Phormidium persicinum, Porphyridium cruentum, P. sordidum, P. aerugineum, Rhodosorus marinus). Isolation was carried out in 0.75 molar K-phosphate (pH 6.8 to 7.0) at 20 to 23 C on sucrose step gradients. Lower temperature (4 to 10 C) was usually unfavorable resulting in uncoupling of energy transfer and partial dissociation of the phycobilisomes, sometimesmore » with complete loss of allophycocyanin. Intact phycobilisomes were characterized by fluorescence emission peaks of 670 to 675 nanometers at room temperature, and 678 to 685 nanometers at liquid nitrogen temperature. Uncoupling and subsequent dissociation of phycobilisomes, in lowered ionic conditions, varied with the species and the degree of dissociation but occurred preferentially between phycocyanin and allophycocyanin, or between phycocyanin and phycoerythrin.« less

Thermal and volumetric properties of methanol-hexamethylphosphortriamide mixtures under standard conditions

NASA Astrophysics Data System (ADS)

Batov, D. V.; Kustov, A. V.; Antonova, O. A.; Smirnova, N. L.

2017-02-01

Enthalpic and volumetric characteristics of mixing in a methanol (MeOH)-hexamethylphosphortriamide (HMPT, 2) mixture are studied. Based on an analysis of concentration changes in the obtained data and the calculated partial molar characteristics, it is shown that at 0.2 molar fractions > x 2 > 0.7 molar fractions, the variation in the composition of the mixture slightly alters the character of intermolecular interactions characteristic of pure components. It is found that MeOH-HMPT mixtures experience most changes in intermolecular interaction and structure within the range of 0.2-0.7 molar fractions of HMPT.

Ion Transport and Structural Properties of Polymeric Electrolytes and Ionic Liquids from Molecular Dynamics Simulations

NASA Astrophysics Data System (ADS)

Borodin, Oleg

2010-03-01

Molecular dynamics simulations are well suited for exploring electrolyte structure and ion transport mechanisms on the nanometer length scale and the nanosecond time scales. In this presentation we will describe how MD simulations assist in answering fundamental questions about the lithium transport mechanisms in polymeric electrolytes and ionic liquids. In particular, in the first part of the presentation the extent of ion aggregation, the structure of ion aggregates and the lithium cation diffusion in binary polymeric electrolytes will be compared with that of single-ion conducting polymers. In the second part of the talk, the lithium transport in polymeric electrolytes will be compared with that of three ionic liquids ( [emim][FSI] doped with LiFSI , [pyr13][FSI] doped with LiFSI, [emim][BF4] doped with LiBF4). The relation between ionic liquid self-diffusion, conductivity and thermodynamic properties will be discussed in details. A number of correlations between heat of vaporization Hvap, cation-anion binding energy (E+/-), molar volume (Vm), self-diffusion coefficient (D) and ionic conductivity for 29 ionic liquids have been investigated using MD simulations. A significant correlation between D and Hvap has been found, while best correlation was found for -log((D Vm)) vs. Hvap+0.28E+/-. A combination of enthalpy of vaporization and a fraction of the cation-anion binding energy was suggested as a measure of the effective cohesive energy for ionic liquids.

Ionic Channels as Natural Nanodevices

DTIC Science & Technology

2006-05-01

introduce the numerical techniques required to simulate charge transport in ion channels. [1] Using Poisson- Nernst -Planck-type (PNP) equations ...Eisenberg. 2003. Ionic diffusion through protein channels: from molecular description to continuum equations . Nanotech 2003, 3: 439-442. 4...Nadler, B., Schuss, Z., Singer, A., and R. S. Eisenberg. 2004. Ionic diffusion through confined geometries: from Langevin equations to partial

Chemical thermodynamics of ultrasound speed in solutions and liquid mixtures.

PubMed

Reis, João Carlos R; Santos, Angela F S; Lampreia, Isabel M S

2010-02-01

A comprehensive formalism is developed to treat thermodynamically speed of ultrasound data for solutions and liquid mixtures. For solutions, the apparent speed of ultrasound of a solute is introduced and proposed to take the place of empirically defined quantities. The partial speed of ultrasound of a solute is defined and related to the partial molar volume and partial molar isentropic compression. For liquid mixtures, the concept of speed of sound before mixing pure liquids is presented and used to define the change in speed of ultrasound upon ideal mixing, which is predicted to be generally a negative quantity. A new thermodynamic equation is derived linking the values for excess speed of ultrasound, excess molar volume and excess molar isentropic compression of a mixture, and its applications are discussed. Ideal and excess apparent speeds of ultrasound, as well as ideal and excess partial speeds of ultrasound, are defined for substances making up a liquid mixture. Accurate speeds of ultrasound in 31 mixtures of water with the amphiphile 2-(ethylamino)ethanol at 293.15 K are reported. These data are used to demonstrate the ability of the apparent speed of ultrasound to describe the impact of solutes on sonic properties of solutions and the advantages of analysing thermodynamic properties of binary liquid mixtures in terms of the dependence on composition of Balankina's ratios between excess and ideal values. It is concluded that the new thermodynamic functions defined for speeds of ultrasound in solutions and liquid mixtures give, at the least, equivalent information on molecular aspects to the usual functions related to the isentropic compressibility, without needing density data for this purpose.

The interactions between ionic surfactants and phosphatidylcholine vesicles: Conductometry

NASA Astrophysics Data System (ADS)

Tsao, Heng-Kwong; Tseng, Wen Liang

2001-11-01

The interaction between ionic surfactants and phosphatidylcholine vesicles, which are prepared without addition of buffer and salt, is investigated by conductivity measurements. On the basis of the vesicle acting as a trap of charge carriers, the bilayer/aqueous phase partition coefficient K and the surfactant/lipid molar ratio Re of nine surfactants are determined. The thermodynamic consistency is satisfied by the measured parameters. The effects of the alkyl chain length (C10-C16) and ionic head group are then studied. The inverse partition coefficient K-1 is linearly related to the critical micelle concentration. The solubilizing ability Reb is a consequence of the competition between the surfactant incorporation into the bilayer and the formation of micelles. Consequently, the K parameter rises whereas the Reb parameter declines as the chain length is increased. The influence due to addition of salt is also discussed.

Biodiesel production using alkaline ionic liquid and adopted as lubricity additive for low-sulfur diesel fuel.

PubMed

Luo, Hui; Fan, Weiyu; Li, Yang; Nan, Guozhi

2013-07-01

Preparation of biodiesel from vegetable oils, such as rapeseed oil, soybean oil and sunflower oil, catalyzed by an alkaline ionic liquid 1-butyl-3-methylimidazolium imidazolide ([Bmim]Im) was investigated in this work. The results demonstrated that [Bmim]Im exhibited high activity and the yield of biodiesel was up to 95% or more when molar ratio of methanol to vegetable oil was 6:1, ionic liquid dosage was 6 wt.%, reaction temperature was 60°C, and reaction time was 60 min. After [Bmim]Im was used for the sixth time, the yield of biodiesel still remained at about 95%. The effects of the biodiesels on the lubricity of low-sulfur diesel fuel were also investigated using the High Frequency Reciprocating Rig method, and the results showed that sunflower biodiesel and soybean biodiesel had higher lubrication performance than that of rapeseed biodiesel. Copyright © 2012 Elsevier Ltd. All rights reserved.

Partial molar volume of anionic polyelectrolytes in aqueous solution.

PubMed

Salamanca, Constain; Contreras, Martín; Gamboa, Consuelo

2007-05-15

In this work the partial molar volumes (V) of different anionic polyelectrolytes and hydrophobically modified polyelectrolytes (PHM) were measured. Polymers like polymaleic acid-co-styrene, polymaleic acid-co-1-olefin, polymaleic acid-co-vinyl-2-pyrrolidone, and polyacrylic acid (abbreviated as MAS-n, PA-n-K2, AMVP, and PAA, respectively) were employed. These materials were investigated by density measurements in highly dilute aqueous solutions. The molar volume results allow us to discuss the effect of the carboxylic groups and the contributions from the comonomeric principal chain. The PAA presents the smaller V, while the largest V value was for AMVP. The V of PHM shows a linear relationship with the number of methylene groups in the lateral chain. It is found that the magnitude of the contribution per methylene group decreases as the hydrophobic character of the environment increases.

Infinitely Dilute Partial Molar Properties of Proteins from Computer Simulation

PubMed Central

2015-01-01

A detailed understanding of temperature and pressure effects on an infinitely dilute protein’s conformational equilibrium requires knowledge of the corresponding infinitely dilute partial molar properties. Established molecular dynamics methodologies generally have not provided a way to calculate these properties without either a loss of thermodynamic rigor, the introduction of nonunique parameters, or a loss of information about which solute conformations specifically contributed to the output values. Here we implement a simple method that is thermodynamically rigorous and possesses none of the above disadvantages, and we report on the method’s feasibility and computational demands. We calculate infinitely dilute partial molar properties for two proteins and attempt to distinguish the thermodynamic differences between a native and a denatured conformation of a designed miniprotein. We conclude that simple ensemble average properties can be calculated with very reasonable amounts of computational power. In contrast, properties corresponding to fluctuating quantities are computationally demanding to calculate precisely, although they can be obtained more easily by following the temperature and/or pressure dependence of the corresponding ensemble averages. PMID:25325571

Choline chloride based ionic liquid analogues as tool for the fabrication of agar films with improved mechanical properties

USDA-ARS?s Scientific Manuscript database

In the present paper, we test the suitability of Choline-Cl/urea (DES-U) and Choline-Cl/glycerol (DES-G) eutectic mixtures at 1:2 molar ratios for the production of agar biodegradable films. A three-step process is proposed: pre-solubilization of polymer in DES followed by compression-molding and s...

Ultrastructure of the surface of dental enamel with molar incisor hypomineralization (MIH) with and without acid etching.

PubMed

Bozal, Carola B; Kaplan, Andrea; Ortolani, Andrea; Cortese, Silvina G; Biondi, Ana M

2015-01-01

The aim of the present work was to analyze the ultrastructure and mineral composition of the surface of the enamel on a molar with MIH, with and without acid etching. A permanent tooth without clinical MIH lesions (control) and a tooth with clinical diagnosis of mild and moderate MIH, with indication for extraction, were processed with and without acid etching (H3PO4 37%, 20") for observation with scanning electron microscope (SEM) ZEISS (Supra 40) and mineral composition analysis with an EDS detector (Oxford Instruments). The control enamel showed normal prismatic surface and etching pattern. The clinically healthy enamel on the tooth with MIH revealed partial loss of prismatic pattern. The mild lesion was porous with occasional cracks. The moderate lesion was more porous, with larger cracks and many scales. The mineral composition of the affected surfaces had lower Ca and P content and higher O and C. On the tooth with MIH, even on normal looking enamel, the demineralization does not correspond to an etching pattern, and exhibits exposure of crystals with rods with rounded ends and less demineralization in the inter-prismatic spaces. Acid etching increased the presence of cracks and deep pores in the adamantine structure of the enamel with lesion. In moderate lesions, the mineral composition had higher content of Ca, P and Cl. Enamel with MIH, even on clinically intact adamantine surfaces, shows severe alterations in the ultrastructure and changes in ionic composition, which affect the acid etching pattern and may interfere with adhesion.

The Partial Molar Volume and Compressibility of the FeO Component in Model Basalts (Mixed CaAl2Si2O8-CaMgSi2O6-CaFeSi2O6 Liquids) at 0 GPa: evidence of Fe2+ in 6-fold coordination

NASA Astrophysics Data System (ADS)

Guo, X.; Lange, R. A.; Ai, Y.

2010-12-01

FeO is an important component in magmatic liquids and yet its partial molar volume at one bar is not as well known as that for Fe2O3 because of the difficulty of performing double-bob density measurements under reducing conditions. Moreover, there is growing evidence from spectroscopic studies that Fe2+ occurs in 4, 5, and 6-fold coordination in silicate melts, and it is expected that the partial molar volume and compressibility of the FeO component will vary accordingly. We have conducted both density and relaxed sound speed measurements on four liquids in the An-Di-Hd (CaAl2Si2O8-CaMgSi2O6-CaFeSi2O6) system: (1) Di-Hd (50:50), (2) An-Hd (50:50), (3) An-Di-Hd (33:33:33) and (4) Hd (100). Densities were measured between 1573 and 1838 K at one bar with the double-bob Archimedean method using molybdenum bobs and crucibles in a reducing gas (1%CO-99%Ar) environment. The sound speeds were measured under similar conditions with a frequency-sweep acoustic interferometer, and used to calculate isothermal compressibility. All the density data for the three multi-component (model basalt) liquids were combined with density data on SiO2-Al2O3-CaO-MgO-K2O-Na2O liquids (Lange, 1997) in a fit to a linear volume equation; the results lead to a partial molar volume (±1σ) for FeO =11.7 ± 0.3(±1σ) cm3/mol at 1723 K. This value is similar to that for crystalline FeO at 298 K (halite structure; 12.06 cm3/mol), which suggests an average Fe2+ coordination of ~6 in these model basalt compositions. In contrast, the fitted partial molar volume of FeO in pure hedenbergite liquid is 14.6 ± 0.3 at 1723 K, which is consistent with an average Fe2+ coordination of 4.3 derived from EXAFS spectroscopy (Rossano, 2000). Similarly, all the compressibility data for the three multi-component liquids were combined with compressibility data on SiO2-Al2O3-CaO-MgO liquids (Ai and Lange, 2008) in a fit to an ideal mixing model for melt compressibility; the results lead to a partial molar compressibility (±1σ) for FeO = 2.4 (± 0.3) 10-2 GPa-1 at 1723 K. In contrast, the compressibility of FeO in pure hedenbergite liquid is more than twice as large: 6.3 (± 0.2) 10-2 GPa-1. When these results are combined with density and sound speed data on CaO-FeO-SiO2 liquids at one bar (Guo et al., 2009), a systematic and linear variation between the partial molar volume and compressibility of the FeO component is obtained, which appears to track changes in the average Fe2+ coordination in these liquids. Therefore, the three most important conclusions of this study are: (1) ideal mixing of volume and compressibility does not occur for all FeO-bearing magmatic liquids, owing to changes in Fe2+ coordination, (2) the partial molar volume and compressibility of FeO varies linearly and systematically with Fe2+ coordination, and (3) ideal mixing of volume and compressibility does occur among the three mixed An-Di-Hd liquids, presumably because of a common, average Fe2+ coordination of ~6.

What Determines CO₂ Solubility in Ionic Liquids? A Molecular Simulation Study.

PubMed

Klähn, Marco; Seduraman, Abirami

2015-08-06

Molecular dynamics (MD) simulations of 10 different pure and CO2-saturated ionic liquids are performed to identify the factors that determine CO2 solubility. Imidazolium-based cations with varying alkyl chain length and functionalization are paired with anions of different hydrophobicity and size. Simulations are carried out with an empirical force field based on liquid-phase charges. The partial molar volume of CO2 in ionic liquids (ILs) varies from 30 to 40 cm(3)/mol. This indicates that slight ion displacements are necessary to enable CO2 insertions. However, the absorption of CO2 does not affect the overall organization of ions in the ILs as demonstrated by almost equal cation-anion radial distribution functions of pure ILs and ILs saturated with CO2. The solubility of CO2 in ILs is not influenced by direct CO2-ion interactions. Instead, a strong correlation between the ratio of unoccupied space in pure ILs and their ability to absorb CO2 is found. This preformed unoccupied space is regularly dispersed throughout the ILs and needs to be expanded by slight ion displacements to accommodate CO2. The amount of preformed unoccupied space is a good indicator for ion cohesion in ILs. Weak electrostatic cation-anion interaction densities in ILs, i.e., weak ion cohesion, leads to larger average distances between ions and hence to more unoccupied space. Weak ion cohesion facilitates ion displacement to enable an expansion of empty space to accommodate CO2. Moreover, it is demonstrated that the strength of ion cohesion is primarily determined by the ion density, which in turn is given by the ion sizes. Ion cohesion is influenced additionally to a smaller extent by local electrostatic interactions among ion moieties between which CO2 is inserted and which do not depend on the ion density. Overall, the factors that determine the solubility of CO2 in ILs are identified consistently across a large variety of constituting ions through MD simulations.

Local probing of ionic diffusion by electrochemical strain microscopy: Spatial resolution and signal formation mechanisms

NASA Astrophysics Data System (ADS)

Morozovska, A. N.; Eliseev, E. A.; Balke, N.; Kalinin, S. V.

2010-09-01

Electrochemical insertion-deintercalation reactions are typically associated with significant change in molar volume of the host compound. This strong coupling between ionic currents and strains underpins image formation mechanisms in electrochemical strain microscopy (ESM), and allows exploring the tip-induced electrochemical processes locally. Here we analyze the signal formation mechanism in ESM, and develop the analytical description of operation in frequency and time domains. The ESM spectroscopic modes are compared to classical electrochemical methods including potentiostatic and galvanostatic intermittent titration, and electrochemical impedance spectroscopy. This analysis illustrates the feasibility of spatially resolved studies of Li-ion dynamics on the sub-10-nm level using electromechanical detection.

Theory of chromatography of partially cyclic polymers: Tadpole-type and manacle-type macromolecules.

PubMed

Vakhrushev, Andrey V; Gorbunov, Alexei A

2016-02-12

A theory of chromatography is developed for partially cyclic polymers of tadpole- and manacle-shaped topological structures. We present exact equations for the distribution coefficient K at different adsorption interactions; simpler approximate formulae are also derived, relevant to the conditions of size-exclusion, adsorption, and critical chromatography. Theoretical chromatograms of heterogeneous partially cyclic polymers are simulated, and conditions for good separation by topology are predicted. According to the theory, an effective SEC-radius of tadpoles and manacles is mostly determined by the molar mass M, and by the linear-cyclic composition. In the interactive chromatography, the effect of molecular topology on the retention becomes significant. At the critical interaction point, partial dependences K(Mlin) and K(Mring) are qualitatively different: while being almost independent of Mlin, K increases with Mring. This behavior could be realized in critical chromatography-for separation of partially cyclic polymers by the number and molar mass of cyclic elements. Copyright © 2015 Elsevier B.V. All rights reserved.

Aluminium electrodeposition in chloroaluminate ionic liquid.

PubMed

Zhang, Lipeng; Wang, Enqi; Mu, Jiechen; Yu, Xianjin; Wang, Qiannan; Yang, Lina; Zhao, Zengdian

2014-08-01

An efficient microwave enhanced synthesis of ambient temperature chloroaluminate ionic liquid ([EMIM]Br) that preceeds reaction of 1-methylimidazolium with bromoethane in a closed vessel, was described in our work. The reaction time was drastically reduced as compared to the conventional methods. The electrochemical techniques of impedance spectroscopy, cyclic voltammetry and chronoamperometry were used to investigate the mechanism of Al electrodeposition from 2:1 (molar ratio) AlCl3/[EMIM]Br ionic liquid at room temperature. Results indicated that Al electrode- position from this ionic liqud was a quasi-reversible process, and the kinetic complications during the reaction was probably attributed to the electron transfer or mass transport cooperative controlled processes, instantaneous nucleation with diffusion-controlled growth was also investigated. Electrodepositon experiment was conducted using constant current density of 40 mA·cm(-2) for 20 minutes at room temperature and the qualitative analysis of the deposits were performed using X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) and energy dispersive spectroscope (EDS). The deposits obtained on copper cathode were dense and compact and most Al crystal shows granular structure spherical with high purity.

Determination of the solubility parameter of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate by inverse gas chromatography.

PubMed

Ma, Xiaohong; Wang, Qiang; Li, Xiaoping; Tang, Jun; Zhang, Zhengfang

2015-11-01

Thermodynamic properties of ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM] BF4) were determined via inverse gas chromatography (IGC). Two groups of solvents with different chemical natures and polarities were used to obtain information about [BMIM] BF4-solvent interactions. The specific retention volume, molar heat of sorption, weight fraction activity coefficient, Flory-Huggins interaction parameter as well as solubility parameter were also determined in a temperature range of 333 - 373 K. The results showed that the selected solvents n-C10 to n-C12, carbon tetrachloride, cyclohexane and toluene were poor solvents for [BMIM] BF4, while dichloromethane, acetone, chloroform, methyl acetate, ethanol and methanol were favorite solvents for [BMIM] BF4. In addition, the solubility parameter of [ BMIM] BF4 was determined as 23.39 (J/cm3)0.5 by the extrapolation at 298 K. The experiment proved that IGC was a simple and accurate method to obtain the thermodynamic properties of ionic liquids. This study could be used as a reference to the application and research of the ionic liquids.

Performance of magnetic zirconium-iron oxide nanoparticle in the removal of phosphate from aqueous solution

NASA Astrophysics Data System (ADS)

Zhang, Chang; Li, Yongqiu; Wang, Fenghua; Yu, Zhigang; Wei, Jingjing; Yang, Zhongzhu; Ma, Chi; Li, Zihao; Xu, ZiYi; Zeng, Guangming

2017-02-01

In this study, magnetic zirconium-iron oxide nanoparticles (MZION) of different Fe/Zr molar ratios were successfully prepared using the co-precipitation method, and their performance for phosphate removal was systematically evaluated. The as-obtained adsorbents were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Zeta potential analyzer, Fourier transform infrared spectroscopy (FT-IR) and Brunauer Emmett Teller (BET) specific surface area analysis. The effects of pH, ionic strength, and co-existing ions (including Cl-, SO42-, NO3- and HCO3-) were measured to evaluate the adsorption performance in batch experiments. The results showed that decreasing the Fe/Zr molar ratios increased the specific surface area that was propitious to adsorption process, but the adsorption capacity enhanced with the decrease of Fe/Zr molar ratios. Phosphate adsorption on MZION could be well described by the Freundlich equilibrium model and pseudo-second-order kinetics. The adsorption of phosphate was highly pH dependent and decreased with increasing pH from 1.5 to 10.0. The adsorption was slightly affected by ionic strength. With the exception of HCO3-, co-existing anions showed minimum or no effect on their adsorption performance. After adsorption, phosphate on these MZION could be easily desorbed by 0.1 M NaOH solution. The phosphate adsorption mechanism of MZION followed the inner-sphere complexing mechanism, and the surface sbnd OH groups played a significant role in the phosphate adsorption. Additionally, the main advantages of MZION consisted in its separation convenience and highly adsorption capacity compared to other adsorbents.

MD simulations of the formation of stable clusters in mixtures of alkaline salts and imidazolium-based ionic liquids.

PubMed

Méndez-Morales, Trinidad; Carrete, Jesús; Bouzón-Capelo, Silvia; Pérez-Rodríguez, Martín; Cabeza, Óscar; Gallego, Luis J; Varela, Luis M

2013-03-21

Structural and dynamical properties of room-temperature ionic liquids containing the cation 1-butyl-3-methylimidazolium ([BMIM](+)) and three different anions (hexafluorophosphate, [PF6](-), tetrafluoroborate, [BF4](-), and bis(trifluoromethylsulfonyl)imide, [NTf2](-)) doped with several molar fractions of lithium salts with a common anion at 298.15 K and 1 atm were investigated by means of molecular dynamics simulations. The effect of the size of the salt cation was also analyzed by comparing these results with those for mixtures of [BMIM][PF6] with NaPF6. Lithium/sodium solvation and ionic mobilities were analyzed via the study of radial distribution functions, coordination numbers, cage autocorrelation functions, mean-square displacements (including the analysis of both ballistic and diffusive regimes), self-diffusion coefficients of all the ionic species, velocity and current autocorrelation functions, and ionic conductivity in all the ionic liquid/salt systems. We found that lithium and sodium cations are strongly coordinated in two different positions with the anion present in the mixture. Moreover, [Li](+) and [Na](+) cations were found to form bonded-like, long-lived aggregates with the anions in their first solvation shell, which act as very stable kinetic entities within which a marked rattling motion of salt ions takes place. With very long MD simulation runs, this phenomenon is proved to be on the basis of the decrease of self-diffusion coefficients and ionic conductivities previously reported in experimental and computational results.

Molecular analysis of 16S rRNA genes identifies potentially periodontal pathogenic bacteria and archaea in the plaque of partially erupted third molars.

PubMed

Mansfield, J M; Campbell, J H; Bhandari, A R; Jesionowski, A M; Vickerman, M M

2012-07-01

Small subunit rRNA sequencing and phylogenetic analysis were used to identify cultivable and uncultivable microorganisms present in the dental plaque of symptomatic and asymptomatic partially erupted third molars to determine the prevalence of putative periodontal pathogens in pericoronal sites. Template DNA prepared from subgingival plaque collected from partially erupted symptomatic and asymptomatic mandibular third molars and healthy incisors was used in polymerase chain reaction with broad-range oligonucleotide primers to amplify 16S rRNA bacterial and archaeal genes. Amplicons were cloned, sequenced, and compared with known nucleotide sequences in online databases to identify the microorganisms present. Two thousand three hundred two clones from the plaque of 12 patients carried bacterial sequences from 63 genera belonging to 11 phyla, including members of the uncultivable TM7, SR1, and Chloroflexi, and difficult-to-cultivate Synergistetes and Spirochaetes. Dialister invisus, Filifactor alocis, Fusobacterium nucleatum, Porphyromonas endodontalis, Prevotella denticola, Tannerella forsythia, and Treponema denticola, which have been associated with periodontal disease, were found in significantly greater abundance in pericoronal compared with incisor sites. Dialister invisus and F nucleatum were found in greater abundance in sites exhibiting clinical symptoms. The archaeal species, Methanobrevibacter oralis, which has been associated with severe periodontitis, was found in 3 symptomatic patients. These findings have provided new insights into the complex microbiota of pericoronitis. Several bacterial and archaeal species implicated in periodontal disease were recovered in greater incidence and abundance from the plaque of partially erupted third molars compared with incisors, supporting the hypothesis that the pericoronal region may provide a favored niche for periodontal pathogens in otherwise healthy mouths. Copyright © 2012 American Association of Oral and Maxillofacial Surgeons. Published by Elsevier Inc. All rights reserved.

Synthesis and different optical properties of Gd2O3 doped sodium zinc tellurite glasses

NASA Astrophysics Data System (ADS)

Samanta, Buddhadev; Dutta, Dibakar; Ghosh, Subhankar

2017-06-01

A series of Gd2O3 doped sodium zinc tellurite [xGd2O3-(0.8-x) TeO2-0.1Na2O-0.1ZnO] glasses are prepared by the conventional melt quenching method and their optical properties have been studied. UV-vis spectrophotometric studies within the wavelength range from 230 nm-800 nm are carried out in the integrating sphere mode to study the effect of Gd2O3 doping on the optical band gap (Eg), refractive index (n), dielectric constant (εr) and susceptibility (χ). Other physical properties like molar volume, molar refraction, polarizability, metallization criterion, number density of rare-earth ions (N), polaron radius (rp), inter ionic distance (ri), molar cation polarizability (∑αi), number of oxide ions in chemical composition (NO2-), optical band gap based electronic oxide ion polarizability (αO2-) and optical basicity (Λ) of glass samples have been studied on the basis of UV-vis spectra and density profile of the different glasses.

Exploring Solute-Solvent Interactions of -Amino Acids in Aqueous [] Arrangements by Volumetric, Viscometric, Refractometric, and Acoustic Approach

NASA Astrophysics Data System (ADS)

Roy, Mahendra Nath; Roy, Milan Chandra; Basak, Saptarshi

2014-05-01

Qualitative and quantitative analysis of molecular interaction prevailing in glycine, l-alanine, l-valine, and aqueous solution of ionic liquid (IL) [1-ethylpyridinium tetrafluoroborate (] have been investigated by thermophysical properties. The apparent molar volume (), viscosity -coefficient, molal refraction (), and adiabatic compressibility ( of glycine, l-alanine, and l-valine have been studied in 0.001 mol , 0.003 mol , and 0.005 mol aqueous 1-ethylpyridinium tetrafluoroborate [] solutions at 298.15 K from the values of densities , viscosities (), refractive index (, and speed of sound , respectively. The extent of interaction, i.e., the solute-solvent interaction is expressed in terms of the limiting apparent molar volume (, viscosity -coefficient, and limiting apparent molar adiabatic compressibility (. The limiting apparent molar volumes (, experimental slopes ( derived from the Masson equation, and viscosity - and -coefficients using the Jones-Dole equation have been interpreted in terms of ion-ion and ion-solvent interactions, respectively. Molal refractions ( have been calculated with the help of the Lorentz-Lorenz equation. The role of the solvent (aqueous IL solution) and the contribution of solute-solute and solute-solvent interactions to the solution complexes have also been analyzed through the derived properties.

Ionic liquid-facilitated preparation of lignocellulosic composites

USDA-ARS?s Scientific Manuscript database

Lignocellulosic composites (LCs) were prepared by partially dissolving cotton along with steam exploded Aspen wood and burlap fabric reinforcements utilizing an ionic liquid (IL) solvent. Two methods of preparation were employed. In the first method, a controlled amount of IL was added to preassembl...

Mutual solubility of water and structural/positional isomers of N-alkylpyridinium-based ionic liquids.

PubMed

Freire, Mara G; Neves, Catarina M S S; Shimizu, Karina; Bernardes, Carlos E S; Marrucho, Isabel M; Coutinho, João A P; Canongia Lopes, José N; Rebelo, Luís Paulo N

2010-12-09

Despite many previous important contributions to the characterization of the liquid-liquid phase behavior of ionic liquids (ILs) plus water systems, a gap still exists as far as the effect of isomers (of ILs) is concerned. Therefore, in this work, a comprehensive study of the liquid-liquid equilibria between water and isomeric pyridinium-based ionic liquids has been performed. Atmospheric pressure mutual solubilities between water and pyridinium-based ionic liquids combined with the common anion bis[(trifluoromethyl)sulfonyl]imide were experimentally determined between (288.15 and 318.15) K. The main goal of this work is to study the isomeric effects on the pyridinium-based cation, namely, the structural and positional isomerism, as well as the alkyl side chain length. To the best of our knowledge, the influence of both structural and positional isomerism on the liquid-liquid behavior in ionic-liquid-water-containing systems is an unexplored field and is here assessed for the first time. Moreover, from the experimental solubility data, several infinite dilution molar thermodynamic functions of solution, namely, the Gibbs energy, the enthalpy, and the entropy, were estimated and discussed. In addition, aiming at gathering a broader picture of the underlying thermodynamic solvation phenomenon, molecular dynamics simulations were also carried out for the same experimental systems.

Determination of thermodynamic properties of isotactic poly(1-butene) at infinite dilution using density and inverse gas chromatography.

PubMed

Kozłowska, Marta Karolina; Domańska, Urszula; Lempert, Małgorzata; Rogalski, Marek

2005-03-18

The partial molar volumes, V1(M), and the molar volume of isotactic crystalline low-molecular-weight poly(1-butene), iPBu-1, V1, have been calculated from the measured density of {iPBu-1 + solvent (n-hexane, n-heptane, n-nonane, n-decane, p-xylene, cyclohexane and chloroform)} systems. Some of the thermodynamic quantities were also obtained for the iPBu-1 with eight hydrocarbons (n-octane, n-decane, n-undecane, n-dodecane, n-tridecane, o-xylene, m-xylene, p-xylene) by the method of inverse gas chromatography at various temperatures. The weight fraction activity coefficients of the solvent at infinite dilution, omega2(infinity) and the Flory-Huggins thermodynamic interaction parameters, chi21(infinity), between polymer and solvents were determined. The partial molar free energy, deltaG2(infinity), the partial molar heat of mixing, deltaH2(infinity), at infinite dilution and the polymer solubility parameter, delta1, were calculated. Additionally, the (solid + liquid) binary mixtures equilibria, SLE, of iPBu-1 with three hydrocarbons (n-octane, n-decane and m-xylene) were studied by a dynamic method. By performing these experiments over a large concentration range, the T-x phase diagrams of the polymer-solvent systems were constructed. The excess Gibbs energy models were used to describe the nonideal behaviour of the liquid phase. The omega2(infinity) were determined from the solubility measurements and were predicted by using the UNIFAC FV model.

Note: Nonpolar solute partial molar volume response to attractive interactions with water.

PubMed

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.

Note: Nonpolar solute partial molar volume response to attractive interactions with water

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

Williams, Steven M.; Ashbaugh, Henry S., E-mail: hanka@tulane.edu

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.

Zn-Al layered double hydroxide prepared at different molar ratios: Preparation, characterization, optical and dielectric properties

NASA Astrophysics Data System (ADS)

Ahmed, Abdullah Ahmed Ali; Talib, Zainal Abidin; bin Hussein, Mohd Zobir; Zakaria, Azmi

2012-07-01

The co-precipitation method was used to prepare Zn-Al-NO3-LDH at different Zn2+/Al3+ molar ratios (2, 3, 4, 5 and 6) and pH value of 7.5. The structure, textural, composition and morphological properties were investigated using powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) and scanning electron microscope (SEM), respectively. The crystallinity of LDH samples were found to improve as molar ratio decreased which is attributed to the distortion of the hydroxide layers networks of the LDH crystal by the larger difference in ionic radii of Zn2+ and Al3+. The optical band gap energy of LDH samples were evaluated using absorbance data from UV-Vis-NIR Diffuse reflectance spectroscopy. Band gaps were affected by the variation of the Zn2+/Al3+ molar ratio is due to the formation of the low crystalline phases (ZnO and ZnAl2O4). The water molecules and anionic NO3- in the LDH interlayer were responsible for the generation of the dielectric response. This response can be described by an anomalous low frequency dispersion using the second type of Universal Power Law. The dominance of ZnO dipoles and charge carriers (NO3- ions) in the dielectric relaxation increases with the increasing molar ratio.

[Surgery of lower third molars and lesions of the lingual nerve].

PubMed

Chiapasco, M; Pedrinazzi, M; Motta, J; Crescentini, M; Ramundo, G

1996-11-01

The authors describe a technical expedient applied during the removal of totally or partially impacted lower third molars, in order to prevent lingual nerve damage. EXPERIMENTAL ASSAY: Retrospective study. The sample includes 1835 extractions of totally or partially impacted lower third molars, performed on 1030 patients, 493 males and 537 females, aging between 12 and 72 years. All the operations were carried out under local anaesthesia with standardization of the surgical protocol. A mucoperiosteal paramarginal flap was used in case of germectomy, whereas a mucoperiosteal marginal flap with mesial releasing incision was used in case of fully mature teeth. Ostectomy and tooth sectioning were performed using a round and fissure bur respectively, assembled on a straight low-speed handpiece and under irrigation with sterile saline. The authors reported only one case of transient lingual nerve paresthesia (0.05%) which occurred in a 19-years old female presenting a totally impacted third molar mesial-lingual inclination. Symptoms disappeared spontaneously one week postoperatively. Therefore the overall incidence of permanent nerve damage was equal to 0%. The data reported in literature show a lingual nerve lesion incidence ranging between 0% and 22%. With this simple surgical expedient the incidence of permanent lingual damage was 0%. Thus, it is the authors' opinion that this simple expedient should be applied in all cases of impacted third molar removal.

Ultrasonographic signs of partial hydatidiform mole.

PubMed

Muminhodzic, Lejla; Bogdanovic, Gordana

2013-01-01

This study aimed at investigating ultrasonographic features of partial hydatidiform mole to establish a proper diagnosis. This was a retrospective study of 70 pregnancies which were divided into two groups: group I--35 pregnant women with a molar pregnancy diagnosed in the first trimester; group II--35 pregnant women with physiological pregnancy spontaneously aborted in the first trimester caused by the cervical insufficiency. Evacuation of the uterus by uterine suction or curettage and pathomorphological analysis ofovular tissue were conducted in both groups. Ultrasonographic parameters were analyzed. Theca lutein cysts and hydropic degeneration of villi, enlarged uterus and empty gestational sac, intrauterine hematoma significantly prevailed in the pregnant women with the molar pregnancies. Diagnosis of the partial hydatidiform mole in the first trimester is likely though not enough reliable. Thereby, additional diagnostic methods might be important as well to confirm an early diagnosis of mole.

Plasma Jet Interactions with Liquids in Partial Fulfillment of an NRL Karles Fellowship

DTIC Science & Technology

2015-11-30

water (DI H2O) as the reference solution, two concentrations of NaCl mixtures (0.6 Molar, and 1.0 Molar saturated NaCl), and three electroless solutions...by diffusion) to the bulk surface in net excess; that oxygen ions/radicals are being consumed from the bulk by an electrolysis path way; or that the

Computation of methodology-independent single-ion solvation properties from molecular simulations. IV. Optimized Lennard-Jones interaction parameter sets for the alkali and halide ions in water

NASA Astrophysics Data System (ADS)

Reif, Maria M.; Hünenberger, Philippe H.

2011-04-01

The raw single-ion solvation free energies computed from atomistic (explicit-solvent) simulations are extremely sensitive to the boundary conditions and treatment of electrostatic interactions used during these simulations. However, as shown recently [M. A. Kastenholz and P. H. Hünenberger, J. Chem. Phys. 124, 224501 (2006), 10.1529/biophysj.106.083667; M. M. Reif and P. H. Hünenberger, J. Chem. Phys. 134, 144103 (2010)], the application of appropriate correction terms permits to obtain methodology-independent results. The corrected values are then exclusively characteristic of the underlying molecular model including in particular the ion-solvent van der Waals interaction parameters, determining the effective ion size and the magnitude of its dispersion interactions. In the present study, the comparison of calculated (corrected) hydration free energies with experimental data (along with the consideration of ionic polarizabilities) is used to calibrate new sets of ion-solvent van der Waals (Lennard-Jones) interaction parameters for the alkali (Li+, Na+, K+, Rb+, Cs+) and halide (F-, Cl-, Br-, I-) ions along with either the SPC or the SPC/E water models. The experimental dataset is defined by conventional single-ion hydration free energies [Tissandier et al., J. Phys. Chem. A 102, 7787 (1998), 10.1021/jp982638r; Fawcett, J. Phys. Chem. B 103, 11181] along with three plausible choices for the (experimentally elusive) value of the absolute (intrinsic) hydration free energy of the proton, namely, Δ G_hyd^{ominus }[H+] = -1100, -1075 or -1050 kJ mol-1, resulting in three sets L, M, and H for the SPC water model and three sets LE, ME, and HE for the SPC/E water model (alternative sets can easily be interpolated to intermediate Δ G_hyd^{ominus }[H+] values). The residual sensitivity of the calculated (corrected) hydration free energies on the volume-pressure boundary conditions and on the effective ionic radius entering into the calculation of the correction terms is also evaluated and found to be very limited. Ultimately, it is expected that comparison with other experimental ionic properties (e.g., derivative single-ion solvation properties, as well as data concerning ionic crystals, melts, solutions at finite concentrations, or nonaqueous solutions) will permit to validate one specific set and thus, the associated Δ G_hyd^{ominus }[H+] value (atomistic consistency assumption). Preliminary results (first-peak positions in the ion-water radial distribution functions, partial molar volumes of ionic salts in water, and structural properties of ionic crystals) support a value of Δ G_hyd^{ominus }[H+] close to -1100 kJ.mol-1.

Ion transferring in polyelectrolyte networks in electric fields

NASA Astrophysics Data System (ADS)

Li, Honghao; Erbas, Aykut; Zwanikken, Jos; Olvera de La Cruz, Monica

Ion-conducting polyelectrolyte gels have drawn the attention of many researchers in the last few decades as they have wide applications not only in lithium batteries but also as stretchable, transparent ionic conductor or ionic cables devices. However, ion dynamics in polyelectrolyte gels has been much less studied analytically or computationally due to the complicated interplay of long-range electrostatic and short-range interactions. Here we propose a coarse-grained non-equilibrium molecular dynamics simulation to study the ion dynamics in polyelectrolyte gels under external electric fields. We found a nonlinear response region where the molar conductivity of polyelectrolyte gels increases with external fields. We propose counterion redistribution under electric fields as the driving mechanism. We also found the ionic conductivity to be modulated by changing polylelectrolyte network topology such as the chain length. Our discovery reveals the essential difference of ion dynamics between electrolytes and polyelectrolyte gels. These results will expand our understanding in charged polymeric systems and help in designing ion-conducting devices with higher conductivity.

Size and Charge Dependence of Ion Transport in Human Nail Plate

PubMed Central

Baswan, Sudhir M.; Li, S. Kevin; LaCount, Terri D.; Kasting, Gerald B.

2016-01-01

The electrical properties of human nail plate are poorly characterized, yet are a key determinate of the potential to treat nail diseases such as onychomycosis using iontophoresis. In order to address this deficiency, molar conductivities of 17 electrolytes comprising 12 ionic species were determined in hydrated human nail plate in vitro. Cation transport numbers across the nail for 11 of these electrolytes were determined by the electromotive force method. Effective ionic mobilities and diffusivities at infinite dilution for all ionic species were determined by regression analysis. The ratios of diffusivities in nail to those in solution were found to correlate inversely with the hydrodynamic radii of the ions according to a power law relationship having an exponent of −1.75 ± 0.27, a substantially steeper size dependence than observed for similar experiments in skin. Effective diffusivities of cations in nail were three-fold higher than those of comparably sized anions. These results reflect the strong size and charge selectivity of the nail plate for ionic conduction and diffusion. The analysis implies that efficient transungual iontophoretic delivery of ionized drugs having radii upwards of 5 Å (approximately MW ≥ 340 Da) will require chemical or mechanical alteration of the nail plate. PMID:26886342

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

PubMed

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

2017-08-30

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

Reactive solid surface morphology variation via ionic diffusion.

PubMed

Sun, Zhenchao; Zhou, Qiang; Fan, Liang-Shih

2012-08-14

In gas-solid reactions, one of the most important factors that determine the overall reaction rate is the solid morphology, which can be characterized by a combination of smooth, convex and concave structures. Generally, the solid surface structure varies in the course of reactions, which is classically noted as being attributed to one or more of the following three mechanisms: mechanical interaction, molar volume change, and sintering. Here we show that if a gas-solid reaction involves the outward ionic diffusion of a solid-phase reactant then this outward ionic diffusion could eventually smooth the surface with an initial concave and/or convex structure. Specifically, the concave surface is filled via a larger outward diffusing surface pointing to the concave valley, whereas the height of the convex surface decreases via a lower outward diffusion flux in the vertical direction. A quantitative 2-D continuum diffusion model is established to analyze these two morphological variation processes, which shows consistent results with the experiments. This surface morphology variation by solid-phase ionic diffusion serves to provide a fourth mechanism that supplements the traditionally acknowledged solid morphology variation or, in general, porosity variation mechanisms in gas-solid reactions.

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

PubMed

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

2003-10-01

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

Interpretations of complications following third molar extraction.

PubMed

Schwartz-Arad, Devorah; Lipovsky, Anat; Pardo, Michal; Adut, Oren; Dolev, Eran

2017-11-21

Surgical removal of third molars is often associated with complications. The aim of the present study was to analyze the incidence of complications following extraction of third molars relative to the risk factors. This retrospective study included 463 patients who had mandibular third molar extraction (performed by a single surgeon, DSA) in the years 2001 to 2011. In total, 665 mandibular third molars were extracted. The average patient's age was 29 ± 11.30 years, median 26 years, and the patient age ranged from 13 to 75 years. Patients' records were obtained for medical/general data. The overall prevalence of postsurgical complications was 17%. Dry sockets showed the highest incidence (11.6%). Partially impacted teeth showed the highest incidence of complications (67.3%). Cigarette smoking correlated with increased complications and dry sockets, and complications were more prevalent on the left side (62.8%). Complications after mandibular third molar extraction increase with age, level of impaction, side of extraction, and cigarette smoking.

Theoretical study of the partial molar volume change associated with the pressure-induced structural transition of ubiquitin

PubMed Central

Imai, Takashi; Ohyama, Shusaku; Kovalenko, Andriy; Hirata, Fumio

2007-01-01

The partial molar volume (PMV) change associated with the pressure-induced structural transition of ubiquitin is analyzed by the three-dimensional reference interaction site model (3D-RISM) theory of molecular solvation. The theory predicts that the PMV decreases upon the structural transition, which is consistent with the experimental observation. The volume decomposition analysis demonstrates that the PMV reduction is primarily caused by the decrease in the volume of structural voids in the protein, which is partially canceled by the volume expansion due to the hydration effects. It is found from further analysis that the PMV reduction is ascribed substantially to the penetration of water molecules into a specific part of the protein. Based on the thermodynamic relation, this result implies that the water penetration causes the pressure-induced structural transition. It supports the water penetration model of pressure denaturation of proteins proposed earlier. PMID:17660257

Theoretical study of the partial molar volume change associated with the pressure-induced structural transition of ubiquitin.

PubMed

Imai, Takashi; Ohyama, Shusaku; Kovalenko, Andriy; Hirata, Fumio

2007-09-01

The partial molar volume (PMV) change associated with the pressure-induced structural transition of ubiquitin is analyzed by the three-dimensional reference interaction site model (3D-RISM) theory of molecular solvation. The theory predicts that the PMV decreases upon the structural transition, which is consistent with the experimental observation. The volume decomposition analysis demonstrates that the PMV reduction is primarily caused by the decrease in the volume of structural voids in the protein, which is partially canceled by the volume expansion due to the hydration effects. It is found from further analysis that the PMV reduction is ascribed substantially to the penetration of water molecules into a specific part of the protein. Based on the thermodynamic relation, this result implies that the water penetration causes the pressure-induced structural transition. It supports the water penetration model of pressure denaturation of proteins proposed earlier.

Fast Computation of Solvation Free Energies with Molecular Density Functional Theory: Thermodynamic-Ensemble Partial Molar Volume Corrections.

PubMed

Sergiievskyi, Volodymyr P; Jeanmairet, Guillaume; Levesque, Maximilien; Borgis, Daniel

2014-06-05

Molecular density functional theory (MDFT) offers an efficient implicit-solvent method to estimate molecule solvation free-energies, whereas conserving a fully molecular representation of the solvent. Even within a second-order approximation for the free-energy functional, the so-called homogeneous reference fluid approximation, we show that the hydration free-energies computed for a data set of 500 organic compounds are of similar quality as those obtained from molecular dynamics free-energy perturbation simulations, with a computer cost reduced by 2-3 orders of magnitude. This requires to introduce the proper partial volume correction to transform the results from the grand canonical to the isobaric-isotherm ensemble that is pertinent to experiments. We show that this correction can be extended to 3D-RISM calculations, giving a sound theoretical justification to empirical partial molar volume corrections that have been proposed recently.

Fullerol ionic fluids.

PubMed

Fernandes, Nikhil; Dallas, Panagiotis; Rodriguez, Robert; Bourlinos, Athanasios B; Georgakilas, Vasilios; Giannelis, Emmanuel P

2010-09-01

We report for the first time an ionic fluid based on hydroxylated fullerenes (fullerols). The ionic fluid was synthesized by neutralizing the fully protonated fullerol with an amine terminated polyethylene/polypropylene oxide oligomer (Jeffamine). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding significantly perturbs the thermal transitions and melting/crystallization behavior of the amine. In contrast, both the normalized heat of fusion and crystallization of the amine in the control are similar to those of the neat amine consistent with a physical mixture of the fullerols/amine with minimal interactions. In addition to differences in thermal behavior, the fullerol ionic fluid exhibits a complex viscoelastic behavior intermediate between the neat Jeffamine (liquid-like) and the control (solid-like).

Fullerol ionic fluids

NASA Astrophysics Data System (ADS)

Fernandes, Nikhil; Dallas, Panagiotis; Rodriguez, Robert; Bourlinos, Athanasios B.; Georgakilas, Vasilios; Giannelis, Emmanuel P.

2010-09-01

We report for the first time an ionic fluid based on hydroxylated fullerenes (fullerols). The ionic fluid was synthesized by neutralizing the fully protonated fullerol with an amine terminated polyethylene/polypropylene oxide oligomer (Jeffamine®). The ionic fluid was compared to a control synthesized by mixing the partially protonated form (sodium form) of the fullerols with the same oligomeric amine in the same ratio as in the ionic fluids (20 wt% fullerol). In the fullerol fluid the ionic bonding significantly perturbs the thermal transitions and melting/crystallization behavior of the amine. In contrast, both the normalized heat of fusion and crystallization of the amine in the control are similar to those of the neat amine consistent with a physical mixture of the fullerols/amine with minimal interactions. In addition to differences in thermal behavior, the fullerol ionic fluid exhibits a complex viscoelastic behavior intermediate between the neat Jeffamine® (liquid-like) and the control (solid-like).

Efficacy of orally administered prednisolone versus partial endodontic treatment on pain reduction in emergency care of acute irreversible pulpitis of mandibular molars: study protocol for a randomized controlled trial.

PubMed

Kérourédan, Olivia; Jallon, Léonard; Perez, Paul; Germain, Christine; Péli, Jean-François; Oriez, Dominique; Fricain, Jean-Christophe; Arrivé, Elise; Devillard, Raphaël

2017-03-28

Irreversible pulpitis is a highly painful inflammatory condition of the dental pulp which represents a common dental emergency. Recommended care is partial endodontic treatment. The dental literature reports major difficulties in achieving adequate analgesia to perform this emergency treatment, especially in the case of mandibular molars. In current practice, short-course, orally administered corticotherapy is used for the management of oral pain of inflammatory origin. The efficacy of intraosseous local steroid injections for irreversible pulpitis in mandibular molars has already been demonstrated but resulted in local comorbidities. Oral administration of short-course prednisolone is simple and safe but its efficacy to manage pain caused by irreversible pulpitis has not yet been demonstrated. This trial aims to evaluate the noninferiority of short-course, orally administered corticotherapy versus partial endodontic treatment for the emergency care of irreversible pulpitis in mandibular molars. This study is a noninferiority, open-label, randomized controlled clinical trial conducted at the Bordeaux University Hospital. One hundred and twenty subjects will be randomized in two 1:1 parallel arms: the intervention arm will receive one oral dose of prednisolone (1 mg/kg) during the emergency visit, followed by one morning dose each day for 3 days and the reference arm will receive partial endodontic treatment. Both groups will receive planned complete endodontic treatment 72 h after enrollment. The primary outcome is the proportion of patients with pain intensity below 5 on a Numeric Scale 24 h after the emergency visit. Secondary outcomes include comfort during care, the number of injected anesthetic cartridges when performing complete endodontic treatment, the number of antalgic drugs and the number of patients coming back for consultation after 72 h. This randomized trial will assess the ability of short-term corticotherapy to reduce pain in irreversible pulpitis as a simple and rapid alternative to partial endodontic treatment and to enable planning of endodontic treatment in optimal analgesic conditions. ClinicalTrials.gov, identifier: NCT02629042 . Registered on 7 December 2015. (Version n°1.1 28 July 2015).

Composite mixed oxide ionic and electronic conductors for hydrogen separation

DOEpatents

Gopalan, Srikanth [Westborough, MA; Pal, Uday B [Dover, MA; Karthikeyan, Annamalai [Quincy, MA; Hengdong, Cui [Allston, MA

2009-09-15

A mixed ionic and electronic conducting membrane includes a two-phase solid state ceramic composite, wherein the first phase comprises an oxygen ion conductor and the second phase comprises an n-type electronically conductive oxide, wherein the electronically conductive oxide is stable at an oxygen partial pressure as low as 10.sup.-20 atm and has an electronic conductivity of at least 1 S/cm. A hydrogen separation system and related methods using the mixed ionic and electronic conducting membrane are described.

Ion Conduction in Perfectly Aligned Block Copolymer-Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Choi, Jae-Hong; Elabd, Yossef A.; Winey, Karen I.

2011-03-01

Our earlier work to correlate the transport measurements in diblock copolymer-ionic liquid mixtures was limited by our bulk samples that have only partial alignment. Here, thin films with perfect alignment of lamellar microdomains from mixtures of a poly(methyl methacrylate- b -styrene) diblock copolymer and an ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, have been studied. The morphologies will be characterized by cross-sectional transmission electron microscopy. Ion conduction will be presented within and through the thin film.

Occlusion and Temporomandibular Function among Subjects with Mandibular Distal Extension Removable Partial Dentures

PubMed Central

Creugers, N. H. J.; Witter, D. J.; Van 't Spijker, A.; Gerritsen, A. E.; Kreulen, C. M.

2010-01-01

Objective. To quantify effects on occlusion and temporomandibular function of mandibular distal extension removable partial dentures in shortened dental arches. Methods. Subjects wearing mandibular extension removable partial dentures (n = 25) were compared with subjects with shortened dental arches without extension (n = 74) and with subjects who had worn a mandibular extension removable partial denture in the past (n = 19). Subjects with complete dentitions (n = 72) were controls. Data were collected at baseline and at 3-, 6-, and 9-year observations. Results. Occlusal activity in terms of reported awareness of bruxism and occlusal tooth wear of lower anterior teeth did not differ significantly between the groups. In contrast, occlusal tooth wear of premolars in shortened dental arches with or without extension dentures was significantly higher than in the controls. Differences amongst groups with respect to signs and symptoms related to temporomandibular disorders were not found. Occlusal support of the dentures did not influence anterior spatial relationship. Occlusal contacts of the denture teeth decreased from 70% for second premolars via 50% for first molars, to 30% for second molars. Conclusions. Mandibular distal extension removable partial dentures in moderate shortened dental arches had no effects on occlusion and temporomandibular function. PMID:20671961

Entropy of adsorption of mixed surfactants from solutions onto the air/water interface

USGS Publications Warehouse

Chen, L.-W.; Chen, J.-H.; Zhou, N.-F.

1995-01-01

The partial molar entropy change for mixed surfactant molecules adsorbed from solution at the air/water interface has been investigated by surface thermodynamics based upon the experimental surface tension isotherms at various temperatures. Results for different surfactant mixtures of sodium dodecyl sulfate and sodium tetradecyl sulfate, decylpyridinium chloride and sodium alkylsulfonates have shown that the partial molar entropy changes for adsorption of the mixed surfactants were generally negative and decreased with increasing adsorption to a minimum near the maximum adsorption and then increased abruptly. The entropy decrease can be explained by the adsorption-orientation of surfactant molecules in the adsorbed monolayer and the abrupt entropy increase at the maximum adsorption is possible due to the strong repulsion between the adsorbed molecules.

Deep extractive and oxidative desulfurization of dibenzothiophene with C5H9NO·SnCl2 coordinated ionic liquid.

PubMed

Li, Fa-tang; Kou, Cheng-guang; Sun, Zhi-min; Hao, Ying-juan; Liu, Rui-hong; Zhao, Di-shun

2012-02-29

A new C5H9NO·SnCl2 coordinated ionic liquid (IL) was prepared by reacting N-methyl-pyrrolidone with anhydrous SnCl2. Desulfurization of dibenzothiophene (DBT) via extraction and oxidation with C5H9NO·SnCl2 IL as extractant, H2O2 and equal mol of CH3COOH as oxidants was investigated. The Nernst partition coefficients k(N) of C5H9NO·SnCl2 IL for the DBT in n-octane was above 5.0, showing its excellent extraction ability. During the oxidative desulfurization process, the optimal molar ratio of H2O2/DBT was six. Sulfur removal of DBT in n-octane was 94.8% in 30 min at 30 °C under the conditions of H2O2/DBT molar ratio of six and V (IL):V (oil)=1:3. Moreover, the sulfur removal increased with increasing temperature because of the high reaction rate constant, low viscosity, and high solubility of dibenzothiophene-sulfone in the IL. The kinetics of oxidative desulfurization of DBT was also investigated, and the apparent activation energy was found to be 32.5 kJ/mol. The IL could be recycled six times without a significant decrease in activity. Copyright © 2011 Elsevier B.V. All rights reserved.

Size-exclusion chromatography of perfluorosulfonated ionomers.

PubMed

Mourey, T H; Slater, L A; Galipo, R C; Koestner, R J

2011-08-26

A size-exclusion chromatography (SEC) method in N,N-dimethylformamide containing 0.1 M LiNO(3) is shown to be suitable for the determination of molar mass distributions of three classes of perfluorosulfonated ionomers, including Nafion(®). Autoclaving sample preparation is optimized to prepare molecular solutions free of aggregates, and a solvent exchange method concentrates the autoclaved samples to enable the use of molar-mass-sensitive detection. Calibration curves obtained from light scattering and viscometry detection suggest minor variation in the specific refractive index increment across the molecular size distributions, which introduces inaccuracies in the calculation of local absolute molar masses and intrinsic viscosities. Conformation plots that combine apparent molar masses from light scattering detection with apparent intrinsic viscosities from viscometry detection partially compensate for the variations in refractive index increment. The conformation plots are consistent with compact polymer conformations, and they provide Mark-Houwink-Sakurada constants that can be used to calculate molar mass distributions without molar-mass-sensitive detection. Unperturbed dimensions and characteristic ratios calculated from viscosity-molar mass relationships indicate unusually free rotation of the perfluoroalkane backbones and may suggest limitations to applying two-parameter excluded volume theories for these ionomers. Copyright © 2011 Elsevier B.V. All rights reserved.

Size and Charge Dependence of Ion Transport in Human Nail Plate.

PubMed

Baswan, Sudhir M; Li, S Kevin; LaCount, Terri D; Kasting, Gerald B

2016-03-01

The electrical properties of human nail plate are poorly characterized yet are a key determinate of the potential to treat nail diseases, such as onychomycosis, using iontophoresis. To address this deficiency, molar conductivities of 17 electrolytes comprising 12 ionic species were determined in hydrated human nail plate in vitro. Cation transport numbers across the nail for 11 of these electrolytes were determined by the electromotive force method. Effective ionic mobilities and diffusivities at infinite dilution for all ionic species were determined by regression analysis. The ratios of diffusivities in nail to those in solution were found to correlate inversely with the hydrodynamic radii of the ions according to a power law relationship having an exponent of -1.75 ± 0.27, a substantially steeper size dependence than observed for similar experiments in skin. Effective diffusivities of cations in nail were 3-fold higher than those of comparably sized anions. These results reflect the strong size and charge selectivity of the nail plate for ionic conduction and diffusion. The analysis implies that efficient transungual iontophoretic delivery of ionized drugs having radii upward of 5 Å (molecular weight, ca. ≥ 340 Da) will require chemical or mechanical alteration of the nail plate. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Evaluation of factors influencing the enantioselective enzymatic esterification of lactic acid in ionic liquid.

PubMed

Findrik, Zvjezdana; Németh, Gergely; Gubicza, László; Bélafi-Bakó, Katalin; Vasić-Rački, Durđa

2012-05-01

In this paper esterification of ethanol and lactic acid catalyzed by Candida antarctica B (Novozyme 435) in ionic liquid (Cyphos 104) was studied. The influence of different variables on lipase enantioselectivity and lactic acid conversion was investigated. The variables investigated were ionic liquid mass/lipase mass ratio, water content, alcohol excess and temperature. Using the Design Expert software 2(3) factorial experimental plan (two levels, three factors) was performed to ascertain the effect of selected variables and their interactions on the ethyl lactate enantiomeric excess and lactic acid conversion. The results of the experiments and statistical processing suggest that temperature and alcohol excess have the highest effect on the ethyl lactate enantiomeric excess, while temperature and water content have the highest influence on the lactic acid conversion. The statistical mathematical model developed on the basis of the experimental data showed that the highest enantiomeric excess achieved in the investigated variable range is 34.3%, and the highest conversion is 63.8% at the initial conditions of water content at 8%; 11-fold molar excess of alcohol and temperature at 30 °C.

A Survey of Removable Partial Denture (RPD) Retentive Elements in Relation to the Type of Edentulism and Abutment Teeth Found in Commercial Laboratories, Athens, Greece

PubMed Central

Sotiriou, Michael; Zissis, Alcibiades

2014-01-01

Objective The aim of this survey was to record removable partial denture (RPD) retentive elements and abutment teeth in partially edentulous patients, identified in commercial laboratories in Athens, Greece. Material and Methods 628 master casts with the corresponding cast metal frameworks used in the construction of RPDs were evaluated. Casts were photographed to identify the number and position of existing teeth, the partial edentulism class and the retentive elements. Prevalence tables and the x2 test were used for the statistical analysis of the collected data (α=.05). Results There were 276 maxillary (43.9%) and 352 (56.1%) mandibular casts. Maxillary edentulism entailed almost a total absence of right third molars in 96.7% and left third molars 96.0% of casts, with lower rates for the first and second molars. Edentulism in the posterior mandible presented a similar pattern. The most profound findings concerning retentive elements were: 91.9% of the retainers used were clasps and the remaining 8.1% were attachments. Of the clasps used, 48.9% were of the Roach Τ type, a finding more common in Kennedy Class I as compared to other Kennedy Classes (p<0.01). The circumferential clasps accounted for 19.3% of the total clasps used, and it was less frequently presented (8.8%) in Kennedy I Classes (p<0.01). Conclusions Roach clasps were used in the majority of cases whereas RPI clasps and attachments were rarely used. PMID:27688367

Hydrophobic hydration and the anomalous partial molar volumes in ethanol-water mixtures

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

Tan, Ming-Liang; Te, Jerez; Cendagorta, Joseph R.

2015-02-14

The anomalous behavior in the partial molar volumes of ethanol-water mixtures at low concentrations of ethanol is studied using molecular dynamics simulations. Previous work indicates that the striking minimum in the partial molar volume of ethanol V{sub E} as a function of ethanol mole fraction X{sub E} is determined mainly by water-water interactions. These results were based on simulations that used one water model for the solute-water interactions but two different water models for the water-water interactions. This is confirmed here by using two more water models for the water-water interactions. Furthermore, the previous work indicates that the initial decreasemore » is caused by association of the hydration shells of the hydrocarbon tails, and the minimum occurs at the concentration where all of the hydration shells are touching each other. Thus, the characteristics of the hydration of the tail that cause the decrease and the features of the water models that reproduce this type of hydration are also examined here. The results show that a single-site multipole water model with a charge distribution that mimics the large quadrupole and the p-orbital type electron density out of the molecular plane has “brittle” hydration with hydrogen bonds that break as the tails touch, which reproduces the deep minimum. However, water models with more typical site representations with partial charges lead to flexible hydration that tends to stay intact, which produces a shallow minimum. Thus, brittle hydration may play an essential role in hydrophobic association in water.« less

Solution properties and taste behavior of lactose monohydrate in aqueous ascorbic acid solutions at different temperatures: Volumetric and rheological approach.

PubMed

Sarkar, Abhijit; Sinha, Biswajit

2016-11-15

The densities and viscosities of lactose monohydrate in aqueous ascorbic acid solutions with several molal concentrations m=(0.00-0.08)molkg(-1) of ascorbic acid were determined at T=(298.15-318.15)K and pressure p=101kPa. Using experimental data apparent molar volume (ϕV), standard partial molar volume (ϕV(0)), the slope (SV(∗)), apparent specific volumes (ϕVsp), standard isobaric partial molar expansibility (ϕE(0)) and its temperature dependence [Formula: see text] the viscosity B-coefficient and solvation number (Sn) were determined. Viscosity B-coefficients were further employed to obtain the free energies of activation of viscous flow per mole of the solvents (Δμ1(0≠)) and of the solute (Δμ2(0≠)). Effects of molality, solute structure and temperature and taste behavior were analyzed in terms of solute-solute and solute-solvent interactions; results revealed that the solutions are characterized predominantly by solute-solvent interactions and lactose monohydrate behaves as a long-range structure maker. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cloud point extraction: an alternative to traditional liquid-liquid extraction for lanthanides(III) separation.

PubMed

Favre-Réguillon, Alain; Draye, Micheline; Lebuzit, Gérard; Thomas, Sylvie; Foos, Jacques; Cote, Gérard; Guy, Alain

2004-06-17

Cloud point extraction (CPE) was used to extract and separate lanthanum(III) and gadolinium(III) nitrate from an aqueous solution. The methodology used is based on the formation of lanthanide(III)-8-hydroxyquinoline (8-HQ) complexes soluble in a micellar phase of non-ionic surfactant. The lanthanide(III) complexes are then extracted into the surfactant-rich phase at a temperature above the cloud point temperature (CPT). The structure of the non-ionic surfactant, and the chelating agent-metal molar ratio are identified as factors determining the extraction efficiency and selectivity. In an aqueous solution containing equimolar concentrations of La(III) and Gd(III), extraction efficiency for Gd(III) can reach 96% with a Gd(III)/La(III) selectivity higher than 30 using Triton X-114. Under those conditions, a Gd(III) decontamination factor of 50 is obtained.

Elasticity-driven partial demixing in cholesteric liquid crystal films.

PubMed

Schmidtke, Jürgen; Coles, Harry J

2009-07-01

We discuss the partial demixing of a chiral nematic mixture of a chiral and an achiral compound, induced by inhomogeneous confinement between substrates. While the effect is tiny in low molar mass mixtures, it is predicted to be noticeable in polymeric systems. The potential of the effect for improving performance of liquid crystal based photonic devices is discussed.

Pressure effects on the structure, kinetic, and thermodynamic properties of heat-induced aggregation of protein studied by FT-IR spectroscopy

NASA Astrophysics Data System (ADS)

Taniguchi, Y.; Okuno, A.; Kato, M.

2010-03-01

Pressure can retrain the heat-induced aggregation and dissociate the heat-induced aggregates. We observed the aggregation-preventing pressure effect and the aggregates-dissociating pressure effect to characterize the heat-induced aggregation of equine serum albumin (ESA) by FT-IR spectroscopy. The results suggest the α-helical structure collapses at the beginning of heat-induced aggregation through the swollen structure, and then the rearrangement of structure to the intermolecular β-sheet takes place through partially unfolded structure. We determined the activation volume for the heat-induced aggregation (ΔV# = +93 ml/mol) and the partial molar volume difference between native state and heat-induced aggregates (ΔV=+32 ml/mol). This positive partial molar volume difference suggests that the heat-induced aggregates have larger internal voids than the native structure. Moreover, the positive volume change implies that the formation of the intermolecular β-sheet is unfavorable under high pressure.

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

PubMed

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

2008-07-01

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

Self-Consistent Determination of Atomic Charges of Ionic Liquid through a Combination of Molecular Dynamics Simulation and Density Functional Theory.

PubMed

Ishizuka, Ryosuke; Matubayasi, Nobuyuki

2016-02-09

A self-consistent scheme is developed to determine the atomic partial charges of ionic liquid. Molecular dynamics (MD) simulation was conducted to sample a set of ion configurations, and these configurations were subject to density functional theory (DFT) calculations to determine the partial charges. The charges were then averaged and used as inputs for the subsequent MD simulation, and MD and DFT calculations were repeated until the MD results are not altered any more. We applied this scheme to 1,3-dimethylimidazolium bis(trifluoromethylsulfonyl) imide ([C1mim][NTf2]) and investigated its structure and dynamics as a function of temperature. At convergence, the average ionic charges were ±0.84 e at 350 K due to charge transfer among ions, where e is the elementary charge, while the reduced ionic charges do not affect strongly the density of [C1mim][NTf2] and radial distribution function. Instead, major effects are found on the energetics and dynamics, with improvements of the overestimated heat of vaporization and the too slow motions of ions observed in MD simulations using commonly used force fields.

QSPR models for various physical properties of carbohydrates based on molecular mechanics and quantum chemical calculations.

PubMed

Dyekjaer, Jane Dannow; Jónsdóttir, Svava Osk

2004-01-22

Quantitative Structure-Property Relationships (QSPR) have been developed for a series of monosaccharides, including the physical properties of partial molar heat capacity, heat of solution, melting point, heat of fusion, glass-transition temperature, and solid state density. The models were based on molecular descriptors obtained from molecular mechanics and quantum chemical calculations, combined with other types of descriptors. Saccharides exhibit a large degree of conformational flexibility, therefore a methodology for selecting the energetically most favorable conformers has been developed, and was used for the development of the QSPR models. In most cases good correlations were obtained for monosaccharides. For five of the properties predictions were made for disaccharides, and the predicted values for the partial molar heat capacities were in excellent agreement with experimental values.

Pathological (late) fractures of the mandibular angle after lower third molar removal: a case series.

PubMed

Cutilli, Tommaso; Bourelaki, Theodora; Scarsella, Secondo; Fabio, Desiderio Di; Pontecorvi, Emanuele; Cargini, Pasqualino; Junquera, Luis

2013-04-30

Pathological (late) fracture of the mandibular angle after third molar surgery is very rare (0.005% of third molar removals). There are 94 cases reported in the literature; cases associated with osseous pathologies such as osteomyelitis or any local and systemic diseases that may compromise mandibular bone strength have not been included. We describe three new cases of pathological (late) fracture of the mandibular angle after third molar surgery. The first patient was a 27-year-old Caucasian man who had undergone surgical removal of a 3.8, mesioangular variety, class II-C third molar 20 days before admission to our clinic. The fracture of his left mandibular angle, complete and composed, occurred during chewing. The second patient was a 32-year-old Caucasian man. He had undergone surgical removal of a 3.8, mesioangular variety, class II-B third molar 22 days before his admission. The fracture, which occurred during mastication, was studied by computed tomography that showed reparative tissue in the fracture site. The third patient was a 36-year-old Caucasian man who had undergone surgical removal of a 3.8, vertical variety, class II-C third molar 25 days before the observation. In this case the fracture of his mandibular angle was oblique (unfavorable), complete and composed. The fracture had occurred during chewing. We studied the fracture by optical projection tomography and computed tomography.All of the surgical removals of the 3.8 third molars, performed by the patients' dentists who had more than 10 years of experience, were difficult. We treated the fractures with open surgical reduction, internal fixation by titanium miniplates and intermaxillary elastic fixation removed after 6 weeks. The literature indicates that the risk of pathological (late) fracture of the mandibular angle after third molar surgery for total inclusions (class II-III, type C) is twice that of partial inclusions due to the necessity of ostectomies more generous than those for partial inclusions. Other important factors are the anatomy of the teeth and the features of the teeth roots. These fractures predominantly occur in patients who are older than 25 years. The highest incidence (67.8% of cases) is found in the second and third week postsurgery. We emphasize that before the third molar surgery it is extremely important to always provide adequate instructions to the patient in order to avoid early masticatory loads and prevent this rare event.

The in vitro effect of Antimicrobial Photodynamic Therapy on dental microcosm biofilms from partially erupted permanent molars: A pilot study.

PubMed

de Oliveira, Fabiana Sodré; Cruvinel, Thiago; Cusicanqui Méndez, Daniela Alejandra; Dionísio, Evandro José; Rios, Daniela; Machado, Maria Aparecida Andrade Moreira

2018-03-01

Antimicrobial Photodynamic Therapy (aPDT) could enhance the prevention of dental caries lesions in pits and fissures of partially erupted molars, by killing microorganisms from complex dental biofilms. This pilot study aimed to evaluate the effect of Antimicrobial Photodynamic Therapy (aPDT) on the viability of specific microorganism groups of dental microcosm biofilms from occlusal surfaces of first permanent molars in eruption. Dental microcosm biofilms grown on bovine enamel blocks, from dental plaque collected on occlusal surfaces of a partially erupted lower right first permanent molar, with McBain medium plus 1% sucrose in anaerobic condition at 37 °C for 72 h. The experiments were performed in eight groups: L-P- = no treatment (control), L18.75P- = 18.75 J/cm 2 LED, L37.5P- = 37.5 J/cm 2 LED, L75P- = 75 J/cm 2 LED, L-P+ = 200 mM TBO, L18.75P+ = 200 mM TBO + 18.75 J/cm 2 LED, L37.5P+ = 200 mM TBO + 37.5 J/cm 2 LED, and L75P+ = 200 mM TBO + 75 J/cm 2 LED. The counts of total microorganisms, total streptococci and mutans streptococci were determined on selective media agar plates by colony-forming units per mL. The log-transformed counts were analyzed by Kruskal-Wallis and post-hoc Dunn's test (P < 0.05). The counts of all microorganisms treated in the group L75P+ were statistically lower than those treated in L-P-. The aPDT promoted a significant reduction of microorganisms, with a trend of dose-dependent effect. TBO-mediated aPDT was effective in reducing the viability of specific microbial groups in dental microcosm biofilms originated from occlusal of permanent molars in eruption. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of design of experiments for formulation development and mechanistic evaluation of iontophoretic tacrine hydrochloride delivery.

PubMed

Patel, Niketkumar; Jain, Shashank; Madan, Parshotam; Lin, Senshang

2016-11-01

The objective of this investigation is to develop mathematical equation to understand the impact of variables and establish statistical control over transdermal iontophoretic delivery of tacrine hydrochloride. In addition, possibility of using conductivity measurements as a tool of predicting ionic mobility of the participating ions for the application of iontophoretic delivery was explored. Central composite design was applied to study effect of independent variables like current strength, buffer molarity, and drug concentration on iontophoretic tacrine permeation flux. Molar conductivity was determined to evaluate electro-migration of tacrine ions with application of Kohlrausch's law. The developed mathematic equation not only reveals drug concentration as the most significant variable regulating tacrine permeation, followed by current strength and buffer molarity, but also is capable to optimize tacrine permeation with respective combination of independent variables to achieve desired therapeutic plasma concentration of tacrine in treatment of Alzheimer's disease. Moreover, relative higher mobility of sodium and chloride ions was observed as compared to estimated tacrine ion mobility. This investigation utilizes the design of experiment approach and extends the primary understanding of imapct of electronic and formulation variables on the tacrine permeation for the formulation development of iontophoretic tacrine delivery.

Molar volume and adsorption isotherm dependence of capillary forces in nanoasperity contacts.

PubMed

Asay, David B; Kim, Seong H

2007-11-20

The magnitude of the capillary force at any given temperature and adsorbate partial pressure depends primarily on four factors: the surface tension of the adsorbate, its liquid molar volume, its isothermal behavior, and the contact geometry. At large contacting radii, the adsorbate surface tension and the contact geometry are dominating. This is the case of surface force apparatus measurements and atomic force microscopy (AFM) experiments with micrometer-size spheres. However, as the size of contacting asperities decreases to the nanoscale as in AFM experiments with sharp tips, the molar volume and isotherm of the adsorbate become very important to capillary formation as well as capillary adhesion. This effect is experimentally and theoretically explored with simple alcohol molecules (ethanol, 1-butanol, and 1-pentanol) which have comparable surface tensions but differing liquid molar volumes. Adsorption isotherms for these alcohols on silicon oxide are also reported.

Endodontic treatment of a fused tooth. Report of a case.

PubMed

Gallottini, L; Barbato Bellatini, R C; Migliau, G

2007-01-01

Dental fusion, a rare developmental anomaly present in 0.2% of the general population, consists of the union of two teeth originating from two different tooth germs. The irregular coronal morphology and the complex endodontic anatomy, characterized by the partial or total union of the pulp chambers, together with the peculiarity of the root canal systems, make diagnosis, therapy and rehabilitation difficult. The authors describe the endodontic treatment of a permanent lower second molar fused with a third molar and having four root canals.

A prospective study on transplantation of third molars with complete root formation.

PubMed

Mejàre, Bertil; Wannfors, Karin; Jansson, Leif

2004-02-01

The study objective was to evaluate the prognosis for autotransplantation of third molar teeth with fully developed roots followed by endodontic treatment on the basis of a time-table analysis. A total of 50 third molars with completely developed roots were autotransplanted to replace a lost first or second molar in the same number of admitted patients. Root canal treatment was started 3 to 4 weeks later. Clinical and radiographic checkup of the transplanted and root-filled third molars was done annually according to a predesigned record form. Descriptive statistics including a life table and statistical analysis were performed. The cumulative survival rate during 4 years' follow-up was 81.4%. In all, 7 transplants were lost during the follow-up time, 4 of them due to marginal periodontal pathosis and the other 3 due to root resorption. None of the root resorptions was observed before the second postoperative year. The radiographic periapical status was considered normal in 96% of the transplants at the latest follow-up visit. Autotransplantation of mature third molar teeth is a reasonable treatment alternative to conventional prosthetic rehabilitation or implant treatment in cases of partial edentualism from both a therapeutic and an economic point of view.

Metric and geometric morphometric analysis of new hominin fossils from Maba (Guangdong, China).

PubMed

Xiao, Dongfang; Bae, Christopher J; Shen, Guanjun; Delson, Eric; Jin, Jennie J H; Webb, Nicole M; Qiu, Licheng

2014-09-01

We present an analysis of a set of previously unreported hominin fossils from Maba (Guangdong, China), a cave site that is best known for the presence of a partial hominin cranium currently assigned as mid-Pleistocene Homo and that has been traditionally dated to around the Middle-Late Pleistocene transition. A more recent set of Uranium series dates indicate that the Maba travertine may date to >237 ka (thousands of years ago), as opposed to the original U-series date, which placed Maba at 135-129 ka. The fossils under study include five upper first and second molars and a partial left mandible with a socketed m3, all recovered from different parts of the site than the cranium or the dated sediments. The results of our metric and 2D geometric morphometric ('GM') study suggest that the upper first molars are likely from modern humans, suggesting a more recent origin. The upper second molars align more closely with modern humans, though the minimum spanning tree from the 2D GM analysis also connects Maba to Homo neanderthalensis. The patterning in the M2s is not as clear as with the M1s. The m3 and partial mandible are morphometrically intermediate between Holocene modern humans and older Homo sapiens. However, a minimum spanning tree indicates that both the partial mandible and m3 align most closely with Holocene modern humans, and they also may be substantially younger than the cranium. Because questions exist regarding the context and the relationship of the dated travertine with the hominin fossils, we suggest caution is warranted in interpreting the Maba specimens. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of rhamnolipid biosurfactant on solubilization of polycyclic aromatic hydrocarbons.

PubMed

Li, Shudong; Pi, Yongrui; Bao, Mutai; Zhang, Cong; Zhao, Dongwei; Li, Yiming; Sun, Peiyan; Lu, Jinren

2015-12-15

Rhamnolipid biosurfactant-producing bacteria, Bacillus Lz-2, was isolated from oil polluted water collected from Dongying Shengli oilfield, China. The factors that influence PAH solubilization such as biosurfactant concentration, pH, ionic strength and temperature were discussed. The results showed that the solubilities of naphthalene, phenanthrene and pyrene increased linearly with the rise of rhamnolipid biosurfactant dose above the biosurfactant critical micelle concentration (CMC). Furthermore, the molar solubilization ratio (MSR) values decreased in the following order: naphthalene>phenanthrene>pyrene. However, the solubility percentage increased and followed the opposite order: pyrene>phenanthrene>naphthalene. The solubilities of PAHs in rhamnolipid biosurfactant solution increased with the rise of pH and ionic strength, and reached the maximum values under the conditions of pH11 and NaCl concentration 8 g · L(-1). The solubility of phenanthrene and pyrene increased with the rise of temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.

Oxidative desulfurization of model diesel via dual activation by a protic ionic liquid.

PubMed

Lü, Hongying; Wang, Shunan; Deng, Changliang; Ren, Wanzhong; Guo, Baocun

2014-08-30

A novel and green carboxylate-anion-based protic ionic liquid (PIL), [Hnmp]HCOO, was prepared through a simple and atom economic neutralization reaction between N-methyl-2-pyrrolidonium (NMP) and formic acids. Both FT-IR spectra and (1)H NMR confirmed its simple salt structure. [Hnmp]HCOO exhibited so high catalytic activity that the dibenzothiophene (DBT) removal reached 99% at 50°C in 3h under conditions of VPIL/Vmodel oil=1:10 and H2O2/DBT (O/S, molar ratio)=5. The catalytic oxidation reactivity of S-compounds was found to be in the order of DBT>4,6-dimethyldibenzothiophene (4,6-DMDBT)>benzothiophene (BT). The investigation on mechanism showed that oxidative desulfurization was realized through dual activation of PIL. Moreover, [Hnmp]HCOO can be recycled for five times with an unnoticeable decrease in desulfurization activity. Copyright © 2014 Elsevier B.V. All rights reserved.

Volumetric Properties of the Ionic Liquid, 1-Butyl-3-methylimidazolium Tetrafluoroborate, in Organic Solvents at T = 298.15K

NASA Astrophysics Data System (ADS)

Shekaari, Hemayat; Zafarani-Moattar, Mohammed Taghi

2008-04-01

Apparent molar volumes, V_φ , and compressibilities, kappa _φ , of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]) have been determined from precise density and speed-of-sound measurements in organic solvents, methanol (MeOH), acetonitrile (MeCN), tetrahydrofuran (THF), N, N-dimethylacetamide (DMA), and dimethylsulfoxide (DMSO) in the dilute region of the ionic liquid. Corresponding values at infinite dilution are estimated by the Redlich-Mayer and Pitzer equations. The results have been interpreted by the interaction of the [BMIm][BF4] in the organic solvents. Results show that the structure and dielectric constant of the organic solvents play an important role for the ion-solvent interactions in these mixtures. It was found that the strength of interaction between [BMIm][BF4] with the studied organic solvents has the order DMSO > DMA > MeOH > MeCN > THF.

Physical properties and solubility parameters of 1-ethyl-3-methylimidazolium based ionic liquids/DMSO mixtures at 298.15 K

NASA Astrophysics Data System (ADS)

Saba, H.; Yumei, Z.; Huaping, W.

2015-12-01

Densities, refractive indices, conductivities and viscosities of binary mixtures of 1-ethyl-3-methylimidazolium-based ionic liquids (ILs) with dimethyl sulfoxide at 298.15 K are reported. Excess molar volumes have been calculated from experimental data and were fitted with Redlich-Kister equation. The density and refractive index were found to increase with increasing concentration in all cases except [EMIM]COOH. The free mobility of ions has found to enhance conductivity and decrease viscosity to varying extent in all mixtures being studied. It has been observed that solubility parameters, dielectric constants and nature of anions of ILs being used play a vital role in determining the subsequent characteristics. As DMSO has high dielectric constant therefore, it was able to form interactions with most of ILs except with [EMIM]COOH due to anomalous nature of anion.

Carprofen-imprinted monolith prepared by reversible addition-fragmentation chain transfer polymerization in room temperature ionic liquids.

PubMed

Ban, Lu; Han, Xu; Wang, Xian-Hua; Huang, Yan-Ping; Liu, Zhao-Sheng

2013-10-01

To obtain fast separation, ionic liquids were used as porogens first in combination with reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare a new type of molecularly imprinted polymer (MIP) monolith. The imprinted monolithic column was synthesized using a mixture of carprofen (template), 4-vinylpyridine, ethylene glycol dimethacrylate, [BMIM]BF4, and chain transfer agent (CTA). Some polymerization factors, such as template-monomer molar ratio, the degree of crosslinking, the composition of the porogen, and the content of CTA, on the column efficiency and imprinting effect of the resulting MIP monolith were systematically investigated. Affinity screening of structurally similar compounds with the template can be achieved in 200 s on the MIP monolith due to high column efficiency (up to 12,070 plates/m) and good column permeability. Recognition mechanism of the imprinted monolith was also investigated.

Effect of race/ethnicity on clinical presentation and risk of gestational trophoblastic neoplasia in patients with complete and partial molar pregnancy at a tertiary care referral center.

PubMed

Gockley, Allison A; Joseph, Naima T; Melamed, Alexander; Sun, Sue Yazaki; Goodwin, Benjamin; Bernstein, Marilyn; Goldstein, Donald P; Berkowitz, Ross S; Horowitz, Neil S

2016-09-01

The reported incidence of molar pregnancy varies widely among different geographic locations. This variation has been attributed, at least in part, to racial/ethnic differences. While the incidence of molar pregnancies is decreasing, certain ethnic groups such as Hispanics, Asians, and American Indians continue to have an increased risk of developing gestational trophoblastic disease across the globe. We sought to describe the potential effect of ethnicity/race on the presentation and clinical course of complete mole and partial mole. All patients followed up for complete mole and partial mole at a single institution referral center from 1994 through 2013 were identified. Variables including age, race, gravidity, parity, gestational age, presenting signs/symptoms, serum human chorionic gonadotropin values, and development of gestational trophoblastic neoplasia were extracted from medical records and patient surveys. Patients with complete mole and partial mole were categorized into race/ethnicity groups defined as white, black, Asian, or Hispanic. Due to low numbers of non-white patients with partial mole in each non-white category, patients with partial mole were grouped as white or non-white. Continuous variables were compared using the Kruskal-Wallis test and binary variables were compared using the Fisher exact test. A total of 167 complete mole patients with known race/ethnicity status were included (57.48% white, 14.97% Asian, 14.37% black, 13.17% Hispanic). Hispanics presented at younger age (median 24.5 years) compared to whites (median 32.0 years, P = .04) and Asians (median 31.0 years, P = .03). Blacks had higher gravidity than whites (P < .001) and Hispanics (P = .05). There was no significant difference in presenting symptoms, gestational age at diagnosis, and preevacuation serum human chorionic gonadotropin level by race/ethnicity. Hispanics were significantly less likely than whites to develop gestational trophoblastic neoplasia (absolute risk difference, 28.6%; 95% confidence interval, 8.1-39.2%; P = .02). A total of 144 patients with partial mole were analyzed. There were 108 white and 36 non-white patients. Median age was 31 years for white and 29 years for non-white patients (P = .006). Median gravidity was 2 for white and 3 for non-white patients (P < .001), and median parity was 0 for white patients and 1 for non-white patients (P = .003). There were no significant differences with respect to presenting signs and symptoms, gestational age, preevacuation human chorionic gonadotropin level, or risk of progression to gestational trophoblastic neoplasia. Hispanic patients with complete molar pregnancy had a significantly lower risk of developing gestational trophoblastic neoplasia than white patients. There were no significant differences among groups in terms of presenting symptoms, gestational age at diagnosis, or preevacuation human chorionic gonadotropin levels for either complete mole or partial mole patients. Copyright © 2016. Published by Elsevier Inc.

Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure.

PubMed

Lima, Thamires A; Paschoal, Vitor H; Faria, Luiz F O; Ribeiro, Mauro C C; Giles, Carlos

2016-06-14

X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2]. The peak in the diffraction data characteristic of charge ordering in [N1444][NTf2] is shifted to longer distances in comparison to [N1114][NTf2], but the peak characteristic of short-range correlations is shifted in [N1444][NTf2] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N1114](+) and [N1444](+) proposed in this work. The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N1444](+) as to [N1114](+) because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N1114](+) cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N1114][NTf2], whereas polar and non-polar structure factors are essentially the same in [N1444][NTf2]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids.

Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure

NASA Astrophysics Data System (ADS)

Lima, Thamires A.; Paschoal, Vitor H.; Faria, Luiz F. O.; Ribeiro, Mauro C. C.; Giles, Carlos

2016-06-01

X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2]. The peak in the diffraction data characteristic of charge ordering in [N1444][NTf2] is shifted to longer distances in comparison to [N1114][NTf2], but the peak characteristic of short-range correlations is shifted in [N1444][NTf2] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N1114]+ and [N1444]+ proposed in this work. The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N1444]+ as to [N1114]+ because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N1114]+ cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N1114][NTf2], whereas polar and non-polar structure factors are essentially the same in [N1444][NTf2]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids.

An Ionic Liquid Reaction and Separation Process for Production of Hydroxymethylfurfural from Sugars

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

Liu, Wei; Zheng, Feng; Li, Joanne

2014-01-01

There has been world-wide interest to making plastics out of renewable biomass feedstock for recent years. Hydroxymethylfurfural (HMF) is viewed as an attractive alternate to terephthalic acid (TPA) for production of polyesters (PET) and polyamides. Conversion of sugars into HMF has been studied in numerous publications. In this work, a complete ionic liquid reaction and separation process is presented for nearly stoichiometric conversion of fructose into HMF. Different adsorbent materials are evaluated and silicalite material is demonstrated effective for isolation of 99% pure HMF from actual ionic liquid reaction mixtures and for recovery of the un-converted sugars and reaction intermediatemore » along with the ionic liquid. Membrane-coated silicalite particles are prepared and studied for a practical adsorption process operated at low pressure drops but with separation performances comparable or better than the powder material. Complete conversion of fresh fructose feed into HMF in the recycled ionic liquid is shown under suitable reaction conditions. Stability of HMF product is characterized. A simplified process flow diagram is proposed based on these research results, and the key equipment such as reactor and adsorbent bed is sized for a plant of 200,000 ton/year of fructose processing capacity. The proposed HMF production process is much simpler than the current paraxylene (PX) manufacturing process from petroleum oil, which suggests substantial reduction to the capital cost and energy consumption be possible. At the equivalent value to PX on the molar basis, there can be a large gross margin for HMF production from fructose and/or sugars.« less

Molecular interactions in high conductive gel electrolytes based on low molecular weight gelator.

PubMed

Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

2017-03-15

Organic ionic gel (OIG) electrolytes, also known as gel electrolytes or ionogels are one example of modern functional materials with the potential to use in wide range of electrochemical applications. The functionality of OIGs arises from the thermally reversible solidification of electrolytes or ionic liquids and their superior ionic conductivity. To understand and to predict the properties of these systems it is important to get the knowledge about the interactions on molecular level between the solid gelator matrix and the electrolyte solution. This paper reports the spectroscopic studies (FT-IR, UV-Vis and Raman) of the gel electrolyte based on low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside and solution of quaternary ammonium salt, tetramethylammonium bromide. The solidification process was based on sol-gel technique. Below characteristic temperature, defined as gel to sol phase transition temperature, T gs , the samples were solid-like and showed high conductivity values of the same order as observed for pure liquid electrolytes. The investigations were performed for a OIGs in a wide range of molar concentrations of the electrolyte solution. Copyright © 2016 Elsevier Inc. All rights reserved.

Analysis of Serotonin Molecules on Silver Nanocolloids—A Raman Computational and Experimental Study

PubMed Central

Manciu, Felicia S.; Ciubuc, John D.; Sundin, Emma M.; Qiu, Chao; Bennet, Kevin E.

2017-01-01

Combined theoretical and experimental analysis of serotonin by quantum chemical density functional calculations and surface-enhanced Raman spectroscopy, respectively, is presented in this work to better understand phenomena related to this neurotransmitter’s detection and monitoring at very low concentrations specific to physiological levels. In addition to the successful ultrasensitive analyte detection on silver nanoparticles for concentrations as low as 10−11 molar, the relatively good agreement between the simulated and experimentally determined results indicates the presence of all serotonin molecular forms, such as neutral, ionic, and those oxidized through redox reactions. Obvious structural molecular deformations such as bending of lateral amino chains are observed for both ionic and oxidized forms. Not only does this combined approach reveal more probable adsorption of serotonin into the silver surface through hydroxyl/oxygen sites than through NH/nitrogen sites, but also that it does so predominantly in its neutral (reduced) form, somewhat less so in its ionic forms, and much less in its oxidized forms. If the development of opto-voltammetric biosensors and their effective implementation is envisioned for the future, this study provides some needed scientific background for comprehending changes in the vibrational signatures of this important neurotransmitter. PMID:28640186

High-pressure NaCl-phase of tetrahedral compounds

NASA Astrophysics Data System (ADS)

Soma, T.; -Matsuo Kagaya, H.

1984-04-01

The phase transition of tetrahedral compounds such as GaP, InP, ZnS, ZnSe, ZnTe and CdTe under pressure is investigated from the electronic theory of solids by using our recently presented binding force, which includes mainly covalent interactions in the pseudopotential formalism and partially ionic interactions. The partially ionic forces give the important contributions to the high-pressure phase and stabilize the NaCl-type structure for the high-pressure phase of these compounds, although not reported for GaP experimentally. Then, the numerical results such as the transition pressure, the volume-discontinuity, the transition heat with respect to the pressure-induced phase transition from the zinc-blende-to the NaCl-type lattice are obtained theoretically.

Lattice potential energy and standard molar enthalpy in the formation of 1—dodecylamine hydrobromide (1-C12H25NH3·Br)(s)

NASA Astrophysics Data System (ADS)

Liu, Yu-Pu; Di, You-Ying; Dan, Wen-Yan; He, Dong-Hua; Kong, Yu-Xia; Yang, Wei-Wei

2011-02-01

This paper reports that 1-dodecylamine hydrobromide (1-C12H25NH3·Br)(s) has been synthesized using the liquid phase reaction method. The lattice potential energy of the compound 1-C12H25NH3·Br and the ionic volume and radius of the 1-C12H25NH3+ cation are obtained from the crystallographic data and other auxiliary thermodynamic data. The constant-volume energy of combustion of 1-C12H25NH3·Br(s) is measured to be ΔcUmo(1-C12H25NH3·Br, s) = -(7369.03±3.28) kJ·mol-1 by means of an RBC-II precision rotating-bomb combustion calorimeter at T = (298.15±0.001) K. The standard molar enthalpy of combustion of the compound is derived to be ΔcHmo(1-C12H25NH3·Br, s) = -(7384.52±3.28) kJ·mol-1 from the constant-volume energy of combustion. The standard molar enthalpy of formation of the compound is calculated to be ΔfHmo(1-C12H25NH3·Br, s)=-(1317.86±3.67) kJ·mol-1 from the standard molar enthalpy of combustion of the title compound and other auxiliary thermodynamic quantities through a thermochemical cycle.

Thermodynamic studies of aqueous and CCl4 solutions of 15-crown-5 at 298.15 K: an application of McMillan-Mayer and Kirkwood-Buff theories of solutions.

PubMed

Dagade, Dilip H; Shetake, Poonam K; Patil, Kesharsingh J

2007-07-05

The density and osmotic coefficient data for solutions of 15-crown-5 (15C5) in water and in CCl4 solvent systems at 298.15 K have been reported using techniques of densitometry and vapor pressure osmometry in the concentration range of 0.01-2 mol kg-1. The data are used to obtain apparent molar and partial molar volumes, activity coefficients of the components as a function of 15C5 concentration. Using the literature heat of dilution data for aqueous system, it has become possible to calculate entropy of mixing (DeltaS(mix)), excess entropy of solution (DeltaS(E)), and partial molar entropies of the components at different concentrations. The results of all these are compared to those obtained for aqueous 18-crown-6 solutions reported earlier. It has been observed that the partial molar volume of 15C5 goes through a minimum and that of water goes through a maximum at approximately 1.2 mol kg(-1) in aqueous solutions whereas the opposite is true in CCl4 medium but at approximately 0.5 mol kg(-1). The osmotic and activity coefficients of 15C5 and excess free energy change for solution exhibit distinct differences in the two solvent systems studied. These results have been explained in terms of hydrophobic hydration and interactions in aqueous solution while weak solvophobic association of 15C5 molecules in CCl4 solutions is proposed. The data are further subjected to analysis by applying McMillan-Mayer and Kirkwood-Buff theories of solutions. The analysis shows that osmotic second virial coefficient value for 15C5 is marginally less than that of 18C6 indicating that reduction in ring flexibility does not affect the energetics of the interactions much in aqueous solution while the same gets influenced much in nonpolar solvent CCl4.

Molecular simulation of excess isotherm and excess enthalpy change in gas-phase adsorption.

PubMed

Do, D D; Do, H D; Nicholson, D

2009-01-29

We present a new approach to calculating excess isotherm and differential enthalpy of adsorption on surfaces or in confined spaces by the Monte Carlo molecular simulation method. The approach is very general and, most importantly, is unambiguous in its application to any configuration of solid structure (crystalline, graphite layer or disordered porous glass), to any type of fluid (simple or complex molecule), and to any operating conditions (subcritical or supercritical). The behavior of the adsorbed phase is studied using the partial molar energy of the simulation box. However, to characterize adsorption for comparison with experimental data, the isotherm is best described by the excess amount, and the enthalpy of adsorption is defined as the change in the total enthalpy of the simulation box with the change in the excess amount, keeping the total number (gas + adsorbed phases) constant. The excess quantities (capacity and energy) require a choice of a reference gaseous phase, which is defined as the adsorptive gas phase occupying the accessible volume and having a density equal to the bulk gas density. The accessible volume is defined as the mean volume space accessible to the center of mass of the adsorbate under consideration. With this choice, the excess isotherm passes through a maximum but always remains positive. This is in stark contrast to the literature where helium void volume is used (which is always greater than the accessible volume) and the resulting excess can be negative. Our definition of enthalpy change is equivalent to the difference between the partial molar enthalpy of the gas phase and the partial molar enthalpy of the adsorbed phase. There is no need to assume ideal gas or negligible molar volume of the adsorbed phase as is traditionally done in the literature. We illustrate this new approach with adsorption of argon, nitrogen, and carbon dioxide under subcritical and supercritical conditions.

Synthesis of substituted thiophenes by palladium-catalyzed heterocyclodehydration of 1-mercapto-3-yn-2-ols in conventional and nonconventional solvents.

PubMed

Gabriele, Bartolo; Mancuso, Raffaella; Veltri, Lucia; Maltese, Vito; Salerno, Giuseppe

2012-11-02

A variety of readily available 1-mercapto-3-yn-2-ols 5 were conveniently converted into the corresponding thiophenes 6 in good to high yields in MeOH as the solvent at 50-100 °C in the presence of catalytic amounts (1-2%) of PdI(2) in conjunction with KI (KI:PdI(2) molar ratio = 10). The catalyst could be made recyclable employing an ionic liquid, such as BmimBF(4), as the solvent under suitable conditions.

A high performance hybrid battery based on aluminum anode and LiFePO4 cathode.

PubMed

Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; Fang, Youxing; Bridges, Craig A; Paranthaman, M Parans; Dai, Sheng; Brown, Gilbert M

2016-01-28

A novel hybrid battery utilizing an aluminum anode, a LiFePO4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl3) (EMImCl-AlCl3, 1-1.1 in molar ratio) with or without LiAlCl4 is proposed. The hybrid ion battery delivers an initial high capacity of 160 mA h g(-1) at a current rate of C/5. It also shows good rate capability and cycling performance.

A high performance hybrid battery based on aluminum anode and LiFePO 4 cathode

DOE PAGES

Sun, Xiao-Guang; Bi, Zhonghe; Liu, Hansan; ...

2015-12-07

A unique battery hybrid utilizes an aluminum anode, a LiFePO 4 cathode and an acidic ionic liquid electrolyte based on 1-ethyl-3-methylimidazolium chloride (EMImCl) and aluminum trichloride (AlCl 3) (EMImCl-AlCl 3, 1-1.1 in molar ratio) with or without LiAlCl 4 is proposed. This hybrid ion battery delivers an initial high capacity of 160 mAh g -1 at a current rate of C/5. It also shows good rate capability and cycling performance.

Chromium(VI) Removal from Aqueous Solution by Magnetite Coated by a Polymeric Ionic Liquid-Based Adsorbent

PubMed Central

Ferreira, Thania Alexandra; Rodriguez, Jose Antonio; Paez-Hernandez, María Elena; Guevara-Lara, Alfredo; Barrado, Enrique; Hernandez, Prisciliano

2017-01-01

An evaluation of the chromium(VI) adsorption capacity of four magnetite sorbents coated with a polymer phase containing polymethacrylic acid or polyallyl-3-methylimidazolium is presented. Factors that influence the chromium(VI) removal such as solution pH and contact time were investigated in batch experiments and in stirred tank reactor mode. Affinity and rate constants increased with the molar ratio of the imidazolium. The highest adsorption was obtained at pH 2.0 due to the contribution of electrostatic interactions. PMID:28772865

Discovering a Change in Equilibrium Constant with Change in Ionic Strength: An Empirical Laboratory Experiment for General Chemistry

NASA Astrophysics Data System (ADS)

Stolzberg, Richard J.

1999-05-01

Students are challenged to investigate the hypothesis that an equilibrium constant, Kc, measured as a product and quotient of molar concentrations, is constant at constant temperature. Spectrophotometric measurements of absorbance of a solution of Fe3+(aq) and SCN-(aq) treated with different amounts of KNO3 are made to determine Kc for the formation of FeSCN2+(aq). Students observe a regular decrease in the value of Kc as the concentration of added KNO3 is increased.

The Partial Molar Volume and Compressibility of FeO in CaO-SiO2 Liquids: Systematic Variation with Fe2+ Coordination Change

NASA Astrophysics Data System (ADS)

Guo, X.; Lange, R. A.; Ai, Y.

2009-12-01

Iron is an important element in magmatic liquid, since its concentration can range up to 18% in some basaltic liquids, and it has two oxidation states. In order to model magmatic processes, thermodynamic descriptions of silicate melts must include precise information for both the FeO and Fe2O3 components. Currently, the partial molar volume of FeO is not as well known as that for Fe2O3 because of the difficulty of performing double-bob density measurements under reducing conditions. Yet these data are required in order to convert sound speed measurements on FeO-bearing liquids into compressibility data, which in turn are needed extend density models for magmatic liquids to elevated pressures. Moreover, there is growing evidence from the spectroscopic literature that Fe2+ occurs in 4, 5, and 6-fold coordination in silicate melts, and thus it is possible that the partial molar volume and compressibility of FeO may vary with Fe2+ coordination, and thus with melt composition. To explore these issues, we have conducted both density and relaxed sound speed measurements on liquids in the CaO-FeO-SiO2 system, where the CaO/SiO2 ratio was systematically varied at constant FeO concentration (40 mol%). Density was measured between 1594 and 1813K with the double-bob Archimedean method using molybdenum bobs and crucible in a reducing gas (1%CO-99%Ar) environment. The sounds speeds were measured under similar conditions with a frequency-sweep acoustic interferometer. The derived partial molar volume of FeO increases systematically from 13.7 to 15.2 cm3/mol at 1673 K as the CaO/SiO2 ratio increases and the Fe2+ coordination number decreases. From a comparison with the crystalline volume of FeO (halite structure; 12.06 cm3/mol), which serves as a lower limit for VFeO in silicate liquids when Fe2+ is in 6-fold coordination, we estimate that the average Fe2+ coordination in our experimental melts extends up to values between 5 and 4, consistent with the spectroscopic literature. The partial molar compressibility of FeO also increases systematically as Fe2+ coordination decreases, and its maximum measured value (7.01 x 10-2 GPa-1) is nearly identical to that for the SiO2 component in 4-fold coordination (7.14 x 10-2 GPa-1) and is considerably larger than that for the relatively incompressible component MgO (0.65 x 10-2 GPa-1). Thus, our data indicate that the volumetric properties of FeO component have more in common with those for SiO2 than for MgO.

Zn-Al layered double hydroxide prepared at different molar ratios: Preparation, characterization, optical and dielectric properties

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

Ahmed, Abdullah Ahmed Ali; Talib, Zainal Abidin, E-mail: zainalat@science.upm.edu.my; Zobir bin Hussein, Mohd

2012-07-15

The co-precipitation method was used to prepare Zn-Al-NO{sub 3}-LDH at different Zn{sup 2+}/Al{sup 3+} molar ratios (2, 3, 4, 5 and 6) and pH value of 7.5. The structure, textural, composition and morphological properties were investigated using powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), Fourier transform infrared (FT-IR) and scanning electron microscope (SEM), respectively. The crystallinity of LDH samples were found to improve as molar ratio decreased which is attributed to the distortion of the hydroxide layers networks of the LDH crystal by the larger difference in ionic radii of Zn{sup 2+} and Al{sup 3+}. The optical band gap energymore » of LDH samples were evaluated using absorbance data from UV-Vis-NIR Diffuse reflectance spectroscopy. Band gaps were affected by the variation of the Zn{sup 2+}/Al{sup 3+} molar ratio is due to the formation of the low crystalline phases (ZnO and ZnAl{sub 2}O{sub 4}). The water molecules and anionic NO{sub 3}{sup -} in the LDH interlayer were responsible for the generation of the dielectric response. This response can be described by an anomalous low frequency dispersion using the second type of Universal Power Law. The dominance of ZnO dipoles and charge carriers (NO{sub 3}{sup -} ions) in the dielectric relaxation increases with the increasing molar ratio. - Graphical abstract: (a) Schematic diagram of Zn-Al- NO{sub 3}-LDH shows the LDH structure, (b) Kubelka-Munk transformed reflectance spectra and c. The dielectric constant versus frequency of Zn-Al- NO{sub 3}-LDH samples. Highlights: Black-Right-Pointing-Pointer Zn-Al-NO{sub 3}-LDH was prepared at different Zn{sup 2+}/Al{sup 3+} molar ratios (2, 3, 4, 5 and 6). Black-Right-Pointing-Pointer The crystallinity of LDH phase decreased with increase of Zn{sup 2+}/Al{sup 3+} molar ratio. Black-Right-Pointing-Pointer The optical band gaps of LDH samples have been measured. Black-Right-Pointing-Pointer Dielectric response of LDH can be described by anomalous low frequency dispersion.« less

A notable difference between ideal gas and infinite molar volume limit of van der Waals gas

NASA Astrophysics Data System (ADS)

Liu, Q. H.; Shen, Y.; Bai, R. L.; Wang, X.

2010-05-01

The van der Waals equation of state does not sufficiently represent a gas unless a thermodynamic potential with two proper and independent variables is simultaneously determined. The limiting procedures under which the behaviour of the van der Waals gas approaches that of an ideal gas are letting two van der Waals coefficients be zero rather than letting the molar volume become infinitely large; otherwise, the partial derivative of internal energy with respect to pressure at a fixed temperature does not vanish.

Volumetric and calorimetric properties of aqueous ionene solutions

PubMed Central

Lukšič, Miha; Hribar-Lee, Barbara

2016-01-01

The volumetric (partial and apparent molar volumes) and calorimetric properties (apparent heat capacities) of aqueous cationic polyelectrolyte solutions – ionenes – were studied using the oscillating tube densitometer and differential scanning calorimeter. The polyion’s charge density and the counterion properties were considered as variables. The special attention was put to evaluate the contribution of electrostatic and hydrophobic effects to the properties studied. The contribution of the CH2 group of the polyion’s backbone to molar volumes and heat capacities was estimated. Synergistic effect between polyion and counterions was found. PMID:28503012

Partial molar enthalpies and reaction enthalpies from equilibrium molecular dynamics simulation

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

Schnell, Sondre K.; Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720; Department of Chemistry, Faculty of Natural Science and Technology, Norwegian University of Science and Technology, 4791 Trondheim

2014-10-14

We present a new molecular simulation technique for determining partial molar enthalpies in mixtures of gases and liquids from single simulations, without relying on particle insertions, deletions, or identity changes. The method can also be applied to systems with chemical reactions. We demonstrate our method for binary mixtures of Weeks-Chandler-Anderson particles by comparing with conventional simulation techniques, as well as for a simple model that mimics a chemical reaction. The method considers small subsystems inside a large reservoir (i.e., the simulation box), and uses the construction of Hill to compute properties in the thermodynamic limit from small-scale fluctuations. Results obtainedmore » with the new method are in excellent agreement with those from previous methods. Especially for modeling chemical reactions, our method can be a valuable tool for determining reaction enthalpies directly from a single MD simulation.« less

In Vivo Effect of Calcium Hydroxide and Resin-modified Glass Ionomer Cement on Carious Dentin in Young Permanent Molars: An Ultrastructural and Macroscopic Study.

PubMed

Opal, Shireen; Garg, Shalini; Sharma, Deepak; Dhindsa, Abhishek; Jatana, Isha

2017-01-15

The purpose of this study was to evaluate macroscopically and ultrastructurally the effect of calcium hydroxide cement (CH) and resin-modified glass ionomer cement (RMGIC) compared with gutta percha (control) as a lining material on carious dentin after partial caries removal and sealing. Twenty-seven permanent molars with deep carious lesions underwent partial caries removal with the application of CH, RMGIC, or gutta percha (control) and were then sealed for three months. After a partial caries removal and sealing period, the dentin was macroscopically assessed (for color, consistency, and humidity) and further analyzed by scanning electron microscope to assess the ultrastructural changes in dentin (lumen size, mineralization of tubules, occlusion of tubules by cements, and bacterial ingress). The effect of treatment in each group was statistically analyzed. Dentin darkening and hardening were observed after the sealing period in all groups. However, there was no difference in the color after treatment among the three groups. It was observed that RMGIC showed a significant reduction in the size of the lumen compared to CH and the control. Partial caries removal and sealing resulted in dentin hardening, darkening, and dentin remineralization, irrespective of the dentin protection used.

Sieve-based device for MALDI sample preparation. III. Its power for quantitative measurements.

PubMed

Molin, Laura; Cristoni, Simone; Seraglia, Roberta; Traldi, Pietro

2011-02-01

The solid sample inhomogeneity is a weak point of traditional MALDI deposition techniques that reflects negatively on quantitative analysis. The recently developed sieve-based device (SBD) sample deposition method, based on the electrospraying of matrix/analyte solutions through a grounded sieve, allows the homogeneous deposition of microcrystals with dimensions smaller than that of the laser spot. In each microcrystal the matrix/analyte molar ratio can be considered constant. Then, by irradiating different portions of the microcrystal distribution an identical response is obtained. This result suggests the employment of SBD in the development of quantitative procedures. For this aim, mixtures of different proteins of known molarity were analyzed, showing a good relationship between molarity and intensity ratios. This behaviour was also observed in the case of proteins with quite different ionic yields. The power of the developed method for quantitative evaluation was also tested by the measurement of the abundance of IGPP[Oxi]GPP[Oxi]GLMGPP (m/z 1219) present in the collagen-α-5(IV) chain precursor, differently expressed in urines from healthy subjects and diabetic-nephropathic patients, confirming its overexpression in the presence of nephropathy. The data obtained indicate that SBD is a particularly effective method for quantitative analysis also in biological fluids of interest. Copyright © 2011 John Wiley & Sons, Ltd.

Composition and stability of complexes of maleic and succinic acids with Cu2+ ions in water-ethanol solutions at 298 K

NASA Astrophysics Data System (ADS)

Tukumova, N. V.; Usacheva, T. R.; Thuan, Tran Thi Dieu; Sharnin, V. A.

2014-10-01

The composition and stability of coordination compounds of the anions of maleic (H2L) and succinic (H2Y) acids with copper(II) ions in water-ethanol solutions is studied by means of potentiometric titration at a sodium perchlorate ionic strength of 0.1 and a temperature of 298.15 K. The composition of the water-ethanol solvent was varied from 0 to 0.7 molar parts of ethanol for maleic acid and from 0 to 0.4 molar parts for succinic acid. The stability of monoligand complexes of copper ions with the anions of maleic and succinic acids grows with increase of ethanol concentration from 3.86 to 6.62 for logβCuL and from 2.98 to 6.01 for logβCuY. It is shown that a monotonic rise in stability upon an increase in the content of ethanol in solution is observed, while the values of logβCuL change more sharply. The succinic acid anion forms a stronger complex with copper ions than maleic acid anions do at an ethanol content of 0.4 molar parts. The possibility of the formation of a protonated CuHY+ particle is established.

Solvation structures of water in trihexyltetradecylphosphonium-orthoborate ionic liquids

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

Wang, Yong-Lei, E-mail: wangyonl@gmail.com; System and Component Design, Department of Machine Design, KTH Royal Institute of Technology, SE-100 44 Stockholm; Sarman, Sten

2016-08-14

Atomistic molecular dynamics simulations have been performed to investigate effective interactions of isolated water molecules dispersed in trihexyltetradecylphosphonium-orthoborate ionic liquids (ILs). The intrinsic free energy changes in solvating one water molecule from gas phase into bulk IL matrices were estimated as a function of temperature, and thereafter, the calculations of potential of mean force between two dispersed water molecules within different IL matrices were performed using umbrella sampling simulations. The systematic analyses of local ionic microstructures, orientational preferences, probability and spatial distributions of dispersed water molecules around neighboring ionic species indicate their preferential coordinations to central polar segments in orthoboratemore » anions. The effective interactions between two dispersed water molecules are partially or totally screened as their separation distance increases due to interference of ionic species in between. These computational results connect microscopic anionic structures with macroscopically and experimentally observed difficulty in completely removing water from synthesized IL samples and suggest that the introduction of hydrophobic groups to central polar segments and the formation of conjugated ionic structures in orthoborate anions can effectively reduce residual water content in the corresponding IL samples.« less

Distal caries of the second molar in the presence of a mandibular third molar - a prevention protocol.

PubMed

Toedtling, V; Coulthard, P; Thackray, G

2016-09-23

Objectives The objectives of the prospective study were to establish the prevalence of distal caries (DC) in the mandibular second molar and to assess the outcomes of these diseased teeth in our population. Further aims were to identify associated risk factors and to design a protocol for prevention.Methods Clinical and radiographic data from 210 consecutive patients were ascertained over a three-month period. The sample population included all patients who had been referred to a hospital oral surgery department for a lower wisdom tooth assessment.Results A total of 224 mandibular third molars were included and assessed. The prevalence of caries affecting the distal aspect of the second molar was 38% (n = 85) in this population. In 18% of patients there was evidence of early enamel caries. Fifty-eight percent of caries was managed with restorative treatment but 11% of patients required second molar extraction and 13% of patients required the removal of the second and third molars. The prevalence of distal caries was significantly higher in patients with partially erupted wisdom teeth positioned below the amelocemental junction (P <0.05) of the adjacent second molar and in patients who presented with mesioangular impactions (P <0.001). However there was no difference in dental health when comparing this group to the remaining study population (P = 0.354). The Pearson chi-square test and Pearson correlation coefficient were used to verify the association between the tested variables.Conclusion This study demonstrates that the eruption status, type of angulation and the nature of tooth contact between both molars are useful disease predictors which can be used to indicate the likelihood of a caries process occurring on the distal aspect of the second mandibular molar. If patients' third molar teeth are not removed then consideration needs to be given to prevention and regular monitoring.

Theoretical and experimental study on the effects of particle size and temperature on the reaction kinetics of cubic nano-Cu2O

NASA Astrophysics Data System (ADS)

Tang, Huanfeng; Huang, Zaiyin; Xiao, Ming; Liang, Min; Chen, Liying; Tan, XueCai

2017-09-01

The activities, selectivities, and stabilities of nanoparticles in heterogeneous reactions are size-dependent. In order to investigate the influencing laws of particle size and temperature on kinetic parameters in heterogeneous reactions, cubic nano-Cu2O particles of four different sizes in the range of 40-120 nm have been controllably synthesized. In situ microcalorimetry has been used to attain thermodynamic data on the reaction of Cu2O with aqueous HNO3 and, combined with thermodynamic principles and kinetic transition-state theory, the relevant reaction kinetic parameters have been evaluated. The size dependences of the kinetic parameters are discussed in terms of the established kinetic model and the experimental results. It was found that the reaction rate constants increased with decreasing particle size. Accordingly, the apparent activation energy, pre-exponential factor, activation enthalpy, activation entropy, and activation Gibbs energy decreased with decreasing particle size. The reaction rate constants and activation Gibbs energies increased with increasing temperature. Moreover, the logarithms of the apparent activation energies, pre-exponential factors, and rate constants were found to be linearly related to the reciprocal of particle size, consistent with the kinetic models. The influence of particle size on these reaction kinetic parameters may be explained as follows: the apparent activation energy is affected by the partial molar enthalpy, the pre-exponential factor is affected by the partial molar entropy, and the reaction rate constant is affected by the partial molar Gibbs energy. [Figure not available: see fulltext.

Comprehensive two-dimensional liquid chromatographic analysis of poloxamers.

PubMed

Malik, Muhammad Imran; Lee, Sanghoon; Chang, Taihyun

2016-04-15

Poloxamers are low molar mass triblock copolymers of poly(ethylene oxide) (PEO) and poly(propylene oxide) (PPO), having number of applications as non-ionic surfactants. Comprehensive one and two-dimensional liquid chromatographic (LC) analysis of these materials is proposed in this study. The separation of oligomers of both types (PEO and PPO) is demonstrated for several commercial poloxamers. This is accomplished at the critical conditions for one of the block while interaction for the other block. Reversed phase LC at CAP of PEO allowed for oligomeric separation of triblock copolymers with regard to PPO block whereas normal phase LC at CAP of PPO renders oligomeric separation with respect to PEO block. The oligomeric separation with regard to PEO and PPO are coupled online (comprehensive 2D-LC) to reveal two-dimensional contour plots by unconventional 2D IC×IC (interaction chromatography) coupling. The study provides chemical composition mapping of both PEO and PPO, equivalent to combined molar mass and chemical composition mapping for several commercial poloxamers. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular dynamics of acetamide based ionic deep eutectic solvents

NASA Astrophysics Data System (ADS)

Srinivasan, H.; Dubey, P. S.; Sharma, V. K.; Biswas, R.; Mitra, S.; Mukhopadhyay, R.

2018-04-01

Deep eutectic solvents are multi-component mixtures that have freezing point lower than their individual components. Mixture of acetamide+ lithium nitrate in the molar ratio 78:22 and acetamide+ lithium perchlorate in the molar ratio 81:19 are found to form deep eutectic solvents with melting point lower than the room temperature. It is known that the depression in freezing point is due to the hydrogen bond breaking ability of anions in the system. Quasielastic neutron scattering experiments on these systems were carried out to study the dynamics of acetamide molecules which may be influenced by this hydrogen bond breaking phenomena. The motion of acetamide molecules is modeled using jump diffusion mechanism to demonstrate continuous breaking and reforming hydrogen bonds in the solvent. Using the jump diffusion model, it is inferred that the jump lengths of acetamide molecules are better approximated by a Gaussian distribution. The shorter residence time of acetamide in presence of perchlorate ions suggest that the perchlorate ions have a higher hydrogen bond breaking ability compared to nitrate ions.

In Vitro Comparison of Marginal and Internal Fit of Press-on-Metal Ceramic (PoM) Restorations with Zirconium-Supported and Conventional Metal Ceramic Fixed Partial Dentures Before and After Veneering.

PubMed

Varol, Seda; Kulak-Özkan, Yasemin

2015-07-01

To compare marginal and internal fit between 3- and 4-unit press-on-metal (PoM) ceramic, zirconia-supported, and conventional metal ceramic fixed partial dentures (FPDs) before and after veneering. Ten pieces for each 3- and 4-unit MC, IPS InLine PoM, and IPS e.max ZirCAD/Zir Press FPDs were produced. Cross-sections from silicone replicas were examined and measured with a light microscope. Occlusal, axial, intermarginal, and marginal mean adaptation scores of cross-sectioned replicas and means of measurements obtained from 4 sites were calculated independently. Mean values for molars were 78.44 ± 32.01 μm (MC), 89.84 ± 29.20 μm (PoM), and 85.17 ± 28.49 μm (Zir). Premolar values were 76.08 ± 27.92 μm (MC), 89.94 ± 23.49 μm (PoM), and 87.18 ± 28.25 μm (Zir). No difference existed between the means of 3- and 4-unit FPDs except the molar-intermarginal region. The mean value of 4-unit FPDs (93.88 ± 25.41 μm) was less than the 3-unit FPDs (103.68 ± 24.55 μm) at the molar-inter marginal region. A gap increase was observed in all sites except the molar-axio-occlusal region after veneering. According to the mean difference, gap increases at the molar-marginal, molar-intermarginal, and premolar-intermarginal regions were statistically significant. A statistical difference was found at the molar-marginal region for 4-unit MCR (p = 0.041) and 4-unit PoM FPDs (p = 0.042) before and after veneering. Gap increase after veneering of 4-unit metal ceramics at molar-intermarginal, premolar-marginal, and premolar-intermarginal regions (p = 0.020; p = 0.015; p = 0.004) was significant. The gap measurements of the IPS InLine PoM and IPS e.max ZirCAD/Zir Press groups were all clinically acceptable. No studies on marginal and internal fit in the IPS InLine PoM system have been published to date. This study should be supported with future studies. No significant increase was observed after press-veneering the IPS e.max ZirCAD frameworks with an IPS e.max ZirPress material; therefore, we recommend the use of this combination. © 2014 by the American College of Prosthodontists.

Design, characterization and applications of new ionic liquid matrices for multifunctional analysis of biomolecules: a novel strategy for pathogenic bacteria biosensing.

PubMed

Abdelhamid, Hani Nasser; Khan, M Shahnawaz; Wu, Hui-Fen

2014-05-01

The design, preparation and performance for novel UV-light absorbing (room-temperature) ionic liquid matrices (UV-RTILMs) for matrix assisted laser desorption/ionization mass spectrometry (MALDI-MS) were reported. A series of UV-RTILMs was prepared by ultrasonication of equimolar of acid (mefenamic acid) and bases (aniline (ANI), pyridine (Pyr), dimethyl aniline (DMANI) and 2-methyl picoline (2-P)). The UV-RTILMs have not only significant absorbance at the desired wavelength (337 nm of the N2 Laser), but also have available protons that can easily undergo proton transfer reactions to ionize the target molecules. The novel UV-RTILMs have the ability to ionize different and wide classes of compounds such as drugs, carbohydrate, and amino acids. The new UV-RTILMs series have been successfully and selectively applied for biosensing the lysates of pathogenic bacteria in the presence of the cell macromolecules. A new strategy for biosensing pathogens was presented via sensing the pathogens lysate in the cell suspension. The new materials can effectively detect the bacterial toxins without separation or any pretreatment. They offered excellent ionization of labile oligosaccharides with protonated peaks. They could significantly enhance the analyte signals, produce homogeneous spotting, reducing spot-to-spot variation, excellent vacuum stability, higher ion peak intensity, and wide application possibility. The physical parameters such as molar refractivity, molar volume, parachor, surface tension, density and polarizability were calculated and tabulated. The new UV-RTILMs could offer excellent reproducibility and great repeatability and they are promising matrices for wide applications on MALDI-MS. Copyright © 2014. Published by Elsevier B.V.

Physical and absorption properties of titanium nanoparticles incorporated into zinc magnesium phosphate glass

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

Ismail, S.F.; Sahar, M.R., E-mail: mrahim057@gmail.com; Ghoshal, S.K.

We report the influences of Titania (TiO{sub 2}) nanoparticles (NPs) on the physical and optical properties of melt quench synthesized zinc magnesium phosphate glasses. Five glass samples with composition (42 − x)P{sub 2}O{sub 5}–50ZnO–8MgO–xTiO{sub 2}, where x = 0, 1, 2, 3, 4 mol% are prepared and characterized. XRD pattern verified the amorphous nature of all samples. TEM images manifested the growth of Ti NPs of average size ≈ 5.78 nm. TiO{sub 2} NP concentration dependent variation in the physical properties including glass density, molar volume, molar refractivity, electronic polarizability and ionic packing density are determined. The values of glassmore » refractive indices, density and ionic packing density are increased with the increase of TiO{sub 2} NP contents. Conversely, the Urbach energy, direct and indirect optical band gap are found to decrease with the increase of TiO{sub 2} NP concentration. These glass compositions may be potential for various solid state devices including laser. - Highlights: • TiO{sub 2} NP embedded self-cleaning phosphate glass are synthesized for the first time. • Well dispersed and uniform sized TiO{sub 2} NPs are grown. • Absorption spectra revealed prominent peak in the UV region. • TiO{sub 2} NPs strongly influenced the physical and absorption features of synthesized glasses. • The effects of TiO{sub 2} NPs on the physical and optical properties of these glasses are determined.« less

[Membrane lipids and electron transfer. Effects of four detergents on NADH-ferricyanide reductase and NADH-cytochrome c reductase activities of potato tuber microsomes].

PubMed

Jolliot, A; Mazliak, P

1977-10-17

The NADH-ferricyanure reductase activity of Potato microsomes is stimulated by non ionic detergents (Triton X100 and Tween80) and is partially inhibited by ionic detergents (sodium-cholate and deoxycholate). All these four detergents progressively decreased the NADH-cytochrome c reductase in the following order: sodium deoxycholate greater than Triton X100 greater than sodium cholate greater than Tween80.

Iodopropyl-branched polysiloxane gel electrolytes with improved ionic conductivity upon cross-linking.

PubMed

De Gregorio, G L; Giannuzzi, R; Cipolla, M P; Agosta, R; Grisorio, R; Capodilupo, A; Suranna, G P; Gigli, G; Manca, M

2014-11-21

We here report the implementation of poly[(3-N-methylimidazoliumpropyl)methylsiloxane-co-dimethylsiloxane]iodides as suitable polymeric hosts for a novel class of in situ cross-linkable iodine/iodide-based gel-electrolytes for dye-sensitized solar cells. The polymers are first partially quaternized and then subjected to a thermal cross-linking which allows the formation of a 3D polymeric network which is accompanied by a dramatic enhancement of the ionic conductivity.

Interfacial Shear Strength and Adhesive Behavior of Silk Ionomer Surfaces.

PubMed

Kim, Sunghan; Geryak, Ren D; Zhang, Shuaidi; Ma, Ruilong; Calabrese, Rossella; Kaplan, David L; Tsukruk, Vladimir V

2017-09-11

The interfacial shear strength between different layers in multilayered structures of layer-by-layer (LbL) microcapsules is a crucial mechanical property to ensure their robustness. In this work, we investigated the interfacial shear strength of modified silk fibroin ionomers utilized in LbL shells, an ionic-cationic pair with complementary ionic pairing, (SF)-poly-l-glutamic acid (Glu) and SF-poly-l-lysine (Lys), and a complementary pair with partially screened Coulombic interactions due to the presence of poly(ethylene glycol) (PEG) segments and SF-Glu/SF-Lys[PEG] pair. Shearing and adhesive behavior between these silk ionomer surfaces in the swollen state were probed at different spatial scales and pressure ranges by using functionalized atomic force microscopy (AFM) tips as well as functionalized colloidal probes. The results show that both approaches were consistent in analyzing the interfacial shear strength of LbL silk ionomers at different spatial scales from a nanoscale to a fraction of a micron. Surprisingly, the interfacial shear strength between SF-Glu and SF-Lys[PEG] pair with partially screened ionic pairing was greater than the interfacial shear strength of the SF-Glu and SF-Lys pair with a high density of complementary ionic groups. The difference in interfacial shear strength and adhesive strength is suggested to be predominantly facilitated by the interlayer hydrogen bonding of complementary amino acids and overlap of highly swollen PEG segments.

The gelation influence on diffusion and conductivity enhancement effect in renewable ionic gels based on a LMWG.

PubMed

Bielejewski, M; Rachocki, A; Kaszyńska, J; Tritt-Goc, J

2018-02-21

This paper reports the interdisciplinary study on molecular dynamics, ionic interactions and electrical conductivity in a quaternary ammonium salt (TMABr) ionogel based on a low molecular weight gelator (LMWG) in a wide range of electrolyte molar concentrations. The thermal scanning conductometry (TSC) was used to investigate the electric properties of the ionogels. The prepared TMABr/H 2 O/LMWG ionogel exhibits better ion transport properties than the dissociated TMA + cation in solution. The enhanced ionic conductivity effect (EICE) was observed in the concentration range of the TMABr salt up to 1 M. To investigate the transport properties of the TMA + cation and solvent molecules in the gel and sol phase, the NMR diffusiometry method was used. The field-cycling relaxometry method (FFC NMR) was applied to study the local motions of the electrolyte at the surface of the gelator matrix. On the basis of the obtained data, the higher ionic conductivity observed in the gel phase has been related to the microstructure of the gel matrix. The possible explanation for the origin of this effect has been given. The investigated system is a thermally reversible physical gel, all registered data were reproducible upon transforming the sample from gel to sol and back to the gel state, confirming the enhancement effect as a permanent property of the investigated ionogels. Therefore, the EICE has been proposed to be used as an internal sensor to monitor the condition of the ionogel phase, thus making them smart materials.

Amine-functionalized, multi-arm star polymers: A novel platform for removing glyphosate from aqueous media.

PubMed

Samuel, Lianna; Wang, Ran; Dubois, Geraud; Allen, Robert; Wojtecki, Rudy; La, Young-Hye

2017-02-01

We describe a novel method for efficiently removing glyphosate from aqueous media via adsorption onto highly functionalized star-shaped polymeric particles. These particles have a polystyrene core with more than 35 attached methacrylate polymer arms, each containing a plurality of pendant amines (poly(dimethylamino ethyl methacrylate): PDMAEMA) that are partially protonated in water. Kinetic studies demonstrate that these star-polymers successfully remove up to 93% of glyphosate present in aqueous solution (feed concentration: 5 ppm), within 10 min contact time, outperforming activated carbon, which removed 33% after 20 min. On these star-polymers, glyphosate adsorption closely follows the Langmuir model indicating monolayer coverage at most. Ionic interaction between the protonated amines and glyphosate's dissociated carboxylic and phosphoric acid groups lead to effective glyphosate capture even at feed concentrations below 1 ppm. Surface charge of these star polymers and dissociation of glyphosate are both influenced by pH, thus glyphosate removal efficiency increases from 63% to 93% when pH increases from 4.2 to 7.7. NMR studies conducted with butylamine as a proxy for these polymeric particles confirm that the amine group binds with both glyphosate's carboxylic and phosphoric acid groups when its concentrations are in a 2:1 or higher molar ratio with glyphosate. Copyright © 2016 Elsevier Ltd. All rights reserved.

Determination of gas-liquid partition coefficients of several organic solutes in trihexyl(tetradecyl)phosphonium bromide using capillary gas chromatography columns.

PubMed

Ronco, Nicolás R; Menestrina, Fiorella; Romero, Lílian M; Castells, Cecilia B

2017-06-09

In this paper, we report gas-liquid partition constants for thirty-five volatile organic solutes in the room temperature ionic liquid trihexyl(tetradecyl)phosphonium bromide measured by gas-liquid chromatography using capillary columns. The relative contribution of gas-liquid partition and interfacial adsorption to retention was evaluated through the use of columns with different the phase ratio. Four capillary columns with exactly known phase ratios were constructed and employed to measure the solute retention factors at four temperatures between 313.15 and 343.15K. The partition coefficients were calculated from the slopes of the linear regression between solute retention factors and the reciprocal of phase ratio at a given temperature according to the gas-liquid chromatographic theory. Gas-liquid interfacial adsorption was detected for a few solutes and it has been considered for the calculations of partition coefficient. Reliable solute's infinite dilution activity coefficients can be obtained when retention data are determined by a unique partitioning mechanism. The partial molar excess enthalpies at infinite dilution have been estimated from the dependence of experimental values of solute activity coefficients with the column temperature. A thorough discussion of the uncertainties of the experimental measurements and the main advantages of the use of capillary columns to acquire the aforementioned relevant thermodynamic information was performed. Copyright © 2017 Elsevier B.V. All rights reserved.

Polyaspartic acid functionalized gold nanoparticles for tumor targeted doxorubicin delivery.

PubMed

Khandekar, Sameera V; Kulkarni, M G; Devarajan, Padma V

2014-01-01

In this paper, we present polyaspartic acid, a biodegradable polymer as a reducing and functionalizing agent for the synthesis of doxorubicin loaded gold nanoparticles by a green process. Gold nanoparticles were stable to electrolytes and pH. Secondary amino groups of polyaspartic acid enabled reduction of gold chloride to form gold nanoparticles of size 55 +/-10 nm, with face centered cubic crystalline structure as confirmed by UV, TEM, SAED and XRD studies. Cationic doxorubicin was readily loaded onto anionic polyaspartic acid gold nanoparticles by ionic complexation. Fluorescence studies confirmed doxorubicin loading while FTIR spectra confirmed ionic complexation. Doxorubicin loading onto polyaspartic acid gold nanoparticles was studied at doxorubicin/polyaspartic acid molar ratios 1:10 to 1:1. As the molar ratio tended to unity, although loading up to 60% was achieved, colloidal instability resulted and is attributed to effective covering of negative charges of polyaspartic acid. Stable doxorubicin loaded polyaspartic acid gold nanoparticles of 105 +/- 15.1 nm with doxorubicin loading of 23.85% w/w and zeta potential value of -28 +/- 0.77 mV were obtained at doxorubicin/polyaspartic acid molar ratio 1:10. Higher doxorubicin release rate from the doxorubicin loaded polyaspartic acid gold nanoparticles in an acid medium (i.e., pH 5.5) as compared to that in pH 7.4 and deionized water is a desirable characteristic for tumor targeted delivery. Enhanced cytotoxicity and 3 fold higher uptake of doxorubicin loaded polyaspartic acid gold nanoparticles as compared to doxorubicin solution were seen in MCF-7 breast cancer cells while polyaspartic acid gold nanoparticles revealed no cytotoxicity confirming safety. Prominent regression in tumor size in-vivo in fibrosarcoma tumor induced mouse model was observed upto 59 days with doxorubicin loaded polyaspartic acid gold nanoparticles while doxorubicin solution treated mice showed regrowth beyond 23rd day. Moreover, a decrease of body weight of 35% indicating severe toxicity with doxorubicin solution as compared to only 20% with gradual recovery after day 30 in case of doxorubicin loaded polyaspartic acid gold nanoparticles confirmed their lower toxicity and enhanced efficacy.

Enhanced gas absorption in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]) confined in silica slit pores: a molecular simulation study.

PubMed

Shi, Wei; Luebke, David R

2013-05-07

Two-dimensional NPxyT and isostress-osmotic (N2PxyTf1) Monte Carlo simulations were used to compute the density and gas absorption properties of the ionic liquid (IL) 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]) confined in silica slit pores (25-45 Å). Self-diffusivity values for both gas and IL were calculated from NVE molecular dynamics simulations using both smooth and atomistic potential models for silica. The simulations showed that the molar volume of [hmim][Tf2N] confined in 25-45-Å silica slit pores is 12-31% larger than that of the bulk IL at 313-573 K and 1 bar. The amounts of CO2, H2, and N2 absorbed in the confined IL are 1.1-3 times larger than those in the bulk IL because of the larger molar volume of the confined IL compared to the bulk IL. The CO2, N2, and H2 molecules are generally absorbed close to the silica wall where the IL density is very low. This arrangement causes the self-diffusivities of these gases in the confined IL to be 2-8 times larger than those in the bulk IL at 298-573 K. The solubilities of water in the confined and bulk ILs are similar, which is likely due to strong water interactions with [hmim][Tf2N] through hydrogen bonding, so that the molar volume of the confined IL plays a less important role in determining the H2O solubility. Water molecules are largely absorbed in the IL-rich region rather than close to the silica wall. The self-diffusivities of water correlate with those of the confined IL. The confined IL exhibits self-diffusivities larger than those of the bulk IL at lower temperatures, but smaller than those of the bulk IL at higher temperatures. The findings from our simulations are consistent with available experimental data for similar confined IL systems.

Electrodeposition mechanism and characterization of Ni-Cu alloy coatings from a eutectic-based ionic liquid

NASA Astrophysics Data System (ADS)

Wang, Shaohua; Guo, Xingwu; Yang, Haiyan; Dai, JiChun; Zhu, Rongyu; Gong, Jia; Peng, Liming; Ding, Wenjiang

2014-01-01

The electrodeposition mechanism, microstructures and corrosion resistances of Ni-Cu alloy coatings on Cu substrate were investigated in a choline chloride-urea (1:2 molar ratio) eutectic-based ionic liquid (1:2 ChCl-urea IL) containing nickel and copper chlorides. Cyclic voltammetry showed that the onset reduction potentials for Cu (∼-0.32 V) and for Ni (∼-0.47 V) were close to each other, indicating that Ni-Cu co-deposition could be easily achieved in the absence of complexing agent which was indispensable in aqueous plating electrolyte. Chronoamperometric investigations revealed that Ni-Cu deposits followed the three-dimensional instantaneous nucleation/growth mechanism, thus producing a solid solution. The compositions, microstructures and corrosion resistances of Ni-Cu alloy coatings were significantly dependent on the deposition current densities. Ni-Cu alloy coatings were α-Ni(Cu) solid solutions, and the coating containing ∼17.6 at.% Cu exhibited the best corrosion resistance because of its dense and crack-free structure.

Can an ammonium-based room temperature ionic liquid counteract the urea-induced denaturation of a small peptide?

PubMed

Ghosh, Soumadwip; Dey, Souvik; Patel, Mahendra; Chakrabarti, Rajarshi

2017-03-15

The folding/unfolding equilibrium of proteins in aqueous medium can be altered by adding small organic molecules generally termed as co-solvents. Denaturants such as urea are instrumental in the unfolding of proteins while protecting osmolytes favour the folded ensemble. Recently, room temperature ionic liquids (ILs) have been shown to counteract the deleterious effect of urea on proteins. In this paper, using atomistic molecular dynamics we show that a ternary mixture containing a particular ammonium-based IL, triethylammonium acetate (TEAA), and urea (in 1 : 5 molar ratio) helps a small 15-residue S-peptide analogue regain most of its native structure, whereas a binary aqueous mixture containing a large amount of urea alone completely distorts it. Our simulations show that the denaturant urea directly interacts with the peptide backbone in the binary mixture while for the ternary mixture both urea as well as the IL are preferentially excluded from the peptide surface.

Ideal gas solubilities and solubility selectivities in a binary mixture of room-temperature ionic liquids.

PubMed

Finotello, Alexia; Bara, Jason E; Narayan, Suguna; Camper, Dean; Noble, Richard D

2008-02-28

This study focuses on the solubility behaviors of CO2, CH4, and N2 gases in binary mixtures of imidazolium-based room-temperature ionic liquids (RTILs) using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][Tf2N]) and 1-ethyl-3-methylimidazolium tetrafluoroborate ([C2mim][BF4]) at 40 degrees C and low pressures (approximately 1 atm). The mixtures tested were 0, 25, 50, 75, 90, 95, and 100 mol % [C2mim][BF4] in [C2mim][Tf2N]. Results show that regular solution theory (RST) can be used to describe the gas solubility and selectivity behaviors in RTIL mixtures using an average mixture solubility parameter or an average measured mixture molar volume. Interestingly, the solubility selectivity, defined as the ratio of gas mole fractions in the RTIL mixture, of CO2 with N2 or CH4 in pure [C2mim][BF4] can be enhanced by adding 5 mol % [C2mim][Tf2N].

Solution behavior of metoclopramide in aqueous-alcoholic solutions at 30°C

NASA Astrophysics Data System (ADS)

Deosarkar, S. D.; Sawale, R. T.; Tawde, P. D.; Kalyankar, T. M.

2016-07-01

Densities (ρ) and refractive indices ( n D) of solutions of antiemetic drug metoclopramide (4-amino-5-chloro- N-(2-(diethylamino)ethyl)-2-methoxybenzamide hydrochloride hydrate) in methanolwater and ethanol-water mixtures of different compositions were measured at 30°C. Apparent molar volume (φv) of the drug was calculated from density data and partial molar volumes (φ v 0 ) were determined from Massons relation. Concentration dependence of nD has been studied to determine refractive indices of solution at infinite dilution ( n D 0 ). Results have been interpreted in terms of solute-solvent interactions.

Experimental Techniques for Thermodynamic Measurements of Ceramics

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.; Putnam, Robert L.; Navrotsky, Alexandra

1999-01-01

Experimental techniques for thermodynamic measurements on ceramic materials are reviewed. For total molar quantities, calorimetry is used. Total enthalpies are determined with combustion calorimetry or solution calorimetry. Heat capacities and entropies are determined with drop calorimetry, differential thermal methods, and adiabatic calorimetry . Three major techniques for determining partial molar quantities are discussed. These are gas equilibration techniques, Knudsen cell methods, and electrochemical techniques. Throughout this report, issues unique to ceramics are emphasized. Ceramic materials encompass a wide range of stabilities and this must be considered. In general data at high temperatures is required and the need for inert container materials presents a particular challenge.

Intramaxillary and intermaxillary absolute anchorage with an endosseous dental implant and rare-earth magnets.

PubMed

Uribe, Flavio; Nanda, Ravindra

2009-07-01

This case report describes the management of a partially edentulous adult with a severe deepbite malocclusion and a collapsed buccal segment because of supraeruption of the maxillary second and third molars. The treatment involved placement of an endosseous dental implant to achieve absolute intermaxillary and intramaxillary anchorage. Rare-earth magnets embedded in acrylic bite-blocks were used to intrude the supraerupted maxillary molars on the right side. After use as an anchorage device, the implant was restored and brought into occlusion. Good occlusal and esthetic results were achieved with this cost-effective treatment.

Ionic relaxation in PEO/PVDF-HFP-LiClO4 blend polymer electrolytes: dependence on salt concentration

NASA Astrophysics Data System (ADS)

Das, S.; Ghosh, A.

2016-06-01

In this paper, we have studied the effect of LiClO4 salt concentration on the ionic conduction and relaxation in poly ethylene oxide (PEO) and poly (vinylidene fluoride hexafluoropropylene) (PVDF-HFP) blend polymer electrolytes, in which the molar ratio of ethylene oxide segments to lithium ions (R  =  EO: Li) has been varied between 3 and 35. We have observed two phases in the samples containing low salt concentrations (R  >  9) and single phase in the samples containing high salt concentrations (R  ⩽  9). The scanning electron microscopic images indicate that there exists no phase separation in the blend polymer electrolytes. The temperature dependence of the ionic conductivity shows two slopes corresponding to high and low temperatures and follows Arrhenius relation for the samples containing low salt concentrations (R  >  9). The conductivity relaxation as well as the structural relaxation has been clearly observed at around 104 Hz and 106 Hz for these concentrations of the blended electrolytes. However, a single conductivity relaxation peak has been observed for the compositions with R  ⩽  9. The scaling of the conductivity spectra shows that the relaxation mechanism is independent of temperature, but depends on salt concentration.

Tuning the Selectivity of Single-Site Supported Metal Catalysts with Ionic Liquids

DOE PAGES

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

2017-09-11

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

The synthesis and the chemical and physical properties of non-aqueous silylamine solvents for carbon dioxide capture.

PubMed

Rohan, Amy L; Switzer, Jackson R; Flack, Kyle M; Hart, Ryan J; Sivaswamy, Swetha; Biddinger, Elizabeth J; Talreja, Manish; Verma, Manjusha; Faltermeier, Sean; Nielsen, Paul T; Pollet, Pamela; Schuette, George F; Eckert, Charles A; Liotta, Charles L

2012-11-01

Silylamine reversible ionic liquids were designed to achieve specific physical properties in order to address effective CO₂ capture. The reversible ionic liquid systems reported herein represent a class of switchable solvents where a relatively non-polar silylamine (molecular liquid) is reversibly transformed to a reversible ionic liquid (RevIL) by reaction with CO₂ (chemisorption). The RevILs can further capture additional CO₂ through physical absorption (physisorption). The effects of changes in structure on (1) the CO₂ capture capacity (chemisorption and physisorption), (2) the viscosity of the solvent systems at partial and total conversion to the ionic liquid state, (3) the energy required for reversing the CO₂ capture process, and (4) the ability to recycle the solvents systems are reported. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synergistic Impacts of Electrolyte Adsorption on the Thermoelectric Properties of Single-Walled Carbon Nanotubes.

PubMed

Nakano, Motohiro; Nakashima, Takuya; Kawai, Tsuyoshi; Nonoguchi, Yoshiyuki

2017-08-01

Single-walled carbon nanotubes are promising candidates for light-weight and flexible energy materials. Recently, the thermoelectric properties of single-walled carbon nanotubes have been dramatically improved by ionic liquid addition; however, controlling factors remain unsolved. Here the thermoelectric properties of single-walled carbon nanotubes enhanced by electrolytes are investigated. Complementary characterization with absorption, Raman, and X-ray photoelectron spectroscopy reveals that shallow hole doping plays a partial role in the enhanced electrical conductivity. The molecular factors controlling the thermoelectric properties of carbon nanotubes are systematically investigated in terms of the ionic functionalities of ionic liquids. It is revealed that appropriate ionic liquids show a synergistic enhancement in conductivity and the Seebeck coefficient. The discovery of significantly precise doping enables the generation of thermoelectric power factor exceeding 460 µW m - 1 K -2 . © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Partial breaking of the Coulombic ordering of ionic liquids confined in carbon nanopores

PubMed Central

Futamura, Ryusuke; Iiyama, Taku; Takasaki, Yuma; Gogotsi, Yury; Biggs, Mark J.; Salanne, Mathieu; Ségalini, Julie; Simon, Patrice; Kaneko, Katsumi

2017-01-01

Ionic liquids are composed of equal quantities of positive and negative ions. In the bulk, electrical neutrality occurs in these liquids due to Coulombic ordering, in which ion shells of alternating charge form around a central ion. Their structure under confinement is far less well understood. This hinders the widespread application of ionic liquids in technological applications. Here we use scattering experiments to resolve the structure of the widely used ionic liquid (EMI-TFSI) when it is confined inside nanoporous carbons. We show that Coulombic ordering reduces when the pores can only accommodate a single layer of ions. Instead, equally-charged ion pairs are formed due to the induction of an electric potential of opposite sign in the carbon pore walls. This non-Coulombic ordering is further enhanced in the presence of an applied external electric potential. This finding opens the door for the design of better materials for electrochemical applications. PMID:28920938

The dual exo/endo-type mode and the effect of ionic strength on the mode of catalysis of chitinase 60 (CHI60) from Serratia sp. TU09 and its mutants.

PubMed

Kuttiyawong, K; Nakapong, S; Pichyangkura, R

2008-11-03

Mutations of the tryptophan residues in the tryptophan-track of the N-terminal domain (W33F/Y and W69F/Y) and in the catalytic domain (W245F/Y) of Serratia sp. TU09 Chitinase 60 (CHI60) were constructed, as single and double point substitutions to either phenylalanine or tyrosine. The enzyme-substrate interaction and mode of catalysis, exo/endo-type, of wild type CHI60 and mutant enzymes on soluble (partially N-acetylated chitin), amorphous (colloidal chitin), and crystalline (β-chitin) substrates were studied. All CHI60 mutants exhibited a reduced substrate binding activity on colloidal chitin. CHI60 possesses a dual mode of catalysis with both exo- and endo-type activities allowing the enzyme to work efficiently on various substrate types. CHI60 preferentially uses the endo-type mode on soluble and amorphous substrates and the exo-type mode on crystalline substrate. However, the prevalent mode of hydrolysis mediated by CHI60 is regulated by ionic strength. Slightly elevated ionic strength, 0.1-0.2M NaCl, which promotes enzyme-substrate interactions, enhances CHI60 hydrolytic activity on amorphous substrate and, interestingly, on partially N-acetylated chitin. High ionic strength, 0.5-2.0M NaCl, prevents the enzyme from dissociating from amorphous substrate, occupying the enzyme in an enzyme-substrate non-productive complex. However, on crystalline substrates, the activity of CHI60 was only inhibited approximately 50% at high ionic strength, suggesting that the enzyme hydrolyzes crystalline substrates with an exo-type mode processively while remaining tightly bound to the substrate. Moreover, substitution of Trp-33 to either phenylalanine or tyrosine reduced the activity of the enzyme at high ionic strength, suggesting an important role of Trp-33 on enzyme processivity.

Weekday/weekend differences in ambient aerosol level and chemical characteristics of water-soluble components in the city centre

NASA Astrophysics Data System (ADS)

Khoder, M. I.; Hassan, S. K.

Weekday and weekend ambient aerosol samples were collected from the city centre of Cairo, namely "Ramsis" during the summer season of the year 2006, and have been analyzed for water-soluble ionic species. The average concentrations of the total suspended particulate matter (TSP) and their water-soluble components were higher during weekdays than on weekends, indicating that the decreased traffic density on weekends leads to a decrease in the levels of the TSP and their water-soluble ionic species. The average concentrations of the TSP were 454 μg m -3 on weekdays and 298 μg m -3 on weekends. The weekday/weekend concentration ratios were 1.52 for TSP, 1.27 for SO 42-, 1.64 for Cl -, 1.54 for NO 3-, 1.17 for NH 4+, 1.67 for Ca 2+, 1.83 for Na +, 1.75 for K + and 1.73 for Mg 2+. City centre of Cairo has high levels of the TSP and their water-soluble ionic species compared with many polluted cities in the world. Among all of the measured water-soluble components, SO 42- was the most abundant species followed by Ca 2+ on weekdays and weekends. The average mass ratios of NO 3-/SO 42- in the TSP were 0.41 on weekdays and 0.34 on weekends, suggesting that the stationary source emissions were more predominant. The NH 4+/SO 42- molar ratios and its relation with the concentrations of TSP and Ca 2+ during the weekdays and weekends indicate that the chemical form of sulfate and ammonium in aerosol particles varies with TSP and Ca 2+ levels. At high TSP and Ca 2+ levels, and NH 4+/SO 42- molar ratios less than one, SO 42- in aerosol particles may be present as CaSO 4 and (NH 4) 2SO 4·CaSO 4·2H 2O, whereas it is expected to be present as (NH 4) 2SO 4, (NH 4) 2SO 4·CaSO 4·2H 2O and CaSO 4 at low levels of TSP and Ca 2+, and NH 4+/SO 42- molar ratios between 1 and 2. The mean pH values of the TSP were 7.65 on weekdays and 6.97 on weekends, indicating that aerosol particles brought a large amount of crustal species, and might alleviate the tendency of acidification. The relationships between the concentrations of acidic components (NO 3- and SO 42-) and basic components (NH 4+, Ca 2+ and Mg 2+) on weekdays and weekends indicate that the acidity of aerosol particles is neutralized. Ca 2+ and NH 4+ are the most dominant neutralization substances in Cairo atmosphere.

Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure

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

Lima, Thamires A.; Paschoal, Vitor H.; Faria, Luiz F. O.

2016-06-14

X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1114}][NTf{sub 2}], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N{sub 1444}][NTf{sub 2}]. The peak in the diffraction data characteristic of charge ordering in [N{sub 1444}][NTf{sub 2}] is shifted to longer distances in comparison to [N{sub 1114}][NTf{sub 2}], but the peak characteristic of short-range correlations is shifted in [N{sub 1444}][NTf{sub 2}] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N{sub 1114}]{sup +} and [N{sub 1444}]{sup +} proposed in this work.more » The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N{sub 1444}]{sup +} as to [N{sub 1114}]{sup +} because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N{sub 1114}]{sup +} cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N{sub 1114}][NTf{sub 2}], whereas polar and non-polar structure factors are essentially the same in [N{sub 1444}][NTf{sub 2}]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids.« less

Volumetric and acoustical behaviour of sodium saccharin in aqueous system over temperature range (20.0-45.0)°C.

PubMed

Jamal, Muhammad Asghar; Rashad, Muhammad; Khosa, Muhammad Kaleem; Bhatti, Haq Nawaz

2015-04-15

Densities and ultrasonic velocity values for aqueous solutions of sodium saccharin (SS) has been measured as a function of concentration at 20.0-45.0 °C and atmospheric pressure using DSA-5000 M. The density and ultrasonic velocity values have been further used to calculate apparent molar volume, apparent specific volume, isentropic apparent molar compressibility and compressibility hydration numbers and reported. The values for apparent molar volume obtained at given temperatures showed negative deviations from Debye-Hückel limiting law and used as a direct measure of the ion-ion and ion-solvent interactions. The apparent specific volumes of the solute were calculated and it was found that these values of the investigated solutions lie on the borderline between the values reported for sweet substances. The sweetness response of the sweeteners is then explained in terms of their solution behaviours. Furthermore, the partial molar expansibility, its second derivative, (∂(2)V°/∂T(2)) as Hepler's constant and thermal expansion coefficient have been estimated. Copyright © 2014 Elsevier Ltd. All rights reserved.

Radiographic evaluation of bone regeneration after the application of plasma rich in growth factors in a lower third molar socket: a case report

PubMed Central

2009-01-01

A 42-year-old Mediterranean male presented complaining of inability to sustain good oral care at the posterior aspect of the lower right jaw. The main problems were food impaction in the area and the subsequent malodor. The patient reported remarkable medical history. Clinical examination revealed local erytherma with noticeable bone defect distal to the second molar with obvious defect in the mesial wall of the third molar; the penetration depth was found to be up to 6 mm. Radiological evaluation confirmed the defect and it was attributed to the mesioangularly partially impacted lower third molar. It was decided that third molar should be extracted and concentrate of the patient's growth factors (PRGF) to be applied into the bony defect to stimulate bone regeneration and promote healing. The third molar tooth was, then, removed surgically and the PRGF, which was prepared preoperatively, was implanted in the socket. At the first postoperative day, moderate pain was the main complaint and was controlled by NSAIDs. One week postoperatively, the sutures were removed and there was good tissue healing on examination. On the fiftieth postoperative day, radiographic evaluation took place and showed noticeable enhancement of density and radio-opacity in the third molar socket area, in comparison with the baseline image. Further, clinical examination showed significant reduction of periodontal pocketing and evidence of new bone formation. In conclusion, PRGF was very successful in stimulating bone regeneration and promote healing following dental extraction. PMID:20062651

Low severity coal conversion by ionic hydrogenation: Quarterly report, October--December 1988

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

Maioriello, J.; Larsen, J.W.

1988-12-31

A newly developed reaction system consisting of H/sub 2/O:BF/sub 3//H/sub 2//(CH/sub 3/CN)/sub 2/PtCl/sub 2/ was applied to the ionic hydrogenation of aromatic and functionalized aromatic compounds. Hydrogenations were carried out in this aqueous system at 50/degree/C and 500 psi H/sub 2/. Aryl ethers were hydrogenated and cleaved, yielding deoxygenated, fully saturated compounds as the major products. Reactions of nitrogen-containing aromatic compounds resulted in partial saturation of aromatic rings without cleavage of the C-N bonds. Aromatic and PNA compounds can be fully or partially hydrogenated depending on their structures. Aromatic thiols, sulfides and thiophenes poison the catalyst; the oxidized sulfur formsmore » (sulfonic acids, sulfones) were not reduced and did not poison the catalyst. It was found that certain aromatic compounds were easier to hydrogenate than others. Ionic hydrogenation of Wyodak cola using a H/sub 2/O:BF/sub 3//H/sub 2//(MeCN)/sub 2/PtCl/sub 2/ resulted in no significant increase in THF extractability (5.8--9.6% THF-extractables, wt) over that of the parent coal (4.6--6.7% THF-extractables, wt). Ionic hydrogenation of a demineralized Wyodak coal (1 M aq. citric acid, reflux 1 day) resulted in a slight increase in THF extractability (10.4%) over the untreated parent coal (5.6--5.8%). 4 refs., 1 fig., 1 tab.« less

Influence of hydrostatic pressure on dynamics and spatial distribution of protein partial molar volume: time-resolved surficial Kirkwood-Buff approach.

PubMed

Yu, Isseki; Tasaki, Tomohiro; Nakada, Kyoko; Nagaoka, Masataka

2010-09-30

The influence of hydrostatic pressure on the partial molar volume (PMV) of the protein apomyoglobin (AMb) was investigated by all-atom molecular dynamics (MD) simulations. Using the time-resolved Kirkwood-Buff (KB) approach, the dynamic behavior of the PMV was identified. The simulated time average value of the PMV and its reduction by 3000 bar pressurization correlated with experimental data. In addition, with the aid of the surficial KB integral method, we obtained the spatial distributions of the components of PMV to elucidate the detailed mechanism of the PMV reduction. New R-dependent PMV profiles identified the regions that increase or decrease the PMV under the high pressure condition. The results indicate that besides the hydration in the vicinity of the protein surface, the outer space of the first hydration layer also significantly influences the total PMV change. These results provide a direct and detailed picture of pressure induced PMV reduction.

Intrinsic alterations in the partial molar volume on the protein denaturation: surficial Kirkwood-Buff approach.

PubMed

Yu, Isseki; Takayanagi, Masayoshi; Nagaoka, Masataka

2009-03-19

The partial molar volume (PMV) of the protein chymotrypsin inhibitor 2 (CI2) was calculated by all-atom MD simulation. Denatured CI2 showed almost the same average PMV value as that of native CI2. This is consistent with the phenomenological question of the protein volume paradox. Furthermore, using the surficial Kirkwood-Buff approach, spatial distributions of PMV were analyzed as a function of the distance from the CI2 surface. The profiles of the new R-dependent PMV indicate that, in denatured CI2, the reduction in the solvent electrostatic interaction volume is canceled out mainly by an increment in thermal volume in the vicinity of its surface. In addition, the PMV of the denatured CI2 was found to increase in the region in which the number density of water atoms is minimum. These results provide a direct and detailed picture of the mechanism of the protein volume paradox suggested by Chalikian et al.

Studies on the phase diagram of Pb-Fe-O system and standard molar Gibbs energy of formation of 'PbFe5O8.5' and Pb2Fe2O5

NASA Astrophysics Data System (ADS)

Sahu, Sulata Kumari; Ganesan, Rajesh; Gnanasekaran, T.

2012-07-01

Partial phase diagram of Pb-Fe-O system has been established by phase equilibration studies over a wide temperature range coupled with high temperature solid electrolyte based emf cells. Ternary oxides are found to coexist with liquid lead only at temperatures above 900 K. At temperatures below 900 K, iron oxides coexist with liquid lead. Standard molar Gibbs energy of formation of ternary oxides 'PbFe5O8.5' and Pb2Fe2O5 were determined by measuring equilibrium oxygen partial pressures over relevant phase fields using emf cells and are given by the following expressions: ΔfGmo 'PbFeO'±1.0(kJ mol)=-2208.1+0.6677(T/K) (917⩽T/K⩽1117) ΔfGmo PbFeO±0.8(kJ mol)=-1178.4+0.3724(T/K) (1050⩽T/K⩽1131) .

Modeling the effects of pH and ionic strength on swelling of anionic polyelectrolyte gels

NASA Astrophysics Data System (ADS)

Drozdov, A. D.; deClaville Christiansen, J.

2015-07-01

A constitutive model is developed for the elastic response of an anionic polyelectrolyte gel under swelling in water with an arbitrary pH and an arbitrary molar fraction of dissolved monovalent salt. A gel is treated as a three-phase medium consisting of a solid phase (polymer network), solvent (water), and solute (mobile ions). Transport of solvent and solute is thought of as their diffusion through the polymer network accelerated by an electric field formed by mobile and fixed ions and accompanied by chemical reactions (dissociation of functional groups attached to polymer chains and formation of ion pairs between bound charges and mobile counter-ions). Constitutive equations are derived by means of the free energy imbalance inequality for an arbitrary three-dimensional deformation with finite strains. These relations are applied to analyze equilibrium swelling diagrams on poly(acrylic acid) gel, poly(methacrylic acid) gel, and three composite hydrogels under water uptake in a bath (i) with a fixed molar fraction of salt and varied pH, and (ii) with a fixed pH and varied molar fraction of salt. To validate the ability of the model to predict observations quantitatively, material constants are found by matching swelling curves under one type of experimental conditions and results of simulation are compared with experimental data in the other type of tests.

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

PubMed

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

2015-04-21

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

Raman Line Imaging of Poly(ε-caprolactone)/Carbon Dioxide Solutions at High Pressures: A Combined Experimental and Computational Study for Interpreting Intermolecular Interactions and Free-Volume Effects.

PubMed

Pastore Carbone, Maria Giovanna; Musto, Pellegrino; Pannico, Marianna; Braeuer, Andreas; Scherillo, Giuseppe; Mensitieri, Giuseppe; Di Maio, Ernesto

2016-09-01

In the present study, a Raman line-imaging setup was employed to monitor in situ the CO2 sorption at elevated pressures (from 0.62 to 7.10 MPa) in molten PCL. The method allowed the quantitative measurement of gas concentration in both the time-resolved and the space-resolved modes. The combined experimental and theoretical approach allowed a molecular level characterization of the system. The dissolved CO2 was found to occupy a volume essentially coincident with its van der Waals volume and the estimated partial molar volume of the probe did not change with pressure. Lewis acid-Lewis base interactions with the PCL carbonyls was confirmed to be the main interaction mechanism. The geometry of the supramolecular complex and the preferential interaction site were controlled more by steric than electronic effects. On the basis of the indications emerging from Raman spectroscopy, an equation of state thermodynamic model for the PCL-CO2 system, based upon a compressible lattice fluid theory endowed with specific interactions, has been tailored to account for the interaction types detected spectroscopically. The predictions of the thermodynamic model in terms of molar volume of solution have been compared with available volumetric measurements while predictions for CO2 partial molar volume have been compared with the values estimated on the basis of Raman spectroscopy.

Influence of posterior dental arch length on brain activity during chewing in patients with mandibular distal extension removable partial dentures.

PubMed

Shoi, K; Fueki, K; Usui, N; Taira, M; Wakabayashi, N

2014-07-01

It is well known that shortened dental arch decreases masticatory function. However, its potential to change brain activity during mastication is unknown. The present study investigates the effect of a shortened posterior dental arch with mandibular removable partial dentures (RPDs) on brain activity during gum chewing. Eleven subjects with missing mandibular molars (mean age, 66.1 years) on both sides received experimental RPDs with interchangeable artificial molars in a crossover trial design. Brain activity during gum chewing with RPDs containing (full dental arch) and lacking artificial molars (shortened dental arch) was measured using functional magnetic resonance imaging. Additionally, masticatory function was evaluated for each dental arch type. Food comminuting and mixing ability and the perceived chewing ability were significantly lower in subjects with a shortened dental arch than those with a full dental arch (P < 0.05). Brain activation during gum chewing with the full dental arch occurred in the middle frontal gyrus, primary sensorimotor cortex extending to the pre-central gyrus, supplementary motor area, putamen, insula and cerebellum. However, middle frontal gyrus activation was not observed during gum chewing with the shortened dental arch. These results suggest that shortened dental arch affects human brain activity in the middle frontal gyrus during gum chewing, and the decreased middle frontal gyrus activation may be associated with decreased masticatory function. © 2014 John Wiley & Sons Ltd.

Polystyrene-block-Poly(ionic liquid) Copolymers as Work Function Modifiers in Inverted Organic Photovoltaic Cells.

PubMed

Park, Jong Baek; Isik, Mehmet; Park, Hea Jung; Jung, In Hwan; Mecerreyes, David; Hwang, Do-Hoon

2018-02-07

Interfacial layers play a critical role in building up the Ohmic contact between electrodes and functional layers in organic photovoltaic (OPV) solar cells. These layers are based on either inorganic oxides (ZnO and TiO 2 ) or water-soluble organic polymers such as poly[(9,9-dioctyl-2,7-fluorene)-alt-(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)] and polyethylenimine ethoxylated (PEIE). In this work, we have developed a series of novel poly(ionic liquid) nonconjugated block copolymers for improving the performance of inverted OPV cells by using them as work function modifiers of the indium tin oxide (ITO) cathode. Four nonconjugated polyelectrolytes (n-CPEs) based on polystyrene and imidazolium poly(ionic liquid) (PSImCl) were synthesized by reversible addition-fragmentation chain transfer polymerization. The ratio of hydrophobic/hydrophilic block copolymers was varied depending on the ratio of polystyrene to the PSImCl block. The ionic density, which controls the work function of the electrode by forming an interfacial dipole between the electrode and the block copolymers, was easily tuned by simply changing the PSImCl molar ratio. The inverted OPV device with the ITO/PS 29 -b-PSImCl 60 cathode achieved the best power conversion efficiency (PCE) of 7.55% among the synthesized block copolymers, exhibiting an even higher PCE than that of the reference OPV device with PEIE (7.30%). Furthermore, the surface properties of the block copolymers films were investigated by contact angle measurements to explore the influence of the controlled hydrophobic/hydrophilic characters on the device performances.

Guggenheim's rule and the enthalpy of vaporization of simple and polar fluids, molten salts, and room temperature ionic liquids.

PubMed

Weiss, Volker C

2010-07-22

One of Guggenheim's many corresponding-states rules for simple fluids implies that the molar enthalpy of vaporization (determined at the temperature at which the pressure reaches 1/50th of its critical value, which approximately coincides with the normal boiling point) divided by the critical temperature has a value of roughly 5.2R, where R is the universal gas constant. For more complex fluids, such as strongly polar and ionic fluids, one must expect deviations from Guggenheim's rule. Such a deviation has far-reaching consequences for other empirical rules related to the vaporization of fluids, namely Guldberg's rule and Trouton's rule. We evaluate these characteristic quantities for simple fluids, polar fluids, hydrogen-bonding fluids, simple inorganic molten salts, and room temperature ionic liquids (RTILs). For the ionic fluids, the critical parameters are not accessible to direct experimental observation; therefore, suitable extrapolation schemes have to be applied. For the RTILs [1-n-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides, where the alkyl chain is ethyl, butyl, hexyl, or octyl], the critical temperature is estimated by extrapolating the surface tension to zero using Guggenheim's and Eotvos' rules; the critical density is obtained using the linear-diameter rule. It is shown that the RTILs adhere to Guggenheim's master curve for the reduced surface tension of simple and moderately polar fluids, but that they deviate significantly from his rule for the reduced enthalpy of vaporization of simple fluids. Consequences for evaluating the Trouton constant of RTILs, the value of which has been discussed controversially in the literature, are indicated.

Hydrogen bonding in ionic liquids.

PubMed

Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

2015-03-07

Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak through to very strong H-bonds.

Measuring and predicting Delta(vap)H298 values of ionic liquids.

PubMed

Deyko, Alexey; Lovelock, Kevin R J; Corfield, Jo-Anne; Taylor, Alasdair W; Gooden, Peter N; Villar-Garcia, Ignacio J; Licence, Peter; Jones, Robert G; Krasovskiy, Vladimir G; Chernikova, Elena A; Kustov, Leonid M

2009-10-14

We report the enthalpies of vaporisation (measured using temperature programmed desorption by mass spectrometry) of twelve ionic liquids (ILs), covering four imidazolium, [C(m)C(n)Im]+, five pyrrolidinium, [C(n)C(m)Pyrr]+, two pyridinium, [C(n)Py]+, and a dication, [C3(C1Im)2]2+ based IL. These cations were paired with a range of anions: [BF4]-, [FeCl4]-, [N(CN)2]-, [PF3(C2F5)3]- ([FAP]-), [(CF3SO2)2N]- ([Tf2N]-) and [SCN]-. Using these results, plus those for a further eight imidazolium based ILs published earlier (which include the anions [CF3SO3]- ([TfO]-), [PF6]- and [EtSO4]-), we show that the enthalpies of vaporisation can be decomposed into three components. The first component is the Coulombic interaction between the ions, DeltaU(Cou,R), which is a function of the IL molar volume, V(m), and a parameter R(r) which quantifies the relative change in anion-cation distance on evaporation from the liquid phase to the ion pair in the gas phase. The second and third components are the van der Waals contributions from the anion, DeltaH(vdw,A), and the cation, DeltaH(vdw,C). We derive a universal value for R(r), and individual values of DeltaH(vdw,A) and DeltaH(vdw,C) for each of the anions and cations considered in this study. Given the molar volume, it is possible to estimate the enthalpies of vaporisation of ILs composed of any combination of the ions considered here; values for fourteen ILs which have not yet been studied experimentally are given.

Mechanically Tunable, Readily Processable Ion Gels by Self-Assembly of Block Copolymers in Ionic Liquids.

PubMed

Lodge, Timothy P; Ueki, Takeshi

2016-01-01

Room temperature ionic liquids are of great interest for many advanced applications, due to the combination of attractive physical properties with essentially unlimited tunability of chemical structure. High chemical and thermal stability, favorable ionic conductivity, and complete nonvolatility are just some of the most important physical characteristics that make ionic liquids promising candidates for emerging technologies. Examples include separation membranes, actuators, polymer gel electrolytes, supercapacitors, ion batteries, fuel cell membranes, sensors, printable plastic electronics, and flexible displays. However, in these and other applications, it is essential to solidify the ionic liquid, while retaining the liquid state properties of interest. A broadly applicable solidification strategy relies on gelation by addition of suitable triblock copolymers with the ABA architecture, producing ion gels or ionogels. In this paradigm, the A end blocks are immiscible with the ionic liquid, and consequently self-assemble into micellar cores, while some fraction of the well-solvated B midblocks bridge between micelles, forming a percolating network. The chemical structures of the A and B repeat units, the molar mass of the blocks, and the concentration of the copolymer in the ionic liquid are all independently tunable to attain desired property combinations. In particular, the modulus of the resulting ion gel can be readily varied between 100 Pa and 1 MPa, with little sacrifice of the transport properties of the ionic liquid, such as ionic conductivity or gas diffusivity. Suitable A blocks can impart thermoreversible gelation (with solidification either on heating or cooling) or even photoreversible gelation. By virtue of the nonvolatility of ionic liquids, a wide range of processing strategies can be employed directly to prepare ion gels in thin or thick film forms, including solvent casting, spin coating, aerosol jet printing, photopatterning, and transfer printing. For higher modulus ion gels it is even possible to employ a manual "cut and stick" strategy for easy device fabrication. Ion gels prepared from common triblock copolymers, for example, with A = polystyrene and B = poly(ethylene oxide) or poly(methyl methacrylate), in imidazolium based ionic liquids provide exceptional performance in membranes for separating CO 2 from N 2 or CH 4 . The same materials also are the best available gate dielectrics for printed plastic electronics, because their high capacitance endows organic transistors with milliamp output currents for sub-1 V applied bias, with switching speeds that can go well beyond 100 kHz, while being amenable to large area roll-to-roll printing. Incorporation of well-designed electroluminescent (e.g., Ru(bpy) 3 -based) or electrochromic (e.g., viologen-based) moieties into ion gels held between transparent electrodes yields flexible color displays operating with sub-1 V dc inputs.

Synthesis of Mixed Cu/Ce Oxide Nanoparticles by the Oil-in-Water Microemulsion Reaction Method.

PubMed

Pemartin-Biernath, Kelly; Vela-González, Andrea V; Moreno-Trejo, Maira B; Leyva-Porras, César; Castañeda-Reyna, Iván E; Juárez-Ramírez, Isaías; Solans, Conxita; Sánchez-Domínguez, Margarita

2016-06-16

Cerium oxide and mixed Cu/Ce oxide nanoparticles were prepared by the oil-in-water (O/W) microemulsion reaction method in mild conditions. The Cu/Ce molar ratio was varied between 0/100 and 50/50. According to X-ray diffraction (XRD), below 30/70 Cu/Ce molar ratio, the materials presented a single phase consistent with cubic fluorite CeO₂. However, above Cu/Ce molar ratio 30/70, an excess monoclinic CuO phase in coexistence with the predominant Cu/Ce mixed oxide was detected by XRD and High-Resolution Transmission Electron Microscopy (HRTEM). Raman spectroscopy showed that oxygen vacancies increased significantly as the Cu content was increased. Band gap ( E g ) was investigated as a function of the Cu/Ce molar ratio, resulting in values from 2.91 eV for CeO₂ to 2.32 eV for the mixed oxide with 30/70 Cu/Ce molar ratio. These results indicate that below 30/70 Cu/Ce molar ratio, Cu 2+ is at least partially incorporated into the ceria lattice and very well dispersed in general. In addition, the photodegradation of Indigo Carmine dye under visible light irradiation was explored for selected samples; it was shown that these materials can remove such contaminants, either by adsorption and/or photodegradation. The results obtained will encourage investigation into the optical and photocatalytic properties of these mixed oxides, for widening their potential applications.

Synthesis of Mixed Cu/Ce Oxide Nanoparticles by the Oil-in-Water Microemulsion Reaction Method

PubMed Central

Pemartin-Biernath, Kelly; Vela-González, Andrea V.; Moreno-Trejo, Maira B.; Leyva-Porras, César; Castañeda-Reyna, Iván E.; Juárez-Ramírez, Isaías; Solans, Conxita; Sánchez-Domínguez, Margarita

2016-01-01

Cerium oxide and mixed Cu/Ce oxide nanoparticles were prepared by the oil-in-water (O/W) microemulsion reaction method in mild conditions. The Cu/Ce molar ratio was varied between 0/100 and 50/50. According to X-ray diffraction (XRD), below 30/70 Cu/Ce molar ratio, the materials presented a single phase consistent with cubic fluorite CeO2. However, above Cu/Ce molar ratio 30/70, an excess monoclinic CuO phase in coexistence with the predominant Cu/Ce mixed oxide was detected by XRD and High-Resolution Transmission Electron Microscopy (HRTEM). Raman spectroscopy showed that oxygen vacancies increased significantly as the Cu content was increased. Band gap (Eg) was investigated as a function of the Cu/Ce molar ratio, resulting in values from 2.91 eV for CeO2 to 2.32 eV for the mixed oxide with 30/70 Cu/Ce molar ratio. These results indicate that below 30/70 Cu/Ce molar ratio, Cu2+ is at least partially incorporated into the ceria lattice and very well dispersed in general. In addition, the photodegradation of Indigo Carmine dye under visible light irradiation was explored for selected samples; it was shown that these materials can remove such contaminants, either by adsorption and/or photodegradation. The results obtained will encourage investigation into the optical and photocatalytic properties of these mixed oxides, for widening their potential applications. PMID:28773602

Properties of an ionic liquid-tolerant Bacillus amyloliquefaciens CMW1 and its extracellular protease.

PubMed

Kurata, Atsushi; Senoo, Humiya; Ikeda, Yasuyuki; Kaida, Hideaki; Matsuhara, Chiaki; Kishimoto, Noriaki

2016-07-01

An ionic liquid-tolerant bacterium, Bacillus amyloliquefaciens CMW1, was isolated from a Japanese fermented soybean paste. Strain CMW1 grew in the presence of 10 % (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), a commonly used ionic liquid. Additionally, strain CMW1 grew adequately in the presence of the hydrophilic ionic liquids 10 % (v/v) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate ([EMIM]CF3SO3) or 2.5 % (v/v) 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([BMIM]CF3SO3). Strain CMW1 produced an extracellular protease (BapIL) in the culture medium. BapIL was stable in the presence of 80 % (v/v) ionic liquids, [EMIM]CF3SO3, [BMIM]Cl, [BMIM]CF3SO3, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium hexafluorophosphate, and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and functioned in 10 % (v/v) these ionic liquids. BapIL was stable at pH 4.0-12.6 or in 4004 mM NaCl solution, and exhibited activity in the presence of 50 % (v/v) hydrophilic or hydrophobic organic solvents. BapIL was completely inhibited by 1 mM PMSF and partially by 5 mM EDTA. BapIL belongs to the true subtilisins according to analysis of the deduced amino acid sequence. We showed that BapIL from the ionic liquid-tolerant B. amyloliquefaciens CMW1 exhibited tolerance to ionic liquid and halo, alkaline, and organic solvents.

Clinical study of Mineral Trioxide Aggregate in primary molars. Comparison between Grey and White MTA--a long term follow-up (84 months).

PubMed

Cardoso-Silva, Cristina; Barbería, Elena; Maroto, Myriam; García-Godoy, Franklin

2011-02-01

The aim of the present study was to conduct a clinical and radiographic long-term evaluation of pulpotomy in temporary molars performed with Grey and White Mineral Trioxide Aggregate (MTA) and compare the results of Grey and White MTA pulpotomies in a sample of 233 primary molars with a maximum follow-up period of 84 months. The sample was selected from patients treated at the Department of Pediatric Dentistry, Faculty of Dentistry, Complutense University of Madrid, Spain. This prospective study included first and second primary molars treated with pulpotomy with Grey or White MTA, controlled for a maximum follow-up period of 84 months. Statistical analysis of clinical and radiographic findings was completed using ANOVA (P<0.05). Follow-up evaluations, performed every 6 months, revealed that only 2 molars treated with White MTA presented abscess and pathological mobility. Radiographic examination of the 210 molars revealed unfavourable pulp response in only 6 molars (internal or furcation root resorption), without statistically significant differences between Grey and White MTA. Two radiological findings were noticed: dentine bridge formation and partial or total root canal stenosis. Grey MTA induced a higher percentage of dentine bridges with statistically significant differences (P<0.05), and a higher percentage of pulp canal stenosis, without a statistically significant difference. Grey and White MTA presented high levels of clinical and radiographic success. Although the present study showed evidence of a very good biologic response with both types of MTA, Grey MTA showed significantly higher number of dentine bridge formation than White MTA. Copyright © 2010 Elsevier Ltd. All rights reserved.

Label-free biosensing with functionalized nanopipette probes.

PubMed

Umehara, Senkei; Karhanek, Miloslav; Davis, Ronald W; Pourmand, Nader

2009-03-24

Nanopipette technology can uniquely identify biomolecules such as proteins based on differences in size, shape, and electrical charge. These differences are determined by the detection of changes in ionic current as the proteins interact with the nanopipette tip coated with probe molecules. Here we show that electrostatic, biotin-streptavidin, and antibody-antigen interactions on the nanopipette tip surface affect ionic current flowing through a 50-nm pore. Highly charged polymers interacting with the glass surface modulated the rectification property of the nanopipette electrode. Affinity-based binding between the probes tethered to the surface and their target proteins caused a change in the ionic current due to a partial blockade or an altered surface charge. These findings suggest that nanopipettes functionalized with appropriate molecular recognition elements can be used as nanosensors in biomedical and biological research.

Impact of the lower third molar presence and position on the fragility of mandibular angle and condyle: A Three-dimensional finite element study.

PubMed

Antic, Svetlana; Vukicevic, Arso M; Milasinovic, Marko; Saveljic, Igor; Jovicic, Gordana; Filipovic, Nenad; Rakocevic, Zoran; Djuric, Marija

2015-07-01

The aim of the present study was to investigate the influences of the presence and position of a lower third molar (M3) on the fragility of mandibular angle and condyle, using finite element analysis. From computed tomographic scans of a human mandible with normally erupted M3, two additional virtual models were generated: a mandibular model with partially impacted M3 and a model without M3. Two cases of impact were considered: a frontal and a lateral blow. The results are based on the chromatic analysis of the distributed von Mises and principal stresses, and calculation of their failure indices. In the frontal blow, the angle region showed the highest stress in the case with partially impacted M3, and the condylar region in the case without M3. Compressive stresses were dominant but caused no failure. Tensile stresses were recorded in the retromolar areas, but caused failure only in the case with partially impacted M3. In the lateral blow, the stress concentrated at the point of impact, in the ipsilateral and contralateral angle and condylar regions. The highest stresses were recorded in the case with partially impacted M3. Tensile stresses caused the failure on the ipsilateral side, whereas compressive stresses on the contralateral side. Copyright © 2015 European Association for Cranio-Maxillo-Facial Surgery. Published by Elsevier Ltd. All rights reserved.

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

PubMed

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

2018-05-10

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

Evaporation Study of an Ionic Liquid with a Double-Charged Cation.

PubMed

Chilingarov, Norbert S; Zhirov, Maksim S; Shmykova, Anna M; Martynova, Ekaterina A; Glukhov, Lev M; Chernikova, Elena A; Kustov, Leonid M; Markov, Vitaliy Yu; Ioutsi, Vitaliy A; Sidorov, Lev N

2018-05-07

The evaporation of a dicationic ionic liquid, 1,3-bis(3-methylimidazolium-1-yl)propane bis(trifluoromethanesulfonyl)amide ([C 3 (MIm) 2 2+ ][Tf 2 N - ] 2 ), was studied by Knudsen effusion mass spectrometry. Its evaporation is accompanied by a partial thermal decomposition producing monocationic ionic liquids, 1,3-dimethylimidazolium and 1-(2-propenyl)-3-methylimidazolium bis(trifluoromethanesulfonyl)amides, as volatile products. This decomposition does not affect the vaporization characteristics of [C 3 (MIm) 2 2+ ][Tf 2 N - ] 2 , which were established to be as follows. The vaporization enthalpy (550 K) is equal to (155.5 ± 3.2) kJ·mol -1 ; the saturated vapor pressure is described by the equation ln( p/Pa) = -(18699 ± 381)/( T/K) + (30.21 ± 0.82) in the range of 508-583 K. 1,3-Bis(3-methylimidazolium-1-yl)propane bis(trifluoromethanesulfonyl)amide is the first dicationic ionic liquid, the vaporization characteristics of which were determined with an acceptable accuracy.

Studying of drug solubility in water and alcohols using drug-ammonium ionic liquid-compounds.

PubMed

Halayqa, Mohammad; Pobudkowska, Aneta; Domańska, Urszula; Zawadzki, Maciej

2018-01-01

Synthesis of three mefenamic acid (MEF) derivatives - ionic liquid compounds composed of MEF in an anionic form and ammonium cation (choline, MEF1), or {di(2-hydroxyethyl)dimethyl ammonium (MEF2)}, or {tri(2-hydroxyethyl)methyl ammonium compound (MEF3)} is presented. The basic thermal properties of pure compounds i.e. fusion temperatures, and the enthalpy of fusion of these compounds have been measured with differential scanning microcalorimetry technique (DSC). Molar volumes have been calculated with the Barton group contribution method. The solubilities of MEF1, MEF2 and MEF3 using the dynamic method were measured at constant pH in a range of temperature from (290 to 370) K in three solvents: water, ethanol and 1-octanol. The experimental solubility data have been correlated by means of three commonly known G E equations: the Wilson, NRTL and UNIQUAC with the assumption that the systems studied here present simple eutectic behaviour. The activity coefficients of pharmaceuticals at saturated solutions in each binary mixture were calculated from the experimental data. The formation of MEF-ionic liquid compounds greatly increases the solubility in water in comparison with pure MEF or complexes with 2-hydroxypropyl-β-cyclodextrin. The development of these compounds formulations will assist in medication taking into account oral solid or gel medicines. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and characterization of Ag+ ion conducting glassy electrolytes

NASA Astrophysics Data System (ADS)

Chandra, Angesh; Bhatt, Alok; Chandra, Archana

2013-07-01

Synthesis and characterization of new Ag+ ion conducting glassy systems: x[0.75AgI:0.25AgC1]: (1 - x)[Ag2O:P2O5], where 0.1 < x < 1 in molar weight fraction, are reported. The present glassy electrolytes have been synthesized by melt-quench technique using a high-speed twin roller-quencher. An alternate host salt: "quenched [0.75AgI:0.25AgC1] mixed system/solid solution", has been used in place of the traditional host AgI. The compositional dependence conductivity studies on the glassy systems: x[0.75AgI:0.25AgC1]:(1 - x)[Ag2O:P2O5] as well as xAgI:(1 - x)[Ag2O:P2O5] prepared identically, indicated that the composition at x = 0.75 exhibited the highest room temperature conductivity (σ ~ 5.5 x 10-3 S cm-1). The composition: 0.75[0.75AgI:0.25AgC1]:0.25[Ag2O:P2O5] has been referred to as optimum conducting composition (OCC). The some basic ion transport parameters viz. ionic conductivity (σ), ionic mobility (μ), mobile ion concentration (n), ionic drift velocity (vd), ion transference number (tion) and activation energy (Ea) values have been characterized with the help of various experimental techniques. A solid state battery was fabricated and its basic cell parameters calculated.

Divergent trend in density versus viscosity of ionic liquid/water mixtures: a molecular view from guanidinium ionic liquids.

PubMed

Singh, Akhil Pratap; Gardas, Ramesh L; Senapati, Sanjib

2015-10-14

Ionic liquids (ILs) have shown great potential in the dissolution and stability of biomolecules when a low-to-moderate quantity of water is added. Hence, determining the thermophysical properties and understanding these novel mixtures at the molecular level are of both fundamental and practical importance. In this context, here we report the synthesis of two nontoxic guanidinium cation based ILs, tetramethylguanidinium benzoate [TMG][BEN] and tetramethylguanidinium salicylate [TMG][SAL], and present a detailed comparison of their thermophysical properties in the presence of water. The results show that the [TMG][SAL]/water mixtures have higher density and higher apparent molar volume, but a lower viscosity and higher compressibility than the [TNG][BEN]/water mixtures. The measured viscosity and compressibility data are explained from ab initio quantum mechanical calculations and liquid-phase molecular dynamics simulations, where salicylate anions of denser [TMG][SAL]/water were found to exist as isolated ions due to intramolecular H-bonding. On the contrary, intermolecular H-bonding among the benzoate anions and their strong tendency to form an extended H-bonding network with water made [TMG][BEN]/water solutions more viscous and less compressible. This study shows the importance of probing these emerging solvents at the molecular-to-atomic level, which could be helpful in their optimal usage for task-specific applications.

Study on aggregation behavior of Cytochrome C-conjugated silver nanoparticles using asymmetrical flow field-flow fractionation.

PubMed

Kim, Sun Tae; Lee, Yong-Ju; Hwang, Yu-Sik; Lee, Seungho

2015-01-01

In this study, 40 nm silver nanoparticles (AgNPs) were synthesized using the citrate reduction method and then the surface of AgNPs was modified by conjugating Cytochrome C (Cyto C) to improve stability and to enhance bioactivity and biocompatibility of AgNPs. It is known that Cyto C may undergo conformational changes under various conditions of pH, temperature, ionic strength, etc., resulting in aggregation of the particles. These parameters also affect the size and size distribution of Cyto C-conjugated AgNPs (Cyto C-AgNP). ζ-potential measurement revealed that the adsorption of Cyto C on the surface of AgNPs is saturated at the molar ratio [Cyto C]/[AgNPs] above about 300. Asymmetrical flow field-flow fractionation (AsFlFFF) analysis showed that hydrodynamic diameter of AgNPs increases by about 4 nm when the particle is saturated by Cyto C. The aggregation behavior of Cyto C-AgNP at various conditions of pH, temperature and ionic strength were investigated using AsFlFFF and UV-vis spectroscopy. It was found that the aggregation of Cyto C-AgNP increases with decreasing pH, increasing temperature and ionic strength due to denaturation of Cyto C on AgNPs and reduction in the thickness of electrostatic double layer on the surface of Cyto C-AgNP. Copyright © 2014 Elsevier B.V. All rights reserved.

Results from the Heavy Ions In Space (HIIS) experiment on the ionic charge state of solar energetic particles

NASA Technical Reports Server (NTRS)

Tylka, Allan J.; Boberg, Paul R.; Adams, James H., Jr.; Beahm, Lorraine P.; Kleis, Thomas

1995-01-01

It has long been known that low-energy solar energetic particles (SEP's) are partially-ionized. For example, in large, so-called 'gradual' solar energetic particle events, at approximately 1 MeV/nucleon the measured mean ionic charge state, Q, of Fe ions is 14.1 +/- 0.2, corresponding to a plasma temperature of approximately 2 MK in the coronal or solar-wind source material. Recent studies, which have greatly clarified the origin of solar energetic particles and their relation to solar flares, suggest that ions in these SEP events are accelerated not at a flare site, but by shocks propagating through relatively low-density regions in the interplanetary medium. As a result, the partially-ionized states observed at low energies are expected to continue to higher energies. However, up to now there have been no high-energy measurements of ionic charge states to confirm this notion. We report here HIIS observations of Fe-group ions at 50-600 MeV/nucleon, at energies and fluences which cannot be explained by fully-ionized galactic cosmic rays, even in the presence of severe geomagnetic cutoff suppression. Above approximately 200 MeV/nucleon, all features of our data -- fluence, energy spectrum, elemental composition, and arrival directions -- can be explained by the large SEP events of October 1989, provided that the mean ionic charge state at these high energies is comparable to the measured value at approximately 1 MeV/nucleon. By comparing the HIIS observations with measurements in interplanetary space in October 1989, we determine the mean ionic charge state of SEP Fe ions at approximately 200-600 MeV/nucleon to be Q = 13.4 plus or minus 1.0, in good agreement with the observed value at approximately 1 MeV/nucleon. The source of the ions below approximately 200 MeV/nucleon is not yet clear. Partially-ionized ions are less effectively deflected by the Earth's magnetic field than fully-ionized cosmic rays and therefore have greatly enhanced access to low-Earth orbit. Moreover, at the high energies observed in HIIS, these ions can penetrate typical amounts of shielding. We discuss the significance of the HIIS results for estimates of the radiation hazard posed by large SEP events to satellites in low-Earth orbit, including the proposed Space Station orbit. Finally, we comment on previous reports of low-energy below-cutoff Fe-group ions, which some authors have interpreted as evidence for partially-ionized galactic cosmic rays. The LDEF flux levels are much smaller than the corresponding fluxes in these previous reports, implying that the source of these ions has an unusual solar-cycle variation and/or strongly increases with decreasing altitude.

The Partial Molar Volume and Thermal Expansivity of Fe2O3 in Alkali Silicate Liquids: Evidence for the Average Coordination of Fe3+

NASA Astrophysics Data System (ADS)

Liu, Q.; Lange, R.

2003-12-01

Ferric iron is an important component in magmatic liquids, especially in those formed at subduction zones. Although it has long been known that Fe3+ occurs in four-, five- and six-fold coordination in crystalline compounds, only recently have all three Fe3+ coordination sites been confirmed in silicate glasses utilizing XANES spectroscopy at the Fe K-edge (Farges et al., 2003). Because the density of a magmatic liquid is largely determined by the geometrical packing of its network-forming cations (e.g., Si4+, Al3+, Ti4+, and Fe3+), the capacity of Fe3+ to undergo composition-induced coordination change affects the partial molar volume of the Fe2O3 component, which must be known to calculate how the ferric-ferrous ratio in magmatic liquids changes with pressure. Previous work has shown that the partial molar volume of Fe2O3 (VFe2O3) varies between calcic vs. sodic silicate melts (Mo et al., 1982; Dingwell and Brearley, 1988; Dingwell et al., 1988). The purpose of this study is to extend the data set in order to search for systematic variations in VFe2O3 with melt composition. High temperature (867-1534° C) density measurements were performed on eleven liquids in the Na2O-Fe2O3-FeO-SiO2 (NFS) system and five liquids in the K2O-Fe2O3-FeO-SiO2 (KFS) system using Pt double-bob Archimedean method. The ferric-ferrous ratio in the sodic and potassic liquids at each temperature of density measurement were calculated from the experimentally calibrated models of Lange and Carmichael (1989) and Tangeman et al. (2001) respectively. Compositions range (in mol%) from 4-18 Fe2O3, 0-3 FeO, 12-39 Na2O, 25-37 K2O, and 43-78 SiO2. Our density data are consistent with those of Dingwell et al. (1988) on similar sodic liquids. Our results indicate that for all five KFS liquids and for eight of eleven NFS liquids, the partial molar volume of the Fe2O3 component is a constant (41.57 ñ 0.14 cm3/mol) and exhibits zero thermal expansivity (similar to that for the SiO2 component). This value was obtained in a fit to a linear volume equation in which the other oxide components have the following fitted partial molar volumes (cm3/mol) at 1100° C: SiO2 = 26.85+/-0.04, Na2O = 26.57+/-0.07, K2O = 42.34+/-0.10, and FeO = 12.84+/-0.28, and the following fitted fitted partial molar thermal expansivities (10-3 cm3/mol-K): Na2O = 7.73+/-0.12, K2O = 11.99+/-0.24, and FeO = 2.88+/-1.22. For the three sodic liquids not included in this regression, the most iron-rich (18.2 mol% Fe2O3) has a value for VFe2O3 of 44.1 cm3/mole, whereas the most iron-poor (4.4 mol% Fe2O3) has a value for VFe2O3 of 37.0 cm3/mole. This trend may reflect a greater proportion of four-fold ferric iron in iron-rich liquids, which mirrors the trend of increasing ferric-ferrous ratios in sodic liquids as a function of total iron content (Lange and Carmichael, 1989). The most polymerized liquid in our data set was a sodic liquid that has a value for VFe2O3 of 45.0 cm3/mole. It thus appears that most (13 of 16) of our experimental liquids, which span a wide compositional range, lead to a VFe2O3 (41.6 cm3/mol) which is constant with composition and temperature. However, there are three important outliers that may have implications for the appropriate value to apply to magmatic liquids.

Volume of reaction by the Archibald ultracentrifuge method (lobster hemocyanin).

PubMed

Saxena, V P; Kegeles, G; Kikas, R

1976-07-01

Samples of lobster hemocyanin (Homarus americanus) under conditions of reversible reaction between whole (25 S) and half (17 S) molecules have been subjected to accurately known nitrogen pressures in analytical ultracentrifuge cells. A modified pressurization chamber of the type developed by Schumaker and colleagues has been constructed for this purpose. The molecular weight was then determined at the top (liquid-gas) meniscus, by means of the Archibald method. The logarithmic dependence upon pressure of the derived equilibrium constant then gave directly the volume of reaction. Experiments were performed in veronal-citrate buffers at pH 8, where the molar volume of formation of whole (dodecameric) molecules from half molecules appears to be negative, and at pH 8.46 in veronal-citrate buffer in the presence of 0.003 molar free calcium ion, where the molar volume of formation was estimated to be + 390 cm3/mole. In glycine-sodium hydroxide buffer at pH 9.6 containing 0.0047 molar free calcium, the molar volume of formation of whole molecules was estimated to be +120 +/- 70 cm3, corresponding to an estimated difference in partial specific volume between whole molecules and half molecules of only 1.3 (10)-4cm3/gram. The correctness of the sign of this value in glycine buffer has been verified by pressure-jump light-scattering experiments.

Disaggregation of adenylate cyclase during polyacrylamide-gel electrophoresis in mixtures of ionic and non-ionic detergents.

PubMed

Newby, A C; Chrambach, A

1979-02-01

1. Adenylate cyclase [ATP pyrophosphate-lyase (cyclizing), EC 4.6.1.1] solubilized from the rat liver plasma membrane with 1% Lubrol PX and partially purified by gel filtration in buffer containing 0.01% Lubrol PX was physically characterized by polyacrylamide-gel electrophoresis. 2. The molecular radius determined for the partially purified enzyme was 4.9nm, compared with the value of 3.9nm obtained for the enzyme before gel filtration. 3. This difference, representing an approximate doubling of the molecular volume of the enzyme, implied that aggregation with itself or other proteins had occurred during partial purification. 4. Aggregation was not reversed by electrophoresis in the presence of high Lubrol concentrations. 5. Substitution of deoxycholate or N-dodecylsarcosinate for Lubrol PX either for solubilization or during electrophoresis led to poorer resolution of membrane proteins at concentrations giving greater than 70% loss of enzyme activity. 6. Partially purified adenylate cyclase was electrophoresed in the presence of mixed micelles of Lubrol PX and deoxycholate or Lubrol PX and N-dodecylsarcosinate. Different mixtures were examined simultaneously in a suitable apparatus. 7. Electrophoresis in the presence of 0.1% Lubrol plus 0.03% deoxycholate decreased the molecular radius of the cyclase to 4.0nm, with greater than 90% recovery of enzymic activity. The net charge of the enzyme was also increased, indicating ionic detergent binding. 8. With 0.1% Lubrol plus 0.03% N-dodecylsarcosinate the molecular radius was 4.3nm, recovery approx. 50% and net charge similar to that seen in Lubrol plus deoxycholate. 9. The resolution of cyclase from bulk protein, on an analytical scale, was improved in the presence of detergent mixtures, as compared with resolution in Lubrol alone. 10. The results demonstrate the usefulness of polyacrylamide-gel electrophoresis to detect and overcome aggregation problems with membrane proteins and suggest that detergent mixtures in specific ratios may be useful in the purification of adenylate cyclase and other intrinsic membrane proteins.

Interaction of the dietary pigment curcumin with hemoglobin: energetics of the complexation.

PubMed

Basu, Anirban; Kumar, Gopinatha Suresh

2014-08-01

Thermodynamics of the interaction of the chemotherapeutic and chemopreventive dietary pigment, curcumin, with hemoglobin was studied by isothermal titration calorimetry. The binding was characterized to be exothermic. At 293.15 K, the equilibrium constant for curcumin-Hb complexation was found to be (4.88 ± 0.06) × 10(5) M(-1). The binding stoichiometry was calculated to be 1.08 ± 0.05, confirming a 1:1 complexation. The binding was driven by a large negative standard molar enthalpy change (ΔH(0) = -118.45 ± 0.05 kJ mol(-1)) and an unfavorable standard molar entropy change (TΔS(0) = -86.53 ± 0.01 kJ mol(-1)) at 293.15 K. Increasing the temperature favoured the binding, and the magnitude of the negative standard molar heat capacity change suggested the involvement of significant hydrophobic forces in the binding process. With increasing salt concentration, the magnitude of the equilibrium constant decreased slightly; and the complexation mostly involved non-polyelectrolytic forces contributing about 92-94% of the standard molar Gibbs energy change. DSC studies revealed that curcumin binding caused a partial unfolding of the protein.

[Effects of shortened mandibular dental arch on human brain activity during chewing: an fMRI study].

PubMed

Shoi, Kazuhito

2014-03-01

According to the shortened dental arch concept, missing molars should not always be restored with prosthetic treatment. A shortened dental arch with missing molars is associated with a decrease in masticatory function. However, it is not known whether a shortened dental arch influences brain activity during chewing. This study aimed to clarify the effect of posterior arch length of mandibular bilateral distal extension removable partial dentures (RPDs) on brain activity during chewing. Eleven subjects with bilaterally missing mandibular molars (mean age, 66.1 years) participated in the study. RPDs with full dental arch and shortened dental arch were fabricated and brain activity during gum chewing under each dental condition was measured using functional magnetic resonance imaging. Brain activation during gum chewing with the full dental arch was observed in the middle frontal gyrus, primary sensorimotor cortex extending to the premotor cortex, supplementary motor area, putamen, insula and cerebellum. However, activation of the middle frontal gyrus was not observed during gum chewing with the shortened dental arch. The results of this study suggest that human brain activity during chewing in the middle frontal gyrus may be associated with chewing in the presence of the molar region.

Interaction of Triton X-100 with acyl pocket of butyrylcholinesterase: effect on esterase activity and inhibitor sensitivity of the enzyme.

PubMed

Jaganathan, L; Boopathy, R

1998-06-01

The effect of non-ionic detergents like Triton X-100, Lubrol PX, Brij 35 and Tween 80 on the esterase activity and inhibitor sensitivity of human serum butyrylcholinesterase (BuChE) were studied. The results showed that though BuChE is not a detergent dependent enzyme, the esterase activity and inhibitor sensitivity of it can be modulated by the presence of detergents. All the detergents caused a marginal activation of the esterase activity. The presence of Lubrol PX, Brij 35 or Tween 80 did not affect the 50% molar inhibition concentration (IC50) of the inhibitors tested. But in the presence of Triton X-100 the IC50 values were increased for neostigmine, eserine and tetraisopropylpyrophosphoramide (acylation site interacting inhibitors), whereas for inhibitors like ethopropazine, imipramine and procainamide (choline binding pocket specific inhibitors) the IC50 values were unaltered. In addition, in the presence of Triton X-100 the bimolecular reaction constant for phosphorylation reaction (ki) of BuChE for the acyl pocket specific tetraisopropylpyrophosphoramide was reduced. Triton X-100 partially protected BuChE against this tetraisopropylpyrophosphoramide inactivation. These results indicate that Triton X-100 by interacting with the acyl pocket hydrophobic region is able to activate the esterase activity of BuChE. Further it reduces the capacity of the enzyme to react with inhibitors that inactivate it by interacting with the serine residue of the acylation site.

Bulk and interfacial structures of reline deep eutectic solvent: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Kaur, Supreet; Sharma, Shobha; Kashyap, Hemant K.

2017-11-01

We apply all-atom molecular dynamics simulations to describe the bulk morphology and interfacial structure of reline, a deep eutectic solvent comprising choline chloride and urea in 1:2 molar ratio, near neutral and charged graphene electrodes. For the bulk phase structural investigation, we analyze the simulated real-space radial distribution functions, X-ray/neutron scattering structure functions, and their partial components. Our study shows that both hydrogen-bonding and long-range correlations between different constituents of reline play a crucial role to lay out the bulk structure of reline. Further, we examine the variation of number density profiles, orientational order parameters, and electrostatic potentials near the neutral and charged graphene electrodes with varying electrode charge density. The present study reveals the presence of profound structural layering of not only the ionic components of reline but also urea near the electrodes. In addition, depending on the electrode charge density, the choline ions and urea molecules render different orientations near the electrodes. The simulated number density and electrostatic potential profiles for reline clearly show the presence of multilayer structures up to a distance of 1.2 nm from the respective electrodes. The observation of positive values of the surface potential at zero charge indicates the presence of significant nonelectrostatic attraction between the choline cation and graphene electrode. The computed differential capacitance (Cd) for reline exhibits an asymmetric bell-shaped curve, signifying different variation of Cd with positive and negative surface potentials.

Bulk and interfacial structures of reline deep eutectic solvent: A molecular dynamics study.

PubMed

Kaur, Supreet; Sharma, Shobha; Kashyap, Hemant K

2017-11-21

We apply all-atom molecular dynamics simulations to describe the bulk morphology and interfacial structure of reline, a deep eutectic solvent comprising choline chloride and urea in 1:2 molar ratio, near neutral and charged graphene electrodes. For the bulk phase structural investigation, we analyze the simulated real-space radial distribution functions, X-ray/neutron scattering structure functions, and their partial components. Our study shows that both hydrogen-bonding and long-range correlations between different constituents of reline play a crucial role to lay out the bulk structure of reline. Further, we examine the variation of number density profiles, orientational order parameters, and electrostatic potentials near the neutral and charged graphene electrodes with varying electrode charge density. The present study reveals the presence of profound structural layering of not only the ionic components of reline but also urea near the electrodes. In addition, depending on the electrode charge density, the choline ions and urea molecules render different orientations near the electrodes. The simulated number density and electrostatic potential profiles for reline clearly show the presence of multilayer structures up to a distance of 1.2 nm from the respective electrodes. The observation of positive values of the surface potential at zero charge indicates the presence of significant nonelectrostatic attraction between the choline cation and graphene electrode. The computed differential capacitance (C d ) for reline exhibits an asymmetric bell-shaped curve, signifying different variation of C d with positive and negative surface potentials.

Sorghum Roots are Inefficient in Uptake of EDTA-chelated Lead

PubMed Central

Xu, Yong; Yamaji, Naoki; Shen, Renfang; Ma, Jian Feng

2007-01-01

Background and Aims Ethylene diamine tetraacetic acid (EDTA)-assisted phytoremediation has been developed to clean up lead (Pb)-contaminated soil; however, the mechanism responsible for the uptake of EDTA–Pb complex is not well understood. In this study, the accumulation process of Pb from EDTA–Pb is characterized in comparison to ionic Pb [Pb(NO3)2] in sorghum (Sorghum bicolor). Methods Sorghum seedlings were exposed to a 0·5 mm CaCl2 (pH 5·0) solution containing 0, 1 mm Pb(NO3)2 or EDTA–Pb complexes at a molar ratio of 1:0·5, 1:1, 1:2 and 1:4 (Pb:EDTA). The root elongation of sorghum at different ratios of Pb:EDTA was measured. Xylem sap was collected after the stem was severed at different times. The concentration of Pb in the shoots and roots were determined by an atomic absorption spectrometer. In addition, the roots were stained with Fluostain I for observation of the root structure. Key Results Lead accumulation in the shoots of the plants exposed to EDTA–Pb at 1:1 ratio was only one-fifth of that exposed to ionic Pb at the same concentration. Lead accumulation decreased when transpiration was suppressed. The concentration of Pb in the xylem sap from the EDTA–Pb-treated plants was about 1/25 000 of that in the external solution. Root elongation was severely inhibited by ionic Pb, but not by EDTA–Pb at a 1:1 ratio. Root staining showed that a physiological barrier was damaged in the roots exposed to ionic Pb, but not in the roots exposed to EDTA–Pb. Conclusions All these results suggest that sorghum roots are inefficient in uptake of EDTA-chelated Pb and that enhanced Pb accumulation from ionic Pb was attributed to the damaged structure of the roots. PMID:17452378

Renewable High-Performance Fibers from the Chemical Recycling of Cotton Waste Utilizing an Ionic Liquid.

PubMed

Asaadi, Shirin; Hummel, Michael; Hellsten, Sanna; Härkäsalmi, Tiina; Ma, Yibo; Michud, Anne; Sixta, Herbert

2016-11-23

A new chemical recycling method for waste cotton is presented that allows the production of virgin textile fibers of substantially higher quality than that from the mechanical recycling methods that are used currently. Cotton postconsumer textile wastes were solubilized fully in the cellulose-dissolving ionic liquid 1,5-diazabicyclo[4.3.0]non-5-enium acetate ([DBNH]OAc) to be processed into continuous filaments. As a result of the heterogeneous raw material that had a different molar mass distribution and degree of polymerization, pretreatment to adjust the cellulose degree of polymerization by acid hydrolysis, enzyme hydrolysis, or blending the waste cotton with birch prehydrolyzed kraft pulp was necessary to ensure spinnability. The physical properties of the spun fibers and the effect of the processing parameters on the ultrastructural changes of the fibers were measured. Fibers with a tenacity (tensile strength) of up to 58 cN tex -1 (870 MPa) were prepared, which exceeds that of native cotton and commercial man-made cellulosic fibers. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of cation structure on the oxygen solubility and diffusivity in a range of bis{(trifluoromethyl)sulfonyl}imide anion based ionic liquids for lithium-air battery electrolytes.

PubMed

Neale, Alex R; Li, Peilin; Jacquemin, Johan; Goodrich, Peter; Ball, Sarah C; Compton, Richard G; Hardacre, Christopher

2016-04-28

This paper reports on the solubility and diffusivity of dissolved oxygen in a series of ionic liquids (ILs) based on the bis{(trifluoromethyl)sulfonyl}imide anion with a range of related alkyl and ether functionalised cyclic alkylammonium cations. Cyclic voltammetry has been used to observe the reduction of oxygen in ILs at a microdisk electrode and chronoamperometric measurements have then been applied to simultaneously determine both the concentration and the diffusion coefficient of oxygen in different ILs. The viscosity of the ILs and the calculated molar volume and free volume are also reported. It is found that, within this class of ILs, the oxygen diffusivity generally increases with decreasing viscosity of the neat IL. An inverse relationship between oxygen solubility and IL free volume is reported for the two IL families implying that oxygen is not simply occupying the available empty space. In addition, it is reported that the introduction of an ether-group into the IL cation structure promotes the diffusivity of dissolved oxygen but reduces the solubility of the gas.

Two-dimensional Si(x)Ge(1-x) films with variable composition made via multilayer colloidal template-guided ionic liquid electrodeposition.

PubMed

Xin, Wuhong; Zhao, Jiupeng; Ge, Dengteng; Ding, Yanbo; Li, Yao; Endres, Frank

2013-02-21

The binary alloy system Si(x)Ge(1-x) provides a continuous series of materials with gradually varying properties. In this paper, we report on a fundamental basis a method to make large-area macroporous Si(x)Ge(1-x) films with variable Ge content by electrodeposition in an ionic liquid, with SiCl(4) and GeCl(4) as precursors. The chemical composition of the products can be modified by changing the molar ratio of the precursors. Periodical macroporous Si(x)Ge(1-x) was made by a multilayer polystyrene (PS) template assembled as face-centered cubic lattice. Two-dimensional (2-D) Si(x)Ge(1-x) bowl-like and fishing-net structures can be obtained by applying different deposition temperatures. The results highlight the potential applications, including photonic bandgap and battery materials, as well as ultra-thin gratings, due to the effect of modification of light and improved tunability of composition, although Si(x)Ge(1-x) made by our method is sensitive to oxidation by air.

Thermophysical Properties of Ionic Liquid, 1-Pentyl-3-methylimidazolium Chloride in Water at Different Temperatures

NASA Astrophysics Data System (ADS)

Shekaari, Hemayat; Mousavi, Sedighehnaz S.; Mansoori, Yagoub

2009-04-01

Osmotic coefficients, {φ}, electrical conductance data, Λ, and refractive indices, n D, of aqueous solutions of the ionic liquid, 1-pentyl-3-methylimidazolium chloride [PnMIm]Cl have been measured at T = (298.15, 308.15, 318.15, and 328.15) K. Measurements of osmotic coefficients were carried out by the vapor-pressure osmometry method (VPO). Osmotic coefficient values show that ion-solvent interactions are stronger at lower temperature. The osmotic coefficients were correlated to the Pitzer-ion interaction and modified NRTL (MNRTL) models. From these data, mean molal activity coefficients, γ±, and excess Gibbs free energies, G E, have been calculated. Electrical conductance data have been applied for determination of association constants, K a, and limiting molar conductances, Λ 0, using the low concentration chemical model (lcCM). Calculated ion-association constant, K a, values show that ion-association effects increase at high temperatures which is in agreement with osmotic coefficient results. Experimental results of refractive indices for the binary system are reported, and have been fitted by a polynomial expansion.

Fabrication and surface enhanced Raman scattering effect of centimeter level AgCuAu composite nanowires

NASA Astrophysics Data System (ADS)

Xu, Dapeng; Zhang, Song; Yang, Wei; Chen, Jian

2017-10-01

Centimeter level AgCuAu composite nanowires were prepared by a solid-state ionics method under a direct current electric field (DCEF) using fast ionic conductor RbAg4I5 films and vacuum thermal evaporation method. The surface morphology and chemical composition of the AuAgCu composite nanowires were characterized by scanning electron microscopy (SEM) and energy dispersive spectrometer (EDS), respectively. Raman enhancement performance of the AgCuAu composite nanowires substrates was detected by Rhodamine 6G (R6G) aqueous solutions as probe molecules. Long-range order and short-range order AgCuAu composite nanowires with the length of 1 cm were prepared. The nanowires were bamboo-shaped with high surface roughness and the diameters of nanowires ranged from 60 to 100 nm. The molar ratio of Ag:Cu:Au in composite nanowires is 15:2:1. The intrinsic Raman peaks of 10-16 mol/L R6G at 612, 773, 1125, 1182, 1307, 1361, 1418, 1506, 1545, 1575, 1597, 1650 cm-1 are all present when AgCuAu composite nanowires were used as the SERS substrates.

Strains Around Abutment Teeth with Different Attachments Used for Implant-Assisted Distal Extension Partial Overdentures: An In Vitro Study.

PubMed

ELsyad, Moustafa Abdou; Omran, Abdelbaset Omar; Fouad, Mohammed Mohammed

2017-01-01

The aim of this study was to evaluate and compare strain around abutment teeth with different attachments used for implant-assisted distal extension partial overdentures (IADEPODs). A mandibular Kennedy class I acrylic model (remaining teeth from first premolar to first premolar) was constructed. A conventional partial denture was constructed over the model (control, group 1). Two laboratory implants were then placed bilaterally in the first molar areas parallel to each other and perpendicular to the residual ridge. Three additional experimental partial overdentures (PODs) were constructed and connected to the implants using ball (group 2), magnetic (group 3), and Locator (group 4) attachments. Three linear strain gauges were bonded buccal, lingual, and distal to the first premolar abutment tooth at the right (loading) and the left (nonloading) sides. For each group, a universal testing device was used to apply a unilateral vertical static load (50 N) on the first molar area, and the strain was recorded using a multichannel digital strainometer. Significant differences between groups and between sites of strain gauges were detected. Strains recorded for all groups were compressive (negative) in nature. Group 1 demonstrated the highest strain, followed by group 3 and group 4; group 2 recorded the lowest strain. For group 2, the highest strain was recoded at the lingual nonloading side. For group 1, group 3, and group 4, the highest strain was recorded at the buccal loading side. Within the limitation of the present study, ball attachments used to retain IADEPODs to the implants were associated with lower strains around abutment teeth than Locator and magnetic attachments. The highest strain was recorded with conventional partial dentures. © 2015 by the American College of Prosthodontists.

Anatomical analysis of the resected roots of mandibular first molars after failed non-surgical retreatment

PubMed Central

2018-01-01

Objectives Understanding the reason for an unsuccessful non-surgical endodontic treatment outcome, as well as the complex anatomy of the root canal system, is very important. This study examined the cross-sectional root canal structure of mandibular first molars confirmed to have failed non-surgical root canal treatment using digital images obtained during intentional replantation surgery, as well as the causative factors of the failed conventional endodontic treatments. Materials and Methods This study evaluated 115 mandibular first molars. Digital photographic images of the resected surface were taken at the apical 3 mm level and examined. The discolored dentin area around the root canal was investigated by measuring the total surface area, the treated areas as determined by the endodontic filling material, and the discolored dentin area. Results Forty 2-rooted teeth showed discolored root dentin in both the mesial and distal roots. Compared to the original filled area, significant expansion of root dentin discoloration was observed. Moreover, the mesial roots were significantly more discolored than the distal roots. Of the 115 molars, 92 had 2 roots. Among the mesial roots of the 2-rooted teeth, 95.7% of the roots had 2 canals and 79.4% had partial/complete isthmuses and/or accessory canals. Conclusions Dentin discoloration that was not visible on periapical radiographs and cone-beam computed tomography was frequently found in mandibular first molars that failed endodontic treatment. The complex anatomy of the mesial roots of the mandibular first molars is another reason for the failure of conventional endodontic treatment. PMID:29765897

Computing gas solubility in reservoir waters for environmental chemistry applications: the role of satellite observations

NASA Astrophysics Data System (ADS)

Rosa, R.; Lima, I.; Ramos, F.; Bambace, L.; Assireu, A.; Stech, J.; Novo, E.; Lorenzeti, L.

Atmospheric greenhouse gases concentration has increased during the past centuries basically due to biogenic and pyrogenic anthopogenic emissions Recent investigations have shown that gas emission methane as an important example from tropical hydroelectric reservoirs may comprise a considerable fraction of the total anthropogenic bulk In order to evaluate the concentration of gases of potential importance in environmental chemistry the solubility of such gases have been collected and converted into a uniform format using the Henry s law which states that the solubility of a gas in a liquid is directly proportional to its partial pressure However the Henry s law can be derived as a function of temperature density molar mixing ratio in the aqueous phase and molar mass of water In this paper we show that due to the complex temperature variation and water composition measured in brazilian tropical reservoirs as Serra da Mesa and Manso expressive secular variation on the traditional solubility constants concentration of a species in the aqueous phase by the partial pressure of that species in the gas phase can change in a rate of approximately 30 in 6 decades This estimation comes from a computational analysis of temperature variation measured during 6 months in Serra da Mesa and Manso reservoirs taking into account a simulated density and molar mass variation of the aqueous composition in these environments As an important global change issue from this preliminary analysis we discuss its role in the current estimations on the concentration emission rates

Enhanced CO2 capture in binary mixtures of 1-alkyl-3-methylimidazolium tricyanomethanide ionic liquids with water.

PubMed

Romanos, George E; Zubeir, Lawien F; Likodimos, Vlassis; Falaras, Polycarpos; Kroon, Maaike C; Iliev, Boyan; Adamova, Gabriela; Schubert, Thomas J S

2013-10-10

Absorption of carbon dioxide and water in 1-butyl-3-methylimidazoliun tricyanomethanide ([C4C1im][TCM]) and 1-octyl-3-methylimidazolium tricyanomethanide ([C8C1im][TCM]) ionic liquids (ILs) was systematically investigated for the first time as a function of the H2O content by means of a gravimetric system together with in-situ Raman spectroscopy, excess molar volume (V(E)), and viscosity deviation measurements. Although CO2 absorption was marginally affected by water at low H2O molar fractions for both ILs, an increase of the H2O content resulted in a marked enhancement of both the CO2 solubility (ca. 4-fold) and diffusivity (ca. 10-fold) in the binary [C(n)C1im][TCM]/H2O systems, in contrast to the weak and/or detrimental influence of water in most physically and chemically CO2-absorbing ILs. In-situ Raman spectroscopy on the IL/CO2 systems verified that CO2 is physically absorbed in the dry ILs with no significant effect on their structural organization. A pronounced variation of distinct tricyanomethanide Raman modes was disclosed in the [C(n)C1im][TCM]/H2O mixtures, attesting to the gradual disruption of the anion-cation coupling by the hydrogen-bonded water molecules to the [TCM](-) anions, in accordance with the positive excess molar volumes and negative viscosity deviations for the binary systems. Most importantly, CO2 absorption in the ILs/H2O mixtures at high water concentrations revealed that the [TCM](-) Raman modes tend to restore their original state for the heavily hydrated ILs, in qualitative agreement with the intriguing nonmonotonous transients of CO2 absorption kinetics unveiled by the gravimetric measurements for the hybrid solvents. A molecular exchange mechanism between CO2 in the gas phase and H2O in the liquid phase was thereby proposed to explain the enhanced CO2 absorption in the hybrid [C(n)C1im][TCM]//H2O solvents based on the subtle competition between the TCM-H2O and TCM-CO2 interactions, which renders these ILs very promising for CO2 separation applications.

In situ metathesis reaction combined with liquid-phase microextraction based on the solidification of sedimentary ionic liquids for the determination of pyrethroid insecticides in water samples.

PubMed

Hu, Lu; Zhang, Panjie; Shan, Wanyu; Wang, Xuan; Li, Songqing; Zhou, Wenfeng; Gao, Haixiang

2015-11-01

A novel dispersion liquid-liquid microextraction method based on the solidification of sedimentary ionic liquids (SSIL-DLLME), in which an in situ metathesis reaction forms an ionic liquid (IL) extraction phase, was developed to determine four pyrethroid insecticides (i.e., permethrin, cyhalothrin, fenpropathrin, and transfluthrin) in water followed by separation using high-performance liquid chromatography. In the developed method, in situ DLLME was used to enhance the extraction efficiency and yield. After centrifugation, the extraction solvent, tributyldodecylphosphonium hexafluorophosphate ([P44412][PF6]), was easily collected by solidification in the bottom of the tube. The effects of various experimental parameters, the quantity of tributyldodecylphosphonium bromide ([P44412]Br), the molar ratio of [P44412]Br to potassium hexafluorophosphate (KPF6), the ionic strength, the temperature of the sample solution, and the centrifugation time, were optimized using a Plackett-Burman design to identify the significant factors that affected the extraction efficiency. These significant factors were then optimized using a central composite design. Under the optimized conditions, the recoveries of the four pyrethroid insecticides at four spiked levels ranged from 87.1% to 101.7%, with relative standard deviations (RSDs) ranging from 0.1% to 5.5%. At concentration levels between 1 and 500 µg/L, good linearity was obtained, with coefficients of determination greater than 0.9995. The limits of detection (LODs) for the four pyrethroid insecticides were in the range of 0.71-1.54 µg/L. The developed method was then successfully used for the determination of pyrethroid insecticides in environmental samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Influence of reaction conditions on formation of ionic liquid-based nanostructured Bi2O3 as an efficient visible-light-driven photocatalyst

NASA Astrophysics Data System (ADS)

Bagheri, Mozhgan; Heydari, Mojgan; Vaezi, Mohammad Reza

2018-01-01

In this study, nanostructured bismuth oxide was synthesized based on the chemical reaction of bismuth nitrate and NaOH in the ionic liquid 1-butyl-3-methylimidazolium chloride ([C4mim]Cl) under ultrasonic irradiation. The effect of sodium hydroxide with a different molar ratio of NaOH to bismuth in the range of 3-10 was investigated. The results of fourier-transform infrared spectroscopy (FT-IR) and X-ray powder diffraction (XRD) showed that NaOH has a critical role in the formation of pure α-Bi2O3. So, at high concentrations of NaOH (NaOH:Bi ≥ 7.5), the chloride anion from the ionic liquid cannot be entered into the crystalline structure of bismuth oxide, which resulted in the formation of pure bismuth oxide, while at lower concentrations of NaOH (NaOH:Bi ≤ 5), Bi3O4Cl was formed with a layered structure. The XRD results revealed that the synthesized α-Bi2O3 has a monoclinic structure and scanning electron microscopy (SEM) images showed that the sample consists of needle like particles with an average thickness of 50 nm. The ionic liquid has an important role in the prevention of an agglomeration of particles in the Bi2O3 sample. The photocatalytic activity of the synthesized Bi2O3 was investigated to study the degradation of malachite green dye as a model pollutant under visible light. The effects of various parameters such as the pH, concentration of the dye, and the catalyst on the degradation of malachite green were also investigated.

Nanostructured protic ionic liquids retain nanoscale features in aqueous solution while precursor Brønsted acids and bases exhibit different behavior.

PubMed

Greaves, Tamar L; Kennedy, Danielle F; Weerawardena, Asoka; Tse, Nicholas M K; Kirby, Nigel; Drummond, Calum J

2011-03-10

Small- and wide-angle X-ray scattering (SWAXS) has been used to investigate the effect that water has on the nanoscale structure of protic ionic liquids (PILs) along with their precursor Brønsted acids and bases. The series of PILs consisted of primary, secondary, and tertiary alkylammonium cations in conjunction with formate, nitrate, or glycolate anions. Significant differences were observed for these systems. The nanoscale aggregates present in neat protic ionic liquids were shown to be stable in size on dilution to high concentrations of water, indicating that the water is localized in the ionic region and has little effect on the nonpolar domains. The Brønsted acid-water solutions did not display nanostructure at any water concentration. Primary amine Brønsted bases formed aggregates in water, which generally displayed characteristics of poorly structured microemulsions or a form of bicontinuous phase. Exceptions were butyl- and pentylamine with high water concentrations, for which the SWAXS patterns fitted well to the Teubner-Strey model for microemulsions. Brønsted base amines containing multiple alkyl chains or hydroxyl groups did not display nanostructure at any water concentration. IR spectroscopy was used to investigate the nature of water in the various solutions. For low PIL concentrations, the water was predominately present as bulk water for PIL molar fractions less than 0.4-0.5. At high PIL concentrations, in addition to the bulk water, there was a significant proportion of perturbed water, which is water influenced in some way by the cations and anions. The molecular state of the water in the studied amines was predominately present as bulk water, with smaller contributions from perturbed water than was seen in the PILs. © 2011 American Chemical Society

Cytochrome c oxidase inhibition by calcium at physiological ionic composition of the medium: Implications for physiological significance of the effect.

PubMed

Vygodina, Tatiana V; Mukhaleva, Elizaveta; Azarkina, Natalia V; Konstantinov, Alexander A

2017-12-01

Cytochrome c oxidase (CcO) from mammalian mitochondria binds Ca 2+ and Na + in a special cation binding site. Binding of Ca 2+ brings about partial inhibition of the enzyme while Na + competes with Ca 2+ for the binding site and protects the enzyme from the inhibition [Vygodina, T., Kirichenko, A. and Konstantinov, A.A. (2013). Direct Regulation of Cytochrome c oxidase by Calcium Ions. PLoS One 8(9): e74436]. In the original studies, the inhibition was found to depend significantly on the ionic composition of the buffer. Here we describe inhibition of CcO by Ca 2+ in media containing the main ionic components of cytoplasm (150mM KCl, 12mM NaCl and 1mM MgCl 2 ). Under these conditions, Ca 2+ inhibits CcO with effective K i of 20-26μM, that is an order of magnitude higher than determined earlier in the absence of Na + . At physiological value of ionic strength, the inhibition can be observed at any turnover number of CcO, rather than only at low TN (<10s -1 ) as found previously. The inhibition requires partially oxidized state of cytochrome c and is favored by high ionic strength with a sharp transition at 0.1-0.2M. The high K i =20-26μM found for CcO inhibition by calcium matches closely the known value of "K m " for Ca 2+ -induced activation of the mitochondrial calcium uniporter. The inhibition of CcO by Ca 2+ is proposed to modulate mitochondrial Ca 2+ -uptake via the mitochondrial calcium uniporter, promote permeability transition pore opening and induce reduction of Mia40 in the mitochondrial intermembrane space. Copyright © 2017 Elsevier B.V. All rights reserved.

A New Class of Ternary Compound for Lithium-Ion Battery: from Composite to Solid Solution.

PubMed

Wang, Jiali; Wu, Hailong; Cui, Yanhua; Liu, Shengzhou; Tian, Xiaoqing; Cui, Yixiu; Liu, Xiaojiang; Yang, Yin

2018-02-14

Searching for high-performance cathode materials is a crucial task to develop advanced lithium-ion batteries (LIBs) with high-energy densities for electrical vehicles (EVs). As a promising lithium-rich material, Li 2 MnO 3 delivers high capacity over 200 mAh g -1 but suffers from poor structural stability and electronic conductivity. Replacing Mn 4+ ions by relatively larger Sn 4+ ions is regarded as a possible strategy to improve structural stability and thus cycling performance of Li 2 MnO 3 material. However, large difference in ionic radii of Mn 4+ and Sn 4+ ions leads to phase separation of Li 2 MnO 3 and Li 2 SnO 3 during high-temperature synthesis. To prepare solid-solution phase of Li 2 MnO 3 -Li 2 SnO 3 , a buffer agent of Ru 4+ , whose ionic radius is in between that of Mn 4+ and Sn 4+ ions, is introduced to assist the formation of a single solid-solution phase. The results show that the Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system evolves from mixed composite phases into a single solid-solution phase with increasing Ru content. Meanwhile, discharge capacity of this ternary system shows significantly increase at the transformation point which is ascribed to the improvement of Li + /e - transportation kinetics and anionic redox chemistry for solid-solution phase. The role of Mn/Sn molar ratio of Li 2 RuO 3 -Li 2 MnO 3 -Li 2 SnO 3 ternary system has also been studied. It is revealed that higher Sn content benefits cycling stability of the system because Sn 4+ ions with larger sizes could partially block the migration of Mn 4+ and Ru 4+ from transition metal layer to Li layer, thus suppressing structural transformation of the system from layered-to-spinel phase. These findings may enable a new route for exploring ternary or even quaternary lithium-rich cathode materials for LIBs.

Experimental study of the bending elasticity of charged lipid bilayers in aqueous solutions with pH5

NASA Astrophysics Data System (ADS)

Mitkova, D.; Stoyanova-Ivanova, A.; Ermakov, Yu A.; Vitkova, V.

2012-12-01

Exposure to high concentrations of contaminations due to air polluting gases, vapours and aerosols and possibly altering the normal pH in the body could lead to undesirable changes in the properties of biological cells. Here, we study experimentally the mechanical properties of synthetic phospholipid bilayers containing increasing molar fractions (up to 0.15) of charged lipid (synthetic phosphatidylserine) in aqueous solutions with controlled ionic strength and at pH 5, which is slightly lower than the physiological values of pH. Our observations in phase contrast and fluorescence testified to the coexistence of two phases in membranes for temperatures below 29°C. Micro-sized inhomogeneities in vesicle membranes were systematically observed at temperatures lower than 29°C and for molar fractions of phosphatidylserine in the bilayer higher than 0.1. For the quantitative determination of the membrane bending rigidity, we applied thermal fluctuation analysis of the shape of quasispherical lipid vesicles. As far as the liquid-crystalline state of the bilayer is a necessary condition for the application of the experimental method, only vesicles satisfying this requirement were processed for determination of their membrane bending rigidity. The value obtained for the bending modulus of bilayers with 0.15 molar content of charged lipid is about two times higher than the bending modulus of uncharged membranes in the same bathing solution. These findings are in qualitative agreement with our previous results for the bending rigidity of charged bilayers, measured by vesicle micromanipulation.

The Density and Compressibility of BaCO3-SrCO3-CaCO3-K2CO3-Na2CO3-Li2CO3 Liquids: New Measurements and a Systematic Trend with Cation Field Strength

NASA Astrophysics Data System (ADS)

Hurt, S. M.; Lange, R. A.; Ai, Y.

2015-12-01

The volumetric properties of multi-component carbonate liquids are required to extend thermodynamic models that describe partial melting of the deep mantle (e.g. pMELTS; Ghiorso et al., 2003) to carbonate-bearing lithologies. Carbonate in the mantle is an important reservoir of carbon, which is released to the atmosphere as CO2 through volcanism, and thus contributes to the carbon cycle. Although MgCO3 is the most important carbonate component in the mantle, it is not possible to directly measure the 1-bar density and compressibility of MgCO3 liquid because, like other alkaline-earth carbonates, it decomposes at a temperature lower than its melting temperature. Despite this challenge, Liu and Lange (2003) and O'Leary et al. (2015) showed that the one bar molar volume, thermal expansion and compressibility of the CaCO3 liquid component could be obtained by measuring the density and sound speeds of stable liquids in the CaCO3-Li2CO3-Na2CO3-K2CO3 quaternary system at one bar. In this study, this same strategy is employed on SrCO3- and BaCO3-bearing alkali carbonate liquids. The density and sound speed of seven liquids in the SrCO3-Li2CO3-Na2CO3-K2CO3 quaternary and three liquids in the BaCO3-Li2CO3-Na2CO3-K2CO3 quaternary were measured from 739-1367K, with SrCO3 and BaCO3 concentrations ranging from 10-50 mol%. The density measurements were made using the double-bob Archimedean method and sound speeds were obtained with a frequency-sweep acoustic interferometer. The molar volume and sound speed measurements were used to calculate the isothermal compressibility of each liquid, and the results show the volumetric properties mix ideally with composition. The partial molar volume and compressibility of the SrCO3 and BaCO3 components are compared to those obtained for the CaCO3 component as a function of cation field strength. The results reveal a systematic trend that allows the partial molar volume and compressibility of the MgCO3 liquid component to be estimated.

HIGH TEMPERATURE SULFATION STUDIES IN AN ISOTHERMAL REACTOR: A COMPARISON OF THEORY AND EXPERIMENT

EPA Science Inventory

The paper gives high-temperature isothermal data on sulfur dioxide (SO2) capture, obtained as a function of temperature, SO2 partial pressure, and Ca/S molar ratio for a pulverized dolomite (34 micrometer mean size) and a high-purity calcite (11 micrometer mean size). The experim...

Label-free biosensing with functionalized nanopipette probes

PubMed Central

Umehara, Senkei; Karhanek, Miloslav; Davis, Ronald W.; Pourmand, Nader

2009-01-01

Nanopipette technology can uniquely identify biomolecules such as proteins based on differences in size, shape, and electrical charge. These differences are determined by the detection of changes in ionic current as the proteins interact with the nanopipette tip coated with probe molecules. Here we show that electrostatic, biotin-streptavidin, and antibody-antigen interactions on the nanopipette tip surface affect ionic current flowing through a 50-nm pore. Highly charged polymers interacting with the glass surface modulated the rectification property of the nanopipette electrode. Affinity-based binding between the probes tethered to the surface and their target proteins caused a change in the ionic current due to a partial blockade or an altered surface charge. These findings suggest that nanopipettes functionalized with appropriate molecular recognition elements can be used as nanosensors in biomedical and biological research. PMID:19264962

A Structural Molar Volume Model for Oxide Melts Part III: Fe Oxide-Containing Melts

NASA Astrophysics Data System (ADS)

Thibodeau, Eric; Gheribi, Aimen E.; Jung, In-Ho

2016-04-01

As part III of this series, the model is extended to iron oxide-containing melts. All available experimental data in the FeO-Fe2O3-Na2O-K2O-MgO-CaO-MnO-Al2O3-SiO2 system were critically evaluated based on the experimental condition. The variations of FeO and Fe2O3 in the melts were taken into account by using FactSage to calculate the Fe2+/Fe3+ distribution. The molar volume model with unary and binary model parameters can be used to predict the molar volume of the molten oxide of the Li2O-Na2O-K2O-MgO-CaO-MnO-PbO-FeO-Fe2O3-Al2O3-SiO2 system in the entire range of compositions, temperatures, and oxygen partial pressures from Fe saturation to 1 atm pressure.

Third molars and premolars extraction in conventional orthodontics and in treatments based on maxillary bone remodeling with temporary anchorage: indications and care.

PubMed

Consolaro, Alberto

2017-02-01

A bone is an anatomic structure in constant remodeling, with different, mutant and wonderfully inconstant designs. With every new and immediate functional demand, there are changes in cortical thickness, trabecular bone density and also in direction and size of trabeculae. Bones' non-stopping search is for adjusting to the functions induced by forces and movements required by a certain life style. Conventional orthodontic planning or with temporary anchorage based on bone remodeling takes into consideration the spaces that are - or may be - occupied by the teeth, in the formation of a functional and esthetic dental arch for the patient. In case it is necessary to extract a tooth and the options are the third molars, partially or totally unerupted, and teeth that belong to other dental groups, obviousness recommends - due to mouth anatomy and physiology, as well as pathologic reasons - extracting the third molars, due to of the several reasons described in the present study.

Third molars and premolars extraction in conventional orthodontics and in treatments based on maxillary bone remodeling with temporary anchorage: indications and care

PubMed Central

Consolaro, Alberto

2017-01-01

ABSTRACT A bone is an anatomic structure in constant remodeling, with different, mutant and wonderfully inconstant designs. With every new and immediate functional demand, there are changes in cortical thickness, trabecular bone density and also in direction and size of trabeculae. Bones' non-stopping search is for adjusting to the functions induced by forces and movements required by a certain life style. Conventional orthodontic planning or with temporary anchorage based on bone remodeling takes into consideration the spaces that are - or may be - occupied by the teeth, in the formation of a functional and esthetic dental arch for the patient. In case it is necessary to extract a tooth and the options are the third molars, partially or totally unerupted, and teeth that belong to other dental groups, obviousness recommends - due to mouth anatomy and physiology, as well as pathologic reasons - extracting the third molars, due to of the several reasons described in the present study. PMID:28444013

[Determination of solubility parameters of high density polyethylene by inverse gas chromatography].

PubMed

Wang, Qiang; Chen, Yali; Liu, Ruiting; Shi, Yuge; Zhang, Zhengfang; Tang, Jun

2011-11-01

Inverse gas chromatographic (IGC) technology was used to determine the solubility parameters of high density polyethylene (HDPE) at the absolute temperatures from 303.15 to 343.15 K. Six solvents were applied as test probes including hexane (n-C6), heptane (n-C7), octane (n-C8), nonane (n-C9), chloroform (CHCl3) and ethyl acetate (EtAc). Some thermodynamic parameters were obtained by IGC data analysis such as the specific retention volumes of the solvents (V(0)(g)), the molar enthalpy of sorption (delta H(S)(1)), the partial molar enthalpy of mixing at infinite dilution (delta H(1)(infinity)), the molar enthalpy of vaporization (delta H(v)), the activity coefficients at infinite dilution (omega (1)(infinity)), and Flow-Huggins interaction parameters (X(1,2)(infinity)) between HDPE and probe solvents. The results showed that the above six probes are poor solvents for HDPE. The solubility parameter of HDPE at room temperature (298.15 K) was also derived as 19.00 (J/cm3)(0.5).

Studying pressure denaturation of a protein by molecular dynamics simulations.

PubMed

Sarupria, Sapna; Ghosh, Tuhin; García, Angel E; Garde, Shekhar

2010-05-15

Many globular proteins unfold when subjected to several kilobars of hydrostatic pressure. This "unfolding-up-on-squeezing" is counter-intuitive in that one expects mechanical compression of proteins with increasing pressure. Molecular simulations have the potential to provide fundamental understanding of pressure effects on proteins. However, the slow kinetics of unfolding, especially at high pressures, eliminates the possibility of its direct observation by molecular dynamics (MD) simulations. Motivated by experimental results-that pressure denatured states are water-swollen, and theoretical results-that water transfer into hydrophobic contacts becomes favorable with increasing pressure, we employ a water insertion method to generate unfolded states of the protein Staphylococcal Nuclease (Snase). Structural characteristics of these unfolded states-their water-swollen nature, retention of secondary structure, and overall compactness-mimic those observed in experiments. Using conformations of folded and unfolded states, we calculate their partial molar volumes in MD simulations and estimate the pressure-dependent free energy of unfolding. The volume of unfolding of Snase is negative (approximately -60 mL/mol at 1 bar) and is relatively insensitive to pressure, leading to its unfolding in the pressure range of 1500-2000 bars. Interestingly, once the protein is sufficiently water swollen, the partial molar volume of the protein appears to be insensitive to further conformational expansion or unfolding. Specifically, water-swollen structures with relatively low radii of gyration have partial molar volume that are similar to that of significantly more unfolded states. We find that the compressibility change on unfolding is negligible, consistent with experiments. We also analyze hydration shell fluctuations to comment on the hydration contributions to protein compressibility. Our study demonstrates the utility of molecular simulations in estimating volumetric properties and pressure stability of proteins, and can be potentially extended for applications to protein complexes and assemblies. Proteins 2010. (c) 2009 Wiley-Liss, Inc.

AFM and SFG studies of pHEMA-based hydrogel contact lens surfaces in saline solution: adhesion, friction, and the presence of non-crosslinked polymer chains at the surface.

PubMed

Kim, Seong Han; Opdahl, Aric; Marmo, Chris; Somorjai, Gabor A

2002-04-01

The surfaces of two types of soft contact lenses neutral and ionic hydrogels--were characterized by atomic force microscopy (AFM) and sum-frequency-generation (SFG) vibrational spectroscopy. AFM measurements in saline solution showed that the presence of ionic functional groups at the surface lowered the friction and adhesion to a hydrophobic polystyrene tip. This was attributed to the specific interactions of water and the molecular orientation of hydrogel chains at the surface. Friction and adhesion behavior also revealed the presence of domains of non-crosslinked polymer chains at the lens surface. SFG showed that the lens surface became partially dehydrated upon exposure to air. On this partially dehydrated lens surface, the non-crosslinked domains exhibited low friction and adhesion in AFM. Fully hydrated in saline solution, the non-crosslinked domains extended more than tens of nanometers into solution and were mobile.

Retrospective chart analysis on survival rate of fixtures installed at the tuberosity bone for cases with missing unilateral upper molars: a study of 7 cases.

PubMed

Park, Young-Jin; Cho, Sung-Am

2010-06-01

To evaluate the survival rate of implants placed in the maxillary tuberosity region using the fixed prosthesis in partially edentulous cases. Of implant-treated patients who visited Kyung Pook National University Hospital, 7 partially edentulous patients (2 male and 5 female; mean age, 52.3 years; range, approximately 43 to 65) were selected according to the following criteria: 1) less than 3-mm thickness alveolar bone reaming at the first molar area and 2) 1 to 2 fixture premolars, with the additional implant at the maxillary tuberosity region. For the control group, patients who had nontuberosity areas were selected. After 1 to 7 years, marginal bone level, fixture mobility, and radiolucency of tuberosity fixtures of the fixed prostheses were evaluated by digital panorama (Starpacs, Infinitt, Seoul, Korea). None of the fixtures of the tuberosity-installed implants for 1 to 7 years failed. The marginal bone level around the implants of the maxillary tuberosity 1 to 6 years (average 3.4 years) after the final prostheses was approximately 0.6 to 1.3 mm, with an average of 0.94 mm. The fixture installation at the maxillary tuberosity using the unilateral partially edentulous implant-fixed prosthesis would be a clinically acceptable treatment module. 2010 American Association of Oral and Maxillofacial Surgeons. Published by Elsevier Inc. All rights reserved.

Three-year clinical follow-up of posterior teeth restored with leucite-reinforced ips empress onlays and partial veneer crowns.

PubMed

Murgueitio, Rafael; Bernal, Guillermo

2012-07-01

The aim of this study was to analyze the survival rate and failure mode of IPS leucite-reinforced ceramic onlays and partial veneer crowns regarding thickness under the following clinical conditions: vital versus nonvital teeth, tooth location, and type of opposing dentition. Teeth were prepared according to established guidelines for ceramic onlays and partial veneer crowns. Before cementation, the restorations were measured for occlusal thickness at the central fossa, mesial, and distal marginal ridges, and functional and nonfunctional cusps. A total of 210 ceramic restorations were cemented in 99 patients within a mean observation period of 2.9 ± 1.89 years. The mode of failure was classified and evaluated as (1) adhesive, (2) cohesive, (3) combined failure, (4) decementation, (5) tooth sensitivity, and (6) pulpal necrosis. Kaplan, log-rank, and Cox regression tests were used for statistical analysis. The failure rate was 3.33% (7/210). Increased material thickness produced less probability of failures. Vital teeth were less likely to fail than nonvital teeth. Second molars were five times more susceptible to failure than first molars. Tooth sensitivity postcementation and the type of opposing dentition were not statistically significant in this study. In this study, thickness of the restorations, tooth vitality, and location of teeth in the dental arch influenced restoration failures. © 2012 by the American College of Prosthodontists.

Glass ionomer ART sealant and fluoride-releasing resin sealant in fissure caries prevention – results from a randomized clinical trial

PubMed Central

2014-01-01

Background The relative performance of ART sealant and fluoride-releasing resin sealant in preventing fissure caries in permanent molars was compared in a randomized clinical trial conducted in southern China (ClinicalTrials.gov NCT01829334). Methods After obtaining ethical approval, healthy schoolchildren who had permanent first molars with occlusal fissures which were sound but deep or presented with only incipient caries were recruited for the study. Included molars were randomly allocated into one of four parallel study groups in units of left/right teeth per mouth. Two of the four groups adopted the methods of ART or fluoride-releasing resin sealant placement while the other two groups adopted the topical fluoride application methods. Fissure status of the molars in each group was evaluated every 6 months. Development of dentine caries and sealant retention over 24 months in the molars in the two sealant-using groups was compared in this report. Outcome on cost-effectiveness of all four groups over 36 months will be reported elsewhere. Results At baseline, a total of 280 children (383 molars) with mean age 7.8 years were involved for the two sealant groups. After 24 months, 261 children (357 molars) were followed. Proportions of molars with dentine caries were 7.3% and 3.9% in the ART sealant and fluoride-releasing resin sealant groups, respectively (chi-square test, p = 0.171). Life-table survival analysis showed that sealant retention (full and partial) rate over 24 months for the resin sealant (73%) was significantly higher than that (50%) for the ART sealant (p < 0.001). Molar survival (no development of dentine caries) rates in the ART sealant (93%) and fluoride-releasing resin sealant (96%) groups were not significantly different (p = 0.169). Multilevel logistic regression (GEE modeling) accounting for the effects of data clustering and confounding factors confirmed this finding. Conclusions Though the retention of fluoride-releasing resin sealant was better than that of the ART sealant, their effectiveness in preventing fissure caries in permanent molars did not differ significantly over 24 months. ART sealants could be a good alternative when and where resources for resin sealant placement are not readily available. PMID:24886444

Molar distalization with pendulum appliances in the mixed dentition: effects on the position of unerupted canines and premolars.

PubMed

Kinzinger, Gero S M; Wehrbein, Heinrich; Gross, Ulrich; Diedrich, Peter R

2006-03-01

The pendulum appliance allows for rapid molar distalization without the need for patient compliance. Its efficiency has been confirmed in a number of clinical studies. However, the potential interactions and positional changes between the deciduous molars used for dental anchorage and the erupted and unerupted permanent teeth have yet to be clarified when this appliance is used for molar distalization in the mixed dentition. Twenty-nine patients in the mixed dentition each received a modified pendulum appliance with a distal screw and a preactivated pendulum spring for bilateral distalization of the maxillary molars. The patients were divided into 4 groups based on dentition stages: patient group 1 (PG 1, n = 10) was in the early mixed dentition; patients had resorption of the distal root areas of the deciduous molars being used for dental anchorage, and the unerupted premolars were located at the distal margin of the deciduous molar root region. Based on radiographs taken before placement of the pendulum appliance, patient group 2 (PG 2, n = 10) was diagnosed as having a central location of the unerupted premolars. In the third group (PG 3, n = 4), the first premolars were already erupted and could be integrated into the dental anchorage, but the canines were not yet erupted. In the fourth group (PG 4, n = 5), the first premolars and both canines were fully erupted. Statistical analysis of the measured results showed significant differences in the side effects between PG 1 and PG 2. In patients being treated with pendulum appliances, the anchorage quality of the deciduous molars that were already partially resorbed in the distal root area was comparatively reduced. Consequently, the mesial drift of the deciduous molars and incisors was increased, without impairing the extent and quality of the molar distalization. Anchorage loss in the supporting area had no direct impact on the sagittal position of the unerupted premolars in the early mixed dentition. If permanent teeth have already started to erupt in the supporting area, additional space restrictions should be avoided in patients with critical topography, especially if there is little space for the unerupted canines. At this stage of the mixed dentition, premolar extraction or augmentation of the supporting area with extraoral headgear offers a therapeutic alternative to intraoral distalization appliances with exclusively dental anchorage.

Particle self-assembly at ionic liquid-based interfaces.

PubMed

Frost, Denzil S; Nofen, Elizabeth M; Dai, Lenore L

2014-04-01

This review presents an overview of the nature of ionic liquid (IL)-based interfaces and self-assembled particle morphologies of IL-in-water, oil- and water-in-IL, and novel IL-in-IL Pickering emulsions with emphasis on their unique phenomena, by means of experimental and computational studies. In IL-in-water Pickering emulsions, particles formed monolayers at ionic liquid-water interfaces and were close-packed on fully covered emulsion droplets or aggregated on partially covered droplets. Interestingly, other than equilibrating at the ionic liquid-water interfaces, microparticles with certain surface chemistries were extracted into the ionic liquid phase with a high efficiency. These experimental findings were supported by potential of mean force calculations, which showed large energy drops as hydrophobic particles crossed the interface into the IL phase. In the oil- and water-in-IL Pickering emulsions, microparticles with acidic surface chemistries formed monolayer bridges between the internal phase droplets rather than residing at the oil/water-ionic liquid interfaces, a significant deviation from traditional Pickering emulsion morphology. Molecular dynamics simulations revealed aspects of the mechanism behind this bridging phenomenon, including the role of the droplet phase, surface chemistry, and inter-particle film. Novel IL-in-IL Pickering emulsions exhibited an array of self-assembled morphologies including the previously observed particle absorption and bridging phenomena. The appearance of these morphologies depended on the particle surface chemistry as well as the ILs used. The incorporation of particle self-assembly with ionic liquid science allows for new applications at the intersection of these two fields, and have the potential to be numerous due to the tunability of the ionic liquids and particles incorporated, as well as the particle morphology by combining certain groups of particle surface chemistry, IL type (protic or aprotic), and whether oil or water is incorporated. © 2013.

Effect of Amount of Carbon on the Reduction Efficiency of Iron Ore-Coal Composite Pellets in Multi-layer Bed Rotary Hearth Furnace (RHF)

NASA Astrophysics Data System (ADS)

Mishra, Srinibash; Roy, Gour Gopal

2016-08-01

The effect of carbon-to-hematite molar ratio has been studied on the reduction efficiency of iron ore-coal composite pellet reduced at 1523 K (1250 °C) for 20 minutes in a laboratory scale multi-layer bed rotary hearth furnace (RHF). Reduced pellets have been characterized through weight loss measurement, estimation of porosity, shrinkage, qualitative and quantitative phase analysis by XRD. Performance parameters such as the degree of reduction, metallization, carbon efficiency, productivity, and compressive strength have been calculated to compare the process efficacy at different carbon levels in the pellets. Pellets with optimum carbon-to-hematite ratio (C/Fe2O3 molar ratio = 1.66) that is much below the stoichiometric carbon required for direct reduction of hematite yielded maximum reduction, better carbon utilization, and productivity for all three layers. Top layer exhibited maximum reduction at comparatively lower carbon level (C/Fe2O3 molar ratio <2.33) in the pellet, while bottom layer exceeded top layer reduction at higher carbon level (C/Fe2O3 molar ratio >2.33). Correlation between degree of reduction and metallization indicated non-isothermal kinetics influenced by heat and mass transfer in multi-layer bed RHF. Compressive strength of the partially reduced pellet with optimum carbon content (C/Fe2O3 molar ratio = 1.66) showed that they could be potentially used as an alternate feed in a blast furnace or any other smelting reactor.

The retrotransposon Tf1 assembles virus-like particles that contain excess Gag relative to integrase because of a regulated degradation process.

PubMed

Atwood, A; Lin, J H; Levin, H L

1996-01-01

The retrotransposon Tf1, isolated from Schizosaccharomyces pombe, contains a single open reading frame with sequences encoding Gag, protease, reverse transcriptase, and integrase (IN). Tf1 has previously been shown to possess significant transposition activity. Although Tf1 proteins do assemble into virus-like particles, the assembly does not require readthrough of a translational reading frame shift or stop codon, common mechanisms used by retroelements to express Gag in molar excess of the polymerase proteins. This study was designed to determine if Tf1 particles contain equal amounts of Gag and polymerase proteins or whether they contain the typical molar excess of Gag. After using two separate methods to calibrate the strength of our antibodies, we found that both S. pombe extracts and partially purified Tf1 particles contained a 26-fold molar excess of Gag relative to IN. Knowing that Gag and IN are derived from the same Tf1 primary translation product, we concluded that the excess Gag most likely resulted from specific degradation of IN. We obtained evidence of regulated IN degradation in comparisons of Tf1 protein extracted from log-phase cells and that extracted from stationary-phase cells. The log-phase cells contained equal molar amounts of Gag and IN, whereas cells approaching stationary phase rapidly degraded IN, leaving an excess of Gag. Analysis of the reverse transcripts indicated that the bulk of reverse transcription occurred within the particles that possess a molar excess of Gag.

Clinical performance of a glass ionomer sealant protected with two different resin-based agents over a 2-year follow-up period.

PubMed

Ulusoy, A T; Tunc, E S; Bayrak, Ş

2017-03-01

To evaluate the effects of two different resin coating materials on the clinical performance of a conventional glass ionomer sealant. Permanent first mandibular molars of 60 children aged 6-9 years were sealed with Fuji VII. In each child, G-Coat Plus coating agent was applied to molars on one side and Heliobond coating agent to molars on the opposite side of the mouth. Clinical evaluations were carried out at 1, 6, 12, 18 and 24 months after sealant and coating application. At 1, 6, 12, 18 and 24 months after sealant and coating application, total sealant retention rates were 88%, 40%, 19%, 15% and 9% for molars coated with G-Coat Plus, and 93%, 47%, 17%, 15% and 7% for those coated with Heliobond. The differences between the two coating agents were not statistically significant (p>0.05). No incidence of caries was observed in either group during the two-year evaluation period. Wilcoxon signed rank test was used to compare differences in retention rates and caries incidence by coating agent. Although retention rates of Fuji VII were relatively low and similar for both resin coating agents tested, dental caries were not observed in either group during the 24-month study period. In children with a high risk of caries and partially erupted molars, the use of a glass ionomer sealant with a resin-based coating agent should be encouraged.

[Evaluation of cermet fillings in abutment teeth in removable partial prostheses].

PubMed

Saulic, S; Tihacek-Sojic, Lj

2001-01-01

The aim of the study was to describe the clinical process of setting the purpose filling on abutment teeth, after finishing the removable partial dentures. The aim was also to investigate the use of cermet glass-ionomer cement for the purpose filling in the abutment teeth for removable partial dentures, as well as to investigate the surface of the purpose filling. For the clinical evaluation of purpose filling slightly modified criteria according to Ryg's were used in 20 patients with different type of edentulousness. Changes occurring on the surface of purpose filling have been experimentally established by the method of scanning electron microscopy on the half-grown third molars in seven patients. It could be concluded that cement glass-ionomer was not the appropriate material for the purpose fillings in abutment teeth for removable partial dentures.

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

PubMed

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

2017-01-25

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

Effect of various pH values, ionic strength, and temperature on papain hydrolysis of salivary film.

PubMed

Yao, Jiang-Wu; Xiao, Yin; Lin, Feng

2012-04-01

Stimulated human whole saliva (WS) was used to study the dynamics of papain hydrolysis at defined pH, ionic strength, and temperature with the view of reducing an acquired pellicle. A quartz crystal microbalance with dissipation (QCM-D) was used to monitor the changes in frequency caused by enzyme hydrolysis of WS films, and the hydrolytic parameters were calculated using an empirical model. The morphological and conformational changes of the salivary films before and after enzymatic hydrolysis were characterized by atomic force microscopy (AFM) imaging and grazing-angle Fourier transform infrared (GA-FTIR ) spectra, respectively. The characteristics of papain hydrolysis of WS films were pH-, ionic strength-, and temperature-dependent. The WS films were partially removed by the action of papain, resulting in thinner and smoother surfaces. The infrared data suggested that hydrolysis-induced deformation did not occur on the remnants of salivary films. The processes of papain hydrolysis of WS films can be controlled by properly regulating pH, ionic strength, and temperature. © 2012 Eur J Oral Sci.

Viscosity, conductivity, and electrochemical property of dicyanamide ionic liquids

NASA Astrophysics Data System (ADS)

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-03-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands.

Charge-based characterization of nanometric cationic bifunctional maghemite/silica core/shell particles by capillary zone electrophoresis.

PubMed

d'Orlyé, Fanny; Varenne, Anne; Georgelin, Thomas; Siaugue, Jean-Michel; Teste, Bruno; Descroix, Stéphanie; Gareil, Pierre

2009-07-01

In view of employing functionalized nanoparticles (NPs) in the context of an immunodiagnostic, aminated maghemite/silica core/shell particles were synthesized so as to be further coated with an antibody or an antigen via the amino groups at their surface. Different functionalization rates were obtained by coating these maghemite/silica core/shell particles with 3-(aminopropyl)triethoxysilane and 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane at different molar ratios. Adequate analytical performances with CE coupled with UV-visible detection were obtained through semi-permanent capillary coating with didodecyldimethyl-ammonium bromide, thus preventing particle adsorption. First, the influence of experimental conditions such as electric field strength, injected particle amount as well as electrolyte ionic strength and pH, was evaluated. A charge-dependent electrophoretic mobility was evidenced and the separation selectivity was tuned according to electrolyte ionic strength and pH. The best resolutions were obtained at pH 8.0, high ionic strength (ca. 100 mM), and low total particle volume fraction (ca. 0.055%), thus eliminating interference effects between different particle populations in mixtures. A protocol derived from Kaiser's original description was performed for quantitation of the primary amino groups attached onto the NP surface. Thereafter a correlation between particle electrophoretic mobility and the density of amino groups at their surface was established. Eventually, CE proved to be an easy, fast, and reliable method for the determination of NP effective surface charge density.

Viscosity, Conductivity, and Electrochemical Property of Dicyanamide Ionic Liquids

PubMed Central

Yuan, Wen-Li; Yang, Xiao; He, Ling; Xue, Ying; Qin, Song; Tao, Guo-Hong

2018-01-01

The instructive structure-property relationships of ionic liquids (ILs) can be put to task-specific design of new functionalized ILs. The dicyanamide (DCA) ILs are typical CHN type ILs which are halogen free, chemical stable, low-viscous, and fuel-rich. The transport properties of DCA ionic liquids are significant for their applications as solvents, electrolytes, and hypergolic propellants. This work systematically investigates several important transport properties of four DCA ILs ([C4mim][N(CN)2], [C4m2im][N(CN)2], N4442[N(CN)2], and N8444[N(CN)2]) including viscosity, conductivity, and electrochemical property at different temperatures. The melting points, temperature-dependent viscosities and conductivities reveal the structure-activity relationship of four DCA ILs. From the Walden plots, the imidazolium cations exhibit stronger cation–anion attraction than the ammonium cations. DCA ILs have relatively high values of electrochemical windows (EWs), which indicates that the DCA ILs are potential candidates for electrolytes in electrochemical applications. The cyclic voltammograms of Eu(III) in these DCA ILs at GC working electrode at various temperatures 303–333 K consists of quasi-reversible waves. The electrochemical properties of the DCA ILs are also dominated by the cationic structures. The current intensity (ip), the diffusion coefficients (Do), the charge transfer rate constants (ks) of Eu(III) in DCA ILs all increased with the molar conductivities increased. The cationic structure-transport property relationships of DCA ILs were constructed for designing novel functionalized ILs to fulfill specific demands. PMID:29600245

Ionic liquid-assisted preparation of square-shaped Y{sub 2}O{sub 3} nanoplates

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

Wang, Lei; Fang, Hao; Xu, Hualan

Highlights: • Y{sub 4}O(OH){sub 9}(NO{sub 3}) nanosheets were prepared by an ionic liquid-assisted mixed solvothermal route. • Y{sub 2}O{sub 3} nanosheets were obtained after calcining the Y{sub 4}O(OH){sub 9}(NO{sub 3}) nanosheets. • The Y{sub 2}O{sub 3} nanosheets are with length of about 300 nm and thickness of several nanometers. - Abstract: Uniform square-shaped Y{sub 4}O(OH){sub 9}(NO{sub 3}) nanoplates with side length of about 300 nm and thickness of tens of nanometers have been successfully prepared by an ionic liquid-assisted mixed solvothermal route. Y{sub 2}O{sub 3} nanoplates with similar size were obtained after calcining the Y{sub 4}O(OH){sub 9}(NO{sub 3}) nanoplates atmore » 800 °C. The products were analyzed by powder X-ray diffraction (XRD), thermogravimetric analysis (TG), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution TEM (HRTEM), and electron diffraction (ED). The effects of reaction time, composition of solvents, and the molar ratio of reagents on the morphology of the products have been investigated. The possible formation mechanism of the Y{sub 4}O(OH){sub 9}(NO{sub 3}) nanoplates was also discussed. Y{sub 2}O{sub 3}:Eu{sup 3+} nanoplates were also synthesized and their photoluminescent properties were examined.« less

Concomitant Ordering and Symmetry Lowering

ERIC Educational Resources Information Center

Boo, William O. J.; Mattern, Daniell L.

2008-01-01

Examples of concomitant ordering include magnetic ordering, Jahn-Teller cooperative ordering, electronic ordering, ionic ordering, and ordering of partially-filled sites. Concomitant ordering sets in when a crystal is cooled and always lowers the degree of symmetry of the crystal. Concomitant ordering concepts can also be productively applied to…

Force microscopy of layering and friction in an ionic liquid

NASA Astrophysics Data System (ADS)

Hoth, Judith; Hausen, Florian; Müser, Martin H.; Bennewitz, Roland

2014-07-01

The mechanical properties of the ionic liquid 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl) trifluorophosphate ([Py1,4][FAP]) in confinement between a SiOx and a Au(1 1 1) surface are investigated by means of atomic force microscopy (AFM) under electrochemical control. Up to 12 layers of ion pairs can be detected through force measurements while approaching the tip of the AFM to the surface. The particular shape of the force versus distance curve is explained by a model for the interaction between tip, gold surface and ionic liquid, which assumes an exponentially decaying oscillatory force originating from bulk liquid density correlations. Jumps in the tip-sample distance upon approach correspond to jumps of the compliant force sensor between branches of the oscillatory force curve. Frictional force between the laterally moving tip and the surface is detected only after partial penetration of the last double layer between tip and surface.

Physicochemical properties and ion-solvent interactions in aqueous sodium, ammonium, and lead acetate solution

NASA Astrophysics Data System (ADS)

Deosarkar, S. D.; Mendkudle, M. S.

2014-09-01

Densities (ρ), viscosities (η) and refractive indices ( n D) of aqueous sodium acetate (SA), ammonium acetate (AA), and lead acetate (LA) solutions have been measured for different concentrations of salts at 302.15 K. Apparent molar volumes (φv) for studied solutions were calculated from density data, and fitted to Masson's relation and partial molar volume (φ{v/o}) was determined. Viscosity data were fitted to Jones-Dole equation and viscosity A- and B-coefficients were determined. Refractive index and density data were fitted to Lorentz and Lorenz equation and specific refraction ( R D) were calculated. Behavior of various physicochemical properties indicated presence of strong ion-solvent interactions in present systems and the acetate salts structure maker in water.

Commentary on the sphalerite geobarometer

USGS Publications Warehouse

Toulmin, P.; Barton, P.B.; Wiggins, L.B.

1991-01-01

The FeS content of sphalerite in assemblages with pyrite and pyrrhotite has been widely used and widely criticized as a geobarometer. The commonly accepted form of the geobarometer is based on the composition of sphalerite being independent of temperature below about 550??C at all pressures up to at least 10 kbar, but strong thermodynamic arguments require a significant temperature dependence in this region. Most minor components have a negligible effect on the relevant equilibria, but the effect of CuS is somewhat more significant. Molar and partial molar volumes for binary (ZnS-FeS) and ternary (ZnS-FeS-CuS) sphalerite solutions are presented; the ternary data are consistent with charge transfer between Cu and Fe. -from Authors

Vaginal inserts based on chitosan and carboxymethylcellulose complexes for local delivery of chlorhexidine: preparation, characterization and antimicrobial activity.

PubMed

Bigucci, Federica; Abruzzo, Angela; Vitali, Beatrice; Saladini, Bruno; Cerchiara, Teresa; Gallucci, Maria Caterina; Luppi, Barbara

2015-01-30

The aim of this work was to prepare vaginal inserts based on chitosan/carboxymethylcellulose polyelectrolyte complexes for local delivery of chlorhexidine digluconate. Complexes were prepared with different chitosan/carboxymethylcellulose molar ratios at a pH value close to pKa interval of the polymers and were characterized in terms of physico-chemical properties, complexation yield and drug loading. Then complexes were used to prepare inserts as vaginal dosage forms and their physical handling, morphology, water-uptake ability and drug release properties as well as antimicrobial activity toward Candida albicans and Escherichia coli were evaluated. Results confirmed the ionic interaction between chitosan and carboxymethylcellulose and the influence of the charge amount on the complexation yield. Complexes were characterized by high values of drug loading and showed increasing water-uptake ability with the increase of carboxymethylcellulose amount. The selection of appropriate chitosan/carboxymethylcellulose molar ratios allowed to obtain cone-like shaped solid inserts, easy to handle and able to hydrate releasing the drug over time. Finally, the formulated inserts showed antimicrobial activity against common pathogens responsible for vaginal infections. Copyright © 2014 Elsevier B.V. All rights reserved.

A systematic review of dental disease management in cancer patients.

PubMed

Hong, Catherine H L; Hu, Shijia; Haverman, Thijs; Stokman, Monique; Napeñas, Joel J; Braber, Jacolien Bos-den; Gerber, Erich; Geuke, Margot; Vardas, Emmanouil; Waltimo, Tuomas; Jensen, Siri Beier; Saunders, Deborah P

2018-01-01

This systematic review aims to update on the prevalence of odontogenic-related infections and the efficacy of dental strategies in preventing dental-related complications in cancer patients since the 2010 systematic review. A literature search was conducted in the databases MEDLINE/PubMed and EMBASE for articles published between 1 January 2009 and 30 June 2016. Each study was assessed by 2 reviewers and the body of evidence for each intervention was assigned an evidence level. After examination of the abstracts and full-text articles, 59 articles satisfied the inclusion criteria. The weighted prevalence of dental infections and pericoronitis during cancer therapy was 5.4 and 5.3%, respectively. The frequency of dental-related infections during intensive chemotherapy after complete, partial, and minimal pre-cancer dental evaluation/treatment protocols ranged from 0 to 4%. Protocols involving third molars extractions had the highest complications (40%). In view of the low prevalence of infections and the potential for complications after third molar extractions, it is suggested that partial dental evaluation/treatment protocols prior to intensive chemotherapy; whereby minor caries (within dentin), asymptomatic third molars or asymptomatic teeth without excessive probing depth (<8 mm), mobility (mobility I or II) or with periapical lesions of <5 mm were observed; is a viable option when there is insufficient time for complete dental evaluation/treatment protocols. The use of chlorhexidine, fluoride mouth rinses as well as composite resin, resin-modified glass ionomer cement (GIC), and amalgam restorations over conventional GIC in post head and neck radiation patients who are compliant fluoride users is recommended.

The thiocyanate anion is a primary driver of carbon dioxide capture by ionic liquids

NASA Astrophysics Data System (ADS)

Chaban, Vitaly

2015-01-01

Carbon dioxide, CO2, capture by room-temperature ionic liquids (RTILs) is a vivid research area featuring both accomplishments and frustrations. This work employs the PM7-MD method to simulate adsorption of CO2 by 1,3-dimethylimidazolium thiocyanate at 300 K. The obtained result evidences that the thiocyanate anion plays a key role in gas capture, whereas the impact of the 1,3-dimethylimidazolium cation is mediocre. Decomposition of the computed wave function on the individual molecular orbitals confirms that CO2-SCN binding extends beyond just expected electrostatic interactions in the ion-molecular system and involves partial sharing of valence orbitals.

Teaching Nanochemistry: Madelung Constants of Nanocrystals

ERIC Educational Resources Information Center

Baker, Mark D.; Baker, A. David

2010-01-01

The Madelung constants for binary ionic nanoparticles are determined. The computational method described here sums the Coulombic interactions of each ion in the particle without the use of partial charges commonly used for bulk materials. The results show size-dependent lattice energies. This is a useful concept in teaching how properties such as…

Can surface-applied zeolite reduce ammonia losses from feedyard manure? A laboratory study

USDA-ARS?s Scientific Manuscript database

Ammonia emission from beef cattle feedyard manure results in losses of nitrogen (N), which may negatively affect air, soil, and water quality. The magnitude and rate of ammonia volatilization from feedyards partially depends on the amount of urinary urea excreted and dissociation of ionic ammonium ...

Predicting the Stability of Hypervalent Molecules

ERIC Educational Resources Information Center

Mitchell, Tracy A.; Finnocchio, Debbie; Kua, Jeremy

2007-01-01

An exercise is described which introduces students to using concepts in thermochemistry to predict relative stability of a hypervalent molecule. Students will compare the energies of formation for both fluoride and the hydride by calculations and they will also explore the issue of partial ionic character in polar covalent bonds.

Comparison of nanosilver and ionic silver toxicity in Daphnia magna and Pimephales promelas

EPA Science Inventory

This work evaluates the relative contribution of soluble (Ag+) silver and and nano-scale silver particles (n-Ag) and thus addresses an important issue relative to potential ecological risk of n-Ag and of other partially-soluble metal nanoparticles. We used acute to chronic (based...

Conductance of solutions of lithium tris(trifluoromethanesulfonyl) methide in water, acetonitrile, propylene carbonate, N,N-dimethylformamide, and nitromethane at 25 C

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

Croce, F.; D`Aprano, A.; Nanjundiah, C.

1996-01-01

In order to determine the solution properties of lithium tris(trifluoromethanesulfonyl) methide (LiMe) in water and the aprotic solvents acetonitrile (AN), propylene carbonate (PC), N,N-dimethylformamide (DMF), and nitromethane (MeNO{sub 2}), conductance measurements have been carried out at 25 C. Molar conductivities at infinite dilution ({Lambda}{degree}) and ion pair association constants (K{sub a}) were obtained analyzing the experimental data with the Fuoss-Hsia conductance equation using the expansion of Fernandez-Prini and Justice with and without inclusion of the Chen effect. The results show that according to the ability of the solvents to solvate lithium ion, ion-pair formation is small or nonexistent in solventsmore » with high donor number (water, PC, DMF, and AN) but fairly moderate in nitromethane. Single-ion molar conductivities at infinite dilution for ClO{sub 4}{sup {minus}}, AsF{sub 6}{sup {minus}}, PF{sub 6}{sup {minus}} CF{sub 3}SO{sub 3}{sup {minus}}, N(CF{sub 3}SO{sub 2}){sub 2}{sup {minus}}, and C(CF{sub 3}SO{sub 2}){sub 3}{sup {minus}} anions, obtained by combining these results with literature data, decrease as expected as the ionic radius increases, and with one exception are always greater than that of the lithium ion. This general trend does not, however, apply in water where the limiting ionic conductance of the lithium cation is greater than that of the methide anion. This anomalous behavior is attributed to significant solvation of the methide ion in water. Voltammetric measurements indicate high electrochemical stability of methide anion. Such anodic stability and the increase in the transference number of lithium ion in LiMe solutions strongly support the use of this electrolyte in high energy, high voltage lithium batteries.« less

Odd-even effect on the formation of aqueous biphasic systems formed by 1-alkyl-3-methylimidazolium chloride ionic liquids and salts

NASA Astrophysics Data System (ADS)

Belchior, Diana C. V.; Sintra, Tânia E.; Carvalho, Pedro J.; Soromenho, Mário R. C.; Esperança, José M. S. S.; Ventura, Sónia P. M.; Rogers, Robin D.; Coutinho, João A. P.; Freire, Mara G.

2018-05-01

This work provides a comprehensive evaluation of the effect of the cation alkyl side chain length of the 1-alkyl-3-methylimidazolium chloride series ([CnC1im]Cl, n = 2-14) of ionic liquids (ILs) on their capability to form aqueous biphasic systems (ABSs) with salts and self-aggregation derived properties. The liquid-liquid phase behavior of ternary systems composed of [CnC1im]Cl, water, and K3PO4 or K2CO3 and the respective Setschenow salting-out coefficients (ks), a quantitative measure of the two-phase formation ability, were determined. An odd-even effect in the ks values along the number of methylene groups of the longest IL cation alkyl side chain was identified for the ABS formed by K2CO3, a weaker salting-out agent where the phenomenon is clearly identified. In general, cations with even alkyl side chains, being likely to display higher molar volumes, are more easily salted-out and thus more prone to undergo phase separation. The odd-even effect in the ks values is, however, more significant in ILs up to n = 6, where the nanostructuration/nanosegregation of ILs plays a less relevant role. Still, with the [CnC1im]Cl (n = 7-14) series of ILs, an odd-even effect was also identified in the ILs' ionization degree, molar conductivity, and conductivity at infinite dilution. In summary, it is shown here that the ILs' odd-even effect occurs in IL aqueous solutions and not just in neat ILs, an already well-established phenomenon occurring in a series of ILs' properties described as a result of the orientation of the terminal methyl groups to the imidazolium ring cation and consequent effect in the ILs' cohesive energy.

Disaggregation of adenylate cyclase during polyacrylamide-gel electrophoresis in mixtures of ionic and non-ionic detergents

PubMed Central

Newby, Andrew C.; Chrambach, Andreas

1979-01-01

1. Adenylate cyclase [ATP pyrophosphate-lyase (cyclizing), EC 4.6.1.1] solubilized from the rat liver plasma membrane with 1% Lubrol PX and partially purified by gel filtration in buffer containing 0.01% Lubrol PX was physically characterized by polyacrylamide-gel electrophoresis. 2. The molecular radius determined for the partially purified enzyme was 4.9nm, compared with the value of 3.9nm obtained for the enzyme before gel filtration. 3. This difference, representing an approximate doubling of the molecular volume of the enzyme, implied that aggregation with itself or other proteins had occurred during partial purification. 4. Aggregation was not reversed by electrophoresis in the presence of high Lubrol concentrations. 5. Substitution of deoxycholate or N-dodecylsarcosinate for Lubrol PX either for solubilization or during electrophoresis led to poorer resolution of membrane proteins at concentrations giving greater than 70% loss of enzyme activity. 6. Partially purified adenylate cyclase was electrophoresed in the presence of mixed micelles of Lubrol PX and deoxycholate or Lubrol PX and N-dodecylsarcosinate. Different mixtures were examined simultaneously in a suitable apparatus. 7. Electrophoresis in the presence of 0.1% Lubrol plus 0.03% deoxycholate decreased the molecular radius of the cyclase to 4.0nm, with greater than 90% recovery of enzymic activity. The net charge of the enzyme was also increased, indicating ionic detergent binding. 8. With 0.1% Lubrol plus 0.03% N-dodecylsarcosinate the molecular radius was 4.3nm, recovery approx. 50% and net charge similar to that seen in Lubrol plus deoxycholate. 9. The resolution of cyclase from bulk protein, on an analytical scale, was improved in the presence of detergent mixtures, as compared with resolution in Lubrol alone. 10. The results demonstrate the usefulness of polyacrylamide-gel electrophoresis to detect and overcome aggregation problems with membrane proteins and suggest that detergent mixtures in specific ratios may be useful in the purification of adenylate cyclase and other intrinsic membrane proteins. ImagesFig. 3. PMID:435255

The effect of human microtubule-associated-protein tau on the assembly structure of microtubules and its ionic strength dependence

NASA Astrophysics Data System (ADS)

Choi, M. C.; Raviv, U.; Miller, H. P.; Gaylord, M. R.; Kiris, E.; Ventimiglia, D.; Needleman, D. J.; Chung, P. J.; Deek, J.; Lapointe, N.; Kim, M. W.; Wilson, L.; Feinstein, S. C.; Safinya, C. R.

2010-03-01

Microtubules (MTs), 25 nm protein nanotubes, are among the major filamentous elements of the eukaryotic cytoskeleton involved in intracellular trafficking, cell division and the establishment and maintenance of cell shape. Microtubule-associated-protein tau regulates tubulin assembly, MT dynamics and stability. Aberrant tau action has long been correlated with numerous neurodegenerative diseases, including Alzheimer's, and fronto-temporal dementia with Parkinsonism linked to chromosome 17 (FTDP-17) Using synchrotron small angle x-ray scattering (SAXS) and binding assay, we examine the effects of tau on the assembly structure of taxol-stabilized MTs. We find that tau regulates the distribution of protofilament numbers in MTs as reflected in the observed increase in the average radius of MTs with increasing the tau/tubulin molar ratio. Additionally, tau-MT interactions are mediated to a large extent via electrostatic interactions: the binding affinity of tau to MTs is ionic strength dependent. Supported by DOE-BES DE-FG02-06ER46314, NSF DMR-0803103, NIH NS35010, NIH NS13560. (Ref) M.C. Choi, S.C. Feinstein, and C.R. Safinya et al. Biophys. J. 97; 519 (2009).

Dielectric response and transport properties of alkylammonium formate ionic liquids

NASA Astrophysics Data System (ADS)

Nazet, Andreas; Buchner, Richard

2018-05-01

Dielectric relaxation spectra of three members of the alkylammonium formate family of protic ionic liquids (PILs), namely, ethylammonium formate (EAF), n-butylammonium formate (BuAF), and n-pentylammonium formate (PeAF), as well as the pseudo-PIL triethylamine + formic acid (molar ratio 1:2; TEAF) have been studied over a wide frequency (50 MHz to 89 GHz) and temperature range (5-65 °C), complemented by measurements of their density, viscosity, and conductivity. It turned out that the dominating relaxation of EAF, BuAF, and PeAF arises from both cation and anion reorientations which are synchronized in their dynamics due to hydrogen bonding. Amplitudes and relaxation times of this mode reflect the—compared to nitrate—different nature of H bonding between the formate anion and ethylammonium cation, as well as increasing segregation of the PIL structure into polar and non-polar domains. The TEAF data suggest that its dominating relaxation is due to the rotation of the complex triethylamineṡ(formic acid)2 in which no significant proton transfer to an ion pair occurred. Weak dissociation of this complex into ions was postulated to account for the high conductivity of TEAF.

Hydrogen uptake characteristics of mischmetal based alloy

NASA Astrophysics Data System (ADS)

Jain, Ankur; Jain, R. K.; Jain, I. P.

Hydrogen storage properties of Mm 39.2Ni 42.1Mn 4.9Al 1.25Co 10.2Fe 2.35 alloy have been systematically studied in the present work. An attempt is made to relate the content of hydrogen with change in resistance. It is found that the resistance of material increases with the increase in value of H/ M due to hydrogen absorption. Pressure composition (P-C-T) isotherm using water displacement method has been investigated in the temperature and pressure ranges of 308 ≤ T ≤ 338 K and 0.5 ≤ P ≤ 10 bar, respectively. The P-C isotherms show the presence of two single α and β regions one mixed α + β phase. The maximum H (wt%) was found to be around 1.53 at 308 K and around 6 bar. Since enthalpy is an index of thermochemical stability of metal hydride the thermo dynamical parameters viz., the relative partial molar enthalpy (Δ H) and relative partial molar entropy (Δ S) of dissolved hydrogen have been calculated by plotting the Van't Hoff plot. The variation of Δ H and Δ S with the hydrogen concentration confirm the phase boundaries.

Molar mass, radius of gyration and second virial coefficient from new static light scattering equations for dilute solutions: application to 21 (macro)molecules.

PubMed

Illien, Bertrand; Ying, Ruifeng

2009-05-11

New static light scattering (SLS) equations for dilute binary solutions are derived. Contrarily to the usual SLS equations [Carr-Zimm (CZ)], the new equations have no need for the experimental absolute Rayleigh ratio of a reference liquid and solely rely on the ratio of scattered intensities of solutions and solvent. The new equations, which are based on polarizability equations, take into account the usual refractive index increment partial differential n/partial differential rho(2) complemented by the solvent specific polarizability and a term proportional to the slope of the solution density rho versus the solute mass concentration rho(2) (density increment). Then all the equations are applied to 21 (macro)molecules with a wide range of molar mass (0.2500 kg mol(-1)), for which the scattered intensity is no longer independent of the scattering angle, the new equations give the same value of the radius of gyration as the CZ equation and consistent values of the second virial coefficient.

The e[sup [minus

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

Holroyd, R.A.; Schwarz, H.A.; Stradowska, E.

The rate constants for attachment of excess electrons to 1,3-butadiene (k[sub a]) and detachment from the butadiene anion (k[sub d]) in n-hexane are reported. The equilibrium constant, K[sub eq] = k[sub a]/k[sub d], increases rapidly with pressure and decreases as the temperature increases. At -7[degree]C attachment is observed at 1 bar. At high pressures the attachment rate is diffusion controlled. The activation energy for detachment is about 21 kcal/mol; detachment is facilitated by the large entropy of activation. The reaction volumes for attachment range from -181 cm[sup 3]/mol at 400 bar to-122 cm[sup 3]/mol at 1500 bar and are largelymore » attributed to the electrostriction volume of the butadiene anion ([Delta][bar V][sub el]). Values of [Delta][bar V][sub el] calculated by a model, which includes a glassy shell of solvent molecules around the ion, are in agreement with experimental reaction volumes. The analysis indicates the partial molar volume of the electron in hexane is small and probably negative. It is shown that the entropies of reaction are closely related to the partial molar volumes of reaction. 22 refs., 5 figs., 5 tabs.« less

Partial hydatidiform mole with false-negative urine human chorionic gonadatropin test in the emergency department.

PubMed

Mundangepfupfu, Tichaendepi; Waseem, Muhammad

2014-03-01

Hydatidiform mole (molar pregnancy) is a benign tumor of placental trophoblastic cells, which release human chorionic gonadotropin (hCG). Several case reports have described complete hydatidiform moles with false-negative urine qualitative hCG tests. These negative pregnancy tests have been attributed to the hook effect. We report an unusual presentation of a partial mole and review an alternative explanation for the negative hCG test. As partial moles are usually not associated with a large proliferation of trophoblastic cells, levels of hCG are commonly < 100,000 mIU/mL. The most common presentation of a hydatidiform mole is vaginal bleeding. Hydatidiform mole is associated with a risk of malignant transformation and disseminated disease. In a pregnant patient, vaginal bleeding and abdominal pain are common presentations. Molar pregnancy is an uncommon cause of abdominal pain and vaginal bleeding that should be considered. A 47-year-old female presented to the emergency department with abdominal pain and vaginal bleeding. Urine qualitative hCG was negative and serum quantitative hCG was 1,094,950 mIU/mL. Pelvic ultrasonography showed a uterine cavity containing a soft-tissue mass with multiple cystic lesions and the hydatidiform mole was extracted with suction curettage. Tissue pathology confirmed partial hydatidiform mole. In addition to the hook effect, we present another possible explanation for the false-negative test; namely the inability of some assays to detect hCG-degradation products, which may be higher in clinical samples from patients with hydatidiform mole. This case underscores the importance of knowing the limitations of the commonly used hCG assays. Copyright © 2014 Elsevier Inc. All rights reserved.

Ultrasonic speed, densities and viscosities of xylitol in water and in aqueous tyrosine and phenylalanine solutions at different temperatures

NASA Astrophysics Data System (ADS)

Ali, A.; Bidhuri, P.; Uzair, S.

2014-07-01

Ultrasonic speed u, densities ρ and viscosities η of xylitol in water and in 0.001 m aqueous l-tyrosine (Tyr) and l-phenylalanine (Phe) have been measured at different temperatures. From the density and ultrasonic speed measurements apparent molar isentropic compression κ_{φ}, apparent molar isentropic compressions at infinite dilution κ_{{S,φ}}0 , experimental slope S K , hydration number n H , transfer partial molar isentropic compressibility Δ_{tr} κ_{{S,φ}}0 of xylitol from water to aqueous Tyr and Phe have been obtained. From the viscosity data, B-coefficient and B-coefficient of transfer Δ tr B of xylitol from water to aqueous Phe and Tyr at different temperatures have also been estimated. Gibbs free energies of activation of viscous flow per mole of solvent Δ μ 1 0# and per mole of solute Δ μ 2 0# have been calculated by using Feakins transition state theory for the studied systems. The calculated parameters have been interpreted in terms of solute-solute and solute-solvent interactions and hydration behavior of xylitol.

[Determination of the solubility parameter of organosolv lignin by inverse gas chromatography].

PubMed

Yu, Yachen; Li, Kunlan; Ma, Yingchong; Wei, Ligang

2013-02-01

An inverse gas chromatographic (IGC) method has been used to measure the solubility parameters (delta2) of organosolv lignin at the absolute temperatures from 333.15 K to 373.15 K. The test probe solvents were n-octane (n-C8), n-decane (n-C10), n-dodecane (n-C12), and n-tetradecane (n-C14). The specific retention volumes of the solvents (Vg0), the molar enthalpy of sorption (deltaH1S), the partial molar enthalpy of mixing at infinite dilution (deltaH1infinity), the molar enthalpy of vaporization (deltaHv), the activity coefficients at infinite dilution (Omega1- infinity), and Flory-Huggins inter action parameters (chi12infinity) between organosolv lignin and probe solvents were obtained. The results showed that the above four probes are poor solvents for organosolv lignin; at the same temperature, the chi12infinity reduced with the increase of the carbon number of probe solvents. The average solubility parameter of organosolv lignin was determined as 19.03 (J x cm(-3))1/2.

The CPA Equation of State and an Activity Coefficient Model for Accurate Molar Enthalpy Calculations of Mixtures with Carbon Dioxide and Water/Brine

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

Myint, P. C.; Hao, Y.; Firoozabadi, A.

2015-03-27

Thermodynamic property calculations of mixtures containing carbon dioxide (CO 2) and water, including brines, are essential in theoretical models of many natural and industrial processes. The properties of greatest practical interest are density, solubility, and enthalpy. Many models for density and solubility calculations have been presented in the literature, but there exists only one study, by Spycher and Pruess, that has compared theoretical molar enthalpy predictions with experimental data [1]. In this report, we recommend two different models for enthalpy calculations: the CPA equation of state by Li and Firoozabadi [2], and the CO 2 activity coefficient model by Duanmore » and Sun [3]. We show that the CPA equation of state, which has been demonstrated to provide good agreement with density and solubility data, also accurately calculates molar enthalpies of pure CO 2, pure water, and both CO 2-rich and aqueous (H 2O-rich) mixtures of the two species. It is applicable to a wider range of conditions than the Spycher and Pruess model. In aqueous sodium chloride (NaCl) mixtures, we show that Duan and Sun’s model yields accurate results for the partial molar enthalpy of CO 2. It can be combined with another model for the brine enthalpy to calculate the molar enthalpy of H 2O-CO 2-NaCl mixtures. We conclude by explaining how the CPA equation of state may be modified to further improve agreement with experiments. This generalized CPA is the basis of our future work on this topic.« less

Hippocampus-dependent spatial memory impairment due to molar tooth loss is ameliorated by an enriched environment.

PubMed

Kondo, Hiroko; Kurahashi, Minori; Mori, Daisuke; Iinuma, Mitsuo; Tamura, Yasuo; Mizutani, Kenmei; Shimpo, Kan; Sonoda, Shigeru; Azuma, Kagaku; Kubo, Kin-ya

2016-01-01

Teeth are crucial, not only for mastication, but for overall nutrition and general health, including cognitive function. Aged mice with chronic stress due to tooth loss exhibit impaired hippocampus-dependent learning and memory. Exposure to an enriched environment restores the reduced hippocampal function. Here, we explored the effects of an enriched environment on learning deficits and hippocampal morphologic changes in aged senescence-accelerated mouse strain P8 (SAMP8) mice with tooth loss. Eight-month-old male aged SAMP8 mice with molar intact or with molars removed were housed in either a standard environment or enriched environment for 3 weeks. The Morris water maze was performed for spatial memory test. The newborn cell proliferation, survival, and differentiation in the hippocampus were analyzed using 5-Bromodeoxyuridine (BrdU) immunohistochemical method. The hippocampal brain-derived neurotrophic factor (BDNF) levels were also measured. Mice with upper molars removed (molarless) exhibited a significant decline in the proliferation and survival of newborn cells in the dentate gyrus (DG) as well as in hippocampal BDNF levels. In addition, neuronal differentiation of newly generated cells was suppressed and hippocampus-dependent spatial memory was impaired. Exposure of molarless mice to an enriched environment attenuated the reductions in the hippocampal BDNF levels and neuronal differentiation, and partially improved the proliferation and survival of newborn cells, as well as the spatial memory ability. These findings indicated that an enriched environment could ameliorate the hippocampus-dependent spatial memory impairment induced by molar tooth loss. Copyright © 2015 Elsevier Ltd. All rights reserved.

Triple paternal contribution to a normal/complete molar chimeric singleton placenta.

PubMed

Ariel, I; Goldman-Wohl, D; Yagel, S; Gazit, E; Loewenthal, R

2017-05-01

A comprehensive study of unusual cases of placental pathology may provide insight into mechanisms of normal human fertilization and early embryonic development by examining the exception to the rule. A gravida three para two 39-year-old woman was monitored by ultrasound from 16 weeks of gestation for cystic placenta. A female newborn was born at 36 weeks gestation. Pathologic examination of the partially cystic placenta revealed a singleton placenta comprised of 2/3 normal placenta and 1/3 complete hydatidiform mole, largely degenerated. Immunostaining for p57 was negative in stromal cells of the molar villi. Chromogenic in-situ hybridization revealed diploidy in both normal and molar parts. A total of 16 microsatellites were studied by short tandem repeat analysis, 11 of which were informative. The analysis revealed bipaternal molar tissue of dispermic origin. The paternal monospermic contribution to the normal part was different from that in the molar part, thus resulting in tripaternal contribution to the conceptus. A chimera is a single organism composed of two or more different populations of genetically distinct cells that originated from different zygotes (tetragametic) whereas mosaic is a mixture of two cell lines in one organism originating from one zygote. The possible mechanisms leading to the formation of chimeric/mosaic placenta in our case (one of the components being complete hydatidiform mole), including twinning, fusion at an early embryonic stage and diploidization of triploids, are discussed. © The Author 2017. Published by Oxford University Press on behalf of the European Society of Human Reproduction and Embryology. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Reconstructing temporal variation of fluoride uptake in eastern grey kangaroos (Macropus giganteus) from a high-fluoride area by analysis of fluoride distribution in dentine.

PubMed

Kierdorf, Horst; Rhede, Dieter; Death, Clare; Hufschmid, Jasmin; Kierdorf, Uwe

2016-04-01

Trace element profiling in the incrementally formed dentine of mammalian teeth can be applied to reconstruct temporal variation of incorporation of these elements into the tissue. Using an electron microprobe, this study analysed fluoride distribution in dentine of first and third mandibular molars of free-ranging eastern grey kangaroos inhabiting a high-fluoride area, to assess temporal variation in fluoride uptake of the animals. Fluoride content in the early-formed dentine of first molars was significantly lower than in the late-formed dentine of these teeth, and was also lower than in both, the early and the late-formed dentine of third molars. As early dentine formation in M1 takes place prior to weaning, this finding indicates a lower dentinal fluoride uptake during the pre-weaning compared to the post-weaning period. This is hypothetically attributed to the action of a partial barrier to fluoride transfer from blood to milk in lactating females and a low bioavailability of fluoride ingested together with milk. Another factor contributing to lower plasma fluoride levels in juveniles compared to adults is the rapid clearance of fluoride from blood plasma in the former due to their intense skeletal growth. The combined action of these mechanisms is considered to explain why in kangaroos from high-fluoride areas, the (early-formed) first molars are not affected by dental fluorosis while the (later-formed) third and fourth molars regularly exhibit marked to severe fluorotic lesions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Interfacial Structures of Trihexyltetradecylphosphonium-bis(mandelato)borate Ionic Liquid Confined between Gold Electrodes.

PubMed

Wang, Yong-Lei; Golets, Mikhail; Li, Bin; Sarman, Sten; Laaksonen, Aatto

2017-02-08

Atomistic molecular dynamics simulations have been performed to study microscopic the interfacial ionic structures, molecular arrangements, and orientational preferences of trihexyltetradecylphosphonium-bis(mandelato)borate ([P 6,6,6,14 ][BMB]) ionic liquid confined between neutral and charged gold electrodes. It was found that both [P 6,6,6,14 ] cations and [BMB] anions are coabsorbed onto neutral electrodes at different temperatures. The hexyl and tetradecyl chains in [P 6,6,6,14 ] cations lie preferentially flat on neutral electrodes. The oxalato and phenyl rings in [BMB] anions are characterized by alternative parallel-perpendicular orientations in the mixed innermost ionic layer adjacent to neutral electrodes. An increase in temperature has a marginal effect on the interfacial ionic structures and molecular orientations of [P 6,6,6,14 ][BMB] ionic species in a confined environment. Electrifying gold electrodes leads to peculiar changes in the interfacial ionic structures and molecular orientational arrangements of [P 6,6,6,14 ] cations and [BMB] anions in negatively and positively charged gold electrodes, respectively. As surface charge density increases (but lower than 20 μC/cm 2 ), the layer thickness of the mixed innermost interfacial layer gradually increases due to a consecutive accumulation of [P 6,6,6,14 ] cations and [BMB] anions at negatively and positively charged electrodes, respectively, before the formation of distinct cationic and anionic innermost layers. Meanwhile, the molecular orientations of two oxalato rings in the same [BMB] anions change gradually from a parallel-perpendicular feature to being partially characterized by a tilted arrangement at an angle of 45° from the electrodes and finally to a dominant parallel coordination pattern along positively charged electrodes. Distinctive interfacial distribution patterns are also observed accordingly for phenyl rings that are directly connected to neighboring oxalato rings in [BMB] anions.

Partial Pressures of Te2 and Thermodynamic Properties of Ga-Te System

NASA Technical Reports Server (NTRS)

Su, Ching-Hua; Curreri, Peter A. (Technical Monitor)

2001-01-01

The partial pressures of Te2 in equilibrium with Ga(1-x)Te(x) samples were measured by optical absorption technique from 450 to 1100 C for compositions, x, between 0.333 and 0.612. To establish the relationship between the partial pressure of Te, and the measured optical absorbance, the calibration runs of a pure Te sample were also conducted to determine the Beer's Law constants. The partial pressures of Te2 in equilibrium with the GaTe(s) and Ga2Te3(s)compounds, or the so-called three-phase curves, were established. These partial pressure data imply the existence of the Ga3Te4(s) compound. From the partial pressures of Te2 over the Ga-Te melts, partial molar enthalpy and entropy of mixing for Te were derived and they agree reasonable well with the published data. The activities of Te in the Ga-Te melts were also derived from the measured partial pressures of Te2. These data agree well with most of the previous results. The possible reason for the high activity of Te measured for x less than 0.60 is discussed.

Thermodynamics and kinetics of reactions involving vanadium in natural systems: Accumulation of vanadium in sedimentary rocks

USGS Publications Warehouse

Wanty, R.B.; Goldhaber, M.B.

1992-01-01

A critical review of thermodynamic data for aqueous and solid V species is presented to evaluate dissolution, transport, and precipitation of V under natural conditions. Emphasis is given to results of experimental studies of V chemistry, especially those for which the experimental conditions are near those found in nature. Where possible, data are obtained for or corrected to the reference conditions of 298.15K, 1 atm (1.01325 bar) and zero ionic strength. Vanadium [IV] (VIV) and vanadium[V] (VV) are the most soluble forms of V in nature, and their complexes with fluoride, sulfate, and oxalate may act to increase V solubility under oxidizing conditions. Because redox behavior is of fundamental importance to understanding natural V chemistry, the kinetics of reduction of VIV to VIII H2S were studied. Although H2S is predicted from thermodynamic data to be capable of reducing VIV to VIII, this reaction has not been demonstrated experimentally. Experiments were carried out under conditions of temperature (45??C), pH (3.6-6.8), ionic strength (0.05-0.1 m), and V concentrations (9.8-240 ??molar) likely to be found in nature. Because the reaction is very slow, H2S concentrations in excess of natural conditions were used (8.1 ?? 10-4 to 0.41 atm). The results show that VIV is reduced to VIII under a variety of conditions. The rate increases with increasing pH, but is not appreciably affected by ionic strength (as represented by the concentration of KCl, which was used as the supporting electrolyte in all cases). Prior to initiation of the reaction, there is an induction period, the length of which increases with increasing KCl concentration or decreasing pH. Attempts to model the reaction mechanism by numerical methods have failed to produce a satisfying fit of the results, indicating partial reaction orders, a complex mechanism, or involvement of a variety of intermediate species. The results of the thermodynamic and kinetic studies were applied to understanding the genesis of V deposits such as those commonly found on the Colorado Plateau. Vanadium in these sandstone-hosted deposits is present mostly in the reduced oxidation state, VIII. Because of the insolubility of VIII oxyhydroxides, it is likely that a more oxidized form of V (either [IV] or [V]) was transported to the site of mineralization, and that the V was reduced in situ and subsequently precipitated. A probable reductant is hydrogen sulfide; the presence of pyrite cogenetic with the V minerals documents the presence of H2S during mineralization. The experiments described here show that H2S could have reduced VIV to V III, and thus led to the formation of these deposits. ?? 1992.

Liquid-liquid separation in solutions of normal and sickle cell hemoglobin

NASA Astrophysics Data System (ADS)

Galkin, Oleg; Chen, Kai; Nagel, Ronald L.; Elison Hirsch, Rhoda; Vekilov, Peter G.

2002-06-01

We show that in solutions of human hemoglobin (Hb)oxy- and deoxy-Hb A or Sof near-physiological pH, ionic strength, and Hb concentration, liquid-liquid phase separation occurs reversibly and reproducibly at temperatures between 35 and 40°C. In solutions of deoxy-HbS, we demonstrate that the dense liquid droplets facilitate the nucleation of HbS polymers, whose formation is the primary pathogenic event for sickle cell anemia. In view of recent results that shifts of the liquid-liquid separation phase boundary can be achieved by nontoxic additives at molar concentrations up to 30 times lower than the protein concentrations, these findings open new avenues for the inhibition of the HbS polymerization.

Synthesis and Spectroscopic Evaluation of Two Novel Glycosylated Zinc(II)-Phthalocyanines.

PubMed

Bächle, Felix; Hanack, Michael; Ziegler, Thomas

2015-10-09

In continuation of our work on glycoconjugated phthalocyanines, two new water soluble, non-ionic zinc(II) phthalocyanines have been prepared and fully characterized by means of ¹H-NMR, 13C-NMR, MALDI-TOF, ESI-TOF, UV-Vis spectroscopy, emission spectroscopy and fluorescence lifetime measurements. The carbohydrate-containing phthalonitrile precursors were synthesized through a copper-catalyzed azide-alkyne cycloaddition (CuAAC). The 2-methoxyethoxymethyl protecting group (MEM) was used to protect the carbohydrate moieties. It resisted the harsh basic cyclotetramerization conditions and could be easily cleaved under mild acidic conditions. The glycoconjugated zinc(II) phthalocyanines described here have molar extinction coefficents εmax>10⁵ m(-1) cm(-1) and absorption maxima λ>680 nm, which make them attractive photosensitizers for photo-dynamic therapy.

Colloidal nickel/gallium nanoalloys obtained from organometallic precursors in conventional organic solvents and in ionic liquids: noble-metal-free alkyne semihydrogenation catalysts

NASA Astrophysics Data System (ADS)

Schütte, Kai; Doddi, Adinarayana; Kroll, Clarissa; Meyer, Hajo; Wiktor, Christian; Gemel, Christian; van Tendeloo, Gustaaf; Fischer, Roland A.; Janiak, Christoph

2014-04-01

Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)2] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)3] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)4]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions.Efforts to replace noble-metal catalysts by low-cost alternatives are of constant interest. The organometallic, non-aqueous wet-chemical synthesis of various hitherto unknown nanocrystalline Ni/Ga intermetallic materials and the use of NiGa for the selective semihydrogenation of alkynes to alkenes are reported. Thermal co-hydrogenolysis of the all-hydrocarbon precursors [Ni(COD)2] (COD = 1,5-cyclooctadiene) and GaCp* (Cp* = pentamethylcyclopentadienyl) in high-boiling organic solvents mesitylene and n-decane in molar ratios of 1 : 1, 2 : 3 and 3 : 1 yields the nano-crystalline powder materials of the over-all compositions NiGa, Ni2Ga3 and Ni3Ga, respectively. Microwave induced co-pyrolysis of the same precursors without additional hydrogen in the ionic liquid [BMIm][BF4] (BMIm = 1-butyl-3-methyl-imidazolium) selectively yields the intermetallic phases NiGa and Ni3Ga from the respective 1 : 1 and 3 : 1 molar ratios of the precursors. The obtained materials are characterized by transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), IR, powder X-ray diffraction (PXRD) and atomic absorption spectroscopy (AAS). The single-source precursor [Ni(GaCp*)(PMe3)3] with a fixed Ni : Ga stoichiometry of 1 : 1 was employed as well. In comparison with the co-hydrogenolytic dual precursor source approach it turned out to be less practical due to inefficient nickel incorporation caused by the parasitic formation of stable [Ni(PMe3)4]. The use of ionic liquid [BMIm][BF4] as a non-conventional solvent to control the reaction and stabilize the nanoparticles proved to be particularly advantageous and stable colloids of the nanoalloys NiGa and Ni3Ga were obtained. A phase-selective Ni/Ga colloid synthesis in conventional solvents and in the presence of surfactants such as hexadecylamine (HDA) was not feasible due to the undesired reactivity of HDA with GaCp* leading to inefficient gallium incorporation. Recyclable NiGa nanoparticles selectively semihydrogenate 1-octyne and diphenylacetylene (tolan) to 1-octene and diphenylethylene, respectively, with a yield of about 90% and selectivities of up to 94 and 87%. Ni-NPs yield alkanes with a selectivity of 97 or 78%, respectively, under the same conditions. Electronic supplementary information (ESI) available: Ni-Ga phase diagrams, EDX (XPS) of NP1-NP8, table of Ni : Ga ratios, TG of Ni-Ga SSPs, analysis of NP4, dec. of [Ni(GaCp*)3(PCy3)] with characterization, local resolution EDX of NP3-IL, Ni-NP characterization from Ni(COD)2 and details of (semi-)hydrogenation catalysis. See DOI: 10.1039/c4nr00111g

Plasma membrane surface potential: dual effects upon ion uptake and toxicity

USDA-ARS?s Scientific Manuscript database

Electrical properties of plasma membranes (PMs), partially controlled by the ionic composition of the bathing medium, play significant roles in the distribution of ions at the exterior surface of PMs and in the transport of ions across PMs. The effects of coexistent cations (commonly Al3+, Ca2+, Mg...

Integrated study of first principles calculations and experimental measurements for Li-ionic conductivity in Al-doped solid-state LiGe2(PO4)3 electrolyte

NASA Astrophysics Data System (ADS)

Kang, Joonhee; Chung, Habin; Doh, Chilhoon; Kang, Byoungwoo; Han, Byungchan

2015-10-01

Understanding of the fundamental mechanisms causing significant enhancement of Li-ionic conductivity by Al3+ doping to a solid LiGe2(PO4)3 (LGP) electrolyte is pursued using first principles density functional theory (DFT) calculations combined with experimental measurements. Our results indicate that partial substitution Al3+ for Ge4+ in LiGe2(PO4)3 (LGP) with aliovalent (Li1+xAlxGe2-x(PO4)3, LAGP) improves the Li-ionic conductivity about four-orders of the magnitude. To unveil the atomic origin we calculate plausible diffusion paths of Li in LGP and LAGP materials using DFT calculations and a nudged elastic band method, and discover that LAGP had additional transport paths for Li with activation barriers as low as only 34% of the LGP. Notably, these new atomic channels manifest subtle electrostatic environments facilitating cooperative motions of at least two Li atoms. Ab-initio molecular dynamics predict Li-ionic conductivity for the LAGP system, which is amazingly agreed experimental measurement on in-house made samples. Consequently, we suggest that the excess amounts of Li caused by the aliovalent Al3+ doping to LGP lead to not only enhancing Li concentration but also opening new conducting paths with substantially decreases activation energies and thus high ionic conductivity of LAGP solid-state electrolyte.

Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li 3PS 4

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

Phani Dathar, Gopi Krishna; Balachandran, Janakiraman; Kent, Paul R. C.

The attractive safety and long-term stability of all solid-state batteries has added a new impetus to the discovery and development of solid electrolytes for lithium batteries. Recently several superionic lithium conducting solid electrolytes have been discovered. All the superionic lithium containing compounds (β-Li 3PS 4 and Li 10GeP 2S 12 and oxides, predominantly in the garnet phase) have partially occupied sites. This naturally begs the question of understanding the role of partial site occupancies (or site disorder) in optimizing ionic conductivity in these family of solids. In this paper, we find that for a given topology of the host lattice,more » maximizing the number of sites with similar Li-ion adsorption energies, which gives partial site occupancy, is a natural way to increase the configurational entropy of the system and optimize the conductivity. For a given topology and density of Li-ion adsorption sites, the ionic conductivity is maximal when the number of mobile Li-ions are equal to the number of mobile vacancies, also the very condition for achieving maximal configurational entropy. We demonstrate applicability of this principle by elucidating the role of Li-ion site disorder and the local chemical environment in the high ionic conductivity of β-Li 3PS 4. In addition, for β-Li 3PS 4 we find that a significant density of vacancies in the Li-ion sub-lattice (~25%) leads to sub-lattice melting at (~600 K) leading to a molten form for the Li-ions in an otherwise solid anionic host. This gives a lithium site occupancy that is similar to what is measured experimentally. We further show that quenching this disorder can improve conductivity at lower temperatures. As a consequence, we discover that (a) one can optimize ionic conductivity in a given topology by choosing a chemistry/composition that maximizes the number of mobile-carriers i.e. maximizing both mobile Li-ions and vacancies, and (b) when the concentration of vacancies becomes significant in the Li-ion sub-lattice, it becomes energetically as well as entropically favorable for it to remain molten well below the bulk decomposition temperature of the solid. Finally, this principle may already apply to several known superionic conducting solids.« less

Li-ion site disorder driven superionic conductivity in solid electrolytes: a first-principles investigation of β-Li 3PS 4

DOE PAGES

Phani Dathar, Gopi Krishna; Balachandran, Janakiraman; Kent, Paul R. C.; ...

2016-12-09

The attractive safety and long-term stability of all solid-state batteries has added a new impetus to the discovery and development of solid electrolytes for lithium batteries. Recently several superionic lithium conducting solid electrolytes have been discovered. All the superionic lithium containing compounds (β-Li 3PS 4 and Li 10GeP 2S 12 and oxides, predominantly in the garnet phase) have partially occupied sites. This naturally begs the question of understanding the role of partial site occupancies (or site disorder) in optimizing ionic conductivity in these family of solids. In this paper, we find that for a given topology of the host lattice,more » maximizing the number of sites with similar Li-ion adsorption energies, which gives partial site occupancy, is a natural way to increase the configurational entropy of the system and optimize the conductivity. For a given topology and density of Li-ion adsorption sites, the ionic conductivity is maximal when the number of mobile Li-ions are equal to the number of mobile vacancies, also the very condition for achieving maximal configurational entropy. We demonstrate applicability of this principle by elucidating the role of Li-ion site disorder and the local chemical environment in the high ionic conductivity of β-Li 3PS 4. In addition, for β-Li 3PS 4 we find that a significant density of vacancies in the Li-ion sub-lattice (~25%) leads to sub-lattice melting at (~600 K) leading to a molten form for the Li-ions in an otherwise solid anionic host. This gives a lithium site occupancy that is similar to what is measured experimentally. We further show that quenching this disorder can improve conductivity at lower temperatures. As a consequence, we discover that (a) one can optimize ionic conductivity in a given topology by choosing a chemistry/composition that maximizes the number of mobile-carriers i.e. maximizing both mobile Li-ions and vacancies, and (b) when the concentration of vacancies becomes significant in the Li-ion sub-lattice, it becomes energetically as well as entropically favorable for it to remain molten well below the bulk decomposition temperature of the solid. Finally, this principle may already apply to several known superionic conducting solids.« less

Synthesis of Non-Toxic Silica Particles Stabilized by Molecular Complex Oleic-Acid/Sodium Oleate

PubMed Central

Spataru, Catalin Ilie; Ianchis, Raluca; Petcu, Cristian; Nistor, Cristina Lavinia; Purcar, Violeta; Trica, Bogdan; Nitu, Sabina Georgiana; Somoghi, Raluca; Alexandrescu, Elvira; Oancea, Florin; Donescu, Dan

2016-01-01

The present work is focused on the preparation of biocompatible silica particles from sodium silicate, stabilized by a vesicular system containing oleic acid (OLA) and its alkaline salt (OLANa). Silica nanoparticles were generated by the partial neutralization of oleic acid (OLA), with the sodium cation present in the aqueous solutions of sodium silicate. At the molar ratio OLA/Na+ = 2:1, the molar ratio (OLA/OLANa = 1:1) required to form vesicles, in which the carboxyl and carboxylate groups have equal concentrations, was achieved. In order to obtain hydrophobically modified silica particles, octadecyltriethoxysilane (ODTES) was added in a sodium silicate sol–gel mixture at different molar ratios. The interactions between the octadecyl groups from the modified silica and the oleyl chains from the OLA/OLANa stabilizing system were investigated via simultaneous thermogravimetry (TG) and differential scanning calorimetry (DSC) (TG-DSC) analyses.A significant decrease in vaporization enthalpy and an increase in amount of ODTES were observed. Additionally, that the hydrophobic interaction between OLA and ODTES has a strong impact on the hybrids’ final morphology and on their textural characteristics was revealed. The highest hydrodynamic average diameter and the most negative ζ potential were recorded for the hybrid in which the ODTES/sodium silicate molar ratio was 1:5. The obtained mesoporous silica particles, stabilized by the OLA/OLANa vesicular system, may find application as carriers for hydrophobic bioactive molecules. PMID:27869768

Morphoregulation of teeth: modulating the number, size, shape and differentiation by tuning Bmp activity

PubMed Central

Plikus, Maksim V.; Zeichner-David, Maggie; Mayer, Julie-Ann; Reyna, Julia; Bringas, Pablo; Thewissen, J. G. M.; Snead, Malcolm L.; Chai, Yang; Chuong, Cheng-Ming

2015-01-01

SUMMARY During development and evolution, the morphology of ectodermal organs can be modulated so that an organism can adapt to different environments. We have proposed that morphoregulation can be achieved by simply tilting the balance of molecular activity. We test the principles by analyzing the effects of partial downregulation of Bmp signaling in oral and dental epithelia of the keratin 14-Noggin transgenic mouse. We observed a wide spectrum of tooth phenotypes. The dental formula changed from 1.0.0.3/1.0.0.3 to 1.0.0.2(1)/1.0.0.0. All mandibular and M3 maxillary molars were selectively lost because of the developmental block at the early bud stage. First and second maxillary molars were reduced in size, exhibited altered crown patterns, and failed to form multiple roots. In these mice, incisors were not transformed into molars. Histogenesis and differentiation of ameloblasts and odontoblasts in molars and incisors were abnormal. Lack of enamel caused misocclusion of incisors, leading to deformation and enlargement in size. Therefore, subtle differences in the level, distribution, and timing of signaling molecules can have major morphoregulatory consequences. Modulation of Bmp signaling exemplifies morphoregulation hypothesis: simple alteration of key signaling pathways can be used to transform a prototypical conical-shaped tooth into one with complex morphology. The involvement of related pathways and the implication of morphoregulation in tooth evolution are discussed. PMID:16174037

An ion interaction model for the volumetric properties of natural waters: Density of the solution and partial molal volumes of electrolytes to high concentrations at 25°C

NASA Astrophysics Data System (ADS)

Monnin, Christophe

1989-06-01

Literature density data for binary and common ion ternary solutions in the Na-K-Ca-Mg-Cl-SO 4-HCO 3-CO3-H 2O system at 25°C have been analysed with Pitzer's ion interaction model, which provides an adequate representation of the experimental data for binary and common ion ternary solutions up to high concentration. This analysis yields Pitzer's interaction parameters for the apparent and partial molal volumes, which are the first derivatives with respect to pressure of the interaction parameters for the free energy. From this information, densities of natural waters as well as partial molal volumes of their solutes can be predicted with good accuracy, as shown by several comparisons of calculated and measured values. It is shown that V¯MX - V¯0mx, the excess partial molal volume of the salt MX, depends more on the type of salt than on the electrolyte itself and that it increases with the charges of the salt components. The influence of concentration and composition on the variation of activity coefficients with pressure and on the partial molal volumes of the salts is discussed, using as an example the partial molal volume of CaSO 4(aq) in solutions of various compositions. The increase of V¯CaSO 4, with ionic strength is very large but is not very different for a NaCl-dominated natural water like the Red Sea lower brine than for a simple NaCl solution. Although the variation of activity coefficients with pressure is usually ignored for moderate pressures, like those found in hydrothermal environments, the present example shows that it can be as large as 30% for a 2-2 salt for a pressure increase from 1 to 500 bars at high ionic strength.

Impact of Ionic Liquids on the Structure and Dynamics of Collagen.

PubMed

Tarannum, Aafiya; Adams, Alina; Blümich, Bernhard; Fathima, Nishter Nishad

2018-01-25

The changes in the structure and dynamics of collagen treated with two different classes of ionic liquids, bis-choline sulfate (CS) and 1-butyl-3-methyl imidazolium dimethyl phosphate (IDP), have been studied at the molecular and fibrillar levels. At the molecular level, circular dichroic studies revealed an increase in molar ellipticity values for CS when compared with native collagen, indicating cross-linking, albeit pronounced conformational changes for IDP were witnessed indicating denaturation. The impedance was analyzed to correlate the conformational changes with the hydration dynamics of protein. Changes in the dielectric properties of collagen observed upon treatment with CS and IDP reported molecular reorientation in the surrounding water milieu, suggesting compactness or destabilization of the collagen. This was further confirmed by proton transverse NMR relaxation time measurements, which demonstrated that the water mobility changes in the presence of the ILs. At the fibrillar level, differential scanning calorimetry thermograms for rat tail tendon collagen fibers treated with CS show a 5 °C increase in denaturation temperature, suggesting imparted stability. On the contrary, a significant temperature decrease was noticed for IDP, indicating the destabilization of collagen fibers. The obtained results clearly indicate that the changes in the secondary structure of protein are due to the changes in the hydration dynamics of collagen upon interaction with ILs. Thus, this study on the interaction of collagen with ionic liquids unfolds the propensity of ILs to stabilize or destabilize collagen depending on the changes invoked at the molecular level in terms of structure and dynamics of protein, which also got manifested at the fibrillar level.

Is There Any Preferential Interaction of Ions of Ionic Liquids with DMSO and H2O? A Comparative Study from MD Simulation.

PubMed

Zhao, Yuling; Wang, Jianji; Wang, Huiyong; Li, Zhiyong; Liu, Xiaomin; Zhang, Suojiang

2015-06-04

Recently, some binary ionic liquid (IL)/cosolvent systems have shown better performance than the pure ILs in fields such as CO2 absorption, catalysis, cellulose dissolution, and electrochemistry. However, interactions of ILs with cosolvents are still not well understood at the molecular level. In this work, H2O and DMSO were chosen as the representative protic and aprotic solvents to study the effect of cosolvent nature on solvation of a series of ILs by molecular dynamics simulations and quantum chemistry calculations. The concept of preferential interaction of ions was proposed to describe the interaction of cosolvent with cation and anion of the ILs. By comparing the interaction energies between IL and different cosolvents, it was found that there were significantly preferential interactions of anions of the ILs with water, but the same was not true for the interactions of cations/anions of the ILs with DMSO. Then, a detailed analysis and comparison of the interactions in IL/cosolvent systems, hydrogen bonds between cations and anions of the ILs, and the structure of the first coordination shells of the cations and the anions were performed to reveal the existing state of ions at different molar ratios of the cosolvent to a given IL. Furthermore, a systematic knowledge for the solvation of ions of the ILs in DMSO was given to understand cellulose dissolution in IL/cosolvent systems. The conclusions drawn from this study may provide new insight into the ionic solvation of ILs in cosolvents, and motivate further studies in the related applications.

Airborne pollutant characteristics in an urban, industrial and agricultural complex metroplex with high emission loading and ammonia concentration.

PubMed

Tsai, Jiun-Horng; Chang, Li-Peng; Chiang, Hung-Lung

2014-10-01

The size distribution of particulate mass and water-soluble ionic constituents and their gaseous precursors was investigated in a subtropical area, southern Taiwan. Field sampling and chemical analysis of particulate matter (PM) were conducted using a Micro Orifice Uniform Deposition Impactor (MOUDI) and a Nano-MOUDI, and gaseous pollutants were determined by a denuder-filter pack system. PM size mass distribution, mass concentration and ionic species concentration were measured during the day and at night in the winter and summer. Average PM concentrations in the winter were as high as 132 ± 42 μg/m(3), and PM mass concentrations in the summer were as low as 38 ± 19 μg/m(3). Generally, PM concentration was 111 ± 60 μg/m(3) at night, which was 20% higher than that in the daytime. The size-segregated mass distribution of PM mass concentration was over 85% in the 0.1-3.2 μm range. Ammonium, nitrate, and sulfate were the dominant water-soluble ionic species in PM, contributing 34%-48% of PM mass. High ammonia (12.9-49 μg/m(3)) and SO2 (2.6-27 μg/m(3)) were observed in the gas precursors. The molar ratio [Formula: see text] was 3.18 ± 1.20 at PM1.0, which indicated that the PM was rich in ammonium. Therefore, the excess ammonium could neutralize nitrate to form ammonium nitrate, after the more stable ammonium sulfate and ammonium bisulfate formation. Copyright © 2014 Elsevier B.V. All rights reserved.

Fabrication and photoactivity of ionic liquid-TiO2 structures for efficient visible-light-induced photocatalytic decomposition of organic pollutants in aqueous phase.

PubMed

Gołąbiewska, Anna; Paszkiewicz-Gawron, Marta; Sadzińska, Aleksandra; Lisowski, Wojciech; Grabowska, Ewelina; Zaleska-Medynska, Adriana; Łuczak, Justyna

2018-01-01

To investigate the effect of the ionic liquid (IL) chain length on the surface properties and photoactivity of TiO 2 , a series of TiO 2 microspheres have been synthesized via a solvothermal method assisted by 1-methyl-3-octadecylimidazolium chloride ([ODMIM][Cl]) and 1-methyl-3-tetradecylimidazolium chloride ([TDMIM][Cl]). All as-prepared samples were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), diffuse reflectance spectroscopy (DRS), scanning transmission microscopy (STEM) and the Brunauer-Emmett-Teller (BET) surface area method, whereas the photocatalytic activity was evaluated by the degradation of phenol in aqueous solution under visible light irradiation (λ > 420 nm). The highest photoefficiency (four times higher than pristine TiO 2 ) was observed for the TiO 2 sample obtained in the presence of [TDMIM][Cl] for a IL to TiO 2 precursor molar ratio of 1:3. It was revealed that interactions between the ions of the ionic liquid and the surface of the growing titanium dioxide spheres results in a red-shift of absorption edge for the IL-TiO 2 semiconductors. In this regard, the direct increase of the photoactivity of IL-TiO 2 in comparison to pristine TiO 2 was observed. The active species trapping experiments indicated that O 2 •- is the main active species, created at the surface of the IL-TiO 2 material under visible-light illumination, and is responsible for the effective phenol degradation.

Effects of ammonium-based ionic liquids and 2,4-dichlorophenol on the phospholipid fatty acid composition of zebrafish embryos.

PubMed

Piotrowska, Aleksandra; Syguda, Anna; Wyrwas, Bogdan; Chrzanowski, Lukasz; Luckenbach, Till; Heipieper, Hermann J

2018-01-01

Ionic liquids consisting of a combination of herbicidal anions with a quaternary ammonium cation act as efficient herbicides, which are under consideration to be used in the agriculture. In the present study, we used embryos of the zebrafish (Danio rerio) as a model to assess the toxic potential of ammonium-based ionic liquids for aquatic organisms. As we assumed interference of the partially hydrophobic ionic liquid cation with lipids, we investigated the adaptation response in the lipid composition of the zebrafish embryos, triggered by the ionic compound. Therefore, the impact of ammonium-based ionic liquids with different lengths of the alkyl chain ([C6,C6,C1,C1N][Br], [C8,C8,C1,C1N][Br]) on the phospholipid fatty acid (PLFA) profile of zebrafish embryos up to 72 hours post fertilization (hpf) was examined. Furthermore, the changes in the unsaturation index (UI) of PLFAs, as the sum parameter of membrane fluidity in eukaryotic cells, were presented. The PLFA's UI in the zebrafish embryos upon exposure to quaternary ammonium salts was compared to the UI of the embryos upon exposure to nonionic 2,4-dichlorophenol, which has a similar hydrophobicity but is structurally different to [C8,C8,C1,C1N][Br]. It was shown that for ammonium-based ionic liquid precursors non-specific mode of action occurs and the toxic effect on lipid composition of zebrafish embryos can be well predicted based on chemical properties, like hydrophobicity. Furthermore, the changes in PLFAs, expressed by the UI, can be useful to study toxic effects of organic contamination. However, for zebrafish embryos, after ionic liquids and 2,4-DCP exposure, the changes were observed at high lethal concentrations, which caused the incidence of lethality of 30 and 50% of a group of test animals.

Effects of ammonium-based ionic liquids and 2,4-dichlorophenol on the phospholipid fatty acid composition of zebrafish embryos

PubMed Central

Piotrowska, Aleksandra; Syguda, Anna; Wyrwas, Bogdan; Chrzanowski, Lukasz; Luckenbach, Till

2018-01-01

Ionic liquids consisting of a combination of herbicidal anions with a quaternary ammonium cation act as efficient herbicides, which are under consideration to be used in the agriculture. In the present study, we used embryos of the zebrafish (Danio rerio) as a model to assess the toxic potential of ammonium-based ionic liquids for aquatic organisms. As we assumed interference of the partially hydrophobic ionic liquid cation with lipids, we investigated the adaptation response in the lipid composition of the zebrafish embryos, triggered by the ionic compound. Therefore, the impact of ammonium-based ionic liquids with different lengths of the alkyl chain ([C6,C6,C1,C1N][Br], [C8,C8,C1,C1N][Br]) on the phospholipid fatty acid (PLFA) profile of zebrafish embryos up to 72 hours post fertilization (hpf) was examined. Furthermore, the changes in the unsaturation index (UI) of PLFAs, as the sum parameter of membrane fluidity in eukaryotic cells, were presented. The PLFA’s UI in the zebrafish embryos upon exposure to quaternary ammonium salts was compared to the UI of the embryos upon exposure to nonionic 2,4-dichlorophenol, which has a similar hydrophobicity but is structurally different to [C8,C8,C1,C1N][Br]. It was shown that for ammonium-based ionic liquid precursors non-specific mode of action occurs and the toxic effect on lipid composition of zebrafish embryos can be well predicted based on chemical properties, like hydrophobicity. Furthermore, the changes in PLFAs, expressed by the UI, can be useful to study toxic effects of organic contamination. However, for zebrafish embryos, after ionic liquids and 2,4-DCP exposure, the changes were observed at high lethal concentrations, which caused the incidence of lethality of 30 and 50% of a group of test animals. PMID:29342167

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

PubMed

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

2015-03-01

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

Empirical parameters for solvent acidity, basicity, dipolarity, and polarizability of the ionic liquids [BMIM][BF4] and [BMIM][PF6].

PubMed

del Valle, J C; García Blanco, F; Catalán, J

2015-04-02

The empirical solvent scales for polarizability (SP), dipolarity (SdP), acidity (SA), and basicity (SB) have been successfully used to interpret the solvatochromism of compounds dissolved in organic solvents and their solvent mixtures. Providing that the published solvatochromic parameters for the ionic liquids 1-(1-butyl)-3-methylimidazolium tetrafluoroborate, [BMIM][BF4] and 1-(1-butyl)-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], are excessively widespread, their SP, SdP, SA, and SB values are measured herein at temperatures from 293 to 353 K. Four key points are emphasized herein: (i) the origin of the solvatochromic solvent scales--the gas phase, that is the absence of any medium perturbation--; (ii) the separation of the polarizability and dipolarity effects; (iii) the simplification of the probing process in order to obtain the solvatochromic parameters; and (iv) the SP, SdP, SA, and SB solvent scales can probe the polarizability, dipolarity, acidity, and basicity of ionic liquids as well as of organic solvents and water-organic solvent mixtures. From the multiparameter approach using the four pure solvent scales one can draw the conclusion that (a) the solvent influence of [BMIM][BF4] parallels that of formamide at 293 K, both of them miscible with water; (b) [BMIM][PF6] shows a set of solvatochromic parameters similar to that of chloroacetonitrile, both of them water insoluble; and (c) that the corresponding solvent acidity and basicity of the ionic liquids can be explained to a great extent from the cation species by comparing the empirical parameters of [BMIM](+) with those of the solvent 1-methylimidazole. The insolubility of [BMIM][PF6] in water as compared to [BMIM][BF4] is tentatively connected to some extent to the larger molar volume of the anion [PF6](-), and to the difference in basicity of [PF6](-) and [BF4](-).

Distinct physiological and molecular responses in Arabidopsis thaliana exposed to aluminum oxide nanoparticles and ionic aluminum.

PubMed

Jin, Yujian; Fan, Xiaoji; Li, Xingxing; Zhang, Zhenyan; Sun, Liwei; Fu, Zhengwei; Lavoie, Michel; Pan, Xiangliang; Qian, Haifeng

2017-09-01

Nano-aluminium oxide (nAl 2 O 3 ) is one of the most widely used nanomaterials. However, nAl 2 O 3 toxicity mechanisms and potential beneficial effects on terrestrial plant physiology remain poorly understood. Such knowledge is essential for the development of robust nAl 2 O 3 risk assessment. In this study, we studied the influence of a 10-d exposure to a total selected concentration of 98 μM nAl 2 O 3 or to the equivalent molar concentration of ionic Al (AlCl 3 ) (196 μM) on the model plant Arabidopsis thaliana on the physiology (e.g., growth and photosynthesis, membrane damage) and the transcriptome using a high throughput state-of-the-art technology, RNA-seq. We found no evidence of nAl 2 O 3 toxicity on photosynthesis, growth and lipid peroxidation. Rather the nAl 2 O 3 treatment stimulated root weight and length by 48% and 39%, respectively as well as photosynthesis opening up the door to the use of nAl 2 O 3 in biotechnology and nano agriculture. Transcriptomic analyses indicate that the beneficial effect of nAl 2 O 3 was related to an increase in the transcription of several genes involved in root growth as well as in root nutrient uptake (e.g., up-regulation of the root hair-specific gene family and root development genes, POLARIS protein). By contrast, the ionic Al treatment decreased shoot and root weight of Arabidopsis thaliana by 57.01% and 45.15%, respectively. This toxic effect was coupled to a range of response at the gene transcription level including increase transcription of antioxidant-related genes and transcription of genes involved in plant defense response to pathogens. This work provides an integrated understanding at the molecular and physiological level of the effects of nAl 2 O 3 and ionic Al in Arabidopsis. Copyright © 2017 Elsevier Ltd. All rights reserved.

Elucidation of the effect of ionic liquid pretreatment on rice husk via structural analyses

PubMed Central

2012-01-01

Background In the present study, three ionic liquids, namely 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc), and 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIM]DEP), were used to partially dissolve rice husk, after which the cellulose were regenerated by the addition of water. The aim of the investigation is to examine the implications of the ionic liquid pretreatments on rice husk composition and structure. Results From the attenuated total reflectance Fourier transform-infrared (ATR FT-IR) spectroscopy, X-ray diffraction (XRD) and scanning electron microscopy (SEM) results, the regenerated cellulose were more amorphous, less crystalline, and possessed higher structural disruption compared with untreated rice husk. The major component of regenerated cellulose from [BMIM]Cl and [EMIM]DEP pretreatments was cellulose-rich material, while cellulose regenerated from [EMIM]OAc was a matrix of cellulose and lignin. Cellulose regenerated from ionic pretreatments could be saccharified via enzymatic hydrolysis, and resulted in relatively high reducing sugars yields, whereas enzymatic hydrolysis of untreated rice husk did not yield reducing sugars. Rice husk residues generated from the ionic liquid pretreatments had similar chemical composition and amorphousity to that of untreated rice husk, but with varying extent of surface disruption and swelling. Conclusions The structural architecture of the regenerated cellulose and rice husk residues showed that they could be used for subsequent fermentation or derivation of cellulosic compounds. Therefore, ionic liquid pretreatment is an alternative in the pretreatment of lignocellulosic biomass in addition to the conventional chemical pretreatments. PMID:22958710

Polycation induced actin bundles.

PubMed

Muhlrad, Andras; Grintsevich, Elena E; Reisler, Emil

2011-04-01

Three polycations, polylysine, the polyamine spermine and the polycationic protein lysozyme were used to study the formation, structure, ionic strength sensitivity and dissociation of polycation-induced actin bundles. Bundles form fast, simultaneously with the polymerization of MgATP-G-actins, upon the addition of polycations to solutions of actins at low ionic strength conditions. This indicates that nuclei and/or nascent filaments bundle due to attractive, electrostatic effect of polycations and the neutralization of repulsive interactions of negative charges on actin. The attractive forces between the filaments are strong, as shown by the low (in nanomolar range) critical concentration of their bundling at low ionic strength. These bundles are sensitive to ionic strength and disassemble partially in 100 mM NaCl, but both the dissociation and ionic strength sensitivity can be countered by higher polycation concentrations. Cys374 residues of actin monomers residing on neighboring filaments in the bundles can be cross-linked by the short span (5.4Å) MTS-1 (1,1-methanedyl bismethanethiosulfonate) cross-linker, which indicates a tight packing of filaments in the bundles. The interfilament cross-links, which connect monomers located on oppositely oriented filaments, prevent disassembly of bundles at high ionic strength. Cofilin and the polysaccharide polyanion heparin disassemble lysozyme induced actin bundles more effectively than the polylysine-induced bundles. The actin-lysozyme bundles are pathologically significant as both proteins are found in the pulmonary airways of cystic fibrosis patients. Their bundles contribute to the formation of viscous mucus, which is the main cause of breathing difficulties and eventual death in this disorder. Copyright © 2011 Elsevier B.V. All rights reserved.

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

NASA Astrophysics Data System (ADS)

de Jongh, P. E.; Blanchard, D.; Matsuo, M.; Udovic, T. J.; Orimo, S.

2016-03-01

A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible with Li-metal anodes, prevent Li dendrite formation, and eliminate risks associated with flammable organic solvents. Less than 10 years ago, LiBH4 was proposed as a solid-state electrolyte. It showed a high ionic conductivity, but only at elevated temperatures. Since then a range of other complex metal hydrides has been reported to show similar characteristics. Strategies have been developed to extend the high ionic conductivity of LiBH4 down to room temperature by partial anion substitution or nanoconfinement. The present paper reviews the recent developments in complex metal hydrides as solid electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries.

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

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

Wang, Wenjie; Sung, Woongmo; Ao, Mingqi

2013-10-07

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

Characterization of charged polymer self-assemblies by multidetector thermal field-flow fractionation in aqueous mobile phases.

PubMed

Greyling, Guilaume; Pasch, Harald

2018-01-12

Charged block copolymer self-assemblies, such as charged micelles, have attracted much attention as versatile drug delivery systems due to their readily tunable characteristics such as size and surface charge. However, current column-based analytical techniques are not suitable to fractionate and comprehensively characterize charged micelles in terms of size, molar mass, chemical composition and morphology. Multidetector thermal field-flow fractionation (ThFFF) is shown to be a unique characterization platform that can be used to characterize charged micelles in terms of size, molar mass, chemical composition and morphology in aqueous mobile phases with various ionic strengths and pH. This is demonstrated by the characterization of poly(methacrylic acid)-b-poly(methyl methacrylate) self-assemblies in high pH buffers as well as the characterization of cationic poly(2-vinyl pyridine)-b-polystyrene and poly(4-vinyl pyridine)-b-polystyrene self-assemblies in low pH buffers. Moreover, it is shown that ThFFF is capable of separating charged micelles according to the corona composition. These investigations prove convincingly that ThFFF is broadly applicable to the comprehensive characterization of amphiphilic self-assemblies even when aqueous mobile phases are used. Copyright © 2017 Elsevier B.V. All rights reserved.

Binding of Divalent Cations to Polygalacturonate: A Mechanism Driven by the Hydration Water.

PubMed

Huynh, Uyen T D; Lerbret, Adrien; Neiers, Fabrice; Chambin, Odile; Assifaoui, Ali

2016-02-11

We have investigated the interactions between polygalacturonate (polyGal) and four divalent cations (M(2+) = Ba(2+), Ca(2+), Mg(2+), Zn(2+)) that differ in size and affinity for water. Our results evidence that M(2+)-polyGal interactions are intimately linked to the affinity of M(2+) for water. Mg(2+) interacts so strongly with water that it remains weakly bound to polyGal (polycondensation) by sharing water molecules from its first coordination shell with the carboxylate groups of polyGal. In contrast, the other cations form transient ionic pairs with polyGal by releasing preferentially one water molecule (for Zn(2+)) or two (for Ca(2+) and Ba(2+)), which corresponds to monodentate and bidentate binding modes with carboxylates, respectively. The mechanism for the binding of these three divalent cations to polyGal can be described by two steps: (i) monocomplexation and formation of point-like cross-links between polyGal chains (at low M(2+)/Gal molar ratios, R) and (ii) dimerization (at higher R). The threshold molar ratio, R*, between these two steps depends on the nature of divalent cations and is lower for calcium ions (R* < 0.1) than for zinc and barium ions (R* > 0.3). This difference may be explained by the intermediate affinity of Ca(2+) for water with respect to those of Zn(2+) and Ba(2+), which may induce the formation of cross-links of intermediate flexibility. By comparison, the lower and higher flexibilities of the cross-links formed by Zn(2+) and Ba(2+), respectively, may shift the formation of dimers to higher molar ratios (R*).

Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped and lead-free Bi-2212 systems

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Maroni, V. A.

1996-02-01

Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made on lead-doped and lead-free Bi 2- zPb zSr 2Ca 1Cu 2O x superconducting ceramics in the temperature range ≈ 700-815°C by means of an oxygen-titration techique that employs an yttria-stabilized zirconia electrolyte. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Thermodynamic assessments of the partial molar quantities Δ overlineH(O 2) and Δ overlineS(O 2) for lead-doped Bi-2212 and lead-free Bi-2212 indicate that the solid-state decomposition of these bismuth cuprates at low oxygen partial pressure can be represented by the diphasic CuOCu 2O system.

Some aspects of the thermodynamic behaviour of the lead-doped Bi-2223 system

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Maroni, V. A.

1996-02-01

A thermodynamic assessment of lead-doped Bi-2223 with emphasis on compositions and oxygen partial pressures within the homogeneity region prior to solid-state decomposition is presented. Equations for the variation of oxygen partial pressure with composition and temperature have been derived from our EMF measurements. Long-term metastability was indicated during cycling over a temperature range of ∼ 700-815°C of a lead-doped Bi-2223 sample having an oxygen-deficient stoichiometry of 9.64 prior to solid-state decomposition corresponding to the diphasic CuOCu 2O system. A trend of increasing negative values of the partial molar enthalpy Δ overlineH( O 2) and entropy Δ overlineS( O2 with increasing oxygen deficiency of the condensed phase indicated an increase in ordering of the cuprate structure prior to solid-state decomposition.

Technology transfer opportunities: patent license: electrochemical technique for introducing and redistributing ionic species into the earth

USGS Publications Warehouse

Leinz, Reinhard

1996-01-01

Scientists at the U.S. Geological Survey have expanded applications of the Chim electrode, technology used to perform partial geochemical extractions from soils. Recent applications of the the improved electrode technology show that geochemical extraction efficiencies can be improved by 2 orders of magnitude or better to about 30%.

Cutaneous Sinus Tract from Mandibular Second Molar with C-shaped Canal System and Improper Former Root Canal Treatment: A Case Report.

PubMed

Gharechahi, Maryam; Dastmalchi, Parisa

2016-01-01

Here, we report the diagnosis and treatment of an extraoral cutaneous sinus tract originating in a mandibular second molar with a C-shaped root canal system. The patient was referred to our department by a dermatologist after a series of unsuccessful treatments, including antibiotics. Diffuse radiolucency on a preoperative radiograph revealed that earlier root canal treatment had been only partially successful. Consequently, we performed retreatment of the root canal comprising removal of the former restoration and gutta-percha, cleaning and shaping, and passive irrigation with sodium hypochlorite. The patient responded well, and the cutaneous lesion completely resolved uneventfully within 1 month postoperatively. Preoperative recognition and thorough knowledge of the root canal anatomy and conventional methods of obturation are necessary in performing successful endodontic treatment.

Thermodynamic studies of aqueous solutions of 2,2,2-cryptand at 298.15 K: enthalpy-entropy compensation, partial entropies, and complexation with K+ ions.

PubMed

Shaikh, Vasim R; Terdale, Santosh S; Ahamad, Abdul; Gupta, Gaurav R; Dagade, Dilip H; Hundiwale, Dilip G; Patil, Kesharsingh J

2013-12-19

The osmotic coefficient measurements for binary aqueous solutions of 2,2,2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane) in the concentration range of ~0.009 to ~0.24 mol·kg(-1) and in ternary aqueous solutions containing a fixed concentration of 2,2,2-cryptand of ~0.1 mol·kg(-1) with varying concentration of KBr (~0.06 to ~0.16 mol·kg(-1)) have been reported at 298.15 K. The diamine gets hydrolyzed in aqueous solutions and needs proper approach to obtain meaningful thermodynamic properties. The measured osmotic coefficient values are corrected for hydrolysis and are used to determine the solvent activity and mean ionic activity coefficients of solute as a function of concentration. Strong ion-pair formation is observed, and the ion-pair dissociation constant for the species [CrptH](+)[OH(-)] is reported. The excess and mixing thermodynamic properties (Gibbs free energy, enthalpy, and entropy changes) have been obtained using the activity data from this study and the heat data reported in the literature. Further, the data are utilized to compute the partial molal entropies of solvent and solute at finite as well as infinite dilution of 2,2,2-cryptand in water. The concentration dependent non-linear enthalpy-entropy compensation effect has been observed for the studied system, and the compensation temperature along with entropic parameter are reported. Using solute activity coefficient data in ternary solutions, the transfer Gibbs free energies for transfer of the cryptand from water to aqueous KBr as well as transfer of KBr from water to aqueous cryptand were obtained and utilized to obtain the salting constant (ks) and thermodynamic equilibrium constant (log K) values for the complex (2,2,2-cryptand:K(+)) at 298.15 K. The value of log K = 5.8 ± 0.1 obtained in this work is found to be in good agreement with that reported by Lehn and Sauvage. The standard molar entropy for complexation is also estimated for the 2,2,2-cryptand-KBr complex in aqueous medium.

Synthesis and electrochemical assessment of Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} ceramics and derived composite electrolytes

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

Martins, Natércia C.T.; Rajesh, Surendran; Marques, Fernando M.B.

2015-10-15

Highlights: • Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} prepared for the first time through solid state reaction. • High energy milling needed to assist the ceramic route. • Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} is oxide-ion conductor in air and n-type conductor at low pO{sub 2}. • Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} decomposes slightly when exposed to alkaline carbonates. • Composites based on Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} show standard electrical performance. - Abstract: Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} was prepared for the first time through high temperature (1600 °C for 5 h) solid state reaction, after high energy milling to enhance the mechano-chemical interaction of precursormore » oxides (CeO{sub 2} and Yb{sub 2}O{sub 3}). Single phase formation was confirmed by powder X-ray diffraction. Impedance spectroscopy data obtained under wide temperature (300–800 °C) and oxygen partial pressure (0.21 to about 10{sup −25} atm) ranges indicates that this material exhibits predominant oxide-ion conductivity under oxidizing conditions while n-type electronic conductivity prevails at low oxygen partial pressure. The mixed oxide shows modest ionic conductivity (1.1 × 10{sup −3} S cm{sup −1} at 800 °C) with activation energy of 1.3 eV in the 600–800 °C temperature range. When combined with molten carbonates (Li{sub 2}CO{sub 3} + Na{sub 2}CO{sub 3}, 1:1 molar ratio) to produce composite electrolytes, Ce{sub 0.5}Yb{sub 0.5}O{sub 1.75} slightly decomposed. However, the composite electrical performance is still acceptable and closely matches the conductivity of similar materials (>0.1 S cm{sup −1} immediately above 500 °C)« less

Diffusion in silicate melts: III. Empirical models for multicomponent diffusion

NASA Astrophysics Data System (ADS)

Yan, Liang; Richter, Frank M.; Chamberlin, Laurinda

1997-12-01

Empirical models for multicomponent diffusion in an isotropic fluid were derived by splitting the component's dispersion velocity into two parts: (a) an intrinsic velocity which is proportional to each component's electrochemical potential gradient and independent of reference frame and (b) a net interaction velocity which is both model and reference frame dependent. Simple molecules (e.g., M pO q) were chosen as endmember components. The interaction velocity is assumed to be either the same for each component (leading to a common relaxation velocity U) or proportional to a common interaction force ( F). U or F is constrained by requiring no local buildup in either volume or charge. The most general form of the model-derived diffusion matrix [ D] can be written as a product of a model-dependent kinetic matrix [ L] and a model independent thermodynamic matrix [ G], [ D] = [ L] · [ G]. The elements of [ G] are functions of derivatives of chemical potential with respect to concentration. The elements of [ L] are functions of concentration and partial molar volume of the endmember components, Cio and Vio, and self diffusivity Di, and charge number zi of individual diffusing species. When component n is taken as the dependent variable they can be written in a common form L ij = D jδ ij + C io[V noD n - V joD j)A i + (p nz nD n - p jz jD j)B i] where the functional forms of the scaling factors Ai and Bi depend on the model considered. The off-diagonal element Lij ( i ≠ j) is directly proportional to the concentration of component i, and thus negligible when i is a dilute component. The salient feature of kinetic interaction or relaxation is to slow down larger (volume or charge) and faster diffusing components and to speed up smaller (volume or charge) and slower moving species, in order to prevent local volume or charge buildup. Empirical models for multicomponent diffusion were tested in the ternary system CaOAl 2O 3SiO 2 at 1500°C and 1 GPa over a large range of melt compositions. Model-derived diffusion matrices calculated using measured self diffusivities (Ca, Al, Si, and O), partial molar volumes, and activities were compared with experimentally derived diffusion matrices at two melt compositions. Chemical diffusion profiles computed using the model-derived diffusion matrices, accounting for the compositional dependency of self diffusivities and activity coefficients, were also compared with the experimentally measured ones. Good agreement was found between the ionic common-force model derived diffusion profiles and the experimentally measured ones. Secondary misfits could result from either inadequacies of the model or inaccuracies in activity-composition relationship. The results show that both kinetic interactions and thermodynamic nonideality contribute significantly to the observed diffusive coupling in the molten CaOAl 2O 3SiO 2.

Vaporization and thermodynamics of forsterite-rich olivine and some implications for silicate atmospheres of hot rocky exoplanets

NASA Astrophysics Data System (ADS)

Costa, Gustavo C. C.; Jacobson, Nathan S.; Fegley, Bruce, Jr.

2017-06-01

We describe an experimental and theoretical study of olivine [Mg2SiO4 (Fo)-Fe2SiO4 (Fa)] vaporization. The vaporization behavior and thermodynamic properties of a fosterite-rich olivine (Fo95Fa5) have been explored by high-temperature Knudsen effusion mass spectrometry (KEMS) from 1750 to 2250 K. The gases observed (in order of decreasing partial pressure) are Fe, SiO, Mg, O2 and O. We measured the solidus temperature (∼2050 K), partial pressures of individual gases, the total vapor pressure, and thermodynamic activities and partial molar enthalpies of MgO, 'FeO', and SiO2 for the Fo95Fa5 olivine. The results are compared to other measurements and models of the olivine system. Our experimental data show olivine vaporizes incongruently. We discuss this system both as a psuedo-binary of Fo-Fa and a psuedo-ternary of MgO-'FeO'-SiO2. Iron/magnesium molar ratios in the sample before (∼0.05) and after (∼0.04) vaporization are consistent with the small positive deviations from ideality of fayalite (γ ∼ 1.17) in olivine of the composition studied (e.g., Nafziger and Muan, 1967). Our data for olivine + melt confirm prior theoretical models predicting fractional vaporization of Fe relative to Mg from molten silicates (Fegley and Cameron, 1987; Schaefer and Fegley, 2009; Ito et al., 2015). If loss of silicate atmospheres occurs from hot rocky exoplanets with magma oceans the residual planet may be enriched in magnesium relative to iron.

Enthalpy of mixing of liquid Co–Sn alloys

PubMed Central

Yakymovych, A.; Fürtauer, S.; Elmahfoudi, A.; Ipser, H.; Flandorfer, H.

2014-01-01

A literature overview of enthalpy of mixing data for liquid Co–Sn alloys shows large scattering but no clear temperature dependence. Therefore drop calorimetry was performed in the Co–Sn system at twelve different temperatures in 100 K steps in the temperature range (673 to 1773) K. The integral enthalpy of mixing was determined starting from 1173 K and fitted to a standard Redlich–Kister polynomial. In addition, the limiting partial molar enthalpy of Co in Sn was investigated by small additions of Co to liquid Sn at temperatures (673 to 1773) K. The integral and partial molar enthalpies of the Co–Sn system generally show an exothermic mixing behavior. Significant temperature dependence was detected for the enthalpies of mixing. The minimum integral enthalpy values vary with rising temperature from approx. −7820 J/mol at T = 1173 K to −1350 J/mol at T = 1773 K; the position of the minimum is between (59 and 61) at.% Co. The results are discussed and compared with literature data available for this system. X-ray studies and scanning electron microscopy of selected alloys obtained from the calorimetric measurements were carried out in order to check the completeness of the solution process. PMID:24994940

Fully transparent, non-volatile bipolar resistive memory based on flexible copolyimide films

NASA Astrophysics Data System (ADS)

Yu, Hwan-Chul; Kim, Moon Young; Hong, Minki; Nam, Kiyong; Choi, Ju-Young; Lee, Kwang-Hun; Baeck, Kyoung Koo; Kim, Kyoung-Kook; Cho, Soohaeng; Chung, Chan-Moon

2017-01-01

Partially aliphatic homopolyimides and copolyimides were prepared from rel-(1'R,3S,5'S)-spiro[furan-3(2H),6'-[3]oxabicyclo[3.2.1]octane]-2,2',4',5(4H)-tetrone (DAn), 2,6-diaminoanthracene (AnDA), and 4,4'-oxydianiline (ODA) by varying the molar ratio of AnDA and ODA. We utilized these polyimide films as the resistive switching layer in transparent memory devices. While WORM memory behavior was obtained with the PI-A100-O0-based device (molar feed ratio of DAn : AnDA : ODA = 1 : 1 : 0), the PI-A70-O30-based device (molar feed ratio of DAn : AnDA : ODA = 1 : 0.7 : 0.3) exhibited bipolar resistive switching behavior with stable retention for 104 s. This result implies that the memory properties can be controlled by changing the polyimide composition. The two devices prepared from PI-A100-O0 and PI-A70-O30 showed over 90% transmittance in the visible wavelength range from 400 to 800 nm. The behavior of the memory devices is considered to be governed by trap-controlled, space-charge limited conduction (SCLC) and local filament formation. [Figure not available: see fulltext.

Experimental Study on Rise Husk Ash & Fly Ash Based Geo-Polymer Concrete Using M-Sand

NASA Astrophysics Data System (ADS)

Nanda Kishore, G.; Gayathri, B.

2017-08-01

Serious environmental problems by means of increasing the production of Ordinary Portland cement (OPC), which is conventionally used as the primary binder to produce cement concrete. An attempt has been made to reduce the use of ordinary Portland cement in cement concrete. There is no standard mix design of geo-polymer concrete, an effort has been made to know the physical, chemical properties and optimum mix of geo-polymer concrete mix design. Concrete cubes of 100 x 100 x 100 mm were prepared and cured under steam curing for about 24 hours at temperature range of 40°C to 60°C. Fly ash is replaced partially with rice husk ash at percentage of 10%, 15% and 25%. Sodium hydroxide and sodium silicate are of used as alkaline activators with 5 Molar and 10 Molar NaOH solutions. Natural sand is replaced with manufacture sand. Test results were compared with controlled concrete mix of grade M30. The results shows that as the percentage of rice husk ash and water content increases, compressive strength will be decreases and as molarity of the alkaline solution increases, strength will be increases.

Oxygen ion conductivity of La0.8Sr0.2Ga0.83Mg0.17-xCoxO3-δ synthesized by laser rapid solidification

NASA Astrophysics Data System (ADS)

Zhang, Jie; Yuan, Chao; Wang, Jun-Qiao; Liang, Er-Jun; Chao, Ming-Ju

2013-08-01

Materials La0.8Sr0.2Ga0.83Mg0.17-xCoxO3-δ with x = 0, 0.05, 0.085, 0.10, and 0.15 are synthesized by laser rapid solidification. It is shown that the samples prepared by laser rapid solidification give rise to unique spear-like or leaf-like microstructures which are orderly arranged and densely packed. Their electrical properties each show a general dependence of the Co content and the total conductivities of La0.8Sr0.2Ga0.83Mg0.085Co0.085O3-δ prepared by laser rapid solidification are measured to be 0.067, 0.124, and 0.202 S·cm-1 at 600, 700, and 800 °C, respectively, which are much higher than by conventional solid state reactions. Moreover, the electrical conductivities each as a function of the oxygen partial pressure are also measured. It is shown that the samples with the Co content values <= 8.5 mol% each exhibit basically ionic conduction while those for Co content values >= 10 mol % each show ionic mixed electronic conduction under oxygen partial pressures from 10-16 atm (1 atm = 1.01325 × 105 Pa) to 0.98 atm. The improved ionic conductivity of La0.8Sr0.2Ga0.83Mg0.085Co0.085O3-δ prepared by laser rapid solidification compared with by solid state reactions is attributed to the unique microstructure of the sample generated during laser rapid solidification.

Determination of Activities of Niobium in Cu-Nb Melts Containing Dilute Nb

NASA Astrophysics Data System (ADS)

Wang, Daya; Yan, Baijun; Sichen, Du

2015-04-01

The activity coefficients of niobium in Cu-Nb melts were measured by equilibrating solid NbO2 with liquid copper under controlled oxygen potentials in the temperature range of 1773 K to 1898 K (1500 °C to 1625 °C). Either CO-CO2 gas mixture or H2-CO2 gas mixture was employed to obtain the desired oxygen partial pressures. Cu-Nb system was found to follow Henry's law in the composition range studied. The temperature dependence of Henry's constant in the Cu-Nb melts could be expressed as follows: The partial molar excess Gibbs energy change of niobium in Cu-Nb melts can be expressed as follows:

Rheology of polyelectrolyte complex materials

NASA Astrophysics Data System (ADS)

Tirrell, Matthew

Fluid polyelectrolyte complexes, sometimes known as complex coacervates, have rheological properties that are very sensitive to structure and salt concentration. Dynamic moduli of such viscoelastic materials very many orders of magnitude between solutions of no added salt to of order tenth molar salt, typical, for example of physiological saline. Indeed, salt plays a role in the rheology of complex coacervates analogous to that which temperature plays on polymer melts, leading to an empirical observation of what may be termed time-salt or frequency salt superposition. Block copolymers containing complexing ionic blocks also exhibit strong salt sensitivity of their rheological properties. Data representing these phenomena will be presented and discussed. Support from NIST, Department of Commerce, via the Center for Hierarchical Materials Design at Northwestern University and the University of Chicago is gratefully acknowledged.

Enthalpies of solvation for dopamine hydrochloride in water-ethanol solutions

NASA Astrophysics Data System (ADS)

Vandyshev, V. N.; Ledenkov, S. F.; Molchanov, A. S.

2012-10-01

The enthalpies of dissolution of dopamine hydrochloride (H2Dop · HCl) in water-ethanol solvents containing from 0 to 0.8 mole fraction of ethanol are measured by calorimetry at 298.15 K. Standard enthalpies of transfer (Δtr H ∘) for the molecular (H2Dop) and cationic (H3Dop+) forms of dopamine from water into binary solvents are calculated from the obtained data. The enthalpies of transfer of H3Dop+ cation are determined from the enthalpies of dissolution of H2Dop · HCl using the familiar method of separating the molar quantities into ionic contributions (Ph4P+ = BPh{4/-}), and by an original alternative procedure. The effect of the composition of the binary solvent on the solvation of dopamine is considered.

New eutectic ionic liquids for lipase activation and enzymatic preparation of biodiesel†

PubMed Central

Zhao, Hua; Baker, Gary A.; Holmes, Shaletha

2012-01-01

The enzymatic preparation of biodiesel has been hampered by the lack of suitable solvents with desirable properties such as high lipase compatibility, low cost, low viscosity, high biodegradability, and ease of product separation. Recent interest in using ionic liquids (ILs) as advanced reaction media has led to fast reaction rates and high yields in the enzymatic synthesis of biodiesel. However, conventional (i.e., cation–anion paired) ILs based on imidazolium and other quaternary ammonium salts remain too expensive for wide application at industrial scales. In this study, we report on newly-synthesized eutectic ILs derived from choline acetate or choline chloride coupled with biocompatible hydrogen-bond donors, such as glycerol. These eutectic solvents have favorable properties including low viscosity, high biodegradability, and excellent compatibility with Novozym® 435, a commercial immobilized Candida antarctica lipase B. Furthermore, in a model biodiesel synthesis system, we demonstrate high reaction rates for the enzymatic transesterification of Miglyol® oil 812 with methanol, catalyzed by Novozym® 435 in choline acetate/glycerol (1 : 1.5 molar ratio). The high conversion (97%) of the triglyceride obtained within 3 h, under optimal conditions, suggests that these novel eutectic solvents warrant further exploration as potential media in the enzymatic production of biodiesel. PMID:21283901

Physicochemical Properties of Glycine-Based Ionic Liquid [QuatGly-OEt][EtOSO3] (2-Ethoxy-1-ethyl-1,1-dimethyl-2-oxoethanaminium ethyl sulfate) and Its Binary Mixtures with Poly(ethylene glycol) (Mw = 200) at Various Temperatures

PubMed Central

Wu, Tzi-Yi; Chen, Bor-Kuan; Hao, Lin; Lin, Yuan-Chung; Wang, H. Paul; Kuo, Chung-Wen; Sun, I-Wen

2011-01-01

This work includes specific basic characterization of synthesized glycine-based Ionic Liquid (IL) [QuatGly-OEt][EtOSO3] by NMR, elementary analysis and water content. Thermophysical properties such as density, ρ, viscosity, η, refractive index, n, and conductivity, κ, for the binary mixture of [QuatGly-OEt][EtOSO3] with poly(ethylene glycol) (PEG) [Mw = 200] are measured over the whole composition range. The temperature dependence of density and dynamic viscosity for neat [QuatGly-OEt][EtOSO3] and its binary mixture can be described by an empirical polynomial equation and by the Vogel-Tammann-Fucher (VTF) equation, respectively. The thermal expansion coefficient of the ILs is ascertained using the experimental density results, and the excess volume expansivity is evaluated. The negative values of excess molar volume for the mixture indicate the ion-dipole interactions and packing between IL and PEG oligomer. The results of binary excess property (VmE ) and deviations (Δη, Δxn, ΔΨn, ΔxR, and ΔΨR) are discussed in terms of molecular interactions and molecular structures in the binary mixture. PMID:22272102

Phosphate Removal by Anion Binding on Functionalized Nanoporous Sorbents

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

Chouyyok, Wilaiwan; Wiacek, Robert J.; Pattamakomsan, Kanda

2010-03-26

Phosphate was captured from aqueous solutions by cationic metal-EDA complexes anchored inside mesoporous silica MCM-41 supports (Cu(II)-EDA-SAMMS and Fe(III)-EDA-SAMMS). Fe-EDA-SAMMS was more effective at capturing phosphate than the Cu-EDA-SAMMS and was further studied for matrix effects (e.g., pH, ionic strength, and competing anions) and sorption performance (e.g., capacity and rate). The adsorption of phosphate was highly pH dependent; it increased with increasing pH from 1.0 to 6.5, and decreased above pH 6.5. The adsorption was affected by high ionic strength (0.1 M of NaCl). In the presence of 1000-fold molar excess of chloride and nitrate anions, phosphate removal by Fe-EDA-SAMMSmore » was not affected. Slight, moderate and large impacts were seen with bicarbonate, sulfate and citrate anions, respectively. The phosphate adsorption data on Fe-EDA-SAMMS agreed well with the Langmuir model with the estimated maximum capacity of 43.3 mg/g. The material displayed rapid sorption rate (99% of phosphate removal within 1 min) and lowering the phosphate content to ~ 10 µg/L of phosphorus, which is lower than the EPA’s established freshwater contaminant level for phosphorous (20 µg/L).« less

Dissecting ion-specific from electrostatic salt effects on amyloid fibrillation: A case study of insulin.

PubMed

Kutsch, Miriam; Hortmann, Pascal; Herrmann, Christian; Weibels, Sebastian; Weingärtner, Hermann

2016-03-03

Diseases like Alzheimer, type II diabetes mellitus, and others go back to fibril formation of partially unfolded proteins. The impact of sodium, potassium, choline, guanidinium, and 1-ethyl-3-methylimidazolium chloride on the fibrillation kinetics of insulin in an acid-denaturing solvent environment is studied by fluorescence spectroscopy using thioflavin T as a fibril-specific stain. The fibrillation kinetics reveal a sigmoidal behavior, characterized by the lag time τlag and the maximum elongation rate k of the fibrils. Up to ionic strengths of about 70 mM, the elongation rate increases with salt concentration. This increase is nonspecific with regard to the salts. Below ionic strengths of ∼50 mM, it can be explained by a Debye-Hückel type model, indicating a dominant role of Coulomb interactions between the charged reactants and products screened by the ionic environment. At higher ionic strength, the elongation rates pass maxima, followed by a Hofmeister type ion-specific decrease. There is a correlation between the lag time τlag and the inverse elongation rate k, which can be described by a power law of the form τlag ∝  aτ(α) with a sublinear exponent α ≅ 1/2.

The Predictive Power of Electronic Polarizability for Tailoring the Refractivity of High Index Glasses Optical Basicity Versus the Single Oscillator Model

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

McCloy, John S.; Riley, Brian J.; Johnson, Bradley R.

Four compositions of high density (~8 g/cm3) heavy metal oxide glasses composed of PbO, Bi2O3, and Ga2O3 were produced and refractivity parameters (refractive index and density) were computed and measured. Optical basicity was computed using three different models – average electronegativity, ionic-covalent parameter, and energy gap – and the basicity results were used to compute oxygen polarizability and subsequently refractive index. Refractive indices were measured in the visible and infrared at 0.633 μm, 1.55 μm, 3.39 μm, 5.35 μm, 9.29 μm, and 10.59 μm using a unique prism coupler setup, and data were fitted to the Sellmeier expression to obtainmore » an equation of the dispersion of refractive index with wavelength. Using this dispersion relation, single oscillator energy, dispersion energy, and lattice energy were determined. Oscillator parameters were also calculated for the various glasses from their oxide values as an additional means of predicting index. Calculated dispersion parameters from oxides underestimate the index by 3 to 4%. Predicted glass index from optical basicity, based on component oxide energy gaps, underpredicts the index at 0.633 μm by only 2%, while other basicity scales are less accurate. The predicted energy gap of the glasses based on this optical basicity overpredicts the Tauc optical gap as determined by transmission measurements by 6 to 10%. These results show that for this system, density, refractive index in the visible, and energy gap can be reasonably predicted using only composition, optical basicity values for the constituent oxides, and partial molar volume coefficients. Calculations such as these are useful for a priori prediction of optical properties of glasses.« less

Reversible capture of SO2 through functionalized ionic liquids.

PubMed

Yang, Dezhong; Hou, Minqiang; Ning, Hui; Ma, Jun; Kang, Xinchen; Zhang, Jianling; Han, Buxing

2013-07-01

Emission of SO2 in flue gas from the combustion of fossil fuels leads to severe environmental problems. Exploration of green and efficient methods to capture SO2 is an interesting topic, especially at lower SO2 partial pressures. In this work, ionic liquids (ILs) 1-(2-diethylaminoethyl)-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Et2 NEMim][Tf2 N]) and 1-(2-diethylaminoethyl)-3-methylimidazolium tetrazolate ([Et2 NEMim][Tetz]) were synthesized. The performances of the two ILs to capture SO2 were studied under different conditions. It was demonstrated that the ILs were very efficient for SO2 absorption. The [Et2 NEMim][Tetz] IL designed in this work could absorb 0.47 g(SO2)g(IL)(-1) at 0.0101 MPa SO2 partial pressure, which is the highest capacity reported to date under the same conditions. The main reason for the large capacity was that both the cation and the anion could capture SO2 chemically. In addition, the IL could easily be regenerated, and the very high absorption capacity and rapid absorption/desorption rates were not changed over five repeated cycles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Wintertime water-soluble aerosol composition and particle water content in Fresno, California

NASA Astrophysics Data System (ADS)

Parworth, Caroline L.; Young, Dominique E.; Kim, Hwajin; Zhang, Xiaolu; Cappa, Christopher D.; Collier, Sonya; Zhang, Qi

2017-03-01

The composition and concentrations of water-soluble gases and ionic aerosol components were measured from January to February 2013 in Fresno, CA, with a particle-into-liquid sampler with ion chromatography and annular denuders. The average (±1σ) ionic aerosol mass concentration was 15.0 (±9.4) µg m-3, and dominated by nitrate (61%), followed by ammonium, sulfate, chloride, potassium, nitrite, and sodium. Aerosol-phase organic acids, including formate and glycolate, and amines including methylaminium, triethanolaminium, ethanolaminium, dimethylaminium, and ethylaminium were also detected. Although the dominant species all came from secondary aerosol formation, there were primary sources of ionic aerosols as well, including biomass burning for potassium and glycolate, sea spray for sodium, chloride, and dimethylamine, and vehicles for formate. Particulate methanesulfonic acid was also detected and mainly associated with terrestrial sources. On average, the molar concentration of ammonia was 49 times greater than nitric acid, indicating that ammonium nitrate formation was limited by nitric acid availability. Particle water was calculated based on the Extended Aerosol Inorganics Model (E-AIM) thermodynamic prediction of inorganic particle water and κ-Köhler theory approximation of organic particle water. The average (±1σ) particle water concentration was 19.2 (±18.6) µg m-3, of which 90% was attributed to inorganic species. The fractional contribution of particle water to total fine particle mass averaged at 36% during this study and was greatest during early morning and night and least during the day. Based on aqueous-phase concentrations of ions calculated by using E-AIM, the average (±1σ) pH of particles in Fresno during the winter was estimated to be 4.2 (±0.2).

Effect of ionic activity products on the structure and composition of mineral self assembled on three-dimensional poly(lactide-co-glycolide) scaffolds

PubMed Central

Shin, Kyungsup; Jayasuriya, Ambalangodage C.; Kohn, David H.

2009-01-01

A biomimetic approach involving the self-assembly of mineral within the pores of three-dimensional porous polymer scaffolds is a promising strategy to integrate advantages of inorganic and organic phases into a single material for hard tissue engineering. Such a material enhances the ability of progenitor cells to differentiate down an osteoblast lineage in vitro and in vivo, compared with polymer scaffolds. The mechanisms regulating mineral formation in this one-step process, however, are poorly understood, especially the effects of ionic activity products (IP) of the mineralizing solution and incubation time. The aims of this study were to define the structure and composition of mineral formed within the pores of biodegradable polymer scaffolds as a function of IP and time. Three-dimensional poly(lactide-co-glycolide) scaffolds were fabricated by solvent casting/particulate leaching and incubated for 4–16 days in six variants of simulated body fluid whose IPs were varied by adjusting ionic concentrations. Scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy demonstrated the formation of carbonated apatite with sub-micrometer sized crystals that grew into spherical globules extending out of the scaffold pore surfaces. As IP increased, more mineral grew on the scaffold pore surfaces, but the apatite became less crystalline and the Ca/P molar ratio decreased from 1.63 ± 0.005 to 1.51 ± 0.002. Since morphology, composition, and structure of mineral are factors that affect cell function, this study demonstrates that the IP of the mineralizing solution is an important modulator of material properties, potentially leading to enhanced control of cell function. PMID:17584901

Oxidative desulfurization of fuels catalyzed by Fenton-like ionic liquids at room temperature.

PubMed

Jiang, Yunqing; Zhu, Wenshuai; Li, Huaming; Yin, Sheng; Liu, Hua; Xie, Qingjie

2011-03-21

Oxidation of the sulfur-containing compounds benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been studied in a desulfurization system composed of model oil, hydrogen peroxide, and different types of ionic liquids [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3), [(C(8)H(17))(3)CH(3)N]Cl/CuCl(2), [(C(8)H(17))(3)CH(3)N]Cl/ZnCl(2), [(C(8)H(17))(3)CH(3)N]Cl/SnCl(2), [(C(4)H(9))(3)CH(3)N]Cl/FeCl(3), [C(10)H(21)(CH(3))(3)N]Cl/FeCl(3), [(C(10)H(21))(2)(CH(3))(2)N]Cl/FeCl(3). Deep desulfurization is achieved in the Fenton-like ionic liquid [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) at 25 °C for 1 h. The desulfurization of DBT reaches 97.9%, in consuming very low amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) (only 0.702 mmol). The reaction conditions, for example, the amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) or H(2)O(2), the temperature, and the molar ratio of FeCl(3) to [(C(8)H(17))(3)CH(3)N]Cl, are investigated for this system. The oxidation reactivity of the different sulfur-containing compounds is found to decrease in the order of DBT>BT>4,6-DMDBT. The desulfurization system can be recycled six times without significant decrease in activity. The sulfur level of FCC gasoline could be reduced from 360 ppm to 110 ppm. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic Asymmetry and Solvent Excluded Volume Effects on Spherical Electric Double Layers: A Density Functional Approach

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

Medasani, Bharat; Ovanesyan, Zaven; Thomas, Dennis G.

In this article we present a classical density functional theory for electrical double layers of spherical macroions that extends the capabilities of conventional approaches by accounting for electrostatic ion correlations, size asymmetry and excluded volume effects. The approach is based on a recent approximation introduced by Hansen-Goos and Roth for the hard sphere excess free energy of inhomogeneous fluids (J. Chem. Phys. 124, 154506). It accounts for the proper and efficient description of the effects of ionic asymmetry and solvent excluded volume, especially at high ion concentrations and size asymmetry ratios including those observed in experimental studies. Additionally, we utilizemore » a leading functional Taylor expansion approximation of the ion density profiles. In addition, we use the Mean Spherical Approximation for multi-component charged hard sphere fluids to account for the electrostatic ion correlation effects. These approximations are implemented in our theoretical formulation into a suitable decomposition of the excess free energy which plays a key role in capturing the complex interplay between charge correlations and excluded volume effects. We perform Monte Carlo simulations in various scenarios to validate the proposed approach, obtaining a good compromise between accuracy and computational cost. We use the proposed computational approach to study the effects of ion size, ion size asymmetry and solvent excluded volume on the ion profiles, integrated charge, mean electrostatic potential, and ionic coordination number around spherical macroions in various electrolyte mixtures. Our results show that both solvent hard sphere diameter and density play a dominant role in the distribution of ions around spherical macroions, mainly for experimental water molarity and size values where the counterion distribution is characterized by a tight binding to the macroion, similar to that predicted by the Stern model.« less

Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization

NASA Astrophysics Data System (ADS)

Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.

2017-12-01

We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

Molecular dynamics simulations of the structure and single-particle dynamics of mixtures of divalent salts and ionic liquids

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

Gómez-González, Víctor; Docampo-Álvarez, Borja; Gallego, Luis J.

2015-09-28

We report a molecular dynamics study of the structure and single-particle dynamics of mixtures of a protic (ethylammonium nitrate) and an aprotic (1-butyl-3-methylimidazolium hexaflurophosphate [BMIM][PF{sub 6}]) room-temperature ionic liquids doped with magnesium and calcium salts with a common anion at 298.15 K and 1 atm. The solvation of these divalent cations in dense ionic environments is analyzed by means of apparent molar volumes of the mixtures, radial distribution functions, and coordination numbers. For the protic mixtures, the effect of salt concentration on the network of hydrogen bonds is also considered. Moreover, single-particle dynamics of the salt cations is studied by means ofmore » their velocity autocorrelation functions and vibrational densities of states, explicitly analyzing the influence of salt concentration, and cation charge and mass on these magnitudes. The effect of the valency of the salt cation on these properties is considered comparing the results with those for the corresponding mixtures with lithium salts. We found that the main structural and dynamic features of the local solvation of divalent cations in ionic liquids are similar to those of monovalent salts, with cations being localized in the polar nanoregions of the bulk mixture coordinated in monodentate and bidentate coordination modes by the [NO{sub 3}]{sup −} and [PF{sub 6}]{sup −} anions. However, stronger electrostatic correlations of these polar nanoregions than in mixtures with salts with monovalent cations are found. The vibrational modes of the ionic liquid (IL) are seen to be scarcely affected by the addition of the salt, and the effect of mass and charge on the vibrational densities of states of the dissolved cations is reported. Cation mass is seen to exert a deeper influence than charge on the low-frequency vibrational spectra, giving a red shift of the vibrational modes and a virtual suppression of the higher energy vibrational modes for the heavier Ca{sup 2+} cations. No qualitative difference with monovalent cations was found in what solvation is concerned, which suggests that no enhanced reduction of the mobility of these cations and their complexes in ILs respective to those of monovalent cations is to be expected.« less

Thermodynamic-ensemble independence of solvation free energy.

PubMed

Chong, Song-Ho; Ham, Sihyun

2015-02-10

Solvation free energy is the fundamental thermodynamic quantity in solution chemistry. Recently, it has been suggested that the partial molar volume correction is necessary to convert the solvation free energy determined in different thermodynamic ensembles. Here, we demonstrate ensemble-independence of the solvation free energy on general thermodynamic grounds. Theoretical estimates of the solvation free energy based on the canonical or grand-canonical ensemble are pertinent to experiments carried out under constant pressure without any conversion.

Activity coefficients from molecular simulations using the OPAS method

NASA Astrophysics Data System (ADS)

Kohns, Maximilian; Horsch, Martin; Hasse, Hans

2017-10-01

A method for determining activity coefficients by molecular dynamics simulations is presented. It is an extension of the OPAS (osmotic pressure for the activity of the solvent) method in previous work for studying the solvent activity in electrolyte solutions. That method is extended here to study activities of all components in mixtures of molecular species. As an example, activity coefficients in liquid mixtures of water and methanol are calculated for 298.15 K and 323.15 K at 1 bar using molecular models from the literature. These dense and strongly interacting mixtures pose a significant challenge to existing methods for determining activity coefficients by molecular simulation. It is shown that the new method yields accurate results for the activity coefficients which are in agreement with results obtained with a thermodynamic integration technique. As the partial molar volumes are needed in the proposed method, the molar excess volume of the system water + methanol is also investigated.

Zero-valent iron for the abatement of arsenate and selenate from flowback water of hydraulic fracturing.

PubMed

Sun, Yuqing; Chen, Season S; Tsang, Daniel C W; Graham, Nigel J D; Ok, Yong Sik; Feng, Yujie; Li, Xiang-Dong

2017-01-01

Zero-valent iron (ZVI) was tested for the removal of 150 μg L -1 As(V) and 350 μg L -1 Se(VI) in high-salinity (ionic strength 0.35-4.10 M) flowback water of hydraulic fracturing. Over 90% As(V) and Se(VI) was removed by 2.5 g L -1 ZVI in Day-14 flowback water up to 96-h reaction, with the remaining concentration below the maximum contaminant level for As(V) and criterion continuous concentration for Se(VI) recommended by US EPA. The kinetics of As(V) and Se(VI) removal followed a pseudo-second-order rate expression with the observed rates of 4.51 × 10 -2 -4.91 × 10 -1 and 3.48 × 10 -2 -6.58 × 10 -1 h -1 (with 0.5-10 g L -1 ZVI), respectively. The results showed that Se(VI) removal significantly decreased with increasing ionic strength, while As(V) removal showed little variation. Common competing anions (nitrate, bicarbonate, silicate, and phosphate), present in shallow groundwater and stormwater, caused marginal Se(VI) desorption (2.42 ± 0.13%) and undetectable As(V) desorption from ZVI. The competition between As(V) and Se(VI) for ZVI removal depended on the initial molar ratio and surface sites, which occurred when the Se(VI) concentration was higher than the As(V) concentration in this study. The characterization of As(V)- and Se(VI)-loaded ZVI by X-ray diffraction and Raman analysis revealed that ZVI gradually converted to magnetite/maghemite corrosion products with lepidocrocite in flowback water over 30 days. Similar corrosion compositions were confirmed in aerobic and anaerobic conditions regardless of the molar ratio of As(V) to Se(VI). The high reactivity and stability of ZVI showed its suitability for in-situ prevention of As(V) and Se(VI) migration due to accidental leakage, spillage, or overflow of flowback water. Copyright © 2016 Elsevier Ltd. All rights reserved.

Synthesis, characterization and biological activity of some transition metals with Schiff base derived from 2-thiophene carboxaldehyde and aminobenzoic acid.

PubMed

Mohamed, Gehad G; Omar, M M; Hindy, Ahmed M M

2005-12-01

Metal complexes of Schiff base derived from 2-thiophene carboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The ligand dissociation as well as the metal-ligand stability constants were calculated pH metrically at 25 degrees C and ionic strength mu=0.1 (1M NaCl). The complexes are found to have the formulae [M(HL)2](X)n.yH2O (where M=Fe(III) (X=Cl, n=3, y=3), Co(II) (X=Cl, n=2, y=1.5), Ni(II) (X=Cl, n=2, y=1) and UO2(II) (X=NO3, n=2, y=0)) and [M(L)2] (where M=Cu(II) (X=Cl) and Zn(II) (X=AcO)). The molar conductance data reveal that Fe(III) and Co(II), Ni(II) and UO2(II) chelates are ionic in nature and are of the type 3:1 and 2:1 electrolytes, respectively, while Cu(II) and Zn(II) complexes are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a terdentate manner with ONS donor sites of the carboxylate O, azomethine N and thiophene S. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species.

Synthesis, characterization and biological activity of some transition metals with Schiff base derived from 2-thiophene carboxaldehyde and aminobenzoic acid

NASA Astrophysics Data System (ADS)

Mohamed, Gehad G.; Omar, M. M.; Hindy, Ahmed M. M.

2005-12-01

Metal complexes of Schiff base derived from 2-thiophene carboxaldehyde and 2-aminobenzoic acid (HL) are reported and characterized based on elemental analyses, IR, 1H NMR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The ligand dissociation as well as the metal-ligand stability constants were calculated pH metrically at 25 °C and ionic strength μ = 0.1 (1 M NaCl). The complexes are found to have the formulae [M(HL) 2](X) n· yH 2O (where M = Fe(III) (X = Cl, n = 3, y = 3), Co(II) (X = Cl, n = 2, y = 1.5), Ni(II) (X = Cl, n = 2, y = 1) and UO 2(II) (X = NO 3, n = 2, y = 0)) and [M(L) 2] (where M = Cu(II) (X = Cl) and Zn(II) (X = AcO)). The molar conductance data reveal that Fe(III) and Co(II), Ni(II) and UO 2(II) chelates are ionic in nature and are of the type 3:1 and 2:1 electrolytes, respectively, while Cu(II) and Zn(II) complexes are non-electrolytes. IR spectra show that HL is coordinated to the metal ions in a terdentate manner with ONS donor sites of the carboxylate O, azomethine N and thiophene S. From the magnetic and solid reflectance spectra, it is found that the geometrical structure of these complexes are octahedral. The thermal behaviour of these chelates shows that the hydrated complexes losses water molecules of hydration in the first step followed immediately by decomposition of the anions and ligand molecules in the subsequent steps. The activation thermodynamic parameters, such as, E*, Δ H*, Δ S* and Δ G* are calculated from the DrTG curves using Coats-Redfern method. The synthesized ligands, in comparison to their metal complexes also were screened for their antibacterial activity against bacterial species, Escherichia coli, Pseudomonas aeruginosa, Staphylococcus pyogones and Fungi (Candida). The activity data show that the metal complexes to be more potent/antibacterial than the parent Schiff base ligand against one or more bacterial species.

Density functional theory study of ethylene partial oxidation on Ag 7 clusters

NASA Astrophysics Data System (ADS)

Yu, Hua-Gen

2006-11-01

The partial oxidation reaction of ethylene on neutral and anionic Ag 7 clusters has been studied using the BPW91 hybrid DFT method with the Stuttgart RSC97 relativistic pseudopotential for the 28-electron ionic core of Ag. The atomic oxygen reaction mechanism is mainly addressed. Results show that the reaction occurs via a stable oxametallacycle intermediate ( AgOCH4p, p = 0 or -1), but it involves small reaction barriers along the reaction path. The ZPE-corrected barrier heights are obtained as 0.7-6.5 kcal/mole. In addition, the structure and anionic effects of Ag 7 clusters are also discussed.

In situ XANES and EXAFS Analysis of Redox Active Fe Center Ionic Liquids

DOE PAGES

Apblett, Christopher A.; Stewart, David M.; Fryer, Robert T.; ...

2015-10-23

We apply in situ X-Ray Absorption Near Edge Spectroscopy (XANES) and Extended X-Ray Absorption Fine Structure (EXAFS) techniques to a metal center ionic liquid undergoing oxidation and reduction in a three electrode spectroscopic cell. Furthermore, the determination of the extent of reduction under negative bias on the working electrode and the extent of oxidation are determined after pulse voltammetry to quiescence. While the ionic liquid undergoes full oxidation, it undergoes only partial reduction, likely due to transport issues on the timescale of the experiment. Nearest neighbor Fe-O distances in the fully oxidized state match well to expected values for similarlymore » coordinated solids, but reduction does not result in an extension of the Fe-O bond length, as would be expected from comparisons to the solid phase. Instead, little change in bond length is observed. Finally, we suggest that this may be due to a more complex interaction between the monodentate ligands of the metal center anion and the surrounding charge cloud, rather than straightforward electrostatics between the metal center and the nearest neighbor grouping.« less

Artificial solid electrolyte interphase to address the electrochemical degradation of silicon electrodes.

PubMed

Li, Juchuan; Dudney, Nancy J; Nanda, Jagjit; Liang, Chengdu

2014-07-09

Electrochemical degradation on silicon (Si) anodes prevents them from being successfully used in lithium (Li)-ion battery full cells. Unlike the case of graphite anodes, the natural solid electrolyte interphase (SEI) films generated from carbonate electrolytes do not self-passivate on Si, causing continuous electrolyte decomposition and loss of Li ions. In this work, we aim at solving the issue of electrochemical degradation by fabricating artificial SEI films using a solid electrolyte material, lithium phosphorus oxynitride (Lipon), which conducts Li ions and blocks electrons. For Si anodes coated with Lipon of 50 nm or thicker, a significant effect is observed in suppressing electrolyte decomposition, while Lipon of thinner than 40 nm has a limited effect. Ionic and electronic conductivity measurements reveal that the artificial SEI is effective when it is a pure ionic conductor, but electrolyte decomposition is only partially suppressed when the artificial SEI is a mixed electronic-ionic conductor. The critical thickness for this transition in conducting behavior is found to be 40-50 nm. This work provides guidance for designing artificial SEI films for high-capacity Li-ion battery electrodes using solid electrolyte materials.

Ionic High-Pressure Form of Elemental Boron

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

Oganov, A.; Chen, J; Gatti, C

2009-01-01

This Letter presents the results of high-pressure experiments and ab initio evolutionary crystal structure predictions, and found a new boron phase that we named gamma-B28. This phase is comprised of icosahedral B12 clusters and B2 pairs in a NaCl-type arrangement, stable between 19 and 89 GPa, and exhibits evidence for charge transfer (for which our best estimate is delta approximately 0.48) between the constituent clusters to give (B2)delta+(B12)delta-. We have recently found that the same high-pressure boron phase may have given rise to the Bragg reflections reported by Wentorf in 1965 (ref. 1), although the chemical composition was not analysedmore » and the data (subsequently deleted from the Powder Diffraction File database) seems to not have been used to propose a structure model. We also note that although we used the terms 'partially ionic' and 'ionic' to emphasize the polar nature of the high-pressure boron phase and the influence this polarity has on several physical properties of the elemental phase, the chemical bonding in gamma-B28 is predominantly covalent.« less

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

PubMed

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

2011-09-15

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

Polarizability effects on the structure and dynamics of ionic liquids

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

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

2014-04-14

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

Ionic scattering factors of atoms that compose biological molecules

PubMed Central

Matsuoka, Rei; Yamashita, Yoshiki; Yamane, Tsutomu; Kidera, Akinori; Maki-Yonekura, Saori

2018-01-01

Ionic scattering factors of atoms that compose biological molecules have been computed by the multi-configuration Dirac–Fock method. These ions are chemically unstable and their scattering factors had not been reported except for O−. Yet these factors are required for the estimation of partial charges in protein molecules and nucleic acids. The electron scattering factors of these ions are particularly important as the electron scattering curves vary considerably between neutral and charged atoms in the spatial-resolution range explored in structural biology. The calculated X-ray and electron scattering factors have then been parameterized for the major scattering curve models used in X-ray and electron protein crystallography and single-particle cryo-EM. The X-ray and electron scattering factors and the fitting parameters are presented for future reference. PMID:29755750

Capturing the effect of [PF3(C2F5)3]-vs. [PF6]-, flexible anion vs. rigid, and scaled charge vs. unit on the transport properties of [bmim]+-based ionic liquids: a comparative MD study.

PubMed

Kowsari, Mohammad H; Ebrahimi, Soraya

2018-05-16

Comprehensive molecular dynamics simulations are performed to study the average single-particle dynamics and the transport properties of 1-butyl-3-methylimidazolium hexafluorophosphate, [bmim][PF6], and 1-butyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [bmim][FAP], ionic liquids (ILs) at 400 K. We applied one of the most widely used nonpolarizable all-atom force fields for ILs, both with the original unit (±1) charges on each ion and with the partial charges uniformly scaled to 80-85%, taking into account the average polarizability and tracing the experimentally compatible transport properties. In all simulations, [bmim]+ was considered to be flexible, while the effect of a flexible vs. rigid structure of the anions and the effect of two applied charge sets on the calculated properties were separately investigated in detail. The simulation results showed that replacing [PF6]- with [FAP]-, considering anion flexibility, and applying the charge-scaled model significantly enhanced the ionic self-diffusion, ionic conductivity, inverse viscosity, and hyper anion preference (HAP). Both of the calculated self-diffusion coefficients from the long-time linear slope of the mean-square displacement (MSD) and from the integration of the velocity autocorrelation function (VACF) for the centers of mass of the ions were used for evaluation of the ionic transference number, HAP, ideal Nernst-Einstein ionic conductivity (σNE), and the Stokes-Einstein viscosity. In addition, for quantification of the degree of complicated ionic association (known as the Nernst-Einstein deviation parameter, Δ) and ionicity phenomena in the two studied ILs, the ionic conductivity was determined more rigorously by the Green-Kubo integral of the electric-current autocorrelation function (ECACF), and then the σGK/σNE ratio was evaluated. It was found that the correlated motion of the (cationanion) neighbors in [bmim][FAP] is smaller than in [bmim][PF6]. The relaxation times of the normalized reorientational autocorrelation functions were computed to gain a deep, molecular-level insight into the rotational motion of the ions. The geometric shape of the ion is a key factor in determining its reorientational dynamics. [bmim]+ shows faster translational and slower rotational dynamics in contrast to [PF6]-.

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

NASA Astrophysics Data System (ADS)

Monrolin, Nicolas; Praud, Olivier; Plouraboué, Franck

2018-06-01

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

Partial purification and characterization of a Ca(2+)-dependent protein kinase from the green alga, Dunaliella salina

NASA Technical Reports Server (NTRS)

Roux, S. J.

1990-01-01

A calcium-dependent protein kinase was partially purified and characterized from the green alga Dunaliella salina. The enzyme was activated at free Ca2+ concentrations above 10(-7) molar. and half-maximal activation was at about 3 x 10(-7) molar. The optimum pH for its Ca(2+)-dependent activity was 7.5. The addition of various phospholipids and diolein had no effects on enzyme activity and did not alter the sensitivity of the enzyme toward Ca2+. The enzyme was inhibited by calmodulin antagonists, N-(6-aminohexyl)-1-naphthalene sulfonamide and N-(6-aminohexyl)-5-chloro-1-naphthalene sulfonamide in a dose-dependent manner while the protein kinase C inhibitor, sphingosine, had little effect on enzyme activity up to 800 micromolar. Immunoassay showed some calmodulin was present in the kinase preparations. However, it is unlikely the kinase was calmodulin regulated, since it still showed stimulation by Ca2+ in gel assays after being electrophoretically separated from calmodulin by two different methods. This gel method of detection of the enzyme indicated that a protein band with an apparent molecular weight of 40,000 showed protein kinase activity at each one of the several steps in the purification procedure. Gel assay analysis also showed that after native gel isoelectric focusing the partially purified kinase preparations had two bands with calcium-dependent activity, at isoelectric points 6.7 and 7.1. By molecular weight, by isoelectric point, and by a comparative immunoassay, the Dunaliella kinase appears to differ from at least some of the calcium-dependent, but calmodulin and phospholipid independent kinases described from higher plants.

Effects of fiber-glass-reinforced composite restorations on fracture resistance and failure mode of endodontically treated molars.

PubMed

Nicola, Scotti; Alberto, Forniglia; Riccardo, Michelotto Tempesta; Allegra, Comba; Massimo, Saratti Carlo; Damiano, Pasqualini; Mario, Alovisi; Elio, Berutti

2016-10-01

The study evaluated the fracture resistance and fracture patterns of endodontically treated mandibular first molars restored with glass-fiber-reinforced direct composite restorations. In total, 60 extracted intact first molars were treated endodontically; a mesio-occluso-distal (MOD) cavity was prepared and specimens were then divided into six groups: sound teeth (G1), no restoration (G2), direct composite restoration (G3), fiber-post-supported direct composite restoration (G4), direct composite reinforced with horizontal mesio-distal glass-fibers (G5), and buccal-palatal glass-fibers (G6). Specimens were subjected to 5000 thermocycles and 20,000 cycles of 45° oblique loading force at 1.3Hz and 50N; they were then loaded until fracture. The maximum fracture loads were recorded in Newtons (N) and data were analyzed with one-way ANOVA and post-hoc Tukey tests (p<0.05). Fractured specimens were analyzed with a scanning electron microscope (SEM). The mean static loads (in Newtons) were: G1, 831.83; G2, 282.86; G3, 364.18; G4, 502.93; G5, 499.26; and G6, 582.22. Fracture resistance did not differ among G4, G5, and G6, but was significantly higher than G3 (p=0.001). All specimens fractured in a catastrophic way. In G6, glass fibers inducted a partial deflection of the fracture, although they were not able to stop crack propagation. For the direct restoration of endodontically treated molars, reinforcement of composite resins with glass-fibers or fiber posts can enhance fracture resistance. The SEM analysis showed a low ability of horizontal glass-fibers to deviate the fracture, but this effect was not sufficient to lead to more favorable fracture patterns above the cement-enamel junction (CEJ). The fracture resistance of endodontically treated molars restored with direct composite restorations seems to be increased by reinforcement with fibers, even if it is insufficient to restore sound molar fracture resistance and cannot avoid vertical fractures. Copyright © 2016 Elsevier Ltd. All rights reserved.

The coupling of carbon dioxide and epoxides by phenanthroline derivatives containing different Cu(II) complexes as catalyst

NASA Astrophysics Data System (ADS)

Kilic, Ahmet; Palali, Ahmet Arif; Durgun, Mustafa; Tasci, Zeynep; Ulusoy, Mahmut

2013-09-01

A series of the mononuclear Cu(II) metal complexes containing the ligand Bdppz [(9a,13a-dihydro-4,5,9,14-tetraaza-benzo[b]triphenylene-11-yl)-phenyl-methanone] (L1) and Aqphen [(12,17-dihydronaphthol[2,3-h]dipyrido[3,2-a:2‧,3‧-c]-phenazine-12,17-dione)] (L2) were synthesized and used as catalyst for the coupling of carbon dioxide (CO2) and liquid epoxide which served as both reactant and solvent. Dimethylamino pyridine (DMAP) was used as co-catalyst. The yields of epoxides to corresponding cyclic carbonates were determined by comparing the ratio of product to substrate in the 1H NMR spectrum of an aliquot of the reaction mixture. The mononuclear Cu(II) complexes of these ligands were synthesized by treating an ethanol solvent of the appropriate ligand with a different molar amount of CuCl2·2H2O. The Cu(II) complexes were characterized by FT-IR, UV-Vis, elemental analysis, melting point analysis, mass spectra, molar conductivity measurements and magnetic susceptibility techniques. The reaction of the Bdppz and Aqphen ligands in a 1:1, 1:2 or 1:3 mole ratio with CuCl2·2H2O afforded ionic Cu(II) complexes in the presence of Et3N.

Palladium(II) and zinc(II) complexes of neutral [N2O2] donor Schiff bases derived from furfuraldehyde: synthesis, characterization, fluorescence and corrosion inhibitors of ligands.

PubMed

Ali, Omyma A M

2014-11-11

Metal complexes of Schiff bases derived from furfuraldehyde and 4,5-dimethyl-1,2-phenylendiamine (L1) or 4,5-dichloro-1,2-phenylendiamine (L2) have been reported and characterized based on elemental analyses, IR, 1H NMR, UV-Vis, magnetic moment, molar conductance and thermal analysis. The complexes are found to have the formulae [PdL1-2]Cl2 and [ZnL1-2](AcO)2·H2O. The molar conductance data reveal that Pd(II) and Zn(II) chelates are ionic in nature and are of the type 2:1 electrolytes. The spectral data are consistent with a square planar and tetrahedral geometry around Pd(II) and Zn(II), respectively, in which the ligands act as tetradentate ligands. The thermal behavior of some chelates is studied and the activation thermodynamic parameters are calculated using Coats-Redfern method. The corrosion inhibition of stainless steel types 410 and 304 in 1 M HCl using the synthesized Schiff bases as inhibitors have been studied by weight loss method. The obtained data considered these ligands as efficient corrosion inhibitors. The ligands and their metal complexes exhibited considerable antibacterial activity against Staphylococcusaureus, and Escherichiacoli and antifungal activity against Candida albicans. Copyright © 2014 Elsevier B.V. All rights reserved.

Melt densities in the CaO-FeO-Fe 2O 3-SiO 2 system and the compositional dependence of the partial molar volume of ferric iron in silicate melts

NASA Astrophysics Data System (ADS)

Dingwell, Donald B.; Brearley, Mark

1988-12-01

The densities of 10 melts in the CaO-FeO-Fe 2O 3-SiO 2 system were determined in equilibrium with air, in the temperature range of 1200 to 1550°C, using the double-bob Archimedean technique. Melt compositions range from 6 to 58 wt% SiO 2, 14 to 76 wt% Fe 2O 3 and 10 to 46 wt% CaO. The ferric-ferrous ratios of glasses drop-quenched from loop fusion equilibration experiments were determined by 57Fe Mössbauer spectroscopy. Melt densities range from 2.689 to 3.618 gm/cm 3 with a mean standard deviation from replicate experiments of 0.15%. Least-squares regressions of molar volume versus molar composition have been performed and the root mean squared deviation shows that a linear combination of partial molar volumes for the oxide components (CaO, FeO, Fe 2O 3 and SiO 2) cannot describe the data set within experimental error. Instead, the inclusion of excess terms in CaFe 3+ and CaSi (product terms using the oxides) is required to yield a fit that describes the experimental data within error. The nonlinear compositional-dependence of the molar volumes of melts in this system can be explained by structural considerations of the roles of Ca and Fe 3+. The volume behavior of melts in this system is significantly different from that in the Na 2O-FeO-Fe 2O 3-SiO 2 system, consistent with the proposal that a proportion of Fe 3+ in melts in the CaO-FeO-Fe 2O 3-SiO 2 system is not tetrahedrally-coordinated by oxygen, which is supported by differences in 57Fe Mössbauer spectra of glasses. Specifically, this study confirms that the 57Fe Mössbauer spectra exhibit an area asymmetry and higher values of isomer shift of the ferric doublet that vary systematically with composition and temperature (this study; Dingwell and Virgo, 1987, 1988). These observations are consistent with a number of other lines of evidence ( e.g., homogeneous redox equilibria, Dickenson and Hess, 1986; viscosity, Dingwell and Virgo, 1987,1988). Two species of ferric iron, varying in proportions with temperature, composition and redox state, are sufficient to describe the above observations. The presence of more than one coordination geometry for Fe 3+ in low pressure silicate melts has several implications for igneous petrogenesis. The possible effects on compressibility, the pressure dependence of the redox ratio, and redox enthalpy are briefly noted.

Tooth loss in well-maintained patients with chronic periodontitis during long-term supportive therapy in Brazil.

PubMed

Chambrone, Luiz A; Chambrone, Leandro

2006-10-01

The objective of this retrospective study was to assess the reasons for tooth loss in a sample of patients who underwent periodontal therapy and supportive periodontal therapy (SPT) in a Brazilian private periodontal practice. A sample of 120 subjects who had been treated and maintained for 10 years or longer was selected from patients attending a periodontal practice. All patients followed a similar treatment: basic procedures, re-evaluation and periodontal surgery where indicated. Reasons for tooth loss were categorized as periodontal, caries, endodontal, root fractures and extraction of retained or partially erupted third molars. Of the 2927 teeth present at the completion of active periodontal treatment, 53 (1.8%) were lost due to periodontal disease, 16 (0.5%) for root fracture, six (0.2%) to caries, five (0.2%) for endodontic reasons and 31 (1.0%) were lost to extraction of retained or partially erupted third molars. Logistic regression analysis was performed to investigate the association between five independent variables with tooth loss due to periodontitis. Only age (> 60 years) and smoking were statistically significant (p < 0.05). The findings of this survey were consistent with previous studies. Older subjects and smokers were more susceptible to periodontal tooth loss. In addition, patients with generalized chronic periodontitis were treated and maintained for long-term periods with low rates of tooth loss.

Heterogeneous uptake of ammonia and dimethylamine into sulfuric and oxalic acid particles

NASA Astrophysics Data System (ADS)

Sauerwein, Meike; Keung Chan, Chak

2017-05-01

Heterogeneous uptake is one of the major mechanisms governing the amounts of short-chain alkylamines and ammonia (NH3) in atmospheric particles. Molar ratios of aminium to ammonium ions detected in ambient aerosols often exceed typical gas phase ratios. The present study investigated the simultaneous uptake of dimethylamine (DMA) and NH3 into sulfuric and oxalic acid particles at gaseous DMA / NH3 molar ratios of 0.1 and 0.5 at 10, 50 and 70 % relative humidity (RH). Single-gas uptake and co-uptake were conducted under identical conditions and compared. Results show that the particulate dimethyl-aminium/ammonium molar ratios (DMAH / NH4) changed substantially during the uptake process, which was severely influenced by the extent of neutralisation and the particle phase state. In general, DMA uptake and NH3 uptake into concentrated H2SO4 droplets were initially similarly efficient, yielding DMAH / NH4 ratios that were similar to DMA / NH3 ratios. As the co-uptake continued, the DMAH / NH4 gradually dropped due to a preferential uptake of NH3 into partially neutralised acidic droplets. At 50 % RH, once the sulfate droplets were neutralised, the stronger base DMA displaced some of the ammonium absorbed earlier, leading to DMAH / NH4 ratios up to four times higher than the corresponding gas phase ratios. However, at 10 % RH, crystallisation of partially neutralised sulfate particles prevented further DMA uptake, while NH3 uptake continued and displaced DMAH+, forming almost pure ammonium sulfate. Displacement of DMAH+ by NH3 has also been observed in neutralised, solid oxalate particles. The results can explain why DMAH / NH4 ratios in ambient liquid aerosols can be larger than DMA / NH3, despite an excess of NH3 in the gas phase. An uptake of DMA to aerosols consisting of crystalline ammonium salts, however, is unlikely, even at comparable DMA and NH3 gas phase concentrations.

The management of an endodontically abscessed tooth: patient health state utility, decision-tree and economic analysis

PubMed Central

Balevi, Ben; Shepperd, Sasha

2007-01-01

Background A frequent encounter in clinical practice is the middle-aged adult patient complaining of a toothache caused by the spread of a carious infection into the tooth's endodontic complex. Decisions about the range of treatment options (conventional crown with a post and core technique (CC), a single tooth implant (STI), a conventional dental bridge (CDB), and a partial removable denture (RPD)) have to balance the prognosis, utility and cost. Little is know about the utility patients attach to the different treatment options for an endontically abscessed mandibular molar and maxillary incisor. We measured patients' dental-health-state utilities and ranking preferences of the treatment options for these dental problems. Methods Forty school teachers ranked their preferences for conventional crown with a post and core technique, a single tooth implant, a conventional dental bridge, and a partial removable denture using a standard gamble and willingness to pay. Data previously reported on treatment prognosis and direct "out-of-pocket" costs were used in a decision-tree and economic analysis Results The Standard Gamble utilities for the restoration of a mandibular 1st molar with either the conventional crown (CC), single-tooth-implant (STI), conventional dental bridge (CDB) or removable-partial-denture (RPD) were 74.47 [± 6.91], 78.60 [± 5.19], 76.22 [± 5.78], 64.80 [± 8.1] respectively (p < 0.05). Their respective Willingness-to-Pay ($CDN) were 1,782.05 [± 361.42], 1,871.79 [± 349.44], 1,605.13 [± 348.10], 1,351.28 [± 368.62] (p < 0.05). The standard gamble utilities for the restoration of a maxillary central incisor with a CC, STI, CDB and RPD were 88.50 [± 6.12], 90.68 [± 3.41], 89.78 [± 3.81] and 91.10 [± 3.57] respectively (p > 0.05). Their respective willingness-to-pay ($CDN) were: 1,782.05 [± 361.42], 1,871.79 [± 349.44], 1,605.13 [± 348.10] and 1,351.28 [± 368.62]. A statistical difference was found between the utility of treating a maxillary central incisor and mandibular 1st-molar (p < 0.05). The expected-utility-value for a 5-year prosthetic survival was highest for the CDB and the STI treatment of an abscessed mandibular molar (74.75 and 71.47 respectively) and maxillary incisor (86.24 and 84.91 respectively). This held up to a sensitivity analysis when the success of root canal therapy and the risk of damage to the adjacent tooth were varied. The RPD for both the molar and incisor was the favored treatment based on a cost-utility (3.85 and 2.74 CND$ per year of tooth saved respectively) and cost-benefit analysis (0.92 to 0.60 CND$ of cost per $ of benefit, respectively) for a prosthetic clinical survival of 5-years. Conclusion The position of the abscessed tooth and the amount of insurance coverage influences the utility and rank assigned by patients to the different treatment options. STI and CDB have optimal EUVs for a 5-year survival outcome, and RPD has significantly lower cost providing the better cost:benefit ratio. PMID:18053267

Oxygen stoichiometry, phase stability, and thermodynamic behavior of the lead-doped Bi-2223 and Ag/Bi-2223 systems

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Luo, J. S.; Maroni, V. A.

1995-02-01

Electromotive-force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made in the lead-doped Bi-2223 superconducting system in the temperature range 700-815°C by means of an oxygen titration technique that employs an yttria-stabilized zirconia electrolyte. The results of our studies indicate that processing or annealing lead-doped Bi-2223 at temperatures ranging from 750 to 815°C and at oxygen partial pressures ranging from ∼ 0.02 to 0.2 atm should preserve Bi-2223 as essentially single-phase material. Thermodynamic assessments of the partial molar quantities ΔS¯( O2) andΔH¯( O2) indicate that the plateau regions in the plot of oxygen partial pressure versus oxygen stoichiometry ( x) can be represented by the diphasic CuOCu 2O system. In accord with the EMF measurements, it was found that lead-doped Bi-2223 in a silver sheath is stable at 815°C for oxygen partial pressures between 0.02 and 0.13 atm.

Thermodynamic and nonstoichiometric behavior of the lead-doped Bi-2223 system

NASA Astrophysics Data System (ADS)

Tetenbaum, M.; Hash, M.; Tani, B. S.; Luo, J. S.; Maroni, V. A.

1994-12-01

Electromotive force (EMF) measurements of oxygen fugacities as a function of stoichiometry have been made in the lead-doped Bi-2223 superconducting system in the temperature range 700-815°C by means of an oxygen titration technique. The results of our studies indicate that processing or annealing lead-doped Bi-2223 at temperatures ranging from 700 to 815°C and at oxygen partial pressures ranging from ∼0.02 to 0.2 atm should tend to preserve Bi-2223 as essentially single-phase material. Thermodynamic assessments of partial molar quantities indicate that the plateau regions can be represented by the diphasic CuOCu 2O system. In accord with the EMF measurements, it was found that lead-doped Bi-2223 in a silver sheath is stable at 815°C for oxygen partial pressures between 0.02 and 0.13 atm. Long-duration post anneals of silver-clad Bi-2223 filaments at 825°C and an oxygen partial pressure of 0.075 atm eliminated Bi-2212 intergrowths with a concomitant increase in the superconducting transition sharpness.

Solubility of carbon dioxide in aqueous mixtures of alkanolamines

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

Dawodu, O.F.; Meisen, A.

1994-07-01

The solubility of CO[sub 2] in water + N-methyldiethanolamine + monoethanolamine (MDEA + MEA) and water + N-methyldiethanolamine + diethanolamine (MDEA + DEA) are reported at two compositions of 3.4 M MDEA + 0.8 M MEA or DEA and 2.1 M MDEA + 2.1 M MEA or DEA at temperatures from 70 to 180 C and CO[sub 2] partial pressures from 100 to 3,850 kPa. The solubility of CO[sub 2] in the blends decreased with an increase in temperature but increased with an increase in CO[sub 2] partial pressure. At low partial pressures of CO[sub 2] and the same totalmore » amine concentration, the equilibrium CO[sub 2] loadings were in the order MDEA + MEA > MDEA + DEA > MDEA. However, at high CO[sub 2] partial pressures, the equilibrium CO[sub 2] loadings in the MDEA solutions were higher than those of the MDEA + MEA and MDEA + DEA blends of equal molar strengths due to the stoichiometric loading limitations of MEA and DEA. The nonadditivity of the equilibrium loadings for single amine systems highlights the need for independent measurements on amine blends.« less

Synthesis and characterisation of ionic liquids based on 1-butyl-3-methylimidazolium chloride and MCl(4), M = Hf and Zr.

PubMed

Campbell, Paul S; Santini, Catherine C; Bouchu, Denis; Fenet, Bernard; Rycerz, Leszek; Chauvin, Yves; Gaune-Escard, Marcelle; Bessada, Catherine; Rollet, Anne-Laure

2010-02-07

Dialkylimidazolium chlorometallate molten salts resulting from the combination of zirconium or hafnium tetrachloride and 1-butyl-3-methylimidazolium chloride, [C(1)C(4)Im][Cl], have been prepared with a molar fraction of MCl(4), R = n(MCl4)/n(MCl4) + n([C1C4IM][Cl]) equal to 0, 0.1, 0.2, 0.33, 0.5, 0.67. The structure and composition were studied by Differential Scanning Calorimetry (DSC), (35)Cl (263 to 333 K), (1)H and (13)C solid state and solution NMR spectroscopy, and electrospray ionisation (ESI) mass spectrometry. The primary anions of the MCl(4)-based ILs were [MCl(5)], [MCl(6)] and [M(2)Cl(9)], whose relative abundances varied with R. For R = 0.33, pure solid [C(1)C(4)Im](2)[MCl(6)], for both M = Zr and Hf are formed (m.p. = 366 and 385 K, respectively). For R = 0.67 pure ionic liquids [C(1)C(4)Im][M(2)Cl(9)] for both M = Zr and Hf are formed (T(g) = 224 and 220 K, respectively). The thermal dissociation has been attempted of [C(1)C(4)Im](2)[HfCl(6)], and [C(1)C(4)Im](2)[ZrCl(6)] monitored by (35)Cl and (91)Zr solid NMR (high temperature up to 551 K).

Using solid phase micro extraction to determine salting-out (Setschenow) constants for hydrophobic organic chemicals.

PubMed

Jonker, Michiel T O; Muijs, Barry

2010-06-01

With increasing ionic strength, the aqueous solubility and activity of organic chemicals are altered. This so-called salting-out effect causes the hydrophobicity of the chemicals to be increased and sorption in the marine environment to be more pronounced than in freshwater systems. The process can be described with empirical salting-out or Setschenow constants, which traditionally are determined by comparing aqueous solubilities in freshwater and saline water. Aqueous solubilities of hydrophobic organic chemicals (HOCs) however are difficult to determine, which might partly explain the limited size of the existing data base on Setschenow constants for these chemicals. In this paper, we propose an alternative approach for determining the constants, which is based on the use of solid phase micro extraction (SPME) fibers. Partitioning of polycyclic aromatic hydrocarbons (PAHs) to SPME fibers increased about 1.7 times when going from de-ionized water to seawater. From the log-linear relationship between SPME fiber-water partition coefficients and ionic strength, Setschenow constants were derived, which measured on average 0.35 L mol(-1). These values agreed with literature values existing for some of the investigated PAHs and were independent of solute hydrophobicity or molar volume. Based on the present data, SPME seems to be a convenient and suitable alternative technique to determine Setschenow constants for HOCs. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Combined modification by LiAl11O17 and NaAl11O17 to enhance the electrochemical performance of Li4Ti5O12

NASA Astrophysics Data System (ADS)

Zhang, Bo; Han, Jian-Ping; Wang, Li-Ying; Lun, Ning; Zhu, Hui-Ling; Yin, Long-Wei; Li, Hui; Qi, Yong-Xin; Bai, Yu-Jun

2018-07-01

The intrinsically moderate Li-ion diffusion coefficient and poor electronic conductivity of Li4Ti5O12 (LTO) restricts the practical application in Li-ion batteries. In view of the rapid two-dimensional diffusion channels in ionic conductor of LiNaAl22O34 for Li-ions, the LTO modified by combining equivalent molar ratio of LiAl11O17 with NaAl11O17 (LNAO) was fabricated by a simple reaction between LiNO3, Na2CO3, Al(NO3)3ṡ9H2O and LTO at various sintering temperatures. The product with a LNAO/LTO mass ratio of 0.0106 and calcined at 600 °C achieved reversible capacities of 163.8, 160.6, 156.5, 150.9, 132.9 and 163.4 mAh g-1 at the current rates of 100, 200, 400, 800, 1600 and 100 mA g-1, respectively. Even cycled 800 times at 500 mA g-1, a capacity of 147.9 mAh g-1 was retained. The outstanding cycling and rate performance is attributable to the simultaneously formed LNAO coating on the LTO particles and superficial Al3+ doping in the LTO, achieving combined improvement in the ionic and electronic conductivities of LTO and thus boosting the comprehensive electrochemical performance of LTO.

Assessment of solubilization characteristics of different surfactants for carvedilol phosphate as a function of pH.

PubMed

Chakraborty, Subhashis; Shukla, Dali; Jain, Achint; Mishra, Brahmeshwar; Singh, Sanjay

2009-07-15

The effect of surfactants on the solubility of a new phosphate salt of carvedilol was investigated at different biorelevent pH to evaluate their solubilization capacity. Solutions of different classes of surfactants viz., anionic-sodium dodecyl sulfate (SDS) and sodium taurocholate (STC), cationic-cetyltrimethylammonium bromide (CTAB) and non-ionic-Tween 80 (T80) were prepared in the concentration range of 5-35 mmol dm(-3) in buffer solutions of pH 1.2, 3.0, 4.5, 5.8, 6.8 and 7.2. The solubility data were used to calculate the solubilization characteristics viz. molar solubilization capacity, water micelle partition coefficient, free energy of solubilization and binding constant. Solubility enhancement in basic pH was in following order: CTAB>T80>SDS>STC. CTAB and T80 showed remarkable solubility enhancement in acidic pH as well. Among the anionic surfactants, solubility in acidic medium was retarded except at pH 1.2 in case of SDS. Cationic and non-ionic surfactants were found to be suitable for enhancing the solubility of CP which can be employed for maintaining the in vitro sink condition in the basic dissolution medium. While anionic surfactants showed solubility retardant behavior which may be exploited in increasing the drug entrapment efficiency of a colloidal drug delivery system formulated by emulsification technique.

Optical absorption and photoconductivity in iodine-excess ionic liquids: the case of 1-alkyl-3-methyl imidazolium iodides.

PubMed

Aono, Masami; Miyazaki, Hisashi; Takekiyo, Takahiro; Tsuzuki, Seiji; Abe, Hiroshi

2018-02-21

We investigated the optical absorption and photoconductivity of iodine-excess ionic liquids (ILs) based on 1-alkyl-3-methyl imidazolium iodide ([C n mim][I]; n = 3, 4, and 6). The iodide concentration m was 2 ≦ m ≦ 8, which was determined by the molar fraction [C n mim] +  : [I m ] - = 1 : m. By adding iodine, an absorption edge shifted from 282 nm in the UV region to around 600 nm in the visible-light region. The optical bandgaps E o decreased gradually from 2.3 eV to 1.9 eV with increasing m from 2 to 8. The alkyl-side chain lengths of the cations have little effect on the E o . This experimental result was confirmed by ab initio molecular orbital calculations. The effects were reflected in the photoconductivity of the ILs, as expected. [C 4 mim][I m ] exhibited greater photo-induced electron generation compared with [C 3 mim][I m ] and [C 6 mim][I m ]. The photoconductivity in both [C 3 mim][I m ] and [C 6 mim][I m ] increased slightly with increasing m. The trend of photoconductivity in [C 4 mim][I m ] exhibited an N-shaped form. The highest photoconductivity 1.6 was observed in [C 4 mim][I 8 ].

Rapid and sensitive analysis of polychlorinated biphenyls and acrylamide in food samples using ionic liquid-based in situ dispersive liquid-liquid microextraction coupled to headspace gas chromatography.

PubMed

Zhang, Cheng; Cagliero, Cecilia; Pierson, Stephen A; Anderson, Jared L

2017-01-20

A simple and rapid ionic liquid (IL)-based in situ dispersive liquid-liquid microextraction (DLLME) method was developed and coupled to headspace gas chromatography (HS-GC) employing electron capture (ECD) and mass spectrometry (MS) detection for the analysis of polychlorinated biphenyls (PCBs) and acrylamide at trace levels from milk and coffee samples. The chemical structures of the halide-based ILs were tailored by introducing various functional groups to the cations to evaluate the effect of different structural features on the extraction efficiency of the target analytes. Extraction parameters including the molar ratio of IL to metathesis reagent and IL mass were optimized. The effects of HS oven temperature and the HS sample vial volume on the analyte response were also evaluated. The optimized in situ DLLME method exhibited good analytical precision, good linearity, and provided detection limits down to the low ppt level for PCBs and the low ppb level for acrylamide in aqueous samples. The matrix-compatibility of the developed method was also established by quantifying acrylamide in brewed coffee samples. This method is much simpler and faster compared to previously reported GC-MS methods using solid-phase microextraction (SPME) for the extraction/preconcentration of PCBs and acrylamide from complex food samples. Copyright © 2016 Elsevier B.V. All rights reserved.

A high performance ceramic-polymer separator for lithium batteries

NASA Astrophysics Data System (ADS)

Kumar, Jitendra; Kichambare, Padmakar; Rai, Amarendra K.; Bhattacharya, Rabi; Rodrigues, Stanley; Subramanyam, Guru

2016-01-01

A three-layered (ceramic-polymer-ceramic) hybrid separator was prepared by coating ceramic electrolyte [lithium aluminum germanium phosphate (LAGP)] over both sides of polyethylene (PE) polymer membrane using electron beam physical vapor deposition (EB-PVD) technique. Ionic conductivities of membranes were evaluated after soaking PE and LAGP/PE/LAGP membranes in a 1 Molar (1M) lithium hexafluroarsenate (LiAsF6) electrolyte in ethylene carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC) in volume ratio (1:1:1). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques were employed to evaluate morphology and structure of the separators before and after cycling performance tests to better understand structure-property correlation. As compared to regular PE separator, LAGP/PE/LAGP hybrid separator showed: (i) higher liquid electrolyte uptake, (ii) higher ionic conductivity, (iii) lower interfacial resistance with lithium and (iv) lower cell voltage polarization during lithium cycling at high current density of 1.3 mA cm-2 at room temperature. The enhanced performance is attributed to higher liquid uptake, LAGP-assisted faster ion conduction and dendrite prevention. Optimization of density and thickness of LAGP layer on PE or other membranes through manipulation of PVD deposition parameters will enable practical applications of this novel hybrid separator in rechargeable lithium batteries with high energy, high power, longer cycle life, and higher safety level.

Catalytic reforming of methane to syngas in an oxygen-permeative membrane reactor

NASA Astrophysics Data System (ADS)

Urano, Takeshi; Kubo, Keiko; Saito, Tomoyuki; Hitomi, Atsushi

2011-05-01

For fuel cell applications, partial oxidative reforming of methane to syngas, hydrogen and carbon monoxide, was performed via a dense oxygen-permeative ceramic membrane composed by both ionic and electronic conductive materials. The modification of Ni-based catalyst by noble metals was investigated to increase oxygen permeation flux and decrease carbon deposition during reforming reaction. The role of each component in catalyst was also discussed.

The Leaky Dielectric Model as a Weak Electrolyte Limit of an Electrodiffusion Model

NASA Astrophysics Data System (ADS)

Mori, Yoichiro; Young, Yuan-Nan

2017-11-01

The Taylor-Melcher (TM) model is the standard model for the electrohydrodynamics of poorly conducting leaky dielectric fluids under an electric field. The TM model treats the fluid as an ohmic conductor, without modeling ion dynamics. On the other hand, electrodiffusion models, which have been successful in describing electokinetic phenomena, incorporates ionic concentration dynamics. Mathematical reconciliation between electrodiffusion and the TM models has been a major issue for electrohydrodynamic theory. Here, we derive the TM model from an electrodiffusion model where we explicitly model the electrochemistry of ion dissociation. We introduce salt dissociation reaction in the bulk and take the limit of weak salt dissociation (corresponding to poor conductors in the TM model.) Assuming small Debye length we derive the TM model with or without the surface charge advection term depending upon the scaling of relevant dimensionless parameters. Our analysis also gives a description of the ionic concentration distribution within the Debye layer, which hints at possible scenarios for electrohydrodynamic singularity formation. In our analysis we also allow for a jump in voltage across the liquid interface which causes a drifting velocity for a liquid drop under an electric field. YM is partially supported by NSF-DMS-1516978 and NSF-DMS-1620316. YNY is partially supported by NSF-DMS-1412789 and NSF-DMS-1614863.

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

PubMed

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

2017-04-06

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

Biochemical thermodynamics: applications of Mathematica.

PubMed

Alberty, Robert A

2006-01-01

The most efficient way to store thermodynamic data on enzyme-catalyzed reactions is to use matrices of species properties. Since equilibrium in enzyme-catalyzed reactions is reached at specified pH values, the thermodynamics of the reactions is discussed in terms of transformed thermodynamic properties. These transformed thermodynamic properties are complicated functions of temperature, pH, and ionic strength that can be calculated from the matrices of species values. The most important of these transformed thermodynamic properties is the standard transformed Gibbs energy of formation of a reactant (sum of species). It is the most important because when this function of temperature, pH, and ionic strength is known, all the other standard transformed properties can be calculated by taking partial derivatives. The species database in this package contains data matrices for 199 reactants. For 94 of these reactants, standard enthalpies of formation of species are known, and so standard transformed Gibbs energies, standard transformed enthalpies, standard transformed entropies, and average numbers of hydrogen atoms can be calculated as functions of temperature, pH, and ionic strength. For reactions between these 94 reactants, the changes in these properties can be calculated over a range of temperatures, pHs, and ionic strengths, and so can apparent equilibrium constants. For the other 105 reactants, only standard transformed Gibbs energies of formation and average numbers of hydrogen atoms at 298.15 K can be calculated. The loading of this package provides functions of pH and ionic strength at 298.15 K for standard transformed Gibbs energies of formation and average numbers of hydrogen atoms for 199 reactants. It also provides functions of temperature, pH, and ionic strength for the standard transformed Gibbs energies of formation, standard transformed enthalpies of formation, standard transformed entropies of formation, and average numbers of hydrogen atoms for 94 reactants. Thus loading this package makes available 774 mathematical functions for these properties. These functions can be added and subtracted to obtain changes in these properties in biochemical reactions and apparent equilibrium constants.

Concentration dependences of the density, viscosity, and refraction index of Cu(NO3)2 · 3H2O solutions in DMSO at 298 K

NASA Astrophysics Data System (ADS)

Mamyrbekova, A. K.

2013-03-01

Physicochemical properties (density, dynamic viscosity, refraction index) of the DMSO-Cu(NO3)2 · 3H2O system are studied in the concentration range of 0.01-2 M at 298 K. The refraction index of a solution of copper(II) nitrate in dimethylsulfoxide (DMSO) is measured at 288-318 K. The excess and partial molar volumes of the solvent and dissolved substance are calculated analytically.

Computer simulation of the carbon activity in austenite

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

Murch, G.E.; Thorn, R.J.

1979-02-01

Carbon activity in austenite is described in terms of an Ising-like f.c.c. lattice gas model in which carbon interstitials repel only at the distance of nearest neighbors. A Monte Carlo simulation method in the petit canonical ensemble is employed to calculate directly the carbon activity as a function of composition and temperature. The computed activities are in satisfactory agreement with the experimental data, similarly for the decompostion of the activity to the partial molar enthalpy and entropy.

Composite fabrication and polymer modification using neoteric solvents

NASA Astrophysics Data System (ADS)

Eastman, Scott A.

This thesis is divided into two research initiatives: The fabrication and study of bulk, co-continuous, cellulosic-polymer composites with the aid of supercritical CO2 (SC CO2); and the study of poly(vinyl alcohol) (PVOH) modification and surface activity in ionic liquids. The first part of this thesis utilizes the tunable solubility, gas-like diffusivity, and omniphilic wettability of SC CO2 to incorporate and subsequently polymerize silicone and poly(enemer) prepolymer mixtures throughout various cellulosic substrates. Chapters two and three investigate the mechanical properties of these composites and demonstrate that nearly every resulting composite demonstrates an improved flexural modulus and energy release rate upon splitting. Fire resistance of these composites was also investigated and indicates that the heat release rate, total heat released, and char yield were significantly improved upon for all silicone composites compared to the untreated cellulosic material. Chapter four looks specifically at aspen-silicone composites for thermo-oxidative studies under applied loads in order to study the effect of silicone incorporation on the failure kinetics of aspen. The aspen-silicone composites tested under these conditions demonstrated significantly longer lifetimes under the same loading and heating conditions compared with untreated aspen. The second part of this thesis focuses on studying ionic liquids as potentially useful solvents and reaction media for poly(vinyl alcohol). Two ionic liquids (1-Butyl-3-methylimidizolium chloride and tributylethylphosphonium diethylphosphate) were found to readily dissolve PVOH. More importantly, we have demonstrated that these solvents can be used as inert reaction media for PVOH modification. Both ionic liquids were found to facilitate the quantitative esterification of PVOH, while only the phosphonium ionic liquid supports the quantitative urethanation of the polymer. In an attempt to tune the surface properties of ionic liquid/polymer solutions, PVOH was also partially esterified with low surface energy substituents. Both surface tension and surface composition of the ionic liquid/polymer solutions can be manipulated by the stoichiometric addition of low surface energy acid chlorides. This work on the modification of PVOH can be directly applied to the modification of polysaccharides such as cellulose which could have important implications from a sustainability and energy standpoint.

Simultaneous recording of electrical activity and the underlying ionic currents in NG108-15 cells cultured on gold substrate.

PubMed

Acosta-García, Ma Cristina; Morales-Reyes, Israel; Jiménez-Anguiano, Anabel; Batina, Nikola; Castellanos, N P; Godínez-Fernández, R

2018-02-01

This paper shows the simultaneous recording of electrical activity and the underlying ionic currents by using a gold substrate to culture NG108-15 cells. Cells grown on two different substrates (plastic Petri dishes and gold substrates) were characterized quantitatively through scanning electron microscopy (SEM) as well as qualitatively by optical and atomic force microscopy (AFM). No significant differences were observed between the surface area of cells cultured on gold substrates and Petri dishes, as indicated by measurements performed on SEM images. We also evaluated the electrophysiological compatibility of the cells through standard patch-clamp experiments by analyzing features such as the resting potential, membrane resistance, ionic currents, etc. Cells grown on both substrates showed no significant differences in their dependency on voltage, as well as in the magnitude of the Na+ and K+ current density; however, cells cultured on the gold substrate showed a lower membrane capacitance when compared to those grown on Petri dishes. By using two separate patch-clamp amplifiers, we were able to record the membrane current with the conventional patch-clamp technique and through the gold substrate simultaneously. Furthermore, the proposed technique allowed us to obtain simultaneous recordings of the electrical activity (such as action potentials firing) and the underlying membrane ionic currents. The excellent conductivity of gold makes it possible to overcome important difficulties found in conventional electrophysiological experiments such as those presented by the resistance of the electrolytic bath solution. We conclude that the technique here presented constitutes a solution to the problem of the simultaneous recording of electrical activity and the underlying ionic currents, which for decades, had been solved only partially.

Revival of nitrogen-containing bisphosphonate-induced inhibition of osteoclastogenesis and osteoclast function by water-soluble microfibrous borate glass.

PubMed

Yuan, He; Niu, Li-Na; Jiao, Kai; Pei, Dan-Dan; Pramanik, Chandrani; Li, Ji-Yao; Messer, Regina; Kumar, Satish; Pashley, David H; Tay, Franklin R

2016-02-01

Bisphosphonate-related osteonecrosis of the jaw (BRONJ) is a serious skeletal complication associated with the long-term oral or intravenous use of nitrogen-containing bisphosphonates (N-BPs). Here, we investigated the effects of an ionic cocktail prepared from water-soluble microfibrous borate glass on neutralizing the inhibitory effects of two heterocyclic N-BPs, risedronate or zoledronic acid, on osteoclastogenesis, apoptosis of differentiated osteoclasts and osteoclast function. Cell growth and proliferation assays were first performed on RAW 264.7 cells to optimize the concentrations of the ionic cocktail and N-BPs to be used for static cell culture. The pre-osteoclasts were then stimulated with RANKL to differentiate into osteoclasts. The effects of the ionic cocktail and N-BPs on osteoclast differentiation, apoptosis and function were subsequently examined using 3 series of experiments conducted at the gene, protein, morphological and functional levels. After concentration optimization, the ionic cocktail was found to partially reverse N-BP-induced inhibition of osteoclastogenesis, stimulation of osteoclasts apoptosis and reduction of osteoclast resorptive activity. Ultrastructural examination of osteoclasts that had been exposed to either N-BP identified classical features of late apoptosis and secondary necrosis, while osteoclasts exposed simultaneously to the concentration-optimized ionic cocktail and N-BPs exhibited only signs of early apoptosis that were possibly reversible. Taken together, the results of the 4 series of experiments indicate that the ionic cocktail produced from dissolution of borate glass dressings has the potential to rescue the adverse effects of heterocyclic N-BPs on osteoclast differentiation and function. These results warrant further confirmation using dynamic cell culture and small animal BRONJ models. Long-term oral and intravenous use of nitrogen-containing bisphosphonates (N-BPs) may result in bisphosphonate-related osteonecrosis of the jaw (BRONJ) due to the suppression of normal bone turnover. There is no effective treatment for such a complication to date. This work reported the use of an ionic cocktail derived from water-soluble microfibrous borate glass to revert heterocyclic N-BP-induced inhibition of osteoclastogenesis, stimulation of osteoclasts apoptosis and reduction of osteoclasts resorption in static cell culture condition. This ionic cocktail may have the potential to be further developed into a new adjunctive treatment for BRONJ. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Solubility of oxygen in a seawater medium in equilibrium with a high-pressure oxy-helium atmosphere.

PubMed

Taylor, C D

1979-06-01

The molar oxygen concentration in a seawater medium in equilibrium with a high-pressure oxygen-helium atmosphere was measured directly in pressurized subsamples, using a modified version of the Winkler oxygen analysis. At a partial pressure of oxygen of 1 atm or less, its concentration in the aqueous phase was adequately described by Henry's Law at total pressures up to 600 atm. This phenomenon, which permits a straightforward determination of dissolved oxygen within hyperbaric systems, resulted from pressure-induced compensatory alterations in the Henry's Law variables rather than from a true obedience to the Ideal Gas Law. If the partial pressure of a gas contributes significantly to the hydrostatic pressure, Henry's Law is no longer adequate for determining its solubility within the compressed medium.

Charge-transfer potentials for ionic crystals: Cauchy violation, LO-TO splitting, and the necessity of an ionic reference state.

PubMed

Sukhomlinov, Sergey V; Müser, Martin H

2015-12-14

In this work, we study how including charge transfer into force fields affects the predicted elastic and vibrational Γ-point properties of ionic crystals, in particular those of rock salt. In both analytical and numerical calculations, we find that charge transfer generally leads to a negative contribution to the Cauchy pressure, P(C) ≡ C12 - C66, where C12 and C66 are elements of the elastic tensor. This contribution increases in magnitude with pressure for different charge-transfer approaches in agreement with results obtained with density functional theory (DFT). However, details of the charge-transfer models determine the pressure dependence of the longitudinal optical-transverse optical splitting and that for partial charges. These last two quantities increase with density as long as the chemical hardness depends at most weakly on the environment while experiments and DFT find a decrease. In order to reflect the correct trends, the charge-transfer expansion has to be made around ions and the chemical (bond) hardness has to increase roughly exponentially with inverse density or bond lengths. Finally, the adjustable force-field parameters only turn out meaningful, when the expansion is made around ions.

Charge-transfer potentials for ionic crystals: Cauchy violation, LO-TO splitting, and the necessity of an ionic reference state

NASA Astrophysics Data System (ADS)

Sukhomlinov, Sergey V.; Müser, Martin H.

2015-12-01

In this work, we study how including charge transfer into force fields affects the predicted elastic and vibrational Γ-point properties of ionic crystals, in particular those of rock salt. In both analytical and numerical calculations, we find that charge transfer generally leads to a negative contribution to the Cauchy pressure, PC ≡ C12 - C66, where C12 and C66 are elements of the elastic tensor. This contribution increases in magnitude with pressure for different charge-transfer approaches in agreement with results obtained with density functional theory (DFT). However, details of the charge-transfer models determine the pressure dependence of the longitudinal optical-transverse optical splitting and that for partial charges. These last two quantities increase with density as long as the chemical hardness depends at most weakly on the environment while experiments and DFT find a decrease. In order to reflect the correct trends, the charge-transfer expansion has to be made around ions and the chemical (bond) hardness has to increase roughly exponentially with inverse density or bond lengths. Finally, the adjustable force-field parameters only turn out meaningful, when the expansion is made around ions.

Lyotropic liquid crystalline phase behaviour in amphiphile-protic ionic liquid systems.

PubMed

Chen, Zhengfei; Greaves, Tamar L; Fong, Celesta; Caruso, Rachel A; Drummond, Calum J

2012-03-21

Approximate partial phase diagrams for nine amphiphile-protic ionic liquid (PIL) systems have been determined by synchrotron source small angle X-ray scattering, differential scanning calorimetry and cross polarised optical microscopy. The binary phase diagrams of some common cationic (hexadecyltrimethyl ammonium chloride, CTAC, and hexadecylpyridinium bromide, HDPB) and nonionic (polyoxyethylene (10) oleyl ether, Brij 97, and Pluronic block copolymer, P123) amphiphiles with the PILs, ethylammonium nitrate (EAN), ethanolammonium nitrate (EOAN) and diethanolammonium formate (DEOAF), have been studied. The phase diagrams were constructed for concentrations from 10 wt% to 80 wt% amphiphile, in the temperature range 25 °C to >100 °C. Lyotropic liquid crystalline phases (hexagonal, cubic and lamellar) were formed at high surfactant concentrations (typically >50 wt%), whereas at <40 wt%, only micelles or polydisperse crystals were present. With the exception of Brij 97, the thermal stability of the phases formed by these surfactants persisted to temperatures above 100 °C. The phase behaviour of amphiphile-PIL systems was interpreted by considering the PIL cohesive energy, liquid nanoscale order, polarity and ionicity. For comparison the phase behaviour of the four amphiphiles was also studied in water.

Room-Temperature Ionic Liquids and Biomembranes: Setting the Stage for Applications in Pharmacology, Biomedicine, and Bionanotechnology.

PubMed

Benedetto, Antonio; Ballone, Pietro

2018-03-21

Empirical evidence and conceptual elaboration reveal and rationalize the remarkable affinity of organic ionic liquids for biomembranes. Cations of the so-called room-temperature ionic liquids (RTILs), in particular, are readily absorbed into the lipid fraction of biomembranes, causing a variety of observable biological effects, including generic cytotoxicity, broad antibacterial potential, and anticancer activity. Chemical physics analysis of model systems made of phospholipid bilayers, RTIL ions, and water confirm and partially explain this evidence, quantifying the mild destabilizing effect of RTILs on the structural, dynamic, and thermodynamic properties of lipids in biomembranes. Our Feature Article presents a brief introduction to these systems and to their roles in biophysics and biotechnology, summarizing recent experimental and computational results on their properties. More importantly, it highlights the many developments in pharmacology, biomedicine, and bionanotechnology expected from the current research effort on this topic. To anticipate future developments, we speculate on (i) potential applications of (magnetic) RTILs to affect and control the rheology of cells and biological tissues, of great relevance for diagnostics and (ii) the use of RTILs to improve the durability, reliability, and output of biomimetic photovoltaic devices.

Improved classical united-atom force field for imidazolium-based ionic liquids: tetrafluoroborate, hexafluorophosphate, methylsulfate, trifluoromethylsulfonate, acetate, trifluoroacetate, and bis(trifluoromethylsulfonyl)amide.

PubMed

Zhong, Xiujuan; Liu, Zhiping; Cao, Dapeng

2011-08-25

A cost-effective, classical united-atom (UA) force field for ionic liquids (ILs) was proposed, which can be used in simulations of ILs composed by 1-alkyl-3-methyl-imidazolium cations ([C(n)mim](+)) and seven kinds of anions, including tetrafluoroborate ([BF(4)](-)), hexafluorophosphate ([PF(6)](-)), methylsulfate ([CH(3)SO(4)](-)), trifluoromethylsulfonate ([CF(3)SO(3)](-)), acetate ([CH(3)CO(2)](-)), trifluoroacetate ([CF(3)CO(2)](-)), and bis(trifluoromethylsulfonyl)amide ([NTf(2)](-)). The same strategy in our previous work (J. Phys. Chem. B 2010, 114, 4572) was used to parametrize the force field, in which the effective atom partial charges are fitted by the electrostatic potential surface (ESP) of ion pair dimers to account for the overall effects of polarization in ILs. The total charges (absolute values) on the cation/anion are in the range of 0.64-0.75, which are rescaled to 0.8 for all kinds of ions by a compromise between transferability and accuracy. Extensive molecular dynamics (MD) simulations were performed over a wide range of temperatures to validate the force field, especially on the enthalpies of vaporization (ΔH(vap)) and transport properties, including the self-diffusion coefficient and shear viscosity. The liquid densities were predicted very well for all of the ILs studied in this work with typical deviations of less than 1%. The simulated ΔH(vap) at 298 and 500 K are also in good agreement with the measured values by different experimental methods, with a slight overestimation of about 5 kJ/mol. The influence of ΔC(p) (the difference between the molar heat capacity at constant pressure of the gas and that of liquid) on the calculation of ΔH(vap) is also discussed. The transport coefficients were estimated by the equilibrium MD method using 20-60 ns trajectories to improve the sampling. The proposed force field gives a good description of the self-diffusion coefficients and shear viscosities, which is comparable to the recently developed polarizable force field. Although slightly lower dynamics is found in simulations by our force field, the order of magnitude of the self-diffusion coefficient and viscosity are reproduced for all the ILs very well over a wide temperature range. The largest underestimation of the self-diffusion coefficient is about one-third of the experimental values, while the largest overestimation of the viscosity is about two times the experimental values. © 2011 American Chemical Society

The distribution and ultrastructure of the forming blood capillaries and the effect of apoptosis on vascularization in mouse embryonic molar mesenchyme.

PubMed

Yuan, Guohua; Zhang, Li; Yang, Guobin; Yang, Jingwen; Wan, Chunyan; Zhang, Lu; Song, Guangtai; Chen, Shuo; Chen, Zhi

2014-04-01

Vascularization is essential for organ and tissue development. Teeth develop through interactions between epithelium and mesenchyme. The developing capillaries in the enamel organ, the dental epithelial structure, occur simultaneously by mechanisms of vasculogenesis and angiogenesis at the onset of dentinogenesis. The vascular neoformation in the dental mesenchyme has been reported to start from the cap stage. However, the mechanisms of vascularization in the dental mesenchyme remain unknown. In the hope of understanding the mechanisms of the formation of dental mesenchymal vasculature, mouse lower molar germs from embryonic day (E) 13.5 to E16.5 were processed for immunostaining of CD31 and CD34, terminal deoxynucleotidyltransferase-mediated dUTP-biotin nick end labeling (TUNEL) and transmission electron microscopy (TEM). In addition, the role of apoptosis for the vascularization in dental mesenchyme was examined by in vitro culture of E14.0 lower molars in the presence of the apoptosis inhibitor (z-VAD-fmk) and a subsequent subrenal culture. Our results showed that CD31- and CD34-positive cells progressively entered the central part of the dental papilla from the peridental mesenchyme. For TEM, angioblasts, young capillaries with thick endothelium and endothelial cells containing vacuoles were observed in peripheral dental mesenchyme, suggesting vasculogenesis was taking place. The presence of lateral sprouting, cytoplasmic filopodia and transluminal bridges in the dental papilla suggested angiogenesis was also occurring. Inhibition of apoptosis delayed the angiogenic vascularization of the dental papilla. Therefore, these data demonstrated that molar mesenchyme is progressively vascularized by mechanisms of both vasculogenesis and angiogenesis and apoptosis partially contributes to the vascularization of the dental papilla.

Analysis of C-shaped canal systems in mandibular second molars using surgical operating microscope and cone beam computed tomography: A clinical approach.

PubMed

Chhabra, Sanjay; Yadav, Seema; Talwar, Sangeeta

2014-05-01

The study was aimed to acquire better understanding of C-shaped canal systems in mandibular second molar teeth through a clinical approach using sophisticated techniques such as surgical operating microscope and cone beam computed tomography (CBCT). A total of 42 extracted mandibular second molar teeth with fused roots and longitudinal grooves were collected randomly from native Indian population. Pulp chamber floors of all specimens were examined under surgical operating microscope and classified into four types (Min's method). Subsequently, samples were subjected to CBCT scan after insertion of K-files size #10 or 15 into each canal orifice and evaluated using the cross-sectional and 3-dimensional images in consultation with dental radiologist so as to obtain more accurate results. Minimum distance between the external root surface on the groove and initial file placed in the canal was also measured at different levels and statistically analyzed. Out of 42 teeth, maximum number of samples (15) belonged to Type-II category. A total of 100 files were inserted in 86 orifices of various types of specimens. Evaluation of the CBCT scan images of the teeth revealed that a total of 21 canals were missing completely or partially at different levels. The mean values for the minimum thickness were highest at coronal followed by middle and apical third levels in all the categories. Lowest values were obtained for teeth with Type-III category at all three levels. The present study revealed anatomical variations of C-shaped canal system in mandibular second molars. The prognosis of such complex canal anatomies can be improved by simultaneous employment of modern techniques such as surgical operating microscope and CBCT.

Automation of data processing and calculation of retention parameters and thermodynamic data for gas chromatography

NASA Astrophysics Data System (ADS)

Makarycheva, A. I.; Faerman, V. A.

2017-02-01

The analyses of automation patterns is performed and the programming solution for the automation of data processing of the chromatographic data and their further information storage with a help of a software package, Mathcad and MS Excel spreadsheets, is developed. The offered approach concedes the ability of data processing algorithm modification and does not require any programming experts participation. The approach provides making a measurement of the given time and retention volumes, specific retention volumes, a measurement of differential molar free adsorption energy, and a measurement of partial molar solution enthalpies and isosteric heats of adsorption. The developed solution is focused on the appliance in a small research group and is tested on the series of some new gas chromatography sorbents. More than 20 analytes were submitted to calculation of retention parameters and thermodynamic sorption quantities. The received data are provided in the form accessible to comparative analysis, and they are able to find sorbing agents with the most profitable properties to solve some concrete analytic issues.

Rapid orthodontic treatment after the ridge-splitting technique--a combined surgical-orthodontic approach for implant site development: case report.

PubMed

Amato, Francesco; Mirabella, A Davide; Borlizzi, Diego

2012-08-01

This article presents a clinical case of bilateral partial edentulism in the posterior mandible with severe horizontal and moderate vertical bone atrophy. A new technique using rapid orthodontics after ridge splitting is presented. The split-crest technique was carried out using piezosurgical instruments in the first molar and second premolar areas to widen the bone crest and open a channel for tooth movement. Immediately after, orthodontic appliances were used to move the first premolars distally and the second molars mesially into the surgical site. The rationale was to facilitate and accelerate orthodontic movement of the teeth, which is otherwise difficult in a cortical knife-edged ridge. The bone defect was filled with the alveolar bone of the adjacent teeth that were moved into the surgically opened path. Adequate bone volume for implant placement was generated in the first premolar area. Implants were then inserted, and the patient was rehabilitated.

Fabrication of fixed implant prostheses using function bite impression technique (FBI technique).

PubMed

Suzuki, Yasunori; Shimpo, Hidemasa; Ohkubo, Chikahiro; Kurtz, Kenneth S

2012-10-01

The patient was partially edentulous, lacking both the first mandibular molars. The FBI and the conventional impression technique were used for the fabrication of implant-fixed prosthesis replacing the right and left molars, respectively. In the FBI technique, the definitive impression was made under occlusal force and functionally generated path (FGP) recording at the same time. The right and left occlusal contact areas were compared after completing the implant-fixed prosthesis rehabilitation. It has been suggested that accuracy of the impression and maxillomandibular registration is necessary to ensure a satisfactory long-term clinical outcome. The transfer of the exact position of the implants to the working cast is even more important because implants lack the mobility of natural teeth. There are displacement differences between implants and natural teeth under occlusal force. The FBI technique may compensate for this difference in accuracy. Using the FBI technique, a precise prosthesis could be produced by completing simultaneously the maxillomandibular registration, impression and FGP. Copyright © 2012 Japan Prosthodontic Society. All rights reserved.

Stability and activity of lysozyme in stoichiometric and non-stoichiometric protic ionic liquid (PIL)-water systems

NASA Astrophysics Data System (ADS)

Wijaya, Emmy C.; Separovic, Frances; Drummond, Calum J.; Greaves, Tamar L.

2018-05-01

There has been a substantial increase in enzyme applications within the biochemical and pharmaceutical industries, for example, as industrial biocatalysts. However, enzymes have narrow marginal stability which makes them prone to become inactive and/or denature with a slight change in the solvent environment. Typically industrial applications require harsher solvent environments than enzyme native environments, and hence there is a need to understand solvent-protein interactions in order to develop strategies to maintain, or enhance, the enzymatic activity under industrially relevant solvent conditions. Previously we have shown that protic ionic liquids (PILs) with water can have a stabilising effect on lysozyme, with a large variation dependent on which PIL ions are present, and the water concentration [E. C. Wijaya et al., Phys. Chem. Chem. Phys. 18(37), 25926-25936 (2016)]. Here we extend on this work using non-stoichiometric aqueous PIL solvents to investigate, and isolate, the role of pH and ionicity on enzymes. We have used the PILs ethylammonium nitrate (EAN) and ethanolammonium formate (EOAF) since our previous work has identified these as good solvents for lysozyme. Solvent libraries were made from these two PILs with an additional precursor acid or base to modify the acidity/basicity of the neutral stoichiometric PIL, and with water added, to have solutions with 4-17 mol. % of the PIL ions in water. Molar ratios of base:acid were varied between 1:1.05 and 2:1 for EAN and 1:1.25 and 2:1 for EOAF, which enabled from highly basic to highly acidic solutions to be obtained. This was to modify the acidity/basicity of the neutral stoichiometric PILs, without the addition of buffers. The structure and stability of hen egg white lysozyme (HEWL) were explored under these solvent conditions using synchrotron small angle X-ray scattering (SAXS), Fourier transform infrared (FTIR), and activity assays. The radius of gyration and Kratky plots obtained from the SAXS data showed little change with varying ionicity or acid:base ratio. FTIR showed that α-helix was maintained in all, except for the most acidic solvent conditions. The activity data show that HEWL was active between pH 0 and 11 for the EA:N-water system and pH 4.4 and 11 for the EOA:F-water system. This work indicates that ionic liquids have the potential to enable enzymes to maintain activity across a broader range of solvent conditions.

RETRACTED: Neoteric FT-IR investigation on the functional groups of phosphonium-based deep eutectic solvents.

PubMed

Aissaoui, Tayeb; AlNashef, Inas M; Hayyan, Maan; Hashim, Mohd Ali

2015-10-05

Deep eutectic solvents (DESs) are novel solvent media that are currently under investigation as an alternative to ionic liquids and conventional solvents. The physical properties of DESs as well as their mild environmental footprint and potentially critical industrial application necessitate understanding the interaction of functional groups on both the salt and hydrogen bond donor (HBD). In this study, four DESs were prepared by mixing triethylenglycol, diethylenglycol, ethylenglycol, and glycerol as HBDs with methyltriphenylphosphonium bromide as a salt at a molar ratio of 1:4. Fourier transform infrared spectroscopy was conducted to highlight the chemical structure and mechanism of the combination of the four DESs. New spectra illustrating the combination of the functional groups of the HBDs and salt were observed and interpreted. This study is the first to investigate the properties of neoteric phosphonium-based DESs. Copyright © 2015 Elsevier B.V. All rights reserved.

Protease activation in glycerol-based deep eutectic solvents.

PubMed

Zhao, Hua; Baker, Gary A; Holmes, Shaletha

2011-11-01

Deep eutectic solvents (DESs) consisting of mixtures of a choline salt (chloride or acetate form) and glycerol are prepared as easily accessible, biodegradable, and inexpensive alternatives to conventional aprotic cation-anion paired ionic liquids. These DES systems display excellent fluidity coupled with thermal stability to nearly 200 °C. In this work, the transesterification activities of cross-linked proteases (subtilisin and α-chymotrypsin), immobilized on chitosan, were individually examined in these novel DESs. In the 1:2 molar ratio mixture of choline chloride/glycerol containing 3% (v/v) water, cross-linked subtilisin exhibited an excellent activity (2.9 μmo l min(-1) g(-1)) in conjunction with a selectivity of 98% in the transesterification reaction of N-acetyl-L-phenylalanine ethyl ester with 1-propanol. These highly encouraging results advocate more extensive exploration of DESs in protease-mediated biotransformations of additional polar substrates and use of DESs in biocatalysis more generally.

Modified pineapple peel cellulose hydrogels embedded with sepia ink for effective removal of methylene blue.

PubMed

Dai, Hongjie; Huang, Huihua

2016-09-05

Novel composite hydrogels based on pineapple peel cellulose and sepia ink were synthesized by homogeneous acetylation of cellulose in ionic liquid 1-butyl-3-methylimidazolium chloride. The structure and morphology of the prepared hydrogels were characterized by Fourier transform infrared spectroscopy, field emission scanning electron microscope, X-ray diffraction, thermogravimetry and differential scanning calorimetry. The effects of acetylation time, acetylation temperature, molar ratio of acetic anhydride/anhydroglucose unit and the additive amount of sepia ink on methylene blue adsorption capacity of the hydrogels embedded with sepia ink were also investigated. Methylene blue adsorption of the hydrogels followed pseudo-second-order kinetic model and sepia ink improved adsorption capacity significantly. The adsorption capacity at equilibrium was increased from 53.72 to 138.25mg/g when the additive amount of sepia ink of the hydrogels was 10%. Copyright © 2016 Elsevier Ltd. All rights reserved.

Dependence of the enthalpies of formation of glycylglycinate complexes of nickel(II) on the composition of a mixed water-dimethylsulfoxide solvent

NASA Astrophysics Data System (ADS)

Naumov, V. V.; Kovaleva, Yu. A.; Isaeva, V. A.; Usacheva, T. R.; Sharnin, V. A.

2014-06-01

The heat effects of the complexation reactions of nickel(II) with a glycylglycinate ion in a water-dimethylsulfoxide solvent in a range of compositions of 0.00-0.60 molar parts of dimethylsulfoxide (DMSO) (an ionic strength of 0.1 was maintained using sodium perchlorate) were determined by means of calorimetry at 298.15 K. It is established that the exothermicity of complexation reactions rises by the first two steps and falls upon the addition of a third glycylglycinate anion with an increase in the concentration of DMSO. It is shown that the formation of mono- and bis-glycylglycinate complexes of nickel(II) in a water-DMSO solvent is determined mostly by the enthalpic contribution. It is concluded that the formation of tris-ligand complexes is more associated with the entropic contribution.

Liquid crystals in tribology.

PubMed

Carrión, Francisco-José; Martínez-Nicolás, Ginés; Iglesias, Patricia; Sanes, José; Bermúdez, María-Dolores

2009-09-18

Two decades ago, the literature dealing with the possible applications of low molar mass liquid crystals, also called monomer liquid crystals (MLCs), only included about 50 references. Today, thousands of papers, conference reports, books or book chapters and patents refer to the study and applications of MLCs as lubricants and lubricant additives and efforts are made to develop new commercial applications. The development of more efficient lubricants is of paramount technological and economic relevance as it is estimated that half the energy consumption is dissipated as friction. MLCs have shown their ability to form ordered boundary layers with good load-carrying capacity and to lower the friction coefficients, wear rates and contact temperature of sliding surfaces, thus contributing to increase the components service life and to save energy. This review includes the use of MLCs in lubrication, and dispersions of MLCs in conventional polymers (PDMLCs). Finally, new lubricating system composed of MLC blends with surfactants, ionic liquids or nanophases are considered.

Liquid Crystals in Tribology

PubMed Central

Carrión, Francisco-José; Martínez-Nicolás, Ginés; Iglesias, Patricia; Sanes, José; Bermúdez, María-Dolores

2009-01-01

Two decades ago, the literature dealing with the possible applications of low molar mass liquid crystals, also called monomer liquid crystals (MLCs), only included about 50 references. Today, thousands of papers, conference reports, books or book chapters and patents refer to the study and applications of MLCs as lubricants and lubricant additives and efforts are made to develop new commercial applications. The development of more efficient lubricants is of paramount technological and economic relevance as it is estimated that half the energy consumption is dissipated as friction. MLCs have shown their ability to form ordered boundary layers with good load-carrying capacity and to lower the friction coefficients, wear rates and contact temperature of sliding surfaces, thus contributing to increase the components service life and to save energy. This review includes the use of MLCs in lubrication, and dispersions of MLCs in conventional polymers (PDMLCs). Finally, new lubricating system composed of MLC blends with surfactants, ionic liquids or nanophases are considered. PMID:19865534

Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

PubMed Central

Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

2017-01-01

A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm−1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications. PMID:28067301

Fluorine-free electrolytes for all-solid sodium-ion batteries based on percyano-substituted organic salts

NASA Astrophysics Data System (ADS)

Bitner-Michalska, Anna; Nolis, Gene M.; Żukowska, Grażyna; Zalewska, Aldona; Poterała, Marcin; Trzeciak, Tomasz; Dranka, Maciej; Kalita, Michał; Jankowski, Piotr; Niedzicki, Leszek; Zachara, Janusz; Marcinek, Marek; Wieczorek, Władysław

2017-01-01

A new family of fluorine-free solid-polymer electrolytes, for use in sodium-ion battery applications, is presented. Three novel sodium salts withdiffuse negative charges: sodium pentacyanopropenide (NaPCPI), sodium 2,3,4,5-tetracyanopirolate (NaTCP) and sodium 2,4,5-tricyanoimidazolate (NaTIM) were designed andtested in a poly(ethylene oxide) (PEO) matrix as polymer electrolytes for anall-solid sodium-ion battery. Due to unique, non-covalent structural configurations of anions, improved ionic conductivities were observed. As an example, “liquid-like” high conductivities (>1 mS cm-1) were obtained above 70 °C for solid-polymer electrolyte with a PEO to NaTCP molar ratio of 16:1. All presented salts showed high thermal stability and suitable windows of electrochemical stability between 3 and 5 V. These new anions open a new class of compounds with non-covalent structure for electrolytes system applications.

Synthesis, spectroscopic characterization, DNA interaction and antibacterial study of metal complexes of tetraazamacrocyclic Schiff base

NASA Astrophysics Data System (ADS)

Shakir, Mohammad; Khanam, Sadiqa; Firdaus, Farha; Latif, Abdul; Aatif, Mohammad; Al-Resayes, Saud I.

The template condensation reaction between benzil and 3,4-diaminotoulene resulted mononuclear 12-membered tetraimine macrocyclic complexes of the type, [MLCl2] [M = Co(II), Ni(II), Cu(II) and Zn(II)]. The synthesized complexes have been characterized on the basis of the results of elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz. FT-IR, 1H and 13C NMR, FAB mass, UV-vis and EPR. An octahedral geometry has been envisaged for all these complexes, while a distorted octahedral geometry has been noticed for Cu(II) complex. Low conductivity data of all these complexes suggest their non-ionic nature. The interactive studies of these complexes with calf thymus DNA showed that the complexes are avid binders of calf thymus DNA. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria proved them as growth inhibiting agents.

The brilliant blue FCF ion-molecular forms in solutions according to the spectrophotometry data

NASA Astrophysics Data System (ADS)

Chebotarev, A. N.; Bevziuk, K. V.; Snigur, D. V.; Bazel, Ya. R.

2017-10-01

The brilliant blue FCF acid-base properties in aqueous solutions have been studied and its ionization constants have been defined by tristimulus colorimetry and spectrophotometry methods. The scheme of the acid-base dye equilibrium has been proposed and a diagram of the distribution of its ionic-molecular forms has been built. It has been established that the dominant form of the dye was the electroneutral form, which molar absorptivity (ɛ625 = 0.97 × 105) increases with the increase of the dielectric permittivity of the solvent. It has been shown that the replacement of polar solvents by less polar ones is causing a bathochromic shift of the maximum absorption band of the dye, the value of which is correlated with the value of the Hansen parameter. Tautomerization constants have been defined in a number of solvents and associated with the value of the Dimroth-Reichardt parameter.

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

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

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

Octanol-Water Partition Coefficient from 3D-RISM-KH Molecular Theory of Solvation with Partial Molar Volume Correction.

PubMed

Huang, WenJuan; Blinov, Nikolay; Kovalenko, Andriy

2015-04-30

The octanol-water partition coefficient is an important physical-chemical characteristic widely used to describe hydrophobic/hydrophilic properties of chemical compounds. The partition coefficient is related to the transfer free energy of a compound from water to octanol. Here, we introduce a new protocol for prediction of the partition coefficient based on the statistical-mechanical, 3D-RISM-KH molecular theory of solvation. It was shown recently that with the compound-solvent correlation functions obtained from the 3D-RISM-KH molecular theory of solvation, the free energy functional supplemented with the correction linearly related to the partial molar volume obtained from the Kirkwood-Buff/3D-RISM theory, also called the "universal correction" (UC), provides accurate prediction of the hydration free energy of small compounds, compared to explicit solvent molecular dynamics [ Palmer , D. S. ; J. Phys.: Condens. Matter 2010 , 22 , 492101 ]. Here we report that with the UC reparametrized accordingly this theory also provides an excellent agreement with the experimental data for the solvation free energy in nonpolar solvent (1-octanol) and so accurately predicts the octanol-water partition coefficient. The performance of the Kovalenko-Hirata (KH) and Gaussian fluctuation (GF) functionals of the solvation free energy, with and without UC, is tested on a large library of small compounds with diverse functional groups. The best agreement with the experimental data for octanol-water partition coefficients is obtained with the KH-UC solvation free energy functional.

Development of isothermal-isobaric replica-permutation method for molecular dynamics and Monte Carlo simulations and its application to reveal temperature and pressure dependence of folded, misfolded, and unfolded states of chignolin

NASA Astrophysics Data System (ADS)

Yamauchi, Masataka; Okumura, Hisashi

2017-11-01

We developed a two-dimensional replica-permutation molecular dynamics method in the isothermal-isobaric ensemble. The replica-permutation method is a better alternative to the replica-exchange method. It was originally developed in the canonical ensemble. This method employs the Suwa-Todo algorithm, instead of the Metropolis algorithm, to perform permutations of temperatures and pressures among more than two replicas so that the rejection ratio can be minimized. We showed that the isothermal-isobaric replica-permutation method performs better sampling efficiency than the isothermal-isobaric replica-exchange method and infinite swapping method. We applied this method to a β-hairpin mini protein, chignolin. In this simulation, we observed not only the folded state but also the misfolded state. We calculated the temperature and pressure dependence of the fractions on the folded, misfolded, and unfolded states. Differences in partial molar enthalpy, internal energy, entropy, partial molar volume, and heat capacity were also determined and agreed well with experimental data. We observed a new phenomenon that misfolded chignolin becomes more stable under high-pressure conditions. We also revealed this mechanism of the stability as follows: TYR2 and TRP9 side chains cover the hydrogen bonds that form a β-hairpin structure. The hydrogen bonds are protected from the water molecules that approach the protein as the pressure increases.

Thermodynamic properties of calcium-bismuth alloys determined by emf measurements

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

Kim, H; Boysen, DA; Bradwell, DJ

2012-01-15

The thermodynamic properties of Ca-Bi alloys were determined by electromotive force (emf) measurements to assess the suitability of Ca-Bi electrodes for electrochemical energy storage applications. Emf was measured at ambient pressure as a function of temperature between 723 K and 1173 K using a Ca(s)vertical bar CaF2(s)vertical bar Ca(in Bi) cell for twenty different Ca-Bi alloys spanning the entire range of composition from chi(Ca) = 0 to 1. Reported are the temperature-independent partial molar entropy and enthalpy of calcium for each Ca-Bi alloy. Also given are the measured activities of calcium, the excess partial molar Gibbs energy of bismuth estimatedmore » from the Gibbs-Duhem equation, and the integral change in Gibbs energy for each Ca-Bi alloy at 873 K, 973 K, and 1073 K. Calcium activities at 973 K were found to be nearly constant at a value a(Ca) = 1 x 10(-8) over the composition range chi(Ca) = 0.32-0.56, yielding an emf of similar to 0.77 V. Above chi(Ca) = 0.62 and coincident with Ca5Bi3 formation, the calcium activity approached unity. The Ca-Bi system was also characterized by differential scanning calorimetry over the entire range of composition. Based upon these data along with the emf measurements, a revised Ca-Bi binary phase diagram is proposed. (C) 2011 Elsevier Ltd. All rights reserved.« less

The density, compressibility and seismic velocity of hydrous melts at crustal and upper mantle conditions

NASA Astrophysics Data System (ADS)

Ueki, K.; Iwamori, H.

2015-12-01

Various processes of subduction zone magmatism, such as upward migration of partial melts and fractional crystallization depend on the density of the hydrous silicate melt. The density and the compressibility of the hydrous melt are key factors for the thermodynamic calculation of phase relation of the hydrous melt, and the geophysical inversion to predict physicochemical conditions of the melting region based on the seismic velocity. This study presents a new model for the calculations of the density of the hydrous silicate melts as a function of T, P, H2O content and melt composition. The Birch-Murnaghan equation is used for the equation of state. We compile the experimentally determined densities of various hydrous melts, and optimize the partial molar volume, compressibility, thermal expansibility and its pressure derivative, and K' of the H2O component in the silicate melt. P-T ranges of the calibration database are 0.48-4.29 GPa and 1033-2073 K. As such, this model covers the P-T ranges of the entire melting region of the subduction zone. Parameter set provided by Lange and Carmichael [1990] is used for the partial molar volume and KT value of the anhydrous silicate melt. K' of anhydrous melt is newly parameterized as a function of SiO2 content. The new model accurately reproduces the experimentally determined density variations of various hydrous melts from basalt to rhyolite. Our result shows that the hydrous melt is more compressive and less dense than the anhydrous melt; with the 5 wt% of H2O in melt, density and KT decrease by ~10% and ~30% from those of the anhydrous melt, respectively. For the application of the model, we calculated the P-wave velocity of the hydrous melt. With the 5 wt% of H2O, P-wave velocity of the silicate melt decreases by >10%. Based on the melt P-wave velocity, we demonstrate the effect of the melt H2O content on the seismic velocity of the partially molten zone of the subduction zone.

Occlusion of artificial teeth in partial dentures in the "chewing center"--first exploratory population-based evaluations.

PubMed

Kordass, B; Ruge, S; Quooss, A; Hugger, A; Mundt, T

2014-01-01

Occlusal performance is a substantial determinant of the quality of dental prosthetic restorations. In the follow-up (SHIP 1) to the Study of Health in Pomerania (SHIP), a representative population of 3300 subjects was studied in the first exploratory evaluation of the occlusion of artificial teeth in the chewing center (first molar region) of partial dentures. A digital analysis of interocclusal records of habitual intercuspation position (ICP) was performed using the Greifswald Digital Analyzing System (GEDAS), a software package that identifies contact points as transparent areas. 562 subjects (280 men aged 61.7 ± 11.9 years and 282 women aged 60.7 ± 10.7 years) had maxillary removable partial dentures (RPDs), and 619 (271 men aged 65.0 ± 11.5 years and 348 women aged 62.4 ± 10.6 years) had mandibular RPDs. Most RPDs were retained with either attachment retainers (11.7% maxilla, 11.7% mandible), cast clasps (38.4% maxilla, 40.7% mandible), telescopes with double crowns (15.7% maxilla, 19.1% mandible), or wrought wire clasps (16.4% maxilla, 8.2% mandible). Some had a combination of different retention elements. The mean number of artificial teeth was 7.8 ± 2.9 in the maxilla and 7.5 ± 3.0 in the mandible. Only the artificial teeth (first molars) in mandibular partial dentures showed differences in the frequency of occlusal contacts between groups (chi-square test). Of these, telescopic crown-retained RPDs had the highest frequency of occlusal contacts (74.4% at tooth 36 and 77.1% at tooth 46), and wrought wire-retained RPDs had the lowest (48.4% at tooth 36 and 45.2% at tooth 46). The results for RPDs with a free-end saddle were comparable and analogous; contact frequencies for those with an interdental saddle did not differ significantly. Notably, the overall frequency of occlusal contacts was greater for tooth 46 (62.9%) than for tooth 36. In conclusion, when replacing teeth in the chewing center, particularly in the mandible, telescopic crown-retained RPDs offer a distinct advantage in terms of occlusal contacts and thus provide better occlusal stability.

[Three-dimensional finite analysis of the stress in first mandibular molar with composite class I restoration when various mixing ratios of bases were used].

PubMed

Zhou, Lan; Yang, Jin-Bo; Liu, Dan; Liu, Zhan; Chen, Ying; Gao, Bo

2008-06-01

To analyze the possible damage to the remaining tooth and composite restorations when various mixing ratios of bases were used. Testing elastic modulus and poission's ratio of glass-ionomer Vitrebond and self-cured calcium hydroxide Dycal with mixing ratios of 1:1, 3:4, 4:3. Micro-CT was used to scan the first mandibular molar, and the three-dimensional finite element model of the first permanent mandibular molar with class I cavity was established. Analyzing the stress of tooth structure, composite and base cement under physical load when different mixing ratios of base cement were used. The elastic modulus of base cement in various mixing ratios was different, which had the statistic significance. The magnitude and location of stress in restored tooth made no differences when the mixing ratios of Vitrebond and Dycal were changed. The peak stress and spreading area in the model with Dycal was more than that with Vitrebond. Changing the best mixing ratio of base cement can partially influence the mechanistic character, but make no differences on the magnitude and location of stress in restored tooth. During the treatment of deep caries, the base cement of the elastic modulus which is proximal to the dentin and restoration should be chosen to avoid the fracture of tooth or restoration.

Preparation of a highly concentrated, completely monomeric, active sarcoplasmic reticulum Ca2+-ATPase.

PubMed

Lüdi, H; Hasselbach, W

1985-11-21

Sarcoplasmic reticulum vesicles from fast skeletal muscle were partially delipidated with sodium cholate at high ionic strength and sedimented in a discontinuous sucrose gradient. Phospholipid content was reduced from 0.777 mumol/mg protein to 0.242 mumol/mg protein. As judged from gel electrophoresis and high pressure liquid gel chromatography, accessory proteins were removed during centrifugation and the Ca2+-ATPase was obtained in an almost pure form. Addition of myristoylglycerophosphocholine (1 mg/mg protein) reactivates ATPase and dinitrophenylphosphatase activity to the same degree obtained with native vesicles. Using the analytical ultracentrifuge it could be demonstrated that the reactivated Ca2+-ATPase was present exclusively in a monomeric state. These results were obtained at high and low ionic strength and up to a protein concentration of 10 mg/ml. Therefore this preparation should be very useful to investigate differences between oligomeric and monomeric Ca2+-ATPase.

Anion channels in the sea urchin sperm plasma membrane.

PubMed

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

1993-10-01

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

A study in the adsorption of Fe(2+) and NO(3)(-) on pine needles based hydrogels.

PubMed

Chauhan, Ghanshyam S; Chauhan, Sandeep; Kumar, Sunil; Kumari, Anita

2008-09-01

Novel supports for use as cation and anion adsorbents were prepared from lignocellulosics using pine needles and their carboxymethylated forms by network/hydrogel formation with acrylamide and N,N-methylene bisacrylamide. The hydrogels thus prepared were further functionalized by partial alkaline hydrolysis with 0.5 N NaOH and were characterized by FTIR, SEM and nitrogen analysis. Adsorption of Fe(2+) on these hydrogels was carried as a function of time, temperature, pH and ionic strength. The hydrogel having the maximum adsorption capacity was loaded with Fe(2+) at the conditions those afforded maximum uptake and was used as novel anionic adsorbent for NO(3)(-). The water uptake capacities and biodegradability of the hydrogels before and after the ion loading was studied to evaluate the possible end-uses of these hydrogels as alternate materials in the removal of ionic species from water.

Optical and Physical Investigations of Lanthanum Bismuth Borate glasses doped with Ho2O3

NASA Astrophysics Data System (ADS)

Ramesh, P.; Jagannath, G.; Eraiah, B.; Kokila, M. K.

2018-02-01

Holmium doped 10La2O3-15Bi2O3-(75-x) B2O3 (Ho3+: LBB) glasses have been prepared by melt quench technique and the impact of holmium ions concentration on optical and physical properties of present glasses have been examined. Ho3+ dependent density, molar volume, refractive index, rare earth ion concentration, polaron radius, inter ionic distance, field strength and energy band gap are calculated and tabulated. Amorphous nature of the all glasses has been confirmed by XRD patterns. The room temperature (RT) Uv-Vis absorption spectrum doped with 1 mol% of Ho2O3 exhibit eight prominent bands centred at 895, 641, 537, 486, 472, 467, 451 and 416 due to transition between ground state to various excited states. The results show that, the density is increases and molar volume of the glasses is decreases with an increase in Ho2O3 concentration and consequently generate more non-bridging oxygen (NBOs) in the glass matrix. The Urbach energy is increases with holmium concentration which exemplifies the degree of disorder present in the LBB glasses. The considerable increase in field strength observed in present glasses is attributed to occurrence of strong bridge between Ho3+ and B- ions and this strong bridge is possibly due to the displacement between Ho3+ and oxygen atoms which are generated from the conversion BO3-BO4 units.

Purification and Partial Characterization of Two Soluble NAD(P)H Dehydrogenases from Arum maculatum Mitochondria 1

PubMed Central

Chauveau, Michèle; Lance, Claude

1991-01-01

Two enzyme systems carrying out the oxidation of NAD(P)H in the presence of various electron acceptors have been isolated and partially characterized from the supernatant of frozen-thawed mitochondria from Arum maculatum spadices. The two systems contain flavoproteins and differ by their ability to oxidize NADH or NADPH, optimum pH and pI values, sensitivity to Ca2+ and EGTA, denaturation by 4 molar urea, molecular mass, and number of subunits. These properties, together with methodological considerations, are compatible with the location of these enzyme activities on the outer surface of the inner mitochondrial membrane, and support the hypothesis of the existence of two separate dehydrogenases responsible for the mitochondrial oxidation of cytosolic NADH and NADPH. Images Figure 1 Figure 3 Figure 7 PMID:16668075

Fusion Welding Research.

DTIC Science & Technology

1985-04-30

rA( LA - AH) [watt cm 2] f3 ,5_ - . where " . ._.... L is the heat of evaporation of pure A and ~o ---30 3opo WA is the partial molar heat of mixing...steel; average voltage II V, current 2t atEL = rA( LA - ’-A)twatt cm 2 s], 14] 15 A; averae ample size I g. where t is time. In most cases XHA is small...B. Gates, Metrologia 17(3), 103 (1981). 7. R. D. Hudson, Jr., Infrared Engineering, Chap. 2, John Wiley, New York (1969). 8 R. Siegel and J. R

Effect of the Army Oral Health Maintenance Program (AOHMP) on the Dental Health Status of Army Personnel. AOHMP Evaluation Study. Part 3. Dental Care Requirements of Active Duty Army Personnel, 1978

DTIC Science & Technology

1979-06-01

endodontics , crown and bridge, full and partial dentures, and periodontal therapy , account for about one- third of the time requirements for the...Examiners indicated the numbers of restorations, extractions, teeth needing endodontic therapy , units of crown and bridge, complete den- tures...might be that lieutenants and captains are in a younger age range where the removal of third molars is usually recommended. (3) In the care need areas

Pressure-dependent boron isotopic fractionation observed by column chromatography

NASA Astrophysics Data System (ADS)

Musashi, M.; Oi, T.; Matsuo, M.; Nomura, M.

2007-12-01

Boron isotopic fractionation factor ( S ) between boron taken up in strongly basic anion exchange resin and boron in aqueous solution was determined by breakthrough column chromatography at 5 and 17 MPa at 25°C, using 0.1 mmol/L boric acid solution as feed solution. The S values obtained were 1.018 and 1.012, respectively, which were smaller than the value reported by using the same chromatographic method at atmospheric pressure at 25°C with the boron concentration of 10 mmol/L, but were larger than the values at the same condition with much higher concentration of 100 and 501 mmol/L, indicating that borate-polymerization reducing the isotopic fractionation was negligible. However, calculations based on the theory of isotope distribution between two phases estimated that 21% (5MPa) and 47% (17MPa) of boron taken up in the resin phase was in the three-coordinated B(OH)3-form, instead of in the four-coordinated B(OH)4--form, at high pressures even with the very diluted solution. We discussed this discrepancy by introducing (1) hydration or (2) a partial molar volume difference between isotopic molecules. It was inferred that borate ions were partially dehydrated upon transfer from the solution phase to the resin phase at high pressures, which resulted in smaller S values compared with those at the atmospheric pressure. Alternatively, it was likely that the S value decreased with increasing pressure, because the difference of the partial isotopic molar volumes between 10B(OH)3 and 11B(OH)3 was larger than that between 10B(OH)4- and 11B(OH)4-. If either will be the case, the influence of a pressure upon the isotope effect may not be negligible for boron isotopic exchange equilibrium. This knowledge is crucial for the principle of the boron isotopic pH-metry reconstructing a chemical variation at the paleo-deep oceanic environment where the early life may have been evolved.

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

PubMed

Umapathi, Reddicherla; Attri, Pankaj; Venkatesu, Pannuru

2014-06-05

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

Influence of carboxyl anion on the dissolution of chitosan in cholinium-based ionic liquids

NASA Astrophysics Data System (ADS)

Liu, Dong; Chen, Qingtai; Li, Min; Lou, Bin; Yu, Ran; Li, Zhiheng; Zhang, Yadong

2018-06-01

Chitosan can be applied in because of its excellent antimicrobial activity and abundant bio renewable and biodegradable resource. To better utilize this kind of native polysaccharide, it is still necessary to develop an efficient chitosan solvent system. Tn present study, 6 kinds of novel choline carboxylate ionic liquids (ILs) were developed. The solubility of chitosan in these H2O-ILs with different molar ratio were measured at 25 °C. The effect of the carboxylate anion of the ILs on chitosan solubility was estimated and found that the solubility of chitosan in the H2O-IL increased with the increasing of alkyl chain length in the anion. Moreover, the H2O-IL solution would not able to dissolve chitosan because the proton H was alternated by employing NH2 or OH group. The H2O-[Ch][CH3CH2CH2COO] (Rmol=6:1) solvent system exhibits highly efficient capacity for the dissolution of chitosan, and the solubility of chitosan reached up to 20.8 wt.%. From NMR measurement, these results could be explained by the possible interaction between carboxylate anion and chitosan and the strong hydration of the carboxyl group in the IL, suggesting that anionic structure have a significant impact on the dissolution of chitosan in the H2O-IL solvent system. Altogether, these results would provide an important evaluation indicator for screening the most suitable solvent system of chitosan.

[Study on the interaction of hemoglobin and Cu(II)-ARS complex].

PubMed

Wu, Xiao-Hua; Miao, Ji-Gen; Miao, Yu-Qing; Chen, Jian-Rong

2007-06-01

The reaction of hemoglobin (Hb) with copper(II)-Alizarin red S (ARS) complex was studied in H3PO4-KH2PO4 buffer solution (pH 4. 2) by ultraviolet-visible spectrophotometry. The results show that the interaction of Hb and Cu(II)-ARS complex produces red ionic association complex with its maximum absorption peak at 537 nm. At the maximum absorption, the composition of the complex was determined to be n(Hb) : n(Cu(II)) : n(ARS) =1 : 4 : 8, and the apparent molar absorptivity was 1.52 x 10(5) L x mol(-1) x cm(-1). The concentration of Hb is linear with the absorbency in the range of 1.0 x 10(-7)-2.0 x 10(-6) mol x L(-1) and the regression equation was established as A = 0.026 9 + 151 675c (mol x L(-1)) with the coefficient r = 0.997 2. The effects of solution acidity, reagent amount, reaction time, temperature, ionic strength and the added surfactant were examined on the formation of the Hb-Cu(II)-ARS complex. A preliminary investigation was carried out to elucidate the reaction mechanism, and it could be concluded that the Hb and Cu(II)-ARS complex are combined mainly by electrostatic attraction. Further investigation was also undertaken to find out the effects of common amino acids and metallic ions on the formation of Hb-Cu(II)-ARS complex.

Electrostatic interactions lead to the formation of asymmetric collagen-phosphophoryn aggregates.

PubMed

Dahl, Thomas; Veis, Arthur

2003-01-01

In bone and dentin the formation and mineralization of the extra cellular matrix structure is a complex process highly dependent on intermolecular interactions. In dentin, the phosphophoryns (PP) and type I collagen (COL1) are the major constituents implicated in mineralization. Thus, as a first step in understanding the tissue organization, we have initiated a study of their interaction as a function of pH, ionic strength, and relative concentrations or mixing ratios. Complex formation has been analyzed by dynamic light scattering to detect aggregate formation and by rotary shadowing electron microscopy (EM) to determine aggregate shape. The EM data showed that at the pH values studied, the PP-COL1 interaction leads to the formation of large fibrillar aggregates in which the PP are present along the fibril surfaces. The quantitative phase distribution data showed a 1/1 molar equivalence at the maximum aggregation point, not at electrostatic PP-COL1 equivalence. As the ionic strength was raised, the PP-COL1 aggregates became smaller but the binding and asymmetric fibrillar aggregation persisted. In EM, the PP appear as dense spheres. Along the surfaces of the collagen aggregates, the PP are larger and more open or extended, suggesting that COL1-bound PP may undergo a conformational change, opening up so that a single PP molecule might interact with and electrostatically link several COL1 molecules. This might have important implications for dentin structure, stability, and mineralization.

Probing the cellular damage in bacteria induced by GaN nanoparticles using confocal laser Raman spectroscopy

NASA Astrophysics Data System (ADS)

Sahoo, Prasana; Murthy, P. Sriyutha; Dhara, S.; Venugopalan, V. P.; Das, A.; Tyagi, A. K.

2013-08-01

Understanding the mechanism of nanoparticle (NP) induced toxicity in microbes is of potential importance to a variety of disciplines including disease diagnostics, biomedical implants, and environmental analysis. In this context, toxicity to bacterial cells and inhibition of biofilm formation by GaN NPs and their functional derivatives have been investigated against gram positive and gram negative bacterial species down to single cellular level. High levels of inhibition of biofilm formation (>80 %) was observed on treatments with GaN NPs at sub-micro molar concentrations. These results were substantiated with morphological features investigated with field emission scanning electron microscope, and the observed changes in vibrational modes of microbial cells using Raman spectroscopy. Raman spectra provided molecular interpretation of cell damage by registering signatures of molecular vibrations of individual living microbial cells and mapping the interplay of proteins at the cell membrane. As compared to the untreated cells, Raman spectra of NP-treated cells showed an increase in the intensities of characteristic protein bands, which confirmed membrane damage and subsequent release of cellular contents outside the cells. Raman spectral mapping at single cellular level can facilitate understanding of the mechanistic aspect of toxicity of GaN NPs. The effect may be correlated to passive diffusion causing mechanical damage to the membrane or ingress of Ga3+ (ionic radius 0.076 nm) which can potentially interfere with bacterial metabolism, as it resembles Fe2+ (ionic radius 0.077 nm), which is essential for energy metabolism.

High Coulombic efficiency aluminum-ion battery using an AlCl3-urea ionic liquid analog electrolyte.

PubMed

Angell, Michael; Pan, Chun-Jern; Rong, Youmin; Yuan, Chunze; Lin, Meng-Chang; Hwang, Bing-Joe; Dai, Hongjie

2017-01-31

In recent years, impressive advances in harvesting renewable energy have led to a pressing demand for the complimentary energy storage technology. Here, a high Coulombic efficiency (∼99.7%) Al battery is developed using earth-abundant aluminum as the anode, graphite as the cathode, and a cheap ionic liquid analog electrolyte made from a mixture of AlCl 3 and urea in a 1.3:1 molar ratio. The battery displays discharge voltage plateaus around 1.9 and 1.5 V (average discharge = 1.73 V) and yielded a specific cathode capacity of ∼73 mAh g -1 at a current density of 100 mA g -1 (∼1.4 C). High Coulombic efficiency over a range of charge-discharge rates and stability over ∼150-200 cycles was easily demonstrated. In situ Raman spectroscopy clearly showed chloroaluminate anion intercalation/deintercalation of graphite (positive electrode) during charge-discharge and suggested the formation of a stage 2 graphite intercalation compound when fully charged. Raman spectroscopy and NMR suggested the existence of AlCl 4 - , Al 2 Cl 7 - anions and [AlCl 2 ·(urea) n ] + cations in the AlCl 3 /urea electrolyte when an excess of AlCl 3 was present. Aluminum deposition therefore proceeded through two pathways, one involving Al 2 Cl 7 - anions and the other involving [AlCl 2 ·(urea) n ] + cations. This battery is a promising prospect for a future high-performance, low-cost energy storage device.

Analysis of quaternary ammonium and phosphonium ionic liquids by reversed-phase high-performance liquid chromatography with charged aerosol detection and unified calibration.

PubMed

Stojanovic, Anja; Lämmerhofer, Michael; Kogelnig, Daniel; Schiesel, Simone; Sturm, Martin; Galanski, Markus; Krachler, Regina; Keppler, Bernhard K; Lindner, Wolfgang

2008-10-31

Several hydrophobic ionic liquids (ILs) based on long-chain aliphatic ammonium- and phosphonium cations and selected aromatic anions were analyzed by reversed-phase high-performance liquid chromatography (RP-HPLC) employing trifluoroacetic acid as ion-pairing additive to the acetonitrile-containing mobile phase and adopting a step-gradient elution mode. The coupling of charged aerosol detection (CAD) for the non-chromophoric aliphatic cations with diode array detection (DAD) for the aromatic anions allowed their simultaneous analysis in a set of new ILs derived from either tricaprylmethylammonium chloride (Aliquat 336) and trihexyltetradecylphosphonium chloride as precursors. Aliquat 336 is a mix of ammonium cations with distinct aliphatic chain lengths. In the course of the studies it turned out that CAD generates an identical detection response for all the distinct aliphatic cations. Due to lack of single component standards of the individual Aliquat 336 cation species, a unified calibration function was established for the quantitative analysis of the quaternary ammonium cations of the ILs. The developed method was validated according to ICH guidelines, which confirmed the validity of the unified calibration. The application of the method revealed molar ratios of cation to anion close to 1 indicating a quantitative exchange of the chloride ions of the precursors by the various aromatic anions in the course of the synthesis of new ILs. Anomalies of CAD observed for the detection of some aromatic anions (thiosalicylate and benzoate) are discussed.

Morphological assessment of the mandibular canal trajectory in edentate subjects.

PubMed

Nimigean, Victor; Sîrbu, Valentin Daniel; Nimigean, Vanda Roxana; Bădiţă, Daniela Gabriela; Poll, Alexandru; Moraru, Simona Andreea; Păun, Diana Loreta

2018-01-01

The mandibular canal and its content represent the vital structure, which can complicate dentoalveolar surgical procedures in the posterior region of the mandible. The purpose of the present study was to determine the path the mandibular canal takes in relation to the horizontal and the vertical anatomical reference planes in edentate subjects, in order to minimize the risk of affecting its neurovascular content during various oral surgery procedures. Morphometric evaluations were performed on 12 dried fully edentulous human mandibles and on cone-beam computed tomography (CBCT) cross-sectional images of the mandible, from 20 patients with either partial or complete edentulism. Both methods were utilized, in three target areas (corresponding to the second premolar, to the first molar and to the second molar regions), in order to measure the distance between the mandibular canal and the following reference points: (i) the lateral (buccal) surface of the mandible (MC-BS distance); (ii) the medial (lingual) surface of the mandible (MC-LS distance); (iii) the alveolar surface of the mandible (MC-AS distance). The results were statistically processed in Stata MP/13 software package using analysis of variance (ANOVA) test. The mandibular canal crossed the trabecular bone from the posterior towards the anterior, and from the lingual towards the buccal, reaching the premolar region, distal to the mental foramen, where it was located in the centre of the trabecular bone, main topographic pattern encountered in 27 (84.37%) of the cases. In five (15.63%) of the cases, in the premolar region, the mandibular canal was located near the buccal cortical plate. The mandibular canal descended from the second molar region towards the premolar region, main topographic pattern found in 28 (87.5%) of the cases. In four (12.5%) cases, the mandibular canal had a descending trajectory in the molar regions and it took a slightly ascending course in the premolar region. According to the results, the second molar region represents the highest risk area in the accidental injury to the content of the mandibular canal, during various oral surgery procedures.

Self-Healable Electrical Insulation for High Voltage Applications

NASA Technical Reports Server (NTRS)

Williams, Tiffany S.

2017-01-01

Polymeric aircraft electrical insulation normally degrades by partial discharge with increasing voltage, which causes excessive localized Joule heating in the material and ultimately leads to dielectric failure of the insulator through thermal breakdown. Developing self-healing insulation could be a viable option to mitigate permanent mechanical degradation, thus increasing the longevity of the insulation. Instead of relying on catalyst and monomer-filled microcapsules to crack, flow, and cure at the damaged sites described in well-published mechanisms, establishment of ionic crosslinks could allow for multiple healing events to occur with the added benefit of achieving full recovery strength under certain thermal environments. This could be possible if the operating temperature of the insulator is the same as or close to the temperature where ionic crosslinks are formed. Surlyn, a commercial material with ionic crosslinks, was investigated as a candidate self-healing insulator based off prior demonstrations of self-healing behavior. Thin films of varying thicknesses were investigated and the effects of thickness on the dielectric strength were evaluated and compared to representative polymer insulators. The effects of thermal conditioning on the recovery strength and healing were observed as a function of time following dielectric breakdown. Moisture absorption was also studied to determine if moisture absorption rates in Surlyn were lower than that of common polyimides.

Predicting the partitioning of biological compounds between room-temperature ionic liquids and water by means of the solvation-parameter model.

PubMed

Padró, Juan M; Ponzinibbio, Agustín; Mesa, Leidy B Agudelo; Reta, Mario

2011-03-01

The partition coefficients, P(IL/w), for different probe molecules as well as for compounds of biological interest between the room-temperature ionic liquids (RTILs) 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF(6)], 1-hexyl-3-methylimidazolium hexafluorophosphate, [HMIM][PF(6)], 1-octyl-3-methylimidazolium tetrafluoroborate, [OMIM][BF(4)] and water were accurately measured. [BMIM][PF(6)] and [OMIM][BF(4)] were synthesized by adapting a procedure from the literature to a simpler, single-vessel and faster methodology, with a much lesser consumption of organic solvent. We employed the solvation-parameter model to elucidate the general chemical interactions involved in RTIL/water partitioning. With this purpose, we have selected different solute descriptor parameters that measure polarity, polarizability, hydrogen-bond-donor and hydrogen-bond-acceptor interactions, and cavity formation for a set of specifically selected probe molecules (the training set). The obtained multiparametric equations were used to predict the partition coefficients for compounds not present in the training set (the test set), most being of biological interest. Partial solubility of the ionic liquid in water (and water into the ionic liquid) was taken into account to explain the obtained results. This fact has not been deeply considered up to date. Solute descriptors were obtained from the literature, when available, or else calculated through commercial software. An excellent agreement between calculated and experimental log P(IL/w) values was obtained, which demonstrated that the resulting multiparametric equations are robust and allow predicting partitioning for any organic molecule in the biphasic systems studied.

Electronic structures of WAlO(y) and WAlO(y)(-) (y = 2-4) determined by anion photoelectron spectroscopy and density functional theory calculations.

PubMed

Mann, Jennifer E; Waller, Sarah E; Jarrold, Caroline Chick

2012-07-28

The anion photoelectron spectra of WAlO(y)(-) (y = 2-4) are presented and assigned based on results of density functional theory calculations. The WAlO(2)(-) and WAlO(3)(-) spectra are both broad, with partially resolved vibrational structure. In contrast, the WAlO(4)(-) spectrum features well-resolved vibrational structure with contributions from three modes. There is reasonable agreement between experiment and theory for all oxides, and calculations are in particular validated by the near perfect agreement between the WAlO(4)(-) photoelectron spectrum and a Franck-Condon simulation based on computationally determined spectroscopic parameters. The structures determined from this study suggest strong preferential W-O bond formation, and ionic bonding between Al(+) and WO(y)(-2) for all anions. Neutral species are similarly ionic, with WAlO(2) and WAlO(3) having electronic structure that suggests Al(+) ionically bound to WO(y)(-) and WAlO(4) being described as Al(+2) ionically bound to WO(4)(-2). The doubly-occupied 3sp hybrid orbital localized on the Al center is energetically situated between the bonding O-local molecular orbitals and the anti- or non-bonding W-local molecular orbitals. The structures determined in this study are very similar to structures recently determined for the analogous MoAlO(y)(-)/MoAlO(y) cluster series, with subtle differences found in the electronic structures [S. E. Waller, J. E. Mann, E. Hossain, M. Troyer, and C. C. Jarrold, J. Chem. Phys. 137, 024302 (2012)].

Physical gelation of chitosan in the presence of beta-glycerophosphate: the effect of temperature.

PubMed

Cho, Jaepyoung; Heuzey, Marie-Claude; Bégin, André; Carreau, Pierre J

2005-01-01

When adding beta-glycerophosphate (beta-GP), a weak base, to chitosan aqueous solutions, the polymer remains in solution at neutral pH and room temperature, while homogeneous gelation of this system can be triggered upon heating. It is therefore one of the rare true physical chitosan hydrogels. In this study, physicochemical and rheological properties of chitosan solutions in the presence of acetic acid and beta-GP were investigated as a function of temperature in order to gain a better understanding of the gelation mechanisms. The gel structure formed at high temperature was only partially thermoreversible upon cooling to 5 degrees C because of the existence of remaining associations, confirmed by the spontaneous recovery of the gel after breakup at low temperature. Increasing temperature had no effect on the pH values of this system, while conductivity (and calculated ionic strength) increased. Values from the pH measurements were used to estimate the degree of protonation of each species as a function of temperature. The decreasing ratio of -NH3+ in chitosan and -OPO(O-)2 in beta-GP suggested reduced chitosan solubility along with a diminution of ionic interactions such as ionic bridging with increasing temperature. On the other hand, the increased ionic strength as a function of temperature, in the presence of beta-GP, enhanced screening of electrostatic repulsion and increased hydrophobic effect, resulting in favorable conditions for gel formation. Therefore, our study suggests that hydrophobic interactions and reduced solubility are the main driving force for chitosan gelation at high temperature in the presence of beta-GP.

Electric current-producing device having sulfone-based electrolyte

DOEpatents

Angell, Charles Austen; Sun, Xiao-Guang

2010-11-16

Electrolytic solvents and applications of such solvents including electric current-producing devices. For example, a solvent can include a sulfone compound of R1--SO2--R2, with R1 being an alkyl group and R2 a partially oxygenated alkyl group, to exhibit high chemical and thermal stability and high oxidation resistance. For another example, a battery can include, between an anode and a cathode, an electrolyte which includes ionic electrolyte salts and a non-aqueous electrolyte solvent which includes a non-symmetrical, non-cyclic sulfone. The sulfone has a formula of R1--SO2--R2, wherein R1 is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms, and R2 is a linear or branched or partially or fully fluorinated linear or branched oxygen containing alkyl group having 1 to 7 carbon atoms. The electrolyte can include an electrolyte co-solvent and an electrolyte additive for protective layer formation.

Actinide-ion sensor

DOEpatents

Li, Shelly X; Jue, Jan-fong; Herbst, Ronald Scott; Herrmann, Steven Douglas

2015-01-13

An apparatus for the real-time, in-situ monitoring of actinide-ion concentrations. A working electrolyte is positioned within the interior of a container. The working electrolyte is separated from a reference electrolyte by a separator. A working electrode is at least partially in contact with the working electrolyte. A reference electrode is at least partially in contact with the reference electrolyte. A voltmeter is electrically connected to the working electrode and the reference electrode. The working electrolyte comprises an actinide-ion of interest. The separator is ionically conductive to the actinide-ion of interest. The separator comprises an actinide, Zr, and Nb. Preferably, the actinide of the separator is Am or Np, more preferably Pu. In one embodiment, the actinide of the separator is the actinide of interest. In another embodiment, the separator further comprises P and O.

Properties of lubrol-extracted uridine diphosphate glucuronyltransferase.

PubMed

Howland, R D; Burkhalter, A; Trevor, A J; Hegeman, S; Shirachi, D Y

1971-12-01

1. A partially purified UDP-glucuronyltransferase was obtained by extracting rat liver microsomal preparations with Lubrol, a non-ionic detergent. 2. The soluble enzyme catalysed conjugation of both o-aminophenol and p-nitrophenol and was extremely stable when compared with untreated microsomal preparations. 3. The characteristics of the conjugation of the two phenols were found to differ with respect to pH optimum, bivalent cation requirement and Michaelis constants, suggesting that more than one enzyme is involved in the conjugation reaction.

Properties of Lubrol-extracted uridine diphosphate glucuronyltransferase

PubMed Central

Howland, R. D.; Burkhalter, A.; Trevor, A. J.; Hegeman, S.; Shirachi, D. Y.

1971-01-01

1. A partially purified UDP-glucuronyltransferase was obtained by extracting rat liver microsomal preparations with Lubrol, a non-ionic detergent. 2. The soluble enzyme catalysed conjugation of both o-aminophenol and p-nitrophenol and was extremely stable when compared with untreated microsomal preparations. 3. The characteristics of the conjugation of the two phenols were found to differ with respect to pH optimum, bivalent cation requirement and Michaelis constants, suggesting that more than one enzyme is involved in the conjugation reaction. PMID:5144269

Distal extension mandibular removable partial denture with implant support

PubMed Central

Bural, Canan; Buzbas, Begum; Ozatik, Sebnem; Bayraktar, Gulsen; Emes, Yusuf

2016-01-01

This case report describes the fabrication of a distal extension removable partial denture (RPD) of a 65-year-old man with implant support. Loss of fibroelasticity of the peripheral tissues and reduced mandibular vestibular sulcular depth due to a previous surgical resection and radiotherapy at the right side were the main clinical factors that created difficulty for denture retention and stability. The fabrication of a mandibular RPD supported by anterior teeth and two bilaterally placed implants in the molar area to convert from Kennedy Class 1 design to Kennedy Class 3 implant-bounded RPD is reported. Retention and stability of the denture were improved with implant support on the distal extension site of the RPD. The common clinical problems about distally extended RPDs are lack of retention and stability due to the movement around the rotational axis. Dental implant placement to the distal edentulous site minimizes the potential dislodgement of the RPD is popular. Implant-supported RPD can be suggested as an advantageous and cost-effective treatment option for the partially edentulous patients. PMID:28042277

Cul3-mediated Nrf2 ubiquitination and antioxidant response element (ARE) activation are dependent on the partial molar volume at position 151 of Keap1.

PubMed

Eggler, Aimee L; Small, Evan; Hannink, Mark; Mesecar, Andrew D

2009-07-29

Nrf2 (nuclear factor erythroid 2-related factor 2) is a transcription factor that activates transcription of a battery of cytoprotective genes by binding to the ARE (antioxidant response element). Nrf2 is repressed by the cysteine-rich Keap1 (kelch-like ECH-associated protein 1) protein, which targets Nrf2 for ubiquitination and subsequent degradation by a Cul3 (cullin 3)-mediated ubiquitination complex. We find that modification of Cys(151) of human Keap1, by mutation to a tryptophan, relieves the repression by Keap1 and allows activation of the ARE by Nrf2. The Keap1 C151W substitution has a decreased affinity for Cul3, and can no longer serve to target Nrf2 for ubiquitination, though it retains its affinity for Nrf2. A series of 12 mutant Keap1 proteins, each containing a different residue at position 151, was constructed to explore the chemistry required for this effect. The series reveals that the extent to which Keap1 loses the ability to target Nrf2 for degradation, and hence the ability to repress ARE activation, correlates well with the partial molar volume of the residue. Other physico-chemical properties do not appear to contribute significantly to the effect. Based on this finding, a structural model is proposed whereby large residues at position 151 cause steric clashes that lead to alteration of the Keap1-Cul3 interaction. This model has significant implications for how electrophiles which modify Cys(151), disrupt the repressive function of Keap1.

Evaluation of stress patterns produced by implant-retained overdentures and implant-retained fixed partial denture.

PubMed

Mazaro, José Vitor Quinelli; Filho, Humberto Gennari; Vedovatto, Eduardo; Pellizzer, Eduardo Piza; Rezende, Maria Cristina Rosifini Alves; Zavanelli, Adriana Cristina

2011-11-01

The purposes of this study were to photoelastically measure the biomechanical behavior of 4 implants retaining different cantilevered bar mandibular overdenture designs and to compare a fixed partial denture (FPD). A photoelastic model of a human edentulous mandible was fabricated, which contained 4 screw-type implants (3.75 × 10 mm) embedded in the parasymphyseal area. An FPD and 3 overdenture designs with the following attachments were evaluated: 3 plastic Hader clips, 1 Hader clip with 2 posterior resilient cap attachments, and 3 ball/O-ring attachments. Vertical occlusal forces of 100 N were applied between the central incisor and unilaterally to the right and left second premolars and second molars. Stresses that developed in the supporting structure were monitored photoelastically and recorded photographically. The results showed that the anterior loading, the overdenture with 3 plastic Hader clips, displayed the largest stress concentration at the medium implant. With premolar loading, the FPD and overdenture with 3 plastic Hader clips displayed the highest stresses to the ipsilateral terminal implant. With molar loading, the overdenture with 3 ball/O-ring attachments displayed the most uniform stress distribution in the posterior edentulous ridge, with less overloading in the terminal implant. It was concluded that vertical forces applied to the bar-clip overdenture and FPD created immediate stress patterns of greater magnitude and concentration on the ipsilateral implants, whereas the ball/O-ring attachments transferred minimal stress to the implants. The increased cantilever in the FPD caused the highest stresses to the terminal implant.

Fracture Strength of Three-Unit Implant Supported Fixed Partial Dentures with Excessive Crown Height Fabricated from Different Materials.

PubMed

Nazari, Vahideh; Ghodsi, Safoura; Alikhasi, Marzieh; Sahebi, Majid; Shamshiri, Ahmad Reza

2016-11-01

Fracture strength is an important factor influencing the clinical long-term success of implant-supported prostheses especially in high stress situations like excessive crown height space (CHS). The purpose of this study was to compare the fracture strength of implant-supported fixed partial dentures (FPDs) with excessive crown height, fabricated from three different materials. Two implants with corresponding abutments were mounted in a metal model that simulated mandibular second premolar and second molar. Thirty 3-unit frameworks with supportive anatomical design were fabricated using zirconia, nickel-chromium alloy (Ni-Cr), and polyetheretherketone (PEEK) (n=10). After veneering, the CHS was equal to 15mm. Then; samples were axially loaded on the center of pontics until fracture in a universal testing machine at a crosshead speed of 0.5 mm/minute. The failure load data were analyzed by one-way ANOVA and Games-Howell tests at significance level of 0.05. The mean failure loads for zirconia, Ni-Cr and PEEK restorations were 2086±362N, 5591±1200N and 1430±262N, respectively. There were significant differences in the mean failure loads of the three groups (P<0.001). The fracture modes in zirconia, metal ceramic and PEEK restorations were cohesive, mixed and adhesive type, respectively. According to the findings of this study, all implant supported three-unit FPDs fabricated of zirconia, metal ceramic and PEEK materials are capable to withstand bite force (even para-functions) in the molar region with excessive CHS.

Crystalline, Glassy and Polymeric Electrolytes:. Similarities and Differences in Ionic Transport Mechanisms

NASA Astrophysics Data System (ADS)

Souquet, Jean Louis

2006-06-01

Ionocovalent crystals or glasses as well as molten salts or salt polymer complexes are currently studied as electrolytes for high energy density batteries. Their large Red/Ox stability range results from their thermodynamic or kinetic characteristics. For all these electrolytes, charge carriers are the consequence of local deviations from electroneutrality, identified as point defects for ionic crystals or partial dissociation in disordered structures. The charge carriers formation derives from a similar activated process. The main difference comes from the migration process, which depends on the dynamic properties of the surrounding medium. When the structural relaxation time is large, an activated process, mainly enthalpic, prevails for charge carriers migration. It is the usual case for ionic crystals or glasses. In the liquid or overcooled liquid states, the structural relaxation time of the medium is shorter that the time required for the activated migration process to occur and a local reorganization of the medium vanishes the energy barrier and provides the free volume necessary to ionic migration. In that case, the migration is mainly an entropic process. The configurational entropy necessary to this process decreases with temperature and vanishes at the so called ideal glass transition temperature which can be estimated by extrapolation of the transport properties or of the thermodynamic characteristics of the medium. However, at the experiment time scale, this configurational entropy disappears at a somewhat higher temperature, the glass transition temperature at which the structural relaxation time corresponds to the measurement time. Some glass forming ionic melts studied in a large temperature scale, over and below the glass transition temperature, evidence the two, enthalpic and entropic, migration mechanisms, allowing the determination of the thermodynamic characteristics of the charge carriers formation and migration. Some recent results indicate that entropic process, associated to long scale deformations, may also exist in crystalline structures.

Extending the applicability of the Tkatchenko-Scheffler dispersion correction via iterative Hirshfeld partitioning

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

Bučko, Tomáš, E-mail: bucko@fns.uniba.sk; Department of Computational Materials Physics, Fakultät für Physik and Center for Computational Materials Science, Universität Wien, Sensengasse, Wien 1090; Lebègue, Sébastien, E-mail: sebastien.lebegue@univ-lorraine.fr

2014-07-21

Recently we have demonstrated that the applicability of the Tkatchenko-Scheffler (TS) method for calculating dispersion corrections to density-functional theory can be extended to ionic systems if the Hirshfeld method for estimating effective volumes and charges of atoms in molecules or solids (AIM’s) is replaced by its iterative variant [T. Bučko, S. Lebègue, J. Hafner, and J. Ángyán, J. Chem. Theory Comput. 9, 4293 (2013)]. The standard Hirshfeld method uses neutral atoms as a reference, whereas in the iterative Hirshfeld (HI) scheme the fractionally charged atomic reference states are determined self-consistently. We show that the HI method predicts more realistic AIMmore » charges and that the TS/HI approach leads to polarizabilities and C{sub 6} dispersion coefficients in ionic or partially ionic systems which are, as expected, larger for anions than for cations (in contrast to the conventional TS method). For crystalline materials, the new algorithm predicts polarizabilities per unit cell in better agreement with the values derived from the Clausius-Mosotti equation. The applicability of the TS/HI method has been tested for a wide variety of molecular and solid-state systems. It is demonstrated that for systems dominated by covalent interactions and/or dispersion forces the TS/HI method leads to the same results as the conventional TS approach. The difference between the TS/HI and TS approaches increases with increasing ionicity. A detailed comparison is presented for isoelectronic series of octet compounds, layered crystals, complex intermetallic compounds, and hydrides, and for crystals built of molecules or containing molecular anions. It is demonstrated that only the TS/HI method leads to accurate results for systems where both electrostatic and dispersion interactions are important, as illustrated for Li-intercalated graphite and for molecular adsorption on the surfaces in ionic solids and in the cavities of zeolites.« less

Importance of sulfide interaction with iron as regulator of the microbial community in biogas reactors and its effect on methanogenesis, volatile fatty acids turnover, and syntrophic long-chain fatty acids degradation.

PubMed

Shakeri Yekta, Sepehr; Ziels, Ryan M; Björn, Annika; Skyllberg, Ulf; Ejlertsson, Jörgen; Karlsson, Anna; Svedlund, Matilda; Willén, Magnus; Svensson, Bo H

2017-05-01

The inhibitory effects of sulfide on microbial processes during anaerobic digestion have been widely addressed. However, other effects of sulfide are less explored, given that sulfide is a potential sulfur source for microorganisms and its high reactivity triggers a suit of abiotic reactions. We demonstrated that sulfide interaction with Fe regulates the dynamics and activities of microbial community during anaerobic digestion. This was manifested by the S:Fe molar ratio, whose increase adversely influenced the acetoclastic methanogens, Methanosaeta, and turnover of acetate. Dynamics of hydrogenotrophic methanogens, Methanoculleus and Methanobrevibacter, were presumably influenced by sulfide-induced changes in the partial pressure of hydrogen. Interestingly, conversion of the long-chain fatty acid (LCFA), oleate, to methane was enhanced together with the abundance of LCFA-degrading, β-oxidizing Syntrophomonas at an elevated S:Fe molar ratio. The results suggested that sulfur chemical speciation is a controlling factor for microbial community functions in anaerobic digestion processes. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Effects of ketoprofen and diclofenac potassium on blood coagulation tests after removal of third molars.

PubMed

Naclério-Homem, Maria da Graça; Deboni, Maria Christina Zindel; Rapoport, Abrăo; Chin, Veronica Kei Len

2009-04-01

Nonsteroidal anti-inflammatory drugs inhibit platelet aggregation and increase bleeding time; however, they are required to control pain and swelling following dental surgery. The objective of this study was to evaluate possible changes on blood coagulation tests by using ketoprofen and diclofenac potassium after removal of mandibular third molars. Fifty-one subjects between 16 and 30 years old, with no history of gastrointestinal disorders or allergy to anti-inflammatory components, were randomly assigned to 2 groups: 27 patients received 50 mg of ketoprofen, and 24 patients received 25 mg of diclofenac potassium. Subjects started the oral medication 2 hours before surgery and continued taking it every 8 hours for 5 days. Blood samples were collected preoperatively and on the final day of the drug regime to evaluate prothrombin time, activated partial thromboplastin time, clot retraction, and platelet count. Student t test for matched pairs did not show a significant difference between pre- and posttreatment variables for both anti-inflammatory drugs. These results suggest that the safety of ketoprofen and diclofenac potassium is comparable to their anticoagulation effect.

Salt potentiates methylamine counteraction system to offset the deleterious effects of urea on protein stability and function.

PubMed

Rahman, Safikur; Rehman, Md Tabish; Singh, Laishram R; Warepam, Marina; Ahmad, Faizan; Dar, Tanveer Ali

2015-01-01

Cellular methylamines are osmolytes (low molecular weight organic compounds) believed to offset the urea's harmful effects on the stability and function of proteins in mammalian kidney and marine invertebrates. Although urea and methylamines are found at 2:1 molar ratio in tissues, their opposing effects on protein structure and function have been questioned on several grounds including failure to counteraction or partial counteraction. Here we investigated the possible involvement of cellular salt, NaCl, in urea-methylamine counteraction on protein stability and function. We found that NaCl mediates methylamine counteracting system from no or partial counteraction to complete counteraction of urea's effect on protein stability and function. These conclusions were drawn from the systematic thermodynamic stability and functional activity measurements of lysozyme and RNase-A. Our results revealed that salts might be involved in protein interaction with charged osmolytes and hence in the urea-methylamine counteraction.

Binding of basic amphipathic peptides to neutral phospholipid membranes: a thermodynamic study applied to dansyl-labeled melittin and substance P analogues.

PubMed

Pérez-Payá, E; Porcar, I; Gómez, C M; Pedrós, J; Campos, A; Abad, C

1997-08-01

A thermodynamic approach is proposed to quantitatively analyze the binding isotherms of peptides to model membranes as a function of one adjustable parameter, the actual peptide charge in solution z(p)+. The main features of this approach are a theoretical expression for the partition coefficient calculated from the molar free energies of the peptide in the aqueous and lipid phases, an equation proposed by S. Stankowski [(1991) Biophysical Journal, Vol. 60, p. 341] to evaluate the activity coefficient of the peptide in the lipid phase, and the Debye-Hückel equation that quantifies the activity coefficient of the peptide in the aqueous phase. To assess the validity of this approach we have studied, by means of steady-state fluorescence spectroscopy, the interaction of basic amphipathic peptides such as melittin and its dansylcadaverine analogue (DNC-melittin), as well as a new fluorescent analogue of substance P, SP (DNC-SP) with neutral phospholipid membranes. A consistent quantitative analysis of each binding curve was achieved. The z(p)+ values obtained were always found to be lower than the physical charge of the peptide. These z(p)+ values can be rationalized by considering that the peptide charged groups are strongly associated with counterions in buffer solution at a given ionic strength. The partition coefficients theoretically derived using the z(p)+ values were in agreement with those deduced from the Gouy-Chapman formalism. Ultimately, from the z(p)+ values the molar free energies for the free and lipid-bound states of the peptides have been calculated.

Influence of hydrophobic micelle structure on crystallization of the photosynthetic RC-LH1-PufX complex from Rhodobacter blasticus.

PubMed

Barret, Laurie-Anne; Barrot-Ivolot, Cherone; Raynal, Simon; Jungas, Colette; Polidori, Ange; Bonneté, Françoise

2013-07-25

Small angle X-ray scattering (SAXS) experiments are performed on two non-ionic surfactants, the dodecyl β-maltoside (DDβM) and the propyl(bi)cyclohexyl α-maltoside (PCCαM), a maltoside derivative containing a rigid bicyclohexyl group as hydrophobic chain, in order to compare the influence of both hydrophobic moiety structure and anomeric form on micelle form factors and intermicellar interactions relevant for membrane protein crystallization. Density and refractive index measurements were performed in order to determine volumetric and optical properties of surfactants, essential for determination of micelle molar masses by both SAXS and SEC-MALLS. SAXS form factors were analyzed by Guinier approximation and inverse Fourier transformation, to obtain the radius of gyration (RG) and the pair distribution function (P(r)) of each surfactant. Form factor model fitting was also performed to describe the shape and the assembly of both surfactant micelles. Finally, second virial coefficients were measured at different percentages of polyethylene glycol 3350, in order to correlate surfactant intermicellar interactions and RC-LH1-PufX phase diagram. It is thus found that while size, shape, and dimensions of micelles are slightly similar for both surfactants, their molar mass and aggregation number differ significantly. PCCαM are more densely packed than DDβM, which reflects (1) an increase in van der Waals contacts between PCCαM hydrophobic chains in the micelle bulk and (2) a supplementary intermicellar attraction compared to DDβM. Finally addition of PEG, which induces a depletion attraction, decreases the solubility of the RC-LH1-PufX complex in PCCαM.

Kinetic-Dominated Charging Mechanism within Representative Aqueous Electrolyte-based Electric Double-Layer Capacitors.

PubMed

Yang, Huachao; Yang, Jinyuan; Bo, Zheng; Chen, Xia; Shuai, Xiaorui; Kong, Jing; Yan, Jianhua; Cen, Kefa

2017-08-03

The chemical nature of electrolytes has been demonstrated to play a pivotal role in the charge storage of electric double-layer capacitors (EDLCs), whereas primary mechanisms are still partially resolved but controversial. In this work, a systematic exploration into EDL structures and kinetics of representative aqueous electrolytes is performed with numerical simulation and experimental research. Unusually, a novel charging mechanism exclusively predominated by kinetics is recognized, going beyond traditional views of manipulating capacitances preferentially via interfacial structural variations. Specifically, strikingly distinctive EDL structures stimulated by diverse ion sizes, valences, and mixtures manifest a virtually identical EDL capacitance, where the dielectric nature of solvents attenuates ionic effects on electrolyte redistributions, in stark contradiction with solvent-free counterpart and traditional Helmholtz theory. Meanwhile, corresponding kinetics evolve conspicuously with ionic species, intimately correlated with ion-solvent interactions. The achieved mechanisms are subsequently illuminated by electrochemical measurements, highlighting the crucial interplay between ions and solvents in regulating EDLC performances.

Recent trends in ionic liquid (IL) tolerant enzymes and microorganisms for biomass conversion.

PubMed

Portillo, Maria Del Carmen; Saadeddin, Anas

2015-01-01

Second generation biofuel production depends on lignocellulosic (LC) biomass transformation into simple sugars and their subsequent fermentation into alcohols. However, the main obstacle in this process is the efficient breakdown of the recalcitrant cellulose to sugar monomers. Hence, efficient feedstock pretreatment and hydrolysis are necessary to produce a cost effective biofuel. Recently, ionic liquids (ILs) have been recognized as a promising solvent able to dissolve different biomass feedstocks, providing higher sugar yields. However, most of the hydrolytic enzymes and microorganisms are inactivated, completely or partially, in the presence of even low concentrations of IL, making necessary the discovery of novel hydrolytic enzymes and fermentative microorganisms that are tolerant to ILs. In this review, the current state and the challenges of using ILs as a pretreatment of LC biomass was evaluated, underlining the advances in the discovery and identification of new IL-tolerant enzymes and microorganisms that could improve the bioprocessing of biomass to fuels and chemicals.

[Molecular Dynamics of N- and C-terminal Interactions during Autoinhibition and Activation of Formin mDial].

PubMed

Orshanskiy, I A; Popinako, A V; Volokh, O I; Shaitan, K V; Sokolova, O S

2015-01-01

With the method of molecular dynamics, pairs of amino acid residues have been identified on the surface of the interacting formin mDial domains: DID-DAD, which are responsible for the autoinhibition of formin, and the GTPase Rho-DID domain, and control activation. It was found that the most stable interactions are ionic interactions between Glu178 residue and Arg248 residue, as well as hydrophobic interactions between Thr175 and Phe247. The strongest interactions proved to be between the DID domain with Rho-GTPase. These interactions are mediated by specific triple ionic interactions between positively charged amino acid in Rho, and a triplet of amino acids in DID, consisting of two negatively charged amino acids, separated by one uncharged. Binding sites for Rho-GTPase and DAD partially overlap, but various amino acids on the DID participate in interactions with different domains. We discuss the possible conformational changes in formin domains during activation and inactivation.

Phase relationships and cation disorder in RE{sub 1+x}Ba{sub 2-x}Cu{sub 3}O{sub 7+{delta}}, RE = Pr, Nd, Sm, Gd

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

Kramer, M.J.; Wu, H.; Dennis, K.W.

1995-12-31

Unlike Y123 which forms only a stoichiometric compound, the light arare earth elements (LRE) form a solid solution LRE{sub 1+x}Ba{sub 2-x}Cu{sub 3}O{sub 7+{delta}} (LRE123ss), with increasing substitution of the LRE{sup 3+} for the Ba{sup 2+} as the ionic radii of the LRE increases. The sub-solidus phase relationships around the LRE123ss change for La, Pr and Nd, but are similar for Sm and Gd. However, the solubility limit decreases with decreasing ionic radii. In addition, the solubility limits for Sm and Gd are strongly influenced by PO{sub 2} during high temperature annealing. The range of solubility is, for any given LREmore » system, strongly dependent on the oxygen partial pressure (PO{sub 2}) providing a new means by which to control the microstructure in the RE123 system.« less

Surface potential of methyl isobutyl carbinol adsorption layer at the air/water interface.

PubMed

Phan, Chi M; Nakahara, Hiromichi; Shibata, Osamu; Moroi, Yoshikiyo; Le, Thu N; Ang, Ha M

2012-01-26

The surface potential (ΔV) and surface tension (γ) of MIBC (methyl isobutyl carbinol) were measured on the subphase of pure water and electrolyte solutions (NaCl at 0.02 and 2 M). In contrast to ionic surfactants, it was found that surface potential gradually increased with MIBC concentration. The ΔV curves were strongly influenced by the presence of NaCl. The available model in literature, in which surface potential is linearly proportional to surface excess, failed to describe the experimental data. Consequently, a new model, employing a partial charge of alcohol adsorption layer, was proposed. The new model predicted the experimental data consistently for MIBC in different NaCl solutions. However, the model required additional information for ionic impurity to predict adsorption in the absence of electrolyte. Such inclusion of impurities is, however, unnecessary for industrial applications. The modeling results successfully quantify the influence of electrolytes on surface potential of MIBC, which is critical for froth stability.

Influence of temperature, anions and size distribution on the zeta potential of DMPC, DPPC and DMPE lipid vesicles.

PubMed

Morini, M A; Sierra, M B; Pedroni, V I; Alarcon, L M; Appignanesi, G A; Disalvo, E A

2015-07-01

The purpose of the work is to compare the influence of the multilamellarity, phase state, lipid head groups and ionic media on the origin of the surface potential of lipid membranes. With this aim, we present a new analysis of the zeta potential of multilamellar and unilamellar vesicles composed by phosphatidylcholines (PC) and phosphatidylethanolamines (PE) dispersed in water and ionic solutions of polarizable anions, at temperatures below and above the phase transition. In general, the adsorption of anions seems to explain the origin of the zeta potential in vesicles only above the transition temperature (Tc). In this case, the sign of the surface potential is ascribed to a partial orientation of head group moiety toward the aqueous phase. This is noticeable in PC head groups but not in PEs, due to the strong lateral interaction between PO and NH group in PE. Copyright © 2015 Elsevier B.V. All rights reserved.

Phenomenological Transition of an Aluminum Surface in an Ionic Liquid and Its Beneficial Implementation in Batteries.

PubMed

Shvartsev, B; Gelman, D; Amram, D; Ein-Eli, Y

2015-12-29

Aluminum (Al) electrochemical dissolution in organic nonaqueous media and room temperature ionic liquids (RTILs) is partially hampered by the presence of a native oxide. In this work, Al activation in EMIm(HF)2.3F RTIL is reported. It was confirmed that as a result of the interaction of Al with the RTIL, a new film is formed instead of the pristine oxide layer. Aluminum surface modifications result in a transformation from a passive state to the active behavior of the metal. This was confirmed via the employment of electrochemical methods and characterization by XPS, AFM, and TEM. It was shown that the pristine oxide surface film dissolves in EMIm(HF)2.3F, allowing an Al-O-F layer to be formed instead. This newly built up layer dramatically restricts Al corrosion while enabling high rates of Al anodic dissolution. These beneficial features allow the implementation of Al as an anode in advanced portable power sources, such as aluminum-air batteries.

Charge modeling of ionic polymer-metal composites for dynamic curvature sensing

NASA Astrophysics Data System (ADS)

Bahramzadeh, Yousef; Shahinpoor, Mohsen

2011-04-01

A curvature sensor based on Ionic Polymer-Metal Composite (IPMC) is proposed and characterized for sensing of curvature variation in structures such as inflatable space structures in which using low power and flexible curvature sensor is of high importance for dynamic monitoring of shape at desired points. The linearity of output signal of sensor for calibration, effect of deflection rate at low frequencies and the phase delay between the output signal and the input deformation of IPMC curvature sensor is investigated. An analytical chemo-electro-mechanical model for charge dynamic of IPMC sensor is presented based on Nernst-Planck partial differential equation which can be used to explain the phenomena observed in experiments. The rate dependency of output signal and phase delay between the applied deformation and sensor signal is studied using the proposed model. The model provides a background for predicting the general characteristics of IPMC sensor. It is shown that IPMC sensor exhibits good linearity, sensitivity, and repeatability for dynamic curvature sensing of inflatable structures.

Interdisciplinary treatment for a compensated Class II partially edentulous malocclusion: Orthodontic creation of a posterior implant site.

PubMed

Chiu, Grace; Chang, Chris; Roberts, W Eugene

2018-03-01

A 36-year-old woman with good periodontal health sought treatment for a compensated Class II partially edentulous malocclusion associated with a steep mandibular plane (SN-MP, 45°), 9 missing teeth, a 3-mm midline discrepancy, and compromised posterior occlusal function. She had multiple carious lesions, a failing fixed prostheses in the mandibular right quadrant replacing the right first molar, and a severely atrophic edentulous ridge in the area around the mandibular left first and second molars. After restoration of the caries, the mandibular left third molar served as anchorage to correct the mandibular arch crowding. The mandibular left second premolar was retracted with a light force of 2 oz (about 28.3 cN) on the buccal and lingual surfaces to create an implant site between the premolars. Modest lateral root resorption was noted on the distal surface of the mandibular left second premolar after about 7 mm of distal translation in 7 months. Six months later, implants were placed in the mandibular left and right quadrants; the spaces were retained with the fixed appliance for 5 months and a removable retainer for 1 month. Poor cooperation resulted in relapse of the mandibular left second premolar back into the implant site, and it was necessary to reopen the space. When the mandibular left fixture was uncovered, a 3-mm deep osseous defect on the distobuccal surface was found; it was an area of relatively immature bundle bone, because the distal aspect of the space was reopened after the relapse. Subsequent bone grafting resulted in good osseous support of the implant-supported prosthesis. The relatively thin band of attached gingiva on the implant at the mandibular right first molar healed with a recessed contour that was susceptible to food impaction. A free gingival graft restored soft tissue form and function. This severe malocclusion with a discrepancy index value of 28 was treated to an excellent outcome in 38 months of interdisciplinary treatment. The Cast-Radiograph Evaluation score was 13. However, the treatment was complicated by routine relapse and implant osseous support problems. Retreatment of space opening and 2 additional surgeries were required to correct an osseous defect and an inadequate soft tissue contour. Orthodontic treatment is a viable option for creating implant sites, but fixed retention is required until the prosthesis is delivered. Bone augmentation is indicated at the time of implant placement to offset expected bone loss. Complex restorative treatment may result in routine complications that are effectively managed with interdisciplinary care. Copyright © 2017 American Association of Orthodontists. Published by Elsevier Inc. All rights reserved.