Application of the Hansen solubility Parameters theory to carbon nanotubes.
Detriche, S; Zorzini, G; Colomer, J F; Fonseca, A; Nagy, J B
2008-11-01
Carbon nanotubes (CNT) are very promising nano-objects due to their exceptional properties. However, their tendency to form bundles as well as their insolubility in common solvents makes them difficult to handle. The main way to solve the problem is chemical or physical CNTs functionalisations, with all the problems inherent to the methods. In this contribution, we present a new approach that allows predicting the solubility of carbon nanotubes in many solvents but also predicting the most appropriate solvents to use for given samples of CNTs. Solubilisation and dispersion being directly connected, the present approach of solubilisation proves also to be efficient in dispersing the CNTs bundles. This contribution is a first step toward the control of carbon nanotube's dispersion in polymers and their homogenous functionalisation. Moreover, we also report here a new method, based on solvents, to separate carbon nanotubes by size, the use of mixture of non-solvents in order to obtain good solvents and the use of mixture of good solvents to obtain higher solubility. The use of mixture of good solvents allowed us to obtain high solubility, up to three times higher then that reported in literature. We have also measured and analysed the solubility of some functionalised carbon nanotubes.
Yueyuan Ye
2014-04-01
Full Text Available The Hildebrand solubility parameter (delta-value was applied to explain the effect of organic solvent concentration on lignin removal during organosolv extraction of lignin from enzymatically hydrolyzed cornstalks under atmospheric pressure and low temperature (≤ 75 °C without additional catalyst. The -value of lignin, calculated using the group-contribution method, was 13.70 (cal/cm31/2. The proximity of the delta-value between organic solvent-water and lignin explained the delignification capacity of the organic solvent-water. The concentration of organic solvent in the aqueous mixture that led to the highest delignification (i.e., 34.5%, 41.8%, and 53.7% delignification for ethanol-water, 1,4-dioxane-water, and tetrahydrofuran-water, respectively was around 65 to 75% vol., which was in keeping with the prediction by the solubility parameter theory.
Redefining solubility parameters: the partial solvation parameters.
Panayiotou, Costas
2012-03-21
The present work reconsiders a classical and universally accepted concept of physical chemistry, the solubility parameter. Based on the insight derived from modern quantum chemical calculations, a new definition of solubility parameter is proposed, which overcomes some of the inherent restrictions of the original definition and expands its range of applications. The original single solubility parameter is replaced by four partial solvation parameters reflecting the dispersion, the polar, the acidic and the basic character of the chemical compounds as expressed either in their pure state or in mixtures. Simple rules are adopted for the definition and calculation of these four parameters and their values are tabulated for a variety of common substances. In contrast, however, to the well known Hansen solubility parameters, their design and evaluation does not rely exclusively on the basic rule of "similarity matching" for solubility but it makes also use of the other basic rule of compatibility, namely, the rule of "complementarity matching". This complementarity matching becomes particularly operational with the sound definition of the acidic and basic components of the solvation parameter based on the third σ-moments of the screening charge distributions of the quantum mechanics-based COSMO-RS theory. The new definitions are made in a simple and straightforward manner, thus, preserving the strength and appeal of solubility parameter stemming from its simplicity. The new predictive method has been applied to a variety of solubility data for systems of pharmaceuticals and polymers. The results from quantum mechanics calculations are critically compared with the results from Abraham's acid/base descriptors.
Perea, J Darío; Langner, Stefan; Salvador, Michael; Kontos, Janos; Jarvas, Gabor; Winkler, Florian; Machui, Florian; Görling, Andreas; Dallos, Andras; Ameri, Tayebeh; Brabec, Christoph J
2016-05-19
The solubility of organic semiconductors in environmentally benign solvents is an important prerequisite for the widespread adoption of organic electronic appliances. Solubility can be determined by considering the cohesive forces in a liquid via Hansen solubility parameters (HSP). We report a numerical approach to determine the HSP of fullerenes using a mathematical tool based on artificial neural networks (ANN). ANN transforms the molecular surface charge density distribution (σ-profile) as determined by density functional theory (DFT) calculations within the framework of a continuum solvation model into solubility parameters. We validate our model with experimentally determined HSP of the fullerenes C60, PC61BM, bisPC61BM, ICMA, ICBA, and PC71BM and through comparison with previously reported molecular dynamics calculations. Most excitingly, the ANN is able to correctly predict the dispersive contributions to the solubility parameters of the fullerenes although no explicit information on the van der Waals forces is present in the σ-profile. The presented theoretical DFT calculation in combination with the ANN mathematical tool can be easily extended to other π-conjugated, electronic material classes and offers a fast and reliable toolbox for future pathways that may include the design of green ink formulations for solution-processed optoelectronic devices.
The Solubility Parameters of Ionic Liquids
Andrzej Marciniak
2010-04-01
Full Text Available The Hildebrand’s solubility parameters have been calculated for 18 ionic liquids from the inverse gas chromatography measurements of the activity coefficients at infinite dilution. Retention data were used for the calculation. The solubility parameters are helpful for the prediction of the solubility in the binary solvent mixtures. From the solubility parameters, the standard enthalpies of vaporization of ionic liquids were estimated.
A new expanded solubility parameter approach.
Stefanis, Emmanuel; Panayiotou, Costas
2012-04-15
The partial or Hansen solubility parameters (HSP) are important properties of the various substances and very useful tools for the selection of their solvents or the prediction of their behaviour in numerous applications. Their design and evaluation relies on the basic rule of "similarity matching" for solubility. The present work attempts to enhance the capacity of HSPs by incorporating into their evaluation the other basic rule of solubility, namely, the rule of "complementarity matching". This is done in a simple and straightforward manner by splitting the hydrogen bonding HSP into its acidic or proton donor component and its basic or proton acceptor one. The splitting is based on the third σ-moments of the screening charge distributions or sigma profiles of the quantum-mechanics based COSMO-RS theory. The whole development and application does not involve any sophisticated calculations or any strong specific background. The new method has been applied to a variety of solubility data for systems of pharmaceutical interest in order to verify the significant improvement over the classical HSP approach. The application of the new method requires, of course, the knowledge of the HSPs. For this reason, in Appendix A is presented an updated version of a robust and reliable group-contribution method for the calculation of the HSPs. The key features of this combined tool are critically discussed.
Hansen Solubility Parameters for Octahedral Oligomeric Silsesquioxanes
2012-08-28
and thermal and electrical insulation enhancers. The inorganic core is both mechanically robust, resistant to oxidation, and thermally stable, and...Choi, P.; Kavassalis, T. A.; Rudin, A. Estimation of Hansen Solubility Parameters for (Hydroxyethyl)- Cellulose and (Hydroxypropyl) Cellulose through
Organogel formation rationalized by Hansen solubility parameters.
Raynal, Matthieu; Bouteiller, Laurent
2011-08-07
Some organic compounds gelate particular solvents by forming a network of anisotropic fibres. We show that Hansen solubility parameters can be used to predict the range of solvents that are likely to be gelled by any given gelator.
The Hildebrand Solubility Parameters of Ionic Liquids—Part 2
Andrzej Marciniak
2011-06-01
Full Text Available The Hildebrand solubility parameters have been calculated for eight ionic liquids. Retention data from the inverse gas chromatography measurements of the activity coefficients at infinite dilution were used for the calculation. From the solubility parameters, the enthalpies of vaporization of ionic liquids were estimated. Results are compared with solubility parameters estimated by different methods.
Hansen solubility parameters for polyethylene glycols by inverse gas chromatography.
Adamska, Katarzyna; Voelkel, Adam
2006-11-03
Inverse gas chromatography (IGC) has been applied to determine solubility parameter and its components for nonionic surfactants--polyethylene glycols (PEG) of different molecular weight. Flory-Huggins interaction parameter (chi) and solubility parameter (delta(2)) were calculated according to DiPaola-Baranyi and Guillet method from experimentally collected retention data for the series of carefully selected test solutes. The Hansen's three-dimensional solubility parameters concept was applied to determine components (delta(d), delta(p), delta(h)) of corrected solubility parameter (delta(T)). The molecular weight and temperature of measurement influence the solubility parameter data, estimated from the slope, intercept and total solubility parameter. The solubility parameters calculated from the intercept are lower than those calculated from the slope. Temperature and structural dependences of the entopic factor (chi(S)) are presented and discussed.
Extended Hansen approach: calculating partial solubility parameters of solid solutes.
Wu, P L; Beerbower, A; Martin, A
1982-11-01
A multiple linear regression method, known as the extended Hansen solubility approach, was used to estimate the partial solubility parameters, delta d, delta p, and delta h for crystalline solutes. The method is useful, since organic compounds may decompose near their melting points, and it is not possible, to determine solubility parameters for these solid compounds by the methods used for liquid solvents. The method gives good partial and total solubility parameters for naphthalene; with related compounds, less satisfactory results were obtained. At least three conditions, pertaining to the regression equation and the solvent systems, must be met in order to obtain reasonable solute solubility parameters. In addition to providing partial solubility parameters, the regression equations afford a calculation of solute solubility in both polar and nonpolar solvents.
Selection of solubility parameters for characterization of pharmaceutical excipients.
Adamska, Katarzyna; Voelkel, Adam; Héberger, Károly
2007-11-09
The solubility parameter (delta(2)), corrected solubility parameter (delta(T)) and its components (delta(d), delta(p), delta(h)) were determined for series of pharmaceutical excipients by using inverse gas chromatography (IGC). Principal component analysis (PCA) was applied for the selection of the solubility parameters which assure the complete characterization of examined materials. Application of PCA suggests that complete description of examined materials is achieved with four solubility parameters, i.e. delta(2) and Hansen solubility parameters (delta(d), delta(p), delta(h)). Selection of the excipients through PCA of their solubility parameters data can be used for prediction of their behavior in a multi-component system, e.g. for selection of the best materials to form stable pharmaceutical liquid mixtures or stable coating formulation.
Use of Hansen Solubility Parameters in Fuel Treatment Processes
2014-03-17
Charts 3. DATES COVERED (From - To) Jan 2014- Mar 2014 4. TITLE AND SUBTITLE 5a. CONTRACT NUMBER In-House Use of Hansen Solubility Parameters in...distribution is unlimited. AFRL Public Affairs Clearance # USE OF HANSEN SOLUBILITY PARAMETERS IN FUEL TREATMENT PROCESSES 17 March 2014 Andrew J...Treatment Needs – Hansen Solubility Parameters • Dyes – Experimental HSP Determination – Extrapolation to Other Dyes • Predictions for Extraction Fluids
Bustamante, P; Martin, A; Gonzalez-Guisandez, M A
1993-06-01
A modification of the extended Hansen method is used for estimating the solubility of sulfadiazine and other organic drug molecules in a number of individual solvents ranging from nonpolar to highly polar. The equations obtained for each drug involve the partial solubility parameters of the solvents and allow the prediction of solubility of these drugs in a new solvent. Furthermore, a number of drugs (e.g., sulfadiazine, sulfamethoxypyridazine, naphthalene, and some benzoic acid derivatives) are combined in a single expression including the ideal solubility of the drugs and the partial solubility parameters of the solvents. The equation fits the solubilities of these drugs in a wide variety of solvents and may be used to predict the solubility of other sulfonamides and benzoic acid derivatives in semipolar and highly polar solvents. The solvatochromic parameter approach is also used in models for predicting the solubility of single drugs in individual solvents. It was tested with multiple solutes as was the partial solubility parameter approach. However, the latter approach is superior; the parameters of the solubility parameter method are all statistically significant for drugs tested individually or together in a single equation, a condition that is not obtained with the solvatochromic model.
Multicomponent solubility parameters for single-walled carbon nanotube-solvent mixtures.
Bergin, Shane D; Sun, Zhenyu; Rickard, David; Streich, Philip V; Hamilton, James P; Coleman, Jonathan N
2009-08-25
We have measured the dispersibility of single-walled carbon nanotubes in a range of solvents, observing values as high as 3.5 mg/mL. By plotting the nanotube dispersibility as a function of the Hansen solubility parameters of the solvents, we have confirmed that successful solvents occupy a well-defined range of Hansen parameter space. The level of dispersibility is more sensitive to the dispersive Hansen parameter than the polar or H-bonding Hansen parameter. We estimate the dispersion, polar, and hydrogen bonding Hansen parameter for the nanotubes to be = 17.8 MPa(1/2), = 7.5 MPa(1/2), and = 7.6 MPa(1/2). We find that the nanotube dispersibility in good solvents decays smoothly with the distance in Hansen space from solvent to nanotube solubility parameters. Finally, we propose that neither Hildebrand nor Hansen solubility parameters are fundamental quantities when it comes to nanotube-solvent interactions. We show that the previously calculated dependence of nanotube Hildebrand parameter on nanotube diameter can be reproduced by deriving a simple expression based on the nanotube surface energy. We show that solubility parameters based on surface energy give equivalent results to Hansen solubility parameters. However, we note that, contrary to solubility theory, a number of nonsolvents for nanotubes have both Hansen and surface energy solubility parameters similar to those calculated for nanotubes. The nature of the distinction between solvents and nonsolvents remains to be fully understood.
Internal pressure and solubility parameter as a function of pressure
Verdier, Sylvain Charles Roland; Andersen, Simon Ivar
2005-01-01
The main goal of this work was to measure the solubility parameter of a complex mixture, such as a crude oil, especially as a function of pressure. Thus, its definition is explained, as well as the main approximations generally used in literature. Then, the internal pressure is investigated, since...... it is presented as an alternative of the solubility parameter. In this work, the assumption that internal pressure is a measure of the physical solubility parameter was made, i.e. representing the dispersion and polar forces. As for the pressure influence, it was seen that internal pressure reaches a maximum...... contrary to solubility parameter. An indirect method was chosen to estimate internal pressure, using thermal expansivities (determined by microcalorimetry) and isothermal compressibilities (determined by density measurements). The uncertainty is within 2% for the expansivity and 0.1% for the density. Five...
Tate, Michael P.; Cutler, Charlotte; Sakillaris, Mike; Kaufman, Michael; Estelle, Thomas; Mohler, Carol; Tucker, Chris; Thackeray, Jim
2014-03-01
Understanding fundamental properties of photoresists and how interactions between photoresist components affect performance targets are crucial to the continued success of photoresists. More specifically, polymer solubility is critical to the overall performance capability of the photoresist formulation. While several theories describe polymer solvent solubility, the most common industrially applied method is Hansen's solubility parameters. Hansen's method, based on regular solution theory, describes a solute's ability to dissolve in a solvent or solvent blend using four physical properties determined experimentally through regression of solubility data in many known solvents. The four physical parameters are dispersion, polarity, hydrogen bonding, and radius of interaction. Using these parameters a relative cohesive energy difference (RED), which describes a polymer's likelihood to dissolve in a given solvent blend, may be calculated. Leveraging a high throughput workflow to prepare and analyze the thousands of samples necessary to calculate the Hansen's solubility parameters from many different methacrylate-based polymers, we compare the physical descriptors to reveal a large range of polarities and hydrogen bonding. Further, we find that Hansen's model correctly predicts the soluble/insoluble state of 3-component solvent blends where the dispersion, polar, hydrogen-bonding, and radius of interaction values were determined through regression of experimental values. These modeling capabilities have allowed for optimization of the photoresist solubility from initial blending through application providing valuable insights into the nature of photoresist.
Determination of solubility parameters for poly(3-hydroxyalkanoates).
Terada, M; Marchessault, R H
1999-01-01
The three dimensional solubility parameters defined by Hansen are based on dispersion forces between structural units, interaction between polar groups and hydrogen bonding. For polar polymers such as poly(3-hydroxyalkanoates), P(3HA), this approach was used to obtain the three coordinates of a solubility parameter in terms of: a dispersion part, a polar part and a hydrogen bonding part. Thirty-eight different solvents for poly(3-hydroxybutyrate), PHB, which are mentioned in the literature are examined by this method and the theoretical predictions are compared with the experimental reports. Another overall comparison between PHA polymers provides their Hansen and Hildebrand parameters for side chain lengths up to C13. In this series a linear progression in calculated solubility parameters with side chain length was found. An Appendix provides information and data on calculation of the solubility parameters. While the solubility information is limited and only covers homopolymers, it should help to highlight some of the contradictions regarding PHB solubility. This semi-empirical approach is only valid for amorphous polymers hence crystallinity effects, which are important with PHB, as well as molecular weight effects still require analysis.
Surface state of carbon nanotubes and Hansen solubility parameters.
Detriche, S; Nagy, J B; Mekhalif, Z; Delhalle, J
2009-10-01
Carbon nanotubes (CNTs) are often described as insoluble or poorly soluble in organic solvents. In a recent study, we have reported that nonfunctionalized CNTs can be solubilized in suitably chosen organic solvents. Furthermore, their solubility could be understood in terms of the Hansen Solubility Parameters (HSPs). The present work addresses further the question of the CNTs solubility by considering a larger range of solvents. A second part is devoted to the application of the HSPs to two types of functionalized CNTs: oxidized and silanized. These results stress the critical role played by the surface state of the CNTs, on the one hand, and the interest in using the HSPs to guide solubility investigations, on the other hand.
Predicting the Solubility of 1,1-Difluoroethane in Polystyrene Using the Perturbed Soft Chain Theory
Pretel, Eduardo; Hong, Seong-Uk
1998-01-01
In this study, the solubility of 1,1-difluoroethane in polystyrene was correlated and predicted using the Perturbed Soft Chain Theory (PSCT) and compared with experimental data from the literature. For correlation, a binary interaction parameter was determined by using experimental solubility data...
Predicting the Solubility of 1,1-Difluoroethane in Polystyrene Using the Perturbed Soft Chain Theory
Pretel, Eduardo; Hong, Seong-Uk
1998-01-01
In this study, the solubility of 1,1-difluoroethane in polystyrene was correlated and predicted using the Perturbed Soft Chain Theory (PSCT) and compared with experimental data from the literature. For correlation, a binary interaction parameter was determined by using experimental solubility dat...
Correlation of polymer performance and Hansen solubility parameters
Mania, Daniel Jobse
Ready-to-use (RTU) grout is becoming more important to the finish and remodeling construction industry. Market research shows it to be a fast-growing product that not only is creating its own space but also is beginning to supplant existing technology. The original intent of this research was to investigate formulation parameters and how they affect grout performance. It was learned that particle size and oil absorption (OA) value are important filler properties that affect performance as much as adequate packing density and optimal pigment volume concentration (PVC) without going beyond critical PVC (CPVC). Polymer architecture was also determined to be extremely important, but difficult to predict. Properties such as tensile strength and elongation can be adequately modeled by polymer Tg, however, Tg alone is not a good predictor of hydrophobicity or stain repellency performance. This conundrum led to research into Hansen solubility parameters (HSP) and whether these could be used as performance predictive tools. Since HSP of polymers cannot be directly measured, Group Contribution Theory (GCT) had to be employed to estimate polymer HSP. It was determined that HSP is not as good of a performance predictor for physical strength properties, like tensile strength, as polymer Tg: but HSP does have utility for relative performance prediction of wet state properties such as hydrophobicity, stain repellency, or solvent resistance. It was further discovered that HSP may be useful with predicting relative performance of wet state properties such as wet tensile strength and elongation.
Partial-solubility parameters of naproxen and sodium diclofenac.
Bustamante, P; Peña, M A; Barra, J
1998-09-01
The expanded Hansen method was tested for determination of the solubility parameters of two non-steroidal anti-inflammatory drugs, naproxen and sodium diclofenac. This work describes for the first time the application of the method to the sodium salt of a drug. The original dependent variable of the expanded Hansen method, involving the activity coefficient of the drug, was compared with the direct use of the logarithm of the mole fraction solubility 1nX2 in the solubility models. The solubility of both drugs was measured in pure solvents of several chemical classes and the activity coefficient was obtained from the molar heat and the temperature of fusion. Differential scanning calorimetry was performed on the original powder and on the solid phase after equilibration with the pure solvents, enabling detection of possible changes of the thermal properties of the solid phase that might change the value of the activity coefficient. The molar heat and temperature of fusion of sodium diclofenac could not be determined because this drug decomposed near the fusion temperature. The best results for both drugs were obtained with the dependent variable 1nX2 in association with the four-parameter model which includes the acidic and basic partial-solubility parameters delta(a) and delta(b) instead of the Hansen hydrogen bonding parameter delta(h). Because the dispersion parameter does not vary greatly from one drug to another, the variation of solubility among solvents is largely a result of the dipolar and hydrogen-bonding parameters, a fact that is being consistently found for other drugs of small molecular weight. These results support earlier findings with citric acid and paracetamol that the expanded Hansen approach is suitable for determining partial-solubility parameters. The modification introduced in the expanded Hansen method, i.e. the use of 1nX2 as the dependent variable, provides better results than the activity coefficient used in the original method. This is
Martin, A; Bustamante, P; Escalera, B; Sellés, E
1989-08-01
In the first paper in the series, an expanded system of parameters was devised to account for orientation and induction effects, and the term Wh was introduced to replace delta 1h delta 2h of the extended Hansen solubility approach. In the present report, a new term, Kh = Wh/delta 1h delta 2h is observed to take on values larger or smaller than unity depending on whether the hydrogen bonded solute-solvent interaction is larger or smaller than predicted by the term delta 1h delta 2h. The acidic delta a and basic delta b solubility parameters are used to represent two parameters, sigma and tau, suggested by Small in his study of proton donor-acceptor properties. The Small equation, including a heat of mixing term for hydrogen bonded species, is shown to be capable of semiquantitative evaluation. A partial molar heat delta H2h of hydrogen bonding is calculated using delta h and Wh terms; delta H2h is found to be correlated with the logarithm of the residual activity coefficient, In alpha R, a term representing strong solute-solvent interaction. The terms Wh, delta H2h, and In alpha 2R may be used to test the deviation from the geometric mean assumed in regular solution theory, and to replace the hydrogen bonding terms of the extended Hansen three-parameter model. The solubility of sulfamethoxypyridazine in 30 solvents is used to test the semiempirical solubility equations. The results are interpreted in terms of partial solubility parameters and the proton donor-acceptor properties of the solvents.
Prediction of Hansen Solubility Parameters with a New Group-Contribution Method
Stefanis, Emmanuel; Panayiotou, Costas
2008-04-01
A group-contribution method for the estimation of Hansen solubility parameters of pure organic compounds is presented. It uses two kinds of characteristic groups: first-order groups that describe the basic molecular structure of compounds and second-order groups, which are based on the conjugation theory and improve the accuracy of predictions. A large variety of characteristic groups ensure the prediction of Hansen solubility parameters for a broad series of organic compounds, including those having complex multi-ring, heterocyclic, and aromatic structures. The predictions are exclusively based on the molecular structure of compounds, and no experimental data are needed. The predicted values permit a fairly reliable selection of solvents based on the radius of a Hansen solubility parameter sphere or on a Teas parameter ternary plot. Especially designed algorithms permit the preparation of a list of new molecular structures which, if synthesized, could be the ideally suited solvents for a series of corresponding applications.
Measurement of multicomponent solubility parameters for graphene facilitates solvent discovery.
Hernandez, Yenny; Lotya, Mustafa; Rickard, David; Bergin, Shane D; Coleman, Jonathan N
2010-03-02
We have measured the dispersibility of graphene in 40 solvents, with 28 of them previously unreported. We have shown that good solvents for graphene are characterized by a Hildebrand solubility parameter of delta(T) approximately 23 MPa(1/2) and Hansen solubility parameters of delta(D) approximately 18 MPa(1/2), delta(P) approximately 9.3 MPa(1/2), and delta(H) approximately 7.7 MPa(1/2). The dispersibility is smaller for solvents with Hansen parameters further from these values. We have used transmission electron microscopy (TEM) analysis to show that the graphene is well exfoliated in all cases. Even in relatively poor solvents, >63% of observed flakes have <5 layers.
Role of Hansen solubility parameters in solid phase extraction.
Bielicka-Daszkiewicz, K; Voelkel, A; Pietrzyńska, M; Héberger, K
2010-08-27
The sorbent-eluent systems combined from eight polymeric sorbents and seven solvents as eluents were used for the extraction of phenol and its oxidation products from water samples. The individual interactions between sorbents, eluents and analytes were characterized by Hansen solubility parameters. Principal components analysis (PCA) was used for revealing the dominant interactions (dispersive, polar, and hydrogen bonding type) in sorbent-analyte-eluent systems. The importance of solubility parameters was also determined by a novel procedure based on sum of ranking differences (SRD). Although PCA and ranking by SRD are based on different principles and calculations, they have provided very similar results. The recovery in a given system has been predicted from the magnitudes of mutual interactions (sorbent-analyte, sorbent-eluent, analyte-eluent) by multiple linear regression.
Hildebrand solubility parameters measurement via sessile drops evaporation
Fang, Xiaohua; Li, Bingquan; Sokolov, Jonathan C.; Rafailovich, Miriam H.; Gewaily, Dina
2005-08-01
A method for the measurement of Hildebrand solubility parameter has been developed. This method was based on the measurement of the sessile drop contact angle and contact base width during its evaporation. Experimental results showed that this method is accurate and insensitive to the measurement conditions. The major advantages of this method are that it is time efficient and requires a small amount of liquid (microliter) for the measurement.
Just, Susann; Sievert, Frank; Thommes, Markus; Breitkreutz, Jörg
2013-11-01
Hot-melt extrusion is gaining importance for the production of amorphous solid solutions; in parallel, predictive tools for estimating drug solubility in polymers are increasingly demanded. The Hansen solubility parameter (SP) approach is well acknowledged for its predictive power of the miscibility of liquids as well as the solubility of some amorphous solids in liquid solvents. By solely using the molecular structure, group contribution (GC) methods allow the calculation of Hansen SPs. The GC parameter sets available were derived from liquids and polymers which conflicts with the object of prediction, the solubility of solid drugs. The present study takes a step from the liquid based SPs toward their application to solid solutes. On the basis of published experimental Hansen SPs of solid drugs and excipients only, a new GC parameter set was developed. In comparison with established parameter sets by van Krevelen/Hoftyzer, Beerbower/Hansen, Breitkreutz and Stefanis/Panayiotou, the new GC parameter set provides the highest overall predictive power for solubility experiments (correlation coefficient r = -0.87 to -0.91) as well as for literature data on melt extrudates and casted films (r = -0.78 to -0.96).
Hansen solubility parameters for a carbon fiber/epoxy composite
Launay, Helene; Hansen, Charles M.; Almdal, Kristoffer
2007-01-01
In this study, the physical affinity between an epoxy matrix and oxidized, unsized carbon fibers has been evaluated using Hansen solubility (cohesion) parameters (HSP). A strong physical compatibility has been shown, since their respective HSP are close. The use of a glassy carbon substrate...... as a model for unsized carbon fiber has been demonstrated as appropriate for the study of interactions between the materials in composite carbon fiber-epoxy systems. The HSP of glassy carbon are similar to those of carbon fibers and epoxy matrix. (C) 2007 Elsevier Ltd. All rights reserved....
Hansen solubility parameter as a tool to predict cocrystal formation.
Mohammad, Mohammad Amin; Alhalaweh, Amjad; Velaga, Sitaram P
2011-04-04
The objective of this study was to investigate whether the miscibility of a drug and coformer, as predicted by Hansen solubility parameters (HSPs), can indicate cocrystal formation and guide cocrystal screening. It was also our aim to evaluate various HSPs-based approaches in miscibility prediction. HSPs for indomethacin (the model drug) and over thirty coformers were calculated according to the group contribution method. Differences in the HSPs between indomethacin and each coformer were then calculated using three established approaches, and the miscibility was predicted. Subsequently, differential scanning calorimetry was used to investigate the experimental miscibility and cocrystal formation. The formation of cocrystals was also verified using liquid-assisted grinding. All except one of the drug-coformers that were predicted to be miscible were confirmed experimentally as miscible. All tested theoretical approaches were in agreement in predicting miscibility. All systems that formed cocrystals were miscible. Remarkably, two new cocrystals of indomethacin were discovered in this study. Though it may be necessary to test this approach in a wide range of different coformer and drug compound types for accurate generalizations, the trends with tested systems were clear and suggest that the drug and coformer should be miscible for cocrystal formation. Thus, predicting the miscibility of cocrystal components using solubility parameters can guide the selection of potential coformers prior to exhaustive cocrystal screening work.
Peña, M A; Reíllo, A; Escalera, B; Bustamante, P
2006-09-14
The solubility enhancement produced by two binary mixtures with a common cosolvent (ethanol-water and ethyl acetate-ethanol) was studied against the solubility parameter of the mixtures (delta1) to characterize different types of solubility profiles. Benzocaine, salicylic acid and acetanilide show a single peak in the least polar mixture (ethanol-ethyl acetate) at delta1=22.59, 21.70 and 20.91 MPa1/2, respectively. Phenacetin displays two solubility maxima, at delta1=25.71 (ethanol-water) and at delta1=23.30 (ethyl acetate-ethanol). Acetanilide shows an inflexion point in ethanol-water instead of a peak, and the sign of the slope does not vary when changing the cosolvent. The solubility profiles were compared to those obtained in dioxane-water, having a solubility parameter range similar to that covered with the common cosolvent system. All the drugs reach a maximum at about 90% dioxane (delta1=23 MPa1/2). A modification of the extended Hildebrand method is applicable for curves with a single maximum whereas a model including the Hildebrand solubility parameter delta1 and the acidic partial solubility parameter delta1a is required to calculate more complex solubility profiles (with inflexion point or two maxima). A single equation was able to fit the solubility curves of all drugs in the common cosolvent system. The polarity of the drug is related to the shape of the solubility profile against the solubility parameter delta1 of the solvent mixtures. The drugs with solubility parameters below 24 MPa1/2 display a single peak in ethanol-ethyl acetate. The drugs with delta2 values above 25 MPa1/2 show two maxima, one in each solvent mixture (ethanol-water and ethanol-ethyl acetate). The position of the maximum in ethanol-ethyl acetate shifts to larger polarity values (higher delta1 values) as the solubility parameter of the drug delta2 increases.
Gray, M.; Nilsson, M. [University of California Irvine, 916 Engineering Tower, UC Irvine, Irvine, CA 92697-2575 (United States); Zalupski, P. [Idaho National Laboratory, 2525 Fremont Avenue, Idaho Falls, ID 83415 (United States)
2013-07-01
A thorough understanding of the non-ideal behavior of the chemical components utilized in solvent extraction contributes to the success of any large-scale spent nuclear fuel treatment. To address this, our current work uses vapor pressure osmometry to characterize the non-ideal behavior of the solvent extraction agent di-(2-ethylhexyl) phosphoric acid (HDEHP), a common extractant in proposed separation schemes. Solubility parameters were fit to data on HDEHP at four temperatures using models based on Scatchard Hildebrand regular solution theory with Flory Huggins entropic corrections. The results are comparable but not identical to the activity coefficients from prior slope analysis in the literature. (authors)
Prediction of solubility parameters using partial least square regression.
Tantishaiyakul, Vimon; Worakul, Nimit; Wongpoowarak, Wibul
2006-11-15
The total solubility parameter (delta) values were effectively predicted by using computed molecular descriptors and multivariate partial least squares (PLS) statistics. The molecular descriptors in the derived models included heat of formation, dipole moment, molar refractivity, solvent-accessible surface area (SA), surface-bounded molecular volume (SV), unsaturated index (Ui), and hydrophilic index (Hy). The values of these descriptors were computed by the use of HyperChem 7.5, QSPR Properties module in HyperChem 7.5, and Dragon Web version. The other two descriptors, hydrogen bonding donor (HD), and hydrogen bond-forming ability (HB) were also included in the models. The final reduced model of the whole data set had R(2) of 0.853, Q(2) of 0.813, root mean squared error from the cross-validation of the training set (RMSEcv(tr)) of 2.096 and RMSE of calibration (RMSE(tr)) of 1.857. No outlier was observed from this data set of 51 diverse compounds. Additionally, the predictive power of the developed model was comparable to the well recognized systems of Hansen, van Krevelen and Hoftyzer, and Hoy.
Hansen solubility parameter analysis on the dispersion of zirconia nanocrystals.
Wang, Sho-Hsun; Liu, Jia-Hong; Pai, Chin-Tung; Chen, Chien-Wei; Chung, Pao-Tang; Chiang, Anthony Shiaw-Tseh; Chang, Shinn-Jen
2013-10-01
Nanoparticle dispersible in a broad range of solvents is desirable when preparing an organic/inorganic nanocomposite. In this report, the dispersion behavior of carboxylate-grafted zirconia nanoparticle in 25 solvents covering a wide range of polarity was analyzed based on their Hansen solubility parameters (HSP). Particles grafted with alkyl-chain longer than four carbons could only be dispersed in non-polar solvents, while that grafted with acetic acid was dispersible in polar ones. However, particle modified with methacrylic acid (MA) was compatible with both types of solvents, which was rather unexpected. Further NMR analysis showed that the carboxylate-grafted samples contained a trace amount of triethanolamine (TEA) due to the particular ZrO2 synthesis process employed. The combination of the hydrophilic TEA ligand with the short hydrophobic tail of methacrylate broadened the range of compatible solvents from benzene to methanol. Such an extended solvent compatibility was observed previously only for nanoparticles covered with large polymer surfactants having both hydrophilic and hydrophobic groups. Achieving this with two small molecules having separate functional groups is crucial when one needs to maximize the inorganic content in a composite.
The Chameleonic Behavior of Ionic Liquids and its Impact on the Solubility Parameters Estimation
Batista, Marta; Neves, Catarina S; Carvalho, Pedro Jorge
2011-01-01
of a curious behavior for the ILs that seem to present more than one solubility parameter acting as polar molecules in some situations and as non-polar molecules in others, depending on the medium. This behavior was confirmed by solubility measurements of [C4MIM][PF6] in solvent mixtures. The solubility...
Solubilities of Solutes in Ionic Liquids from a SimplePerturbed-Hard-Sphere Theory
Qin, Yuan; Prausnitz, John M.
2005-09-20
In recent years, several publications have provided solubilities of ordinary gases and liquids in ionic liquids. This work reports an initial attempt to correlate the experimental data using a perturbed-hard-sphere theory; the perturbation is based on well-known molecular physics when the solution is considered as a dielectric continuum. For this correlation, the most important input parameters are hard-sphere diameters of the solute and of the cation and anion that constitute the ionic liquid. In addition, the correlation uses the solvent density and the solute's polarizability and dipole and quadrupole moments, if any. Dispersion-energy parameters are obtained from global correlation of solubility data. Results are given for twenty solutes in several ionic liquids at normal temperatures; in addition, some results are given for gases in two molten salts at very high temperatures. Because the theory used here is much simplified, and because experimental uncertainties (especially for gaseous solutes) are often large, the accuracy of the correlation presented here is not high; in general, predicted solubilities (Henry's constants) agree with experiment to within roughly {+-} 70%. As more reliable experimental data become available, modifications in the characterizing parameters are likely to improve accuracy. Nevertheless, even in its present form, the correlation may be useful for solvent screening in engineering design.
Determination of partial solubility parameters of five benzodiazepines in individual solvents.
Verheyen, S; Augustijns, P; Kinget, R; Van den Mooter, G
2001-10-09
Three and four component partial solubility parameters for diazepam, lorazepam, oxazepam, prazepam and temazepam were determined using the extended and expanded Hansen regression models. A comparison was made also with solubility parameters calculated by the group contribution method proposed by Van Krevelen. Although a limited number of solvents was used, the results from the present study indicate that the partial solubility parameters obtained from the experimental regression models clearly reflect the structural differences in these five structurally related molecules. High R(2)-values were observed in the regression models (0.932 parameter did not improve the R(2)- and F-values in any of the regression models used.
Pharmacokinetic parameters and biodistribution of soluble cytokine receptors.
Jacobs, C A; Beckmann, M P; Mohler, K; Maliszewski, C R; Fanslow, W C; Lynch, D H
1993-01-01
The potential use of soluble cytokine receptors as therapeutics in disease states when excessive or prolonged cytokine expression leads to pathogenesis is just beginning (Van Brunt, 1989). The inhibitory effects of soluble receptors have been found to be highly potent and specific for their respective cytokines (Maliszewski and Fanslow, 1990; Maliszewski et al., 1990). Recent in vivo data have shown that exogenously administered soluble receptors can function as cytokine antagonists and suppress autoimmune inflammatory responses (Jacobs et al., 1991a), allograft rejection, and alloreactivity (Fanslow et al., 1990b). The proposed frequency of administration and dosage of a therapeutic agent is dependent on the half-life of the agent and the route of administration. The elimination or half-life of a drug usually depends on its physiochemical properties (molecular size, glycosylation, isoelectric point, and hydrophobic/hydrophilic properties) (DiPalma and DiGregorio, 1990; Katzung, 1984). The half-life will also depend on the mechanism of clearance for that specific receptor. Once pharmacokinetic data are available for soluble receptors, the therapeutic potential of these molecules can be better evaluated. Only limited pharmacokinetic data are currently available for soluble cytokine receptors (Jacobs et al., 1991b). For sIL-1R, the majority of an intravenously administered dose was cleared in the second elimination phase, with a reasonably long half-life (6.3 hr), such that the entire dose was not eliminated until 35 hr. If administration is by subcutaneous injection, the half-life was even more prolonged. One explanation for the prolonged half-life is the minimal distribution to liver and kidneys and thus low levels of clearance by these organs. In contrast, elimination of intravenously administered sIL-4R was relatively rapid, with a short half-life (2.3 hr). This appeared mainly due to liver distribution and clearance, which has been the highest observed for any
Solubility in supercritical solvents: A comparison of theory and simulation
Tomberli, Bruno Luca
1998-12-01
Solubility at supercritical conditions is studied using thermodynamics and statistical mechanics. The Redlich- Kwong equation of state, virial equation of state and fluctuation theory are used to predict the chemical potential for pure and mixed Lennard-Jones fluids. Where literature results are unavailable, Monte Carlo simulations employing the Widom particle insertion method are also carried out to determine the chemical potential at the same conditions. Several methods are shown to achieve an accuracy on the order of five percent. Based on the success of these theories, qualitative studies of cavity-interaction contributions to the chemical potential and the effect of clustering in supercritical solvation are conducted. Finally, fluctuation theory is shown to be the only available method suitable for ab initio calculations of the chemical potential involving anisotropic potentials. A suitable potential for naphthalene-carbon dioxide systems is developed from existing multi-site exp-6-1 potentials and predictions of the chemical potential of infinitely- dilute naphthalene in supercritical carbon dioxide are made as an example of a possible application of this method.
Forster, A; Hempenstall, J; Tucker, I; Rades, T
2001-09-11
The aim of this study was to determine the miscibility of drug and excipient to predict if glass solutions are likely to form when drug and excipient are melt extruded. Two poorly water-soluble drugs, indomethacin and lacidipine, were selected along with 11 excipients (polymeric and non-polymeric). Estimation of drug/excipient miscibility was performed using a combination of the Hoy and Hoftzyer/Van Krevelen methods for Hansen solubility parameter calculation. Miscibility was experimentally investigated with differential scanning calorimetry (DSC) and hot stage microscopy (HSM). Studies were performed at drug/excipient ratios, 1:4, 1:1 and 4:1. Analysis of the glass transition temperature (T(g)) was performed by quench cooling drug/excipient melts in the DSC. Differences in the drug/excipient solubility parameters of 10 MPa(1/2) were expected to indicate a lack of miscibility and not form glass solutions when melt extruded. Experimentally, miscibility was shown by changes in drug/excipient melting endotherms and confirmed by HSM investigations. Experimental results were in agreement with solubility parameter predictions. In addition, drug/excipient combinations predicted to be largely immiscible often exhibited more than one T(g) upon reheating in the DSC. Melt extrusion of miscible components resulted in amorphous solid solution formation, whereas extrusion of an "immiscible" component led to amorphous drug dispersed in crystalline excipient. In conclusion, combining calculation of Hansen solubility parameters with thermal analysis of drug/excipient miscibility can be successfully applied to predict formation of glass solutions with melt extrusion.
Determination and evaluation of solubility parameter of satranidazole using dioxane-water system
Rathi P
2010-01-01
Full Text Available Satranidazole, a potent broad spectrum antiprotozoal, is a poorly water-soluble drug and has low bioavailability on oral administration. One of the important methods to improve the solubility and bioavailability of a less water-soluble drug is by the use of cosolvents. The solubility enhancement produced by binary blends with a cosolvent (dioxane was studied against the solubility parameter of solvent blends (d1 to evaluate the solubility parameter of drug (d2 . Solubility parameter of drug (d2 was evaluated in blends of dioxane-water system. The results obtained were compared with the d2 values obtained using Molar Volume Method and Fedor′s Group Substitution Method. The binary blend water-dioxane (10:90 gave maximum solubility with an experimental d2 value of 11.34 (Cal/cm 3 0.5 that was comparable to the theoretical values of 11.34 (Cal/cm 3 0.5 determined by Molar Volume Method and 11.3928 (Cal/cm 3 0.5 when determined by Fedor′s Group Substitution Method, which is in good agreement with solubility measurement method.
Jiang, Hao; Panagiotopoulos, Athanassios Z.; Economou, Ioannis G.
2016-03-01
Statistical associating fluid theory (SAFT) is used to model CO2 solubilities in single and mixed electrolyte solutions. The proposed SAFT model implements an improved mean spherical approximation in the primitive model to represent the electrostatic interactions between ions, using a parameter K to correct the excess energies ("KMSA" for short). With the KMSA formalism, the proposed model is able to describe accurately mean ionic activity coefficients and liquid densities of electrolyte solutions including Na+, K+, Ca2+, Mg2+, Cl-, Br- and SO42- from 298.15 K to 473.15 K using mostly temperature independent parameters, with sole exception being the volume of anions. CO2 is modeled as a non-associating molecule, and temperature-dependent CO2-H2O and CO2-ion cross interactions are used to obtain CO2 solubilities in H2O and in single ion electrolyte solutions. Without any additional fitting parameters, CO2 solubilities in mixed electrolyte solutions and synthetic brines are predicted, in good agreement with experimental measurements.
The Ultrastructure of Wood from a Solubility Parameter Point of View
Hansen, C.M.; Bjørkmann, Anders
1998-01-01
In later years scientists have taken increased interest in understanding wood ultrastructure, but with limited emphasis on close molecular relationships of its polymers. This aspect is examined from the Hansen solubility parameter concept and from the requirement that contacts between wood polymers...... strive to reduce the free energy. Polymer segments with matching solubility parameters tend to locate near each other. Wood polymers have larger solubility parameters than the test solvents used to the test solvents used to characterize them, but the use of model compounds and group contribution methods...... yields consistent solubility parameters for the key wood components. Lignin and cellulose are not compatible. Cellulose regions and backbones of hemicelluloses are compatible to a degree. Some hemicellulose segments with hydroxylated side groups are expected to orient themselves towards cellulosic...
A new method to determine the partial solubility parameters of polymers from intrinsic viscosity.
Bustamante, Pilar; Navarro-Lupión, Javier; Escalera, Begoña
2005-02-01
A modification of the extended Hansen method, formerly used to determine the partial solubility parameters of drugs and non-polymeric excipients is tested with a polymer for the first time. The proposed method relates the logarithm of the intrinsic viscosities of the polymer in a series of solvents and solvent mixtures with the Hansen (three parameter model) and Karger (four parameter model) partial solubility parameters. The viscosity of diluted solutions of hydroxypropyl methylcellulose (HPMC) was determined in pure solvents and binary mixtures of varying polarity. The intrinsic viscosity was obtained from the common intercept of the Huggins and Kraemer relationships. The intrinsic viscosity tends to increase with increasing the solubility parameter of the medium. The results show that hydrogen bonding and polarity of the polymer largely determine polymer-solvent interactions. The models proposed provided reasonable partial and total solubility parameters for the polymer and enable one to quantitatively characterize, for the first time, the Lewis acid-base ability of a polymer thus, providing a more realistic picture of hydrogen bonding for solvent selection/compatibility and to predict drug-polymer interactions. Combination of the dispersion and polar parameters into a single non-specific solubility parameter was also tested. The results extend earlier findings and suggest that the models are quite versatile and may be applied to drugs, non-polymeric and polymeric excipients.
Bayesian parameter estimation for effective field theories
Wesolowski, S; Furnstahl, R J; Phillips, D R; Thapaliya, A
2015-01-01
We present procedures based on Bayesian statistics for effective field theory (EFT) parameter estimation from data. The extraction of low-energy constants (LECs) is guided by theoretical expectations that supplement such information in a quantifiable way through the specification of Bayesian priors. A prior for natural-sized LECs reduces the possibility of overfitting, and leads to a consistent accounting of different sources of uncertainty. A set of diagnostic tools are developed that analyze the fit and ensure that the priors do not bias the EFT parameter estimation. The procedures are illustrated using representative model problems and the extraction of LECs for the nucleon mass expansion in SU(2) chiral perturbation theory from synthetic lattice data.
Bayesian parameter estimation for effective field theories
Wesolowski, S.; Klco, N.; Furnstahl, R. J.; Phillips, D. R.; Thapaliya, A.
2016-07-01
We present procedures based on Bayesian statistics for estimating, from data, the parameters of effective field theories (EFTs). The extraction of low-energy constants (LECs) is guided by theoretical expectations in a quantifiable way through the specification of Bayesian priors. A prior for natural-sized LECs reduces the possibility of overfitting, and leads to a consistent accounting of different sources of uncertainty. A set of diagnostic tools is developed that analyzes the fit and ensures that the priors do not bias the EFT parameter estimation. The procedures are illustrated using representative model problems, including the extraction of LECs for the nucleon-mass expansion in SU(2) chiral perturbation theory from synthetic lattice data.
Madsen, Claus G; Skov, Anders; Baldursdottir, Stefania; Rades, Thomas; Jorgensen, Lene; Medlicott, Natalie J
2015-05-01
This study describes how protein release from polymer matrices correlate with simple measurements on the intrinsic viscosity of the polymer solutions used for casting the matrices and calculations of the solubility parameters of polymers and solvents used. Matrices of poly(dl-lactide-co-glycolide) (PLGA) were cast with bovine serum albumin (BSA) as a model drug using different solvents (acetone, dichloromethane, ethanol and water). The amount of released protein from the different matrices was correlated with the Hildebrand and Hansen solubility parameters of the solvents, and the intrinsic viscosity of the polymer solutions. Matrix microstructure was investigated by transmission and scanning electron microscopy (TEM and SEM). Polycaprolactone (PCL) matrices were used in a similar way to support the results for PLGA matrices. The maximum amount of BSA released and the release profile from PLGA matrices varied depending on the solvent used for casting. The maximum amount of released BSA decreased with higher intrinsic viscosity, and increased with solubility parameter difference between the solvent and polymer used. The solvent used also had an effect on the matrix microstructure as determined by TEM and SEM. Similar results were obtained for the PCL polymer systems. The smaller the difference in the solubility parameter between the polymer and the solvent used for casting a polymer matrix, the lower will be the maximum protein release. This is because of the presence of smaller pore sizes in the cast matrix if a solvent with a solubility parameter close to the one of the polymer is used. Likewise, the intrinsic viscosity of the polymer solution increases as solubility parameter differences decrease, thus, simple measurements of intrinsic viscosity and solubility parameter difference, allow the prediction of protein release profiles. Copyright © 2015 Elsevier B.V. All rights reserved.
Order Parameter Theory for Anderson Localization
Dobrosavljevic, Vladimir; Pastor, Andrei
2001-03-01
The Anderson metal-insulator transition is well known to display many similarities to standard critical phenomena, yet an obvious order parameter has remained difficult to find. In this work, we demonstrate that a relevant local order parameter can be defined and self-consistently determined, providing a simple and physically transparent picture of the Anderson transition. Our formulation proceeds in close analogy with the well-known coherent potential approximation (CPA), with a small but crucial difference. Our theory self-consistently calculates not the average but instead the typical local density of states, which serves as the order parameter, and is found to vanish at the Anderson transition. As a result, we show that both the escape rate of an electron from a given site, and the conductivity vanish in the insulating phase, which emerges for disorder strengths comparable to the electronic bandwidth. Due to the local character of our theory, it can easily be combined with standard dynamical mean-field approaches for strong electronic correlations, thus opening an attractive avenue for the study of the interplay (A. A. Pastor and V. Dobrosavljevic, Phys. Rev. Lett. 83), 4642 (1999) ( V. Dobrosavljevic and G. Kotliar, Phys. Rev. Lett. 78), 3943 (1997) of interaction and disorder.
Navarro-Lupión, Francisco-Javier; Bustamante, Pilar; Escalera, Begoña
2005-07-01
A model that relates the equilibrium swelling of hydroxypropylmethylcellulose to the partial solubility parameters of both the polymer and the solvents is proposed to interpret and correlate the experimental data. The non-specific interactions are expressed as the dispersion delta(d) and polar delta(p) solubility parameters of Hansen, or as a combination of both. Hydrogen bonding is represented by the acidic delta(a) and the basic delta(b) Karger solubility parameters. The results are compared with models including the same parameters for non-specific interactions (delta(d) and delta(p)) and the Hansen hydrogen bonding parameter delta(h). Equilibrium swelling of this hydrophilic polymer that is widely used in drug formulation is measured in pure solvents covering a wide polarity range. In a qualitative way, swelling increases in solvents with higher Hildebrand solubility parameters and stronger hydrogen bonding capability, and it decreases in non-polar solvents. Single polarity indexes, such as the Hildebrand solubility parameter or the partition coefficient (PC), do not fit well the overall experimental data. The best correlations were obtained with the proposed model, providing at the same time an interpretation consistent with the physical meaning of the terms included in the equation. Swelling increases as the non-specific interactions of the polymer and the solvents become alike, and as the Lewis acid-base interactions of the polymer (1) and the solvent (2) represented by the products delta(1a)delta(2b) and delta(1b)delta(2a) become greater. Conversely, hydrogen bonding self association of the solvents (the product delta(1a)delta(1b)) lowers swelling. The results show that the Karger hydrogen bonding parameters provide a better approach than the Hansen hydrogen bonding parameter to correlate the swelling behavior of a hydrophilic polymer. (c) 2005 Wiley-Liss, Inc.
Madsen, Claus G; Skov, Anders; Baldursdottir, Stefania;
2015-01-01
(dl-lactide-co-glycolide) (PLGA) were cast with bovine serum albumin (BSA) as a model drug using different solvents (acetone, dichloromethane, ethanol and water). The amount of released protein from the different matrices was correlated with the Hildebrand and Hansen solubility parameters of the solvents, and the intrinsic......PURPOSE: This study describes how protein release from polymer matrices correlate with simple measurements on the intrinsic viscosity of the polymer solutions used for casting the matrices and calculations of the solubility parameters of polymers and solvents used. METHOD: Matrices of poly...... from PLGA matrices varied depending on the solvent used for casting. The maximum amount of released BSA decreased with higher intrinsic viscosity, and increased with solubility parameter difference between the solvent and polymer used. The solvent used also had an effect on the matrix microstructure...
Barra, J; Lescure, F; Doelker, E; Bustamante, P
1997-07-01
In this study two solubility-parameter models have been compared using as dependent variables the logarithm of the mole fraction solubility, lnX2e, and ln(alpha)/U (originally used in the extended Hansen method), where alpha is the activity coefficient and U is a function of the molar volume of the solute and the volume fraction of the solvent. The results show for the first time the proton-donor and -acceptor hydrogen-bonding capacities of paracetamol, as measured by the acidic and basic partial-solubility parameters. The influence of solvents on the differential scanning calorimetry (DSC) pattern of the solid phases was also studied in relation to the solubility models tested. Citric acid was chosen as a test substance because of its high acidity and its proton donor capacity to form hydrogen bonds with basic solvents. The partial acidic and basic solubility parameters obtained from multiple regression were consistent with this property, validating the model chosen. The results show that the more direct lnX2e variable was more suitable for fitting both models, and the four-parameter model seemed better for describing the interactions between solvent and solute.
Wang, Jun; Yang, Xuzhao; Wu, Jinchao; Song, Hao; Zou, Wenyuan
2015-12-01
Inverse gas chromatographic (IGC) technology was used to determine the solubility parameters of three asymmetrical dicationic ionic liquids ([ PyC5Pi] [ NTf2]2, [MpC5Pi] [NTf2]2 and [PyC6Pi] [NTf2]2) at 343.15-363.15 K. Five alkanes were applied as test probes including octane (n-C8) , decane (n-C10), dodecane (n-C12), tetradecane (n-C14), hexadecane (n-C16). Some thermodynamic parameters were obtained by IGC data analysis, such as the specific retention volumes of the solvents (V0(g)), the molar enthalpies of sorption (ΔHs(1)), the partial molar enthalpies of mixing at infinite dilution (ΔH∞91)), the molar enthalpies of vaporization (ΔH)v)), the activity coefficients at infinite dilution (Ω∞(1)), and Flory-Huggins interaction parameters (χ∞(12)) between ionic liquids and probes. The solubility parameters (δ2) of the three dicationic ionic liquids at room temperature (298.15 K) were 28.52-32.66 (J x cm(-3)) ½. The solubility parameters (δ2) of cationic structure with 4-methyl morpholine are bigger than those of the cationic structure with pyridine. The bigger the solubility parameter (δ2) is, the more the carbon numbers of linking group of the ionic liquids are. The results are of great importance to the study of the solution behavior and the applications of ionic liquid.
Papanicolaou, Fanos; Antoniou, Stella [Chemistry Department, University of Cyprus, P.O. Box 20537, 1678 Nicosia (Cyprus); Pashalidis, Ioannis [Chemistry Department, University of Cyprus, P.O. Box 20537, 1678 Nicosia (Cyprus)], E-mail: pspasch@ucy.ac.cy
2009-10-15
Phosphogypsum is a waste by-product of the phosphate fertilizer industry, which is usually disposed in the environment because of its restricted use in industrial applications. Physico-chemical conditions existing in stack fluids and leachates are of major importance and determine solubility and redox stability of phosphogypsum, as well as radionuclide release from stacks to terrestrial environments. The aim of this study is to assess the effect of key parameters (e.g. ionic strength, temperature, pH) on the solubility of phosphogypsum. Phosphogypsum sampling and in-situ measurements were carried out at a coastal stack in Cyprus, solubility experiments were performed in simulated laboratory systems and thermodynamic calculations by means of MINTEQA2, an equilibrium speciation model. Generally, increasing ionic strength and temperature leads to increased phosphogypsum solubility, with the former being much more effective. The increased solubility of phosphogypsum in saline solutions is attributed solely to ionic strength effects on the activity of ionic species in solution and no solid phase transformations could be observed. The effect of pH on phosphogypsum solubility seems to be insignificant at least in a pH range between 4 and 8. Regarding uranium levels, there is a strong correlation between salinity and uranium concentration and linear correlation between phosphogypsum solubility and uranium levels in stack solutions, indicating the incorporation of uranium into the gypsum lattice and the formation of a solid solution.
Papanicolaou, Fanos; Antoniou, Stella; Pashalidis, Ioannis
2009-10-01
Phosphogypsum is a waste by-product of the phosphate fertilizer industry, which is usually disposed in the environment because of its restricted use in industrial applications. Physico-chemical conditions existing in stack fluids and leachates are of major importance and determine solubility and redox stability of phosphogypsum, as well as radionuclide release from stacks to terrestrial environments. The aim of this study is to assess the effect of key parameters (e.g. ionic strength, temperature, pH) on the solubility of phosphogypsum. Phosphogypsum sampling and in-situ measurements were carried out at a coastal stack in Cyprus, solubility experiments were performed in simulated laboratory systems and thermodynamic calculations by means of MINTEQA2, an equilibrium speciation model. Generally, increasing ionic strength and temperature leads to increased phosphogypsum solubility, with the former being much more effective. The increased solubility of phosphogypsum in saline solutions is attributed solely to ionic strength effects on the activity of ionic species in solution and no solid phase transformations could be observed. The effect of pH on phosphogypsum solubility seems to be insignificant at least in a pH range between 4 and 8. Regarding uranium levels, there is a strong correlation between salinity and uranium concentration and linear correlation between phosphogypsum solubility and uranium levels in stack solutions, indicating the incorporation of uranium into the gypsum lattice and the formation of a solid solution.
Moustafa, Nagy Emam; Eissa, Elham Ahmed
2007-11-01
The Flory-Huggins interaction parameter (chi1, 2(infinity)) and solubility parameter (delta2) and its hydrogen bonding sensing component (delta(h)) were determined using inverse gas chromatography (IGC). These parameters were successfully used in the probes of chemical changes that occur during the oxidation of naphthenic and paraffinic base oils in a GC column. Changes in chi1, 2(infinity) values reflect the different types of intermolecular interactions (dispersive, polar, hydrogen bonding) of the given lubricating base oil during oxidation. The obtained results showed that delta(h) component of solubility parameter is the most important parameter for probing the oxidative-chemical changes during the oxidation of given lubricating oils.
Shi, Fenghui; Dai, Zhishuang; Zhang, Baoyan
2010-07-01
Inverse gas chromatography (IGC) was used to measure the surface tension and solubility parameter of E51 epoxy resin in this work. By using the Schultz method, decane, nonane, octane and heptane were chosen as the neutral probes to calculate the dispersive surface tensions (gamma(D)). Based on the Good-van Oss equation, the specific surface tension (gamma(SP)) of E51 epoxy resin was calculated with the acidic probe of dichloromethane and the basic probe of toluene. The results showed that the gamma(D) and gamma(SP) of the E51 resin decreased linearly with the increase of temperature. According to the Flory-Huggins parameters (chi) between the resin and a series of probes, the solubility parameters (delta) of E51 resin at different temperatures were estimated using the method developed by DiPaola-Baranyi and Guillet. It was found that the values of delta of the E51 resin were 11.78, 11.57, 11.48 and 11.14 MPa1/2 at 30, 40, 50 and 60 degrees C, respectively. The dispersive component (delta(D)) and the specific component (delta(SP)) of solubility parameter at different temperatures of the E51 resin were investigated according to the relationships between surface tension, cohesion energy and solubility parameter. The results showed that the values of delta(D) were higher than those of delta(SP) for the epoxy resin, and both of them decreased with the increase of temperature.
E. Díaz
2007-06-01
Full Text Available Gas chromatography used to calculate the specific retention volume of several hydrocarbons in different chromatographic liquid phases (Squalane, Carbowax-400, Carbowax-1500, Carbowax-4000, Amine-220, Dinonyl phthalate, Tributyl phosphate and Trixylenyl phosphate. Some thermodynamic parameters, such as enthalpy of sorption and Flory-Huggins parameters relating the interaction between liquid phases and solutes, were also calculated from the determined retention volumes. Liquid phase solubility parameters of Squalane, Carbowax-400, Carbowax-1500 and Carbowax-4000 at 80 ºC as well as the polar and apolar components were calculated too. A new model was proposed to correlate polar contribution to the solubility parameter of a liquid phase with the specific retention volume of a solute in this liquid phase.
Adamska, K; Bellinghausen, R; Voelkel, A
2008-06-27
The Hansen solubility parameter (HSP) seems to be a useful tool for the thermodynamic characterization of different materials. Unfortunately, estimation of the HSP values can cause some problems. In this work different procedures by using inverse gas chromatography have been presented for calculation of pharmaceutical excipients' solubility parameter. The new procedure proposed, based on the Lindvig et al. methodology, where experimental data of Flory-Huggins interaction parameter are used, can be a reasonable alternative for the estimation of HSP values. The advantage of this method is that the values of Flory-Huggins interaction parameter chi for all test solutes are used for further calculation, thus diverse interactions between test solute and material are taken into consideration.
Marczyński Zbigniew
2016-12-01
Full Text Available Introduction: The general Hildebrand-Scatchard theory of solubility supplemented by Fedors’ solubility parameter −δ12$- \\delta ^{{1 \\over 2}} $ was used to estimate the real solubility by −log x2 (log of the mole fraction of phytochemicals contained in Ext. Taraxaci e radix cum herba aqu. siccum. Surface activity of aqueous solution of extracts was determined and quantified – solubilizing capabilities of solutions of cexp. ≥cmc in relation to cholesterol particle size of Ø=1.00 mm, as well as of ketoprofen were defined.
Effect of Surface Modification on the Hansen Solubility Parameters of Single-Walled Carbon Nanotubes
Ma, Jing; Larsen, Mikael
2013-01-01
In this work, seven types of surface-modified single-walled carbon nanotubes (SWNTs) were studied by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy to investigate the functional groups and extent of functionalization. Hansen solubility parameters were determined based on observations...... of the sedimentation and swollen states of the SWNTs in solvents after ultrasonication, and the results were compared with the hydrodynamic sizes of the SWNTs evaluated by the dynamic light scattering method. We found that the solubility of SWNTs is related to their functional groups and degree of functionalization...
Rational Design of Molecular Gelator - Solvent Systems Guided by Solubility Parameters
Lan, Yaqi
Self-assembled architectures, such as molecular gels, have attracted wide interest among chemists, physicists and engineers during the past decade. However, the mechanism behind self-assembly remains largely unknown and no capability exists to predict a priori whether a small molecule will gelate a specific solvent or not. The process of self-assembly, in molecular gels, is intricate and must balance parameters influencing solubility and those contrasting forces that govern epitaxial growth into axially symmetric elongated aggregates. Although the gelator-gelator interactions are of paramount importance in understanding gelation, the solvent-gelator specific (i.e., H-bonding) and nonspecific (dipole-dipole, dipole-induced and instantaneous dipole induced forces) intermolecular interactions are equally important. Solvent properties mediate the self-assembly of molecular gelators into their self-assembled fibrillar networks. Herein, solubility parameters of solvents, ranging from partition coefficients (logP), to Henry's law constants (HLC), to solvatochromic ET(30) parameters, to Kamlet-Taft parameters (beta, alpha and pi), to Hansen solubility parameters (deltap, deltad, deltah), etc., are correlated with the gelation ability of numerous classes of molecular gelators. Advanced solvent clustering techniques have led to the development of a priori tools that can identify the solvents that will be gelled and not gelled by molecular gelators. These tools will greatly aid in the development of novel gelators without solely relying on serendipitous discoveries.
Data mining of solubility parameters for computational prediction of drug-excipient miscibility.
Alhalaweh, Amjad; Alzghoul, Ahmad; Kaialy, Waseem
2014-07-01
Abstract Computational data mining is of interest in the pharmaceutical arena for the analysis of massive amounts of data and to assist in the management and utilization of the data. In this study, a data mining approach was used to predict the miscibility of a drug and several excipients, using Hansen solubility parameters (HSPs) as the data set. The K-means clustering algorithm was applied to predict the miscibility of indomethacin with a set of more than 30 compounds based on their partial solubility parameters [dispersion forces (δd), polar forces (δp) and hydrogen bonding (δh)]. The miscibility of the compounds was determined experimentally, using differential scanning calorimetry (DSC), in a separate study. The results of the K-means algorithm and DSC were compared to evaluate the K-means clustering prediction performance using the HSPs three-dimensional parameters, the two-dimensional parameters such as volume-dependent solubility (δv) and hydrogen bonding (δh) and selected single (one-dimensional) parameters. Using HSPs, the prediction of miscibility by the K-means algorithm correlated well with the DSC results, with an overall accuracy of 94%. The prediction accuracy was the same (94%) when the two-dimensional parameters or the hydrogen-bonding (one-dimensional) parameter were used. The hydrogen-bonding parameter was thus a determining factor in predicting miscibility in such set of compounds, whereas the dispersive and polar parameters had only a weak correlation. The results show that data mining approach is a valuable tool for predicting drug-excipient miscibility because it is easy to use, is time and cost-effective, and is material sparing.
Prediction of Liquid-Liquid Equilibrium Using the Group Solubility Parameter Model
ZHAO Mo; CHEN Fuming
2005-01-01
The group solubility parameter (GSP) model was used to analyze the liquid-liquid equilibrium (LLE) of ternary and quaternary systems. The GSP parameters are divided into four dimensions representing the four major intermolecular forces. The values of the parameters were determined by regression using the nonlinear SIMPLEX optimization method to fit the LLE data of 548 ternary and 26 quaternary systems selected from the literature. LLE predictions of 8 ternary systems were then made using the fit parameters. Comparison of the results with predictions using the modified UNIFAC model shows that the GSP model has less adjustable parameters to achieve a similar accuracy and that the parameter values are easily acquired by analysis of available data.
Tang, Yu; Hu, Chao; Liao, Qiong; Liu, Wen-long; Yang, Yan-tao; He, Hong; He, Fu-yuan
2015-01-01
The solubility parameter determination of astrageloside from Buyang Huanwu decoction with inverse gas chromatography (IGC) method evaluation was investigated in this paper. Di-n-octyl phthalate Kwai alternative sample was used to carry out methodological study. The accuracy of the measured correlation coefficient was 0.992 1. Experimental precision measured by IGC experiments showed that the results were accurate and reliable. The sample was uniformly coated on the surface of an inert carrier and N2 gas was carrier gas, a variety of polar solvents such as isopropanol, toluene, acetone, chloroform, cyclohexane as probes. TCD detector temperature was 150 degrees C, gas room temperature was 120 degrees C. Similar headspace method was used whichever over 1 μL gas into the GC measurement, Retention time t(R), t(0) and all the parameters of air and probes molecules within the column were tested. Astragaloside solubility parameter was (21.02 ± 2.4) [J x cm(-3)] ½, literature value was 19.24 [J x cm(-3)] ½, and relevant coefficient was 0.984 5. IGC method is effective and accurate to measure ingredients solubility parameter.
Gordon, Madeleine; Boucher, David
2015-03-01
We have studied the assembly and crystallinity of poly(3-hexylthiophene) (P3HT) (Mn ~ 28.2 kDa, regioregularity > 96 %, PDI ~ 1.3) in >100 binary solvent mixtures using UV-Vis absorption spectroscopy, and it is clear that the identity of the poor solvent used to drive aggregation has a significant impact on the structural order and crystallinity of the P3HT aggregates in solution. Here we report our findings using Hansen solubility parameters (HSPs), specifically the solubility distance vector, Ra, and the Kamlet-Taft solvatochromic parameters of the solvent mixtures to better understand the dominant solvent forces driving the self assembly of P3HT. We find that the directionality of the Ra vector provides a better measure of the crystallinity of the P3HT assemblies formed in the solvent mixtures than does the magnitude of the Ra vector. Our analysis of the Kamlet-Taft (α, β, π*) and ET(30) solvatochromic parameters reveals that the β parameter correlates best with the crystallinity of P3HT and that, in general, assemblies having higher structural order are formed in solvent mixtures with lower values of β.
Bordes, C; Fréville, V; Ruffin, E; Marote, P; Gauvrit, J Y; Briançon, S; Lantéri, P
2010-01-04
The evolution of regulation on chemical substances (i.e. REACH regulation) calls for the progressive substitution of toxic chemicals in formulations when suitable alternatives have been identified. In this context, the method of Hansen solubility parameters was applied to identify an alternative solvent less toxic than methylene chloride used in a microencapsulation process. During the process based on a multiple emulsion (W/O/W) with solvent evaporation/extraction method, the solvent has to dissolve a polymer, poly(epsilon-caprolactone) (PCL), which forms a polymeric matrix encapsulating or entrapping a therapeutic protein as the solvent is extracted. Therefore the three partial solubility parameters of PCL have been determined by a group contribution method, swelling experiments and turbidimetric titration. The results obtained allowed us to find a solvent, anisole, able to solubilize PCL and to form a multiple emulsion with aqueous solutions. A feasibility test was conducted under standard operating conditions and allowed the production of PCL microspheres.
Prediction of Permeation Resistance of Protective Gloves, etc. from Solubility Parameters
Henriksen, H. Risvig; Madsen, Jørgen Øgaard
1997-01-01
be valuable. This paper is concerned with a method of prediction. The three dimensional solubility parameter was developed to make the formulation af paints and varnishes more easy (Hansen 1967). Later it was transferred (Henriksen 1982) to the field of diffusion and, particularly, permeation in continuous...... layers of polymers as used in chemical protective clothing. Application of a relatively simple mathematical equation made permeability data correlate with solubility parameters of permeants and polymer materials. Permeation could actually be predicted and a concept on selection emerged (MAXIPARDIF......). A starting point was the authoritative conclusion (Coletta et al., 1978), that permeation in protective clothing could not be predicted. As a spin off, the predictive concept indicated that new types of polymers sometimes should be incorporated to reach a reasonable (long) breakthrough time and (low...
Experimental determination of solubility parameters of oils as a function of pressure
Verdier, Sylvain Charles Roland; Duong, Diep; Andersen, Simon Ivar
2005-01-01
In this work, the solubility parameter of dead and live crude oils was measured at 303.15 K and up to 300 bar, using the internal pressure approach. An indirect technique was chosen, using thermal expansivities (determined from microcalorimetric measurements) and isothermal compressibilities...... (calculated from density measurements). This method was tested on seven pure compounds, and the deviation with literature data is oils, and a deviation of
Organogel formation rationalized by Hansen solubility parameters: dos and don'ts
Bonnet, Julien; Suissa, Gad; Raynal, Matthieu; Bouteiller, Laurent
2014-01-01
International audience; Some organic compounds gelate liquids by forming a network of anisotropic fibres. Hansen solubility parameters can be used to predict the range of liquids that are likely to be gelled by any given gelator. We critically review the various approaches recently proposed in the literature. In particular, we discuss the shape of the gelation domain, the relevance of the Teas plot representation and the use of group contribution calculations. We also propose an improved sche...
Jiang, Xiaoli; Wang, Yinling; Li, Maoguo
2014-01-01
The solvent plays an important role in a given chemical reaction. Since most reaction in nature occur in the mixed-solvent systems, a comprehensive principle for solvent optimization was required. By calculating the Hansen solubility parameters (HSP) distance Ra , we designed a model experiment to explore the influence of mixed solvents on the chemical synthesis. The synthesis of polydopamine (PDA) in the water-alcohol system was chosen as model. As predicted, the well-dispersed PDA spheres w...
Belmares, M; Blanco, M; Goddard, W A; Ross, R B; Caldwell, G; Chou, S-H; Pham, J; Olofson, P M; Thomas, Cristina
2004-11-30
We introduce the Cohesive Energy Density (CED) method, a multiple sampling Molecular Dynamics computer simulation procedure that may offer higher consistency in the estimation of Hildebrand and Hansen solubility parameters. The use of a multiple sampling technique, combined with a simple but consistent molecular force field and quantum mechanically determined atomic charges, allows for the precise determination of solubility parameters in a systematic way (sigma = 0.4 hildebrands). The CED method yields first-principles Hildebrand parameter predictions in good agreement with experiment [root-mean-square (rms) = 1.1 hildebrands]. We apply the CED method to model the Caltech electronic nose, an array of 20 polymer sensors. Sensors are built with conducting leads connected through thin-film polymers loaded with carbon black. Odorant detection relies on a change in electric resistivity of the polymer film as function of the amount of swelling caused by the odorant compound. The amount of swelling depends upon the chemical composition of the polymer and the odorant molecule. The pattern is unique, and unambiguously identifies the compound. Experimentally determined changes in relative resistivity of seven polymer sensors upon exposure to 24 solvent vapors were modeled with the CED estimated Hansen solubility components. Predictions of polymer sensor responses result in Pearson R2 coefficients between 0.82 and 0.99.
Application of chaotic theory to parameter estimation
无
2002-01-01
High precision parameter estimation is very important for control system design and compensation. This paper utilizes the properties of chaotic system for parameter estimation. Theoretical analysis and experimental results indicated that this method has extremely high sensitivity and resolving power. The most important contribution of this paper is apart from the traditional engineering viewpoint and actualizing parameter estimation just based on unstable chaotic systems.
Rogers, Michael A; Marangoni, Alejandro G
2016-12-06
Changes in solvent chemistry influenced kinetics of both nucleation and crystallization of 12-hydroxyoctadecenoic, as determined using differential scanning calorimetry and applying a modified Avrami model to the calorimetric data. Altering solvent properties influenced solvent-gelator compatibility, which in turn altered the chemical potential of the system at the onset of crystallization, the kinetics of gelation, and the resulting 12HOA crystal fiber length. The chemical potential at the onset of crystallization was linearly correlated to both the hydrogen-bonding Hansen solubility parameter and the solvent-gelator vectorial distance in Hansen space, Ra. Our work suggests that solvent properties can be modulated to affect the solubility of 12HOA, which in turn influences the kinetics of crystallization and the self-assembly of this organogelator into supramolecular crystalline structures. Therefore, modulation of solvent properties during organogelation can be used to control fiber length and thus engineer the physical properties of the gel.
Cavities in molecular liquids and the theory of hydrophobic solubilities
Pohorille, A.; Pratt, L. R.; MacElroy, R. (Principal Investigator)
1990-01-01
Thermal configurational data on neat liquids are used to obtain the work of formation of hard spherical cavities of atomic size in six molecular solvents: n-hexane, n-dodecane, n-undecyl alcohol, chloroform, carbon tetrachloride, and water. These results are used to test a recent suggestion that the differences between nonaqueous solvents and liquid water in solvation of inert gases are not principally due to the hydrogen-bonded structure of liquid water but rather to the comparatively small size of the water molecule. The frequencies of occurrence of cavities in liquid water can be meaningfully distinguished from those in the organic solvents. Liquid water has a larger fractional free volume, but that free volume is distributed in smaller packets. With respect to cavity work, water is compared to a solvent of the same molecular density and composed of hard spheres of the same size as the water molecule. That comparison indicates that the hard-sphere liquid finds more ways to configure its free volume in order to accommodate an atomic solute of substantial size and thus, would be more favorable solvent for inert gases. The scaled particle model of inert gas solubility in liquid water predicts cavity works 20% below the numerical data for TIP4P water at 300 K and 1.0 g/cm3 for cavity radii near 2.0 angstroms. It is argued that the sign of this difference is just the sign that ought to be expected and that the magnitude of this difference measures structural differences between water and the directly comparable hard-sphere liquid. In conjunction with previous data, these results indicate that atomic sized cavities should be considered submacroscopic.
M. D. Petters
2008-10-01
Full Text Available The ability of a particle to serve as a cloud condensation nucleus in the atmosphere is determined by its size, hygroscopicity and its solubility in water. Usually size and hygroscopicity alone are sufficient to predict CCN activity. Single parameter representations for hygroscopicity have been shown to successfully model complex, multicomponent particles types. Under the assumption of either complete solubility, or complete insolubility of a component, it is not necessary to explicitly include that component's solubility into the single parameter framework. This is not the case if sparingly soluble materials are present. In this work we explicitly account for solubility by modifying the single parameter equations. We demonstrate that sensitivity to the actual value of solubility emerges only in the regime of 2×10^{−1}–5×10^{−4}, where the solubility values are expressed as volume of solute per unit volume of water present in a saturated solution. Compounds that do not fall inside this sparingly soluble envelope can be adequately modeled assuming they are either infinitely soluble in water or completely insoluble.
Hildebrand solubility parameter to predict drug release from hydroxypropyl methylcellulose gels.
Bustamante, P; Navarro-Lupión, J; Peña, M A; Escalera, B
2011-07-29
An equation including the Hildebrand solubility parameter δ of the drugs is used for the first time to model drug release from hydroxypropyl methylcellulose (HPMC) gels: l nM = -21.578 + 2.102 δ-0.037 δ(2)+0.48 ln t + 1.028 ln C(i) (r(2) = 0.94 for a total of 286 cases). The experimentally determined release data of six drugs having different polarity (caffeine, theophylline, paracetamol, salicylic acid, naproxen and diclofenac) at several initial concentrations C(i) were included in the equation. In general, the amount of drug delivered is linear at the first 5-6h of the release profiles and the zero order constants K(o) increase as the solubility parameter of the drugs become larger. The Peppas exponential law M/M(∞) = Kt(n) is applicable to larger fractional release, until 67-87% (48-51 h) for the less polar drugs (diclofenac and naproxen, lower δ values) and more than 80% (26-28 h) for the more polar drugs (higher δ values, theophylline, salicylic acid, caffeine and paracetamol). The Peppas release rate (lnK) shows a parabolic relationship with the drug solubility parameter. The diffusional exponent n varies between 0.40 and 0.58 indicating that drug release is mainly controlled by diffusion. An extended form of the Peppas equation is also tested for each drug including all the initial concentrations: lnM = a + b ln t + c ln C(i) (r(2) = 0.88-0.94). The logarithm of the octanol-water partition coefficients can also be used in combination with the drug concentrations. Copyright © 2011 Elsevier B.V. All rights reserved.
Predicting the solubility of mixtures of sugars and their replacers using the Flory-Huggins theory
Sman, van der R.G.M.
2017-01-01
In this paper we investigate whether the Flory-Huggins theory can describe the thermodynamics of solutions of simple carbohydrates, like sugars and polyols. In particular, we focus on the description of the solubility of the carbohydrates in water. This is investigated for both binary and ternary
Morphologies in Solvent-Annealed Clotrimazole Thin Films Explained by Hansen-Solubility Parameters.
Ehmann, Heike M A; Zimmer, Andreas; Roblegg, Eva; Werzer, Oliver
2014-03-05
The induction of different crystal morphologies is of crucial importance for many applications. In this work, the preparation of various crystal morphologies within clotrimazole films on glass substrates is demonstrated. Amorphous clotrimazole thin films were transformed via vapor annealing into crystalline structures; highly monodisperse/multidisperse crystallites, spherulite, or dendritic structures were obtained as the solvent was exchanged. X-ray diffraction experiments reveal that the same polymorph is present for all samples but with varying texture. The achieved morphologies are explained in terms of Hansen-solubility parameters and vapor pressures; thus, the different morphologies and crystal orientations can be explained by solvent-solid interaction strengths within the thin film samples.
Vay, Kerstin; Scheler, Stefan; Friess, Wolfgang
2011-09-15
In an emulsion solvent extraction/evaporation process for the preparation of microspheres the employed solvents have a tremendous influence on the characteristics of the resulting particles. Nevertheless the solvent selection is often based on empirical data rather than on calculated values. The purpose of this investigation was to use the concept of solubility parameters for interpretation and improved understanding of solvent effects in the process of microparticle preparation. Partial solubility parameters of 3-{2-[4-(6-Fluor-1,2-benzisoxazol-3-yl)piperidino]ethyl}-2-methyl-6,7,8,9-tetrahydro-4H-pyrido[1,2-a]pyrimidin-4-on, which was used as a model drug, were determined experimentally using an extended Hansen regression model. Poly(lactide-co-glycolide) microparticles were prepared with an emulsion solvent removal process employing methylene chloride and its mixtures with benzyl alcohol and n-butanol. It could be shown, that the encapsulation efficiency was influenced by the change of the solvent composition during the extraction process. Furthermore the solvent selection had an essential influence on the morphological state of the drug and it could be shown and explained, that by a decrease of the dissolving power a completely amorphous product was obtained.
Peña, M A; Daali, Y; Barra, J; Bustamante, P
2000-02-01
The modified extended Hansen method was tested for the first time to determine partial solubility parameters of non-polymeric pharmaceutical excipients. The method was formerly tested with drug molecules, and is based upon a regression analysis of the logarithm of the mole fraction solubility of the solute against the partial solubility parameters of a series of solvents of different chemical classes. Two monosaccharides and one disaccharide (lactose monohydrate, saccharose and mannitol) were chosen. The solubility of these compounds was determined in a series of solvents ranging from nonpolar to polar and covering a wide range of the solubility parameter scale. Sugars do not absorb at the UV-vis region, and the saturated solutions were assayed with a recent chromatographic technique coupled to an evaporative light scattering detector. This technique was suitable to determine the concentration dissolved in most solvents. The modified extended Hansen method provided better results than the original approach. The best model was the four parameter equation, which includes the dispersion delta d, dipolar delta p, acidic delta a and basic delta b partial solubility parameters. The partial solubility parameters obtained, expressed as MPa1/2, were delta d = 17.6, delta p = 28.7, delta h = 19, delta a = 14.5, delta b = 12.4, delta T = 32.8 for lactose, delta d = 16.2, delta p = 24.5, delta h = 14.6, delta a = 8.7, delta b = 12.2, delta T = 32.8 for mannitol and delta d = 17.1, delta p = 18.5, delta h = 13, delta a = 11.3, delta b = 7.6, delta T = 28.4 for saccharose. The high total solubility parameters delta T obtained agree with the polar nature of the sugars. The dispersion parameters delta d are quite similar for the three sugars indicating that the polar delta p and hydrogen bonding parameters (delta h, delta a, delta b) are responsible for the variation in the total solubility parameters delta T obtained, as also found for drugs. The results suggest that the method
Zhang Feng; Shen Benxian; Sun Hui; Liu Jichang; Shang Jianfeng
2015-01-01
The performance of four formulated solvents (labeled as UDS-I, UDS-II, UDS-III, and UDS-IV) for removing methyl mercaptan from liqueifed petroleum gas was predicted based on a two-dimensional solubility parameter theory. The calculation results show that UDS-IV has the closest solubility parameter to that of methyl mercaptan as compared with other tested solvents, indicating the strongest afifnity and the highest solubility for methyl mercaptan. The industrial tests at a plant for desulfurization of LPG produced from the delayed coker have shown that the UDS solvents have the excellent performance for removal of organosulfur compounds (mainly methyl mercaptan). Although the sulfur loading dramatically increases, the total sulfur content of LPG treated with UDS-IV can be reduced by about 50% in comparison withN-methyl diethanolamine. In addition, UDS-IV has superior regeneration performance and selectivity for sulfur compounds over hy-drocarbons. The industrial test and the solubility parameter calculation results are in good agreement with each other.
Srinivas, K; King, J W; Monrad, J K; Howard, L R; Hansen, C M
2009-08-01
Process engineering operations in food and nutraceutical industries pertaining to the design of extraction of value-added products from biomass using pressurized liquids involve a careful selection of the solvent and optimal temperature conditions to achieve maximum yield. Complex molecular structure and limited physical property data in the literature of biological solutes extracted from biomass compounds have necessitated the process modeling of such operations. In this study, we have applied the Hansen 3-dimensional solubility parameter concept to optimize the extraction of molecularly complex solutes using subcritical fluid solvents. Hansen solubility spheres characterized by the relative energy differences (RED) have been used to characterize and quantify the solute-subcritical solvent interactions as a function of temperature. The solvent power of subcritical water and compressed hydroethanolic mixtures above their boiling points has been characterized using the above-mentioned method. The use of group contribution methods in collaboration with computerized algorithms to plot the Hansen spheres provides a quantitative prediction tool for optimizing the design of extraction conditions. The method can be used to estimate conditions for solute-solvent miscibility, an optimum temperature range for conducting extractions under pressurized conditions, and approximate extraction conditions of solutes from natural matrices.
Vinod Mokale
2013-01-01
Full Text Available The aim of this study was to formulate and optimize Glyburide (GB nanosuspension which is poorly water-soluble antidiabetic drug with optimization of the dissolution property and bioavailability by reducing the particle at nano size. The nanosuspension is prepared by Top down technique, i.e. high pressure homogenization. The formulation factors which affects particle size including concentration of surfactant while processing parameters includes homogenization pressure and homogenization cycle. After particle size reduction, we observe that there are increases in the surface energy which requires adequate stabilization by surfactant. In this study, practically water insoluble GB was nanoground and surfactant was employed for their stabilizing effect. In-vitro dissolution study revealed that increase in release rate of GB from nanoparticles (NPS as compare to pure raw GB. Field Emission Scanning Electron Microscope (FE-SEM study showed the spherical morphology of NPS. Particles size distribution, zeta potential, and crystal form of the formulated nanosuspension were studied by using particle size analyzer and X-ray powder diffraction. The result showed that the drug dissolution rate in nanosuspension formulation is depending upon crystal form, solubility, preparation procedure, and stabilizer employed.
Using Hansen solubility parameters to study the encapsulation of caffeine in MOFs.
Paseta, Lorena; Potier, Grégory; Abbott, Steven; Coronas, Joaquín
2015-02-14
Hansen solubility parameters (HSP) have found their greatest use in the evaluation of solvent-polymer chemical interactions. Given their great interest among the scientific community, host-guest interactions in metal-organic frameworks (MOFs), with organic and inorganic moieties, could benefit from a HSP approach. In this work we have initiated the application of HSP to the study of caffeine encapsulation in MOFs ZIF-8 and NH2-MIL-88B(Fe). However, the availability of HSP for MOFs is nearly zero. As a first step to evaluating the potential of HSP for rational design we have made the simplifying assumption that the HSP distance of the caffeine-ligand interaction (i.e. ignoring the metal and the MOF structure) dominates the ability to form a MOF host-guest system. Although much work remains to be done, the first indications are that this approach has much potential.
Jiang, Xiaoli; Wang, Yinling; Li, Maoguo
2014-08-01
The solvent plays an important role in a given chemical reaction. Since most reaction in nature occur in the mixed-solvent systems, a comprehensive principle for solvent optimization was required. By calculating the Hansen solubility parameters (HSP) distance Ra, we designed a model experiment to explore the influence of mixed solvents on the chemical synthesis. The synthesis of polydopamine (PDA) in the water-alcohol system was chosen as model. As predicted, the well-dispersed PDA spheres were obtained in selected solvents with smaller Ra values: methanol/water, ethanol/water and 2-propanol/water. In addition, the mixed solvent with smaller Ra values gave a higher conversion of dopamine. The strategy for mixed solvent selection is might be useful to choose optimal reaction media for efficient chemical synthesis.
Jiang, Xiaoli; Wang, Yinling; Li, Maoguo
2014-01-01
The solvent plays an important role in a given chemical reaction. Since most reaction in nature occur in the mixed-solvent systems, a comprehensive principle for solvent optimization was required. By calculating the Hansen solubility parameters (HSP) distance Ra, we designed a model experiment to explore the influence of mixed solvents on the chemical synthesis. The synthesis of polydopamine (PDA) in the water-alcohol system was chosen as model. As predicted, the well-dispersed PDA spheres were obtained in selected solvents with smaller Ra values: methanol/water, ethanol/water and 2-propanol/water. In addition, the mixed solvent with smaller Ravalues gave a higher conversion of dopamine. The strategy for mixed solvent selection is might be useful to choose optimal reaction media for efficient chemical synthesis. PMID:25317902
Ata, Seisuke; Mizuno, Takaaki; Nishizawa, Ayumi; Subramaniam, Chandramouli; Futaba, Don N.; Hata, Kenji
2014-12-01
We report a general approach to fabricate elastomeric composites possessing high electrical conductivity for applications ranging from wireless charging interfaces to stretchable electronics. By using arbitrary nine kinds of rubbers as matrices, we experimentally demonstrate that the matching the solubility parameter of CNTs and the rubber matrix is important to achieve higher electrical conductivity in CNT/rubber composite, resulting in continuous conductive pathways leading to electrical conductivities as high as 15 S/cm with 10 vol% CNT in fluorinated rubber. Further, using thermodynamic considerations, we demonstrate an approach to mix CNTs to arbitrary rubber matrices regardless of solubility parameter of matrices by adding small amounts of fluorinated rubber as a polymeric-compatibilizer of CNTs. We thereby achieved electrical conductivities ranging from 1.2 to 13.8 S/cm (10 vol% CNTs) using nine varieties of rubber matrices differing in chemical structures and physical properties. Finally, we investigated the components of solubility parameter of CNT by using Hansen solubility parameters, these findings may useful for controlling solubility parameter of CNTs.
Marino-Ortega, Linda A; Molina-Bello, Adiel; Polanco-García, Julio C; Muñoz-Valle, José F; Salgado-Bernabé, Aralia B; Guzmán-Guzmán, Iris P; Parra-Rojas, Isela
2015-01-01
The aim of this study was to investigate if anthropometric parameters are associated with both leptin and soluble leptin receptor (sLEPR) levels in newborns and their mothers. This cross-sectional study was performed in 118 mother-newborn pairs. The venous blood sample of mothers was taken before delivery and immediately after delivery an umbilical cord blood sample was collected. Levels of leptin and sLEPR in maternal and umbilical cord sera were assessed by ELISA. Maternal serum concentration of leptin and sLEPR (6.2 and 25.7 ng/ml, respectively) were higher than in umbilical cord blood (2.4 and 14.2 ng/ml, respectively). However, the newborns and their mothers had higher sLEPR levels than leptin levels. In mothers was observed that leptin levels increase with weight gain in pregnancy and decreased sLEPR levels. Cord leptin levels correlated with neonatal birth weight and length, the body circumferences, placental weight and maternal leptin levels. Cord sLEPR levels correlated with maternal sLEPR and leptin levels. Maternal serum concentration of leptin correlated with pre-pregnancy BMI, weight gain, cord sLEPR and leptin levels. Maternal sLEPR concentration correlated with cord sLEPR levels. The leptin and sLEPR levels in mother-newborn pairs are related with anthropometric parameters and an inverse correlation between leptin levels and sLEPR was observed in pairs. PMID:26379933
Petersen, Jacob B; Meruga, Jeevan; Randle, James S; Cross, William M; Kellar, Jon J
2014-12-30
Optimal ink formulations, inclusive of nanoparticles, are often limited to matching the nanoparticle's capping agent or surface degree of polarity to the solvent of choice. Rather than relying on this single attribute, nanoparticle dispersibility was optimized by identifying the Hansen solubility parameters (HSPs) of decanoic-acid-capped 5 nm silver nanoparticles (AgNPs) by broad spectrum dispersion testing and a more specific binary solvent gradient dispersion method. From the HSPs, solvents were chosen to disperse poly(methyl methacrylate) (PMMA) and nanoparticles, give uniform evaporation profiles, and yield a phase-separated microstructure of nanoparticles on PMMA via film formation by solvent evaporation. The goal of this research was to yield a film that is reflective or transparent depending on the angle of incident light (i.e., optically variable). The nanoparticle HSPs were very close to alkanes with added small polar and hydrogen-bonding components. This led to two ink formulations: one of 90:10 vol % toluene/methyl benzoate and one containing 80:10:10 vol % toluene/p-xylene/mesitylene, both of which yielded the desired final microstructure of a nanoparticle layer on a PMMA film. This approach to nanoparticle ink formulation allows one to obtain an ink that has desirable dispersive qualities, rheology, and evaporation to give a desired printed structure.
Amin, Aeshna; Dare, Manish; Sangamwar, Abhay; Bansal, Arvind Kumar
2012-01-01
The aim of this work was to study the interaction of four commonly used ophthalmic antimicrobial preservatives [benzyl alcohol (BA), chlorbutol (CBL), benzalkonium chloride (BKC), and chlorhexidine gluconate (CG)] with Blow-Fill-Seal (BFS) packs. Effect of packaging material [low-density polyethylene (LDPE), polypropylene (PP)], humidity (25% RH, 75% RH) and concentration (0.5, 1.0, 2.0 mM BA/CBL in LDPE) was studied. BKC and CG gave negligible loss (preservative. Loss of BA switched from Case II to anomalous behavior with increasing initial concentration. A two-stage sorption behavior was inherent at all concentrations. Loss of CBL followed anomalous behavior with biphasic kinetics of loss. It was concluded that all the four preservatives were appropriate for use in PP BFS packs. However, only BKC and CG were amenable to be used in LDPE BFS packs. Lastly, an empirical expression consisting of the "solubility parameter distance" and "molar volume" of preservatives was developed to correlate the preservative loss in LDPE with the physicochemical properties of the preservatives.
MODERATING ABILITY OF ITEM RESPONSE THEORY THROUGH PRIOR GUESSING PARAMETER
Siow Hoo Leong
2013-01-01
Full Text Available A psycho-technology approach to discouraging guessing in multiple-choice formatted item can be done through reducing the a priori guessing probability of an item. This study proposes a psychometrics framework of Item Response Theory (IRT to model the effect of having various priori guessing probabilities across different items. A prior guessing parameter is proposed to serves as a moderator of the ability parameter in the two parameter logistic IRT. The results show that the proposed prior guessing parameter successfully moderates the ability parameters of the subjects with different degrees of guessing. However, the prior guessing parameter is insensitive when the performance pattern is mixed within the testlet but similar across testlet with different priori guessing probabilities.
EFFECTS OF INHALATION OF SOLUBLE METALLIC CONSTITUENTS OF PARTICULATE MATTER ON CARDIOPULMONARY, THERMOREGULATORY, AND BIOCHEMICAL PARAMETERS IN GUINEA PIGS. JP Nolan1, LB Wichers2, J Stanek3, UP Kodavanti1, MCJ Schladweiler1, PA Evansky1, ER Lappi1, DL Costa1, and WP Watkinson1...
Hierarchical Bayesian parameter estimation for cumulative prospect theory
Nilsson, H.; Rieskamp, J.; Wagenmakers, E.-J.
2011-01-01
Cumulative prospect theory (CPT Tversky & Kahneman, 1992) has provided one of the most influential accounts of how people make decisions under risk. CPT is a formal model with parameters that quantify psychological processes such as loss aversion, subjective values of gains and losses, and
Zhai, Xuezhen; Lademann, Jürgen; Keck, Cornelia M; Müller, Rainer H
2014-09-01
Nanocrystals are meanwhile applied to increase the dermal penetration of drugs, but were applied by now only to poorly soluble drugs (e.g. 1-10 μg/ml). As a new concept nanocrystals from medium soluble actives were produced, using caffeine as model compound (solubility 16 mg/ml at 20 °C). Penetration should be increased by (a) further increase in solubility and (b) mainly by increased hair follicle targeting of nanocrystals compared to pure solution. Caffeine nanocrystal production in water lead to pronounced crystal growth. Therefore the stability of nanocrystals in water-ethanol (1:9) and ethanol-propylene glycol (3:7) mixtures with lower dielectric constant D was investigated, using various stabilizers. Both mixtures in combination with Carbopol 981 (non-neutralized) yielded stable nanosuspensions over 2 months at 4 °C and room temperature. Storage at 40 °C lead to crystal growth, attributed to too strong solubility increase, supersaturation and Ostwald ripening effects. Stability of caffeine nanocrystals at lower temperatures could not only be attributed to lower solubility, because the solubilities of caffeine in mixtures and in water are not that much different. Other effects such as quantified by reduced dielectric constant D, and specific interactions between dispersion medium and crystal surface seem to play a role. With the 2 mixtures and Carbopol 981, a basic formulation composition for this type of nanocrystals has been established, to be used in the in vivo proof of principle of the new concept.
The Prediction of Item Parameters Based on Classical Test Theory and Latent Trait Theory
Anil, Duygu
2008-01-01
In this study, the prediction power of the item characteristics based on the experts' predictions on conditions try-out practices cannot be applied was examined for item characteristics computed depending on classical test theory and two-parameters logistic model of latent trait theory. The study was carried out on 9914 randomly selected students…
Discussion and improvement of the refined COSMO-SAC parameters for solubility predictions: part 2
Bouillot, Baptiste; Teychené, Sébastien; Biscans, Béatrice
2013-01-01
Solubility of drugs is a key piece of information for the pharmaceutical industry. Despite its importance, particularly at the beginning of a new drug process development, this thermodynamic property of the solid-liquid equilibria (SLE) can hardly be predicted for a given molecule in a given solvent. In our recent works, some thermodynamic models (UNIFAC and its modifications, COSMO-SAC and its refinements, NRTL-SAC) were investigated and compared for solubility prediction. The main drawbacks...
Estimation of poroelastic parameters from seismograms using Biot theory
De Barros, Louis
2010-01-01
We investigate the possibility to extract information contained in seismic waveforms propagating in fluid-filled porous media by developing and using a full waveform inversion procedure valid for layered structures. To reach this objective, we first solve the forward problem by implementing the Biot theory in a reflectivity-type simulation program. We then study the sensitivity of the seismic response of stratified media to the poroelastic parameters. Our numerical tests indicate that the porosity and consolidation parameter are the most sensitive parameters in forward and inverse modeling, whereas the permeability has only a very limited influence on the seismic response. Next, the analytical expressions of the sensitivity operators are introduced in a generalized least-square inversion algorithm based on an iterative modeling of the seismic waveforms. The application of this inversion procedure to synthetic data shows that the porosity as well as the fluid and solid parameters can be correctly reconstructed...
A New Parameter Set for the Relativistic Mean Field Theory
Nerlo-Pomorska, B; Nerlo-Pomorska, Bozena; Sykut, Joanna
2004-01-01
Subtracting the Strutinsky shell corrections from the selfconsistent energies obtained within the Relativistic Mean Field Theory (RMFT) we have got estimates for the macroscopic part of the binding energies of 142 spherical even-even nuclei. By minimizing their root mean square deviations from the values obtained with the Lublin-Srasbourg Drop (LSD) model with respect to the nine RMFT parameters we have found the optimal set (NL4). The new parameters reproduce also the radii of these nuclei with an accuracy comparable with that obtained with the NL1 and NL3 sets.
Mass Deformed Exact S-parameter in Conformal Theories
Sannino, Francesco
2010-01-01
We use the exact expression for the S parameter in the perturbative region of the conformal window to establish its dependence on the explicit introduction of fermion masses. We demonstrate that the relative ordering with which one sends to zero either the fermion mass or the external momentum...... leads to drastically different limiting values of S. Our results apply to any fermion matter representation and can be used as benchmark for the determination of certain relevant properties of the conformal window of any generic vector like gauge theory with fermionic matter. We finally suggest...... the existence of a universal lower bound on the opportunely normalized S parameter and explore its theoretical and phenomenological implications. Our exact results constitute an ideal framework to correctly interpret the lattice studies of the conformal window of strongly interacting theories....
Espinoza, Loredana; Rivas, Issarly; Urbina-Villalba, German
2016-01-01
The solubility of dodecane was determined using the theory of Lifshitz-Slyosov-Wagner for the Ostwald ripening phenomenon. For this purpose, a set of dodecane in water nanoemulsions stabilized with sodium dodecylsulfate was prepared. The average cubic radius of the dispersions was followed as a function of time for volume fractions between 0.001 and 0.00001. The correct solubility (5.5 x 10-9 m3/m3) was only reproduced by the most dilute system.
Yi, Min; Shen, Zhigang; Zhang, Xiaojing; Ma, Shulin
2013-01-01
Although exfoliating graphite to give graphene paves a new way for graphene preparation, a general strategy of low-boiling-point solvents and high graphene concentration is still highly required. In this study, using the strategy of tailoring Hansen solubility parameters (HSP), a method based on exfoliation of graphite in water/acetone mixtures is demonstrated to achieve concentrated graphene dispersions. It is found that in the scope of blending two mediocre solvents, tailoring the HSP of water/acetone mixtures to approach the HSP of graphene could yield graphene dispersions at a high concentration of up to 0.21 mg ml-1. The experimentally determined optimum composition of the mixtures occurs at an acetone mass fraction of ˜75%. The trend of concentration varying with mixture compositions could be well predicated by the model, which relates the concentration to the mixing enthalpy within the scope of HSP theory. The resultant dispersion is highly stabilized. Atomic force microscopic statistical analysis shows that up to ˜50% of the prepared nanosheets are less than 1 nm thick after 4 h sonication and 114g centrifugation. Analyses based on diverse characterizations indicate the graphene sheets to be largely free of basal plane defects and oxidation. The filtered films are also investigated in terms of their electrical and optical properties to show reasonable conductivity and transparency. The strategy of tailoring HSP, which can be easily extended to various solvent systems, and water/acetone mixtures here, extends the scope for large-scale production of graphene in low-boiling-point solutions.
Groning, R; Braun, F J
1996-05-01
The physico-chemical properties of drug substances are major determinants of their transdermal absorption. In the present study the concept of the three-dimensional solubility parameters of Hansen was applied in conjunction with the Bagley projection to describe the permeation of drugs and model substances through the skin. Drug permeation data from the literature were compared with the calculated solubility parameters of the drugs. It was demonstrated that the permeation of drugs can be estimated by their position in the Bagley diagram. There is a linear correlation between the logarithm of the skin permeation of drugs and the exchange cohesive energy for the steroids testosterone, progesterone, hydrocortisone acetate, corticosterone, cortisone, and dexamethasone. A linear correlation can be confirmed for the permeation of glyceryl trinitrate, digitoxin, oestradiol, scopolamine, atropine, diethylcarbamazine, fentanyl, and chlorpheniramine. In the case of morphine, codeine, sufentanil, meperidine and hydromorphone there is a linear relationship, too.
Seisuke Ata; Takaaki Mizuno; Ayumi Nishizawa; Chandramouli Subramaniam; Futaba, Don N.; Kenji Hata
2014-01-01
We report a general approach to fabricate elastomeric composites possessing high electrical conductivity for applications ranging from wireless charging interfaces to stretchable electronics. By using arbitrary nine kinds of rubbers as matrices, we experimentally demonstrate that the matching the solubility parameter of CNTs and the rubber matrix is important to achieve higher electrical conductivity in CNT/rubber composite, resulting in continuous conductive pathways leading to electrical co...
Wagner, K G; Dowe, U; Zadnik, J
2005-05-01
In order to correlate drug adhesion properties of a highly loaded interactive mixture for the use in dry powder inhalers with the surface energy and to establish a link to the solubility parameter, surface free energy was detected for micronized substances (salbutamol sulfate, salbutamol base, theophylline and alpha-lactose monohydrate) using inverse gas chromatography (IGC). Interactive mixtures with coarse crystalline alpha-lactose monohydrate as a carrier were prepared at loading levels from 7.5 to 20% (w/w) and analyzed with respect to their adhesion capacity (CA) using the air jet sieving method. Solubility parameters were taken from literature or calculated. As a result the CA was independent of the drug load and correlated linearly with volume specific surface energy interaction (SEIv) values of the adherents (R2 = 0.98498). A link between SEIv and the size normalized solubility parameter (delta(tot)/d50) was found. Consequently, plotting delta(tot)/d50 versus CA resulted also in a strong linear relationship (R2 = 0.99140). Overall a powerful tool was established to judge and quantify adhesion properties of highly loaded interactive mixtures even for estimates in early preformulation at a time where just the molecular structure of the active ingredient is known.
One of the major by-products of bioethanol production is distillers dried grains with solubles (DDGS). Maize is one of the main sources for the production of this biofuel. In this way, dietary fiber represents the principal fraction of DDGS, which could be a potential source of added-value biomolecu...
Theory of stellar convection: Removing the Mixing-Length Parameter
Pasetto, S; Cropper, M; Grebel, E K
2014-01-01
Stellar convection is customarily described by Mixing-Length Theory, which makes use of the mixing-length scale to express the convective flux, velocity, and temperature gradients of the convective elements and stellar medium. The mixing-length scale is taken to be proportional to the local pressure scale height, and the proportionality factor (the mixing-length parameter) must be determined by comparing the stellar models to some calibrator, usually the Sun. No strong arguments exist to suggest that the mixing-length parameter is the same in all stars and at all evolutionary phases. Because of this, all stellar models in literature are hampered by this basic uncertainty. The aim of this study is to present a new theory of stellar convection that does not require the mixing length parameter. We present a self-consistent analytical formulation of stellar convection that determines the properties of stellar convection as a function of the physical behaviour of the convective elements themselves and the surround...
Hossin, B; Rizi, K; Murdan, S
2016-05-01
We hypothesised that Hansen Solubility Parameters (HSPs) can be used to predict drug-nail affinities. Our aims were to: (i) determine the HSPs (δD, δP, δH) of the nail plate, the hoof membrane (a model for the nail plate), and of the drugs terbinafine HCl, amorolfine HCl, ciclopirox olamine and efinaconazole, by measuring their swelling/solubility in organic liquids, (ii) predict nail-drug interactions by comparing drug and nail HSPs, and (iii) evaluate the accuracy of these predictions using literature reports of experimentally-determined affinities of these drugs for keratin, the main constituent of the nail plate and hoof. Many solvents caused no change in the mass of nail plates, a few solvents deswelled the nail, while others swelled the nail to varying extents. Fingernail and toenail HSPs were almost the same, while hoof HSPs were similar, except for a slightly lower δP. High nail-terbinafine HCl, nail-amorolfine HCl and nail-ciclopirox olamine affinities, and low nail-efinaconazole affinities were then predicted, and found to accurately match experimental reports of these drugs' affinities to keratin. We therefore propose that drug and nail Hansen Solubility Parameters may be used to predict drug-nail interactions, and that these results can assist in the design of drugs for the treatment of nail diseases, such as onychomycosis and psoriasis. To our knowledge, this is the first report of the application of HSPs in ungual research.
Total soluble solids from banana: evaluation and optimization of extraction parameters.
Carvalho, Giovani B M; Silva, Daniel P; Santos, Júlio C; Izário Filho, Hélcio J; Vicente, António A; Teixeira, José A; Felipe, Maria das Graças A; Almeida e Silva, João B
2009-05-01
Banana, an important component in the diet of the global population, is one of the most consumed fruits in the world. This fruit is also very favorable to industry processes (e.g., fermented beverages) due to its rich content on soluble solids and minerals, with low acidity. The main objective of this work was to evaluate the influence of factors such as banana weight and extraction time during a hot aqueous extraction process on the total soluble solids content of banana. The extract is to be used by the food and beverage industries. The experiments were performed with 105 mL of water, considering the moisture of the ripe banana (65%). Total sugar concentrations were obtained in a beer analyzer and the result expressed in degrees Plato (degrees P, which is the weight of the extract or the sugar equivalent in 100 g solution at 20 degrees C), aiming at facilitating the use of these results by the beverage industries. After previous studies of characterization of the fruit and of ripening performance, a 2(2) full-factorial star design was carried out, and a model was developed to describe the behavior of the dependent variable (total soluble solids) as a function of the factors (banana weight and extraction time), indicating as optimum conditions for extraction 38.5 g of banana at 39.7 min.
Bayesian parameter estimation for chiral effective field theory
Wesolowski, Sarah; Furnstahl, Richard; Phillips, Daniel; Klco, Natalie
2016-09-01
The low-energy constants (LECs) of a chiral effective field theory (EFT) interaction in the two-body sector are fit to observable data using a Bayesian parameter estimation framework. By using Bayesian prior probability distributions (pdfs), we quantify relevant physical expectations such as LEC naturalness and include them in the parameter estimation procedure. The final result is a posterior pdf for the LECs, which can be used to propagate uncertainty resulting from the fit to data to the final observable predictions. The posterior pdf also allows an empirical test of operator redundancy and other features of the potential. We compare results of our framework with other fitting procedures, interpreting the underlying assumptions in Bayesian probabilistic language. We also compare results from fitting all partial waves of the interaction simultaneously to cross section data compared to fitting to extracted phase shifts, appropriately accounting for correlations in the data. Supported in part by the NSF and DOE.
Simulation of robust resonance parameters using information theory
Krishna Kumar, P.T. [Reactor Physics Division, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102 (India)], E-mail: gstptk@yahoo.co.in; Phoha, V.V. [Department of Computer Science, Louisiana Tech University, Arizona Avenue, Ruston, LA 71270 (United States)], E-mail: phoha@latech.edu; Iyengar, S.S. [Department of Computer Science, Louisiana State University, Baton Rouge, LA 70803 (United States)], E-mail: iyengar@csc.lsu.edu
2008-08-15
Due to complex nature of resonance region interactions, significant effort has been devoted to quantify the resonance parameter uncertainty information through covariance matrices. Statistical uncertainties arising from measurements contribute only to the diagonal elements of the covariance matrix, but the off-diagonal contributions arise from multiple sources like systematic errors in cross-section measurement, correlation due to nuclear reaction formalism, etc. All the efforts have so far been devoted to minimize the statistical uncertainty by repeated measurements but systematic uncertainty cannot be reduced by mere repetition. The computer codes like SAMMY and KALMAN so far developed to generate resonance parameter covariance have no provision to improve upon the highly correlated experimental data and hence reduce the systematic uncertainty. We propose a new approach called entropy based information theory to reduce the systematic uncertainty in the covariance matrix element wise so that resonance parameters with minimum systematic uncertainty can be simulated. Our simulation approach will aid both the experimentalists and the evaluators to design the experimental facility with minimum systematic uncertainty and thus improve the quality of measurement and the associated instrumentation. We demonstrate, the utility of our approach in simulating the resonance parameters of Uranium-235 and Plutonium-239 with reduced systematic uncertainty.
Ghebremeskel, Alazar N; Vemavarapu, Chandra; Lodaya, Mayur
2007-01-10
Formation of solid dispersions as a means to enhance the dissolution rate of poorly soluble Active pharmaceutical ingredients (APIs) typically employs hydrophilic polymer systems and surfactants. While the utility of the surfactant systems in solubilization is well known, the secondary effects of the same on processing and subsequent physical stability of the solid dispersions needs to be studied further. Physical blends of the poorly soluble API and hydrophilic polymers such as PVP-K30, Plasdone-S630, HPMC-E5, HPMCAS, and Eudragit L100 with mass ratio 1:1 were prepared. The surfactants tested in this study included Tween-80, Docusate sodium, Myrj-52, Pluronic-F68 and SLS. Thermal analysis of the API-polymer-surfactant blends suggested that the surfactants caused solvation/plasticization, manifesting in reduction of (i) the melting (T(m)) of API (ii) T(g) of the polymers and (iii) the combined T(g) of the solid dispersion formed from quench cooling. Explanation of these effects of surfactants is attempted based on their physical state (at the temperature of interest), HLB values and similarity of their solubility parameter values with respect to drug-polymer systems. Furthermore, extruded matrices containing different API-polymer (PVP-K30, Plasdone-S630, and HPMC-E5) mixtures prepared with and without surfactants, were produced by feeding the powder blend through a hot-melt extruder. The melt viscosity of the polymer blends was assessed by torque rheometry using a Haake Rheomix. The physicochemical properties of the extruded API-polymer-surfactant were characterized by differential scanning calorimetry, X-ray diffraction, Raman spectroscopy, and polarized microscopy. The results demonstrated that the glass transition temperature of the carrier polymers decreased as direct result of the surfactants in the extrudate, due to an increase in the chain mobility of polymers. A decrease in the melt viscosity was seen due to a plasticization of the polymer. The drug release
Białecka-Florjańczyk, Ewa
2006-02-16
The phase behavior of some rodlike block molecules has been reviewed with reference to the polarity of constituent segments. It was found that the ability of the mesophase formation is connected with differences in polar character between the flexible chains and rigid cores. Thus the polar poly(oxyethylene) group connected with the polar rigid core reduces mesophase stability but is advantageous when put together with some apolar building blocks. An attempt at quantitative estimation of the incompatibilities of different parts of molecules by means of Hansen solubility parameters delta and Flory interaction parameters chi has also been made. On the basis of chi parameters the Gibbs free energies of mixing of these segments were calculated. The changes of Gibbs free energy reflecting the compatibility of segments and their tendency to the phase separation and the volume fraction of mesogenic rigid core reflecting their ability to arrangement in one direction appear to be crucial in terms of type of the mesophase formation.
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.
Lawson, D. D.
1979-01-01
A group additivity method is generated which allows estimation, from the structural formulas alone, of the energy of vaporization and the molar volume at 25 C of many nonpolar organic liquids. Using these two parameters and appropriate thermodynamic relations, the vapor pressure of the liquid phase and the solubility of various gases in nonpolar organic liquids are predicted. It is also possible to use the data to evaluate organic and some inorganic liquids for use in gas separation stages or liquids as heat exchange fluids in prospective thermochemical cycles for hydrogen production.
Study on solubility of Chinese herbal compound by solubility parameter%溶度参数表征中药复方溶解性能的研究
吴德智; 陈丽华; 王森; 朱卫丰; 管咏梅
2010-01-01
目的:探讨用溶度参数表征中药复方的溶解性能.方法:通过基团贡献法和反相气相色谱法(IGC)测定良肤处方有效成分及全方混合物的Hansen三维溶度参数,利用Hansen solubility parameter in practice(HSPiP)软件绘制Hansen溶解球,考察良肤处方有效成分及全方混合物在不同溶剂中的溶解情况,并采用近似溶解度试验进行验证.结果:在Hansan溶解球中,良肤有效成分与全方混合物能溶解在正辛醇、丙酮、醋酸乙酯、三氯甲烷、乙醚中,微溶于甘油、丙二醇、甲醇、乙醇,在水中难溶,都属于脂溶性物质,这与近似溶解度试验的结果吻合.结论:可利用溶度参数对中药有效成分及复方的溶解性能进行表征,该法与传统方法相比准确、方便、直观.
Ham, Hyeong Taek; Choi, Yeong Suk; Chung, In Jae
2005-06-01
Dispersions of single-walled carbon nanotubes in various solvents and aqueous surfactant emulsions were investigated to correlate the degree of dispersion state with Hansen solubility parameters (deltat2=deltad2+deltap2+deltah2). It was found that the nanotubes were dispersed or suspended very well in the solvents with certain dispersive component (deltad) values. They were precipitated in the solvents with high polar component (deltap) values or hydrogen-bonding component (deltah) values. The solvents in the dispersed group occupied a certain region in a 3-dimensional space of three components. The surfactants with a lipophilic group equal to and longer than decyl, containing 9 methylene groups and 1 methyl group, contributed to the dispersion of nanotubes in water. The surfactants in the dispersed group had a lower limit in the dispersive component (deltad) of the Hansen parameter.
Indecomposability parameters in chiral Logarithmic Conformal Field Theory
Vasseur, Romain; Saleur, Hubert
2011-01-01
Work of the last few years has shown that the key algebraic features of Logarithmic Conformal Field Theories (LCFTs) are already present in some finite lattice systems (such as the XXZ spin-1/2 chain) before the continuum limit is taken. This has provided a very convenient way to analyze the structure of indecomposable Virasoro modules and to obtain fusion rules for a variety of models such as (boundary) percolation etc. LCFTs allow for additional quantum numbers describing the fine structure of the indecomposable modules, and generalizing the `b-number' introduced initially by Gurarie for the c=0 case. The determination of these indecomposability parameters has given rise to a lot of algebraic work, but their physical meaning has remained somewhat elusive. In a recent paper, a way to measure b for boundary percolation and polymers was proposed. We generalize this work here by devising a general strategy to compute matrix elements of Virasoro generators from the numerical analysis of lattice models and their ...
Diehn, Kevin K; Oh, Hyuntaek; Hashemipour, Reza; Weiss, Richard G; Raghavan, Srinivasa R
2014-04-21
Many small molecules can self-assemble by non-covalent interactions into fibrous networks and thereby induce gelation of organic liquids. However, no capability currently exists to predict whether a molecule in a given solvent will form a gel, a low-viscosity solution (sol), or an insoluble precipitate. Gelation has been recognized as a phenomenon that reflects a balance between solubility and insolubility; however, the distinction between these regimes has not been quantified in a systematic fashion. In this work, we focus on a well-known gelator, 1,3:2,4-dibenzylidene sorbitol (DBS), and study its self-assembly in various solvents. From these data, we build a framework for DBS gelation based on Hansen solubility parameters (HSPs). While the HSPs for DBS are not known a priori, the HSPs are available for each solvent and they quantify the solvent's ability to interact via dispersion, dipole-dipole, and hydrogen bonding interactions. Using the three HSPs, we construct three-dimensional plots showing regions of solubility (S), slow gelation (SG), instant gelation (IG), and insolubility (I) for DBS in the different solvents at a given temperature and concentration. Our principal finding is that the above regions radiate out as concentric shells: i.e., a central solubility (S) sphere, followed in order by spheres corresponding to SG, IG, and I regions. The distance (R0) from the origin of the central sphere quantifies the incompatibility between DBS and a solvent-the larger this distance, the more incompatible the pair. The elastic modulus of the final gel increases with R0, while the time required for a super-saturated sol to form a gel decreases with R0. Importantly, if R0 is too small, the gels are weak, but if R0 is too large, insolubility occurs-thus, strong gels fall within an optimal window of incompatibility between the gelator and the solvent. Our approach can be used to design organogels of desired strength and gelation time by judicious choice of a
Ma, Jing; Larsen, Raino Mikael
2013-02-01
Dispersion and interfacial strain transfer of single walled carbon nanotubes (SWNTs) are two major challenges for the utilization of SWNTs as reinforcements in polymer composites. Surface modifications could help change the dispersion and interfacial properties. In this study, nanocomposites were fabricated by solution blending 1 wt % SWNTs with various modification (nonmodified, nitric acid functionalized, and amine functionalized SWNTs) and three kinds of polymeric materials (polycarbonate, polyvinylidene fluoride, and epoxy). Chemical compatibilities between SWNTs and solvents or polymers are calculated by the Hansen solubility parameters (HSP) method. The dispersion of the SWNTs in solvents is evaluated by dynamic light scattering. The dispersion of SWNTs in polymers evaluated by a light optical microscope (LOM) generally agrees with the HSP prediction. The strain transfer from the matrix to SWNTs is mainly related to the dispersion, the bundle size, the residual thermal stresses on the sample, and, to lesser degree, the HSP.
Ma, Jing; Larsen, Mikael
2013-01-01
Dispersion and interfacial strain transfer of single walled carbon nanotubes (SWNTs) are two major challenges for the utilization of SWNTs as reinforcements in polymer composites. Surface modifications could help change the dispersion and interfacial properties. In this study, nanocomposites were...... fabricated by solution blending 1 wt % SWNTs with various modification (nonmodified, nitric acid functionalized, and amine functionalized SWNTs) and three kinds of polymeric materials (polycarbonate, polyvinylidene fluoride, and epoxy). Chemical compatibilities between SWNTs and solvents or polymers...... are calculated by the Hansen solubility parameters (HSP) method. The dispersion of the SWNTs in solvents is evaluated by dynamic light scattering. The dispersion of SWNTs in polymers evaluated by a light optical microscope (LOM) generally agrees with the HSP prediction. The strain transfer from the matrix...
STUDY OF SINGLE WALLED CARBON NANOTUBE REINFORCED POLYMER COMPOSITES BY HANSEN SOLUBILITY PARAMETERS
Ma, Jing
Single Walled carbon nanotubes (SWNTs) possess superior mechanical, thermal and electrical properties. The use of SWNTs as a reinforcement in polymer matrix is a hot research topic. However, the poor dispersion of SWNTs in polymers and the weak interface between the nanotubes and polymers are two...... the chemical compatibility between polymer and SWNTs, and correlate the parameters with the dispersion of SWNTs and interfacial properties between SWNTs and polymers. Several different surface modifications on carbon nanotubes and different polymers are considered. The dispersion of SWNTs in solvents...... is evaluated by Dynamic Light scattering (DLS). The functional groups attached to SWNTs and degree of functionalization, and also the size of the nanotubes affect the HSP of the SWNTs. The extent by which functionalization take place is affected by the amount of defects on the nanotube surface. The strain...
Xiaohui, Niu; Nana, Li; Jingbo, Xia; Dingyan, Chen; Yuehua, Peng; Yang, Xiao; Weiquan, Wei; Dongming, Wang; Zengzhen, Wang
2013-09-07
Protein solubility plays a major role and has strong implication in the proteomics. Predicting the propensity of a protein to be soluble or to form inclusion body is a fundamental and not fairly resolved problem. In order to predict the protein solubility, almost 10,000 protein sequences were downloaded from NCBI. Then the sequences were eliminated for the high homologous similarity by CD-HIT. Thus, there were 5692 sequences remained. Based on protein sequences, amino acid and dipeptide compositions were generally extracted to predict protein solubility. In this study, the entropy in information theory was introduced as another predictive factor in the model. Experiments involving nine different feature vector combinations, including the above-mentioned three kinds of factors, were conducted with support vector machines (SVMs) as prediction engine. Each combination was evaluated by re-substitution test and 10-fold cross-validation test. According to the evaluation results, the accuracies and Matthew's Correlation Coefficient (MCC) values were boosted by the introduction of the entropy. The best combination was the one with amino acid, dipeptide compositions and their entropies. Its accuracy reached 90.34% and Matthew's Correlation Coefficient (MCC) value was 0.7494 in re-substitution test, while 88.12% and 0.7945 respectively for 10-fold cross-validation. In conclusion, the introduction of the entropy significantly improved the performance of the predictive method. Copyright © 2013. Published by Elsevier Ltd.
Neves, Catarina M S S; Held, Christoph; Mohammad, Sultan; Schleinitz, Miko; Coutinho, João A P; Freire, Mara G
2015-12-21
Due to scarce available experimental data, as well as due to the absence of predictive models, the influence of salts on the solubility of ionic liquids (ILs) in water is still poorly understood. To this end, this work addresses the solubility of the IL 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C4C1im][NTf2]), at 298.15 K and 0.1 MPa, in aqueous salt solutions (from 0.1 to 1.5 mol kg(-1)). At salt molalities higher than 0.2 mol kg(-1), all salts caused salting-out of [C4C1im][NTf2] from aqueous solution with their strength decreasing in the following order: Al2(SO4)3 > ZnSO4 > K3C6H5O7 > KNaC4H4O6 > K3PO4 > Mg(CH3CO2)2 > K2HPO4 > MgSO4 > KH2PO4 > KCH3CO2. Some of these salts lead however to the salting-in of [C4C1im][NTf2] in aqueous medium at salt molalities lower than 0.2 mol kg(-1). To attempt the development of a model able to describe the salt effects, comprising both the salting-in and salting-out phenomena observed, the electrolyte Perturbed-Chain Statistical Associating Fluid Theory (ePC-SAFT) was applied using ion-specific parameters. The gathered experimental data was modelled using ePC-SAFT parameters complemented by fitting a single binary parameter between K(+) and the IL-ions to the IL solubility in K3PO4 aqueous solutions. Based on this approach, the description of anion-specific salting-out effects of the remaining potassium salts was found to be in good agreement with experimental data. Remarkably, ePC-SAFT is even able to predict the salting-in effect induced by K2HPO4, based on the single K(+)/IL-ions binary parameter which was fitted to an exclusively salting-out effect promoted by K3PO4. Finally, ePC-SAFT was applied to predict the influence of other sodium salts on the [C4C1im][NTf2] solubility in water, with experimental data taken from literature, leading to an excellent description of the liquid-liquid phase behaviour.
Renormalized parameters and perturbation theory in dynamical mean-field theory for the Hubbard model
Hewson, A. C.
2016-11-01
We calculate the renormalized parameters for the quasiparticles and their interactions for the Hubbard model in the paramagnetic phase as deduced from the low-energy Fermi-liquid fixed point using the results of a numerical renormalization-group calculation (NRG) and dynamical mean-field theory (DMFT). Even in the low-density limit there is significant renormalization of the local quasiparticle interaction U ˜, in agreement with estimates based on the two-particle scattering theory of J. Kanamori [Prog. Theor. Phys. 30, 275 (1963), 10.1143/PTP.30.275]. On the approach to the Mott transition we find a finite ratio for U ˜/D ˜ , where 2 D ˜ is the renormalized bandwidth, which is independent of whether the transition is approached by increasing the on-site interaction U or on increasing the density to half filling. The leading ω2 term in the self-energy and the local dynamical spin and charge susceptibilities are calculated within the renormalized perturbation theory (RPT) and compared with the results calculated directly from the NRG-DMFT. We also suggest, more generally from the DMFT, how an approximate expression for the q ,ω spin susceptibility χ (q ,ω ) can be derived from repeated quasiparticle scattering with a local renormalized scattering vertex.
Ottonello, Giulio, E-mail: giotto@dipteris.unige.it [DISTAV, Università di Genova, Corso Europa 26, 16132 Genova (Italy); Richet, Pascal [Institut de Physique du Globe, Rue Jussieu 2, 75005 Paris (France)
2014-01-28
The existing solubility data on noble gases in high-temperature silicate melts have been analyzed in terms of Scaling Particle Theory coupled with an ab initio assessment of the electronic, dispersive, and repulsive energy terms based on the Polarized Continuum Model (PCM). After a preliminary analysis of the role of the contracted Gaussian basis sets and theory level in reproducing appropriate static dipole polarizabilities in a vacuum, we have shown that the procedure returns Henry's law constants consistent with the values experimentally observed in water and benzene at T = 25 °C and P = 1 bar for the first four elements of the series. The static dielectric constant (ε) of the investigated silicate melts and its optical counterpart (ε{sup ∞}) were then resolved through the application of a modified form of the Clausius-Mossotti relation. Argon has been adopted as a probe to depict its high-T solubility in melts through an appropriate choice of the solvent diameter σ{sub s}, along the guidelines already used in the past for simple media such as water or benzene. The σ{sub s} obtained was consistent with a simple functional form based on the molecular volume of the solvent. The solubility calculations were then extended to He, Ne, and Kr, whose dispersive and repulsive coefficients are available from theory and we have shown that their ab initio Henry's constants at high T reproduce the observed increase with the static polarizability of the series element with reasonable accuracy. At room temperature (T = 25 °C) the calculated Henry's constants of He, Ne, Ar, and Kr in the various silicate media predict higher solubilities than simple extrapolations (i.e., Arrhenius plots) based on high-T experiments and give rise to smooth trends not appreciably affected by the static polarizabilities of the solutes. The present investigation opens new perspectives on a wider application of PCM theory which can be extended to materials of great
Solubility parameter of polysulfone
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of polystyrene
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Barra, J; Peña, M A; Bustamante, P
2000-04-01
The aim of this study is to propose, for the first time, a set of group molar constants for sodium to calculate the partial solubility parameters of sodium salts. The values were estimated using the few experimental partial solubility parameters of acid/sodium salt series available either from the literature (benzoic acid/Na, ibuprofen acid/Na, diclofenac Na) or determined in this work (salicylic acid/Na, p-aminobenzoic acid/Na, diclofenac), the group contribution method of van Krevelen to calculate the partial parameters of the acids, and three reasonable hypothesis. The experimental method used is a modification of the extended Hansen approach based on a regression analysis of the solubility mole fraction of the drug lnX(2) against models including three- or four-partial solubility parameters of a series of pure solvents ranging from non-polar (heptane) to highly polar (water). The modified method combined with the four-parameter model provided the best results for both acids and sodium derivatives. The replacement of the acidic proton by sodium increased the dipolar and basic partial solubility parameters, whereas the dispersion parameter remained unaltered, thus increasing the overall total solubility parameter of the salt. The proposed group molar constants of sodium are consistent with the experimental results as sodium has a relatively low London dispersion molar constant (identical to that of -OH), a very high Keesom dipolar molar constant (identical to that of -NO(2), two times larger than that of -OH), and a very high hydrogen bonding molar constant (identical to that of -OH). The proposed values are: F((Na)d)=270 (J cm(3))(1/2) mol(-1); F((Na)p)=1030 (J cm(3))(1/2) mol(-1); U((Na)h)=17000 J mol(-1). Like the constants for the other groups, the group molar constants proposed for sodium are certainly not the exact values. However, they are believed to be a fair approximation of the impact of sodium on the partial solubility parameters and, therefore, can
陆向红; 杨云财; 计建炳
2011-01-01
Solubility Parameters of fatty acid methyl esters (FAMEs) were calculated by group contribution methods.Results showed that solubility parameters of FAMEs increased with the chain length, but were not affected by the degree of unsaturation.KB values and extraction ability of FAMEs for pyridine in water were measured and compared with solubility parameters.It was shown that the consistency existed among KB value, extraction ability and solubility parameters.Hansen solubility parameters of FAMEs calculated by group contribution methods could reflect the solvency of FAMEs.Solubility parameter of FAMEs, organic solvents and organic impurities were compared.Results showed that FAMEs could instead of organic solvents and be used in industrial fields.FAMEs were a promising green solvent because of its safety, non -toxicity and bio -degradability.%采用基团贡献法计算了单个脂肪酸甲酯的溶解度参数,发现脂肪酸甲酯的溶解度参数随着碳链的增长而降低,而碳链不饱和度的增大对其影响有限.测定了几种脂肪酸甲酯的KB值,考察了生物柴油萃取废水中苯酚的萃取性能,并将其与脂肪酸甲酯的溶解度参数进行了比较,结果显示利用基团贡献法计算得到的脂肪酸甲酯的Hansen溶解度参数可以很好地反映脂肪酸甲酯的溶解性能.在此基础上,比较了脂肪酸甲酯与常用有机溶剂、常见有机污染物的溶解度参数,结果发现,脂肪酸甲酯与常用有机溶剂、常见有机污染物具有相近的溶解度参数,脂肪酸甲酯可以作为一种性能优良的绿色溶剂,替代常用的有机溶剂广泛应用与工业清洗、废弃物处理等方面.
Zhang, Mohan; Selvakumar, Sermadurai; Zhang, Xinran; Sibi, Mukund P; Weiss, Richard G
2015-06-01
Creating structure-property correlations at different distance scales is one of the important challenges to the rational design of molecular gelators. Here, a series of dihydroxylated derivatives of long-chain fatty acids, derived from three naturally occurring molecules-oleic, erucic and ricinoleic acids-are investigated as gelators of a wide variety of liquids. Conclusions about what constitutes a more (or less!) efficient gelator are based upon analyses of a variety of thermal, structural, molecular modeling, and rheological results. Correlations between the manner of molecular packing in the neat solid or gel states of the gelators and Hansen solubility data from the liquids leads to the conclusion that diol stereochemistry, the number of carbon atoms separating the two hydroxyl groups, and the length of the alkanoic chains are the most important structural parameters controlling efficiency of gel formation for these gelators. Some of the diol gelators are as efficient or even more efficient than the well-known, excellent gelator, (R)-12-hydroxystearic acid; others are much worse. The ability to form extensive intermolecular H-bonding networks along the alkyl chains appears to play a key role in promoting fiber growth and, thus, gelation. In toto, the results demonstrate how the efficiency of gelation can be modulated by very small structural changes and also suggest how other structural modifications may be exploited to create efficient gelators.
On the estimation of water pure compound parameters in association theories
Grenner, Andreas; Kontogeorgis, Georgios; Michelsen, Michael Locht;
2007-01-01
Determination of the appropriate number of association sites and estimation of parameters for association (SAFT-type) theories is not a trivial matter. Building further on a recently published manuscript by Clark et al., this work investigates aspects of the parameter estimation for water using two...... different association theories. Their performance for various properties as well as against the results presented earlier is demonstrated....
Loss aversion under prospect theory: A parameter-free measurement
M. Abdellaoui (Mohammed); H. Bleichrodt (Han); C. Paraschiv (Corina)
2007-01-01
textabstractA growing body of qualitative evidence shows that loss aversion, a phenomenon formalized in prospect theory, can explain a variety of field and experimental data. Quantifications of loss aversion are, however, hindered by the absence of a general preference-based method to elicit the uti
Loss Aversion under Prospect Theory: a Parameter-Free Measurement
H. Bleichrodt (Han); M. Abdellaoui (Mohammed); C. Paraschiv (Corina)
2007-01-01
textabstractA growing body of qualitative evidence shows that loss aversion, a phenomenon formalized in prospect theory, can explain a variety of field and experimental data. Quantifications of loss aversion are, however, hindered by the absence of a general preference-based method to elicit the uti
Loss Aversion under Prospect Theory: a Parameter-Free Measurement
H. Bleichrodt (Han); M. Abdellaoui (Mohammed); C. Paraschiv (Corina)
2007-01-01
textabstractA growing body of qualitative evidence shows that loss aversion, a phenomenon formalized in prospect theory, can explain a variety of field and experimental data. Quantifications of loss aversion are, however, hindered by the absence of a general preference-based method to elicit the
Loss aversion under prospect theory: A parameter-free measurement
M. Abdellaoui (Mohammed); H. Bleichrodt (Han); C. Paraschiv (Corina)
2007-01-01
textabstractA growing body of qualitative evidence shows that loss aversion, a phenomenon formalized in prospect theory, can explain a variety of field and experimental data. Quantifications of loss aversion are, however, hindered by the absence of a general preference-based method to elicit the
Kuraev, E A; Torosyan, H T
2013-01-01
Using the Coulomb correction to the screening angular parameter of the Moliere multiple scattering theory we obtained analytically and numerically the Coulomb corrections to the quantities of the Migdal LPM effect theory. We showed that the Coulomb corrections to the spectral bremsstrahlung rate allow completely to eliminate the discrepancy between the predictions of the LPM effect theory and its measuremens and also additionally improve the agreement between predictions of the LPM effect theory analogue for a thin target and experimental data.
Invariant slow-roll parameters in scalar-tensor theories
Kuusk, Piret; Rünkla, Mihkel; Saal, Margus; Vilson, Ott
2016-10-01
A general scalar-tensor theory can be formulated in different parametrizations that are related by a conformal rescaling of the metric and a scalar field redefinition. We compare formulations of slow-roll regimes in the Einstein and Jordan frames using quantities that are invariant under the conformal rescaling of the metric and transform as scalar functions under the reparametrization of the scalar field. By comparing spectral indices, calculated up to second order, we find that the frames are equivalent up to this order, due to the underlying assumptions.
Invariant slow-roll parameters in scalar-tensor theories
Kuusk, Piret; Saal, Margus; Vilson, Ott
2016-01-01
A general scalar-tensor theory can be formulated in different parametrizations that are related by a conformal rescaling of the metric and a scalar field redefinition. We compare formulations of slow-roll regimes in the Einstein and Jordan frames using quantities that are invariant under the conformal rescaling of the metric and transform as scalar functions under the reparametrization of the scalar field. By comparing spectral indices, calculated up to second order, we find that the frames are equivalent up to this order, due to the underlying assumptions.
Demian, B A
2000-10-06
The solubility isotherms of nineteen aromatics and terpenes in aqueous hydroxypropyl-beta-cyclodextrin were determined to be straight lines. This is explained by the host-guest complexation which is characteristic for the whole class of cyclodextrins and derivatives. The slopes of the solubility isotherms correlate with Sterimol L and log P(ow) as descriptors of the steric fit and hydrophobicity match, in accord with the qualitative representation of the phenomenon.
Bustamante, P; Pena, M A; Barra, J
2000-01-20
Sodium salts are often used in drug formulation but their partial solubility parameters are not available. Sodium alters the physical properties of the drug and the knowledge of these parameters would help to predict adhesion properties that cannot be estimated using the solubility parameters of the parent acid. This work tests the applicability of the modified extended Hansen method to determine partial solubility parameters of sodium salts of acidic drugs containing a single hydrogen bonding group (ibuprofen, sodium ibuprofen, benzoic acid and sodium benzoate). The method uses a regression analysis of the logarithm of the experimental mole fraction solubility of the drug against the partial solubility parameters of the solvents, using models with three and four parameters. The solubility of the drugs was determined in a set of solvents representative of several chemical classes, ranging from low to high solubility parameter values. The best results were obtained with the four parameter model for the acidic drugs and with the three parameter model for the sodium derivatives. The four parameter model includes both a Lewis-acid and a Lewis-base term. Since the Lewis acid properties of the sodium derivatives are blocked by sodium, the three parameter model is recommended for these kind of compounds. Comparison of the parameters obtained shows that sodium greatly changes the polar parameters whereas the dispersion parameter is not much affected. Consequently the total solubility parameters of the salts are larger than for the parent acids in good agreement with the larger hydrophilicity expected from the introduction of sodium. The results indicate that the modified extended Hansen method can be applied to determine the partial solubility parameters of acidic drugs and their sodium salts.
[The parameters of a feminist theory of psychotherapy.].
Corbeil, J
1979-01-01
After recalling the origins of the feminist approach to therapy, and of the teaching of psych logy from the 1950's to the introduction of the first groups of self-therapy in 1967-1968, the author presents the basic principles of the traditional therapy that she qualifies as sexist. She then describ the analytical tools developed from the social psychology that the feminists and the radical therapis use to understand the different behavior and pathology of men and women. Finally, she adheres a theory of the personnality sharing with feminity the following features : humanistic philosoph favoring direct expression, speaking of reappropriation, seeing the unconscious and the conscious a continuous process, and considering the unit living-system-and-environment as a whole.
Kolak, Jonathan J.; Burruss, Robert A.
2014-01-01
Samples of three high volatile bituminous coals were subjected to parallel sets of extractions involving solvents dichloromethane (DCM), carbon disulfide (CS2), and supercritical carbon dioxide (CO2) (40 °C, 100 bar) to study processes affecting coal–solvent interactions. Recoveries of perdeuterated surrogate compounds, n-hexadecane-d34 and four polycyclic aromatic hydrocarbons (PAHs), added as a spike prior to extraction, provided further insight into these processes. Soxhlet-DCM and Soxhlet-CS2 extractions yielded similar amounts of extractable organic matter (EOM) and distributions of individual hydrocarbons. Supercritical CO2 extractions (40 °C, 100 bar) yielded approximately an order of magnitude less EOM. Hydrocarbon distributions in supercritical CO2 extracts generally mimicked distributions from the other solvent extracts, albeit at lower concentrations. This disparity increased with increasing molecular weight of target hydrocarbons. Five- and six-ring ring PAHs generally were not detected and no asphaltenes were recovered in supercritical CO2 extractions conducted at 40 °C and 100 bar. Supercritical CO2 extraction at elevated temperature (115 °C) enhanced recovery of four-ring and five-ring PAHs, dibenzothiophene (DBT), and perdeuterated PAH surrogate compounds. These results are only partially explained through comparison with previous measurements of hydrocarbon solubility in supercritical CO2. Similarly, an evaluation of extraction results in conjunction with solubility theory (Hildebrand and Hansen solubility parameters) does not fully account for the hydrocarbon distributions observed among the solvent extracts. Coal composition (maceral content) did not appear to affect surrogate recovery during CS2 and DCM extractions but might affect supercritical CO2 extractions, which revealed substantive uptake (partitioning) of PAH surrogates into the coal samples. This uptake was greatest in the sample (IN-1) with the highest vitrinite content. These
Juanes, Ruben
2011-11-01
The large-scale injection and storage of carbon dioxide (CO2) into deep saline aquifers is a promising tool for reducing atmospheric CO2 emissions to mitigate climate change. Success of geologic sequestration relies on trapping the buoyant CO2, to minimize the risk of leakage into shallower formations through pre- existing wells, fractures or faults. However, traditional reservoir-simulation tools are currently unable to resolve the impact of small-scale trapping processes on fluid flow at the scale of a geologic basin. Here, we formulate a sharp-interface mathematical model for the post-injection migration of a CO2 plume driven by groundwater flow in a sloping aquifer, subject to both capillary trapping and CO2 dissolution by convective mixing. We develop semi-analytical solutions that elucidate the nontrivial interplay between the two trapping mechanisms, and how their synergetic action controls plume migration. We validate the theory by means of laboratory experiments with analogue fluids to study how convective mixing arrests the buoyant current. We use our findings to estimate the dimensionless rate of solubility trapping for several large saline aquifers in the United States, and assess the importance of solubility trapping in practice.
Cosmological parameter dependence in local string theories of structure formation
Copeland, E J; Steer, D A; Magueijo, Joao
2000-01-01
We perform the most accurate study to date of the dependence on cosmological parameters of structure formation with local cosmic strings. The crucial new ingredients are the inclusion of the effects of gravitational backreaction on the evolution of the network, and the accurate evolution of the network through the radiation to matter transition. Our work re-iterates the fact that expanding Universe numerical simulations only probe a transient regime, and we incorporate our results into the unequal time correlators recently measured. We then compute the CMB and CDM fluctuations' power spectra for various values of the Hubble constant $H_0$ and baryon fraction $\\Omega_b$. We find that, whereas the dependence on $\\Omega_b$ is negligible, there is still a strong dependence on $H_0$.
姜广策; 林雄超; 张生娟; 王中奇; 王永刚; 陈强; 朱豫飞
2015-01-01
以丙酮、异丙醇和苯为溶剂在超临界状态下对煤直接液化残渣进行萃取，应用溶度参数分析了超临界萃取环境中溶剂和萃取原料的变化；基于Hansen拓展方法建立了关联Hansen溶度参数和萃取收率的理论方程。结果表明，临界温度较高。以色散力溶度参数为主的苯的萃取收率明显高于其它2种溶剂；液化残渣中可萃出组分的理想溶解度随温度的升高而增大，该效应也是超临界溶剂萃取重质组分时萃取收率提高的重要原因；萃取收率与Hansen溶度参数之间的回归模型与实验结果具有较好的一致性，证明Hansen溶度参数理论和Hansen拓展方法适用于描述煤直接液化残渣的超临界萃取过程。%The supercritical fluid extraction( SFE) of direct coal liquefaction residue using acetone, isopro-panol and benzene as solvents was investigated. The Hansen solubility parameters were used to clarify the variations of both solvent and the solute in SFE process. An empirical equation in terms of the extended Hansen approach was proposed to correlate the extraction capacity with the Hansen solubility parameters of solvents. The results show that the extraction yield using supercritical benzene, of which the dispersive compo-nent is the major in total solubility parameters, obtained the highest extraction yield. The ideal solubility on organic components in direct coal liquefaction residue improved with the extraction temperature increasing. The empirical equation shows high consistency with experimental results. As a consequence, the theory of Hansen solubility parameter and extended Hansen approach are applicable to the study on supercritical fluid extraction of direct coal liquefaction residue.
Testing scalar-tensor theories and PPN parameters in Earth orbit
Schärer, Andreas; Bondarescu, Ruxandra; Jetzer, Philippe; Lundgren, Andrew
2014-01-01
We compute the PPN parameters $\\gamma$ and $\\beta$ for general scalar-tensor theories in the Einstein frame, which we compare to the existing PPN formulation in the Jordan frame for alternative theories of gravity. This computation is important for scalar-tensor theories that are expressed in the Einstein frame, such as chameleon and symmetron theories, which can incorporate hiding mechanisms that predict environment-dependent PPN parameters. We introduce a general formalism for scalar-tensor theories and constrain it using the limit on $\\gamma$ given by the Cassini experiment. In particular we discuss massive Brans-Dicke scalar fields for extended sources. Next, using a recently proposed Earth satellite experiment, in which atomic clocks are used for spacecraft tracking, we compute the observable perturbations in the redshift induced by PPN parameters deviating from their general relativistic values. Our estimates suggest that $|\\gamma - 1| \\sim |\\beta -1| \\sim 10^{-6}$ may be detectable by a satellite that ...
A Theory and Method for Modeling of Structures with Stochastic Parameters
ZHANG Bei; YIN Xue-gang; WANG Fu-ming; ZHONG Yan-hui; CAI Ying-chun
2004-01-01
In order to reflect the stochastic characteristics of structures more comprehensively and accurately, a theory and method for modeling of structures with stochastic parameters is presented by using probability finite element method and stochastic experiment data of structures based on the modeling of structures with deterministic parameters. Double-decker space frame is taken as an example to validate this theory and method, good results are gained.
On jet quenching parameters in strongly coupled non-conformal gauge theories
Buchel, A
2006-01-01
Recently Liu, Rajagopal and Wiedemann (LRW) [hep-ph/0605178] proposed a first principle, nonperturbative quantum field theoretic definition of ``jet quenching parameter'' \\hat{q} used in models of medium-induced radiative parton energy loss in nucleus-nucleus collisions at RHIC. Relating \\hat{q} to a short-distance behavior of a certain light-like Wilson loop, they used gauge theory-string theory correspondence to evaluate \\hat{q} for the strongly coupled N=4 SU(N_c) gauge theory plasma. We generalize analysis of LRW to strongly coupled non-conformal gauge theory plasma. We find that a jet quenching parameter is gauge theory specific (not universal). Furthermore, it appears it's value increases as the number of effective adjoint degrees of freedom of a gauge theory plasma increases.
溶胀法测定HNBR的溶解度参数%Determination of Solubility Parameters of HNBR with Swelling Method
刘广永; 商元元; 曾艳; 王义亮; 邱桂学
2012-01-01
测定了Therban2007,Therban3407,Therban4307和Therban5008 4种氢化丁腈橡胶(HNBR)的溶解度参数,并与其预测值进行了对比.结果表明,溶解度参数的测定值略小于预测值,4种不同丙烯腈含量的HNBR具有相似的溶胀性能,HNBR的溶解度参数范围均为18～22 (J/cm3)1/2.溶解度参数在18～22(J/cm3)1/2的溶剂可有效地溶胀HNBR.%The solubility parameter of hydrogenated nitrile rubber (HNBR) of Therban2007, Therban3407, Therban4307 and Therban5008 were determined and compared with the predicted values. The results showed that the determined values were slightly less than the predicted values, the four kinds of HNBR with different acrylonitrile content exhibited similar swelling properties, and the range of solubility parameter of HNBR was 18～22 (J/cm3)1/2. The solvents with the numerical value of solubility parameter in the range of 18～22 (J/cm3)1/2 could effectively swell the HNBR.
Ramsay-Curve Item Response Theory for the Three-Parameter Logistic Item Response Model
Woods, Carol M.
2008-01-01
In Ramsay-curve item response theory (RC-IRT), the latent variable distribution is estimated simultaneously with the item parameters of a unidimensional item response model using marginal maximum likelihood estimation. This study evaluates RC-IRT for the three-parameter logistic (3PL) model with comparisons to the normal model and to the empirical…
Determination of the QCD Λ Parameter and the Accuracy of Perturbation Theory at High Energies.
Dalla Brida, Mattia; Fritzsch, Patrick; Korzec, Tomasz; Ramos, Alberto; Sint, Stefan; Sommer, Rainer
2016-10-28
We discuss the determination of the strong coupling α_{MS[over ¯]}(m_{Z}) or, equivalently, the QCD Λ parameter. Its determination requires the use of perturbation theory in α_{s}(μ) in some scheme s and at some energy scale μ. The higher the scale μ, the more accurate perturbation theory becomes, owing to asymptotic freedom. As one step in our computation of the Λ parameter in three-flavor QCD, we perform lattice computations in a scheme that allows us to nonperturbatively reach very high energies, corresponding to α_{s}=0.1 and below. We find that (continuum) perturbation theory is very accurate there, yielding a 3% error in the Λ parameter, while data around α_{s}≈0.2 are clearly insufficient to quote such a precision. It is important to realize that these findings are expected to be generic, as our scheme has advantageous properties regarding the applicability of perturbation theory.
Determination of deuterium–tritium critical burn-up parameter by four temperature theory
Nazirzadeh, M.; Ghasemizad, A. [Department of Physics, University of Guilan, 41335-1914 Rasht (Iran, Islamic Republic of); Khanbabei, B. [School of Physics, Damghan University, 36716-41167 Damghan (Iran, Islamic Republic of)
2015-12-15
Conditions for thermonuclear burn-up of an equimolar mixture of deuterium-tritium in non-equilibrium plasma have been investigated by four temperature theory. The photon distribution shape significantly affects the nature of thermonuclear burn. In three temperature model, the photon distribution is Planckian but in four temperature theory the photon distribution has a pure Planck form below a certain cut-off energy and then for photon energy above this cut-off energy makes a transition to Bose-Einstein distribution with a finite chemical potential. The objective was to develop four temperature theory in a plasma to calculate the critical burn up parameter which depends upon initial density, the plasma components initial temperatures, and hot spot size. All the obtained results from four temperature theory model are compared with 3 temperature model. It is shown that the values of critical burn-up parameter calculated by four temperature theory are smaller than those of three temperature model.
Lan, Yaqi; Corradini, Maria G; Liu, Xia; May, Tim E; Borondics, Ferenc; Weiss, Richard G; Rogers, Michael A
2014-12-02
Solvent properties play a central role in mediating the aggregation and self-assembly of molecular gelators and their growth into fibers. Numerous attempts have been made to correlate the solubility parameters of solvents and gelation abilities of molecular gelators, but a comprehensive comparison of the most important parameters has yet to appear. Here, the degree to which partition coefficients (log P), Henry's law constants (HLC), dipole moments, static relative permittivities (ε(r)), solvatochromic E(T)(30) parameters, Kamlet-Taft parameters (β, α, and π), Catalan's solvatochromic parameters (SPP, SB, and SA), Hildebrand solubility parameters (δ(i)), and Hansen solubility parameters (δ(p), δ(d), δ(h)) and the associated Hansen distance (R(ij)) of 62 solvents (covering a wide range of properties) can be correlated with the self-assembly and gelation of 1,3:2,4-dibenzylidene sorbitol (DBS) gelation, a classic molecular gelator, is assessed systematically. The approach presented describes the basis for each of the parameters and how it can be applied. As such, it is an instructional blueprint for how to assess the appropriate type of solvent parameter for use with other molecular gelators as well as with molecules forming other types of self-assembled materials. The results also reveal several important insights into the factors favoring the gelation of solvents by DBS. The ability of a solvent to accept or donate a hydrogen bond is much more important than solvent polarity in determining whether mixtures with DBS become solutions, clear gels, or opaque gels. Thermodynamically derived parameters could not be correlated to the physical properties of the molecular gels unless they were dissected into their individual HSPs. The DBS solvent phases tend to cluster in regions of Hansen space and are highly influenced by the hydrogen-bonding HSP, δ(h). It is also found that the fate of this molecular gelator, unlike that of polymers, is influenced not only by
Molecular Thermodynamic Modeling of Mixed Solvent Solubility
Ellegaard, Martin Dela; Abildskov, Jens; O’Connell, John P.
2010-01-01
A method based on statistical mechanical fluctuation solution theory for composition derivatives of activity coefficients is employed for estimating dilute solubilities of 11 solid pharmaceutical solutes in nearly 70 mixed aqueous and nonaqueous solvent systems. The solvent mixtures range from...... nearly ideal to strongly nonideal. The database covers a temperature range from 293 to 323 K. Comparisons with available data and other existing solubility methods show that the method successfully describes a variety of observed mixed solvent solubility behaviors using solute−solvent parameters from...
Li, Yan; Zheng, Jinkai; Xiao, Hang; McClements, David Julian
2011-01-01
Polymethoxyflavones (PMFs) extracted from citrus peel exhibit potent anti-cancer activity, but are highly hydrophobic molecules with poor solubility in both water and oil at ambient and body temperature, which limits their bioavailability. The possibility of encapsulating PMFs within nanoemulsion-based delivery systems to facilitate their application in nutraceutical and pharmaceutical products was investigated. The influence of oil type (corn oil, MCT, orange oil), emulsifier type (β-lactogl...
An approximation theory for the identification of nonlinear distributed parameter systems
Banks, H. T.; Reich, Simeon; Rosen, I. G.
1990-01-01
An abstract approximation framework for the identification of nonlinear distributed parameter systems is developed. Inverse problems for nonlinear systems governed by strongly maximal monotone operators (satisfying a mild continuous dependence condition with respect to the unknown parameters to be identified) are treated. Convergence of Galerkin approximations and the corresponding solutions of finite dimensional approximating identification problems to a solution of the original finite dimensional identification problem is demonstrated using the theory of nonlinear evolution systems and a nonlinear analog of the Trotter-Kato appproximation result for semigroups of bounded linear operators. The nonlinear theory developed here is shown to subsume an existing linear theory as a special case. It is also shown to be applicable to a broad class of nonlinear elliptic operators and the corresponding nonlinear parabolic partial differential equations to which they lead. An application of the theory to a quasilinear model for heat conduction or mass transfer is discussed.
Li, Yan; Zheng, Jinkai; Xiao, Hang; McClements, David Julian
2012-06-01
Polymethoxyflavones (PMFs) extracted from citrus peel exhibit potent anti-cancer activity, but are highly hydrophobic molecules with poor solubility in both water and oil at ambient and body temperature, which limits their bioavailability. The possibility of encapsulating PMFs within nanoemulsion-based delivery systems to facilitate their application in nutraceutical and pharmaceutical products was investigated. The influence of oil type (corn oil, MCT, orange oil), emulsifier type (β-lactoglobulin, lyso-lecithin, Tween, and DTAB), and neutral cosolvents (glycerol and ethanol) on the formation and stability of PMF-loaded nanoemulsions was examined. Nanoemulsions (r emulsifier types, except DTAB. Lipid droplet charge could be altered from highly cationic (DTAB), to near neutral (Tween), to highly anionic (β-lactoglobulin, lyso-lecithin) by varying emulsifier type. PMF crystals formed in all nanoemulsions after preparation, which had a tendency to sediment during storage. The size, morphology, and aggregation of PMF crystals depended on preparation method, emulsifier type, oil type, and cosolvent addition. These results have important implications for the development of delivery systems for bioactive components that have poor oil and water solubility at application temperatures.
Parameter estimation in nonlinear distributed systems - Approximation theory and convergence results
Banks, H. T.; Reich, Simeon; Rosen, I. G.
1988-01-01
An abstract approximation framework and convergence theory is described for Galerkin approximations applied to inverse problems involving nonlinear distributed parameter systems. Parameter estimation problems are considered and formulated as the minimization of a least-squares-like performance index over a compact admissible parameter set subject to state constraints given by an inhomogeneous nonlinear distributed system. The theory applies to systems whose dynamics can be described by either time-independent or nonstationary strongly maximal monotonic operators defined on a reflexive Banach space which is densely and continuously embedded in a Hilbert space. It is demonstrated that if readily verifiable conditions on the system's dependence on the unknown parameters are satisfied, and the usual Galerkin approximation assumption holds, then solutions to the approximating problems exist and approximate a solution to the original infinite-dimensional identification problem.
Krishna Kumar, P.T. [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, O-Okayama, Meguro-Ku, Tokyo 152-8550 (Japan)], E-mail: gstptk@yahoo.co.in; Sekimoto, Hiroshi [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, 2-12-1, O-Okayama, Meguro-Ku, Tokyo 152-8550 (Japan)], E-mail: hsekimot@nr.titech.ac.jp
2009-02-15
Covariance matrix elements depict the statistical and systematic uncertainties in reactor parameter measurements. All the efforts have so far been devoted only to minimise the statistical uncertainty by repeated measurements but the dominant systematic uncertainty has either been neglected or randomized. In recent years efforts has been devoted to simulate the resonance parameter uncertainty information through covariance matrices in code SAMMY. But, the code does not have any provision to check the reliability of the simulated covariance data. We propose a new approach called entropy based information theory to reduce the systematic uncertainty in the correlation matrix element so that resonance parameters with minimum systematic uncertainty can be modelled. We apply our information theory approach in generating the resonance parameters of {sup 156}Gd with reduced systematic uncertainty and demonstrate the superiority of our technique over the principal component analysis method.
A singular one-parameter family of solutions in cubic superstring field theory
Arroyo, E. Aldo
2016-05-01
Performing a gauge transformation of a simple identity-like solution of superstring field theory, we construct a one-parameter family of solutions, and by evaluating the energy associated to this family, we show that for most of the values of the parameter the solution represents the tachyon vacuum, except for two isolated singular points where the solution becomes the perturbative vacuum and the half brane solution.
Brandt, Heike; Ehmann, Thomas; Otto, Matthias
2010-08-30
The principle relating to the selection of a proper matrix, cationization reagent, and solvent for matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) of synthetic polymers is still a topic of research. In this work we focused on the selection of a suitable MALDI solvent. Polystyrene PS7600 and poly(ethylene glycol) PEG4820 were analyzed by MALDI-TOF MS using various solvents which were selected based on the Hansen solubility parameter system. For polystyrene (PS), dithranol was used as the matrix and silver trifluoroacetate as the cationization reagent whereas, for poly(ethylene glycol) (PEG), the combination of 2,5-dihydroxybenzoic acid and sodium trifluoroacetate was used for all experiments. When employing solvents which dissolve PS and PEG, reliable MALDI mass spectra were obtained while samples in non-solvents (solvents which are not able to dissolve the polymer) failed to provide spectra. It seems that the solubility of the matrix and the cationization reagent are less important than the polymer solubility.
Extended Hansen solubility approach: naphthalene in individual solvents.
Martin, A; Wu, P L; Adjei, A; Beerbower, A; Prausnitz, J M
1981-11-01
A multiple regression method using Hansen partial solubility parameters, delta D, delta p, and delta H, was used to reproduce the solubilities of naphthalene in pure polar and nonpolar solvents and to predict its solubility in untested solvents. The method, called the extended Hansen approach, was compared with the extended Hildebrand solubility approach and the universal-functional-group-activity-coefficient (UNIFAC) method. The Hildebrand regular solution theory was also used to calculate naphthalene solubility. Naphthalene, an aromatic molecule having no side chains or functional groups, is "well-behaved', i.e., its solubility in active solvents known to interact with drug molecules is fairly regular. Because of its simplicity, naphthalene is a suitable solute with which to initiate the difficult study of solubility phenomena. The three methods tested (Hildebrand regular solution theory was introduced only for comparison of solubilities in regular solution) yielded similar results, reproducing naphthalene solubilities within approximately 30% of literature values. In some cases, however, the error was considerably greater. The UNIFAC calculation is superior in that it requires only the solute's heat of fusion, the melting point, and a knowledge of chemical structures of solute and solvent. The extended Hansen and extended Hildebrand methods need experimental solubility data on which to carry out regression analysis. The extended Hansen approach was the method of second choice because of its adaptability to solutes and solvents from various classes. Sample calculations are included to illustrate methods of predicting solubilities in untested solvents at various temperatures. The UNIFAC method was successful in this regard.
Tanha, Matteus; Cappiello, Alex; Gordon, Geoffrey J; Yaron, David J
2013-01-01
A means to take advantage of molecular similarity to lower the computational cost of electronic structure theory is proposed, in which parameters are embedded into a low-cost, low-level (LL) ab initio theory and adjusted to obtain agreement with a higher level (HL) ab initio theory. This approach is explored by training such a model on data for ethane and testing the resulting model on methane, propane and butane. The electronic distribution of the molecules is varied by placing them in strong electrostatic environments consisting of random charges placed on the corners of a cube. The results find that parameters embedded in HF/STO-3G theory can be adjusted to obtain agreement, to within about 2 kcal/mol, with results of HF/6-31G theory. Obtaining this level of agreement requires the use of parameters that are functions of the bond lengths, atomic charges, and bond orders within the molecules. The argument is made that this approach provides a well-controlled means to take advantage of molecular similarity in...
Broer, H.W.; Lunter, G.A.; Vegter, G.
1998-01-01
We consider Hamiltonian systems near equilibrium that can be (formally) reduced to one degree of freedom. Spatiotemporal symmetries play a key role. The planar reduction is studied by equivariant singularity theory with distinguished parameters. The method is illustrated on the conservative spring-p
Estimation of Item Response Theory Parameters in the Presence of Missing Data
Finch, Holmes
2008-01-01
Missing data are a common problem in a variety of measurement settings, including responses to items on both cognitive and affective assessments. Researchers have shown that such missing data may create problems in the estimation of item difficulty parameters in the Item Response Theory (IRT) context, particularly if they are ignored. At the same…
Optimal and Most Exact Confidence Intervals for Person Parameters in Item Response Theory Models
Doebler, Anna; Doebler, Philipp; Holling, Heinz
2013-01-01
The common way to calculate confidence intervals for item response theory models is to assume that the standardized maximum likelihood estimator for the person parameter [theta] is normally distributed. However, this approximation is often inadequate for short and medium test lengths. As a result, the coverage probabilities fall below the given…
Optimal and Most Exact Confidence Intervals for Person Parameters in Item Response Theory Models
Doebler, Anna; Doebler, Philipp; Holling, Heinz
2013-01-01
The common way to calculate confidence intervals for item response theory models is to assume that the standardized maximum likelihood estimator for the person parameter [theta] is normally distributed. However, this approximation is often inadequate for short and medium test lengths. As a result, the coverage probabilities fall below the given…
Method for Predicting Solubilities of Solids in Mixed Solvents
Ellegaard, Martin Dela; Abildskov, Jens; O'Connell, J. P.
2009-01-01
A method is presented for predicting solubilities of solid solutes in mixed solvents, based on excess Henry's law constants. The basis is statistical mechanical fluctuation solution theory for composition derivatives of solute/solvent infinite dilution activity coefficients. Suitable approximations...... are made for a single parameter characterizing solute/solvent interactions. Comparisons with available data show that the method is successful in describing a variety of observed mixed solvent solubility behavior, including nearly ideal systems with small excess solubilities, systems with solute......-independent excess solubilities, and systems deviating from these simple rules. Successful predictions for new solvent mixtures cat? be made using limited data from other mixtures....
Rongfen Gao
2015-01-01
Full Text Available Soluble CD30 (sCD30, a transmembrane glycoprotein that belongs to the tumor necrosis factor receptor (TNFR superfamily, has been shown to be associated with various pathological conditions. This study was designed to measure the levels of serum sCD30 in patients with ankylosing spondylitis (AS and to evaluate the relationships between serum sCD30 levels and other disease severity-related indexes, including bath ankylosing spondylitis disease activity index (BASDAI, ankylosing spondylitis disease activity score (ASDAS, and bath ankylosing spondylitis functional index (BASFI. Our results demonstrated significantly elevated sCD30 levels in AS patients compared to healthy controls (HCs with mean values of 32.0±12.2 and 24.9±8.0 ng/mL, respectively (P**=0.007, suggesting a potential role of sCD30 in the pathogenesis of AS. However, no significant correlations of sCD30 with BASDAI, ASDAS, or BASFI were detected in our study (P>0.05. Therefore, sCD30 cannot be used as a reliable marker for reflecting disease activity and functional ability of AS patients.
Determination of the QCD Λ-parameter and the accuracy of perturbation theory at high energies
Dalla Brida, Mattia [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Fritzsch, Patrick [Univ. Autonoma de Madrid (Spain). Inst. de Fisica Teorica UAM/CSIC; Korzec, Tomasz [Wuppertal Univ. (Germany). Dept. of Physics; Ramos, Alberto [CERN - European Organization for Nuclear Research, Geneva (Switzerland). Theory Div.; Sint, Stefan [Trinity College Dublin (Ireland). School of Mathematics; Sommer, Rainer [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Humboldt-Universitaet, Berlin (Germany). Inst. fuer Physik; Collaboration: ALPHA Collaboration
2016-04-15
We discuss the determination of the strong coupling α{sub MS}(m{sub Z}) or equivalently the QCD Λ-parameter. Its determination requires the use of perturbation theory in α{sub s}(μ) in some scheme, s, and at some energy scale μ. The higher the scale μ the more accurate perturbation theory becomes, owing to asymptotic freedom. As one step in our computation of the Λ-parameter in three-flavor QCD, we perform lattice computations in a scheme which allows us to non-perturbatively reach very high energies, corresponding to α{sub s}=0.1 and below. We find that (continuum) perturbation theory is very accurate there, yielding a three percent error in the Λ-parameter, while data around α{sub s}∼0.2 is clearly insufficient to quote such a precision. It is important to realize that these findings are expected to be generic, as our scheme has advantageous properties regarding the applicability of perturbation theory.
Non-commutative field theory and the parameters of Lorentz violation in QED
S Aghababaei
2011-09-01
Full Text Available Non-commutative field theory as a theory including the Lorentz violation can be constructed in two different ways. In the first method, the non-commutative fields are the same as the ordinary ones while the gauge group is restricted to U(n. For example, the symmetry group of standard model in non-commutative space is U(3×(2×U(1 which can be reduced to SU(3×SU(2×U(1 by two appropriate spontaneous symmetry breaking. In contrast, in the second method, the non-commutative gauge theory can be constructed for SU(n gauge group via Seiberg- Witten map. In this work, we want to find the relation between the NC-parameter and the Lorentz violation parameters for the first method and compare our results with what is already found in the second one. At the end, we obtain new limits on non-commutative parameter by using the existing bounds on the Lorentz Violation parameters.
Bürglová, Kristýna; Hlaváč, Jan; Bartlett, John R.
2015-12-01
Silica nanoparticles with tailored properties have been developed for a variety of biomedical applications, with particular emphasis on their use as carriers for the encapsulation and controlled release of bioactive species. Among the various strategies described, silica nanoparticles with uniform mesoporosity (MSN) prepared in aqueous solution at elevated temperatures using cetyltrimethylammonium bromide as a template have a range of desirable properties. However, the processing windows available to control the dimensions and other key properties of such nanoparticles prepared using fluoride salts as catalysts have not been elucidated, with mixed products containing gel fragments and non-uniform products obtained under many conditions. Here, we present a parametric study of the synthesis of MSN under fluoride-catalysed conditions using tetraethylorthosilicate as silica precursor. The processing conditions required to produce uniform nanoparticles with controlled dimensions are elucidated, together with the conditions under which dried powders can be re-dispersed in aqueous solution after long-term storage to regenerate unaggregated nanospheres with dimensions (as measured by dynamic light scattering) comparable to those measured via scanning electron microscopy analysis of the dried material. The ability to dry and store such powders for extended periods of time is an important requirement for the use of such materials in drug delivery applications. Preliminary results demonstrating the use of such MSNs as hosts for oncology drugs [substituted 3-hydroxyquinolinones ( 3-HQ)] with low water solubility (≪1 µg/g H2O) are presented, with loadings of several wt% demonstrated. The ability of the silica host to protect the 3-HQ from oxidative degradation during impregnation and release is discussed.
Bürglová, Kristýna; Hlaváč, Jan [Institute of Molecular and Translational Medicine, Palacký University Olomouc, Faculty of Medicine and Dentistry (Czech Republic); Bartlett, John R., E-mail: JBartlett@usc.edu.au [University of the Sunshine Coast, Faculty of Science, Health, Education and Engineering (Australia)
2015-12-15
Silica nanoparticles with tailored properties have been developed for a variety of biomedical applications, with particular emphasis on their use as carriers for the encapsulation and controlled release of bioactive species. Among the various strategies described, silica nanoparticles with uniform mesoporosity (MSN) prepared in aqueous solution at elevated temperatures using cetyltrimethylammonium bromide as a template have a range of desirable properties. However, the processing windows available to control the dimensions and other key properties of such nanoparticles prepared using fluoride salts as catalysts have not been elucidated, with mixed products containing gel fragments and non-uniform products obtained under many conditions. Here, we present a parametric study of the synthesis of MSN under fluoride-catalysed conditions using tetraethylorthosilicate as silica precursor. The processing conditions required to produce uniform nanoparticles with controlled dimensions are elucidated, together with the conditions under which dried powders can be re-dispersed in aqueous solution after long-term storage to regenerate unaggregated nanospheres with dimensions (as measured by dynamic light scattering) comparable to those measured via scanning electron microscopy analysis of the dried material. The ability to dry and store such powders for extended periods of time is an important requirement for the use of such materials in drug delivery applications. Preliminary results demonstrating the use of such MSNs as hosts for oncology drugs [substituted 3-hydroxyquinolinones (3-HQ)] with low water solubility (≪1 µg/g H{sub 2}O) are presented, with loadings of several wt% demonstrated. The ability of the silica host to protect the 3-HQ from oxidative degradation during impregnation and release is discussed.
Inverse problem theory methods for data fitting and model parameter estimation
Tarantola, A
2002-01-01
Inverse Problem Theory is written for physicists, geophysicists and all scientists facing the problem of quantitative interpretation of experimental data. Although it contains a lot of mathematics, it is not intended as a mathematical book, but rather tries to explain how a method of acquisition of information can be applied to the actual world.The book provides a comprehensive, up-to-date description of the methods to be used for fitting experimental data, or to estimate model parameters, and to unify these methods into the Inverse Problem Theory. The first part of the book deals wi
PPN parameters in gravitational theory with non-minimally derivative coupling
Zhu, Yi
2015-01-01
The non-minimal coupling of the kinetic term to Einstein's tensor helps the implementation of inflationary models due to the gravitationally enhanced friction. We calculate the parameterized post-Newtonian parameters for the scalar-tensor theory of gravity with non-minimally derivative coupling. We find that under experiment constraint from the orbits of millisecond pulsars in our galaxy, the theory deviates from Einstein's general relativity in the order of $10^{-20}$, and the effect of the non-minimal coupling is negligible if we take the scalar field as dynamical dark energy. Under the assumed conditions, the scalar field is required to be massless.
USING CROSS-CORRELATION THEORY TO EXTRACT MODAL PARAMETERS IN FREQUENCY-DOMAIN
无
2003-01-01
Conventional modal parameter identifications are usually based on frequency response functions, which require measurements of both the input force and the resulting response. However, in many cases, only response data are available while the actual excitations (such as wind/wave load) are not measurable. Modal parameters estimation must base itself on response-only data. Over the past years, many time-domain modal parameter identification techniques from output-only are proposed. A poly-reference frequency-domain modal identification scheme on response-only is presented. It is based on coupling the cross-correlation theory with conventional frequency-domain modal parameter extraction. An experiment using an airplane model is performed to verify the proposed method.
Shhirov V. N.
2015-06-01
Full Text Available The article presents a study of parameters and modes of operation of machines for soil cultivation. In determining the parameters and modes of operation of machinery for tillage we have applied the theory of similarity and dimensions of physical quantities. We have obtained the regularities of disclosing the relationship of the parameters from the medium to the energy characteristics of the process. As the initial data we used test protocols of machines for soil cultivation (Central - Black Earth, Kubanskaya, Sibirskaya, of North - Caucasion MIS, RosNIITiM : KPI - 3.8, AРC - 3.9, AKV - 4, AKM - 6 - V, AMP - 4 APC - 4 A, AРC - 10 APR - 4.4, APU - 6.5 APSH - 6 , CNC - 6.0, CSТ - 3.8, APC - 4. We defined the formula оf dimension parameters and modes of operation of machines for soil cultivation and properties of soil (traction resistance, depth, width, speed, hardness of the soil, acceleration. Based on dimension theory we have received similarity criteria. Based on the correlation analysis and the least squares method we determined the nature of addiction and the coefficients for it. We have also received a graph for determining the operating modes and parameters of machines for soil cultivation
Determination of Scaling Parameter and Dynamical Resonances in Complex-Rotated Hamiltonian Ⅰ: Theory
LI Heng-Mei; ZHAO Fang; YUAN Hong-Chun; ZHAO Mei-Shan
2008-01-01
In this paper we present a theoretical analysis on the determination of the scaling parameter in the complex-rotated Hamiltonian, which has served as a basis for successful applications of the rigged Hilbert space theory for resonances. Based on the complex energy eigenvalue, E(θ) = En(θ) - iF(θ)/2, as a function of the scaling parameter The condition dER(θR)/ dθ = 0 is merely a consequence of the Virial theorem and θⅠ = θR is not a necessary condition for a resonance state. We also provide a harmonic approximation formalism for resonances in scattering over a potential barrier.
Yu Dong-Chuan; Wu Ai-Guo
2006-01-01
A novel La Shalle's invariant set theory (LSIST) based adaptive asymptotic synchronization (LSISAAS) method is proposed to asymptotically synchronize Duffing system with unknown parameters which also are considered as system states. The LSISASS strategy depends on the only information, i.e. one state of the master system. According to the LSIST, the LSISASS method can asymptotically synchronize fully the states of the master system and the unknown system parameters as well. Simulation results also validate that the LSISAAS approach can obtain asymptotic synchronization.
Coulomb Corrections to the Parameters of the Moliere Multiple Scattering Theory
Kuraev, Eduard; Tarasov, Alexander
2013-01-01
High-energy Coulomb corrections to the parameters of the Moliere multiple scattering theory are obtained. Numerical calculations are presented in the range of the nuclear charge number of the target atom 4
Gustavo A. Aucar
2002-08-01
Full Text Available Abstract: A theory for the calculation of self-energy corrections to the nuclear magnetic parameters is given in this paper. It is based on the S-matrix formulation of bound-state quantum electrodynamics (QED. Explicit expressions for the various terms of the S-matrix are given. The interpretation of the self-energy, one- and two-vertex terms and some perspective for possible future developments are discussed.
Parameter-free effective field theory calculation for the solar proton-fusion and hep processes
T.S. Park; L.E. Marcucci; R. Schiavilla; M. Viviani; A. Kievsky; S. Rosati; K. Kubodera; D.P. Min; M. Rho
2002-08-01
Spurred by the recent complete determination of the weak currents in two-nucleon systems up to {Omicron}(Q{sup 3}) in heavy-baryon chiral perturbation theory, we carry out a parameter-free calculation of the threshold S-factors for the solar pp (proton-fusion) and hep processes in an effective field theory that combines the merits of the standard nuclear physics method and systematic chiral expansion. The power of the EFT adopted here is that one can correlate in a unified formalism the weak-current matrix elements of two-, three- and four-nucleon systems. Using the tritium {beta}-decay rate as an input to fix the only unknown parameter in the theory, we can evaluate the threshold S factors with drastically improved precision; the results are S{sub pp}(0) = 3.94 x (1 {+-} 0.004) x 10{sup -25} MeV-b and S{sub hep}(0) = (8.6 {+-} 1.3) x 10{sup -20} keV-b. The dependence of the calculated S-factors on the momentum cutoff parameter {Lambda} has been examined for a physically reasonable range of {Lambda}. This dependence is found to be extremely small for the pp process, and to be within acceptable levels for the hep process, substantiating the consistency of our calculational scheme.
Analysis of the {sup 238}U resonance parameters using random-matrix theory
Courcelle, A. [CEA Cadarache, 13 - Saint Paul lez Durance (France); Derrien, H.; Leal, L.C.; Larson, N.M. [Oak Ridge National Laboratory, Oak Ridge, TN (United States)
2005-07-01
Random-matrix theories (RMTs) provide valuable statistical tools to analyze neutron-resonance data. The predictive power of the random-matrix theories, which do not contain any adjustable parameters, is striking, and the application is rather simple and fast. A new evaluation of {sup 238}U resonance parameters has recently been performed at the Oak Ridge National Laboratory; the objective of this paper is to illustrate the use of RMT in the field of resonance-parameter evaluation with the newly evaluated {sup 239}U energy levels and widths. Several statistics were computed using the s-wave resonances up to 20 keV and compared to the Gaussian Orthogonal Ensemble predictions. It is shown that a good agreement is observed between RMT and the experimental data up to 2.5 keV. The F-Dyson statistic was especially investigated because of its claimed ability to detect locally missed and spurious levels in the sample (p-resonances contamination or unresolved multiplets). As expected, the entire set of evaluated {sup 238}U s-wave resonances up to 20 keV disagrees significantly with the theory. There are two reasons for this: First, it is difficult to distinguish s- and p-wave resonances in the analysis. Secondly, especially above 10 keV, it is impossible to determine reliable resonance energies from the available experimental data. It is concluded that the use of RMT can help nuclear data specialists to improve their evaluations in the resonance range. (authors)
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.
Anke Kelchtermans
2015-01-01
Full Text Available Nanocrystalline ZnO:Al nanoparticles are suitable building blocks for transparent conductive layers. As the concentration of substitutional tetrahedral Al is an important factor for improving conductivity, here we aim to increase the fraction of substitutional Al. To this end, synthesis parameters of a solvothermal reaction yielding ZnO:Al nanorods were varied. A unique set of complementary techniques was combined to reveal the exact position of the aluminium ions in the ZnO lattice and demonstrated its importance in order to evaluate the potential of ZnO:Al nanocrystals as optimal building blocks for solution deposited transparent conductive oxide layers. Both an extension of the solvothermal reaction time and stirring during solvothermal treatment result in a higher total tetrahedral aluminium content in the ZnO lattice. However, only the longer solvothermal treatment effectively results in an increase of the substitutional positions aimed for.
Usability of a theory of visual attention (TVA) for parameter-based measurement of attention I
Finke, Kathrin; Bublak, Peter; Krummenacher, Joseph
2005-01-01
The present study investigated the usability of whole and partial report of briefly displayed letter arrays as a diagnostic tool for the assessment of attentional functions. The tool is based on Bundesen’s (1990, 1998, 2002; Bundesen et al., 2005) theory of visual attention (TVA), which assumes f...... clinical tests measuring similar constructs. The empirical independence of the four TVA parameters is suggested by nonsignificant or, in the case of processing speed and working memory storage capacity, only modest correlations between the parameter values.......The present study investigated the usability of whole and partial report of briefly displayed letter arrays as a diagnostic tool for the assessment of attentional functions. The tool is based on Bundesen’s (1990, 1998, 2002; Bundesen et al., 2005) theory of visual attention (TVA), which assumes...... of these parameters. The present study was designed to examine whether (a) a shortened procedure bears sufficient accuracy and reliability, (b) whether the procedures reveal attentional constructs with clinical relevance, and (c) whether the mathematically independent parameters are also empirically independent...
The Double Feedback Loop and the Parameter Theory of Text Genres
Bundgaard, Peer; Østergaard, Svend
2014-01-01
parameter theory of genres which is presented in Section 3. Here we consider genres as governed by parameters external to them and intrinsic to the situations they are dynamically related to. Genres should thus be understood not simply in terms of inherent textual or formal traits, but also relative......[This article has a double scope. First, we consider the dynamics inherent in the emergence of genres. Our view is that genres emerge relative to two sets of constraints, which we aim to capture in our double feedback loop model for the dynamics of genres. On the one hand, (text) genres, or text...... to a certain set of situational parameters and relative to the degree to which they are governed by them.]...
Ellegaard, Martin Dela; Abildskov, Jens; O’Connell, John P.
2011-01-01
The solubilities of gases in ionic liquids and compressed liquid densities have been successfully described over a wide range of conditions using a reformulated corresponding-states formulation for direct correlation function integrals. In addition, comparisons with experimental data show reliable...... prediction of ionic liquid characteristic properties from simple rules....
Application of grey system theory on the influencing parameters of aerobic granulation in SBR.
Bindhu, B K; Madhu, G
2017-09-01
Aerobic granulation is a promising technology for wastewater treatment. Four operational parameters were selected as influencing factors for this study. Aerobic granulation was experimented with three different values of organic loading rate (3, 6 and 9 kg COD m(-3) d(-1)), superficial upflow air velocity (SUAV) (2, 3 and 4 cm s(-1)), settling time (3, 5 and 10 min) and volume exchange ratio (25%, 50% and 75%) in sequencing batch reactor in nine trials for the optimal performance of aerobic granulation. The influence of compared parameters on five reference parameters (sludge volume index (SVI), time taken for the appearance of granules, size and specific gravity of granules and chemical oxygen demand (COD) removal) was analyzed using grey system theory. The grey relational coefficients and grey entropy relational grade of each parameter were calculated. Hydrodynamic shear force in terms of SUAV was found to have the greatest influence on granule appearance, specific gravity of granules and COD removal efficiency. SVI is greatly affected by settling time. The optimal scopes of all the compared parameters were found.
Parameters of heavy quark effective theory from N{sub f}=2 lattice QCD
Blossier, Benoit [CNRS, Orsay (France). LPT; Paris-11 Univ., 91 - Orsay (France); Della Morte, Michele [Mainz Univ. (Germany). Inst. fuer Kernphysik; Fritzsch, Patrick [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Physik; Garron, Nicolas [Edinburgh Univ. (United Kingdom). School of Physics and Astronomy; Heitger, Jochen [Muenster Univ. (Germany). Inst. fuer Theoretische Physik 1; Simma, Hubert; Sommer, Rainer [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Tantalo, Nazario [Rome-3 Univ. (Italy). Dipt. di Fisica; INFN, Sezione di Roma (Italy)
2012-07-15
We report on a non-perturbative determination of the parameters of the lattice Heavy Quark Effective Theory (HQET) Lagrangian and of the time component of the heavy-light axial-vector current with N{sub f} = 2 flavors of massless dynamical quarks. The effective theory is considered at the 1/m{sub h} order, and the heavy mass m{sub h} covers a range from slightly above the charm to beyond the beauty region. These HQET parameters are needed to compute, for example, the b-quark mass, the heavy-light spectrum and decay constants in the static approximation and to order 1/m{sub h} in HQET. The determination of the parameters is done non-perturbatively. The computation reported in this paper uses the plaquette gauge action and two different static actions for the heavy quark described by HQET. For the light-quark action we choose non-perturbatively O(a)-improved Wilson fermions.
Chiara Dentone
2014-11-01
Full Text Available Introduction: The persistence of immune activation and inflammation in HIV patients with HIV-RNA (VL undetectable causes many co-morbidities [1–3]. The aim of this study is to correlate monocytes (m and NK cell activation levels, soluble markers and oxidative stress with clinical, biochemical and metabolic data in HIV-1 infected patients with VL≤50 copies (cp/mL on antiretroviral therapy. Materials and Methods: Multicentre, cross-sectional study in patients with VL≤50 cp/mL and on antiretroviral therapy by at least six months. We studied: activation/homing markers (CD38, HLA-DR, CCR-2, PDL-1 on inflammatory, intermediate, proinflammatory m; activatory receptors NKp30, NKp46 and HLA-DR on NK cells; soluble inflammatory (sCD14, adiponectina, MCP-1 and stress oxidative markers (dRoms, antiRoms. Univariate analyses are performed with non-parametric and Pearson tests. The significant correlations were adjusted for possible known confounding factors (smoking, Cytomegalovirus IgG serology, Raltegravir, Protease Inhibitor [PI] therapy and HCV-RNA with multivariate analysis. Results: In the 68 patients the positive correlation between age and antiRoms was significant also after adjustment for PI use (p=0.05. The% CD8+T was associated with% proinflammatory m (p=0.043 and with their expression of CCR2 mean fluorescence intensity (MFI (p=0.012. The% NKp46+ was positively correlated with CD4+T count (p=0.001. The fibrinogen was positively associated with dRoms (p=0.052 and the positive correlation between triglycerides and antiRoms has been confirmed (p<0.001; the impact of antiRoms on HDL/triglycerides ratio (p=0.006 was observed after adjustment for PI use. The BMI was associated with smoking (p=0.011. Only the maraviroc-treated patients showed minimal arterial pressure, fibrinogen and antiRoms lower (p=0.001, 0.004 e 0.006 and sCD14 values higher (p=0.029. Conclusions: Patients with long history of HIV infection and stable immunological and
On Basic Parameters and Radiation Theory of Non-Uniform Channel DMOS
LI Ze- hong
2005-01-01
@@ Researching the non-uniform channel DMOS is the basic knowledge of the new generation high voltage power MOS devices and the important domain of the IC, smart power ICs. This dissertation investigates the basic parameters and the radiation theory of non-uniform channel DMOS. The threshold voltage model of micron and deep sub-micron non-uniform channel DMOS, the radiation threshold voltage model,the radiation mobility model and the transient response model of single ion radiation are internationally proposed for the first time.
A. Paonita
2005-06-01
Full Text Available Noble gas solubility in silicate melts and glasses has gained a crucial role in Earth Sciences investigations and in the studies of non-crystalline materials on a micro to a macro-scale. Due to their special geochemical features, noble gases are in fact ideal tracers of magma degassing. Their inert nature also allows them to be used to probe the structure of silicate melts. Owing to the development of modern high pressure and temperature technologies, a large number of experimental investigations have been performed on this subject in recent times. This paper reviews the related literature, and tries to define our present state of knowledge, the problems encountered in the experimental procedures and the theoretical questions which remain unresolved. Throughout the manuscript I will also try to show how the thermodynamic and structural interpretations of the growing experimental dataset are greatly improving our understanding of the dissolution mechanisms, although there are still several points under discussion. Our improved capability of predicting noble gas solubilities in conditions closer to those found in magma has allowed scientists to develop quantitative models of magma degassing, which provide constraints on a number of questions of geological impact. Despite these recent improvements, noble gas solubility in more complex systems involving the main volatiles in magmas, is poorly known and a lot of work must be done. Expertise from other fields would be extremely valuable to upcoming research, thus focus should be placed on the structural aspects and the practical and commercial interests of the study of noble gas solubility.
ZHANG Jian; YE Jian-shu; ZHAO Xin-ming
2007-01-01
The finite strip controlling equation of pinned curve box was deduced on basis of Novozhilov theory and with flexibility method, and the problem of continuous curve box was resolved. Dynamic Bayesian error function of displacement parameters of continuous curve box was found. The corresponding formulas of dynamic Bayesian expectation and variance were derived. After the method of solving the automatic search of step length was put forward, the optimization estimation computing formulas were also obtained by adapting conjugate gradient method. Then the steps of dynamic Bayesian estimation were given in detail. Through analysis of a classic example, the criterion of judging the precision of the known information is gained as well as some other important conclusions about dynamic Bayesian stochastic estimation of displacement parameters of continuous curve box.
A parameter estimation algorithm for spatial sine testing - Theory and evaluation
Rost, R. W.; Deblauwe, F.
1992-01-01
This paper presents the theory and an evaluation of a spatial sine testing parameter estimation algorithm that uses directly the measured forced mode of vibration and the measured force vector. The parameter estimation algorithm uses an ARMA model and a recursive QR algorithm is applied for data reduction. In this first evaluation, the algorithm has been applied to a frequency response matrix (which is a particular set of forced mode of vibration) using a sliding frequency window. The objective of the sliding frequency window is to execute the analysis simultaneously with the data acquisition. Since the pole values and the modal density are obtained from this analysis during the acquisition, the analysis information can be used to help determine the forcing vectors during the experimental data acquisition.
Deforming the theory lambda-phi-4 along the parameters and fields gradient flows
Cartas-Fuentevilla, R
2014-01-01
Considering the action for the theory $\\lambda\\phi^{4}$ for a massive scalar bosonic field as an entropy functional on the space of coupling constants and on the space of fields, we determine the gradient flows for the scalar field, the mass, and the self-interaction parameter. When the flow parameter is identified with the energy scale, we show that there exist phase transitions between unbroken exact symmetry scenarios and spontaneous symmetry breaking scenarios at increasingly high energies. Since a non-linear heat equation drives the scalar field through a {\\it reaction-diffusion} process, in general the flows are not reversible, mimicking the renormalization group flows of the $c$-theorem; the deformation of the field at increasingly high energies can be described as non-linear traveling waves, or solitons associated to self-similar solutions
Shen, Huahua; Niu, Libo; Fan, Kaiqi; Li, Jingjing; Guan, Xidong; Song, Jian
2014-08-05
The gelation behavior of 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (DMDBS) in binary solvents has been systematically investigated. DMDBS is soluble in DMSO and insoluble in toluene (apolar) or 1-propanol (polar). When DMSO is added to a poor solvent at a certain volume fraction, DMDBS forms an organogel in the mixed solvent. With increasing DMSO content, the minimum gelation concentration increases and the gel-to-sol transition temperature decreases in both systems. However, compared with those in toluene-DMSO mixtures, the gelation ability and thermal stability are better in 1-propanol-DMSO mixtures. Scanning electron microscopy images reveal that the gelators aggregate to form three-dimensional networks. X-ray diffraction shows that the gel has a lamellar structure, which is different from the structure of the precipitate. Fourier transform infrared results reveal H-bonding is the main driving force for self-aggregation and indicate that stronger H-bonding interactions exist between gelators in 1-propanol-DMSO mixtures in contrast with toluene-DMSO mixtures. Attempts have been taken to correlate solvent parameters to gelation behavior in binary solvents. A Teas plot exhibits distinctly different solvent zones in the studied mixed solvents. The polar parameter (δp) indicates a narrow favorable domain for gel formation in the range of 1.64-7.99 MPa(1/2) for some apolar solvent-DMSO mixtures. The hydrogen-bonding parameter (δh) predicts that gelation occurs for values of 14.00-16.50 MPa(1/2) for some polar solvent-DMSO mixtures. The result may have potential applications in predicting the gelation behavior of 1,3:2,4-di-O-benzylidene-d-sorbitol derivatives in mixed solvents.
Ickes, Luisa; Welti, André; Lohmann, Ulrike
2017-02-01
Heterogeneous ice formation by immersion freezing in mixed-phase clouds can be parameterized in general circulation models (GCMs) by classical nucleation theory (CNT). CNT parameterization schemes describe immersion freezing as a stochastic process, including the properties of insoluble aerosol particles in the droplets. There are different ways to parameterize the properties of aerosol particles (i.e., contact angle schemes), which are compiled and tested in this paper. The goal of this study is to find a parameterization scheme for GCMs to describe immersion freezing with the ability to shift and adjust the slope of the freezing curve compared to homogeneous freezing to match experimental data. We showed in a previous publication that the resulting freezing curves from CNT are very sensitive to unconstrained kinetic and thermodynamic parameters in the case of homogeneous freezing. Here we investigate how sensitive the outcome of a parameter estimation for contact angle schemes from experimental data is to unconstrained kinetic and thermodynamic parameters. We demonstrate that the parameters describing the contact angle schemes can mask the uncertainty in thermodynamic and kinetic parameters. Different CNT formulations are fitted to an extensive immersion freezing dataset consisting of size-selected measurements as a function of temperature and time for different mineral dust types, namely kaolinite, illite, montmorillonite, microcline (K-feldspar), and Arizona test dust. We investigated how accurate different CNT formulations (with estimated fit parameters for different contact angle schemes) reproduce the measured freezing data, especially the time and particle size dependence of the freezing process. The results are compared to a simplified deterministic freezing scheme. In this context, we evaluated which CNT-based parameterization scheme able to represent particle properties is the best choice to describe immersion freezing in a GCM.
Classical nucleation theory of homogeneous freezing of water: thermodynamic and kinetic parameters.
Ickes, Luisa; Welti, André; Hoose, Corinna; Lohmann, Ulrike
2015-02-28
The probability of homogeneous ice nucleation under a set of ambient conditions can be described by nucleation rates using the theoretical framework of Classical Nucleation Theory (CNT). This framework consists of kinetic and thermodynamic parameters, of which three are not well-defined (namely the interfacial tension between ice and water, the activation energy and the prefactor), so that any CNT-based parameterization of homogeneous ice formation is less well-constrained than desired for modeling applications. Different approaches to estimate the thermodynamic and kinetic parameters of CNT are reviewed in this paper and the sensitivity of the calculated nucleation rate to the choice of parameters is investigated. We show that nucleation rates are very sensitive to this choice. The sensitivity is governed by one parameter - the interfacial tension between ice and water, which determines the energetic barrier of the nucleation process. The calculated nucleation rate can differ by more than 25 orders of magnitude depending on the choice of parameterization for this parameter. The second most important parameter is the activation energy of the nucleation process. It can lead to a variation of 16 orders of magnitude. By estimating the nucleation rate from a collection of droplet freezing experiments from the literature, the dependence of these two parameters on temperature is narrowed down. It can be seen that the temperature behavior of these two parameters assumed in the literature does not match with the predicted nucleation rates from the fit in most cases. Moreover a comparison of all possible combinations of theoretical parameterizations of the dominant two free parameters shows that one combination fits the fitted nucleation rates best, which is a description of the interfacial tension coming from a molecular model [Reinhardt and Doye, J. Chem. Phys., 2013, 139, 096102] in combination with the activation energy derived from self-diffusion measurements [Zobrist
The Kaon B-parameter in Mixed Action Chiral Perturbation Theory
Aubin, C; De van Water, R S; Laiho, Jack; Water, Ruth S. Van de
2006-01-01
We calculate the kaon B-parameter, B_K, in chiral perturbation theory for a partially quenched, mixed action theory with Ginsparg-Wilson valence quarks and staggered sea quarks. We find that the resulting expression is similar to that in the continuum, and in fact has only two additional unknown parameters. At one-loop order, taste-symmetry violations in the staggered sea sector only contribute to flavor-disconnected diagrams by generating an O(a^2) shift to the masses of taste-singlet sea-sea mesons. Lattice discretization errors also give rise to an analytic term which shifts the tree-level value of B_K by an amount of O(a^2). This term, however, is not strictly due to taste-breaking, and is therefore also present in the expression for B_K for pure G-W lattice fermions. We also present a numerical study of the mixed B_K expression in order to demonstrate that both discretization errors and finite volume effects are small and under control on the MILC improved staggered lattices.
The Kaon B-parameter in mixed action chiral perturbation theory
Aubin, C.; /Columbia U.; Laiho, Jack; Van de Water, Ruth S.; /Fermilab
2006-09-01
We calculate the kaon B-parameter, B{sub K}, in chiral perturbation theory for a partially quenched, mixed action theory with Ginsparg-Wilson valence quarks and staggered sea quarks. We find that the resulting expression is similar to that in the continuum, and in fact has only two additional unknown parameters. At one-loop order, taste-symmetry violations in the staggered sea sector only contribute to flavor-disconnected diagrams by generating an {Omicron}(a{sup 2}) shift to the masses of taste-singlet sea-sea mesons. Lattice discretization errors also give rise to an analytic term which shifts the tree-level value of B{sub K} by an amount of {Omicron}(a{sup 2}). This term, however, is not strictly due to taste-breaking, and is therefore also present in the expression for B{sub K} for pure G-W lattice fermions. We also present a numerical study of the mixed B{sub K} expression in order to demonstrate that both discretization errors and finite volume effects are small and under control on the MILC improved staggered lattices.
von Thienen, Wolfhard; Metzler, Dirk; Witte, Volker
2015-05-07
The emergence of self-organizing behavior in ants has been modeled in various theoretical approaches in the past decades. One model explains experimental observations in which Argentine ants (Linepithema humile) selected the shorter of two alternative paths from their nest to a food source (shortest path experiments). This model serves as an important example for the emergence of collective behavior and self-organization in biological systems. In addition, it inspired the development of computer algorithms for optimization problems called ant colony optimization (ACO). In the model, a choice function describing how ants react to different pheromone concentrations is fundamental. However, the parameters of the choice function were not deduced experimentally but freely adapted so that the model fitted the observations of the shortest path experiments. Thus, important knowledge was lacking about crucial model assumptions. A recent study on the Argentine ant provided this information by measuring the response of the ants to varying pheromone concentrations. In said study, the above mentioned choice function was fitted to the experimental data and its parameters were deduced. In addition, a psychometric function was fitted to the data and its parameters deduced. Based on these findings, it is possible to test the shortest path model by applying realistic parameter values. Here we present the results of such tests using Monte Carlo simulations of shortest path experiments with Argentine ants. We compare the choice function and the psychometric function, both with parameter values deduced from the above-mentioned experiments. Our results show that by applying the psychometric function, the shortest path experiments can be explained satisfactorily by the model. The study represents the first example of how psychophysical theory can be used to understand and model collective foraging behavior of ants based on trail pheromones. These findings may be important for other
Singh, Sachin Kumar; Srinivasan, K K; Gowthamarajan, K; Singare, Dhananjay S; Prakash, Dev; Gaikwad, Narayan Babulal
2011-08-01
The objective of this study was to identify and optimize formulation and process variables affecting characteristic and scale-up of nanosuspension manufacturing process on bead mill considering industrial perspective. Formulation factors evaluated were ratio of polymer to drug and ratio of surfactant to drug, whereas process parameters were milling time and milling speed. Responses measured in this study include zeta potential and mean particle size d(90). The test revealed that ratio of polymer to drug and milling speed have significant effect on zeta potential whereas milling time and milling speed have significant effect on the particle size distribution of nanosuspension. The X-ray powder diffraction pattern of drug milled at high and low speed reveals no form conversion when compared with unmilled drug. The formulated nanosuspension has shown a faster dissolution profile (98.97% in 10 min), relative to that of raw glyburide (18.17% in 10 min), mainly due to the formation of nanosized particles. The ANOVA test revealed that there was no significant difference in the dissolution profiles of fresh and aged nanosuspension. These results indicate the suitability of formulation procedure for preparation of nanosized poorly water-soluble drug with significantly improved in vitro dissolution rate and thus possibly enhance fast onset of therapeutic drug effect.
Kayodé, A P Polycarpe; Nout, Martinus J R; Bakker, Evert J; Van Boekel, Martinus A J S
2006-06-14
The purpose of this study was to improve the micronutrient quality of indigenous African infant flour using traditional techniques available in the region. Response surface methodology was used to study the effect of duration of soaking, germination, and fermentation on phytate and phenolic compounds (PC), pH, viscosity, and the in vitro solubility (IVS) of iron and zinc in infant sorghum flour. The phytate and the PC concentrations of the flour were significantly modified as a result of the duration of germination and fermentation and their mutual interaction. These modifications were accompanied by a significant increase in % IVS Zn after 24 h of sprouting. Except for the interaction of soaking and fermentation, none of the processing parameters exerted a significant effect on the % IVS Fe. The viscosity of the porridge prepared with the flour decreased significantly with the duration of germination, making it possible to produce a porridge with high energy and nutrient density. The use of germination in combination with fermentation is recommended in the processing of cereals for infant feeding in developing countries.
Leue, Anja; Beauducel, André
2008-11-01
J. A. Gray's Reinforcement Sensitivity Theory (RST) has produced a wealth of quasi-experimental studies in more than 35 years of research on personality and reinforcement sensitivity. The present meta-analysis builds on this literature by investigating RST in conflict and nonconflict reinforcement tasks in humans. Based on random-effects meta-analysis, we confirmed RST predictions of performance parameters (e.g., number of responses, reaction time) in reinforcement tasks for impulsivity- and anxiety-related traits. In studies on anxiety-related traits, the effect size variance was smaller for conflict tasks than for nonconflict tasks. A larger mean effect size and a larger variability of effect sizes were found for conflict compared to nonconflict tasks in studies on impulsivity-related traits. Our results suggest that problems with RST confirmation in reinforcement tasks are at least partly caused by insufficient statistical power of primary studies, and thus, encourage future research on RST.
Matteucci, M.; S. Mignani, Prof.; Veldkamp, Bernard P.
2012-01-01
In testing, item response theory models are widely used in order to estimate item parameters and individual abilities. However, even unidimensional models require a considerable sample size so that all parameters can be estimated precisely. The introduction of empirical prior information about candi
Reise, Steven; Moore, Tyler; Maydeu-Olivares, Alberto
2011-01-01
Reise, Cook, and Moore proposed a "comparison modeling" approach to assess the distortion in item parameter estimates when a unidimensional item response theory (IRT) model is imposed on multidimensional data. Central to their approach is the comparison of item slope parameter estimates from a unidimensional IRT model (a restricted model), with…
Zhang, Feng; Li, Xiang-yang; Qian, Keran
2017-02-01
Shale is observed to have strong transverse isotropy due to its complex intrinsic properties on a small scale. An improved rock physics model has been developed to effectively model this intrinsic anisotropy. Several effective medium theories (Backus averaging, differential effective medium theory and self-consistent approximation) are validated and used in different steps of the workflow to simulate the effects of clay minerals, crack-like pores, kerogen and their preferred orientation on the elastic anisotropy. Anisotropic solid clay is constructed by using different clay mineral constituents instead of assuming it to be an equivalent isotropic or transversely isotropic medium. We differentiate between the voids associated with clay and the voids associated with other minerals based on their varied geometries and their different contributions to the anisotropy. The degree of alignment of clay particles, interconnected pore fluid and kerogen has a great influence on the elastic properties of shale. Therefore, in addition to the pore aspect ratio (asp), a new parameter called the lamination index (LI) related to the distribution of clay particle orientation is proposed and needs to be estimated during the modeling. We then present a practical inversion scheme to enable the prediction of anisotropy parameters for both vertical and horizontal well logs by estimating the lamination index and the pore aspect ratio simultaneously. The predicted elastic constants are demonstrated by using the published laboratory measurements of some Greenhorn shale, and they show better accuracy than the estimations in the existing literature. This model takes different rock properties into consideration and is thus generalized for shale formations from different areas. The application of this model to the well logs of some Upper Triassic shale in the Sichuan basin, and the analyzed results, are presented in part 2 of this paper.
Dimitrov, Bogdan G
2009-01-01
On the base of the distinction between covariant and contravariant metric tensor components, a new (multivariable) cubic algebraic equation for reparametrization invariance of the gravitational Lagrangian has been derived and parametrized with complicated non - elliptic functions, depending on the (elliptic) Weierstrass function and its derivative. This is different from standard algebraic geometry, where only two-dimensional cubic equations are parametrized with elliptic functions and not multivariable ones. Physical applications of the approach have been considered in reference to theories with extra dimensions. The s.c. "length function" l(x) has been introduced and found as a solution of quasilinear differential equations in partial derivatives for two different cases of "compactification + rescaling" and "rescaling + compactification". New physically important relations (inequalities) between the parameters in the action are established, which cannot be derived in the case $l=1$ of the standard gravitati...
Riipinen, I.; Rastak, N.; Pandis, S. N.
2015-06-01
We present a theoretical study investigating the cloud activation of multicomponent organic particles. We modeled these complex mixtures using solubility distributions (analogous to volatility distributions in the VBS, i.e., volatility basis set, approach), describing the mixture as a set of surrogate compounds with varying water solubilities in a given range. We conducted Köhler theory calculations for 144 different mixtures with varying solubility range, number of components, assumption about the organic mixture thermodynamics and the shape of the solubility distribution, yielding approximately 6000 unique cloud condensation nucleus (CCN)-activation points. The results from these comprehensive calculations were compared to three simplifying assumptions about organic aerosol solubility: (1) complete dissolution at the point of activation; (2) combining the aerosol solubility with the molar mass and density into a single effective hygroscopicity parameter κ; and (3) assuming a fixed water-soluble fraction ϵeff. The complete dissolution was able to reproduce the activation points with a reasonable accuracy only when the majority (70-80%) of the material was dissolved at the point of activation. The single-parameter representations of complex mixture solubility were confirmed to be powerful semi-empirical tools for representing the CCN activation of organic aerosol, predicting the activation diameter within 10% in most of the studied supersaturations. Depending mostly on the condensed-phase interactions between the organic molecules, material with solubilities larger than about 0.1-100 g L-1 could be treated as soluble in the CCN activation process over atmospherically relevant particle dry diameters and supersaturations. Our results indicate that understanding the details of the solubility distribution in the range of 0.1-100 g L-1 is thus critical for capturing the CCN activation, while resolution outside this solubility range will probably not add
Kucharyson, J. F.; Cheng, L.; Tung, S. O.; Curtiss, L. A.; Thompson, L. T.
2017-07-14
New active materials are needed to improve the performance and reduce the cost of non-aqueous redox flow batteries (RFBs) for grid-scale energy storage applications. Efforts to develop better performing materials, which have largely been empirical, would benefit from a better understanding of relationships between structural, electronic and RFB-relevant functional properties. This paper focuses on metal-acetylacetonates, a class of metal coordination complexes that has shown promise for use in RFBs, and describes correlations between their experimentally measured standard potentials, solubilities, and stabilities (cycle lifes), and selected chemical, structural and electronic properties determined from Density Functional Theory (DFT) calculations. The training set consisted of 16 complexes including 5 different metals and 11 different substituents on the acetylacetonate ligand. Standard potentials for those compounds were calculated and are in good agreement with experimentally measured results. A predictive equation based on the solvation energies and dipole moments, two easily computed properties, reasonably modeled the experimentally determined solubilities. Importantly, we were able to identify a descriptor for the stability of acetylacetonates. The experimentally determined stability, quantified as the cycle life to a given degree of degradation, correlated with the percentage of the highest occupied (HOMO) or lowest unoccupied molecular orbital (LUMO) on the metal of the complex. This percentage is influenced by the degree of ligand innocence (irreducibility), and complexes with the most innocent ligands yielded the most stable redox reactions. To this end, VO(acetylacetonate)(2) and Fe(acetylacetonate)(3), with nearly 80% of the HOMO and LUMO on the metal, possessed the most stable oxidation and reduction half-reactions, respectively. The structure-function relationships and correlations presented in this paper could be used to predict new, highly soluble
SELECTION OF POLYMER SOLVENTS AND NEW TWO-DIMENSIONAL SOLUBILITY PARAMETER%聚合物的溶剂选择与新的两维溶解度参数
俞春芳; 黑恩成; 刘国杰
2001-01-01
按照溶解度参数的新定义,建立了一个两维溶解度参数体系,它由物理和化学两个溶解度参数分量构成,这两个分量的拆分借鉴了Wiehe新近提出的原则.对每一种聚合物在不同液体中的溶解度实验数据作图表明,所有溶剂几乎都聚集在溶解度参数图的某一区域内,这个区域可用一椭圆表示.通过一个简单的加和规则,它能用来满意地预测混合溶剂的溶解能力,为聚合物选择溶剂提供了重要的依据.广泛的检验表明,新的两维溶解度参数要比Hansen三维溶解度参数更加可靠.%Based on the new definition of solubility parameter obtained by our previous work, a new two-dimensional solubility parameter consisted of the physical and chemical (solubility parameter) components has been established. The method proposed by Wiehe is used as a reference to divide the two components. From the profile of solubility data, it can be seen that all solvents are almost located within some area of solubility parameter diagram for every polymer. This area can be expressed by an ellipse, which provides an important basis for the selection of polymer solvents. Using a simple adding rule, it can be satisfactorily used to predict the solvency of mixing solvents. The results of extensive testing show that the new two-dimensional solubility parameter is more reliable than Hansen's three-dimensional solubility parameter for the selection of polymer solvents.
Percolation theory and the role of maize starch as a disintegrant for a low water-soluble drug.
Kimura, Go; Puchkov, Maxim; Betz, Gabriele; Leuenberger, Hans
2007-01-01
The objective of the present work is to investigate the presence or absence of a critical concentration of maize starch according to the percolation theory for a truly ternary system with respect to a minimum disintegration time. The results of this study show that the application of percolation theory is not limited to the study of binary systems. In this work it is shown how it can be used to analyze the behavior of binary and ternary systems for caffeine and mefenamic acid formulations containing a starch-based disintegrant. The percolation threshold p(c) can be described by the volumetric ratio of the disintegrant to the drug substance being equal to p(c) = 0.2 (v/v) in in which both components have similar average particle sizes. In addition, the behavior of the disintegration time in the neighborhood of the percolation threshold can be mathematically modeled with the basic equation of the percolation theory yielding a critical exponent q = 0.28 +/- 0.06.
Yedavalli, R. K.
1992-01-01
The problem of analyzing and designing controllers for linear systems subject to real parameter uncertainty is considered. An elegant, unified theory for robust eigenvalue placement is presented for a class of D-regions defined by algebraic inequalities by extending the nominal matrix root clustering theory of Gutman and Jury (1981) to linear uncertain time systems. The author presents explicit conditions for matrix root clustering for different D-regions and establishes the relationship between the eigenvalue migration range and the parameter range. The bounds are all obtained by one-shot computation in the matrix domain and do not need any frequency sweeping or parameter gridding. The method uses the generalized Lyapunov theory for getting the bounds.
Yedavalli, R. K.
1992-01-01
The problem of analyzing and designing controllers for linear systems subject to real parameter uncertainty is considered. An elegant, unified theory for robust eigenvalue placement is presented for a class of D-regions defined by algebraic inequalities by extending the nominal matrix root clustering theory of Gutman and Jury (1981) to linear uncertain time systems. The author presents explicit conditions for matrix root clustering for different D-regions and establishes the relationship between the eigenvalue migration range and the parameter range. The bounds are all obtained by one-shot computation in the matrix domain and do not need any frequency sweeping or parameter gridding. The method uses the generalized Lyapunov theory for getting the bounds.
Embedding parameters in ab initio theory to develop approximations based on molecular similarity
Tanha, Matteus; Kaul, Shiva; Cappiello, Alexander; Gordon, Geoffrey J; Yaron, David J
2015-01-01
A means to take advantage of molecular similarity to lower the computational cost of electronic structure theory is explored, in which parameters are embedded into a low-cost, low-level (LL) ab initio model and adjusted to obtain agreement with results from a higher-level (HL) ab initio model. A parametrized LL (pLL) model is created by multiplying selected matrix elements of the Hamiltonian operators by scaling factors that depend on element types. Various schemes for applying the scaling factors are compared, along with the impact of making the scaling factors linear functions of variables related to bond lengths, atomic charges, and bond orders. The models are trained on ethane and ethylene, substituted with -NH2, -OH and -F, and tested on substituted propane, propylene and t-butane. Training and test datasets are created by distorting the molecular geometries and applying uniform electric fields. The fitted properties include changes in total energy arising from geometric distortions or applied fields, an...
Jian Zhang; Chu-Wei Zhou; Jia-Shou Zhuo
2011-01-01
The FCSE controlling equation of pinned thinwalled curve box was derived and the indeterminate problem of continuous thin-walled curve box with diaphragm was solved based on flexibility theory. With Bayesian statistical theory, dynamic Bayesian error function of displacement parameters of indeterminate curve box was founded. The corresponding formulas of dynamic Bayesian expectation and variance were deduced. Combined with one-dimensional Fibonacci automatic search scheme of optimal step size,the Powell optimization theory was utilized to research the stochastic identification of displacement parameters of indeterminate thin-walled curve box. Then the identification steps were presented in detail and the corresponding calculation procedure was compiled. Through some classic examples, it is obtained that stochastic performances of systematic parameters and systematic responses are simultaneously deliberated in dynamic Bayesian error function. The one-dimensional optimization problem of the optimal step size is solved by adopting Fibonacci search method. And the Powell identification of displacement parameters of indeterminate thin-walled curve box has satisfied numerical stability and convergence, which demonstrates that the presented method and the compiled procedure are correct and reliable.The project was supported by the National Natural Science Foundation of China ( 10472045.10772078 and 11072108 and the Science Foundation of NUAA(S0851-013).During parameters' iterative processes, the Powell theory is irrelevant with the calculation of finite curve strip element (FCSE) partial differentiation, which proves high computation efficiency of the studied method.
Cook, Paul P
2016-01-01
We investigate two-parameter solutions of sigma-models on two dimensional symmetric spaces contained in E11. Embedding such sigma-model solutions in space-time gives solutions of M* and M'-theory where the metric depends on general travelling wave functions, as opposed to harmonic functions typical in general relativity, supergravity and M-theory. Weyl reflection allows such solutions to be mapped to M-theory solutions where the wave functions depend explicitly on extra coordinates contained in the fundamental representation of E11.
Solubility of nonelectrolytes: a first-principles computational approach.
Jackson, Nicholas E; Chen, Lin X; Ratner, Mark A
2014-05-15
Using a combination of classical molecular dynamics and symmetry adapted intermolecular perturbation theory, we develop a high-accuracy computational method for examining the solubility energetics of nonelectrolytes. This approach is used to accurately compute the cohesive energy density and Hildebrand solubility parameters of 26 molecular liquids. The energy decomposition of symmetry adapted perturbation theory is then utilized to develop multicomponent Hansen-like solubility parameters. These parameters are shown to reproduce the solvent categorizations (nonpolar, polar aprotic, or polar protic) of all molecular liquids studied while lending quantitative rigor to these qualitative categorizations via the introduction of simple, easily computable parameters. Notably, we find that by monitoring the first-order exchange energy contribution to the total interaction energy, one can rigorously determine the hydrogen bonding character of a molecular liquid. Finally, this method is applied to compute explicitly the Flory interaction parameter and the free energy of mixing for two different small molecule mixtures, reproducing the known miscibilities. This methodology represents an important step toward the prediction of molecular solubility from first principles.
H. Kokkola
2003-06-01
Full Text Available We consider the equilibrium behavior of a polydisperse aqueous droplet population as a function of relative humidity (RH when a soluble trace gas, such as nitric acid, is present in the system. The droplet population experiences a splitting when the RH is increased sufficiently. This splitting is not related to the traditional Köhler activation of cloud droplets, as it may occur at relative humidities below 100%. Remarkably, the splitting always takes place in such a way that the largest size class of the (discretized droplet population starts taking up the soluble trace gas efficiently, growing steeply as a function of RH, and forcing the smaller droplets to shrink. We consider this behavior in terms of open and closed system Köhler curves (open system referring to one in which the trace gas concentration remains constant and closed system to one in which the gas concentration decreases as a result of uptake of the trace gas. We show how the open and closed system Köhler curves are related, and that the splitting of the population can be explained in terms of closed system curves crossing the Köhler maxima of the open system curves. We then go on to consider time-dependent situations, and show that due to gas-phase mass transfer limitations, the splitting of the size distributions moves toward smaller sizes as the rate of RH increase becomes more rapid. Finally, we consider stratospheric supercooled ternary solution droplet populations, and show that the splitting described using the new theory may explain observed bimodal size distributions.
Quantum entanglement in non-local games, graph parameters and zero-error information theory
Scarpa, G.
2013-01-01
We study quantum entanglement and some of its applications in graph theory and zero-error information theory. In Chapter 1 we introduce entanglement and other fundamental concepts of quantum theory. In Chapter 2 we address the question of how much quantum correlations generated by entanglement can d
Khajueenejad, F.; Ghanbari, J.
2015-10-01
The internal length parameter of the modified couple stress theory for single walled carbon nanotubes (CNTs) is determined in this paper. Buckling of CNTs have been studied using Timoshenko beam model and modified couple stress theory. The governing equations for three different end conditions, simple-simple, clamped-clamped and clamped-free, are solved using variational methods and an exact solution is provided for the buckling load. The effects of the internal length parameter on the buckling load of various CNT length and diameters are studied. It is observed that the internal length parameter has larger influence on the higher modes of buckling and for shorter nanotubes. A method presented to obtain the internal length parameter of higher order theories. By correlating the obtained results with the more accurate molecular dynamics simulations, the internal length parameter has been calculated for zigzag and armchair nanotubes. It is observed that the internal length parameter has slight dependency on the size of the CNTs and an average value is provided.
Extended Hildebrand solubility approach: Satranidazole in mixtures of dioxane and water
P B Rathi
2011-01-01
Full Text Available The extended Hildebrand solubility parameter approach is used to estimate the solubility of satranidazole in binary solvent systems. The solubility of satranidazole in various dioxane-water mixtures was analyzed in terms of solute-solvent interactions using a modified version of Hildebrand-Scatchard treatment for regular solutions. The solubility of satranidazole in the binary solvent, dioxane-water shows a bell-shaped profile with a solubility maximum well above the ideal solubility of the drug. This is attributed to solvation of the drug with the dioxane-water mixture, and indicates that the solute-solvent interaction energy is larger than the geometric mean (δ1δ2 of regular solution theory. The new approach provides an accurate prediction of solubility once the interaction energy is obtained. In this case, the energy term is regressed against a polynomial in δ1 of the binary mixture. A quartic expression of W in terms of solvent solubility parameter was found for predicting the solubility of satranidazole in dioxane-water mixtures. The method has potential usefulness in preformulation and formulation studies during which solubility prediction is important for drug design.
Extended hildebrand solubility approach: satranidazole in mixtures of dioxane and water.
Rathi, P B; Mourya, V K
2011-05-01
The extended Hildebrand solubility parameter approach is used to estimate the solubility of satranidazole in binary solvent systems. The solubility of satranidazole in various dioxane-water mixtures was analyzed in terms of solute-solvent interactions using a modified version of Hildebrand-Scatchard treatment for regular solutions. The solubility of satranidazole in the binary solvent, dioxane-water shows a bell-shaped profile with a solubility maximum well above the ideal solubility of the drug. This is attributed to solvation of the drug with the dioxane-water mixture, and indicates that the solute-solvent interaction energy is larger than the geometric mean (δ(1)δ(2)) of regular solution theory. The new approach provides an accurate prediction of solubility once the interaction energy is obtained. In this case, the energy term is regressed against a polynomial in δ(1) of the binary mixture. A quartic expression of W in terms of solvent solubility parameter was found for predicting the solubility of satranidazole in dioxane-water mixtures. The method has potential usefulness in preformulation and formulation studies during which solubility prediction is important for drug design.
Relativistic theory of nuclear magnetic resonance parameters in a Gaussian basis representation.
Kutzelnigg, Werner; Liu, Wenjian
2009-07-28
The calculation of NMR parameters from relativistic quantum theory in a Gaussian basis expansion requires some care. While in the absence of a magnetic field the expansion in a kinetically balanced basis converges for the wave function in the mean and for the energy with any desired accuracy, this is not necessarily the case for magnetic properties. The results for the magnetizability or the nuclear magnetic shielding are not even correct in the nonrelativistic limit (nrl) if one expands the original Dirac equation in a kinetically balanced Gaussian basis. This defect disappears if one starts from the unitary transformed Dirac equation as suggested by Kutzelnigg [Phys. Rev. A 67, 032109 (2003)]. However, a new difficulty can arise instead if one applies the transformation in the presence of the magnetic field of a point nucleus. If one decomposes certain contributions, the individual terms may diverge, although their sum is regular. A controlled cancellation may become difficult and numerical instabilities can arise. Various ways exist to avoid these singularities and at the same time get the correct nrl. There are essentially three approaches intermediate between the transformed and the untransformed formulation, namely, the bispinor decomposition, the decomposition of the lower component, and the hybrid unitary transformation partially at operator and partially at matrix level. All three possibilities were first considered by Xiao et al. [J. Chem. Phys. 126, 214101 (2007)] in a different context and in a different nomenclature. Their analysis and classification in a more general context are given here for the first time. Use of an extended balanced basis has no advantages and has other drawbacks and is not competitive, while the use of a restricted magnetic balance basis can be justified.
Temperature Sensitivity as a Microbial Trait Using Parameters from Macromolecular Rate Theory
Charlotte Jean Alster
2016-11-01
Full Text Available The activity of soil microbial extracellular enzymes is strongly controlled by temperature, yet the degree to which temperature sensitivity varies by microbe and enzyme type is unclear. Such information would allow soil microbial enzymes to be incorporated in a traits-based framework to improve prediction of ecosystem response to global change. If temperature sensitivity varies for specific soil enzymes, then determining the underlying causes of variation in temperature sensitivity of these enzymes will provide fundamental insights for predicting nutrient dynamics belowground. In this study, we characterized how both microbial taxonomic variation as well as substrate type affects temperature sensitivity. We measured β-glucosidase, leucine aminopeptidase, and phosphatase activities at six temperatures: 4, 11, 25, 35, 45, and 60°C, for seven different soil microbial isolates. To calculate temperature sensitivity, we employed two models, Arrhenius, which predicts an exponential increase in reaction rate with temperature, and Macromolecular Rate Theory (MMRT, which predicts rate to peak and then decline as temperature increases. We found MMRT provided a more accurate fit and allowed for more nuanced interpretation of temperature sensitivity in all of the enzyme × isolate combinations tested. Our results revealed that both the enzyme type and soil isolate type explain variation in parameters associated with temperature sensitivity. Because we found temperature sensitivity to be an inherent and variable property of an enzyme, we argue that it can be incorporated as a microbial functional trait, but only when using the MMRT definition of temperature sensitivity. We show that the Arrhenius metrics of temperature sensitivity are overly sensitive to test conditions, with activation energy changing depending on the temperature range it was calculated within. Thus, we propose the use of the MMRT definition of temperature sensitivity for accurate
Temperature Sensitivity as a Microbial Trait Using Parameters from Macromolecular Rate Theory.
Alster, Charlotte J; Baas, Peter; Wallenstein, Matthew D; Johnson, Nels G; von Fischer, Joseph C
2016-01-01
The activity of soil microbial extracellular enzymes is strongly controlled by temperature, yet the degree to which temperature sensitivity varies by microbe and enzyme type is unclear. Such information would allow soil microbial enzymes to be incorporated in a traits-based framework to improve prediction of ecosystem response to global change. If temperature sensitivity varies for specific soil enzymes, then determining the underlying causes of variation in temperature sensitivity of these enzymes will provide fundamental insights for predicting nutrient dynamics belowground. In this study, we characterized how both microbial taxonomic variation as well as substrate type affects temperature sensitivity. We measured β-glucosidase, leucine aminopeptidase, and phosphatase activities at six temperatures: 4, 11, 25, 35, 45, and 60°C, for seven different soil microbial isolates. To calculate temperature sensitivity, we employed two models, Arrhenius, which predicts an exponential increase in reaction rate with temperature, and Macromolecular Rate Theory (MMRT), which predicts rate to peak and then decline as temperature increases. We found MMRT provided a more accurate fit and allowed for more nuanced interpretation of temperature sensitivity in all of the enzyme × isolate combinations tested. Our results revealed that both the enzyme type and soil isolate type explain variation in parameters associated with temperature sensitivity. Because we found temperature sensitivity to be an inherent and variable property of an enzyme, we argue that it can be incorporated as a microbial functional trait, but only when using the MMRT definition of temperature sensitivity. We show that the Arrhenius metrics of temperature sensitivity are overly sensitive to test conditions, with activation energy changing depending on the temperature range it was calculated within. Thus, we propose the use of the MMRT definition of temperature sensitivity for accurate interpretation of
Paek, Insu; Cai, Li
2014-01-01
The present study was motivated by the recognition that standard errors (SEs) of item response theory (IRT) model parameters are often of immediate interest to practitioners and that there is currently a lack of comparative research on different SE (or error variance-covariance matrix) estimation procedures. The present study investigated item…
Paek, Insu; Cai, Li
2014-01-01
The present study was motivated by the recognition that standard errors (SEs) of item response theory (IRT) model parameters are often of immediate interest to practitioners and that there is currently a lack of comparative research on different SE (or error variance-covariance matrix) estimation procedures. The present study investigated item…
Cognitive Models of Risky Choice: Parameter Stability and Predictive Accuracy of Prospect Theory
Glockner, Andreas; Pachur, Thorsten
2012-01-01
In the behavioral sciences, a popular approach to describe and predict behavior is cognitive modeling with adjustable parameters (i.e., which can be fitted to data). Modeling with adjustable parameters allows, among other things, measuring differences between people. At the same time, parameter estimation also bears the risk of overfitting. Are…
Seidel, B. S.; Matwey, M. D.; Adamczyk, J. J.
1980-01-01
In the present paper, a semi-actuator-disk theory is reviewed that was developed previously for the distorted inflow to a single-stage axial-flow compressor. Flow distortion occurs far upstream; it may be a distortion in stagnation temperature, stagnation pressure, or both. Losses, quasi-steady deviation angles, and reference incidence correlations are included in the analysis, and both subsonic and transonic relative Mach numbers are considered. The theory is compared with measurements made in a transonic fan stage, and a parameter study is carried out to determine the influence of solidity on the attenuation of distortions in stagnation pressure and stagnation temperature.
Minazzoli, Olivier
2013-01-01
The post-Newtonian parameter \\gamma\\ resulting from a universal scalar/matter coupling is investigated in Brans-Dicke-like Scalar-Tensor theories where the scalar potential is assumed to be negligible. Conversely to previous studies, we use a perfect fluid formalism in order to get the explicit scalar-field equation. It is shown that the metric can be put in its standard post-Newtonian form. However, it is pointed out that 1-\\gamma\\ could be either positive, null or negative for finite value of \\omega_0, depending on the coupling function; while Scalar-Tensor theories without coupling always predict \\gamma<1 for finite value of \\omega_0.
Secher, Thomas
2008-01-01
The neural cell adhesion molecule (NCAM) is a membrane-bound glycoprotein involved in homophilic interactions that facilitate cell-cell adhesion. In addition to a number of membrane-bound isoforms, NCAM also exists in several soluble isoforms that have been identified in cerebrospinal fluid, bloo...
Li, Yuhui; Zhang, Shancai
2004-01-01
The high-gain harmonic generation (HGHG) free-electron laser (FEL) is an important candidate for a fourth-generation light source. Lots of theoretical work has been performed. Recently a further 1D theory about HGHG FEL has been developed. It considers the effects of different parameters for the whole process. An initial program based on this theory has been made. In this paper, a brief comparison of the results from this 1D program and from TDA (3D code) is discussed. It also analyses the parameters for Shanghai deep ultra violate free-electron laser source (SDUV-FEL), including electron beam energy spread, seed laser power, strength of dispersion section etc.
H. S. Negi
2011-04-01
Full Text Available An asymptotic analytical radiative transfer (AART theory was used to retrieve snow optical parameters such as extinction coefficient, diffuse exponent, asymptotic flux extinction coefficient (AFEC, snow optical thickness and probability of photon absorption (PPA. This theory was applied to the reflection and transmission data for a temperate snow cover from 400–1000 nm wavelength region, to retrieve AFEC for different types of snow cover (thick, thin, dry, wet, new and old snow. The AFEC values were found at 450 nm wavelength region in the range from 0.06 to 0.22 cm^{−1}, where high values were observed for increased wetness and impurity in snow. A good agreement between AART retrieved and other radiative transfer model retrieved parameter shows that AART theory can work well for different types of snow. The extinction coefficients for temperate snow ranged from 0.5 to 1.0 mm^{−1} and the e-folding depths ranged from 5 to 25 cm. The snow physical characteristics such as grain size and density were also retrieved using derived optical parameters and found in agreement with ground measurements. The main advantages of the proposed AART method are the simple analytical equations that provide a valuable alternative from complex numerical radiative transfer solutions.
Parameter identification theory of a complex model based on global optimization method
2008-01-01
With the development of computer technology and numerical simulation technol- ogy, computer aided engineering (CAE) technology has been widely applied to many fields. One of the main obstacles, which hinder the further application of CAE technology, is how to successfully identify the parameters of the selected model. An elementary framework for parameter identification of a complex model is pro-vided in this paper. The framework includes the construction of objective function, the design of the optimization method and the evaluation of the identified results, etc. The parameter identification process is described in this framework, taking the parameter identification of the superplastic constitutive model considering grain growth for Ti-6Al-4V at 927℃ as an example. The objective function is the weighted quadratic sums of the difference between the experimental and computational data for the stress-strain relationship and the grain growth relationship; the designed optimization method is a hybrid global optimization method, which is based on the feature of the objective function and incorporates the strengths of genetic algo-rithm (GA), the Levenberg-Marquardt algorithm and the augmented Gauss-Newton algorithm. The reliability evaluation of parameter identification result is made through the comparison between the calculated and experimental results and be-tween the theoretical values of the parameters and the identified ones.
Finke, Kathrin; Bublak, Peter; Krummenacher, Joseph
2005-01-01
The present study investigated the usability of whole and partial report of briefly displayed letter arrays as a diagnostic tool for the assessment of attentional functions. The tool is based on Bundesen's (1990, 1998, 2002; Bundesen et al., 2005) theory of visual attention (TVA), which assumes f...... clinical tests measuring similar constructs. The empirical independence of the four TVA parameters is suggested by nonsignificant or, in the case of processing speed and working memory storage capacity, only modest correlations between the parameter values.......The present study investigated the usability of whole and partial report of briefly displayed letter arrays as a diagnostic tool for the assessment of attentional functions. The tool is based on Bundesen's (1990, 1998, 2002; Bundesen et al., 2005) theory of visual attention (TVA), which assumes...... of these parameters. The present study was designed to examine whether (a) a shortened procedure bears sufficient accuracy and reliability, (b) whether the procedures reveal attentional constructs with clinical relevance, and (c) whether the mathematically independent parameters are also empirically independent...
Lugo-Frías, Rodrigo; Klapp, Sabine H L
2016-06-22
This paper is concerned with the dynamics of a binary mixture of rod-like, repulsive colloidal particles driven out of equilibrium by means of a steady shear flow (Couette geometry). To this end we first derive, starting from a microscopic density functional in Parsons-Lee approximation, a mesoscopic free energy functional whose main variables are the orientational order parameter tensors. Based on this mesoscopic functional we then explore the stability of isotropic and nematic equilibrium phases in terms of composition and rod lengths. Second, by combining the equilibrium theory with the Doi-Hess approach for the order parameter dynamics under shear, we investigate the orientational dynamics of binary mixtures for a range of shear rates and coupling parameters. We find a variety of dynamical states, including synchronized oscillatory states of the two components, but also symmetry breaking behavior where the components display different in-plane oscillatory states.
Theory of two-parameter Markov chain with an application in warranty study
Calvache, Álvaro
2012-01-01
In this paper we present the classical results of Kolmogorov's backward and forward equations to the case of a two-parameter Markov process. These equations relates the infinitesimal transition matrix of the two-parameter Markov process. However, solving these equations is not possible and we require a numerical procedure. In this paper, we give an alternative method by use of double Laplace transform of the transition probability matrix and of the infinitesimal transition matrix of the process. An illustrative example is presented for the method proposed. In this example, we consider a two-parameter warranty model, in which a system can be any of these states: working, failure. We calculate the transition density matrix of these states and also the cost of the warranty for the proposed model.
Evolutionary theory of ageing and the problem of correlated Gompertz parameters.
Burger, Oskar; Missov, Trifon I
2016-11-07
The Gompertz mortality model is often used to evaluate evolutionary theories of ageing, such as the Medawar-Williams' hypothesis that high extrinsic mortality leads to faster ageing. However, fits of the Gompertz mortality model to data often find the opposite result that mortality is negatively correlated with the rate of ageing. This negative correlation has been independently discovered in several taxa and is known in actuarial studies of ageing as the Strehler-Mildvan correlation. We examine the role of mortality selection in determining late-life variation in susceptibility to death, which has been suggested to be the cause of this negative correlation. We demonstrate that fixed-frailty models that account for heterogeneity in frailty do not remove the correlation and that the correlation is an inherent statistical property of the Gompertz distribution. Linking actuarial and biological rates of ageing will continue to be a pressing challenge, but the Strehler-Mildvan correlation itself should not be used to diagnose any biological, physiological, or evolutionary process. These findings resolve some key tensions between theory and data that affect evolutionary and biological studies of ageing and mortality. Tests of evolutionary theories of ageing should include direct measures of physiological performance or condition. Copyright © 2016 Elsevier Ltd. All rights reserved.
Torsion Cosmology of Poincar\\'e gauge theory and the constraints of its parameters via SNeIa data
Ao, Xi-Chen
2011-01-01
Poincar\\`e gauge theory (PGT) is an alternative gravity theory, which attempts to bring the gravity into the gauge-theoretic frame, where the Lagrangian is quadratic in torsion and curvature. Recently, the cosmological models with torsion based on this theory have drawn many attentions, which try to explain the cosmic acceleration in a new way. Among these PGT cosmological models, the one with only even parity dynamical modes -- SNY model, for its realistic meaning, is very attractive. In this paper, we first analyze the past-time cosmic evolution of SNY model analytically. And based on these results we fit this model to the most comprehensive SNeIa data (Union 2) and thus find the best-fit values of model parameters and initial conditions, whose related $\\chi^{2}$ value is consistent with the one from $\\Lambda$CMD at the 1$\\sigma$ level. Also by the $\\chi^{2}$ estimate, we provide certain constraints on these parameters. Using these best-fit values for the Union 2 SNeIa dataset, we are able to predict the ev...
Silver, R Angus
2003-12-15
Synapses are a key determinant of information processing in the central nervous system. Investigation of the mechanisms underlying synaptic transmission at central synapses is complicated by the inaccessibility of synaptic contacts and the fact that their temporal dynamics are governed by multiple parameters. Multiple-probability fluctuation analysis (MPFA) is a recently developed method for estimating quantal parameters from the variance and mean amplitude of evoked steady-state synaptic responses recorded under a range of release probability conditions. This article describes the theoretical basis and the underlying assumptions of MPFA, illustrating how a simplified multinomial model can be used to estimate mean quantal parameters at synapses where quantal size and release probability are nonuniform. Interpretations of the quantal parameter estimates are discussed in relation to uniquantal and multiquantal models of transmission. Practical aspects of this method are illustrated including a new method for estimating quantal size and variability, approaches for optimising data collection, error analysis and a method for identifying multivesicular release. The advantages and limitations of investigating synaptic function with MPFA are explored and contrasted with those for traditional quantal analysis and more recent optical quantal analysis methods.
Milovanović Branislav
2007-01-01
Full Text Available Introduction: There are different proofs about association of autonomic nervous system dysfunction, especially nonlinear parameters, with higher mortality after myocardial infarction. Objective The objective of the study was to determine predictive value of Poincare plot as nonlinear parameter and other significant standard risk predictors: ejection fraction of the left ventricle, late potentials, ventricular arrhythmias, and QT interval. Method The study included 1081 patients with mean follow up of 28 months (ranging fom 0-80 months. End-point of the study was cardiovascular mortality. The following diagnostic methods were used during the second week: ECG with commercial software Schiller AT-10: short time spectral analysis of RR variability with analysis of Poincare plot as nonlinear parameter and late potentials; 24-hour ambulatory ECG monitoring: QT interval, RR interval, QT/RR slope, ventricular arrhythmias (Lown >II; echocardiography examinations: systolic disorder (defined as EF<40 %. Results There were 103 (9.52% cardiovascular deaths during the follow-up. In univariate analysis, the following parameters were significantly correlated with mortality: mean RR interval < 800 ms, QT and RR interval space relationship as mean RR interval < 800 ms and QT interval > 350 ms, positive late potentials, systolic dysfunction, Poincare plot as a point, ventricular arrhythmias (Lown > II. In multivariate analysis, the significant risk predictors were: Poincare plot as a point and mean RR interval lower than 800 ms. Conclusion Mean RR interval lower than 800 ms and nonlinear and space presentation of RR interval as a point Poincare plot were multivariate risk predictors.
Toporkov, M.; Demchenko, D. O.; Zolnai, Z.; Volk, J.; Avrutin, V.; Morkoç, H.; Özgür, Ü.
2016-03-01
BexMgyZn1-x-yO semiconductor solid solutions are attractive for UV optoelectronics and electronic devices owing to their wide bandgap and capability of lattice-matching to ZnO. In this work, a combined experimental and theoretical study of lattice parameters, bandgaps, and underlying electronic properties, such as changes in band edge wavefunctions in BexMgyZn1-x-yO thin films, is carried out. Theoretical ab initio calculations predicting structural and electronic properties for the whole compositional range of materials are compared with experimental measurements from samples grown by plasma assisted molecular beam epitaxy on (0001) sapphire substrates. The measured a and c lattice parameters for the quaternary alloys BexMgyZn1-x with x = 0-0.19 and y = 0-0.52 are within 1%-2% of those calculated using generalized gradient approximation to the density functional theory. Additionally, composition independent ternary BeZnO and MgZnO bowing parameters were determined for a and c lattice parameters and the bandgap. The electronic properties were calculated using exchange tuned Heyd-Scuseria-Ernzerhof hybrid functional. The measured optical bandgaps of the quaternary alloys are in good agreement with those predicted by the theory. Strong localization of band edge wavefunctions near oxygen atoms for BeMgZnO alloy in comparison to the bulk ZnO is consistent with large Be-related bandgap bowing of BeZnO and BeMgZnO (6.94 eV). The results in aggregate show that precise control over lattice parameters by tuning the quaternary composition would allow strain control in BexMgyZn1-x-yO/ZnO heterostructures with possibility to achieve both compressive and tensile strain, where the latter supports formation of two-dimensional electron gas at the interface.
Rakkapao, Suttida; Prasitpong, Singha; Arayathanitkul, Kwan
2016-01-01
This study investigated the multiple-choice test of understanding of vectors (TUV), by applying item response theory (IRT). The difficulty, discriminatory, and guessing parameters of the TUV items were fit with the three-parameter logistic model of IRT, using the parscale program. The TUV ability is an ability parameter, here estimated assuming…
Identification of observer/Kalman filter Markov parameters: Theory and experiments
Juang, Jer-Nan; Phan, Minh; Horta, Lucas G.; Longman, Richard W.
1991-01-01
An algorithm to compute Markov parameters of an observer or Kalman filter from experimental input and output data is discussed. The Markov parameters can then be used for identification of a state space representation, with associated Kalman gain or observer gain, for the purpose of controller design. The algorithm is a non-recursive matrix version of two recursive algorithms developed in previous works for different purposes. The relationship between these other algorithms is developed. The new matrix formulation here gives insight into the existence and uniqueness of solutions of certain equations and gives bounds on the proper choice of observer order. It is shown that if one uses data containing noise, and seeks the fastest possible deterministic observer, the deadbeat observer, one instead obtains the Kalman filter, which is the fastest possible observer in the stochastic environment. Results are demonstrated in numerical studies and in experiments on an ten-bay truss structure.
Order parameters in the Landau–de Gennes theory – the static and dynamic scenarios
Majumdar, Apala
2011-02-17
We obtain quantitative estimates for the scalar order parameters of liquid crystal configurations in three-dimensional geometries, within the Landau-de Gennes framework. We consider both static equilibria and non-equilibrium dynamics and we include external fields and surface anchoring energies in our formulation. Using maximum principle-type arguments, we obtain explicit bounds for the corresponding scalar order parameters in both static and dynamic situations; these bounds are given in terms of the material-dependent thermotropic coefficients, electric field strength and surface anchoring coefficients. These bounds provide estimates for the degree of orientational ordering, quantify the competing effects of the different energetic contributions and can be used to test the accuracy of numerical simulations. © 2011 Taylor & Francis.
Mladenović Zorica
2006-01-01
Full Text Available In this paper different aspects of value-at-risk estimation are considered. Daily returns of CISCO, INTEL and NASDAQ stock indices are analyzed for period: September 1996 - September 2006. Methods that incorporate time varying variability and heavy tails of the empirical distributions of returns are implemented. The main finding of the paper is that standard econometric methods underestimate the value-at-risk parameter if heavy tails of the empirical distribution are not explicitly taken into account. .
Insoluble vs. soluble fiber; Fiber - soluble vs. insoluble ... There are 2 different types of fiber -- soluble and insoluble. Both are important for health, digestion, and preventing diseases. Soluble fiber attracts water and turns to gel during digestion. ...
Cloud droplet activation: solubility revisited
L. T. Padró
2007-02-01
Full Text Available Soluble compounds present in atmospheric aerosol facilitate their transformation into cloud droplets by depressing the equilibrium vapor pressure required for activation. Their impact depends on the amount of dissolved substance in the aerosol aqueous phase, which in turn is controlled by its solubility. This study explores the impact of particle curvature on solubility, expressed in terms of a Kelvin enhancement. The augmented solubility, termed "Curvature Enhanced Solubility" (CES, is then introduced into Köhler theory for assessment of its impact on CCN activity for several organic compounds with a wide range of aqueous solubility. The interfacial energy between solute and aqueous phase required for quantification of CES is determined from existing correlations based on bulk solubility, and concurrent measurements of contact angle and surface tension. A number of important findings arise from this study: i CES can substantially increase solubility and impact CCN activity but only if the aerosol is initially wet, ii CES can stabilize highly supersaturated solutions, and provide a mechanism for retention of an aerosol aqueous phase even at very low relative humidity (RH, and, iii trace amounts of surfactant impurities can magnify the impact of CES.
Zhifeng Zhong
2017-01-01
Full Text Available Owing to the environment, temperature, and so forth, photovoltaic power generation volume is always fluctuating and subsequently impacts power grid planning and operation seriously. Therefore, it is of great importance to make accurate prediction of the power generation of photovoltaic (PV system in advance. In order to improve the prediction accuracy, in this paper, a novel particle swarm optimization algorithm based multivariable grey theory model is proposed for short-term photovoltaic power generation volume forecasting. It is highlighted that, by integrating particle swarm optimization algorithm, the prediction accuracy of grey theory model is expected to be highly improved. In addition, large amounts of real data from two separate power stations in China are being employed for model verification. The experimental results indicate that, compared with the conventional grey model, the mean relative error in the proposed model has been reduced from 7.14% to 3.53%. The real practice demonstrates that the proposed optimization model outperforms the conventional grey model from both theoretical and practical perspectives.
Quantum parameter space and double scaling limits in N=1 super Yang-Mills theory
Ferrari, Frank
2003-04-01
We study the physics of N=1 super Yang-Mills theory with the gauge group U(N) and one adjoint Higgs field, by using the recently derived exact effective superpotentials. Interesting phenomena occur for some special values of the Higgs potential couplings. We find critical points with massless glueballs and/or massless monopoles, confinement without a mass gap, and tensionless domain walls. We describe the transitions between regimes with different patterns of gauge symmetry breaking, or, in the matrix model language, between solutions with a different number of cuts. The standard large N expansion is singular near the critical points, with domain wall tensions scaling as a fractional power of N. We argue that the critical points are four-dimensional analogues of the Kazakov critical points that are commonly found in low dimensional matrix integrals. We define a double scaling limit that yields the exact tension of BPS two-branes in the resulting N=1, four-dimensional noncritical string theory. D-brane states can be deformed continuously into closed string solitonic states, and vice versa, along paths that go over regions where the string coupling is strong.
Quantum parameter space and double scaling limits in N=1 super Yang-Mills theory
Ferrari, F
2003-01-01
We study the physics of N=1 super Yang-Mills theory with gauge group U(Nc) and one adjoint Higgs field, by using the recently derived exact effective superpotentials. Interesting phenomena occur for some special values of the Higgs potential couplings. We find critical points with massless glueballs and/or massless monopoles, confinement without a mass gap, and tensionless domain walls. We describe the transitions between regimes with different patterns of gauge symmetry breaking, or, in the matrix model language, between solutions with a different number of cuts. The standard large Nc expansion is singular near the critical points, with domain walls tensions scaling as a fractional power of Nc. We argue that the critical points are four dimensional analogues of the Kazakov critical points that are commonly found in low dimensional matrix integrals. We define a double scaling limit that yields the exact tension of BPS two-branes in the resulting N=1, four dimensional non-critical string theory. D-brane states...
Miller A Ruidiaz
2011-09-01
Full Text Available Extended Hildebrand Solubility Approach (EHSA was successfully applied to evaluate the solubility of Indomethacin in 1,4-dioxane + water mixtures at 298.15 K. An acceptable correlation-performance of EHSA was found by using a regular polynomial model in order four of the W interaction parameter vs. solubility parameter of the mixtures (overall deviation was 8.9%. Although the mean deviation obtained was similar to that obtained directly by means of an empiric regression of the experimental solubility vs. mixtures solubility parameters, the advantages of EHSA are evident because it requires physicochemical properties easily available for drugs.
2015-01-01
We developed a novel decision-making paradigm that allows us to apply prospect theory in behavioral economics to body mass. 67 healthy young adults completed self-report measures and two decision-making tasks for weight-loss, as well as for monetary rewards. We estimated risk-related preference and loss aversion parameters for each individual, separately for weight-loss and monetary rewards choice data. Risk-seeking tendency for weight-loss was positively correlated with body mass index in in...
Hul, Oleh; Seba, Petr; Sirko, Leszek
2009-06-01
Parameter-dependent statistical properties of spectra of totally connected irregular quantum graphs with Neumann boundary conditions are studied. The autocorrelation functions of level velocities c(x) and c[over ](omega,x) as well as the distributions of level curvatures and avoided crossing gaps are calculated. The numerical results are compared with the predictions of random matrix theory for Gaussian orthogonal ensemble (GOE) and for coupled GOE matrices. The application of coupled GOE matrices was justified by studying localization phenomena in graphs' wave functions Psi(x) using the inverse participation ratio and the amplitude distribution P(Psi(x)) .
Finotello Alexia; Bara Jason E.; Narayan Suguna; Campder Dean; Noble Richard D. [University of Colorado, Boulder, CO (United States)
2008-07-01
This study focuses on the solubility behaviors of CO{sub 2}, CH{sub 4}, and N{sub 2} gases in binary mixtures of imidazolium-based room-temperature ionic liquids (RTILs) using l-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)-imide ((C{sub 2}mim)(Tf{sub 2}N)) and l-ethyl-3-methylimidazolium tetrafluoroborate ((C{sub 2}mim)(BF{sub 4})) at 40{sup o}C and low pressures (about 1 atm). The mixtures tested were 0, 25, 50, 75, 90, 95, and 100 mol % (C{sub 2}mim)(BF{sub 4}) in (C{sub 2}-mim)(Tf2{sub N}). 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 CO{sub 2} with N{sub 2} or CH{sub 4} in pure (C{sub 2}mim)(BF4) can be enhanced by adding 5 mol% (C{sub 2}-mim)(Tf{sub 2}N).
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].
Multi-parameter singular Radon transforms I: the $L^2$ theory
Street, Brian
2010-01-01
The purpose of this paper is to study the $L^2$ boundedness of operators of the form \\[ f\\mapsto \\psi(x) \\int f(\\gamma_t(x)) K(t) dt, \\] where $\\gamma_t(x)$ is a $C^\\infty$ function defined on a neighborhood of the origin in $(t,x)\\in \\R^N\\times \\R^n$, satisfying $\\gamma_0(x)\\equiv x$, $\\psi$ is a $C^\\infty$ cutoff function supported on a small neighborhood of $0\\in \\R^n$, and $K$ is a ``multi-parameter singular kernel'' supported on a small neighborhood of $0\\in \\R^N$. The goal is, given an appropriate class of kernels $K$, to give conditions on $\\gamma$ such that every operator of the above form is bounded on $L^2$. The case when $K$ is a Calder\\'on-Zygmund kernel was studied by Christ, Nagel, Stein, and Wainger; we generalize their conditions to the case when $K$ has a ``multi-parameter'' structure. For example, when $K$ is given by a ``product kernel.'' Even when $K$ is a Calder\\'on-Zygmund kernel, our methods yield some new results. This is the first paper in a three part series, the later two of which a...
张素风; 梅星贤; 张璐璐
2013-01-01
Mixed solvents including benzene-ethanol-water, toluene-ethanol-water and styrene-ethanol-water were used as a separating agent to separate aluminum and plastic composite. The volume ratio of each component of the mixed solvent used for completely separating the aluminum and plastic composite was investigated; the solubility parameter range of the organic adhesive used in the composite could be obtained through calculating the solubility parameter of the mixed solvent. The results showed that the ideal range of solubility parameters of organic adhesive is 29.1 to 34.8; the required volume ratio of toluene is least when using toluene-ethanol-water solvent as the separating agent.%针对混合溶剂处理铝塑复合物工艺的研究,分别以苯-乙醇-水、甲苯-乙醇-水、苯乙烯-乙醇-水3种混合液作为分离剂进行铝塑分离实验.由于苯、甲苯、苯乙烯的溶解度参数相近,当铝塑完全分离时,考察不同分离剂各组分的体积比,通过混合溶剂溶解度参数计算公式得出各混合溶剂的溶解度参数.根据相似相溶原理,得出铝塑复合物间有机胶黏剂溶解度参数的理想范围.结果表明,3种混合溶剂处理铝塑复合物,当铝塑完全分离时,铝塑复合物间胶黏剂的溶解度参数范围为29.1 ～ 34.8；甲苯-乙醇-水混合溶剂作为分离剂,所需的甲苯体积比最小(20％).
The Relation Between Ground Acceleration and Earthquake Source Parameters: Theory and Observations
Lior, Itzhak; Ziv, Alon
2017-04-01
A simple relation between the root-mean-square of the ground acceleration and earthquake spectral (or source) parameters is introduced: 2 ----f20---- Arms = (2π )Ω0 √--( πκf0-)2, πκT 1 + 1.50.25 where Ω0 is the low frequency displacement spectral plateau, f0 is the corner frequency, κ is an attenuation parameter, and T is the data interval. This result uses the omega-squared model for far-field radiation, and accounts for site-specific attenuation. The main advantage of the new relation with respect to that of Hanks' (Hanks, 1979) is that it relaxes the simplifying assumption that the spectral corner frequency is much smaller than the maximum corner frequency resulting from attenuation, and that the spectrum may be approximated as being perfectly flat between the two frequencies. The newly proposed relation is tested using a composite dataset of earthquake records from Japan, California, Mexico and Taiwan. Excellent agreement is found between observed and predicted ground acceleration for any combination of corner frequencies. Thus, use of the above relation enables the extrapolation of ground motion prediction equation inferred from the frequent small magnitude earthquakes to the rare large magnitudes. This capacity is extremely useful near slow-slip plate boundaries, where the seismic moment release rates are low. Reference Hanks, T. C. (1979). b values and ω-γ seismic source models: implications for tectonic stress variations along active crustal fault zones and the estimation of high-frequency strong ground motion, J. Geophys. Res. 84, 2235-2241.
Revisiting a model of ontogenetic growth: estimating model parameters from theory and data.
Moses, Melanie E; Hou, Chen; Woodruff, William H; West, Geoffrey B; Nekola, Jeffery C; Zuo, Wenyun; Brown, James H
2008-05-01
The ontogenetic growth model (OGM) of West et al. provides a general description of how metabolic energy is allocated between production of new biomass and maintenance of existing biomass during ontogeny. Here, we reexamine the OGM, make some minor modifications and corrections, and further evaluate its ability to account for empirical variation on rates of metabolism and biomass in vertebrates both during ontogeny and across species of varying adult body size. We show that the updated version of the model is internally consistent and is consistent with other predictions of metabolic scaling theory and empirical data. The OGM predicts not only the near universal sigmoidal form of growth curves but also the M(1/4) scaling of the characteristic times of ontogenetic stages in addition to the curvilinear decline in growth efficiency described by Brody. Additionally, the OGM relates the M(3/4) scaling across adults of different species to the scaling of metabolic rate across ontogeny within species. In providing a simple, quantitative description of how energy is allocated to growth, the OGM calls attention to unexplained variation, unanswered questions, and opportunities for future research.
Seung-Lark eLim
2015-03-01
Full Text Available We developed a novel decision-making paradigm that allows us to apply prospect theory in behavioral economics to body mass. 67 healthy young adults completed self-report measures and two decision-making tasks for weight-loss, as well as for monetary rewards. We estimated risk-related preference and loss aversion parameters for each individual, separately for weight-loss and monetary rewards choice data. Risk-seeking tendency for weight-loss was positively correlated with body mass index in individuals who desired to lose body weight, whereas the risk-seeking for momentary rewards was not. Risk-seeking for weight-loss was correlated to excessive body shape preoccupations, while aversion to weight-gain was correlated with self-reports of behavioral involvement for successful weight-loss. We demonstrated that prospect theory can be useful in explaining the decision-making process related to body mass. Applying prospect theory is expected to advance our understanding of decision-making mechanisms in obesity, which might prove helpful for improving healthy choices.
Lim, Seung-Lark; Bruce, Amanda S
2015-01-01
We developed a novel decision-making paradigm that allows us to apply prospect theory in behavioral economics to body mass. 67 healthy young adults completed self-report measures and two decision-making tasks for weight-loss, as well as for monetary rewards. We estimated risk-related preference and loss aversion parameters for each individual, separately for weight-loss and monetary rewards choice data. Risk-seeking tendency for weight-loss was positively correlated with body mass index in individuals who desired to lose body weight, whereas the risk-seeking for momentary rewards was not. Risk-seeking for weight-loss was correlated to excessive body shape preoccupations, while aversion to weight-gain was correlated with self-reports of behavioral involvement for successful weight-loss. We demonstrated that prospect theory can be useful in explaining the decision-making process related to body mass. Applying prospect theory is expected to advance our understanding of decision-making mechanisms in obesity, which might prove helpful for improving healthy choices.
Zhou, Shiqi
2011-12-01
Thermodynamic and structural properties of liquids are of fundamental interest in physics, chemistry, and biology, and perturbation approach has been fundamental to liquid theoretical approaches since the dawn of modern statistical mechanics and remains so to this day. Although thermodynamic perturbation theory (TPT) is widely used in the chemical physics community, one of the most popular versions of the TPT, i.e. Zwanzig (Zwanzig, R. W. J. Chem. Phys. 1954, 22, 1420-1426) 1st-order high temperature series expansion (HTSE) TPT and its 2nd-order counterpart under a macroscopic compressibility approximation of Barker-Henderson (Barker, J. A.; Henderson, D. J. Chem. Phys. 1967, 47, 2856-2861), have some serious shortcomings: (i) the nth-order term of the HTSE is involved with reference fluid distribution functions of order up to 2n, and the higher-order terms hence progressively become more complicated and numerically inaccessible; (ii) the performance of the HTSE rapidly deteriorates and the calculated results become even qualitatively incorrect as the temperature of interest decreases. This account deals with the developments that we have made over the last five years or so to advance a coupling parameter series expansion (CPSE) and a non hard sphere (HS) perturbation strategy that has scored some of its greatest successes in overcoming the above-mentioned difficulties. In this account (i) we expatiate on implementation details of our schemes: how input information indispensable to high-order truncation of the CPSE in both the HS and non HS perturbation schemes is calculated by an Ornstein-Zernike integral equation theory; how high-order thermodynamic quantities, such as critical parameters and excess constant volume heat capacity, are extracted from the resulting excess Helmholtz free energy with irregular and inevitable numerical errors; how to select reference potential in the non HS perturbation scheme. (ii) We give a quantitative analysis on why convergence
Shiqi Zhou
2011-12-01
Full Text Available Thermodynamic and structural properties of liquids are of fundamental interest in physics, chemistry, and biology, and perturbation approach has been fundamental to liquid theoretical approaches since the dawn of modern statistical mechanics and remains so to this day. Although thermodynamic perturbation theory (TPT is widely used in the chemical physics community, one of the most popular versions of the TPT, i.e. Zwanzig (Zwanzig, R. W. J. Chem. Phys. 1954, 22, 1420-1426 1st-order high temperature series expansion (HTSE TPT and its 2nd-order counterpart under a macroscopic compressibility approximation of Barker-Henderson (Barker, J. A.; Henderson, D. J. Chem. Phys. 1967, 47, 2856-2861, have some serious shortcomings: (i the nth-order term of the HTSE is involved with reference fluid distribution functions of order up to 2n, and the higher-order terms hence progressively become more complicated and numerically inaccessible; (ii the performance of the HTSE rapidly deteriorates and the calculated results become even qualitatively incorrect as the temperature of interest decreases. This account deals with the developments that we have made over the last five years or so to advance a coupling parameter series expansion (CPSE and a non hard sphere (HS perturbation strategy that has scored some of its greatest successes in overcoming the above-mentioned difficulties. In this account (i we expatiate on implementation details of our schemes: how input information indispensable to high-order truncation of the CPSE in both the HS and non HS perturbation schemes is calculated by an Ornstein-Zernike integral equation theory; how high-order thermodynamic quantities, such as critical parameters and excess constant volume heat capacity, are extracted from the resulting excess Helmholtz free energy with irregular and inevitable numerical errors; how to select reference potential in the non HS perturbation scheme. (ii We give a quantitative analysis on why
Multi-parameter singular Radon transforms II: the L^p theory
Stein, Elias M
2011-01-01
The purpose of this paper is to study the $L^p$ boundedness of operators of the form \\[ f\\mapsto \\psi(x) \\int f(\\gamma_t(x))K(t)\\: dt, \\] where $\\gamma_t(x)$ is a $C^\\infty$ function defined on a neighborhood of the origin in $(t,x)\\in \\R^N\\times \\R^n$, satisfying $\\gamma_0(x)\\equiv x$, $\\psi$ is a $C^\\infty$ cutoff function supported on a small neighborhood of $0\\in \\R^n$, and $K$ is a "multi-parameter singular kernel" supported on a small neighborhood of $0\\in \\R^N$. We also study associated maximal operators. The goal is, given an appropriate class of kernels $K$, to give conditions on $\\gamma$ such that every operator of the above form is bounded on $L^p$ ($1
Toporkov, M.; Avrutin, V.; Morkoç, H.; Özgür, Ü. [Department of Electrical and Computer Engineering, Virginia Commonwealth University, Richmond, Virginia 23284 (United States); Demchenko, D. O. [Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284 (United States); Zolnai, Z. [MTA EK Institute of Technical Physics and Materials Science, Budapest (Hungary); Volk, J. [Department of Electrical and Computer Engineering, Virginia Commonwealth University, Richmond, Virginia 23284 (United States); MTA EK Institute of Technical Physics and Materials Science, Budapest (Hungary)
2016-03-07
Be{sub x}Mg{sub y}Zn{sub 1−x−y}O semiconductor solid solutions are attractive for UV optoelectronics and electronic devices owing to their wide bandgap and capability of lattice-matching to ZnO. In this work, a combined experimental and theoretical study of lattice parameters, bandgaps, and underlying electronic properties, such as changes in band edge wavefunctions in Be{sub x}Mg{sub y}Zn{sub 1−x−y}O thin films, is carried out. Theoretical ab initio calculations predicting structural and electronic properties for the whole compositional range of materials are compared with experimental measurements from samples grown by plasma assisted molecular beam epitaxy on (0001) sapphire substrates. The measured a and c lattice parameters for the quaternary alloys Be{sub x}Mg{sub y}Zn{sub 1−x} with x = 0−0.19 and y = 0–0.52 are within 1%–2% of those calculated using generalized gradient approximation to the density functional theory. Additionally, composition independent ternary BeZnO and MgZnO bowing parameters were determined for a and c lattice parameters and the bandgap. The electronic properties were calculated using exchange tuned Heyd-Scuseria-Ernzerhof hybrid functional. The measured optical bandgaps of the quaternary alloys are in good agreement with those predicted by the theory. Strong localization of band edge wavefunctions near oxygen atoms for BeMgZnO alloy in comparison to the bulk ZnO is consistent with large Be-related bandgap bowing of BeZnO and BeMgZnO (6.94 eV). The results in aggregate show that precise control over lattice parameters by tuning the quaternary composition would allow strain control in Be{sub x}Mg{sub y}Zn{sub 1−x−y}O/ZnO heterostructures with possibility to achieve both compressive and tensile strain, where the latter supports formation of two-dimensional electron gas at the interface.
Solubility Characteristics of PCBM and C60.
Boucher, David; Howell, Jason
2016-11-10
Empirical data indicate that several good solvents for C60 and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) have substantial polar and hydrogen-bonding components, which are not intrinsic to the structure of the C60 and PCBM molecules themselves. Functional solubility parameter (FSP) and convex solubility parameter (CSP) computations are performed on C60 and PCBM using solubility data available in the literature. The CSP and FSP results are compared to previously reported Hansen solubility parameters (HSPs) and to the parameters calculated using additive functional group contribution methods. The CSP and FSP methods confirm the anomalously large polar and hydrogen-bonding parameters, δP and δH, obtained experimentally for C60 and PCBM. This behavior, which is quite irregular given the structure of the molecules, is due to the fact that several good solvents have high δP and δH values. Thus, these irregularities are highlighted by the CSP and FSP calculations. Additional contradictory solubility characteristics are disclosed by comparing the experimental solubility parameters to a linear solvation energy relationship (LSER) model, additive functional group calculations, and COSMO-RS computations. The FSP solubility function strongly suggests that the solubility parameters do not accurately represent the cohesive energy density properties of C60 and PCBM, as intended, but rather they manifest the properties of the solvents, e.g., high δP and δH values, that are necessary to accommodate these molecules in the liquid phase.
Candy, J. [General Atomics, San Diego, CA (United States)
2015-12-01
This work was motivated by the observation, as early as 2008, that GYRO simulations of some ITER operating scenarios exhibited nonlinear zonal-flow generation large enough to effectively quench turbulence inside r /a ~ 0.5. This observation of flow-dominated, low-transport states persisted even as more accurate and comprehensive predictions of ITER profiles were made using the state-of-the-art TGLF transport model. This core stabilization is in stark contrast to GYRO-TGLF comparisons for modern-day tokamaks, for which GYRO and TGLF are typically in very close agreement. So, we began to suspect that TGLF needed to be generalized to include the effect of zonal-flow stabilization in order to be more accurate for the conditions of reactor simulations. While the precise cause of the GYRO-TGLF discrepancy for ITER parameters was not known, it was speculated that closeness to threshold in the absence of driven rotation, as well as electromagnetic stabilization, created conditions more sensitive the self-generated zonal-flow stabilization than in modern tokamaks. Need for nonlinear zonal-flow stabilization: To explore the inclusion of a zonal-flow stabilization mechanism in TGLF, we started with a nominal ITER profile predicted by TGLF, and then performed linear and nonlinear GYRO simulations to characterize the behavior at and slightly above the nominal temperature gradients for finite levels of energy transport. Then, we ran TGLF on these cases to see where the discrepancies were largest. The predicted ITER profiles were indeed near to the TGLF threshold over most of the plasma core in the hybrid discharge studied (weak magnetic shear, q > 1). Scanning temperature gradients above the TGLF power balance values also showed that TGLF overpredicted the electron energy transport in the low-collisionality ITER plasma. At first (in Q3), a model of only the zonal-flow stabilization (Dimits shift) was attempted. Although we were able to construct an ad hoc model of the zonal
Candy, J. [General Atomics, San Diego, CA (United States)
2015-12-01
This work was motivated by the observation, as early as 2008, that GYRO simulations of some ITER operating scenarios exhibited nonlinear zonal-flow generation large enough to effectively quench turbulence inside r /a ~ 0.5. This observation of flow-dominated, low-transport states persisted even as more accurate and comprehensive predictions of ITER profiles were made using the state-of-the-art TGLF transport model. This core stabilization is in stark contrast to GYRO-TGLF comparisons for modern-day tokamaks, for which GYRO and TGLF are typically in very close agreement. So, we began to suspect that TGLF needed to be generalized to include the effect of zonal-flow stabilization in order to be more accurate for the conditions of reactor simulations. While the precise cause of the GYRO-TGLF discrepancy for ITER parameters was not known, it was speculated that closeness to threshold in the absence of driven rotation, as well as electromagnetic stabilization, created conditions more sensitive the self-generated zonal-flow stabilization than in modern tokamaks. Need for nonlinear zonal-flow stabilization: To explore the inclusion of a zonal-flow stabilization mechanism in TGLF, we started with a nominal ITER profile predicted by TGLF, and then performed linear and nonlinear GYRO simulations to characterize the behavior at and slightly above the nominal temperature gradients for finite levels of energy transport. Then, we ran TGLF on these cases to see where the discrepancies were largest. The predicted ITER profiles were indeed near to the TGLF threshold over most of the plasma core in the hybrid discharge studied (weak magnetic shear, q > 1). Scanning temperature gradients above the TGLF power balance values also showed that TGLF overpredicted the electron energy transport in the low-collisionality ITER plasma. At first (in Q3), a model of only the zonal-flow stabilization (Dimits shift) was attempted. Although we were able to construct an ad hoc model of the zonal
Hadi Mirab; Reza Fathi; Vahid Jahangiri; Mir Mohammad Ettefagh; Reza Hassannejad
2015-01-01
One of the new methods for powering low-power electronic devices at sea is a wave energy harvesting system. In this method, piezoelectric material is employed to convert the mechanical energy of sea waves into electrical energy. The advantage of this method is based on avoiding a battery charging system. Studies have been done on energy harvesting from sea waves, however, considering energy harvesting with random JONSWAP wave theory, then determining the optimum values of energy harvested is new. This paper does that by implementing the JONSWAP wave model, calculating produced power, and realistically showing that output power is decreased in comparison with the more simple Airy wave model. In addition, parameters of the energy harvester system are optimized using a simulated annealing algorithm, yielding increased produced power.
Wang Yan-Li; Zhang Jun-Ping; Su Ke-He; Wang Xin; Liu Yan; Sun Xu
2012-01-01
Armchair (n,n) single walled boron nitride nanotubes with n=2-17 are studied by the density functional theory at the B3LYP/3-21G(d) level combined with the periodic boundary conditions for simulating the ultra long model.The results show that the structure parameters and the formation energies bear a strong relationship to n.The fitted analytical equations are developed with correlation coefficients larger than 0.999.The energy gaps of (2,2) and (3,3)tubes are indirect gaps,and the larger tubes (n=4-17) have direct energy gaps.Results show that the armchair boron nitride nanotubes (n=2-17) are insulators with wide energy gaps of between 5.93 eV and 6.23 eV.
Abbruzzese, G.; Campopiano, A.
1994-05-01
The secondary recrystallization (SR) process and the related effects on the magnetic properties of silicon-iron are discussed in the framework of the general statistical theory of grain growth including texture and Zener drag influence. It has been shown that SR in silicon-iron is related to a selective growth process experienced by Goss grains due to specific grain boundary conditions generated by the surrounding grains (texture). In this paper some examples showing the specific role of various microstructural parameters influencing the selectivity of SR (such as Zener drag intensity and its drop rate, initial grain size, etc.), are discussed and related to the magnetic properties, which are mainly controlled by the final average grain size and orientation.
无
2007-01-01
The Flory-Huggins interaction parameter (χ∞1,2) and solubility parameter (δ2) and its hydrogen bonding sensing component (δh) were determined using inverse gas chromatography (IGC). These parameters were successfully used in the probes of chemical changes that occur during the oxidation of naphthenic and paraffinic base oils in a GC column. Changes in χ∞1,2 values reflect the different types of intermolecular interactions ( dispersive, polar, hydrogen bonding) of the given lubricating base oil during oxidation. The obtained results showed that δh component of solubility parameter is the most important parameter for probing the oxidativechemical changes during the oxidation of given lubricating oils.
Solubility parameter of poly(trimethylene sulfide)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(thioethylene)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(propylene oxide)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(propylene glycol)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(vinylidene fluoride)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(vinyl chloride)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(tetramethylene oxide)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(N-vinylcarbazole)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(vinyl propionate)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(vinyl fluoride)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(vinyl acetate)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(vinyl bromide)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(2-vinylpyridine)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(propyl methacrylate)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(tetrafluoroethylene)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Bellasio, Chandra; Beerling, David J; Griffiths, Howard
2016-06-01
The higher photosynthetic potential of C4 plants has led to extensive research over the past 50 years, including C4 -dominated natural biomes, crops such as maize, or for evaluating the transfer of C4 traits into C3 lineages. Photosynthetic gas exchange can be measured in air or in a 2% Oxygen mixture using readily available commercial gas exchange and modulated PSII fluorescence systems. Interpretation of these data, however, requires an understanding (or the development) of various modelling approaches, which limit the use by non-specialists. In this paper we present an accessible summary of the theory behind the analysis and derivation of C4 photosynthetic parameters, and provide a freely available Excel Fitting Tool (EFT), making rigorous C4 data analysis accessible to a broader audience. Outputs include those defining C4 photochemical and biochemical efficiency, the rate of photorespiration, bundle sheath conductance to CO2 diffusion and the in vivo biochemical constants for PEP carboxylase. The EFT compares several methodological variants proposed by different investigators, allowing users to choose the level of complexity required to interpret data. We provide a complete analysis of gas exchange data on maize (as a model C4 organism and key global crop) to illustrate the approaches, their analysis and interpretation. © 2015 John Wiley & Sons Ltd.
Jones, Matthew D; Buckton, Graham
2016-07-25
The abilities of the cohesive-adhesive balance approach to atomic force microscopy (AFM) and the measurement of Hansen partial solubility parameters by inverse gas chromatography (IGC) to predict the performance of carrier-based dry powder inhaler (DPI) formulations were compared. Five model drugs (beclometasone dipropionate, budesonide, salbutamol sulphate, terbutaline sulphate and triamcinolone acetonide) and three model carriers (erythritol, α-lactose monohydrate and d-mannitol) were chosen, giving fifteen drug-carrier combinations. Comparison of the AFM and IGC interparticulate adhesion data suggested that they did not produce equivalent results. Comparison of the AFM data with the in vitro fine particle delivery of appropriate DPI formulations normalised to account for particle size differences revealed a previously observed pattern for the AFM measurements, with a slightly cohesive AFM CAB ratio being associated with the highest fine particle fraction. However, no consistent relationship between formulation performance and the IGC data was observed. The results as a whole highlight the complexity of the many interacting variables that can affect the behaviour of DPIs and suggest that the prediction of their performance from a single measurement is unlikely to be successful in every case.
陈荣圻
2013-01-01
溶解度参数δ是热力学上衡量非极性溶质与溶剂之间作用力的一种方法,将其用于分散染料对PET聚酯纤维染色中,通过计算PET的δ为10.30～11.6之间,与分散染料有很好的相容性,因此染色性能与牢度性能俱佳.将该方法用于分散染料拼混和染厂拼色,可获得极佳效果.PTT聚酯的δ值为10.50,也可用传统分散染料染色.PLA纤维是一类脂肪族聚酯纤维,性能与PET、PTT不同,其δ值为12.8,传统分散染料达不到很好效果,需研发PLA专用分散染料.%Solubility parameters δ is a thermodynamical parameter to evaluate the action between nonpolar solute and solvent. The 5 value of PET fiber is 10.30 ~ 11.6, so it has good compatibility with disperse dyes, and can obtain good dyeing behavior and color fastness. It can be used to evaluate the compound dyeing results in dye house. The 5 value of PTT fiber is 10.50, and it can be dyed with traditional disperse dyes. PLA fiber is a kind of aromatic polyester fiber, and its properties are different from PET and PTT fiber. The S value of PLA fiber is 12.8, if it is dyed with traditional disperse dyes, PLA fiber can not obtain satisfactory dyeing results, so special disperse dyes for PLA is looked forward to be developed.
Minazzoli, Olivier
2012-01-01
The effect of a universal scalar/matter coupling are investigated in Scalar-Tensor theories. It is shown that the metric can be put in its standard post-Newtonian form -- in contradiction with '$\\gamma$ parameter and Solar System constraint in chameleon-Brans-Dicke theory', Phys. Rev. D 83, 104019 (2011), 1201.0271, Saaidi et al. However, assuming the validity of an effective Lagrangian for the matter field, it is pointed out that $1-\\gamma$ could be either positive, null or negative for finite value of $\\omega$, depending on the coupling function; while Scalar-Tensor theories without coupling always predict $\\gamma<1$ for finite value of $\\omega$.
Gas solubilities widespread applications
Gerrard, William
1980-01-01
Gas Solubilities: Widespread Applications discusses several topics concerning the various applications of gas solubilities. The first chapter of the book reviews Henr's law, while the second chapter covers the effect of temperature on gas solubility. The third chapter discusses the various gases used by Horiuti, and the following chapters evaluate the data on sulfur dioxide, chlorine data, and solubility data for hydrogen sulfide. Chapter 7 concerns itself with solubility of radon, thoron, and actinon. Chapter 8 tackles the solubilities of diborane and the gaseous hydrides of groups IV, V, and
Dahms, Rainer N
2015-05-01
The fidelity of Gradient Theory simulations depends on the accuracy of saturation properties and influence parameters, and require equations of state (EoS) which exhibit a fundamentally consistent behavior in the two-phase regime. Widely applied multi-parameter EoS, however, are generally invalid inside this region. Hence, they may not be fully suitable for application in concert with Gradient Theory despite their ability to accurately predict saturation properties. The commonly assumed temperature-dependence of pure component influence parameters usually restricts their validity to subcritical temperature regimes. This may distort predictions for general multi-component interfaces where temperatures often exceed the critical temperature of vapor phase components. Then, the calculation of influence parameters is not well defined. In this paper, one of the first studies is presented in which Gradient Theory is combined with a next-generation Helmholtz energy EoS which facilitates fundamentally consistent calculations over the entire two-phase regime. Illustrated on pentafluoroethane as an example, reference simulations using this method are performed. They demonstrate the significance of such high-accuracy and fundamentally consistent calculations for the computation of interfacial properties. These reference simulations are compared to corresponding results from cubic PR EoS, widely-applied in combination with Gradient Theory, and mBWR EoS. The analysis reveals that neither of those two methods succeeds to consistently capture the qualitative distribution of obtained key thermodynamic properties in Gradient Theory. Furthermore, a generalized expression of the pure component influence parameter is presented. This development is informed by its fundamental definition based on the direct correlation function of the homogeneous fluid and by presented high-fidelity simulations of interfacial density profiles. The new model preserves the accuracy of previous temperature
Zheng, Minyi; Zhang, Bangji; Zhang, Jie; Zhang, Nong
2016-07-01
Physical parameters are very important for vehicle dynamic modeling and analysis. However, most of physical parameter identification methods are assuming some physical parameters of vehicle are known, and the other unknown parameters can be identified. In order to identify physical parameters of vehicle in the case that all physical parameters are unknown, a methodology based on the State Variable Method(SVM) for physical parameter identification of two-axis on-road vehicle is presented. The modal parameters of the vehicle are identified by the SVM, furthermore, the physical parameters of the vehicle are estimated by least squares method. In numerical simulations, physical parameters of Ford Granada are chosen as parameters of vehicle model, and half-sine bump function is chosen to simulate tire stimulated by impulse excitation. The first numerical simulation shows that the present method can identify all of the physical parameters and the largest absolute value of percentage error of the identified physical parameter is 0.205%; and the effect of the errors of additional mass, structural parameter and measurement noise are discussed in the following simulations, the results shows that when signal contains 30 dB noise, the largest absolute value of percentage error of the identification is 3.78%. These simulations verify that the presented method is effective and accurate for physical parameter identification of two-axis on-road vehicles. The proposed methodology can identify all physical parameters of 7-DOF vehicle model by using free-decay responses of vehicle without need to assume some physical parameters are known.
尉志武; 周蕊; 刘芸
2002-01-01
A solubility-related rule, nonzero solubility rule, is introduced in this paper. It is complementary to the existing rules such as the "like dissolves like" rule and can be understood on the basis of classical chemical thermodynamics.
ANALYSIS OF SOLUBLE CHEMICAL TRANSFER BY RUNOFF WATER IN FIELD
TONG Ju-xiu; YANG Jin-zhong
2008-01-01
In order to determine the main factors influencing soluble chemical transfer and corresponding techniques for reducing fertilizer loss caused by runoff in irrigated fields, a physically based two-layer model was developed with incomplete mixing theory. Different forms of incomplete mixing parameters were introduced in the model, which was successfully verified with previous published experimental data. According to comparison, the chemicals loss of fertilizer is very sensitive to the runoff-related parameter while it is not sensitive to the infiltration-related parameter. The calculated results show that the chemicals in infiltration water play an important role in the early time of rainfall even with saturated soil, and it is mainly in the runoff flow in the late rainfall. Therefore, prevention of shallow subsurface drainage in the early rainfall is an effective way to reduce fertilizer loss, and the coverage on soil surface is another effective way.
Weber, Valéry; Tymczak, Christopher J; Challacombe, Matt
2006-06-14
The application of theoretical methods based on density-functional theory is known to provide atomic and cell parameters in very good agreement with experimental values. Recently, construction of the exact Hartree-Fock exchange gradients with respect to atomic positions and cell parameters within the Gamma-point approximation has been introduced. In this article, the formalism is extended to the evaluation of analytical Gamma-point density-functional atomic and cell gradients. The infinite Coulomb summation is solved with an effective periodic summation of multipole tensors. While the evaluation of Coulomb and exchange-correlation gradients with respect to atomic positions are similar to those in the gas phase limit, the gradients with respect to cell parameters needs to be treated with some care. The derivative of the periodic multipole interaction tensor needs to be carefully handled in both direct and reciprocal space and the exchange-correlation energy derivative leads to a surface term that has its origin in derivatives of the integration limits that depend on the cell. As an illustration, the analytical gradients have been used in conjunction with the QUICCA algorithm to optimize one-dimensional and three-dimensional periodic systems at the density-functional theory and hybrid Hartree-Fock/density-functional theory levels. We also report the full relaxation of forsterite supercells at the B3LYP level of theory.
Rizzi, L G
2015-01-01
It is well established that amyloid fibril solubility is protein specific, but how solubility depends on the interactions between the fibril building blocks is not clear. Here we use a simple protein model and perform Monte Carlo simulations to directly measure the solubility of amyloid fibrils as a function of the interaction between the fibril building blocks. Our simulations confirms that the fibril solubility depends on the fibril thickness and that the relationship between the interactions and the solubility can be described by a simple analytical formula. The results presented in this study reveal general rules how side-chain side-chain interactions, backbone hydrogen bonding and temperature affect amyloid fibril solubility, which might prove a powerful tool to design protein fibrils with desired solubility and aggregation properties in general.
WEI Xiao-Yan; GE Zhi-Gang; WANG Zun-Yao; XU Jiao
2007-01-01
Optimization calculations of 209 polychlorinated biphenyls (PCBs) were carried out at the B3LYP/6-31G* level. It was found that there is significant correlation between the Cl substitution position and some structural parameters. Consequently, Cl substitution positions were taken as theoretical descriptors to establish a novel QSPR model for predicting -lgSw of all PCB congeners. The model achieved in this work contains four variables, of which r2 = 0.9527, q2 = 0.9490 and SD = 0.25 with large t values. In addition, the variation inflation factors (VIFs) of variables in this model are all less than 5.0, suggesting high accuracy of the -lgSw predicting model. And the results of cross-validation test and method validation also show that the model exhibits optimum stability and better predictive capability than that from the AM1 method.
Murakami, Yohei; Takada, Shoji
2013-01-01
When model parameters in systems biology are not available from experiments, they need to be inferred so that the resulting simulation reproduces the experimentally known phenomena. For the purpose, Bayesian statistics with Markov chain Monte Carlo (MCMC) is a useful method. Conventional MCMC needs likelihood to evaluate a posterior distribution of acceptable parameters, while the approximate Bayesian computation (ABC) MCMC evaluates posterior distribution with use of qualitative fitness measure. However, none of these algorithms can deal with mixture of quantitative, i.e., likelihood, and qualitative fitness measures simultaneously. Here, to deal with this mixture, we formulated Bayesian formula for hybrid fitness measures (HFM). Then we implemented it to MCMC (MCMC-HFM). We tested MCMC-HFM first for a kinetic toy model with a positive feedback. Inferring kinetic parameters mainly related to the positive feedback, we found that MCMC-HFM reliably infer them using both qualitative and quantitative fitness measures. Then, we applied the MCMC-HFM to an apoptosis signal transduction network previously proposed. For kinetic parameters related to implicit positive feedbacks, which are important for bistability and irreversibility of the output, the MCMC-HFM reliably inferred these kinetic parameters. In particular, some kinetic parameters that have experimental estimates were inferred without using these data and the results were consistent with experiments. Moreover, for some parameters, the mixed use of quantitative and qualitative fitness measures narrowed down the acceptable range of parameters.
Galdón, Eduardo; Casas, Marta; Gayango, Manuel; Caraballo, Isidoro
2016-12-01
The deep understanding of products and processes has become a requirement for pharmaceutical industries to follow the Quality by Design principles promoted by the regulatory authorities. With this aim, SeDeM expert system was developed as a useful preformulation tool to predict the likelihood to process drugs and excipients through direct compression. SeDeM system is a step forward in the rational development of a formulation, allowing the normalisation of the rheological parameters and the identification of the weaknesses and strengths of a powder or a powder blend. However, this method is based on the assumption of a linear behavior of disordered systems. As percolation theory has demonstrated, powder blends behave as non-linear systems that can suffer abrupt changes in their properties near to geometrical phase transitions of the components. The aim of this paper was to analyze for the first time the evolution of the SeDeM parameters in drug/excipient powder blends from the point of view of the percolation theory and to compare the changes predicted by SeDeM with the predictions of Percolation theory. For this purpose, powder blends of lactose and theophylline with varying concentrations of the model drug have been prepared and the SeDeM analysis has been applied to each blend in order to monitor the evolution of their properties. On the other hand, percolation thresholds have been estimated for these powder blends where critical points have been found for important rheological parameters as the powder flow. Finally, the predictions of percolation theory and SeDeM have been compared concluding that percolation theory can complement the SeDeM method for a more accurate estimation of the Design Space.
Boucher Yann G.
2017-01-01
Full Text Available In terms of Linear Algebra, a directional coupler between a single-mode waveguide and a two-mode waveguide can be thought of as formally equivalent to a set of three mutually coupled single-mode waveguides. Its responses, easily derived in the frame of ternary Coupled-Mode Theory, are used to establish analytically the scattering parameters of a hybrid ring-based modal multiplexer.
Boucher, Yann G.; Parini, Alberto; Féron, Patrice
2017-03-01
In terms of Linear Algebra, a directional coupler between a single-mode waveguide and a two-mode waveguide can be thought of as formally equivalent to a set of three mutually coupled single-mode waveguides. Its responses, easily derived in the frame of ternary Coupled-Mode Theory, are used to establish analytically the scattering parameters of a hybrid ring-based modal multiplexer.
P B Rathi
2011-01-01
Full Text Available Extended Hildebrand solubility approach is used to estimate the solubility of satranidazole in binary solvent systems. The solubility of satranidazole in various propylene glycol-water mixtures was analyzed in terms of solute-solvent interactions using a modified version of Hildebrand-Scatchard treatment for regular solutions. The solubility equation employs term interaction energy (W to replace the geometric mean (δ1δ2 , where δ1 and δ2 are the cohesive energy densities for the solvent and solute, respectively. The new equation provides an accurate prediction of solubility once the interaction energy, W, is obtained. In this case, the energy term is regressed against a polynomial in δ1 of the binary mixture. A quartic expression of W in terms of solvent solubility parameter was found for predicting the solubility of satranidazole in propylene glycol-water mixtures. The expression yields an error in mole fraction solubility of ~3.74%, a value approximating that of the experimentally determined solubility. The method has potential usefulness in preformulation and formulation studies during which solubility prediction is important for drug design.
Rathi, P B
2011-11-01
Extended Hildebrand solubility approach is used to estimate the solubility of satranidazole in binary solvent systems. The solubility of satranidazole in various propylene glycol-water mixtures was analyzed in terms of solute-solvent interactions using a modified version of Hildebrand-Scatchard treatment for regular solutions. The solubility equation employs term interaction energy (W) to replace the geometric mean (δ(1)δ(2)), where δ(1) and δ(2) are the cohesive energy densities for the solvent and solute, respectively. The new equation provides an accurate prediction of solubility once the interaction energy, W, is obtained. In this case, the energy term is regressed against a polynomial in δ(1) of the binary mixture. A quartic expression of W in terms of solvent solubility parameter was found for predicting the solubility of satranidazole in propylene glycol-water mixtures. The expression yields an error in mole fraction solubility of ~3.74%, a value approximating that of the experimentally determined solubility. The method has potential usefulness in preformulation and formulation studies during which solubility prediction is important for drug design.
Towards a new determination of the QCD Λ parameter from running couplings in the tree-flavour theory
Dalla Brida, M.; Sint, S. [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Trinity College, Dublin (Ireland). School of Mathematics; Fritzsch, P.; Korzec, T. [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Physik; Ramos, A.; Sommer, R. [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC
2014-12-15
We review our new strategy and current status towards a high precision computation of the Λ parameter from three-flavour simulations in QCD. To reach this goal we combine specific advantages of the Schroedinger functional and gradient flow couplings.
Rawlinson, A.P.; White, J.
1987-06-23
A soluble oil, suitable when diluted with water, for use as a cutting fluid comprises an alkali or alkaline-earth metal alkyl benzene sulphonate, a fatty acid diethanolamide, a mixed alkanolamine borate, a polyisobutenesuccinimide and a major proportion of mineral oil. The soluble oil is relatively stable without the need for a conventional coupling agent and some soluble oil emulsions are bio-static even though conventional biocides are not included.
Muñoz Morales, Aarón A; Vázquez Y Montiel, Sergio
2012-10-01
The determination of optical parameters of biological tissues is essential for the application of optical techniques in the diagnosis and treatment of diseases. Diffuse Reflection Spectroscopy is a widely used technique to analyze the optical characteristics of biological tissues. In this paper we show that by using diffuse reflectance spectra and a new mathematical model we can retrieve the optical parameters by applying an adjustment of the data with nonlinear least squares. In our model we represent the spectra using a Fourier series expansion finding mathematical relations between the polynomial coefficients and the optical parameters. In this first paper we use spectra generated by the Monte Carlo Multilayered Technique to simulate the propagation of photons in turbid media. Using these spectra we determine the behavior of Fourier series coefficients when varying the optical parameters of the medium under study. With this procedure we find mathematical relations between Fourier series coefficients and optical parameters. Finally, the results show that our method can retrieve the optical parameters of biological tissues with accuracy that is adequate for medical applications.
Nhu, Nguyen Van; Singh, Mahendra; Leonhard, Kai
2008-05-08
We have computed molecular descriptors for sizes, shapes, charge distributions, and dispersion interactions for 67 compounds using quantum chemical ab initio and density functional theory methods. For the same compounds, we have fitted the three perturbed-chain polar statistical associating fluid theory (PCP-SAFT) equation of state (EOS) parameters to experimental data and have performed a statistical analysis for relations between the descriptors and the EOS parameters. On this basis, an analysis of the physical significance of the parameters, the limits of the present descriptors, and the PCP-SAFT EOS has been performed. The result is a method that can be used to estimate the vapor pressure curve including the normal boiling point, the liquid volume, the enthalpy of vaporization, the critical data, mixture properties, and so on. When only two of the three parameters are predicted and one is adjusted to experimental normal boiling point data, excellent predictions of all investigated pure compound and mixture properties are obtained. We are convinced that the methodology presented in this work will lead to new EOS applications as well as improved EOS models whose predictive performance is likely to surpass that of most present quantum chemically based, quantitative structure-property relationship, and group contribution methods for a broad range of chemical substances.
Sass, D. A.; Schmitt, T. A.; Walker, C. M.
2008-01-01
Item response theory (IRT) procedures have been used extensively to study normal latent trait distributions and have been shown to perform well; however, less is known concerning the performance of IRT with non-normal latent trait distributions. This study investigated the degree of latent trait estimation error under normal and non-normal…
Sass, D. A.; Schmitt, T. A.; Walker, C. M.
2008-01-01
Item response theory (IRT) procedures have been used extensively to study normal latent trait distributions and have been shown to perform well; however, less is known concerning the performance of IRT with non-normal latent trait distributions. This study investigated the degree of latent trait estimation error under normal and non-normal…
Wang, Bi-Yao; Li, Ze-Rong; Tan, Ning-Xin; Yao, Qian; Li, Xiang-Yuan
2013-04-25
We present a further interpretation of reaction class transition state theory (RC-TST) proposed by Truong et al. for the accurate calculation of rate coefficients for reactions in a class. It is found that the RC-TST can be interpreted through the isodesmic reaction method, which is usually used to calculate reaction enthalpy or enthalpy of formation for a species, and the theory can also be used for the calculation of the reaction barriers and reaction enthalpies for reactions in a class. A correction scheme based on this theory is proposed for the calculation of the reaction barriers and reaction enthalpies for reactions in a class. To validate the scheme, 16 combinations of various ab initio levels with various basis sets are used as the approximate methods and CCSD(T)/CBS method is used as the benchmarking method in this study to calculate the reaction energies and energy barriers for a representative set of five reactions from the reaction class: R(c)CH(R(b))CR(a)CH2 + OH(•) → R(c)C(•)(R(b))CR(a)CH2 + H2O (R(a), R(b), and R(c) in the reaction formula represent the alkyl or hydrogen). Then the results of the approximate methods are corrected by the theory. The maximum values of the average deviations of the energy barrier and the reaction enthalpy are 99.97 kJ/mol and 70.35 kJ/mol, respectively, before correction and are reduced to 4.02 kJ/mol and 8.19 kJ/mol, respectively, after correction, indicating that after correction the results are not sensitive to the level of the ab initio method and the size of the basis set, as they are in the case before correction. Therefore, reaction energies and energy barriers for reactions in a class can be calculated accurately at a relatively low level of ab initio method using our scheme. It is also shown that the rate coefficients for the five representative reactions calculated at the BHandHLYP/6-31G(d,p) level of theory via our scheme are very close to the values calculated at CCSD(T)/CBS level. Finally, reaction
Tassin, Philippe; Soukoulis, Costas M; 10.1016/j.physb.2012.01.119
2012-01-01
An important tool in the field of metamaterials is the extraction of effective material parameters from simulated or measured scattering parameters of a sample. Here we discuss a retrieval method for thin-film structures that can be approximated by a two-dimensional scattering sheet. We determine the effective sheet conductivity from the scattering parameters and we point out the importance of the magnetic sheet current to avoid an overdetermined inversion problem. Subsequently, we present two applications of the sheet retrieval method. First, we determine the effective sheet conductivity of thin silver films and we compare the resulting conductivities with the sheet conductivity of graphene. Second, we apply the method to a cut-wire metamaterial with an electric dipole resonance. The method is valid for thin-film structures such as two-dimensional metamaterials and frequency-selective surfaces and can be easily generalized for anisotropic or chiral media.
Tassin, Philippe; Koschny, Thomas; Soukoulis, Costas
2012-01-30
An important tool in the field of metamaterials is the extraction of effective material parameters from simulated or measured scattering parameters of a sample. Here we discuss a retrieval method for thin-film structures that can be approximated by a two-dimensional scattering sheet. We determine the effective sheet conductivity from the scattering parameters and we point out the importance of the magnetic sheet current to avoid an overdetermined inversion problem. Subsequently, we present two applications of the sheet retrieval method. First, we determine the effective sheet conductivity of thin silver films and we compare the resulting conductivities with the sheet conductivity of graphene. Second, we apply the method to a cut-wire metamaterial with an electric dipole resonance. The method is valid for thin-film structures such as two-dimensional metamaterials and frequency-selective surfaces and can be easily generalized for anisotropic or chiral media.
Tassin, Philippe, E-mail: tassin@ameslab.gov [Ames Laboratory - U.S. DOE and Department of Physics and Astronomy, Iowa State University, Ames, IA 50011 (United States); Koschny, Thomas, E-mail: koschny@ameslab.gov [Ames Laboratory - U.S. DOE and Department of Physics and Astronomy, Iowa State University, Ames, IA 50011 (United States); Soukoulis, Costas M., E-mail: soukoulis@ameslab.gov [Ames Laboratory - U.S. DOE and Department of Physics and Astronomy, Iowa State University, Ames, IA 50011 (United States); Institute of Electronic Structure and Lasers (IESL), FORTH, 71110 Heraklion, Crete (Greece)
2012-10-15
An important tool in the field of metamaterials is the extraction of effective material parameters from simulated or measured scattering parameters of a sample. Here we discuss a retrieval method for thin-film structures that can be approximated by a two-dimensional scattering sheet. We determine the effective sheet conductivity from the scattering parameters and we point out the importance of the magnetic sheet current to avoid an overdetermined inversion problem. Subsequently, we present two applications of the sheet retrieval method. First, we determine the effective sheet conductivity of thin silver films and we compare the resulting conductivities with the sheet conductivity of graphene. Second, we apply the method to a cut-wire metamaterial with an electric dipole resonance. The method is valid for thin-film structures such as two-dimensional metamaterials and frequency-selective surfaces and can be easily generalized for anisotropic or chiral media.
Enhanced dopant solubility in strained silicon
Adey, J [School of Physics, University of Exeter, Exeter EX4 4QL (United Kingdom); Jones, R [School of Physics, University of Exeter, Exeter EX4 4QL (United Kingdom); Briddon, P R [Physics Centre, School of Natural Science, Newcastle upon Tyne NE1 7RU (United Kingdom)
2004-12-22
The effect of biaxial strain on the solubility of the common donor arsenic and acceptor boron is calculated using spin-polarized local density functional theory. The change in solubility with strain is considered in terms of contributions from the change in total energy and Fermi energy with strain. The solubility of boron is found to be enhanced by compressive biaxial strain due to a reduction in the total energy of the small substitutional impurity and an increase in the Fermi energy for compressive strain. The solubility of arsenic is shown to be enhanced by tensile strain and this is due entirely to the change in Fermi energy. For boron as well as arsenic the change in Fermi energy with strain is shown to make the dominant contribution.
Aage, H. K.; Andersen, Bertel Lohmann; Blom, A.
1997-01-01
The solubility of magnesium-amonium-phosphate (struvite) has been studied emloying the radioisotope 32P as tracer. The amount of sample in solution is determined by measuring the Cherenkov radiation due to the beta-particles emitted from this radionuclide. The thermodynamic solubility product...
Brida, M Dalla; Korzec, T; Ramos, A; Sint, S; Sommer, R
2014-01-01
We review our new strategy and current status towards a high precision computation of the Lambda parameter from three-flavour simulations in QCD. To reach this goal we combine specific advantages of the Schr\\"odinger functional and gradient flow couplings.
Rakkapao, Suttida; Prasitpong, Singha; Arayathanitkul, Kwan
2016-12-01
This study investigated the multiple-choice test of understanding of vectors (TUV), by applying item response theory (IRT). The difficulty, discriminatory, and guessing parameters of the TUV items were fit with the three-parameter logistic model of IRT, using the parscale program. The TUV ability is an ability parameter, here estimated assuming unidimensionality and local independence. Moreover, all distractors of the TUV were analyzed from item response curves (IRC) that represent simplified IRT. Data were gathered on 2392 science and engineering freshmen, from three universities in Thailand. The results revealed IRT analysis to be useful in assessing the test since its item parameters are independent of the ability parameters. The IRT framework reveals item-level information, and indicates appropriate ability ranges for the test. Moreover, the IRC analysis can be used to assess the effectiveness of the test's distractors. Both IRT and IRC approaches reveal test characteristics beyond those revealed by the classical analysis methods of tests. Test developers can apply these methods to diagnose and evaluate the features of items at various ability levels of test takers.
Yuki Ebato
2016-05-01
Full Text Available Ornstein-Zernike (OZ integral equation theory is known to overestimate the excess internal energy, Uex, pressure through the virial route, Pv, and excess chemical potential, μex, for one-component Lennard-Jones (LJ fluids under hypernetted chain (HNC and Kovalenko-Hirata (KH approximatons. As one of the bridge correction methods to improve the precision of these thermodynamic quantities, it was shown in our previous paper that the method to apparently adjust σ parameter in the LJ potential is effective [T. Miyata and Y. Ebato, J. Molec. Liquids. 217, 75 (2016]. In our previous paper, we evaluated the actual variation in the σ parameter by using a fitting procedure to molecular dynamics (MD results. In this article, we propose an alternative method to determine the actual variation in the σ parameter. The proposed method utilizes a condition that the virial and compressibility pressures coincide with each other. This method can correct OZ theory without a fitting procedure to MD results, and possesses characteristics of keeping a form of HNC and/or KH closure. We calculate the radial distribution function, pressure, excess internal energy, and excess chemical potential for one-component LJ fluids to check the performance of our proposed bridge function. We discuss the precision of these thermodynamic quantities by comparing with MD results. In addition, we also calculate a corrected gas-liquid coexistence curve based on a corrected KH-type closure and compare it with MD results.
Ebato, Yuki; Miyata, Tatsuhiko
2016-05-01
Ornstein-Zernike (OZ) integral equation theory is known to overestimate the excess internal energy, Uex, pressure through the virial route, Pv, and excess chemical potential, μex, for one-component Lennard-Jones (LJ) fluids under hypernetted chain (HNC) and Kovalenko-Hirata (KH) approximatons. As one of the bridge correction methods to improve the precision of these thermodynamic quantities, it was shown in our previous paper that the method to apparently adjust σ parameter in the LJ potential is effective [T. Miyata and Y. Ebato, J. Molec. Liquids. 217, 75 (2016)]. In our previous paper, we evaluated the actual variation in the σ parameter by using a fitting procedure to molecular dynamics (MD) results. In this article, we propose an alternative method to determine the actual variation in the σ parameter. The proposed method utilizes a condition that the virial and compressibility pressures coincide with each other. This method can correct OZ theory without a fitting procedure to MD results, and possesses characteristics of keeping a form of HNC and/or KH closure. We calculate the radial distribution function, pressure, excess internal energy, and excess chemical potential for one-component LJ fluids to check the performance of our proposed bridge function. We discuss the precision of these thermodynamic quantities by comparing with MD results. In addition, we also calculate a corrected gas-liquid coexistence curve based on a corrected KH-type closure and compare it with MD results.
Botet, Robert; Kuratsuji, Hiroshi
2010-03-01
We present a framework for the stochastic features of the polarization state of an electromagnetic wave propagating through the optical medium with both deterministic (controlled) and disordered birefringence. In this case, the Stokes parameters obey a Langevin-type equation on the Poincaré sphere. The functional integral method provides for a natural tool to derive the Fokker-Planck equation for the probability distribution of the Stokes parameters. We solve the Fokker-Planck equation in the case of a random anisotropic active medium submitted to a homogeneous electromagnetic field. The possible dissipation and relaxation phenomena are studied in general and in various cases, and we give hints about how to validate experimentally the corresponding phenomenological equations.
V. D. Rusov; Glushkov, A. V.; Vaschenko, V. N.; Pavlovich, V. N.; Zelentsova, T. N.; Mihalus, O. T.; Tarasov, V. A.; Saranuk, D. N.
2004-01-01
The energy-balance model of global climate, which is taking into account a nontrivial role of solar and galactic protons, is presented. The model is described by the equation of fold catastrophe relative to increment of temperature, where the variation of a solar insolation and cosmic rays are control parameters. It is shown that the bifurcation equation of the model describes one of two stable states of the climate system. The solution of this equation exhibits the property of the determined...
Dudowicz, Jacek; Freed, Karl F; Douglas, Jack F
2012-02-14
The lattice cluster theory for solutions of telechelic polymer chains, developed in paper I, is applied to determine the enthalpy Δh(p) and entropy Δs(p) of self-assembly of linear telechelics and to evaluate the Flory-Huggins (FH) interaction parameter χ governing the phase behavior of these systems. Particular focus is placed on examining how these interaction variables depend on the composition of the solution, temperature, van der Waals and local "sticky" interaction energies, and the length of the individual telechelic chains. The FH interaction parameter χ is found to exhibit an entropy-enthalpy compensation effect between the "entropic" and "enthalpic" portions as either the composition or mass of the telechelic species is varied, providing unique theoretical insights into this commonly reported, yet, enigmatic phenomenon.
DEVELOPMENT OF SOLUBILITY PRODUCT VISUALIZATION TOOLS
T.F. Turner; A.T. Pauli; J.F. Schabron
2004-05-01
Western Research Institute (WRI) has developed software for the visualization of data acquired from solubility tests. The work was performed in conjunction with AB Nynas Petroleum, Nynashamn, Sweden who participated as the corporate cosponsor for this Jointly Sponsored Research (JSR) task. Efforts in this project were split between software development and solubility test development. The Microsoft Windows-compatible software developed inputs up to three solubility data sets, calculates the parameters for six solid body types to fit the data, and interactively displays the results in three dimensions. Several infrared spectroscopy techniques have been examined for potential use in determining bitumen solubility in various solvents. Reflectance, time-averaged absorbance, and transmittance techniques were applied to bitumen samples in single and binary solvent systems. None of the techniques were found to have wide applicability.
Jang, Seung Woo; Kotani, Takao; Kino, Hiori; Kuroki, Kazuhiko; Han, Myung Joon
2015-07-24
Despite decades of progress, an understanding of unconventional superconductivity still remains elusive. An important open question is about the material dependence of the superconducting properties. Using the quasiparticle self-consistent GW method, we re-examine the electronic structure of copper oxide high-Tc materials. We show that QSGW captures several important features, distinctive from the conventional LDA results. The energy level splitting between d(x(2)-y(2)) and d(3z(2)-r(2)) is significantly enlarged and the van Hove singularity point is lowered. The calculated results compare better than LDA with recent experimental results from resonant inelastic xray scattering and angle resolved photoemission experiments. This agreement with the experiments supports the previously suggested two-band theory for the material dependence of the superconducting transition temperature, Tc.
Yang, Yi; Cai, Canying; Lin, Jianguo; Gong, Lunjun; Yang, Qibin
2017-05-01
In this paper, we used Niggli reduced cell theory to determine lattice constants of a micro/nano crystal by using electron diffraction patterns. The Niggli reduced cell method enhanced the accuracy of lattice constant measurement obviously, because the lengths and the angles of lattice vectors of a primitive cell can be measured directly on the electron micrographs instead of a double tilt holder. With the aid of digitized algorithm and least square optimization by using three digitized micrographs, a valid reciprocal Niggli reduced cell number can be obtained. Thus a reciprocal and real Bravais lattices are acquired. The results of three examples, i.e., Mg4Zn7, an unknown phase (Precipitate phase in nickel-base superalloy) and Ba4Ti13O30 showed that the maximum errors are 1.6% for lengths and are 0.3% for angles.
Maurya, D. Ch., E-mail: dcmaurya563@gmail.com; Zia, R., E-mail: rashidzya@gmail.com; Pradhan, A., E-mail: pradhan.anirudh@gmail.com [GLA University, Department of Mathematics, Institute of Applied Sciences and Humanities (India)
2016-10-15
We discuss a spatially homogeneous and anisotropic string cosmological models in the Brans–Dicke theory of gravitation. For a spatially homogeneous metric, it is assumed that the expansion scalar θ is proportional to the shear scalar σ. This condition leads to A = kB{sup m}, where k and m are constants. With these assumptions and also assuming a variable scale factor a = a(t), we find solutions of the Brans–Dicke field equations. Various phenomena like the Big Bang, expanding universe, and shift from anisotropy to isotropy are observed in the model. It can also be seen that in early stage of the evolution of the universe, strings dominate over particles, whereas the universe is dominated by massive strings at the late time. Some physical and geometrical behaviors of the models are also discussed and observed to be in good agreement with the recent observations of SNe la supernovae.
Mutz, M [The University of Tennessee; Eastwood, Eric Allen [ORNL; Dadmun, Mark D [ORNL
2013-01-01
The dissolution of nanoparticles, particularly those containing boron, is an important area of interest for polymer nanocomposite formation and material development. In this work, the solubility of boron nitride nanotubes (BNNT), functionalized boron nitride nanotubes (FBNNT), and boron nitride sheets (BNZG) is quantified in toluene and THF with static light scattering, refractometry, UV vis spectroscopy, and physical observations. UV vis spectroscopy provides a method to determine the concentration and solubility limits of the solutions tested. Using light scattering, the second virial coefficient, A2, is determined and used to calculate , the solute solvent interaction parameter. The Hildebrand solubility parameter, , is then extracted from this data using the Hildebrand Scatchard Solution Theory. A list of potential good solvents based on the estimated value is provided for each nanoparticle. Single-walled carbon nanotubes (SWNTs) and prepolymers (EN4 and EN8) used to synthesize polyurethanes were also tested, because the published and molar attraction constants of these materials provided a selfconsistent check. The dn/dc of SWNTs and boron-containing particles was measured for the first time in this work. A solvent screen for BN-ZG provides additional information that supports the obtained and . Three systems were found to have values below 0.5 and were thermodynamically soluble: BNNT in THF, EN8 in THF, and EN8 in toluene.
Solubilities of uranium for TILA-99
Ollila, K. [VTT Chemical Technology, Espoo (Finland); Ahonen, L. [Geological Survey of Finland, Espoo (Finland)
1998-11-01
This report presents the evaluation of the uranium solubilities in the reference waters of TILA-99. The behaviour of uranium has been discussed separately in the near-field and far-field conditions. The bentonite/groundwater interactions have been considered in the compositions of the fresh and saline near-field reference waters. The far-field groundwaters` compositions include fresh, brackish, saline and very saline, almost brine-type compositions. The pH and redox conditions, as the main parameters affecting the solubilities, are considered. A literature study was made in order to obtain information on the recent dissolution and leaching experiments of UO{sub 2} and spent fuel. The latest literature includes studies on UO{sub 2} solubility under anoxic conditions, in which the methods for simulating the reducing conditions of deep groundwater have been improved. Studies on natural uraninite and its alteration products give a valuable insight into the long-term behaviour of spent fuel. Also the solubility equilibria for some relevant poorly known uranium minerals have been determined. The solubilities of the selected solubility-limiting phases were calculated using the geochemical code, EQ3/6. The NEA database for uranium was the basis for the modelling. The recently extended and updated SR `97 database was used for comparison. The solubility products for uranophane were taken from the latest literature. The recommended values for solubilities were given after a comparison between the calculated solubilities, experimental information and measured concentrations in natural groundwaters. The experiments include several UO{sub 2} dissolution studies in synthetic groundwaters with compositions close to the reference groundwaters. (author) 81 refs.
Optimizing solubility: kinetic versus thermodynamic solubility temptations and risks.
Saal, Christoph; Petereit, Anna Christine
2012-10-09
The aim of this study was to assess the usefulness of kinetic and thermodynamic solubility data in guiding medicinal chemistry during lead optimization. The solubility of 465 research compounds was measured using a kinetic and a thermodynamic solubility assay. In the thermodynamic assay, polarized-light microscopy was used to investigate whether the result referred to the crystalline or to the amorphous compound. From the comparison of kinetic and thermodynamic solubility data it was noted that kinetic solubility measurements frequently yielded results which show considerably higher solubility compared to thermodynamic solubility. This observation is ascribed to the fact that a kinetic solubility assay typically delivers results which refer to the amorphous compound. In contrast, results from thermodynamic solubility determinations more frequently refer to a crystalline phase. Accordingly, thermodynamic solubility data--especially when used together with an assessment of the solid state form--are deemed to be more useful in guiding solubility optimization for research compounds.
Parkner, Tina; Sørensen, L P; Nielsen, A R
2012-01-01
Soluble CD163 (sCD163) was recently identified as a strong risk marker for developing type 2 diabetes. We hypothesised that sCD163 independently associates with insulin resistance.......Soluble CD163 (sCD163) was recently identified as a strong risk marker for developing type 2 diabetes. We hypothesised that sCD163 independently associates with insulin resistance....
Izmailov, Alexander; Myerson, Allan S.
1993-01-01
A new mathematical ansatz for a solution of the time-dependent Ginzburg-Landau non-linear partial differential equation is developed for non-critical systems such as non-critical binary solutions (solute + solvent) described by the non-conserved scalar order parameter. It is demonstrated that in such systems metastability initiates heterogeneous solute redistribution which results in formation of the non-equilibrium singly-periodic spatial solute structure. It is found how the time-dependent period of this structure evolves in time. In addition, the critical radius r(sub c) for solute embryo of the new solute rich phase together with the metastable state lifetime t(sub c) are determined analytically and analyzed.
Mashayekhi, Mohammad Jalali; Behdinan, Kamran
2017-10-01
The increasing demand to minimize undesired vibration and noise levels in several high-tech industries has generated a renewed interest in vibration transfer path analysis. Analyzing vibration transfer paths within a system is of crucial importance in designing an effective vibration isolation strategy. Most of the existing vibration transfer path analysis techniques are empirical which are suitable for diagnosis and troubleshooting purpose. The lack of an analytical transfer path analysis to be used in the design stage is the main motivation behind this research. In this paper an analytical transfer path analysis based on the four-pole theory is proposed for multi-energy-domain systems. Bond graph modeling technique which is an effective approach to model multi-energy-domain systems is used to develop the system model. In this paper an electro-mechanical system is used as a benchmark example to elucidate the effectiveness of the proposed technique. An algorithm to obtain the equivalent four-pole representation of a dynamical systems based on the corresponding bond graph model is also presented in this paper.
Cohen, S. C.
1979-01-01
A viscoelastic model for deformation and stress associated with earthquakes is reported. The model consists of a rectangular dislocation (strike slip fault) in a viscoelastic layer (lithosphere) lying over a viscoelastic half space (asthenosphere). The time dependent surface stresses are analyzed. The model predicts that near the fault a significant fraction of the stress that was reduced during the earthquake is recovered by viscoelastic softening of the lithosphere. By contrast, the strain shows very little change near the fault. The model also predicts that the stress changes associated with asthenospheric flow extend over a broader region than those associated with lithospheric relaxation even though the peak value is less. The dependence of the displacements, stresses on fault parameters studied. Peak values of strain and stress drop increase with increasing fault height and decrease with fault depth. Under many circumstances postseismic strains and stresses show an increase with decreasing depth to the lithosphere-asthenosphere boundary. Values of the strain and stress at distant points from the fault increase with fault area but are relatively insensitive to fault depth.
Zimmermann, Bernd; Mavropoulos, Phivos; Long, Nguyen H.; Gerhorst, Christian-Roman; Blügel, Stefan; Mokrousov, Yuriy
2016-04-01
The Fermi surfaces and Elliott-Yafet spin-mixing parameter (EYP) of several elemental metals are studied by ab initio calculations. We focus first on the anisotropy of the EYP as a function of the direction of the spin-quantization axis [B. Zimmermann et al., Phys. Rev. Lett. 109, 236603 (2012), 10.1103/PhysRevLett.109.236603]. We analyze in detail the origin of the gigantic anisotropy in 5 d hcp metals as compared to 5 d cubic metals by band structure calculations and discuss the stability of our results against an applied magnetic field. We further present calculations of light (4 d and 3 d ) hcp crystals, where we find a huge increase of the EYP anisotropy, reaching colossal values as large as 6000 % in hcp Ti. We attribute these findings to the reduced strength of spin-orbit coupling, which promotes the anisotropic spin-flip hot loops at the Fermi surface. In order to conduct these investigations, we developed an adapted tetrahedron-based method for the precise calculation of Fermi surfaces of complicated shape and accurate Fermi-surface integrals within the full-potential relativistic Korringa-Kohn-Rostoker Green function method.
Bellasio, Chandra; Beerling, David J; Griffiths, Howard
2016-06-01
Combined photosynthetic gas exchange and modulated fluorometres are widely used to evaluate physiological characteristics associated with phenotypic and genotypic variation, whether in response to genetic manipulation or resource limitation in natural vegetation or crops. After describing relatively simple experimental procedures, we present the theoretical background to the derivation of photosynthetic parameters, and provide a freely available Excel-based fitting tool (EFT) that will be of use to specialists and non-specialists alike. We use data acquired in concurrent variable fluorescence-gas exchange experiments, where A/Ci and light-response curves have been measured under ambient and low oxygen. From these data, the EFT derives light respiration, initial PSII (photosystem II) photochemical yield, initial quantum yield for CO2 fixation, fraction of incident light harvested by PSII, initial quantum yield for electron transport, electron transport rate, rate of photorespiration, stomatal limitation, Rubisco (ribulose 1·5-bisphosphate carboxylase/oxygenase) rate of carboxylation and oxygenation, Rubisco specificity factor, mesophyll conductance to CO2 diffusion, light and CO2 compensation point, Rubisco apparent Michaelis-Menten constant, and Rubisco CO2 -saturated carboxylation rate. As an example, a complete analysis of gas exchange data on tobacco plants is provided. We also discuss potential measurement problems and pitfalls, and suggest how such empirical data could subsequently be used to parameterize predictive photosynthetic models.
Fransson, Thomas; Saue, Trond; Norman, Patrick
2016-05-10
The influences of group 12 (Zn, Cd, Hg) metal-substitution on the valence spectra and phosphorescence parameters of porphyrins (P) have been investigated in a relativistic setting. In order to obtain valence spectra, this study reports the first application of the damped linear response function, or complex polarization propagator, in the four-component density functional theory framework [as formulated in Villaume et al. J. Chem. Phys. 2010 , 133 , 064105 ]. It is shown that the steep increase in the density of states as due to the inclusion of spin-orbit coupling yields only minor changes in overall computational costs involved with the solution of the set of linear response equations. Comparing single-frequency to multifrequency spectral calculations, it is noted that the number of iterations in the iterative linear equation solver per frequency grid-point decreases monotonously from 30 to 0.74 as the number of frequency points goes from one to 19. The main heavy-atom effect on the UV/vis-absorption spectra is indirect and attributed to the change of point group symmetry due to metal-substitution, and it is noted that substitutions using heavier atoms yield small red-shifts of the intense Soret-band. Concerning phosphorescence parameters, the adoption of a four-component relativistic setting enables the calculation of such properties at a linear order of response theory, and any higher-order response functions do not need to be considered-a real, conventional, form of linear response theory has been used for the calculation of these parameters. For the substituted porphyrins, electronic coupling between the lowest triplet states is strong and results in theoretical estimates of lifetimes that are sensitive to the wave function and electron density parametrization. With this in mind, we report our best estimates of the phosphorescence lifetimes to be 460, 13.8, 11.2, and 0.00155 s for H2P, ZnP, CdP, and HgP, respectively, with the corresponding transition
Escalera, J B; Bustamante, P; Martin, A
1994-03-01
An approach to reproduce the solubility profile of a drug in several solvent mixtures showing two solubility maxima is proposed in this work. The solubility of sulphamethoxypyridazine was determined at 25 degrees C in several mixtures of varying polarity (hexane:ethyl acetate, ethyl acetate:ethanol and ethanol:water). Sulphamethoxypyridazine was chosen as a model drug because of its proton-donor and proton-acceptor properties. A plot of the mole fraction of the drug vs the solubility parameter of the solvent mixtures shows two solubility peaks. The two peaks found for sulphamethoxypyridazine demonstrate the chameleonic effect as described by Hoy and suggest that the solute-solvent interaction does not vary uniformly from one mixture to another. The different behaviour of the drug in mixtures of two proton-donor and proton-acceptor solvents (alcohol and water), and in mixtures of one proton acceptor (ethyl acetate) and one proton donor-proton acceptor (ethanol) is rationalized in terms of differences in the proton donor-acceptor ability of the solvent mixtures. An approach based on the acidic and basic partial solubility parameters together with the Hildebrand solubility parameter of the solvent mixtures is developed to reproduce the experimental results quantitatively. The equation predicts the two solubility maxima as found experimentally, and the calculated values closely correspond to the experimental values through the range composition of the solvent mixtures. These results show that the chameleonic effect can be described in a quantitative way in terms of Lewis acid-base interactions; this approach can assist the product formulator to choose the proper solvent mixture for a new drug.
Shibuta, Satoshi; Imamura, Hiroshi; Nishikawa, Keiko; Morita, Takeshi
2017-04-01
To study the structural fluctuation of supercritical solutions, we introduced three fluctuational parameters, a scattering factor, a density factor and a volume factor, which were based on the Bhatia-Thornton theory. In the present study, the density dependence of the structural inhomogeneity in a supercritical aqueous solution of n-pentane was discussed using the scattering factor and the density factor obtained from small-angle X-ray scattering and the fluid density measurements, respectively. Although both these factors have their maxima at the same density position in the case of neat supercritical fluids, a significant difference between the two factors is observed in the binary solution. The large difference occurs by the contribution of the concentration fluctuation in the system. Based on the difference between the factors, it is suggested that a phase separation of the system exists in the higher-fluid-density region.
Wang, Jia; Jiang, Wanrun; Yu, Tianrong; Wang, Zhigang
2016-01-01
The self-consistent charge density functional tight-binding (DFTB) theory is a useful tool for realizing the electronic structures of large molecular complex systems. In this study, we analyze the electronic structure of C61, formed by fullerene C60 with a carbon adatom, using the fully localized limit and pseudo self-interaction correction methods of DFTB to adjust the Hubbard U parameter (DFTB+U). The results show that both the methods used to adjust U can significantly reduce the molecular orbital energy of occupied states localized on the defect carbon atom and improve the gap between highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) of C61. This work will provide a methodological reference point for future DFTB calculations of the electronic structures of carbon materials.
Modeling of Salt Solubilities in Mixed Solvents
Chiavone-Filho, O.; Rasmussen, Peter
2000-01-01
A method to correlate and predict salt solubilities in mixed solvents using a UNIQUAC+Debye-Huckel model is developed. The UNIQUAC equation is applied in a form with temperature-dependent parameters. The Debye-Huckel model is extended to mixed solvents by properly evaluating the dielectric...... constants and the liquid densities of the solvent media. To normalize the activity coefficients, the symmetric convention is adopted. Thermochemical properties of the salt are used to estimate the solubility product. It is shown that the proposed procedure can describe with good accuracy a series of salt...
Modeling of Salt Solubilities in Mixed Solvents
Chiavone-Filho, O.; Rasmussen, Peter
2000-01-01
A method to correlate and predict salt solubilities in mixed solvents using a UNIQUAC+Debye-Huckel model is developed. The UNIQUAC equation is applied in a form with temperature-dependent parameters. The Debye-Huckel model is extended to mixed solvents by properly evaluating the dielectric...... constants and the liquid densities of the solvent media. To normalize the activity coefficients, the symmetric convention is adopted. Thermochemical properties of the salt are used to estimate the solubility product. It is shown that the proposed procedure can describe with good accuracy a series of salt...
Bandura, A V; Sofo, J O; Kubicki, J D
2006-04-27
Plane-wave density functional theory (DFT-PW) calculations were performed on bulk SnO2 (cassiterite) and the (100), (110), (001), and (101) surfaces with and without H2O present. A classical interatomic force field has been developed to describe bulk SnO2 and SnO2-H2O surface interactions. Periodic density functional theory calculations using the program VASP (Kresse et al., 1996) and molecular cluster calculations using Gaussian 03 (Frisch et al., 2003) were used to derive the parametrization of the force field. The program GULP (Gale, 1997) was used to optimize parameters to reproduce experimental and ab initio results. The experimental crystal structure and elastic constants of SnO2 are reproduced reasonably well with the force field. Furthermore, surface atom relaxations and structures of adsorbed H2O molecules agree well between the ab initio and force field predictions. H2O addition above that required to form a monolayer results in consistent structures between the DFT-PW and classical force field results as well.
Adams, Brian M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Ebeida, Mohamed Salah [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Eldred, Michael S [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Jakeman, John Davis [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Swiler, Laura Painton [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Stephens, John Adam [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Vigil, Dena M. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Wildey, Timothy Michael [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Bohnhoff, William J. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Eddy, John P. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Hu, Kenneth T. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Dalbey, Keith R. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Bauman, Lara E [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Hough, Patricia Diane [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
2014-05-01
The Dakota (Design Analysis Kit for Optimization and Terascale Applications) toolkit provides a exible and extensible interface between simulation codes and iterative analysis methods. Dakota contains algorithms for optimization with gradient and nongradient-based methods; uncertainty quanti cation with sampling, reliability, and stochastic expansion methods; parameter estimation with nonlinear least squares methods; and sensitivity/variance analysis with design of experiments and parameter study methods. These capabilities may be used on their own or as components within advanced strategies such as surrogate-based optimization, mixed integer nonlinear programming, or optimization under uncertainty. By employing object-oriented design to implement abstractions of the key components required for iterative systems analyses, the Dakota toolkit provides a exible and extensible problem-solving environment for design and performance analysis of computational models on high performance computers. This report serves as a theoretical manual for selected algorithms implemented within the Dakota software. It is not intended as a comprehensive theoretical treatment, since a number of existing texts cover general optimization theory, statistical analysis, and other introductory topics. Rather, this manual is intended to summarize a set of Dakota-related research publications in the areas of surrogate-based optimization, uncertainty quanti cation, and optimization under uncertainty that provide the foundation for many of Dakota's iterative analysis capabilities.
Tantra, Ratna; Bolea, Eduardo; Bouwmeester, H.; Rey-Castro, Carlos; David, C.A.A.; Dogné, Jean Michel; Laborda, Francisco; Laloy, Julie; Robinson, Kenneth N.; Undas, A.K.; Zande, van der M.
2016-01-01
This chapter gives an overview of different methods that can potentially be used to determine the solubility of nanomaterials. In general, the methods presented can be broadly divided into four categories: separation methods, methods to quantify free ions, methods to quantify total dissolved
Solubility and diffusivity study for light gases in heavy oil and its fractions
Ganapathi, Rajkumar
Solvent-based recovery (VAPEX) is one of the most promising alternatives to thermal techniques to enhance heavy oil/bitumen recovery. Knowledge of the phase behavior and diffusion coefficients of gases in heavy oil is very important when designing recovery operations and facilities. In this work, a gravimetric microbalance was used to measure the solubility of carbon dioxide, ethane, propane and butane in a Lloydminster heavy oil and its fractions. Measurements were carried out on carbon dioxide and ethane at (290, 298 and 313) K over a pressure range from (200 to 2000) kPa. Similar measurements were performed on propane and butane below their vapor pressures. The Peng-Robinson equation of state was used to correlate the experimental results. The Solubility Parameter Theory was used to predict the solubility of CO2 and propane in heavy oil/bitumen over a wide range of pressures and temperatures. The associated Henry's Law constants for carbon dioxide, ethane and propane in heavy oil, its saturate fractions and aromatic fractions, were also determined from the absorption data. The gases had higher solubilities and the strongest interactions at lower temperatures in the heavy oil and its fractions. The diffusion coefficients of carbon dioxide, ethane and propane in heavy oil, its saturate and aromatic fractions were calculated using a simple diffusion model. The diffusion coefficient of carbon dioxide, ethane, propane and butane in heavy oil were calculated at different pressures. Estimated values were in agreement with published results and were found satisfactory.
Mirmehrabi, M; Rohani, S; Murthy, K S K; Radatus, B
2004-09-10
Understanding the polymorphic behavior of pharmaceutical solids during the crystallization process and further in post-processing units is crucial to meet medical and legal requirements. In this study, an analytical technique was developed for determining the composition of two solid forms of ranitidine hydrochloride using two peaks of Fourier transform infrared (FTIR) spectra without the need to grind the samples. Solubility studies of ranitidine hydrochloride showed that Form 2 has a higher solubility than Form 1. Solution-mediated transformation is very slow and occurs from Form 2 to Form 1 and not the reverse. No solid-solid transformation was observed due to grinding or compressing the pure samples of either forms and of a 50/50 wt.% mixture. Grinding was found to be a proper technique for increasing the bulk solid density of the ranitidine hydrochloride without the risk of solid-solid transformation. Dissolution rate found to be equally fast for both forms. The solubility data were modeled using the group contribution parameters and UNIversal QUAsi-Chemical (UNIQUAC) theory. There was a good agreement between the experimental solubility data of ranitidine hydrochloride and the results of UNIQUAC equation.
Bruno, J.; Cera, E.; Duro, L.; Jordana, S. [QuantiSci S.L., Barcelona (Spain); Pablo, J. de [DEQ-UPC, Barcelona (Spain); Savage, D. [QuantiSci Ltd., Henley-on-Thames (United Kingdom)
1997-12-01
The thermochemical behaviour of 24 critical radionuclides for the forthcoming SR97 PA exercise is discussed. The available databases are reviewed and updated with new data and an extended database for aqueous and solid species of the radionuclides of interest is proposed. We have calculated solubility limits for the radionuclides of interest under different groundwater compositions. A sensitivity analysis of the calculated solubilities with the composition of the groundwater is presented. Besides selecting the most likely solubility limiting phases, in this work we have used coprecipitation approaches in order to calculate more realistic solubility limits for minor radionuclides, such as Ra, Am and Cm. The comparison between the calculated solubilities and the concentrations measured in relevant natural systems (NA) and in spent fuel leaching experiments helps to assess the validity of the methodology used and to derive source term concentrations for the radionuclides studied. The uncertainties associated to the solubilities of the main radionuclides involved in the spent nuclear fuel have also been discussed in this work. The variability of the groundwater chemistry; redox conditions and temperature of the system have been considered the main factors affecting the solubilities. In this case, a sensitivity analysis has been performed in order to study solubility changes as a function of these parameters. The uncertainties have been calculated by including the values found in a major extent in typical granitic groundwaters. The results obtained from this analysis indicate that there are some radionuclides which are not affected by these parameters, i.e. Ag, Cm, Ho, Nb, Ni, Np, Pu, Se, Sm, Sn, Sr, Tc and U
Soluble and insoluble fiber (image)
Dietary fiber is the part of food that is not affected by the digestive process in the body. ... of the stool. There are two types of dietary fiber, soluble and insoluble. Soluble fiber retains water and ...
Leturcq, G.; Costenoble, S.; Grandjean, S. [CEA Marcoule DEN/DRCP/SCPS/LCA - BP17171 - 30207 Bagnols sur Ceze cedex (France)
2008-07-01
The solubility of uranyl oxalate was determined at ambient temperature by precipitation in oxalic-nitric solutions, using an initial uranyl concentration of 0.1 mol/L. Oxalic concentration varied from 0.075 to 0.3 mol/L while nitric concentration ranged between 0.75 and 3 mol/L. Dissolution tests, using complementary oxalic-nitric media, were carried out for 550 hours in order to study the kinetic to reach thermodynamic equilibrium. Similar solubility values were reached by dissolution and precipitation. Using the results, it was possible to draw the solubility surface versus oxalic and nitric concentrations and to determine both the apparent solubility constant of UO{sub 2}C{sub 2}O{sub 4}, 3H{sub 2}O (Ks) and the apparent formation constant of the first uranyl-oxalate complex UO{sub 2}C{sub 2}O{sub 4} (log {beta}1), for ionic strengths varying between 1 and 3 mol/L. Ks and log {beta}1 values were found to vary from 1.9 10{sup -8} to 9.2 10{sup -9} and from 5.95 to 6.06, respectively, when ionic strength varied from 1 to 3 mol/L. A second model may fit our data obtained at an ionic strength of 3 mol/L suggesting as reported by Moskvin et al. (1959) that no complexes are formed for [H{sup +}] at 3 M. The Ks value would then be 1.3 10{sup -8}. (authors)
Microscopic views of drug solubility
Bondesson, Laban
2006-01-01
The development of computational models for predicting drug solubility has increased drastically during the last decades. Nevertheless these models still have diffculties to estimate the aqueous solubility as accurate as desired. In this thesis di erent aspects that are known to have a large impact on the aqueous solubility of a molecule have been studied in detail using various theoretical methods with intension to provide microscopic view on drug solubility. The rst aspect studied is the hy...
Reynerson, Charles Martin
This research has been performed to create concept design and economic feasibility data for space business parks. A space business park is a commercially run multi-use space station facility designed for use by a wide variety of customers. Both space hardware and crew are considered as revenue producing payloads. Examples of commercial markets may include biological and materials research, processing, and production, space tourism habitats, and satellite maintenance and resupply depots. This research develops a design methodology and an analytical tool to create feasible preliminary design information for space business parks. The design tool is validated against a number of real facility designs. Appropriate model variables are adjusted to ensure that statistical approximations are valid for subsequent analyses. The tool is used to analyze the effect of various payload requirements on the size, weight and power of the facility. The approach for the analytical tool was to input potential payloads as simple requirements, such as volume, weight, power, crew size, and endurance. In creating the theory, basic principles are used and combined with parametric estimation of data when necessary. Key system parameters are identified for overall system design. Typical ranges for these key parameters are identified based on real human spaceflight systems. To connect the economics to design, a life-cycle cost model is created based upon facility mass. This rough cost model estimates potential return on investments, initial investment requirements and number of years to return on the initial investment. Example cases are analyzed for both performance and cost driven requirements for space hotels, microgravity processing facilities, and multi-use facilities. In combining both engineering and economic models, a design-to-cost methodology is created for more accurately estimating the commercial viability for multiple space business park markets.
Tu, T H; Kim, C-S; Kang, J-H; Nam-Goong, I S; Nam, C W; Kim, E S; Kim, Y I; Choi, J I; Kawada, T; Goto, T; Park, T; Yoon Park, J H; Choi, M-S; Yu, R
2014-08-01
4-1BB, a member of the TNF receptor superfamily, has a role in various inflammatory pathologies through its interaction with 4-1BB ligand. We previously demonstrated that it participates in initiating and promoting obesity-induced adipose inflammation in a rodent model. In this study, we examined whether 4-1BB is related to obesity-induced adipose inflammation and metabolic parameters in humans. A total of 50 subjects, 25 obese (body mass index (BMI)≥25 kg m(-2)) and 25 lean (BMIadipose tissue were measured by quantitative real-time PCR and enzyme-linked immunosorbent assay, respectively. Inflammatory and metabolic parameters were measured by enzymatic analysis and immunoassay. Obese subjects had higher levels of both 4-1BB transcripts and s4-1BB protein in subcutaneous adipose tissue than lean controls, and the levels were correlated with BMI and the expression of inflammatory markers, as well as with serum metabolic parameters. Moreover, s4-1BB was released from human adipocytes, and elicited chemotactic responses from human monocytes/T cells as well as enhancing their inflammatory activity, indicating that it may promote human adipose inflammation. Our data demonstrate that elevated levels of 4-1BB transcripts and s4-1BB in adipose tissue are closely associated with obesity-induced inflammation and metabolic dysregulation. They suggest that both 4-1BB transcripts and s4-1BB could serve as novel biomarkers and/or therapeutic targets for obesity-induced inflammation and metabolic syndrome in humans.
José O Valderrama
2006-01-01
Full Text Available Se ha analizado el efecto de algunos parámetros numéricos en la determinación de la presión de sublimación de un sólido usando datos de solubilidad del sólido en un gas a alta presión. El estudio se basa en un trabajo presentado por Valderrama y Zavaleta (2005 en el que se utiliza algoritmos genéticos como método de optimización. Los valores de algunos parámetros involucrados en el método de los algoritmos genéticos, como el número de individuos, el número de generaciones, la probabilidad de cruzamiento, y la probabilidad de mutación, no fueron analizados con detalle por los autores. En este estudio se analizan los resultados obtenidos haciendo variar el valor de estos parámetros y usando como función objetivo la desviación en la solubilidad en la presión de sublimación calculada. El estudio permite concluir sobre el efecto de estos parámetros y recomienda los mejores valores para este tipo de estudios.The effect of some numerical parameters on the determination of the sublimation pressure of a solid using solubility of the solid in a high pressure gas was specially analyzed. The study is based on a paper presented by Valderrama y Zavaleta (2005 in which genetic algorithms are used as optimization method. The values of some parameters involved in the genetic algorithm method such as number of individuals, number of generations, the crossover probability and the mutation probability, were not analyzed by these authors. In this study the results obtained by varying the values of these parameters using the deviation in the solubility as the objective function is analyzed with details. The study allows to conclude on the effect of these parameters and on the best values of the parameters for the cases studied.
Schubert, Torsten; Finke, Kathrin; Redel, Petra; Kluckow, Steffen; Müller, Hermann; Strobach, Tilo
2015-05-01
Experts with video game experience, in contrast to non-experienced persons, are superior in multiple domains of visual attention. However, it is an open question which basic aspects of attention underlie this superiority. We approached this question using the framework of Theory of Visual Attention (TVA) with tools that allowed us to assess various parameters that are related to different visual attention aspects (e.g., perception threshold, processing speed, visual short-term memory storage capacity, top-down control, spatial distribution of attention) and that are measurable on the same experimental basis. In Experiment 1, we found advantages of video game experts in perception threshold and visual processing speed; the latter being restricted to the lower positions of the used computer display. The observed advantages were not significantly moderated by general person-related characteristics such as personality traits, sensation seeking, intelligence, social anxiety, or health status. Experiment 2 tested a potential causal link between the expert advantages and video game practice with an intervention protocol. It found no effects of action video gaming on perception threshold, visual short-term memory storage capacity, iconic memory storage, top-down control, and spatial distribution of attention after 15 days of training. However, observations of a selected improvement of processing speed at the lower positions of the computer screen after video game training and of retest effects are suggestive for limited possibilities to improve basic aspects of visual attention (TVA) with practice.
Band parameters of phosphorene
Lew Yan Voon, L. C.; Wang, J.; Zhang, Y.;
2015-01-01
Phosphorene is a two-dimensional nanomaterial with a direct band-gap at the Brillouin zone center. In this paper, we present a recently derived effective-mass theory of the band structure in the presence of strain and electric field, based upon group theory. Band parameters for this theory...
Thermal degradation of organo-soluble polyimides
黄俐研; 史燚; 金熹高
1999-01-01
The thermal degradation behavior of two organo-soluble polyimides was investigated by high resolution pyrolysis-gas chromatography/mass spectrometry. The pyrolyzates of the polymers at various temperatures were identified and characterized quantitatively. The relationship between the polymer structure and pyrolyzate distribution was discussed. The kinetic parameters of the thermal degradation were calculated based on thermogravimetric measurements. Finally, the thermal degradation mechanism for the polymers was suggested.
Udayashankar, Paniveni
2016-07-01
I study the complexity of supergranular cells using intensity patterns from Kodaikanal solar observatory. The chaotic and turbulent aspect of the solar supergranulation can be studied by examining the interrelationships amongst the parameters characterizing supergranular cells namely size, horizontal flow field, lifetime and physical dimensions of the cells and the fractal dimension deduced from the size data. The findings are supportive of Kolmogorov's theory of turbulence. The Data consists of visually identified supergranular cells, from which a fractal dimension 'D' for supergranulation is obtained according to the relation P α AD/2 where 'A' is the area and 'P' is the perimeter of the supergranular cells. I find a fractal dimension close to about 1.3 which is consistent with that for isobars and suggests a possible turbulent origin. The cell circularity shows a dependence on the perimeter with a peak around (1.1-1.2) x 105 m. The findings are supportive of Kolmogorov's theory of turbulence.
Gust, Jr., John Devens; Liddell, Paul Anthony
2015-07-07
Porphyrin polymers of Structure 1, where n is an integer (e.g., 1, 2, 3, 4, 5, or greater) ##STR00001## are synthesized by the method shown in FIGS. 2A and 2B. The porphyrin polymers of Structure 1 are soluble in organic solvents such as 2-MeTHF and the like, and can be synthesized in bulk (i.e., in processes other than electropolymerization). These porphyrin polymers have long excited state lifetimes, making the material suitable as an organic semiconductor for organic electronic devices including transistors and memories, as well as solar cells, sensors, light-emitting devices, and other opto-electronic devices.
Cloud condensation nuclei activation of limited solubility organic aerosol
Huff Hartz, Kara E.; Tischuk, Joshua E.; Chan, Man Nin; Chan, Chak K.; Donahue, Neil M.; Pandis, Spyros N.
The cloud condensation nuclei (CCN) activation of 19 organic species with water solubilities ( Csat) ranging from 10 -4 to 10 2 g solute 100 g -1 H 2O was measured. The organic particles were generated by nebulization of an aqueous or an alcohol solution. Use of alcohols as solvents enables the measurement of low solubility, non-volatile organic CCN activity and reduces the likelihood of residual water in the aerosol. The activation diameter of organic species with very low solubility in water ( Csat<0.3 g 100 g -1 H 2O) is in agreement with Köhler theory using the bulk solubility (limited solubility case) of the organic in water. Many species, including 2-acetylbenzoic acid, aspartic acid, azelaic acid, glutamic acid, homophthalic acid, phthalic acid, cis-pinonic acid, and salicylic acid are highly CCN active in spite of their low solubility (0.3 g 100 g -1 H 2O< Csat<1 g 100 g -1 H 2O), and activate almost as if completely water soluble. The CCN activity of most species is reduced, if the particles are produced using non-aqueous solvents. The existence of the particles in a metastable state at low RH can explain the observed enhancement in CCN activity beyond the levels suggested by their solubility.
Reinisch, Elena C.; Cardiff, Michael; Feigl, Kurt L.
2016-07-01
Graph theory is useful for analyzing time-dependent model parameters estimated from interferometric synthetic aperture radar (InSAR) data in the temporal domain. Plotting acquisition dates (epochs) as vertices and pair-wise interferometric combinations as edges defines an incidence graph. The edge-vertex incidence matrix and the normalized edge Laplacian matrix are factors in the covariance matrix for the pair-wise data. Using empirical measures of residual scatter in the pair-wise observations, we estimate the relative variance at each epoch by inverting the covariance of the pair-wise data. We evaluate the rank deficiency of the corresponding least-squares problem via the edge-vertex incidence matrix. We implement our method in a MATLAB software package called GraphTreeTA available on GitHub (https://github.com/feigl/gipht). We apply temporal adjustment to the data set described in Lu et al. (Geophys Res Solid Earth 110, 2005) at Okmok volcano, Alaska, which erupted most recently in 1997 and 2008. The data set contains 44 differential volumetric changes and uncertainties estimated from interferograms between 1997 and 2004. Estimates show that approximately half of the magma volume lost during the 1997 eruption was recovered by the summer of 2003. Between June 2002 and September 2003, the estimated rate of volumetric increase is (6.2 ± 0.6) × 10^6~m^3/year . Our preferred model provides a reasonable fit that is compatible with viscoelastic relaxation in the five years following the 1997 eruption. Although we demonstrate the approach using volumetric rates of change, our formulation in terms of incidence graphs applies to any quantity derived from pair-wise differences, such as range change, range gradient, or atmospheric delay.
Reinisch, Elena C.; Cardiff, Michael; Feigl, Kurt L.
2017-01-01
Graph theory is useful for analyzing time-dependent model parameters estimated from interferometric synthetic aperture radar (InSAR) data in the temporal domain. Plotting acquisition dates (epochs) as vertices and pair-wise interferometric combinations as edges defines an incidence graph. The edge-vertex incidence matrix and the normalized edge Laplacian matrix are factors in the covariance matrix for the pair-wise data. Using empirical measures of residual scatter in the pair-wise observations, we estimate the relative variance at each epoch by inverting the covariance of the pair-wise data. We evaluate the rank deficiency of the corresponding least-squares problem via the edge-vertex incidence matrix. We implement our method in a MATLAB software package called GraphTreeTA available on GitHub (https://github.com/feigl/gipht). We apply temporal adjustment to the data set described in Lu et al. (Geophys Res Solid Earth 110, 2005) at Okmok volcano, Alaska, which erupted most recently in 1997 and 2008. The data set contains 44 differential volumetric changes and uncertainties estimated from interferograms between 1997 and 2004. Estimates show that approximately half of the magma volume lost during the 1997 eruption was recovered by the summer of 2003. Between June 2002 and September 2003, the estimated rate of volumetric increase is (6.2 ± 0.6) × 10^6 m^3/year . Our preferred model provides a reasonable fit that is compatible with viscoelastic relaxation in the five years following the 1997 eruption. Although we demonstrate the approach using volumetric rates of change, our formulation in terms of incidence graphs applies to any quantity derived from pair-wise differences, such as range change, range gradient, or atmospheric delay.
Absorption of Soluble Gases by Atmospheric Nanoaerosols
Elperin, Tov; Krasovitov, Boris; Lushnikov, Alexey
2012-01-01
We investigate mass transfer during absorption of atmospheric trace soluble gases by a single droplet whose size is comparable to the molecular mean free path in air at normal conditions. It is assumed that the trace reactant diffuses to the droplet surface and then reacts with the substances inside the droplet according to the first order rate law. Our analysis applies a flux-matching theory of transport processes in gases and assumes constant thermophysical properties of the gases and liquids. We derive an integral equation of Volterra type for the transient molecular flux density to a liquid droplet and solve it numerically. Numerical calculations are performed for absorption of sulfur dioxide (SO2), dinitrogen trioxide (N2O3) and chlorine (Cl2) by liquid nanoaerosols accompanied by chemical dissociation reaction. It is shown that during gas absorption by nanoaerosols the kinetic effects play significant role, and neglecting kinetic effects leads to significant overestimation of the soluble gas flux into a...
Lakhno, V. D.
2012-10-01
The paper is a reply to the arguments adduced by the authors of [8] against the results obtained by the author in [6,7]. It is shown that these arguments are based on the erroneous approach made in [8] to the strong coupling limit when the cutoff parameter is introduced in the theory.
Sandhiya Jatwani et al.
2012-04-01
Full Text Available Solubility is an important parameter to achieve desired concentration of drug in systemic circulation for pharmacological response to be shown. Among all newly discovered chemical entities most of the drugs are lipophillic and fail to reach market due to their poor water solubility. The solubility behavior remains one of the most challenging aspect informational development. Hence various techniques are used for the improvement of solubility of poorly water soluble drugs which include micronization, chemical modification, pH adjustment, solid dispersion, complexation, co-solvency micellar solubilization, hydrotrophy etc. Of all these approaches solid dispersion have attracted tremendous interest as an efficient means of improving the dissolution rate and hence the bioavailability to arrange of hydrophobic drugs. This article reviews the various preparation techniques and types of solid dispersion based on molecular arrangement. Finally some of the practical aspects have also been considered for the preparation of dispersions.
Soluble haemoglobin is a marker of recent Plasmodium falciparum infections
Jakobsen, P H; Bygbjerg, I C; Theander, T G;
1997-01-01
. falciparum malaria compared to the levels during acute disease. Thus, both soluble Hb and haptoglobin appear to be markers of recent P. falciparum infections. Very high levels of CRP protein were measured in some of the malaria patients at the day of treatment while lower levels were recorded 7 and 30 days...... after treatment. Soluble Hb levels were associated with malariometric parameters in a similar fashion to haptoglobin. The new Mab-based assay for measuring soluble Hb in the peripheral blood of malaria patients may be useful for future epidemiological studies of malaria....
Control of Fusion and Solubility in Fusion Systems
Craven, David A
2009-01-01
In this article, we consider the control of fusion in fusion systems, proving three previously known, non-trivial results in a new, largely elementary way. We then reprove a result of Aschbacher, that the product of two strongly closed subgroups is strongly closed; to do this, we consolidate the theory of quotients of fusion systems into a consistent theory. We move on considering p-soluble fusion systems, and prove that they are constrained, allowing us to effectively characterize fusion systems of p-soluble groups. This leads us to recast Thompson Factorization for Qd(p)-free fusion systems, and consider Thompson Factorization for more general fusion systems.
THE SOLUBILITY OF MILAS BAUXITE ORE IN SULPHURIC ACI
Mustafa GULFEN
2001-06-01
Full Text Available The effects of calcination conditions,sulphuric acid concentrations and dissolvingtemperature and period as parameters to thesolubility of the bauxite ore from Gobekdagı reservesin Mugla-Milas region were investigated. The bauxitesamples were calcined in different periods at differenttemperatures. Then the solubility of the calcinedbauxite samples in sulphuric acid solution wasexamined. Dissolving activation energy (Ea wascalculated using the optimum kinetics equation andthe results obtained from the solubility studiesexamined dissolving temperatures and periods
Water-soluble cavitands - synthesis, solubilities and binding properties
Middel, Oskar; Verboom, Willem; Reinhoudt, David N.
2002-01-01
Water-soluble cavitand receptors have been obtained by the introduction of ionizable groups (5, 21-28, 39) and neutral hydrophilic tetraethylene glycol based dendritic wedges (19, 20). The synthesis of these cavitands and a study of their water solubilities and binding properties toward neutral orga
Tzocheva, Sylvia S; Danov, Krassimir D; Kralchevsky, Peter A; Georgieva, Gergana S; Post, Albert J; Ananthapadmanabhan, Kavssery P
2015-07-01
By analysis of experimental data, a quantitative theoretical interpretation of the solubility limit of medium- and long-chain fatty alcohols in micellar solutions of water-soluble surfactants is presented. A general picture of the phase behavior of the investigated systems is given in the form of phase diagrams. The limited solubility of the fatty alcohols in the micelles of conventional surfactants is explained with the precipitation of their monomers in the bulk, rather than with micelle phase separation. The long chain fatty alcohols (with n=14, 16 and 18 carbon atoms) exhibit an ideal mixing in the micelles of the anionic surfactant sodium laurylethersulfate (SLES) and the zwitterionic surfactant cocamidopropyl betaine (CAPB) at temperatures of 25, 30, 35 and 40 °C. Deviations from ideality are observed for the alcohols of shorter chain (n=10 and 12), which can be explained by a mismatch with the longer chains of the surfactant molecules. Using the determined thermodynamic parameters of the systems, their phase diagrams are constructed. Such a diagram consists of four domains, viz. mixed micelles; coexistent micelles and precipitate (dispersed crystallites or droplets); precipitate without micelles, and molecular solution. The four boundary lines intersect in a quadruple point, Q. For ionic surfactants (like SLES), a detailed theory for calculating the boundary lines of the phase diagrams is developed and verified against data for the positions of the kinks in surface tension isotherms. The theory takes into account the electrostatic interactions in the micellar solutions and the effect of counterion binding. The results can be useful for a quantitative interpretation and prediction of the phase behavior of mixed solutions of two (or more) surfactants, one of them being water soluble and forming micelles, whereas the other one has a limited water solubility, but readily forms mixed micelles with the former surfactant.
Solubility of Sulfur Dioxide in Sulfuric Acid
Chang, K. K.; Compton, L. E.; Lawson, D. D.
1982-01-01
The solubility of sulfur dioxide in 50% (wt./wt.) sulfuric acid was evaluated by regular solution theory, and the results verified by experimental measurements in the temperature range of 25 C to 70 C at pressures of 60 to 200 PSIA. The percent (wt./wt.) of sulfur dioxide in 50% (wt./wt.) sulfuric acid is given by the equation %SO2 = 2.2350 + 0.0903P - 0.00026P 10 to the 2nd power with P in PSIA.
Pure Phase Solubility Limits: LANL
C. Stockman
2001-01-26
The natural and engineered system at Yucca Mountain (YM) defines the site-specific conditions under which one must determine to what extent the engineered and the natural geochemical barriers will prevent the release of radioactive material from the repository. Most important mechanisms for retention or enhancement of radionuclide transport include precipitation or co-precipitation of radionuclide-bearing solid phases (solubility limits), complexation in solution, sorption onto surfaces, colloid formation, and diffusion. There may be many scenarios that could affect the near-field environment, creating chemical conditions more aggressive than the conditions presented by the unperturbed system (such as pH changes beyond the range of 6 to 9 or significant changes in the ionic strength of infiltrated waters). For an extended period of time, the near-field water composition may be quite different and more extreme in pH, ionic strength, and CO{sub 2} partial pressure (or carbonate concentration) than waters at some distance from the repository. Reducing conditions, high pH (up to 11), and low carbonate concentration may be present in the near-field after reaction of infiltrating groundwater with engineered barrier systems, such as cementitious materials. In the far-field, conditions are controlled by the rock-mass buffer providing a near-neutral, oxidizing, low-ionic-strength environment that controls radionuclide solubility limits and sorption capacities. There is the need for characterization of variable chemical conditions that affect solubility, speciation, and sorption reactions. Modeling of the groundwater chemistry is required and leads to an understanding of solubility and speciation of the important radionuclides. Because experimental studies cannot be performed under the numerous potential chemical conditions, solubility limitations must rely on geochemical modeling of the radionuclide's chemistry. Fundamental thermodynamic properties, such as solubility
扶瑾; 贺福元; 罗杰英; 皮凤娟; 吴德智; 戴儒文
2008-01-01
目的 探讨不同梯度洗脱条件下HPLC图谱特征峰位位移变化的规律,快速建立优化的图谱条件.方法 采用HPLC法.以大黄为模型药材,比较两个不同梯度洗脱条件下特征峰的总洗脱液溶度参数.色谱柱:Alltech Apollo C18柱(250 mm×4.6 mm,5 μm);流动相:乙腈-水-1%冰醋酸,梯度洗脱;检测波长:254 nm;柱温:40℃;进样体积10μL.结果 大黄13个相匹配的特征峰,在初始程序和优化程序下,各自的总洗脱液溶度参数基本相等,其中1号匹配峰的偏差最大,为-12.05%,4号匹配峰的偏差最小,为-0.388%.结论 HPLC图谱在不同梯度洗脱条件下特征峰位位移遵循总洗脱液溶度参数相等的规律.
Determination of Hansen solubility parameters of fatty ethyl esters
Matheus Maciel Batista
2010-01-01
Resumo: Os parâmetros de solubilidade tridimensional definidos por Hansen são baseados em forças de dispersão entre as unidades estruturais, interações entre os grupos polares e de ligação de hidrogênio. Para compostos, tais como ésteres graxos que apresentam longas cadeias carbônicas, essa abordagem foi utilizada para obter as três coordenadas de parâmetros de solubilidade em termos de: uma parte de dispersão, uma parte polar e uma parte de ligação de hidrogênio. Está presente neste trabalho...
Solubility parameter of poly(ether imide), Ultem
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(1-vinyl-2-pyrrolidinone)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(styrene-co-butyl methacrylate)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(vinylidene fluoride-co-hexafluoropropylene)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(styrene-co-nonyl methacrylate)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(styrene-co-methyl methacrylate)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(styrene-co-acrylonitrile)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(vinyl methyl ether)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(tetramethyl-p-silphenylene) siloxane
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(styrene-b-butadiene-b-styrene)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(styrene-co-divinylbenzene)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Solubility parameter of poly(styrene-co-isobutyl methacrylate)
Wohlfarth, Ch.
This document is part of Subvolume D2 'Polymer Solutions - Physical Properties and their Relations I (Thermodynamic Properties: PVT -Data and miscellaneous Properties of polymer Solutions) of Volume 6 `Polymers' of Landolt-Börnstein - Group VIII `Advanced Materials and Technologies'.
Effective theories of universal theories
Wells, James D
2015-01-01
It is well-known but sometimes overlooked that constraints on the oblique parameters (most notably $S$ and $T$ parameters) are only applicable to a special class of new physics scenarios known as universal theories. In the effective field theory (EFT) framework, the oblique parameters should not be associated with Wilson coefficients in a particular operator basis, unless restrictions have been imposed on the EFT so that it describes universal theories. We work out these restrictions, and present a detailed EFT analysis of universal theories. We find that at the dimension-6 level, universal theories are completely characterized by 16 parameters. They are conveniently chosen to be: 5 oblique parameters that agree with the commonly-adopted ones, 4 anomalous triple-gauge couplings, 3 rescaling factors for the $h^3$, $hff$, $hVV$ vertices, 3 parameters for $hVV$ vertices absent in the Standard Model, and 1 four-fermion coupling of order $y_f^2$. All these parameters are defined in an unambiguous and basis-indepen...
Abdallah El Hadj. A.
2013-01-01
Full Text Available In this work, the solubilities of some anti-inflammatory (nabumetone, phenylbutazone and salicylamide and statin drugs (fluvastatin, atorvastatin, lovastatin, simvastatin and rosuvastatin were correlated using the Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT with one-parameter mixing rule and commonly used cubic equations of state Peng-Robinson (PR and Soave-Redlich-Kwong (SRK combining with van-der Waals-1 parameter (VDW1 and van-der Waals-2 parameters (VDW2 mixing rules. The experimental data for studied compounds were taken from literature at temperature and pressure in ranges (308-348 K and (100-360 bar respectively. The critical properties required for the correlation with PR and SRK were estimated using Gani and Noonalol contribution group methods whereas, PC-SAFT pure-component parameters; segment number (m, segment diameter (σ and energy parameter (ε/k have been estimated by tihic’s group contribution method for nabumetone. For phenylbutazone and salicylamide those parameters were determined using a linear correlation. For statin drugs, PC-SAFT parameters were fitted to solubility data, and binary interaction parameters (kij and lij have been obtained by fitting the experimental data. The result was found to be in good agreement with the experimental data and showed that PC-SAFT approach can be used to model solid-SCF equilibrium with better correlation accuracy than cubic equations of state.
何壮; 袁淑莉; 赵守盈
2012-01-01
教育考试中专题、短测验等形式是命题的一种主要方式。对这类测验的分析，可以从参数项目反应理论和非参数项目反应理论入手。本研究分别选取Rasch模型和Mokken模型对某高三文科综合地理试卷进行分析比较。使用winsteps和xeaaibre软件进行Rasch分析，得到难度、信息量、项目功能差异等参数；使用MSP软件进行Mokken分析，得到正答率和同质性系数。比较两种结果，得出以下结论：（1）非参数项目反应理论以正答率对题目排序与参数项目反应理论以难度排序一致；（2）而有个别不符合参数项目反应理论标准的题目对提高测验质量同样有意义，不应被删除；（3）进行维度检验和题目筛选时，非参数项目反应理论标准比参数项目反应理论标准更加严格；（4）两种理论的项目功能差异检验结果一致。%As one of the significant types of tests, the test project and short test are popular in educational testing. Parameter and non-parameter item response theory being the starts, these tests were under analysis. Compared was the geography paper in inaugurated arts taken by some senior three students. During this comparison the Rasch and Mokken model were respectively selected. For analyzing software Winsteps and Xcalibre were utilized to analyze item parameters in Rasch model. Analyzed in detail were the parameters of difficulty, differential item functioning and information curve. Software MSP was for the purpose of analyzing items in Mokken model. Besides, the statistics of accurate rate and coefficients of homogeneity were also analyzed in detail. Finally, four conclusions were arrived at as the following: ( 1 ) The estimate results of difficulty between non-parameter and parameter item response theory were equivalent. (2)Those items, which failed to fit parameter item response theory, succeeded in non-parameter item response theory. (3)Non-parameter item
邬时清; 叶章基; 谭振华; 苏雅丽; 王胜龙; 戎宗明
2011-01-01
采用多元函数的变尺度法和遗传算法,对溶胀法聚合物溶解度参数实验数据进行处理计算,通过39个聚合物数据的计算检验,总符合率的平均值为93.5％,较Hansen的计算结果提高了4.5％.采用Delphi 7.0编程语言编制的数据处理计算程序,具有界面友好、操作方便等优点,在科学研究和工业应用中具有相当的实用价值.%By applying the multidimensional unconstrained optimization and the genetic algorithm in multiple-variable function, we calculated the solubility parameters of 39 polymers. Compared to the experimental results obtained from the swelling test, the average overall satisfaction is 93.5%, 4.5% better than that by Hansen's calculation. We coded this new calculation method with Delphi 7.0 and developed it into a practical software package. Its user-friendly interface and simple operation feature are expected to facilitate its wide adoption in research and industry.
Lakhno, V.D.
2012-01-01
The paper is a reply to the arguments adduced by the authors of Ref. [arXiv:1204.4142] against the results obtained by the author in Refs. [6,7]. It is shown that these arguments are based on the erroneous approach made in Ref. [arXiv:1204.4142] to the strong coupling limit when the cutoff parameter is introduced in the theory.
Doungmo Goufo, Emile Franc
2016-08-01
After having the issues of singularity and locality addressed recently in mathematical modelling, another question regarding the description of natural phenomena was raised: How influent is the second parameter β of the two-parameter Mittag-Leffler function Eα,β(z), z∈ℂ? To answer this question, we generalize the newly introduced one-parameter derivative with non-singular and non-local kernel [A. Atangana and I. Koca, Chaos, Solitons Fractals 89, 447 (2016); A. Atangana and D. Bealeanu (e-print)] by developing a similar two-parameter derivative with non-singular and non-local kernel based on Eα , β(z). We exploit the Agarwal/Erdelyi higher transcendental functions together with their Laplace transforms to explicitly establish the Laplace transform's expressions of the two-parameter derivatives, necessary for solving related fractional differential equations. Explicit expression of the associated two-parameter fractional integral is also established. Concrete applications are done on atmospheric convection process by using Lorenz non-linear simple system. Existence result for the model is provided and a numerical scheme established. As expected, solutions exhibit chaotic behaviors for α less than 0.55, and this chaos is not interrupted by the impact of β. Rather, this second parameter seems to indirectly squeeze and rotate the solutions, giving an impression of twisting. The whole graphics seem to have completely changed its orientation to a particular direction. This is a great observation that clearly shows the substantial impact of the second parameter of Eα , β(z), certainly opening new doors to modeling with two-parameter derivatives.
马晓红; 王强; 李晓萍; 唐军; 张正方
2015-01-01
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 param-eter 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 sol-vents 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.%采用反气相色谱法（IGC）表征了离子液体1-丁基-3-甲基咪唑四氟硼酸盐（[BMIM]BF4）在333~373 K 温度范围内的热力学参数。使用两组不同化学结构和性质的探针分子测定了[ BMIM]BF4与溶剂之间的相互作用力。根据探针分子的保留时间计算得到探针分子与[ BMIM]BF4之间的摩尔吸附焓、质量分数活度系数、Flory-Huggins相互作用参数和[ BMIM]BF4的溶解度参数。结果表明，所选溶剂中 n-C10、n-C11、n-C12、四氯化碳，环己烷和甲苯为[BMIM]BF4的不良溶剂；二氯甲烷、丙酮、氯仿、乙酸甲酯、乙醇、甲醇为[BMIM]BF4的良溶剂。运用外推法得到了[HMIM]BF4在室温（298.15K）时的溶解度参数为23.39（J／cm3）0.5。实验结果证明 IGC 法是一种简便准确的获得离子液体热力学参数的方法。本研究为离子液体的应用及相
Mauricio Gantiva
2010-01-01
Full Text Available Extended Hildebrand Solubility Approach (EHSA developed by Martin et al. was applied to evaluate the solubility of ketoprofen (KTP in ethanol + water cosolvent mixtures at 298.15 K. Calculated values of molar volume and solubility parameter for KTP were used. A good predictive capacity of EHSA was found by using a regular polynomial model in order five to correlate the W interaction parameter and the solubility parameters of cosolvent mixtures (δmix. Nevertheless, the deviations obtained in the estimated solubilities with respect to the experimental solubilities were on the same order like those obtained directly by means of an empiric regression of the logarithmic experimental solubilities as a function of δmix values.
Tay, Louis; Huang, Qiming; Vermunt, Jeroen K.
2016-01-01
In large-scale testing, the use of multigroup approaches is limited for assessing differential item functioning (DIF) across multiple variables as DIF is examined for each variable separately. In contrast, the item response theory with covariate (IRT-C) procedure can be used to examine DIF across multiple variables (covariates) simultaneously. To…
Sannino, Francesco
2010-01-01
We propose a direct test of the existence of gauge duals for nonsupersymmetric asymptotically free gauge theories developing an infrared fixed point by computing the S-parameter in the electric and dual magnetic description. In particular we show that at the lower bound of the conformal window...... the magnetic S-parameter, i.e. the one determined via the dual magnetic gauge theory, assumes a simple expression in terms of the elementary magnetic degrees of freedom. The results further support our recent conjecture of the existence of a universal lower bound on the S parameter and indicates...
Thermodynamic approach to boron nitride nanotube solubility and dispersion
Tiano, A. L.; Gibbons, L.; Tsui, M.; Applin, S. I.; Silva, R.; Park, C.; Fay, C. C.
2016-02-01
Inadequate dispersion of nanomaterials is a critical issue that significantly limits the potential properties of nanocomposites and when overcome, will enable further enhancement of material properties. The most common methods used to improve dispersion include surface functionalization, surfactants, polymer wrapping, and sonication. Although these approaches have proven effective, they often achieve dispersion by altering the surface or structure of the nanomaterial and ultimately, their intrinsic properties. Co-solvents are commonly utilized in the polymer, paint, and art conservation industries to selectively dissolve materials. These co-solvents are utilized based on thermodynamic interaction parameters and are chosen so that the original materials are not affected. The same concept was applied to enhance the dispersion of boron nitride nanotubes (BNNTs) to facilitate the fabrication of BNNT nanocomposites. Of the solvents tested, dimethylacetamide (DMAc) exhibited the most stable, uniform dispersion of BNNTs, followed by N,N-dimethylformamide (DMF), acetone, and N-methyl-2-pyrrolidone (NMP). Utilizing the known Hansen solubility parameters of these solvents in comparison to the BNNT dispersion state, a region of good solubility was proposed. This solubility region was used to identify co-solvent systems that led to improved BNNT dispersion in poor solvents such as toluene, hexane, and ethanol. Incorporating the data from the co-solvent studies further refined the proposed solubility region. From this region, the Hansen solubility parameters for BNNTs are thought to lie at the midpoint of the solubility sphere: 16.8, 10.7, and 9.0 MPa1/2 for δd, δp, and δh, respectively, with a calculated Hildebrand parameter of 21.8 MPa1/2.Inadequate dispersion of nanomaterials is a critical issue that significantly limits the potential properties of nanocomposites and when overcome, will enable further enhancement of material properties. The most common methods used to
Pure Phase Solubility Limits: LANL
C. Stockman
2001-01-26
The natural and engineered system at Yucca Mountain (YM) defines the site-specific conditions under which one must determine to what extent the engineered and the natural geochemical barriers will prevent the release of radioactive material from the repository. Most important mechanisms for retention or enhancement of radionuclide transport include precipitation or co-precipitation of radionuclide-bearing solid phases (solubility limits), complexation in solution, sorption onto surfaces, colloid formation, and diffusion. There may be many scenarios that could affect the near-field environment, creating chemical conditions more aggressive than the conditions presented by the unperturbed system (such as pH changes beyond the range of 6 to 9 or significant changes in the ionic strength of infiltrated waters). For an extended period of time, the near-field water composition may be quite different and more extreme in pH, ionic strength, and CO{sub 2} partial pressure (or carbonate concentration) than waters at some distance from the repository. Reducing conditions, high pH (up to 11), and low carbonate concentration may be present in the near-field after reaction of infiltrating groundwater with engineered barrier systems, such as cementitious materials. In the far-field, conditions are controlled by the rock-mass buffer providing a near-neutral, oxidizing, low-ionic-strength environment that controls radionuclide solubility limits and sorption capacities. There is the need for characterization of variable chemical conditions that affect solubility, speciation, and sorption reactions. Modeling of the groundwater chemistry is required and leads to an understanding of solubility and speciation of the important radionuclides. Because experimental studies cannot be performed under the numerous potential chemical conditions, solubility limitations must rely on geochemical modeling of the radionuclide's chemistry. Fundamental thermodynamic properties, such as solubility
Prediction of gas solubilities in ionic liquids.
Oliferenko, Alexander A; Oliferenko, Polina V; Seddon, Kenneth R; Torrecilla, José S
2011-10-14
Ionic liquids (of which it is estimated that there are at least one million simple fluids) generate a rich chemical space, which is now just at the beginning of its systematic exploration. Many properties of ionic liquids are truly unique and, which is more important, can be finely tuned. Differential solubility of industrial chemicals in ionic liquids is particularly interesting, because it can be a basis for novel, efficient, environmentally friendly technologies. Given the vast number of potential ionic liquids, and the impossibility of a comprehensive empirical exploration, it is essential to extract the maximum information from extant data. We report here some computational models of gas solubility. These multiple regression- and neural network-based models cover a chemical space spanned by 48 ionic liquids and 23 industrially important gases. Molecular polarisabilities and special Lewis acidity and basicity descriptors calculated for the ionic liquid cations and anions, as well as for the gaseous solutes, are used as input parameters. The quality of fit "observed versus predicted Henry's law constants" is particularly good for the neural network model. Validation was established with an external dataset, again with a high quality fit. In contrast to many other neural network models published, our model is no "black box", since contributions of the parameters and their nonlinearity characteristics are calculated and analysed.
Thermodynamic Approach to Boron Nitride Nanotube Solubility and Dispersion
Tiano, A. L.; Gibbons, L.; Tsui, M.; Applin, S. I.; Silva, R.; Park, C.; Fay, C. C.
2016-01-01
Inadequate dispersion of nanomaterials is a critical issue that significantly limits the potential properties of nanocomposites and when overcome, will enable further enhancement of material properties. The most common methods used to improve dispersion include surface functionalization, surfactants, polymer wrapping, and sonication. Although these approaches have proven effective, they often achieve dispersion by altering the surface or structure of the nanomaterial and ultimately, their intrinsic properties. Co-solvents are commonly utilized in the polymer, paint, and art conservation industries to selectively dissolve materials. These co-solvents are utilized based on thermodynamic interaction parameters and are chosen so that the original materials are not affected. The same concept was applied to enhance the dispersion of boron nitride nanotubes (BNNTs) to facilitate the fabrication of BNNT nanocomposites. Of the solvents tested, dimethylacetamide (DMAc) exhibited the most stable, uniform dispersion of BNNTs, followed by N,N-dimethylformamide (DMF), acetone, and N-methyl-2-pyrrolidone (NMP). Utilizing the known Hansen solubility parameters of these solvents in comparison to the BNNT dispersion state, a region of good solubility was proposed. This solubility region was used to identify co-solvent systems that led to improved BNNT dispersion in poor solvents such as toluene, hexane, and ethanol. Incorporating the data from the co-solvent studies further refined the proposed solubility region. From this region, the Hansen solubility parameters for BNNTs are thought to lie at the midpoint of the solubility sphere: 16.8, 10.7, and 9.0 MPa(exp 1/2) for delta d, delta p, and delta h, respectively, with a calculated Hildebrand parameter of 21.8 MPa)exp 1/2).
Computational Analysis of Aqueous Drug Solubility – Influence of the Solid State
Wassvik, Carola
2006-01-01
Aqueous solubility is a key parameter influencing the bioavailability of drugs and drug candidates. In this thesis computational models for the prediction of aqueous drug solubility were explored. High quality experimental solubility data for drugs were generated using a standardised protocol and models were developed using multivariate data analysis tools and calculated molecular descriptors. In addition, structural features associated with either solid-state limited or solvation limited sol...
Bustamante, P; Escalera, B
1995-07-01
The solubility of sulphamethoxypyridazine was measured at several temperatures in mixtures of water:ethanol and ethanol:ethyl acetate. Sulphamethoxypyridazine was chosen as a model drug to compare the solvation effects of proton donor-proton acceptor (water and ethanol) and proton acceptor (ethyl acetate) solvents and mixtures of these solvents because this drug contains functional groups capable of Lewis acid-base interaction. A plot of the mole fraction solubility against the solubility parameter (delta 1 = 30.87 MPa1/2 (20:80 v/v water:ethanol) and another at delta 1 = 20.88 MPa1/2 (30:70 v/v ethanol:ethyl acetate) at all the temperatures under study. The enthalpies and entropies of mixing as well as the enthalpies and entropies of transfer of sulphamethoxypyridazine from ethanol of mixing as well as the enthalpies and entropies of transfer of sulphamethoxypyridazine from ethanol to water:ethanol and ethanol:ethyl acetate mixtures were calculated to compare solvation characteristics of the solvent mixtures toward the drug. As ethanol is added to water, the entropy increases and the structure of the solvent mixture became less ordered, favouring the interaction of the drug with the solvent mixture. On the other hand, in the case of the ethanol:ethyl acetate mixture, solubility is favoured by the more negative enthalpy values. This way, the same result, i.e. a solubility maximum, is obtained by different routes. In the ethanol:water mixtures, the dissolution process if entropy-controlled while enthalpy is the driving force in the case of ethanol:ethyl acetate mixtures. The two solvent systems show enthalpy-entropy compensation. Water deviates from the linear relationship due possibly to its hydrophobic effect.
线性模型中参数估计的可容许性理论%The Theory of Admissibility of Parameters Estimation in Linear Models
鹿长余
2001-01-01
This paper make a review about the history and development in the theory of admissibility estimation in linear model and Variance Component Model. Some open questions are also suggested.%本文综述了线性模型中参数估计的可容许性理论的历史及近年来的发展，同时也提出了一些待解决的问题。
A review of Principles and Parameters---An Introduction to Syntactic Theory%《原则与参数》评介
Peter W.Culicover; 伍雅清
2000-01-01
@@《原则与参数》(Principles and Para,eters——An Introduction to Syntactic Theory)是Peter W.Culicover撰写的句法学教材，于1997年由牛津大学出版社出版。这部书与早些年出版的句法学著作如Liliane Haegeman(1991)的《管约论导论》、...
王海军; 吕中元; 黄旭日; 李泽生; 唐敖庆
1999-01-01
By means of the polymer statistical theory, the A_f-A_g type nonlinear free radical polymerization is investigated to give the number of effective elastic chains, the number of effective elastic mers and the average length for the elastic chains. The corresponding quantities for the dangling chains, the number of effective cross-linkage and the modulus are also obtained. Furthermore, the number- and weight-fractions of elastic chains are deduced.
Krebs, H; Meißner, U -G
2009-01-01
In this note we prove to all orders in the small scale expansion that all off-shell parameters which appear in the chiral effective Lagrangian with explicit Delta(1232) isobar degrees of freedom can be absorbed into redefinitions of certain low-energy constants and are therefore redundant.
Zhang, Yilan; Luo, Rui; Chen, Yi; Ke, Xue; Hu, Danrong; Han, Miaomiao
2014-01-01
...) to prepare solid dispersions using hot melt extrusion (HME). Proper carriers and plasticizers were selected by calculating the Hansen solubility parameters, evaluating melting processing condition, and measuring the solubility of obtained melts...
Bustamante, Pilar; Muela, Susana; Escalera, Begoña; Peña, Angeles
2010-05-01
A model based on solubility parameters is proposed to predict the solubility curves of antihelmintic drugs at several temperatures, including aqueous and non-aqueous mixtures. The solubility of the drugs was measured in ethanol-water and ethanol-ethyl acetate mixtures at 15-35 degrees C (mebendazole) and at 25 degrees C (thiabendazole and metronidazole). The solid phases were analyzed by differential scanning calorimerty. The polymorphic form A of mebendazole was also characterized from infrared spectroscopy. Markedly different solubility profile shapes were obtained against the solubility parameter of the mixtures: two symmetrical peaks (metronidazole), two maxima of different height (mebendazole) and a single peak (thiabendazole). The solubility parameter of the drugs was related to the co-solvent action of both mixtures and to the solubility peaks. The single equation proposed was able to predict solubility profiles of different shape, including both mixtures and all temperatures, providing reasonable physical meaning for the regression coefficients. The model was successfully tested for its predictive capability using a limited number of experimental data. More than 100 solubilities were predicted at several temperatures using 20 data point for each drug.
Briggs, Martin; Day-Lewis, Frederick D.; Ong, John B.; Harvey, Judson W.; Lane, Jr., John W.
2014-01-01
Models of dual-domain mass transfer (DDMT) are used to explain anomalous aquifer transport behavior such as the slow release of contamination and solute tracer tailing. Traditional tracer experiments to characterize DDMT are performed at the flow path scale (meters), which inherently incorporates heterogeneous exchange processes; hence, estimated “effective” parameters are sensitive to experimental design (i.e., duration and injection velocity). Recently, electrical geophysical methods have been used to aid in the inference of DDMT parameters because, unlike traditional fluid sampling, electrical methods can directly sense less-mobile solute dynamics and can target specific points along subsurface flow paths. Here we propose an analytical framework for graphical parameter inference based on a simple petrophysical model explaining the hysteretic relation between measurements of bulk and fluid conductivity arising in the presence of DDMT at the local scale. Analysis is graphical and involves visual inspection of hysteresis patterns to (1) determine the size of paired mobile and less-mobile porosities and (2) identify the exchange rate coefficient through simple curve fitting. We demonstrate the approach using laboratory column experimental data, synthetic streambed experimental data, and field tracer-test data. Results from the analytical approach compare favorably with results from calibration of numerical models and also independent measurements of mobile and less-mobile porosity. We show that localized electrical hysteresis patterns resulting from diffusive exchange are independent of injection velocity, indicating that repeatable parameters can be extracted under varied experimental designs, and these parameters represent the true intrinsic properties of specific volumes of porous media of aquifers and hyporheic zones.
SOLUBILITY ENHANCEMENT OF POORLY WATER SOLUBLE DRUGS BY SOLID DISPERSIO
Amita Verm
2012-01-01
Full Text Available Solid dispersions have been employed to enhance the dissolution rates of poorly water-soluble drugs. Many approaches have been investigated for the preparation of solid dispersions. This paper reports the various solubility enhancement strategies in solid dispersion. The approaches described are fusion (melting, solvent evaporation, lyophilization (freeze drying, melt agglomeration process, extruding method, spray drying technology, use of surfactant, electro static spinning method and super critical fluid technology. This paper also highlights the potential applications and limitations of theseapproaches in solid dispersions.
Suitability of analytical methods to measure solubility for the purpose of nanoregulation
Tantra, Ratna; Bouwmeester, Hans; Bolea, Eduardo; Rey-Castro, Carlos; David, Calin A.; Dogné, Jean Michel; Jarman, John; Laborda, Francisco; Laloy, Julie; Robinson, Kenneth N.; Undas, Anna K.; Zande, Van Der Meike
2016-01-01
Solubility is an important physicochemical parameter in nanoregulation. If nanomaterial is completely soluble, then from a risk assessment point of view, its disposal can be treated much in the same way as "ordinary" chemicals, which will simplify testing and characterisation regimes. This review
Bret, A; Benisti, D; Lefebvre, E
2008-01-01
Besides being one of the most fundamental basic issues of plasma physics, the stability analysis of an electron beam-plasma system is of critical relevance in many areas of physics. Surprisingly, decades of extensive investigation had not yet resulted in a realistic unified picture of the multidimensional unstable spectrum within a fully relativistic and kinetic framework. All attempts made so far in this direction were indeed restricted to simplistic distribution functions and/or did not aim at a complete mapping of the beam-plasma parameter space. The present paper comprehensively tackles this problem by implementing an exact linear model. We show that three kinds of modes compete in the linear phase, which can be classified according to the direction of their wavenumber with respect to the beam. We then determine their respective domain of preponderance in a three-dimensional parameter space. All these results are supported by multidimensional particle-in-cell simulations.
Mingshi SONG; Qiang XU; Guixian HU; Sizhu WU
2006-01-01
A general expression for the correlation of the simple shear(tanφ)to the molecular parameters and the shear rate(γ)was deduced. It shows that the simple shear(tanφ)may be resolved into free recoil(recoverable strain)and viscous heating(unrecoverable strain). The magnitudes of the simple shears for recoil(tanφE)and(tanφv)for viscous heating not only depended on the molecular parameters and the operational variables,but also on the exponential fractions of the recoverable(1-(W)γ)and unrecoverable((W)γ)conformations for recoil and viscous heating. Therefore the magnitudes of the simple shears(tanφE)for recoil and(tanφv)for viscous heating are, respectively, expressed as the partition function to the(1-(W)γ)th power and the partition function to the(-(W)γ)th power. Thus correlations of the total recoil and the ultimately recoverable strains to the molecular parameters [n', a, η0, G0NN and(1--(W)γ)] and the operational variables(·γ, (L/D)and tr)were deduced respectively, which show that at very different shear rates(0≤·γ≤∞)the polymeric liquids may exhibit a very different viscoelastic behaviors. After introducing the uniform two-dimensional extension, the definition of swelling ratio and the ratio of L to D [De=(L/D)], two expressions for the ultimate die swelling effect and the ultimate extrudate swelling ratio BEVT5 to the molecular parameters [n', a, η0, G0N and(1--(W)·γ)] and the operational variables(·γ,(L/D)and tr)were obtained. The two correlation expressions were verified by the experimental data of high-density polyethylene (HDPE) which shows that the two correlation expressions can be used to predict the correlations of the ultimate extrudate swelling behaviors of polymeric liquids to the molecular parameters and the operational variables.
The Solubility Rules: Why Are All Acetates Soluble?
van der Sluys, William G.
2001-01-01
According to the solubility rules presented in many introductory chemistry texts, all (or most) acetate salts are soluble in aqueous solution. The thermodynamic factors that contribute to the solubility of acetates are compared with those of other slightly basic anions. In particular, the hydration enthalpy of acetate is calculated using the Born-Haber approach, from lattice energies, heats of solution, and the hydration energies of several cations. The hydration enthalpy of acetate (-375 kJ/mol) is similar to that of chloride ({355 kJ/mol), nitrite ({383 kJ/mol), and nitrate ({370 kJ/mol), which are all considerably less exothermic than fluoride ({497 kJ/mol). This was somewhat unexpected, since hydration enthalpies generally correlate well with the acid-base properties of an ion, and acetate is more basic than fluoride. Factors influencing the solubility and acid-base properties of acetates, such as the electron donating and hydrophobic nature of the methyl group, are discussed in light of the thermodynamic data.
Solubility database for TILA-99
Vuorinen, U.; Carlsson, T. [VTT Chemical Technology, Espoo (Finland); Kulmala, S.; Hakanen, M. [Helsinki Univ. (Finland). Lab. of Radiochemistry; Ahonen, L. [Geological Survey of Finland, Espoo (Finland)
1998-11-01
The safety assessment of spent fuel disposal requires solubility values for several elements estimated in Finnish disposal conditions. In Finland four sites (Haestholmen, Kivetty, Olkiluoto and Romuvaara) are investigated for the disposal of spent fuel. Haestholmen and OLkiluoto are onshore sites, while Kivetty and Romuvaara are inland sites. Based on groundwater analysis and classification according to salinity at the planned disposal depth mainly fresh groundwater is encountered at Kivetty and Romuvaara, while brackish and saline water-types are met at Haestholmen and Olkiluoto. Very saline, almost brine-type water ({approx}70 g/l) has been found in the deepest parts of the investigated bedrock at one of the sites (Olkiluoto). The reference waters and conditions were chosen according to the water-types. The considered reference conditions incorporated both the near- and far-field, and both oxidizing and reducing conditions were considered. In the reference conditions, the changes in solubilities were also estimated as caused by possible variations in the pH, carbonate content and redox conditions. Uranium, which is the main component of spent fuel is dealt with in a separate report presenting the solubility of uranium and spent fuel dissolution. In this work the solubilities of all the other elements of concern (Am, Cu, Nb, Np, Pa, Pd, Pu, Ra, Se, Sn, Tc, Zr, Cm, Ni, Sr, Th, C, Cl, Cs, Fe, Ho, I, and Sm) in the safety assessment are considered. Some discussion on the corrosion of the spent fuel canister is also presented. For the estimation of solubilities of the elements in question, literature data was collected that mainly comprised experimentally measured concentrations. The sources used were spent fuel experiments, concentrations measured in solubility measurements, natural concentrations and concentrations from natural analogue sites (especially Palmottu and Hyrkkoelae in Finland) as well as the concentrations measured at the Finnish investigation sites
Preliminary considerations concerning actinide solubilities
Newton, T.W.; Bayhurst, B.P.; Daniels, W.R.; Erdal, B.R.; Ogard, A.E.
1980-01-01
Work at the Los Alamos Scientific Laboratory on the fundamental solution chemistry of the actinides has thus far been confined to preliminary considerations of the problems involved in developing an understanding of the precipitation and dissolution behavior of actinide compounds under environmental conditions. Attempts have been made to calculate solubility as a function of Eh and pH using the appropriate thermodynamic data; results have been presented in terms of contour maps showing lines of constant solubility as a function of Eh and pH. Possible methods of control of the redox potential of rock-groundwater systems by the use of Eh buffers (redox couples) is presented.
Bates, David Robert
1962-01-01
Quantum Theory: A Treatise in Three Volumes, I: Elements focuses on the principles, methodologies, and approaches involved in quantum theory, including quantum mechanics, linear combinations, collisions, and transitions. The selection first elaborates on the fundamental principles of quantum mechanics, exactly soluble bound state problems, and continuum. Discussions focus on delta function normalization, spherically symmetric potentials, rectangular potential wells, harmonic oscillators, spherically symmetrical potentials, Coulomb potential, axiomatic basis, consequences of first three postula
REFRACTOMETRIC METHOD FOR EVALUATION OF SOYBEAN PROTEIN SOLUBILITY
RODICA CĂPRIŢĂ
2013-07-01
Full Text Available During the manufacture of soybean meal a quick control is essential, so that simple and rapid methods, to enable an immediate decision to be made, are of value A simple and rapid method for estimating soybean protein solubility on the basis of changes in the refractive index of dilute potassium hydroxide solution extracts was tested and we found to be highly correlated with the usual protein solubility test in KOH (r = 0.9382. Determination of biophysical parameters instead of chemical indices has two great advantages: the methods are nonpolluting since they don’t use chemical substances, and the methods are very rapid.
Parameters adjustment in cognition radio spectrum allocation based on game theory%基于博弈论的认知无线电频谱分配
张北伟; 胡琨元; 朱云龙
2012-01-01
With regard to the dynamic spectrum allocation on wireless cognitive network, a dynamic Bertrand game algorithm of the channel pricing of licensed users was proposed using Bertrand equilibrium. Then, the relationship between stability of Nash equilibrium and speed parameter adjustment was analyzed. Consequently, step response function was utilized to replace the non-concussive process of game, and three-value method was proposed for getting step response parameters. The simulation results show that the proposed algorithm can obtain stable channel price when the value of speed parameter is less than 0. 04. Besides, the feasibility of using a step function to analyze the concussion game process is proved, and this method is convenient for licensed users to make real-time price and bring more economic benefits.%为了解决频谱分配中的授权用户定价博弈问题,根据博弈论中的Bertrand均衡理论,提出了基于Bertrand模型的授权用户信道价格竞争的动态博弈算法.分析了稳定的纳什均衡解与速率调整参数的关系,用控制理论中阶跃函数研究价格无震荡博弈过程,提出了三值法确定阶跃响应参数.仿真结果表明,当数率调整参数在小于0.04时,可以获得稳定的信道价格；同时,验证了用阶跃函数分析无震荡博弈过程的可行性,方便授权用户快速实时定价,带来更大的经济效益.
Solid solubility of germanium in silver
Kazemi, Hamed [Laboratory of Mechanical Metallurgy, Ecole Polytechnique Federale de Lausanne, EPFL, CH-1015 Lausanne (Switzerland); Weber, Ludger, E-mail: ludger.weber@epfl.ch [Laboratory of Mechanical Metallurgy, Ecole Polytechnique Federale de Lausanne, EPFL, CH-1015 Lausanne (Switzerland)
2012-09-20
Highlights: Black-Right-Pointing-Pointer The solvus line in the binary Ag-Ge system has been assessed based on measurements of electrical resistivity and specific gravity. Black-Right-Pointing-Pointer The two measurement techniques yield close agreement. Black-Right-Pointing-Pointer The data found in this contribution indicate lower solid solubility than in previous assessments. Black-Right-Pointing-Pointer Redlich-Kister parameters have been evaluated to describe the solvus line. - Abstract: The solid solubility of germanium in silver has been measured in the temperature range of 520 K to 913 K via measurements of density and of electrical conductivity of two near-eutectic Ag-Ge alloys. The atomic fraction of germanium in solid solution varied between 0.014 and 0.089 over the mentioned range of temperature and an extrapolated maximum solubility of 0.093 at the eutectic temperature of 924 K is found. For samples with spheroidized Ge-particles before the equilibrium heat treatments at low temperature for 24 or 48 h, thermodynamic equilibrium was supposedly not achieved at temperatures below 723 K. Much longer heat treatments (tens of days) on the significantly finer as-cast microstructure allowed to reach equilibrium probably down to 600 K. Independently of whether thermodynamic equilibrium was reached or not the electrical conductivity and the density measurements yielded good agreement typically within a few tenth of percent of atomic Ge-concentration in solid solution in {alpha}-Ag for a given temperature. The results are close to, yet consistently slightly lower than, the values given by Owen and Rowland on which the current assessment of the solvus in the Ag-Ge binary is based. More recent results by Filipponi and co-workers are clearly not in agreement with the data presented here.
Natsheh, Ammar N. [Faculty of Engineering, Al-Ahliyya Amman University, Post Code 19328 Amman (Jordan); Nazzal, Jamal M. [Faculty of Engineering, Al-Ahliyya Amman University, Post Code 19328 Amman (Jordan)]. E-mail: jnazzal@ammanu.edu.jo
2007-08-15
This work describes the bifurcational behavior of a modular peak current-mode controlled DC-DC boost converter with multi bifurcation parameters. The parallel-input/parallel-output converter consists of two identical boost circuits and operates in the continuous-current conduction mode (CCM). A nonlinear mapping in closed form is derived and bifurcation diagrams are generated using MATLAB. A comparison is made between the modular converter diagrams with those of the single boost converter. The effect of introducing mutual coupling between the inductors of the constituent modules is also addressed. Results are verified using the circuit analysis package PSPICE.
Li Dan
2014-06-01
Full Text Available The solubility of magnesium minerals and the refractive index of the ternary system MgBr2 + MgSO4 + H2O at 288.15 K were investigated using an isothermal dissolution method. It was found that there are two invariant points in the phase diagram and the solubility isotherm of this ternary system consists of three branches, corresponding to equilibrium crystallization of Epsomite (MgSO4·7H2O, Eps, hexahydrite (MgSO4·6H2O, Hex and magnesium bromide hexahydrate (MgBr2·6H2O, Mb. Neither solid solutions nor double salts were found. The refractive indices calculated from empirical equation are in good agreement with the experimental data. Combining the results from solubility measurements with the single-salt parameters for MgBr2 and MgSO4, and the mixed ion-interaction parameter θBr,S0(4, the parameter ψMg,Br,S0(4 at 288.15 K was fitted using the Pitzer theory and Harvie-Weare (HW approach. In addition, the average equilibrium constants of the stable equilibrium solids at 288.15 K were obtained by a method using the activity product constant. A chemical model, which combined the Pitzer parameters and the average equilibrium constants, was constructed to calculate the solid + liquid equilibria in the ternary system MgBr2 + MgSO4 + H2O at 288.15 K. The model agreed well with the equilibrium solubility data for the magnesium salts.
Asadi, Mozaffar; Asadi, Zahra; Sadi, Somaye Barzegar; Zarei, Leila; Baigi, Fatemeh Moosavi; Amirghofran, Zahra
2014-03-25
Some new water-soluble Schiff base complexes of Na2[M(L)(H2O)n]; (M=Zn, Cu, Ni, Mn) with a new water-soluble Schiff base ligand where L denotes an asymmetric N2O2 Schiff base ligands; N,N'-bis(5-sulfosalicyliden)-3,4-diaminobenzophenone (5-SO3-3,4-salbenz) were synthesized and characterized. The formation constants of the water soluble Schiff base complexes were calculated by Ketelaar's equation. The theoretical molecular structure for the complexes was computed by using the HF method and the 6-311G basis set. The mechanism of binding of Na2[M(L)(H2O)n] with human serum albumin (HSA) was studied by fluorescence spectroscopic technique. The results of fluorescence titration showed that the intrinsic fluorescence of HSA was quenched by the complexes; which was rationalized in terms of the dynamic quenching mechanism. The values of Stern-Volmer constants, quenching rate constants, binding constants, binding sites and average aggregation number of HSA have been determined. The thermodynamic parameters, were calculated by van't Hoff equation, indicate that the binding is entropy driven and enthalpically disfavored. Based on the Förster theory of non-radiation energy transfer, the efficiency of energy transfer and the distance between the donor (Trp residues) and the acceptor (complex) were obtained. Finally, the growth inhibitory effects of the complexes toward the K562 cancer cell line were measured.
Paulson, Eric S.; Prah, Douglas E.; Schmainda, Kathleen M.
2017-01-01
Dynamic contrast-enhanced (DCE) and dynamic susceptibility contrast (DSC) magnetic resonance imaging (MRI) are the perfusion imaging techniques most frequently used to probe the angiogenic character of brain neoplasms. With these methods, T1- and T2/T2*-weighted imaging sequences are used to image the distribution of gadolinium (Gd)-based contrast agents. However, it is well known that Gd exhibits combined T1, T2, and T2* shortening effects in tissue, and therefore, the results of both DCE- and DSC-MRI can be confounded by these opposing effects. In particular, residual susceptibility effects compete with T1 shortening, which can confound DCE-MRI parameters, whereas dipolar T1 and T2 leakage and residual susceptibility effects can confound DSC-MRI parameters. We introduce here a novel perfusion imaging acquisition and postprocessing method termed Spiral Perfusion Imaging with Consecutive Echoes (SPICE) that can be used to simultaneously acquire DCE- and DSC-MRI data, which requires only a single dose of the Gd contrast agent, does not require the collection of a precontrast T1 map for DCE-MRI processing, and eliminates the confounding contrast agent effects due to contrast extravasation. A detailed mathematical description of SPICE is provided here along with a demonstration of its utility in patients with high-grade glioma. PMID:28090589
Lastennet, E; Valls-Gabaud, D; Oblak, E
2003-01-01
Serious discrepancies have recently been observed between predictions of stellar evolution models in the 0.7-1.1 M_sun mass range and accurately measured properties of binary stars with components in this mass range. We study one of these objects, the eclipsing binary UV Piscium, which is particularly interesting because Popper (1997) derived age estimates for each component which differed by more than a factor of two. In an attempt to solve this significant discrepancy (a difference in age of 11 Gyr), we compute a large grid of stellar evolution models with the CESAM code for each component. By fixing the masses to their accurately determined values (relative error smaller than 1% for both stars), we consider a wide range of possible metallicities Z (0.01 to 0.05), and Helium content Y (0.25 to 0.34) uncorrelated to Z. In addition, the mixing length parameter alpha_MLT is left as another free parameter. We obtain a best fit in the T_eff-radius diagram for a common chemical composition (Z, Y)=(0.012, 0.31), b...
Solubility limits on radionuclide dissolution
Kerrisk, J.F.
1984-12-31
This paper examines the effects of solubility in limiting dissolution rates of a number of important radionuclides from spent fuel and high-level waste. Two simple dissolution models were used for calculations that would be characteristics of a Yucca Mountain repository. A saturation-limited dissolution model, in which the water flowing through the repository is assumed to be saturated with each waste element, is very conservative in that it overestimates dissolution rates. A diffusion-limited dissolution model, in which element-dissolution rates are limited by diffusion of waste elements into water flowing past the waste, is more realistic, but it is subject to some uncertainty at this time. Dissolution rates of some elements (Pu, Am, Sn, Th, Zr, Sm) are always limited by solubility. Dissolution rates of other elements (Cs, Tc, Np, Sr, C, I) are never solubility limited; their release would be limited by dissolution of the bulk waste form. Still other elements (U, Cm, Ni, Ra) show solubility-limited dissolution under some conditions. 9 references, 3 tables.
Effects of solubility properties of solvents and biomass on biomass pretreatment.
Weerachanchai, Piyarat; Kwak, Sang Kyu; Lee, Jong-Min
2014-10-01
Hildebrand solubility parameters of biomasses and pretreatment solvents were examined by a method of intrinsic viscosity. This is to be used as basic information in selecting a suitable solvent for biomass pretreatment processes. The effects of mixing1-ethyl-3-methylimidazolium acetate (EMIM-AC) and different solvents, lignin content in a pretreatment solvent, and biomass type on the Hildebrand solubility parameter and thermodynamic properties were carried out and calculated in this work. The Hildebrand solubility parameters of the mixtures are according to those of organic solvents: δH[EMIM-AC/DMA]=25.07biomass compositions (microcrystalline cellulose, xylan and alkali lignin) and biomasses (cassava pulp residue and rice straw) vary in the ranges of 25.14-26.13. The increases of lignin content in the pretreatment solvents lead to the Hildebrand solubility parameter becoming closer to that of lignin.
Tedescol, Marco; Kim, Edward J.; Cline, Don; Graf, Tobias; Koike, Toshio; Armstrong, Richard; Brodzik, Mary J.; Hardy, Janet
2004-01-01
Microwave remote sensing offers distinct advantages for observing the cryosphere. Solar illumination is not required, and spatial and temporal coverage are excellent from polar-orbiting satellites. Passive microwave measurements are sensitive to the two most useful physical quantities for many hydrological applications: physical temperature and water content/state. Sensitivity to the latter is a direct result of the microwave sensitivity to the dielectric properties of natural media, including snow, ice, soil (frozen or thawed), and vegetation. These considerations are factors motivating the development of future cryospheric satellite remote sensing missions, continuing and improving on a 26-year microwave measurement legacy. Perhaps the biggest issues regarding the use of such satellite measurements involve how to relate parameter values at spatial scales as small as a hectare to observations with sensor footprints that may be up to 25 x 25 km. The NASA Cold-land Processes Field Experiment (CLPX) generated a dataset designed to enhance understanding of such scaling issues. CLPX observations were made in February (dry snow) and March (wet snow), 2003 in Colorado, USA, at scales ranging from plot scale to 25 x 25 km satellite footprints. Of interest here are passive microwave observations from ground-based, airborne, and satellite sensors, as well as meteorological and snowpack measurements that will enable studies of the effects of spatial heterogeneity of surface conditions on the observations. Prior to performing such scaling studies, an evaluation of snowpack forward modelling at the plot scale (least heterogeneous scale) is in order. This is the focus of this paper. Many forward models of snow signatures (brightness temperatures) have been developed over the years. It is now recognized that a dense medium radiative transfer (DMRT) treatment represents a high degree of physical fidelity for snow modeling, yet dense medium models are particularly sensitive to
Izmailov, Alexander F.; Myerson, Allan S.
1993-01-01
A new mathematical ansatz is developed for solution of the time-dependent Ginzburg-Landau nonlinear partial differential equation describing metastable state relaxation in binary (solute+solvent) non-critical solutions with non-conserved scalar order parameter in presence of a gravitational field. It has been demonstrated analytically that in such systems metastability initiates heterogeneous solute redistribution which results in the formation of a non-equilibrium singly-periodic spatial solute structure in the new solute-rich phase. The critical radius of nucleation and the induction time in these systems are gravity-dependent. It has also been proved that metastable state relaxation in vertical columns of supersaturated non-critical binary solutions leads to formation of the solute concentration gradient. Analytical expression for this concentration gradient is found and analysed. It is concluded that gravity can initiate phase separation (nucleation or spinodal decomposition).
Xu, Peiliang
2016-01-01
The numerical integration method has been routinely used to produce global standard gravitational models from satellite tracking measurements of CHAMP/GRACE types. It is implemented by solving the differential equations of the partial derivatives of a satellite orbit with respect to the unknown harmonic coefficients under the conditions of zero initial values. From the mathematical point of view, satellite gravimetry from satellite tracking is the problem of estimating unknown parameters in the Newton's nonlinear differential equations from satellite tracking measurements. We prove that zero initial values for the partial derivatives are incorrect mathematically and not permitted physically. The numerical integration method, as currently implemented and used in satellite gravimetry and statistics, is groundless. We use three different methods to derive new local solutions to the Newton's nonlinear governing differential equations of motion with a nominal reference orbit. Bearing in mind that satellite orbits ...
Invariants from classical field theory
Diaz, Rafael
2007-01-01
We introduce a method that generates invariant functions from classical field theories depending on external parameters. We apply our method to several field theories such as abelian BF, Chern-Simons and 2-dimensional Yang-Mills theory.
Ali, Md Ashraf; Kataoka, Noriko; Ranneh, Abdul-Hackam; Iwao, Yasunori; Noguchi, Shuji; Oka, Toshihiko; Itai, Shigeru
2017-01-01
Monoolein cubosomes containing either spironolactone (SPI) or nifedipine (NI) were prepared using a high-pressure homogenization technique and characterized in terms of their solubility and oral bioavailability. The mean particle size, polydispersity index (PDI), zeta potential, solubility and encapsulation efficiency (EE) values of the SPI- and NI-loaded cubosomes were determined to be 90.4 nm, 0.187, -13.4 mV, 163 µg/mL and 90.2%, and 91.3 nm, 0.168, -12.8 mV, 189 µg/mL and 93.0%, respectively, which were almost identical to those of the blank cubosome. Small-angle X-ray scattering analyses confirmed that the SPI-loaded, NI-loaded and blank cubosomes existed in the cubic space group Im3̄m. The lattice parameters of the SPI- and NI-loaded cubosomes were 147.6 and 151.6 Å, respectively, making them almost identical to that of blank cubosome (151.0 Å). The in vitro release profiles of the SPI- and NI-loaded cubosomes showed that they released less than 5% of the drugs into various media over 12-48 h, indicating that most of the drug remained encapsulated within the cubic phase of their lipid bilayer. Furthermore, the in vivo pharmacokinetic results suggested that these cubosomes led to a considerable increase in the systemic oral bioavailability of the drugs compared with pure dispersions of the same materials. Notably, the stability results indicated that the mean particle size and PDI values of these cubosomes were stable for at least 4 weeks. Taken together, these results demonstrate that monoolein cubosomes represent promising drug carriers for enhancing the solubility and oral bioavailability of poorly water-soluble drugs.
Leininger, J-Philippe; Minot, Christian; Lorant, François; Behar, Françoise
2007-04-26
Density functional B3LYP and BH&HLYP calculations with the 6-31G** basis set have been performed to investigate elementary reactions playing an important role in the pyrolysis of 1-methylnaphthalene. The pathways describing the destiny of the main radicals, H, methyl, hydromethylnaphthyl and methylnaphthyl, have been studied. At low temperature, addition of H atoms on the aromatic ring is favored over hydrogen abstraction. Except at low temperature (below 400 K), the hydromethylnaphthyl radical undergoes preferentially a loss of hydrogen rather than a bimolecular hydrogen transfer with methylnaphthalene or addition reaction on methylnaphthalene forming a hydrogenated dimer. In the range 400-750 K, the formation of methane by hydrogen abstraction of methyl radical on methylnaphthalene is predominant compared to the formation of hydrodimethylnaphthalenes by addition reaction. Rate constants of reactions describing the formation of heavy products like methyldinaphthylmethanes or dimethylbinaphthalenes have been calculated and discussed. They are also compared to recombination reactions from the literature. Rate constants of these reactions have been computed using transition state theory and can be integrated in kinetic radical schemes of methylated polyaromatic compounds pyrolysis from geological to laboratory conditions.
Melnikov, Andrey
2012-01-01
We prove the existence of solutions to the Sturm-Liouville (SL) equation -y"(x)+q(x)y(x) = s^2 y(x) with periodic and quasi-periodic potential q(x) using theory of SL vessels, implementing a Backlund transformation of SL equation. In this paper quasi-periodic means a finite sum of periodic integrable functions. The solutions for a general s are explicitly constructed in terms of the solutions zn(x), satisfying the SL equation with initial conditions zn(0)=0, zn'(0)=1 for a discrete Levinson set of numbers s=sn, n-natural number. The tau function tau(x) of the corresponding vessel realizes the given potential via the formula q(x)= - 2(ln(tau(x)))". We also prove an analogue of the inverse scattering theorem in this setting too. Using the notion of "KdV evolutionary vessel", we construct a solution of the Korteweg-de-Vries (KdV) equation q'_t = - 3/2 q q'_x + 1/4 q"'_{xxx}, which coincides for t=0 with a given (periodic or quasi-periodic) potential.
Characterization of Soluble Organics in Produced Water
Bostick, D.T.
2002-01-16
-selective electrodes and inductively coupled plasma (ICP)-atomic emission spectrometry (AES). The WSO found in produced water samples was primarily polar in nature and distributed between the low and midrange carbon ranges. Typical levels of total extractable material (TEM) was about 20 mg/L; that associated with the aromatic fraction was present at 0.2 mg/L and that in the saturated hydrocarbon fraction was present at less than 0.02 mg/L. Formic, acetic, and propionic acids were also found in the produced water, occurring at a total concentration of 30 mg/L. It was estimated that the presence of 30 mg/L organic acids would artificially overstate TEM content by 2 mg/L. Of the five tested parameters, the factor that most controlled the total WSO in produced water was that of aqueous phase pH. Beyond a value of pH7 significant quantities of C{sub 10}-C{sub 20} range material become markedly soluble as they deprotonate in a basic aqueous phase. Both the absolute and relative volumes of GOM brine and crude additionally affected total WSO. Produced water appeared to reach a saturation level of WSO at a.50% water/oil ratio. Pressure slightly enhanced WSO by increasing the relative quantity of C{sub 6}-C{sub 10} range material. Temperature primarily altered the relative ratio of carbon ranges within the WSO without significantly elevating the total WSO in the GOM brine. Salinity had the least affect on the chemical character or the carbon size of WSO in produced water.
Solubility of sparingly soluble drug derivatives of anthranilic acid.
Domańska, Urszula; Pobudkowska, Aneta; Pelczarska, Aleksandra
2011-03-24
This work is a continuation of our systematic study of the solubility of pharmaceuticals (Pharms). All substances here are derivatives of anthranilic acid, and have an anti-inflammatory direction of action (niflumic acid, flufenamic acid, and diclofenac sodium). The basic thermal properties of pure Pharms, i.e., melting and glass-transition temperatures as well as the enthalpy of melting, have been measured with the differential scanning microcalorimetry technique (DSC). Molar volumes have been calculated with the Barton group contribution method. The equilibrium mole fraction solubilities of three pharmaceuticals were measured in a range of temperatures from 285 to 355 K in three important solvents for Pharm investigations: water, ethanol, and 1-octanol using a dynamic method and spectroscopic UV-vis method. The experimental solubility data have been correlated by means of the commonly known G(E) equation: the NRTL, with the assumption that the systems studied here have revealed simple eutectic mixtures. pK(a) precise measurement values have been investigated with the Bates-Schwarzenbach spectrophotometric method.
Quantum Lifshitz Field Theory of a Frustrated Ferromagnet.
Balents, Leon; Starykh, Oleg A
2016-04-29
We propose a universal nonlinear sigma model field theory for one-dimensional frustrated ferromagnets, which applies in the vicinity of a "quantum Lifshitz point," at which the ferromagnetic state develops a spin wave instability. We investigate the phase diagram resulting from perturbations of the exchange and of magnetic field away from the Lifshitz point, and uncover a rich structure with two distinct regimes of different properties, depending upon the value of a marginal, dimensionless, parameter of the theory. In the regime relevant for one-dimensional systems with low spin, we find a metamagnetic transition line to a vector chiral phase. This line terminates in a critical end point, beyond which there is at least one multipolar or "spin nematic" phase. We show that the field theory is asymptotically exactly soluble near the Lifshitz point.
A. S. Avrunin
2013-01-01
Full Text Available Aim: Basing on own and literature date to characterize biological necessity of modification the ability of bone structures to be deformed and carrying capacity of lacunar-channel system to provide the basis for interaction between this pathways and parameters of calcium homeostasis. Results: There are two ways of bone matrix remodeling. The first group of pathways is responsible for slow adaptation of bone structures ability to be deformed within physiological range during weeks, months, years. The second group ensures rapid response of carrying capacity of lacunar-channel system (minutes and ours. This two mechanisms function in conjunction with hierarchically organized calcium metabolism. The first level of the latter is direct two-phase exchange of ionized calcium between extracellular liquid of bone tissue and blood: a paracellular arrival of ionized calcium from blood into the bone; b transcellular arrival of ionized calcium from extracellular liquid of bone into blood. The second hierarchical level is remodeling of perilacunar matrix by osteocytes. The third hierarchical level is bone remodeling with collaboration both osteoclasts and osteoblasts.
Predicting the Solubility Advantage of Amorphous Pharmaceuticals: A Novel Thermodynamic Approach.
Paus, Raphael; Ji, Yuanhui; Vahle, Lisa; Sadowski, Gabriele
2015-08-03
For the solubility and bioavailability of poorly soluble active pharmaceutical ingredients (APIs) to be improved, the transformation of crystalline APIs to the amorphous state has often been shown to be advantageous. As it is often difficult to measure the solubility of amorphous APIs, the application of thermodynamic models is the method of choice for determining the solubility advantage. In this work, the temperature-dependent solubility advantage of an amorphous API versus its crystalline form was predicted for five poorly soluble APIs in water (glibenclamide, griseofulvin, hydrochlorothiazide, indomethacin, and itraconazole) based on modeling the API/solvent phase diagrams using the perturbed-chain statistical associating fluid theory (PC-SAFT). Evaluation of the performance of this approach was performed by comparing the predicted solubility advantage to experimental data and to the solubility advantage calculated by the commonly applied Gibbs-energy-difference method. For all of the systems considered, PC-SAFT predictions of the solubility advantage are significantly more accurate than the results obtained from the Gibbs-energy-difference method.
Rawlinson, A.P.; Whitby, R.D.; White, J.
1989-04-11
A composition for the preparation of a soluble oil for use in a cutting fluid comprises a mineral oil and, as an emuslifier, an effective amount of a sulfonate of a branched polymer of a C/sub 3/ to C/sub 5/ olefin. Preferably the polyolefin chain of the sulphonate has an average molecular weight in the range 275 to 560 and the polyolefin is polyisobutene. A soluble oil can be prepared from the above composition by the addition of a conventional corrosion inhibitor and diluted with water to make a cutting fluid. Advantages of the novel emulsifier are that it is resistant to breakdown by micro-organisms and does not require the addition of a coupling agent.
Study on the polarity, solubility, and stacking characteristics of asphaltenes
Zhang, Long-li
2014-07-01
The structure and transformation of fused aromatic ring system in asphaltenes play an important role in the character of asphaltenes, and in step affect the properties of heavy oils. Polarity, solubility and structural characteristics of asphaltenes derived from Tahe atmospheric residue (THAR) and Tuo-826 heavy crude oil (Tuo-826) were analyzed for study of their internal relationship. A fractionation method was used to separate the asphaltenes into four sub-fractions, based on their solubility in the mixed solvent, for the study of different structural and physical-chemical properties, such as polarity, solubility, morphology, stacking characteristics, and mean structural parameters. Transmission electron microscope (TEM) observation can present the intuitive morphology of asphaltene molecules, and shows that the structure of asphaltenes is in local order as well as long range disorder. The analysis results showed that n-heptane asphaltenes of THAR and Tuo-826 had larger dipole moment values, larger fused aromatic ring systems, larger mean number of stacking layers, and less interlayer spacing between stacking layers than the corresponding n-pentane asphaltenes. The sub-fractions that were inclined to precipitate from the mixture of n-heptane and tetrahydrofuran had larger polarity and less solubility. From the first sub-fraction to the fourth sub-fraction, polarity, mean stacking numbers, and average layer size from the TEM images follow a gradual decrease. The structural parameters derived from TEM images could reflect the largest fused aromatic ring system in asphaltene molecule, yet the parameters derived from 1H NMR data reflected the mean message of poly-aromatic ring systems. The structural parameters derived from TEM images were more consistent with the polarity variation of sub-fractions than those derived from 1H NMR data, which indicates that the largest fused aromatic ring system will play a more important role in the stacking characteristics of
2011-01-01
of optimisation techniques coupled with dynamic solution of the underlying model. Linear and nonlinear approaches to parameter estimation are investigated. There is also the application of maximum likelihood principles in the estimation of parameters, as well as the use of orthogonal collocation to generate a set......In this chapter the importance of parameter estimation in model development is illustrated through various applications related to reaction systems. In particular, rate constants in a reaction system are obtained through parameter estimation methods. These approaches often require the application...... of algebraic equations as the basis for parameter estimation.These approaches are illustrated using estimations of kinetic constants from reaction system models....
Soluble Precursor Route to Polyanilines
1993-01-01
condensation were not successful, but further work produced polymer under the following conditions: Synthesis Diketone I (2.40 g, 10.0 mmol) in 10 mL...goal of producing a processible form of the conducting polymer polyaniline (PANI), the Phase I program concentrated on development of the synthesis of...extension of the original research to a Phase II effort. Diketone - Diamine Polycondensation Towards a Soluble PAni Precursor To achieve the
Linking Atomistic and Mesoscale Simulations of Water Soluble Polymers
Jones, J. L.
2003-03-01
There exist a range of techniques for studying surfactants and polymers in the mesoscale regime. One of the challenges is to link mesoscale theories and simulations to other calculation methods which address different length scales of the system. We introduce some mesoscale methods of calculation for polymers and surfactants and then present a case study of where mesoscale modelling is used for mechanistic understanding, by linking the method to high throughput in-silico screening methods. We look at the adsorption onto silica of ethylene oxide (EO)/ propylene oxide (PO) block copolymers (lutrols) which have been modified by end-grafting of short, cationic dimethylamino ethyl methacrylate (DMAEMA)chains. Given that the silica surface is negatively charged, it is remarkable that in some circumstances, polymers with longercationic chains have a lower adsorption. The effect is attributed to a competition between strong adsorption of the cationic DMAEMA groups driven by electrostatics, and weaker adsorption of the more numerous EO groups. This then raises the question of how we produce the values for the mesoscale parameters in these models and in the second part of the talk we describe a calculation method for doing this for water soluble polymers. The most promising route, but notoriously costly, is based on free energy calculations at the atomistic level. Free energy calculations are computationally intensive in general, but in an aqueous system one is also faced with the additional problem of using complex continuum models and/or accurate interaction potentials for water. Here we show how potential of mean force (PMF)calculations offer a practical alternative which avoids these drawbacks, though one is still faced with extremely long simulations.
熊耀坤; 何雁; 黄恺; 杜焰; 冯怡
2012-01-01
This study was aimed to establish the drying mathematical model of Chinese herbal medicine. The energy changes and influence factors were studied in the process of Chinese herbal medicine dried by thermodynamic theory. The Chinese herbal medicine drying mathematical model and analysis of the parameters ere established. The results showed that the existing drying research of Chinese herbal medicine is the summary of experienced knowledge. There is a big blindness in the choice of the drying method, process and equipment. We quantized the process of drying, and established Chinese herbal medicine drying mathematical model. The established parameters of the external environment are the heat conduction parameter C, the thermal radiation parameter D, and heat exchange parameters E. These parameters reflect the drying efficiency of the drying equipment. The established parameters of medicinal properties are the porosity Φ, specific heat Cp, herbs surface area S. These parameters reflect the herb drying capacity. It was concluded that the strengthening of basic theory study on Chinese herbal medicine drying will provide new methods and ideas for the reasonable selection of drying methods, processes and equipments. Therefore, the drying efficiency will be improved and the energy consumption will be reduced.%目的:建立中药材干燥数学模型,为优化干燥工艺提供理论依据.方法:运用传热学原理,探求中药材干燥过程中影响因数及能量变化过程,建立中药材干燥数学模型,并对参数进行分析.结果:现有中药材的干燥研究多为经验知识的总结,在干燥方法、工艺及设备的选择上存在很大的盲目性.本文量化了中药材干燥过程,建立起中药材干燥数学模型,建立起干燥条件参数:热传导参数C、热辐射参数D、为热交换参数E,用于评价干燥设备的干燥性能;建立起干燥物性参数:孔隙率椎、比热Cp、药材表面积S等,用于评价药材可干燥能力.
Determination and Correlation for Solubility of Aromatic Acids in Solvents
无
2001-01-01
Solubility of benzoic acid, terephthalic acid and 2,6-naphthalene dicarboxylic acid in water, acetic acid, N,N-dimethyfformamide, N,N-dimethylacetamide, dimethyl sulphoxide and N-methyl-2-ketopyrrolidine were measured by dynamic method. The solubilities were calculated by UNIFAC group contribution method, in which new groups, BCCOOH and NCCOOH, were introduced to express the activity coefficients of aromatic acids and new interaction parameters of the new groups were expressed as the function of temperature, which were determined from the experimental data. The new interaction parameters provided good calculated result. The experimental data were also correlated with Wilson and λ-h models, and results were compared with present UNIFAC model.
Thermodynamic Solubility Profile of Carbamazepine-Cinnamic Acid Cocrystal at Different pH.
Keramatnia, Fatemeh; Shayanfar, Ali; Jouyban, Abolghasem
2015-08-01
Pharmaceutical cocrystal formation is a direct way to dramatically influence physicochemical properties of drug substances, especially their solubility and dissolution rate. Because of their instability in the solution, thermodynamic solubility of cocrystals could not be determined in the common way like other compounds; therefore, the thermodynamic solubility is calculated through concentration of their components in the eutectic point. The objective of this study is to investigate the effect of an ionizable coformer in cocrystal with a nonionizable drug at different pH. Carbamazepine (CBZ), a nonionizable drug with cinnamic acid (CIN), which is an acidic coformer, was selected to prepare CBZ-CIN cocrystal and its thermodynamic solubility was studied in pH range 2-7. Instead of HPLC that is a costly and time-consuming method, a chemometric-based approach, net analyte signal standard addition method, was selected for simultaneous determination of CBZ and CIN in solution. The result showed that, as pH increases, CIN ionization leads to change in CBZ-CIN cocrystal solubility and stability in solution. In addition, the results of this study indicated that there is no significant difference between intrinsic solubility of CBZ and cocrystal despite the higher ideal solubility of cocrystal. This verifies that ideal solubility is not good parameter to predict cocrystal solubility.
Wesolowski, David J [ORNL; Bandura, Andrei V. [St. Petersburg State University, St. Petersburg, Russia; Sofo, Jorge O. [Pennsylvania State University; Kubicki, James D. [Pennsylvania State University
2006-01-01
Plane-wave density functional theory (DFT-PW) calculations were performed on bulk SnO{sub 2} (cassiterite) and the (100), (110), (001), and (101) surfaces with and without H{sub 2}O present. A classical interatomic force field has been developed to describe bulk SnO{sub 2} and SnO{sub 2}-H{sub 2}O surface interactions. Periodic density functional theory calculations using the program VASP (Kresse et al., 1996) and molecular cluster calculations using Gaussian 03 (Frisch et al., 2003) were used to derive the parametrization of the force field. The program GULP (Gale, 1997) was used to optimize parameters to reproduce experimental and ab initio results. The experimental crystal structure and elastic constants of SnO{sub 2} are reproduced reasonably well with the force field. Furthermore, surface atom relaxations and structures of adsorbed H{sub 2}O molecules agree well between the ab initio and force field predictions. H{sub 2}O addition above that required to form a monolayer results in consistent structures between the DFT-PW and classical force field results as well.
Iachello, F
1995-01-01
1. The Wave Mechanics of Diatomic Molecules. 2. Summary of Elements of Algebraic Theory. 3. Mechanics of Molecules. 4. Three-Body Algebraic Theory. 5. Four-Body Algebraic Theory. 6. Classical Limit and Coordinate Representation. 8. Prologue to the Future. Appendices. Properties of Lie Algebras; Coupling of Algebras; Hamiltonian Parameters
Solubility Prediction of Active Pharmaceutical Compounds with the UNIFAC Model
Nouar, Abderrahim; Benmessaoud, Ibtissem; Koutchoukali, Ouahiba; Koutchoukali, Mohamed Salah
2016-03-01
The crystallization from solution of an active pharmaceutical ingredient requires the knowledge of the solubility in the entire temperature range investigated during the process. However, during the development of a new active ingredient, these data are missing. Its experimental determination is possible, but tedious. UNIFAC Group contribution method Fredenslund et al. (Vapor-liquid equilibria using UNIFAC: a group contribution method, 1977; AIChE J 21:1086, 1975) can be used to predict this physical property. Several modifications on this model have been proposed since its development in 1977, modified UNIFAC of Dortmund Weidlich et al. (Ind Eng Chem Res 26:1372, 1987), Gmehling et al. (Ind Eng Chem Res 32:178, 1993), Pharma-modified UNIFAC Diedrichs et al. (Evaluation und Erweiterung thermodynamischer Modelle zur Vorhersage von Wirkstofflöslichkeiten, PhD Thesis, 2010), KT-UNIFAC Kang et al. (Ind Eng Chem Res 41:3260, 2002), ldots In this study, we used UNIFAC model by considering the linear temperature dependence of interaction parameters as in Pharma-modified UNIFAC and structural groups as defined by KT-UNIFAC first-order model. More than 100 binary datasets were involved in the estimation of interaction parameters. These new parameters were then used to calculate activity coefficient and solubility of some molecules in various solvents at different temperatures. The model gives better results than those from the original UNIFAC and shows good agreement between the experimental solubility and the calculated one.
Radionuclide solubility control by solid solutions
Brandt, F.; Klinkenberg, M.; Rozov, K.; Bosbach, D. [Forschungszentrum Juelich GmbH (Germany). Inst. of Energy and Climate Research - Nuclear Waste Management and Reactor Safety (IEK-6); Vinograd, V. [Frankfurt Univ. (Germany). Inst. of Geosciences
2015-07-01
The migration of radionuclides in the geosphere is to a large extend controlled by sorption processes onto minerals and colloids. On a molecular level, sorption phenomena involve surface complexation, ion exchange as well as solid solution formation. The formation of solid solutions leads to the structural incorporation of radionuclides in a host structure. Such solid solutions are ubiquitous in natural systems - most minerals in nature are atomistic mixtures of elements rather than pure compounds because their formation leads to a thermodynamically more stable situation compared to the formation of pure compounds. However, due to a lack of reliable data for the expected scenario at close-to equilibrium conditions, solid solution systems have so far not been considered in long-term safety assessments for nuclear waste repositories. In recent years, various solid-solution aqueous solution systems have been studied. Here we present state-of-the art results regarding the formation of (Ra,Ba)SO{sub 4} solid solutions. In some scenarios describing a waste repository system for spent nuclear fuel in crystalline rocks {sup 226}Ra dominates the radiological impact to the environment associated with the potential release of radionuclides from the repository in the future. The solubility of Ra in equilibrium with (Ra,Ba)SO{sub 4} is much lower than the one calculated with RaSO{sub 4} as solubility limiting phase. Especially, the available literature data for the interaction parameter W{sub BaRa}, which describes the non-ideality of the solid solution, vary by about one order of magnitude (Zhu, 2004; Curti et al., 2010). The final {sup 226}Ra concentration in this system is extremely sensitive to the amount of barite, the difference in the solubility products of the end-member phases, and the degree of non-ideality of the solid solution phase. Here, we have enhanced the fundamental understanding regarding (1) the thermodynamics of (Ra,Ba)SO{sub 4} solid solutions and (2) the
Ladefoged, Peter
1980-01-01
Summarizes the 16 parameters hypothesized to be necessary and sufficient for linguistic phonetic specifications. Suggests seven parameters affecting tongue shapes, three determining the positions of the lips, one controlling the position of the velum, four varying laryngeal actions, and one controlling respiratory activity. (RL)
Sales-Cruz, Mauricio; Heitzig, Martina; Cameron, Ian;
2011-01-01
of optimisation techniques coupled with dynamic solution of the underlying model. Linear and nonlinear approaches to parameter estimation are investigated. There is also the application of maximum likelihood principles in the estimation of parameters, as well as the use of orthogonal collocation to generate a set...
Sarmistha Sarkar; Rajib Biswas; Partha Pratim Ray; Biman Bagchi
2015-10-01
Using polydispersity index as an additional order parameter we investigate freezing/melting transition of Lennard-Jones polydisperse systems (with Gaussian polydispersity in size), especially to gain insight into the origin of the terminal polydispersity. The average inherent structure (IS) energy and root mean square displacement (RMSD) of the solid before melting both exhibit quite similar polydispersity dependence including a discontinuity at solid-liquid transition point. Lindemann ratio, obtained from RMSD, is found to be dependent on temperature. At a given number density, there exists a value of polydispersity index (P) above which no crystalline solid is stable. This transition value of polydispersity (termed as transition polydispersity, P) is found to depend strongly on temperature, a feature missed in hard sphere model systems. Additionally, for a particular temperature when number density is increased, P shifts to higher values. This temperature and number density dependent value of P saturates surprisingly to a value which is found to be nearly the same for all temperatures, known as terminal polydispersity (TP). This value (TP ∼ 0.11) is in excellent agreement with the experimental value of 0.12, but differs from hard sphere transition where this limiting value is only 0.048. Terminal polydispersity (TP) thus has a quasiuniversal character. Interestingly, the bifurcation diagram obtained from non-linear integral equation theories of freezing seems to provide an explanation of the existence of unique terminal polydispersity in polydisperse systems. Global bond orientational order parameter is calculated to obtain further insights into mechanism for melting.
Xiao Min [Departement of Chemistry, Zhejiang University, Hangzhou 310027 (China); Shao Yundong [Skyherb Ingredients, Anji 313300 (China); Yan Weidong, E-mail: yanweidong@zju.edu.c [Departement of Chemistry, Zhejiang University, Hangzhou 310027 (China); Zhang Zizhang [Departement of Chemistry, Zhejiang University, Hangzhou 310027 (China)
2011-03-15
The solubilities of apigenin and apigenin 7-O-rhamnosylglucoside in water, methanol, ethanol, 1-propanol, 1-butanol, acetone, and ethyl acetate from T = (288.2 to 328.2) K were measured. The solubilities of apigenin and apigenin 7-O-rhamnosylglucoside in selected solvents increase with increasing temperature, respectively. The experimental solubility data were correlated by a simplified thermodynamic equation and a three-parameter empirical equation.
崔猛; 李佳军; 纪国栋; 陈永恒
2014-01-01
With the drilling targets going increasingly deeper ,a new drilling parameters optimization method based on mechanical specific energy (MSE)theory was investigated to continually improve the rate of penetration in deep formations .From the perspectives of rock mechanics and conservation of energy ,the relationship between drilling parameters and ROP has been derived from comprehensive analysis of opti-mized drilling mechanism based on MSE .Based on the R .Teale MSE model ,by introducing the sliding fric-tion coefficient and rock-broken efficiency of the bit ,the torque was expressed as the function of drilling weight to solve the difficulty of measuring torque directly in conventional drilling ,the optimized models were built on the basis of specific energy theory for different drilling modes ,and a real-time drilling optimi-zation system was developed .The system can monitor all dynamic drilling parameters during drilling opera-tion ,and feed back the performance of drilling parameters and dow nhole situation in real time .A pilot test shows the average ROP increased by 20% to 30% compared with offset wells ,and prolonged the service life of bit .T he research results indicate that specific energy optimized drilling technique can optimize drill-ing parameters in real time ,w hich can be used to drilling design ,parameter optimization and analysis ,so as to raise the ROP in deep formations and reduce drilling cost .%为了进一步提高深部地层钻井速度，利用机械比能理论对复合钻井参数进行优化。从岩石力学和能量守恒角度出发，分析了基于机械比能理论的钻井优化机理，得出了钻进参数与机械钻速之间的相互关系。在T eale机械比能模型的基础上，引入钻头滑动摩擦系数和钻头破岩效率系数，将扭矩表示为钻压的函数，解决了常规钻井中扭矩难以直接测量的问题，建立了基于比能理论的复合钻井参数优化模型，并开发了钻井优化系
Cloud processing of soluble gases
Laj, P.; Fuzzi, S.; Facchini, M. C.; Lind, J. A.; Orsi, G.; Preiss, M.; Maser, R.; Jaeschke, W.; Seyffer, E.; Helas, G.; Acker, K.; Wieprecht, W.; Möller, D.; Arends, B. G.; Mols, J. J.; Colvile, R. N.; Gallagher, M. W.; Beswick, K. M.; Hargreaves, K. J.; Storeton-West, R. L.; Sutton, M. A.
Experimental data from the Great Dun Fell Cloud Experiment 1993 were used to investigate interactions between soluble gases and cloud droplets. Concentrations of H 2O 2, SO 2, CH 3COOOH, HCOOH, and HCHO were monitored at different sites within and downwind of a hill cap cloud and their temporal and spatial evolution during several cloud events was investigated. Significant differences were found between in-cloud and out-of-cloud concentrations, most of which could not be explained by simple dissolution into cloud droplets. Concentration patterns were analysed in relation to the chemistry of cloud droplets and the gas/liquid equilibrium. Soluble gases do not undergo similar behaviour: CH 3COOH simply dissolves in the aqueous phase and is outgassed upon cloud dissipation; instead, SO 2 is consumed by its reaction with H 2O 2. The behaviour of HCOOH is more complex because there is evidence for in-cloud chemical production. The formation of HCOOH interferes with the odd hydrogen cycle by enhancing the liquid-phase production of H 2O 2. The H 2O 2 concentration in cloud therefore results from the balance of consumption by oxidation of SO 2 in-cloud production, and the rate by which it is supplied to the system by entrainment of new air into the clouds.
In vitro solubility assays in drug discovery.
Kerns, Edward H; Di, Li; Carter, Guy T
2008-11-01
The solubility of a compound depends on its structure and solution conditions. Structure determines the lipophilicity, hydrogen bonding, molecular volume, crystal energy and ionizability, which determine solubility. Solution conditions are affected by pH, co-solvents, additives, ionic strength, time and temperature. Many drug discovery experiments are conducted under "kinetic" solubility conditions. In drug discovery, solubility has a major impact on bioassays, formulation for in vivo dosing, and intestinal absorption. A good goal for the solubility of drug discovery compounds is >60 ug/mL. Equilibrium solubility assays can be conducted in moderate throughput, by incubating excess solid with buffer and agitating for several days, prior to filtration and HPLC quantitation. Kinetic solubility assays are performed in high throughput with shorter incubation times and high throughput analyses using plate readers. The most frequently used of these are the nephelometric assay and direct UV assay, which begin by adding a small volume of DMSO stock solution of each test compound to buffer. In nephelometry, this solution is serially diluted across a microtitre plate and undissolved particles are detected via light scattering. In direct UV, undissolved particles are separated by filtration, after which the dissolved material is quantitated using UV absorption. Equilibrium solubility is useful for preformulation. Kinetic solubility is useful for rapid compound assessment, guiding optimization via structure modification, and diagnosing bioassays. It is often useful to customize solubility experiments using conditions that answer specific research questions of drug discovery teams, such as compound selection and vehicle development for pharmacology and PK studies.
Sharma, Sanjay
2017-01-01
This book provides a detailed overview of various parameters/factors involved in inventory analysis. It especially focuses on the assessment and modeling of basic inventory parameters, namely demand, procurement cost, cycle time, ordering cost, inventory carrying cost, inventory stock, stock out level, and stock out cost. In the context of economic lot size, it provides equations related to the optimum values. It also discusses why the optimum lot size and optimum total relevant cost are considered to be key decision variables, and uses numerous examples to explain each of these inventory parameters separately. Lastly, it provides detailed information on parameter estimation for different sectors/products. Written in a simple and lucid style, it offers a valuable resource for a broad readership, especially Master of Business Administration (MBA) students.
Prediction of water solubilities for selected PCDDs/PCCDFs with COSMO-RS model
Oleszek-Kudlak, S.; Grabda, M.; Shibata, E.; Nakamura, T. [Inst. of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku Univ., Sendai (Japan); Rosik-Dulewska, C. [Inst. of Environmental Engineering of the Polish Academy of Sciences, Zabrze (Poland)
2004-09-15
Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are well identified contaminants ubiquitous in the environment. Of the various parameters that affect the fate and behavior of environmental organic compounds, water solubility is one of the most important. However, when we are studying the aqueous behavior of organic chemicals, we should also take into consideration and evaluate several parameters (temperature, salinity, dissolved organic matter) influencing their solubility. Among the 210 congeners (mono- to octa-chlorinated) of PCDDs and PCDFs, water solubility values are available for a few congeners only. The reported aqueous solubilities of PCDDs and PCDFs are often scattered, despite most of them having been measured by the generator column method, recognized as the most accurate for the determination of the water solubility of hydrophobic organic chemicals. These discrepancies reflect an important problem associated with difficulties in the preparation of the saturated solution and in the analytical measurements, particularly of compounds with a solubility below 1 ppb. In practice, the high cost of the experimental determinations also limits the field of research. In recent years, investigators have developed a number of calculational methods to predict the water solubility of organic chemicals. One of them is the Conductor-like Screening Model for Real Solvents (COSMO-RS) introduced by Klamt et al. This model was successfully used for finding the solubilities of chlorobenzenes (ClBZs) at a wider range of temperatures (from 5 to 60 C) and in a salty environment. In this study, we have applied COSMO-RS to determine the aqueous solubilities of 19 PCDDs/ PCDFs at 25 C. Additionally, we measured the solubilities of 7 PCDDs/PCDFs using the generator column method at 25 C. We used these data and those available from the literature to estimate the accuracy of the COSMO-RS calculations.
Explaining Ionic Liquid Water Solubility in Terms of Cation and Anion Hydrophobicity
Johannes Ranke
2009-03-01
Full Text Available The water solubility of salts is ordinarily dictated by lattice energy and ion solvation. However, in the case of low melting salts also known as ionic liquids, lattice energy is immaterial and differences in hydrophobicity largely account for differences in their water solubility. In this contribution, the activity coefficients of ionic liquids in water are split into cation and anion contributions by regression against cation hydrophobicity parameters that are experimentally determined by reversed phase liquid chromatography. In this way, anion hydrophobicity parameters are derived, as well as an equation to estimate water solubilities for cation-anion combinations for which the water solubility has not been measured. Thus, a new pathway to the quantification of aqueous ion solvation is shown, making use of the relative weakness of interactions between ionic liquid ions as compared to their hydrophobicities.
Garimella, S.; Huang, Y.-W.; Seewald, J. S.; Cziczo, D. J.
2014-06-01
This study examines the interaction of clay mineral particles and water vapor for determining the conditions required for cloud droplet formation. Droplet formation conditions are investigated for two common clay minerals, illite and sodium-rich montmorillonite, and an industrially derived sample, Arizona Test Dust. Using wet and dry particle generation coupled to a differential mobility analyzer (DMA) and cloud condensation nuclei counter, the critical activation of the clay mineral particles as cloud condensation nuclei is characterized. Electron microscopy (EM) is used in order to determine non-sphericity in particle shape. It is also used in order to determine particle surface area and account for transmission of multiply charged particles by the DMA. Single particle mass spectrometry and ion chromatography are used to investigate soluble material in wet-generated samples and demonstrate that wet and dry generation yield compositionally different particles. Activation results are analyzed in the context of both κ-Köhler theory (κ-KT) and Frenkel-Halsey-Hill (FHH) adsorption activation theory. This study has two main results: (1) κ-KT is the suitable framework to describe clay mineral nucleation activity. Apparent differences in κ with respect to size arise from an artifact introduced by improper size-selection methodology. For dust particles with mobility sizes larger than ~300 nm, i.e., ones that are within an atmospherically relevant size range, both κ-KT and FHH theory yield similar critical supersaturations. However, the former requires a single hygroscopicity parameter instead of the two adjustable parameters required by the latter. For dry-generated particles, the size dependence of κ is likely an artifact of the shape of the size distribution: there is a sharp drop-off in particle concentration at ~300 nm, and a large fraction of particles classified with a mobility diameter less than ~300 nm are actually multiply charged, resulting in a much
D P Paul; R Jayavel; C Subramanian; P Ramasamy
2000-04-01
Investigations on nucleation thermodynamical parameters are very essential for the successful growth of good quality single crystals from high temperature solution. A theoretical estimation of the nucleation thermodynamical parameters like interfacial energy between the solid Nd123 and its flux BaO–CuO, metastable zone-width, Gibbs free energy, critical energy barrier for nucleation and critical nucleation radius have been calculated from the knowledge of solubility data and by applying the classical nucleation theory. Results are discussed to understand the growth kinetics of Nd123 crystals.
Jonge, de L.H.; Spek, J.W.; Laar, van H.; Dijkstra, J.
2009-01-01
Solubility of N is an important parameter in many protein evaluation systems for ruminants. The influence of different rumen conditions, such as pH, osmolality and temperature of solvents, on solubility of N compounds in various animal feed ingredients was examined in two experiments. In the first e
潘青松; 彭刚; 胡伟华; 徐鑫
2015-01-01
为了解混凝土在不同加载速率下的力学特性，采用微机控制电液伺服大型多功能动静力三轴仪，对强度等级为 C15、边长为150 mm 的立方体混凝土试件在不同加载速率为10－5／s，10－4／s，10－3／s，5×10－3／s 下进行了单轴压缩试验，对不同加载速率下单轴压缩混凝土的抗压强度、变形、基于修正后的 Weibull 统计理论的应力应变全曲线模型参数等进行了研究和分析。结果表明：修正后的 Weibull 统计理论模型能较好地拟合混凝土试件在不同加载速率下的全曲线模型；材料的强度硬化特性可以通过 Weibull 本构模型中的参数 m 和 E 值表征；应变软化特性可以通过 Weibull 本构模型中的参数 c 值表征。%In order to understand the mechanical properties of concrete under different loading rates,we conducted uniaxial compression test on cubic concrete specimens (strength C15,side length 150mm)under different loading rates (10 -5 /s,10 -4 /s,10 -3 /s,5 ×10 -3 /s).The test was carried out by micro-computer controlled electro-hydrau-lic servo static and dynamic multifunctional triaxial apparatus.The compressive strength of concrete under uniaxial compression,deformation,and stress-strain curve model parameters based on the statistical theory of modified Weibull were studied and analyzed.Results revealed that the modified Weibull strain curve model parameters well fit the complete curve model of concrete specimens under different loading rates.The strength hardening properties could be characterized by the values of parameter m and E in the Weibull constitutive model,and the strain soften-ing behavior can be expressed by parameter c in the constitutive Weibull model.
Ochsner, A B; Sokoloski, T D
1985-06-01
There is a need to identify suitable blends of solvents to dissolve drugs. Empirical approaches, such as trial-and-error and response surface, require several solubility measurements. In this study the UNIFAC method was used to predict solubility in highly nonideal multicomponent systems in which only the solute enthalpy of fusion and melting point must by measured. UNIFAC combines a group contribution approach with the UNIQUAC model for activity coefficients. Parameters characterizing interactions among constituent groups of a molecule have been previously determined from binary vapor pressure data. These tabulated group parameters are used to predict activity coefficients for newly synthesized compounds. These coefficients, together with the ideal solubility, permit a prediction of solubility. The solubility of 4-hexylresorcinol in ethyl acetate, ethyl myristate, and hexane mixtures was both measured and calculated using UNIFAC. The predicted solubilities were within 10% of the experimental solubilities for all but 3 of 21 mixtures. Since the method accounted for positive and negative deviations from ideality in a hydrogen-bonding system of molecules having different sizes, it shows great potential for use in pharmacy.
Dye solubility in supercritical carbon dioxide fluid
Yan Jun
2015-01-01
Full Text Available Supercritical carbon dioxide fluid is an alternative solvent for the water of the traditional dyeing. The solubility of dyestuff affects greatly the dyeing process. A theoretical model for predicting the dye solubility is proposed and verified experimentally. The paper concludes that the pressure has a greater impact on the dyestuff solubility than temperature, and an optimal dyeing condition is suggested for the highest distribution coefficient of dyestuff.
Rai, Dhanpat [Rai Enviro-Chem, LLC, Yachats, OR (United States); Kitamura, Akira [Japan Atomic Energy Agency, Ibaraki (Japan); Rosso, Kevin M. [Pacific Northwest National Laboratory, Richland, WA (United States); Sasaki, Takayuki; Kobayashi, Taishi [Kyoto Univ. (Japan)
2016-11-01
Solubility studies were conducted with HfO{sub 2}(cr) solid as a function HCl and ionic strength ranging from 2.0 to 0.004 mol kg{sup -1}. These studies involved (1) using two different amounts of the solid phase, (2) acid washing the bulk solid phase, (3) preheating the solid phase to 1400 C, and (4) heating amorphous HfO{sub 2}(am) suspensions to 90 C to ascertain whether the HfO{sub 2}(am) converts to HfO{sub 2}(cr) and to determine the solubility from the oversaturation direction. Based on the results of these treatments it is concluded that the HfO{sub 2}(cr) contains a small fraction of less crystalline, but not amorphous, material [HfO{sub 2}(lcr)] and this, rather than the HfO{sub 2}(cr), is the solubility-controlling phase in the range of experimental variables investigated in this study. The solubility data are interpreted using both the Pitzer and SIT models and they provide log{sub 10} K{sup 0} values of -(59.75±0.35) and -(59.48±0.41), respectively, for the solubility product of HfO{sub 2}(lcr)[HfO{sub 2}(lcr) + 2H{sub 2}O ↔ Hf{sup 4+} + 4OH{sup -}]. The log{sub 10} of the solubility product of HfO{sub 2}(cr) is estimated to be < -63. The observation of a small fraction of less crystalline higher solubility material is consistent with the general picture that mineral surfaces are often structurally and/or compositionally imperfect leading to a higher solubility than the bulk crystalline solid. This study stresses the urgent need, during interpretation of solubility data, of taking precautions to make certain that the observed solubility behavior for sparingly-soluble solids is assigned to the proper solid phase.
Modeling the Hydrogen Solubility in Liquid Aluminum Alloys
Harvey, Jean-Philippe; Chartrand, Patrice
2010-08-01
The modeling of hydrogen solubility in multicomponent Al-(Li, Mg, Cu, and Si) liquid phase has been performed with a thermodynamic approach using the modified quasichemical model with the pair approximation (MQMPA). All hydrogen solubility data available in literature was assessed critically to obtain the binary parameters of the MQMPA model for the Al-H, Li-H, Mg-H, Cu-H, Zn-H, and Si-H melts. For the Li-H system, a new thermodynamic description of the stable solid lithium hydride was determined based on the c p found in literature. The thermodynamic model for the Al-Li system also was reassessed in this work to take into account the short-range ordering observed for this system. Built-in interpolation techniques allow the model to estimate the thermodynamic properties of the multicomponent liquid solution from the liquid model parameters of the lower order subsystems. A comparison of the calculated hydrogen solubility performed at various equilibrium conditions of temperature, pressure, and composition with the available experimental data found in the literature is presented in this work, as well as a comparison with some results from previous modeling.
Water sorption/solubility of dental adhesive resins.
Malacarne, Juliana; Carvalho, Ricardo M; de Goes, Mario F; Svizero, Nadia; Pashley, David H; Tay, Franklin R; Yiu, Cynthia K; Carrilho, Marcela Rocha de Oliveira; de Oliveira Carrilho, Marcela Rocha
2006-10-01
This study evaluated the water sorption, solubility and kinetics of water diffusion in commercial and experimental resins that are formulated to be used as dentin and enamel bonding agents. Four commercial adhesives were selected along with their solvent-monomer combination: the bonding resins were of Adper Scotchbond Multi-Purpose (MP) and Clearfil SE Bond (SE) systems, and the "one-bottle" systems, Adper Single Bond (SB) and Excite (EX). Five experimental methacrylate-based resins of known hydrophilicities (R1, R2, R3, R4 and R5) were used as reference materials. Specimen disks were prepared by dispensing the uncured resin into a mould (5.8mm x 0.8mm). After desiccation, the cured specimens were weighed and then stored in distilled water for evaluation of the water diffusion kinetics over a 28-day period. Resin composition and hydrophilicity (ranked by their Hoy's solubility parameters) influenced water sorption, solubility and water diffusion in both commercial and experimental dental resins. The most hydrophilic experimental resin, R5, showed the highest water sorption, solubility and water diffusion coefficient. Among the commercial adhesives, the solvated systems, SB and EX, showed water sorption, solubility and water diffusion coefficients significantly greater than those observed for the non-solvated systems, MP and SE (p<0.05). In general, the extent and rate of water sorption increased with the hydrophilicity of the resin blends. The extensive amount of water sorption in the current hydrophilic dental resins is a cause of concern. This may affect the mechanical stability of these resins and favor the rapid and catastrophic degradation of resin-dentin bonds.
Revision of the classical nucleation theory for supersaturated solutions
Borisenko, Alexander
2015-01-01
During the processes of nucleation and growth of a precipitate cluster from a supersaturated solution, the diffusion flux between the cluster and the solution changes the solute concentration near the cluster-solution interface from its average bulk value. This feature affects the rates of attachment and detachment of solute atoms at the interface and, therefore, alters the entire nucleation kinetics. Unless quite obvious, this effect has been ignored in the classical nucleation theory. To illustrate the results of this new approach, for the case of homogeneous nucleation, we calculate the total solubility (including the contribution from heterophase fluctuations) and the nucleation rate as functions of two parameters of the model and compare these results to the classical ones. One can conclude that discrepancies with the classical nucleation theory are great in the diffusion-limited regime, when the bulk diffusion mobility of solute atoms is small compared to the interfacial one, while in the opposite inter...
Sun, Ye; Tao, Jing; Zhang, Geoff G Z; Yu, Lian
2010-09-01
A previous method for measuring solubilities of crystalline drugs in polymers has been improved to enable longer equilibration and used to survey the solubilities of indomethacin (IMC) and nifedipine (NIF) in two homo-polymers [polyvinyl pyrrolidone (PVP) and polyvinyl acetate (PVAc)] and their co-polymer (PVP/VA). These data are important for understanding the stability of amorphous drug-polymer dispersions, a strategy actively explored for delivering poorly soluble drugs. Measuring solubilities in polymers is difficult because their high viscosities impede the attainment of solubility equilibrium. In this method, a drug-polymer mixture prepared by cryo-milling is annealed at different temperatures and analyzed by differential scanning calorimetry to determine whether undissolved crystals remain and thus the upper and lower bounds of the equilibrium solution temperature. The new annealing method yielded results consistent with those obtained with the previous scanning method at relatively high temperatures, but revised slightly the previous results at lower temperatures. It also lowered the temperature of measurement closer to the glass transition temperature. For D-mannitol and IMC dissolving in PVP, the polymer's molecular weight has little effect on the weight-based solubility. For IMC and NIF, the dissolving powers of the polymers follow the order PVP > PVP/VA > PVAc. In each polymer studied, NIF is less soluble than IMC. The activities of IMC and NIF dissolved in various polymers are reasonably well fitted to the Flory-Huggins model, yielding the relevant drug-polymer interaction parameters. The new annealing method yields more accurate data than the previous scanning method when solubility equilibrium is slow to achieve. In practice, these two methods can be combined for efficiency. The measured solubilities are not readily anticipated, which underscores the importance of accurate experimental data for developing predictive models.
Rojas-Oviedo, I.; Retchkiman-Corona, B.; Quirino-Barreda, C. T.; Cárdenas, J.; Schabes-Retchkiman, P. S.
2012-01-01
Mechanochemical activation is a practical cogrinding operation used to obtain a solid dispersion of a poorly water soluble drug through changes in the solid state molecular aggregation of drug-carrier mixtures and the formation of noncovalent interactions (hydrogen bonds) between two crystalline solids such as a soluble carrier, lactose, and a poorly soluble drug, indomethacin, in order to improve its solubility and dissolution rate. Samples of indomethacin and a physical mixture with a weigh...
Gladis Anitha, E; Joseph Vedhagiri, S; Parimala, K
2015-02-05
The molecular structure, geometry optimization, vibrational frequencies of organic dye sensitizer 2,6-Diamino-4-chloropyrimidine (DACP) were studied based on Hartree-Fock (HF) and density functional theory (DFT) using B3LYP methods with 6-311++G(d,p) basis set. Ultraviolet-Visible (UV-Vis) spectrum was investigated by time dependent DFT (TD-DFT). Features of the electronic absorption spectrum in the UV-Visible regions were assigned based on TD-DFT calculation. The absorption bands are assigned to transitions. The interfacial electron transfer between semiconductor TiO2 electrode and dye sensitizer DACP is due to an electron injection process from excited dye to the semiconductor's conduction band. The observed and the calculated frequencies are found to be in good agreement. The energies of the frontier molecular orbitals (FMOS) have also been determined. The chemical shielding anisotropic (CSA) parameters are calculated from the NMR analysis, Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Copyright © 2014 Elsevier B.V. All rights reserved.
The importance of the accuracy of the experimental data for the prediction of solubility
SLAVICA ERIĆ
2010-04-01
Full Text Available Aqueous solubility is an important factor influencing several aspects of the pharmacokinetic profile of a drug. Numerous publications present different methodologies for the development of reliable computational models for the prediction of solubility from structure. The quality of such models can be significantly affected by the accuracy of the employed experimental solubility data. In this work, the importance of the accuracy of the experimental solubility data used for model training was investigated. Three data sets were used as training sets – data set 1, containing solubility data collected from various literature sources using a few criteria (n = 319, data set 2, created by substituting 28 values from data set 1 with uniformly determined experimental data from one laboratory (n = 319, and data set 3, created by including 56 additional components, for which the solubility was also determined under uniform conditions in the same laboratory, in the data set 2 (n = 375. The selection of the most significant descriptors was performed by the heuristic method, using one-parameter and multi-parameter analysis. The correlations between the most significant descriptors and solubility were established using multi-linear regression analysis (MLR for all three investigated data sets. Notable differences were observed between the equations corresponding to different data sets, suggesting that models updated with new experimental data need to be additionally optimized. It was successfully shown that the inclusion of uniform experimental data consistently leads to an improvement in the correlation coefficients. These findings contribute to an emerging consensus that improving the reliability of solubility prediction requires the inclusion of many diverse compounds for which solubility was measured under standardized conditions in the data set.
Soluble P-selectin levels in synovial fluid and serum from patients with psoriatic arthritis
G. Valesini
2011-09-01
Full Text Available Objective: P-selectin is an adhesion molecule expressed by activated endothelial cells and platelets favouring the leukocyte adherence to microvascular endothelium. A soluble form of this molecule has been described, whose serum levels were found to be elevated and correlate with disease activity in rheumatoid arthritis (RA patients. Aim of this study was to determine soluble P-selectin levels in synovial fluid (SF and serum from patients with psoriatic arthritis (PsA, where it has never been investigated, to define its involvement in PsA synovial damage. Methods: we analysed, by ELISA, soluble P-selectin serum and SF levels in 100 patients presenting a knee joint effusion: 38 of them presented PsA, 40 RA and 22 osteoarthritis (OA. We examined the main clinical and laboratory parameters of these patients. Soluble P-selectin serum levels were also detected in 15 healthy subjects. Results: soluble P-selectin SF levels were significantly higher in PsA and RA patients respect to OA subjects. Soluble P-selectin SF levels were lower than those found in serum and the SF/serum ratio was higher in PsA and RA patients respect to OA. Soluble P-selectin serum levels were not significantly different among patients and controls. No correlation was found between SF and serum levels of soluble P-selectin and the main clinical parameters. Conclusions: our study of soluble P-selectin in PsA reveals a prominent local role of this molecule, with no differences respect to RA. Histological findings may be of help in understanding the role of this adhesion molecule in PsA.
Hulterström, Anna Karin; Berglund, Anders; Ruyter, I Eystein
2008-01-01
The wettability, water sorption and solubility of silicone elastomers used for maxillofacial prostheses were studied. The hypothesis was, that a material that has absorbed water would show an increase in the wettability and thus also the surface free energy of the material. Seven silicone elastomers, both addition- and condensation type polymers, were included. Five specimens of each material were subjected to treatment according to ISO standards 1567:1999 and 10477: 2004 for water sorption and solubility. The volumes of the specimens were measured according to Archimedes principle. The contact angle was measured with a contact angle goniometer at various stages of the sorption/solubility test. Wettability changed over the test period, but not according to theory. The addition type silicones showed little or no sorption and solubility, but two of the condensation type polymers tested had a significant sorption and solubility. This study showed that condensation type polymers may show too large volumetric changes when exposed to fluids, and therefore should no longer be used in prosthetic devices. The results of this study also suggests that it might be of interest to test sorption and solubility of materials that are to be implanted, since most of the materials had some solubility.
Applications of soluble dietary fibers in beverages
C. I. Beristain; M. E. Rodríguez-Huezo; C. Lobato-Calleros; F. Cruz-Sosa; R. Pedroza-Islas; J. R. Verde-Calvo
2006-01-01
In this work the importance of soluble dietary fibers in the human diet is discussed. Traditional and new sources of soluble dietary fiber are mentioned, and a description of how to apply them in different types of beverages such as energy drinks, sport drinks, carbonated beverages and protein-based beverages in order to achieve enhanced functional properties is given.
A Colorful Solubility Exercise for Organic Chemistry
Shugrue, Christopher R.; Mentzen, Hans H., II; Linton, Brian R.
2015-01-01
A discovery chemistry laboratory has been developed for the introductory organic chemistry student to investigate the concepts of polarity, miscibility, solubility, and density. The simple procedure takes advantage of the solubility of two colored dyes in a series of solvents or solvent mixtures, and the diffusion of colors can be easily…
A Colorful Solubility Exercise for Organic Chemistry
Shugrue, Christopher R.; Mentzen, Hans H., II; Linton, Brian R.
2015-01-01
A discovery chemistry laboratory has been developed for the introductory organic chemistry student to investigate the concepts of polarity, miscibility, solubility, and density. The simple procedure takes advantage of the solubility of two colored dyes in a series of solvents or solvent mixtures, and the diffusion of colors can be easily…
A framework for API solubility modelling
Conte, Elisa; Gani, Rafiqul; Crafts, Peter
The solubility of solid organic compounds in water and organic solvents is a fundamental thermodynamic property for many purposes such as product-process design and optimization, for the chemical and pharmaceutical industry. Experimental literature solubility data are usually scarce and temperature...
Greisen, Stinne Ravn; Moller, H J; Stengaard-Pedersen, Kristian
2011-01-01
To investigate the expression of the soluble form of the resident macrophage marker CD163 (sCD163) and its association with core parameters for disease activity, including radiographic progression in early rheumatoid arthritis (RA).......To investigate the expression of the soluble form of the resident macrophage marker CD163 (sCD163) and its association with core parameters for disease activity, including radiographic progression in early rheumatoid arthritis (RA)....
Light extinction method for solubility measurement
Shui Wang; Jingkang Wang; Qiuxiang Yin; Yongli Wang
2005-01-01
A novel measurement method for chemical solubility determination is brought forward, in which the advantages of two kinds of traditional methods are united. The results show that the concentration of unsolved particles suspending in the solution can be determined by measuring I/I0 (ratio of the transmission intensity to the incident intensity) of the laser beam permeating through the solution according to Lamben-Beer law. The biggest relative deviation for the solubility data determined is less than 1.5% for the sparingly soluble substances and 0.3% for the opulently soluble substances. By comparison of the experimental solubility data with previous data, the light extinction method is demonstrated to be stable and reliable.
Lee, Teng Huar; Wang, Jianjun; Wang, Chi-Hwa
2002-10-30
Composite double-walled microspheres with biodegradable poly(L-lactic acid) (PLLA) shells and poly(D,L-lactic-co-glycolic acid) (PLGA) cores were fabricated with highly water-soluble etanidazole entrapped within the core as solid crystals. This paper discusses the characterization, in vitro release and the effects of irradiation on this class of microsphere. Through the variation of polymer mass ratios, predictable shell and core dimensions could be fabricated and used to regulate the release rates. A direct and simple method was devised to determine the composition of the shell and core polymer based on the different solubilities of the polymer pair in ethyl acetate. A distribution theory based on solubility parameter explains why highly hydrophilic etanidazole has the tendency to be distributed consistently to the more hydrophilic polymer. Release profiles for normal double-walled samples have about 80% of drug released over 10 days after the initial time lag, while for irradiated double-walled samples, the sustained release lasted for more than 3 weeks. Although sustained release was short of the desired 6-8 weeks required for therapy, a low initial burst of less than 5% and time lags that can be manipulated, allows for administration of these microspheres together with traditional ones to generate pulsatile or new type of releases. The effects of irradiation were also investigated to determine the suitability of these double-walled microspheres as delivery devices to be used in conjunction with radiotherapy. Typical therapeutic dosage of 50 Gy was found to be too mild to have noticeable effects on the polymer and its release profiles, while, sterilization dosages of 25 kGy, lowered the glass transition temperatures and crystalline melting point, indirectly indicating a decrease in molecular weight. This accelerated degradation of the polymer, hence releasing the drug.
Irvine, J M
1972-01-01
Nuclear Structure Theory provides a guide to nuclear structure theory. The book is comprised of 23 chapters that are organized into four parts; each part covers an aspect of nuclear structure theory. In the first part, the text discusses the experimentally observed phenomena, which nuclear structure theories need to look into and detail the information that supports those theories. The second part of the book deals with the phenomenological nucleon-nucleon potentials derived from phase shift analysis of nucleon-nucleon scattering. Part III talks about the phenomenological parameters used to de
Maximum solid solubility of transition metals in vanadium solvent
ZHANG Jin-long; FANG Shou-shi; ZHOU Zi-qiang; LIN Gen-wen; GE Jian-sheng; FENG Feng
2005-01-01
Maximum solid solubility (Cmax) of different transition metals in metal solvent can be described by a semi-empirical equation using function Zf that contains electronegativity difference, atomic diameter and electron concentration. The relation between Cmax and these parameters of transition metals in vanadium solvent was studied.It is shown that the relation of Cmax and function Zf can be expressed as ln Cmax = Zf = 7. 316 5-2. 780 5 (△X)2 -71. 278δ2 -0. 855 56n2/3. The factor of atomic size parameter has the largest effect on the Cmax of the V binary alloy;followed by the factor of electronegativity difference; the electrons concentration has the smallest effect among the three bond parameters. Function Zf is used for predicting the unknown Cmax of the transition metals in vanadium solvent. The results are compared with Darken-Gurry theorem, which can be deduced by the obtained function Zf in this work.
CYCLODEXTRIN INCLUSION COMPLEX TO ENHANCE SOLUBILITY OF POORLY WATER SOLUBLE DRUGS: A REVIEW
V.B. Chaudhary * 1 and J. K. Patel 2
2013-01-01
Full Text Available Low solubility compounds show dissolution rate limited absorption and hence poor absorption, distribution and target organ delivery. Improvement of aqueous solubility in such a case is valuable goal to improve therapeutic efficacy. Complexation with CDs by different methods like physical mixing, melting, kneding, spray drying, freeze drying, co-evaporation has been reported to enhance the solubility, dissolution rate and bioavability of poorly water soluble drugs. The formation of inclusion complex can be confirmed by DSC, FTIR, XRD and SEM study. This review aims to assess the use of cyclodextrines as complexing agents to enhance the solubility of poorly soluble drugs and hence to resolve the many issues associated with developing and commercializing poorly water soluble drugs.
Non-Linear Logging Parameters Inversion
无
2005-01-01
The non-linear logging parameters inversion is based on the field theory, information optimization and predication theory. It uses seismic charaoters,geological model and logging data as a restriction to inverse 2D, 3D logging parameters data volume. Using this method,
Determination of the subcooled liquid solubilities of PAHs in partitioning batch experiments
Lihua Liu
2013-01-01
Full Text Available Subcooled liquid solubility is the water solubility for a hypothetical state of liquid. It is an important parameter for multicomponent nonaqueous phase liquids (NAPLs containing polycyclic aromatic hydrocarbons (PAHs, which can exist as liquids even though most of the solutes are solid in their pure form at ambient temperature. So far, subcooled liquid solubilities were estimated from the solid water solubility and fugacity ratio of the solid and (subcooled liquid phase, but rarely derived from experimental data. In our study, partitioning batch experiments were performed to determine the subcooled liquid solubility of PAHs in NAPL-water system. For selected PAH, a series of batch experiments were carried out at increased mole fractions of the target component in the NAPL and at a constant NAPL/water volume ratio. The equilibrium aqueous PAH concentrations were measured with HPLC and/or GC-MS. The subcooled liquid solubility was derived by extrapolation of the experimental equilibrium aqueous concentration to a mole fraction of unity. With the derived subcooled liquid solubility, the fugacity ratio and enthalpy of fusion of the solute were also estimated. Our results show a good agreement between the experimentally determined and published data.
Elperin, Tov; Fominykh, Andrew; Krasovitov, Boris
2013-11-01
We suggest a one-dimensional model of precipitation scavenging of soluble gaseous pollutants by non-evaporating and evaporating droplets that is valid for arbitrary initial vertical distribution of soluble trace gases in the atmosphere. It is shown that for low gradients of soluble trace gases in the atmosphere, scavenging of gaseous pollutants is governed by a linear wave equation that describes propagation of a wave in one direction. The derived equation is solved by the method of characteristics. Scavenging coefficient and the rates of precipitation scavenging are calculated for wet removal of sulfur dioxide (SO2) and ammonia (NH3) using measured initial distributions of trace gases. It is shown that scavenging coefficient for arbitrary initial vertical distribution of soluble trace gases in the atmosphere is non-stationary and height-dependent. In case of exponential initial distribution of soluble trace gases in the atmosphere, scavenging coefficient for non-evaporating droplets in the region between the ground and the position of a scavenging front is a product of rainfall rate, solubility parameter, and the growth constant in the formula for the initial profile of a soluble trace gas in the atmosphere. This expression yields the same estimate of scavenging coefficient for sulfur dioxide scavenging by rain as field estimates presented in McMahon and Denison (1979). It is demonstrated that the smaller the slope of the concentration profile the higher the value of a scavenging coefficient.
Thermodynamics of chromium in UO{sub 2} fuel: A solubility model
Riglet-Martial, Ch., E-mail: chantal.martial@cea.fr [Commissariat à l’Energie Atomique et aux Energies Alternatives, Direction de l’Energie Nucléaire, Département d’Etudes des Combustibles, Centre d’Etudes de Cadarache, 13108 Saint-Paul-lez-Durance Cedex (France); Martin, Ph. [Commissariat à l’Energie Atomique et aux Energies Alternatives, Direction de l’Energie Nucléaire, Département d’Etudes des Combustibles, Centre d’Etudes de Cadarache, 13108 Saint-Paul-lez-Durance Cedex (France); Testemale, D. [Université Grenoble Alpes, Institut NEEL, F-38042 Grenoble (France); CNRS, Institut NEEL, F-38042 Grenoble (France); Sabathier-Devals, C.; Carlot, G.; Matheron, P.; Iltis, X.; Pasquet, U.; Valot, C. [Commissariat à l’Energie Atomique et aux Energies Alternatives, Direction de l’Energie Nucléaire, Département d’Etudes des Combustibles, Centre d’Etudes de Cadarache, 13108 Saint-Paul-lez-Durance Cedex (France); Delafoy, C. [AREVA NP SAS, 10 rue Juliette Recamier, 69456 Lyon Cedex 06 (France); Largenton, R. [EDF R and D, Mechanics and Material Component Department, Avenue des Renardières, 77818 Moret sur Loing Cedex (France)
2014-04-01
The solubility and speciation of chromium in doped uranium oxide are measured in carefully controlled temperature and oxygen potential conditions using electron probe microanalysis (EPMA) and scanning electron spectroscopy (SEM). The examination of the samples by X-ray Absorption Spectroscopy (XAS) provides evidence that (i) chromium is soluble in the UO{sub 2} matrix under the +3 oxidation state only regardless of the sintering conditions which is in accordance with a soluble species of type CrO{sub 3/2} and (ii) soluble chromium exhibits octahedral symmetry with 6 atoms of oxygen forming CrO{sub 6} patterns in the UO{sub 2} structure. In consistency with all available experimental information including previously published data, the solubility of chromium in UO{sub 2} corresponding to each two-phase field with either Cr, CrO and Cr{sub 2}O{sub 3} may be described in the ranges 1500 °C < T < 2000 °C and −460 < μ{sub O2} < −360 kJ/mol using the standard thermodynamic equations governing solubility equilibria. The characteristic parameters of the solubility laws in UO{sub 2} for the three chromium phases are derived.
Effect of Extent of Supersaturation on the Evolution of Kinetic Solubility Profiles.
Han, Yi Rang; Lee, Ping I
2017-01-03
Solubility limited compounds require enabling formulations such as amorphous solid dispersions (ASDs) to increase the apparent solubility by dissolving to a concentration higher than the equilibrium solubility of the drug. This may lead to subsequent precipitation and thus the loss of the solubility advantage. Although higher supersaturation is known to result in faster precipitation, the overall effect of this faster precipitation on the bioavailability is not well understood. The objective of this study is to gain a better understanding of the impact of extent of supersaturation (i.e., dose) on the resulting kinetic solubility profiles of supersaturating dosage forms. Experimental concentration-time curves of two model compounds with different recrystallization tendencies, indomethacin (IND) and naproxen (NAP), were explored under varying sink indices (SIs) by infusing varying volumes of dissolved drug (e.g., in ethanol) into the dissolution medium. The experimental results were simulated with a mechanistic model considering classical nucleation theory and interface controlled growth on the nucleus surface. In the absence of dissolved polymer to inhibit precipitation, experimental and predicted results show that there exists a critical supersaturation below which no precipitation is observed, and due to this supersaturation maintenance, there exists an optimal dose which maximizes the area under the curve (AUC) of the kinetic solubility concentration-time profile. In the presence of dissolved polymer from ASD dissolution, similar trends were observed except the critical supersaturation was increased due to crystallization inhibition by the dissolved polymer. The importance of measuring the experimental "kinetic solubility" is emphasized. However, we show that the true solubility advantage of amorphous solids depends not on the "kinetic solubility" of amorphous dosage forms, typically arising from the balance between the rate of supersaturation generation and the
Azevedo, Álvaro Bandeira Antunes de; Kieckbusch,Theo Guenter; Tashima,Alexandre Keiji; Mohamed,Rahoma Sadeg; Mazzafera,Paulo; Melo, Silvio Alexandre Beisl Vieira de
2008-01-01
p. 1319-1323. The caffeine solubility in supercritical CO2 was studied by assessing the effects of pressure and temperature on the extraction of green coffee oil (GCO). The Peng-Robinson1 equation of state was used to correlate the solubility of caffeine with a thermodynamic model and two mixing rules were evaluated: the classical mixing rule of van der Waals with two adjustable parameters (PR-VDW) and a density dependent one, proposed by Mohamed and Holder2 with two (PR-MH, two parameters...
tPC-PSAFT modeling of gas solubility in imidazolium-based ionic liquids
Karakatsani, Eirini; Economou, Ioannis; Kroon, M. C.
2007-01-01
experimental evidence. The new set of parameters is used for the correlation of carbon dioxide solubility in various ILs using a binary interaction parameter, k(ij). The correlated k(ij) values are much lower than the values used previously for the same mixtures (Kroon et al., J. Phys. Chem. B 2006, 110, 9262......). Furthermore, the solubilities of carbon monoxide, oxygen, and trifluoromethane in 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim(+)][PF6(-)]) Are correlated. In all cases, the agreement between tPC-PSAFT correlation and experimental data for mixtures is very good....