Influence of an americium solid phase on americium concentrations in solutions

NASA Astrophysics Data System (ADS)

Rai, Dhanpat; Strickert, R. G.; Moore, D. A.; Serne, R. J.

1981-11-01

Americium-241 concentrations in solutions contacting contaminated sediments for up to 2 yr were measured as a function of pH. Steady-state concentrations were reached within a few days. The solubility-limited Am concentration was found to decrease approximately 10-fold with one unit increase in pH. The log equilibrium constant for the solubility of Am (soil) solid [Am (soil) + H + ⇌ Am (aq complex)+] was found to be -4.12. The predictions based upon thermodynamic data suggest that Am (aq complex)+ is likely to be Am(OH) 2+. Although the chemical formula of Am (soil) was not determined, it does not appear to be Am(OH) 3(a). Published data on sorption coefficients of Am by different rocks, soils, and minerals were critically evaluated. Final Am solution concentrations calculated from the sorption coefficients of a variety of earth materials with several solutions agreed well with the concentrations predicted from the solubility of Am (soil) solid, indicating that the sorption coefficient data are controlled by Am precipitation.

Solubility of nano-zinc oxide in environmentally and biologically important matrices

PubMed Central

Reed, Robert B.; Ladner, David A.; Higgins, Christopher P.; Westerhoff, Paul; Ranville, James F.

2011-01-01

Increasing manufacture and use of engineered nanoparticles (NPs) is leading to a greater probability for release of ENPs into the environment and exposure to organisms. In particular, zinc oxide (ZnO) is toxic, although it is unclear whether this toxicity is due to the zinc oxide nanoparticles (ZnO), dissolution to Zn2+, or some combination thereof. The goal of this study was to determine the relative solubilites of both commercially available and in-house synthesized ZnO in matrices used for environmental fate and transport or biological toxicity studies. Dissolution of ZnO was observed in nanopure water (7.18– 7.40 mg/L dissolved Zn, as measured by filtration) and Roswell Park Memorial Institute medium (RPMI-1640) (~5 mg/L), but much more dissolution was observed in Dulbecco’s Modified Eagle’s Medium (DMEM), where the dissolved Zn concentration exceeded 34 mg/L. Moderately hard water exhibited low zinc solubility, likely due to precipitation of a zinc carbonate solid phase. Precipitation of a zinc-containing solid phase in RPMI also appeared to limit zinc solubility. Equilibrium conditions with respect to ZnO solubility were not apparent in these matrices, even after more than 1,000 h of dissolution. These results suggest that solution chemistry exerts a strong influence on ZnO dissolution and can result in limits on zinc solubility due to precipitation of less soluble solid phases. PMID:21994124

Equilibrium studies of oxalate and aluminum containing solutions

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

Hay, M. S.; King, W. D.; Peters, T. B.

2015-11-01

The Savannah River National Laboratory (SRNL) was tasked to develop data on the solubility and conditions leading to precipitation of sodium oxalate, sodium nitrate, Bayerite (a polymorph of gibbsite, Al(OH) 3), and sodium aluminosilicate solids recently found in the Modular Caustic Side Solvent Extraction Unit (MCU). The data generated will be used to improve the OLI Systems thermodynamic database for these compounds allowing better prediction of solids formation by the modeling software in the future.

Solubility of gas in confined systems. Nonextensive thermodynamics approach.

PubMed

Letellier, Pierre; Turmine, Mireille

2013-02-15

The use of the concepts of the nonextensive thermodynamics allows reconsidering the equilibrium of bubble solubilization and more commonly of gaseous aggregates in supersaturated solutions of gas. The introduced relations are general and include as particular cases the equations usually used to describe these phenomena. These equations are discussed. Especially, we specified the domain of application of Kelvin's relation which was illustrated by the solubility of gases in fogs and clouds. Various possibilities of thoughts on the behavior of the gaseous aggregates and nano-systems are proposed. Thus, the introduced relations permit to consider the presence of gaseous aggregates in equilibrium with the solution even for under-saturated solution. Nonextensive thermodynamics admits the notion of negative pressure at the inner of confined phases (solid or liquid). Copyright © 2012 Elsevier Inc. All rights reserved.

Direct Coexistence Methods to Determine the Solubility of Salts in Water from Numerical Simulations. Test Case NaCl.

PubMed

Manzanilla-Granados, Héctor M; Saint-Martín, Humberto; Fuentes-Azcatl, Raúl; Alejandre, José

2015-07-02

The solubility of NaCl, an equilibrium between a saturated solution of ions and a solid with a crystalline structure, was obtained from molecular dynamics simulations using the SPC/E and TIP4P-Ew water models. Four initial setups on supersaturated systems were tested on sodium chloride (NaCl) solutions to determine the equilibrium conditions and computational performance: (1) an ionic solution confined between two crystal plates of periodic NaCl, (2) a solution with all the ions initially distributed randomly, (3) a nanocrystal immersed in pure water, and (4) a nanocrystal immersed in an ionic solution. In some cases, the equilibration of the system can take several microseconds. The results from this work showed that the solubility of NaCl was the same, within simulation error, for the four setups, and in agreement with previously reported values from simulations with the setup (1). The system of a nanocrystal immersed in supersaturated solution was found to equilibrate faster than others. In agreement with laser-Doppler droplet measurements, at equilibrium with the solution the crystals in all the setups had a slight positive charge.

FOURTH ANNUAL REPORT ON DISTRIBUTION STUDIES BETWEEN MELTS AND SOLID PHASES USING RADIOACTIVE TRACERS

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

Ward, R.; Orr, W.C.; Katz, L.

Cerium(III) ion in a barium chloride flux does not readily exchangs with any of the ions in solid BaZrO/sub 3/ or BaTiO/sub 3/. It reacts to form new solid phases, which are identified, and does not enter the original crystal lattices at an appreciable rate. The strontium was found to exchange at a measurable rate with barium in BaTiO/sub 3/ and with the corresponding ions in alkaline-earth zirconates. Results of a series of equilibrium and rate measurements were interpreted to ahow that the exchange produces an additional solid phase, SrTiO/sub 3/, rather than the mixed phase, or solid solution, thatmore » ndght have been expected. The significance of this observation is discussed. The self-exchange of yttnium ions between a solid compound of yttrium and an alkali chloride flux in which yttrium chloride is dissolved appears in the systems studied to depend primaaily on the solubility of the solid. Exchange is rapid and complete in the case of yttrium oxychlonide, which is soluble to the extent of 0.6%, but is limited to the surface of yttrium chromium oxide, which has no measurable solubility in the flux. The introduction of yttrium ion vacancies in the lattice of yttrium chromium oxide has no detectable effect in promoting exchange. (For preceding period see NYO-3279.) (auth)« less

Method for enhancing the solubility of dopants in silicon

DOEpatents

Sadigh, Babak; Lenosky, Thomas J.; De La Rubia, Tomas Diaz

2003-09-30

A method for enhancing the equilibrium solid solubility of dopants in silicon, germanium and silicon-germanium alloys. The method involves subjecting silicon-based substrate to biaxial or compression strain. It has been determined that boron solubility was largely enhanced (more than 100%) by a compressive bi-axial strain, based on a size-mismatch theory since the boron atoms are smaller than the silicon atoms. It has been found that the large enhancement or mixing properties of dopants in silicon and germanium substrates is primarily governed by their, and to second order by their size-mismatch with the substrate. Further, it has been determined that the dopant solubility enhancement with strain is most effective when the charge and the size-mismatch of the impurity favor the same type of strain. Thus, the solid solubility of small p-type (e.g., boron) as well as large n-type (e.g., arsenic) dopants can be raised most dramatically by appropriate bi-axial (compressive) strain, and that solubility of a large p-type dopant (e.g, indium) in silicon will be raised due to size-mismatch with silicon, which favors tensile strain, while its negative charge prefers compressive strain, and thus the two effects counteract each other.

A thermodynamic model for the prediction of phase equilibria and speciation in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to halite saturation

NASA Astrophysics Data System (ADS)

Li, Jun; Duan, Zhenhao

2011-08-01

A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca, CaHCO3+,Ca(OH)+,OH-,Cl-, HCO3-,HSO4-,SO42-, CO32-,CO,CaCO and CaSO 4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results. Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO 2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.

Petrographic and spectroscopic characterization of phosphate-stabilized mine tailings from Leadville, Colorado.

PubMed

Eusden, J D; Gallagher, L; Eighmy, T T; Crannell, B S; Krzanowski, J R; Butler, L G; Cartledge, F K; Emery, E F; Shaw, E L; Francis, C A

2002-01-01

The use of soluble PO4(3-) and lime as a heavy metal chemical stabilization agent was evaluated for mine tailings from Leadville, Colorado. The tailings are from piles associated with the Wolftone and Maid of Erin mines; ore material that was originally mined around 1900, reprocessed in the 1940s, and now requires stabilization. The dominant minerals in the tailings are galena (PbS), cerrusite (PbCO3), pyromorphite (Pb5(PO4)3Cl), plumbojarosite (Pb0.5Fe3(SO4)2(OH)6), and chalcophanites ((Pb,Fe,Zn,Mn)Mn2O5 x 2H2O). The tailings were treated with soluble PO4(3-) and lime to convert soluble heavy metals (principally Pb, Zn, Cu, Cd) into insoluble metal phosphate precipitates. The treatment process caused bulk mineralogical transformations as well as the formation of a reaction rind around the particles dominated by Ca and P. Within the mineral grains, Fe-Pb phosphosulfates, Fe-Pb sulfates (plumbojarosite), and galena convert to Fe-Ca-Pb hydroxides. The Mn-Pb hydroxides and Mn-(+/-Fe)-Pb hydroxides (chalcophanites) undergo chemical alteration throughout the grains during treatment. Bulk and surface spectroscopies showed that the insoluble reaction products in the rind are tertiary metal phosphate (e.g. (Cu,Ca2)(PO4)2) and apatite (e.g. Pb5(PO4)3Cl) family minerals. pH-dependent leaching (pH 4,6,8) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 150 for many metals; particularly Pb2+, Zn2+, Cd2+, and Cu2+. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca2+, PO4(3-) Pb2+, Zn2+, Cd2+, and Cu2+ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids.

Protein solubility modeling

NASA Technical Reports Server (NTRS)

Agena, S. M.; Pusey, M. L.; Bogle, I. D.

1999-01-01

A thermodynamic framework (UNIQUAC model with temperature dependent parameters) is applied to model the salt-induced protein crystallization equilibrium, i.e., protein solubility. The framework introduces a term for the solubility product describing protein transfer between the liquid and solid phase and a term for the solution behavior describing deviation from ideal solution. Protein solubility is modeled as a function of salt concentration and temperature for a four-component system consisting of a protein, pseudo solvent (water and buffer), cation, and anion (salt). Two different systems, lysozyme with sodium chloride and concanavalin A with ammonium sulfate, are investigated. Comparison of the modeled and experimental protein solubility data results in an average root mean square deviation of 5.8%, demonstrating that the model closely follows the experimental behavior. Model calculations and model parameters are reviewed to examine the model and protein crystallization process. Copyright 1999 John Wiley & Sons, Inc.

A quantitative model to evaluate solubility relationship of polymorphs from their thermal properties.

PubMed

Mao, Chen; Pinal, Rodolfo; Morris, Kenneth R

2005-07-01

The objective of the study is to develop a model to estimate the solubility ratio of two polymorphic forms based on the calculation of the free energy difference of two forms at any temperature. This model can be used for compounds with low solubility (a few mole percent) in which infinite dilution can be approximated. The model is derived using the melting temperature and heat of fusion for apparent monotropic systems, and the solid-solid transition temperature and heat of transition for apparent enantiotropic systems. A rigorous derivation also requires heat capacity (Cp) measurement of liquid and two solid forms. This model is validated by collecting thermal properties of polymorphs for several drugs using conventional or modulated differential scanning calorimetry. From these properties the solubility ratio of two polymorphs is evaluated using the model and compared with the experimental value at different temperatures. The predicted values using the full model agree well with the experimental ones. For the purpose of easy measurement, working equations without Cp terms are also applied. Ignoring Cp may result in an error of 10% or less, suggesting that the working equation is applicable in practice. Additional error may be generated for the apparent enantiotropic systems due to the inconsistency between the observed solid-solid transition temperature and the true thermodynamic transition temperature. This inconsistency allows the predicted solubility ratios (low melt/high melt) to be smaller. Therefore, a correction factor of 1.1 is recommended to reduce the error when the working equation is used to estimate the solubility ratio of an enantiotropic system. The study of the free energy changes of two crystalline forms of a drug allows for the development of a model that successfully predicts the solubility ratio at any temperature from their thermal properties. This model provides a thermodynamic foundation as to how the free energy difference of two polymorphs is reflected by their equilibrium solubilities. It also provides a quick and practical way of evaluating the relative solubility of two polymorphs from single differential scanning calorimetry runs.

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

PubMed

Domańska, Urszula; Bogel-Łukasik, Rafał

2005-06-23

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

Theory for solubility in static systems

NASA Astrophysics Data System (ADS)

Gusev, Andrei A.; Suter, Ulrich W.

1991-06-01

A theory for the solubility of small particles in static structures has been developed. The distribution function of the solute in a frozen solid has been derived in analytical form for the quantum and the quasiclassical cases. The solubility at infinitesimal gas pressure (Henry's constant) as well as the pressure dependence of the solute concentration at elevated pressures has been found from the statistical equilibrium between the solute in the static matrix and the ideal-gas phase. The distribution function of a solute containing different particles has been evaluated in closed form. An application of the theory to the sorption of methane in the computed structures of glassy polycarbonate has resulted in a satisfactory agreement with experimental data.

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 2. Light Lanthanides (Ce-Eu)

NASA Astrophysics Data System (ADS)

Mioduski, Tomasz; Gumiński, Cezary; Zeng, Dewen

2015-03-01

This is the second part of the volume devoted to the evaluation of experimental solubility data for rare earth metal (REM) fluorides in water as well as in aqueous ternary and multicomponent systems. Fluorides of Ce, Pr, Nd, Pm, Sm, and Eu (so-called light lanthanides), as the main solutes, are covered in the present part, which has thorough coverage of the experimental literature through the end of 2012. The experimentally unknown solubility value for PmF3 in water was predicted by an interpolation of the solubility values for NdF3 and SmF3 at 298 K. General features of the systems, such as the nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, pH, mixed solvent medium on the solubility, quality of the solubility results, and solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.

Solubility behavior and biopharmaceutical classification of novel high-solubility ciprofloxacin and norfloxacin pharmaceutical derivatives.

PubMed

Breda, Susana A; Jimenez-Kairuz, Alvaro F; Manzo, Ruben H; Olivera, María E

2009-04-17

The hydrochlorides of the 1:3 aluminum:norfloxacin and aluminum:ciprofloxacin complexes were characterized according to the Biopharmaceutics Classification System (BCS) premises in comparison with their parent compounds. The pH-solubility profiles of the complexes were experimentally determined at 25 and 37 degrees C in the range of pH 1-8 and compared to that of uncomplexed norfloxacin and ciprofloxacin. Both complexes are clearly more soluble than the antibiotics themselves, even at the lowest solubility pHs. The increase in solubility was ascribed to the species controlling solubility, which were analyzed in the solid phases at equilibrium at selected pHs. Additionally, permeability was set as low, based on data reported in the scientific literature regarding oral bioavailability, intestinal and cell cultures permeabilities and also considering the influence of stoichiometric amounts of aluminum. The complexes fulfill the BCS criterion to be classified as class 3 compounds (high solubility/low permeability). Instead, the active pharmaceutical ingredients (APIs) currently used in solid dosage forms, norfloxacin and ciprofloxacin hydrochloride, proved to be BCS class 4 (low solubility/low permeability). The solubility improvement turns the complexes as potential biowaiver candidates from the scientific point of view and may be a good way for developing more dose-efficient formulations. An immediate release tablet showing very rapid dissolution was obtained. Its dissolution profile was compared to that of the commercial ciprofloxacin hydrochloride tablets allowing to dissolution of the complete dose at a critical pH such as 6.8.

Relating hydrogen-bonding interactions with the phase behavior of naproxen/PVP K 25 solid dispersions: evaluation of solution-cast and quench-cooled films.

PubMed

Paudel, Amrit; Nies, Erik; Van den Mooter, Guy

2012-11-05

In this work, we investigated the relationship between various intermolecular hydrogen-bonding (H-bonding) interactions and the miscibility of the model hydrophobic drug naproxen with the hydrophilic polymer polyvinylpyrrolidone (PVP) across an entire composition range of solid dispersions prepared by quasi-equilibrium film casting and nonequilibrium melt quench cooling. The binary phase behavior in solid dispersions exhibited substantial processing method dependence. The solid state solubility of crystalline naproxen in PVP to form amorphous solid dispersions was 35% and 70% w/w naproxen in solution-cast films and quench-cooled films, respectively. However, the presence of a single mixed phase glass transition indicated the amorphous miscibility to be 20% w/w naproxen for the films, beyond which amorphous-amorphous and/or crystalline phase separations were apparent. This was further supported by the solution state interactions data such as PVP globular size distribution and solution infrared spectral profiles. The borderline melt composition showed cooling rate dependence of amorphization. The glass transition and melting point depression profiles of the system were treated with the analytical expressions based on Flory-Huggins mixing theory to interpolate the equilibrium solid solubility. FTIR analysis and subsequent spectral deconvolution revealed composition and miscibility dependent variations in the strength of drug-polymer intermolecular H-bonding. Two types of H-bonded populations were evidenced from 25% w/w and 35% w/w naproxen in solution-cast films and quench-cooled films, respectively, with the higher fraction of strongly H-bonded population in the drug rich domains of phase separated amorphous film compositions and highly drug loaded amorphous quench-cooled dispersions.

Halo Formation During Solidification of Refractory Metal Aluminide Ternary Systems

NASA Astrophysics Data System (ADS)

D'Souza, N.; Feitosa, L. M.; West, G. D.; Dong, H. B.

2018-02-01

The evolution of eutectic morphologies following primary solidification has been studied in the refractory metal aluminide (Ta-Al-Fe, Nb-Al-Co, and Nb-Al-Fe) ternary systems. The undercooling accompanying solid growth, as related to the extended solute solubility in the primary and secondary phases can be used to account for the evolution of phase morphologies during ternary eutectic solidification. For small undercooling, the conditions of interfacial equilibrium remain valid, while in the case of significant undercooling when nucleation constraints occur, there is a departure from equilibrium leading to unexpected phases. In Ta-Al-Fe, an extended solubility of Fe in σ was observed, which was consistent with the formation of a halo of μ phase on primary σ. In Nb-Al-Co, a halo of C14 is formed on primary CoAl, but very limited vice versa. However, in the absence of a solidus projection it was not possible to definitively determine the extended solute solubility in the primary phase. In Nb-Al-Fe when nucleation constraints arise, the inability to initiate coupled growth of NbAl3 + C14 leads to the occurrence of a two-phase halo of C14 + Nb2Al, indicating a large undercooling and departure from equilibrium.

A sorption model for alkalis in cement-based materials - Correlations with solubility and electrokinetic properties

NASA Astrophysics Data System (ADS)

Henocq, Pierre

2017-06-01

In cement-based materials, radionuclide uptake is mainly controlled by calcium silicate hydrates (C-S-H). This work presents an approach for defining a unique set of parameters of a surface complexation model describing the sorption behavior of alkali ions on the C-S-H surface. Alkali sorption processes are modeled using the CD-MUSIC function integrated in the Phreeqc V.3.0.6 geochemical code. Parameterization of the model was performed based on (1) retention, (2) zeta potential, and (3) solubility experimental data from the literature. This paper shows an application of this model to sodium ions. It was shown that retention, i.e. surface interactions, and solubility are closely related, and a consistent sorption model for radionuclides in cement-based materials requires a coupled surface interaction/chemical equilibrium model. In case of C-S-H with low calcium-to-silicon ratios, sorption of sodium ions on the C-S-H surface strongly influences the chemical equilibrium of the C-S-H + NaCl system by significantly increasing the aqueous calcium concentration. The close relationship between sorption and chemical equilibrium was successfully illustrated by modeling the effect of the solid-to-liquid ratio on the calcium content in solution in the case of C-S-H + NaCl systems.

Understanding the solution phase chemistry and solid state thermodynamic behavior of pharmaceutical cocrystals

NASA Astrophysics Data System (ADS)

Maheshwari, Chinmay

Cocrystals have drawn a lot of research interest in the last decade due to their potential to favorably alter the physicochemical and biopharmaceutical properties of active pharmaceutical ingredients. This dissertation focuses on the thermodynamic stability and solubility of pharmaceutical cocrystals. Specifically, the objectives are to; (i) investigate the influence of coformer properties such as solubility and ionization characteristics on cocrystal solubility and stability as a function of pH, (ii) to measure the thermodynamic solubility of metastable cocrystals, and study the solubility differences measured by kinetic and equilibrium methods, (iii) investigate the role of surfactants on the solubility and synthesis of cocrystals, (iv) investigate the solid state phase transformation of reactants to cocrystals and the factors that influence the reaction kinetics and, (v) provide models that enable the prediction of cocrystal formation by calculating the free energy of formation for a solid to solid transformation of reactants to cocrystals. Cocrystal solubilities were measured directly when cocrystals were thermodynamically stable, while solubilities were calculated from eutectic concentration measurements when cocrystals were of higher solubility than its components. Cocrystal solubility was highly dependent on coformer solubilities for gabapentin-lactam and lamotrigine cocrystals. It was found that melting point is not a good indicator of cocrystal solubility as solute-solvent interactions quantified by the activity coefficient play a huge role in the observed solubility. Similar to salts, cocrystals also exhibit pHmax, however the salts and cocrystals have different dependencies on the parameters that govern the value of pHmax. It is also shown that cocrystals could provide solubility advantage over salts as lamotrigine-nicotinamide cocrystal hydrate has about 6 fold higher solubility relative to lamotrigine-saccharin salt. In the case of mixtures of solid reactants, it was observed that cocrystals can form spontaneously when the reactants are in physical contact and that temperature, relative humidity, and disorder in the reactants caused by mechanical stress such as milling can enhance the reaction rates. Prediction of spontaneous cocrystal formation was investigated by developing models to calculate the Gibbs free energy of formation. Thermal behavior of cocrystal reactants was investigated by calorimetry and the interaction between the reactants is explained by investigating the heats of mixing in the melt. These principles are applied on cocrystals that are divided into two categories; (i) Where the cocrystal melting point is between that of its reactants and, (ii) where the cocrystal melting point is below that of its components. Generalized equations were developed that enable the calculation of Gibbs free energy of formation from fusion temperatures, enthalpy and entropy of fusion.

Pore-scale dynamics of enzyme adsorption, swelling and reactive dissolution determine sugar yield in hemicellulose hydrolysis for biofuel production

PubMed Central

Dutta, Sajal Kanti; Chakraborty, Saikat

2016-01-01

Hemicelluloses are the earth’s second most abundant structural polymers, found in lignocellulosic biomass. Efficient enzymatic depolymerization of xylans by cleaving their β-(1 → 4)-glycosidic bonds to produce soluble sugars is instrumental to the cost-effective production of liquid biofuels. Here we show that the multi-scale two-phase process of enzymatic hydrolysis of amorphous hemicelluloses is dominated by its smallest scale–the pores. In the crucial first five hours, two to fourfold swelling of the xylan particles allow the enzymes to enter the pores and undergo rapid non-equilibrium adsorption on the pore surface before they hydrolyze the solid polymers, albeit non-competitively inhibited by the products xylose and xylobiose. Rapid pore-scale reactive dissolution increases the solid carbohydrate’s porosity to 80–90%. This tightly coupled experimental and theoretical study quantifies the complex temporal dynamics of the transport and reaction processes coupled across scales and phases to show that this unique pore-scale phenomenon can be exploited to accelerate the depolymerization of hemicelluloses to monomeric sugars in the first 5–6 h. We find that an ‘optimal substrate loading’ of 5 mg/ml (above which substrate inhibition sets in) accelerates non-equilibrium enzyme adsorption and solid hemicellulose depolymerization at the pore-scale, which contributes three-quarters of the soluble sugars produced for bio-alcohol fermentation. PMID:27905534

Pore-scale dynamics of enzyme adsorption, swelling and reactive dissolution determine sugar yield in hemicellulose hydrolysis for biofuel production

NASA Astrophysics Data System (ADS)

Dutta, Sajal Kanti; Chakraborty, Saikat

2016-12-01

Hemicelluloses are the earth’s second most abundant structural polymers, found in lignocellulosic biomass. Efficient enzymatic depolymerization of xylans by cleaving their β-(1 → 4)-glycosidic bonds to produce soluble sugars is instrumental to the cost-effective production of liquid biofuels. Here we show that the multi-scale two-phase process of enzymatic hydrolysis of amorphous hemicelluloses is dominated by its smallest scale-the pores. In the crucial first five hours, two to fourfold swelling of the xylan particles allow the enzymes to enter the pores and undergo rapid non-equilibrium adsorption on the pore surface before they hydrolyze the solid polymers, albeit non-competitively inhibited by the products xylose and xylobiose. Rapid pore-scale reactive dissolution increases the solid carbohydrate’s porosity to 80-90%. This tightly coupled experimental and theoretical study quantifies the complex temporal dynamics of the transport and reaction processes coupled across scales and phases to show that this unique pore-scale phenomenon can be exploited to accelerate the depolymerization of hemicelluloses to monomeric sugars in the first 5-6 h. We find that an ‘optimal substrate loading’ of 5 mg/ml (above which substrate inhibition sets in) accelerates non-equilibrium enzyme adsorption and solid hemicellulose depolymerization at the pore-scale, which contributes three-quarters of the soluble sugars produced for bio-alcohol fermentation.

Identification of the solid phase in relation to the solubility of nickel in alluvial soils.

PubMed

Barman, Mandira; Datta, S P; Rattan, R K

2014-09-01

The chemical equillibria between nickel (Ni) ion present in soil solution and solid phases govern the solubility vis-a-vis availability of Ni in soil. Therefore, stability of various Ni containing minerals in relation to pH was studied to identify the probable solid phases, which govern the solubility of Ni in some alluvial soils under intensive cultivation in and around Delhi. Free Ni2+ activity (pNi2+) as estimated by Baker soil test, ranged from 13.1 to 16.2. Highest free Ni2+ activity (pNi2+ = 13.1) was recorded in industrial effluent irrigated soil collected from Sonepat, Haryana. Free Ni2+ activity was 13.6 in soil collected from agricultural lands of Keshopur, receiving irrigation through sewage effluents. Soils receiving irrigation through tube well water showed relatively lower free Ni2+ activity (pNi2+ = 14.6 to 16.2). Ni-ferrite in equilibrium with Fe(OH)3 (amorphous) is likely to control the activity of Ni in two intensively Ni contaminated soil having pH around 8. Free Ni2+ activity is likely to be buffered by exchangeable Ni in soils having neutral pH.

[Determination of equilibrium solubility and n-octanol/water partition coefficient of pulchinenosiden D by HPLC].

PubMed

Rao, Xiao-Yong; Yin, Shan; Zhang, Guo-Song; Luo, Xiao-Jian; Jian, Hui; Feng, Yu-Lin; Yang, Shi-Lin

2014-05-01

To determine the equilibrium solubility of pulchinenosiden D in different solvents and its n-octanol/water partition coefficients. Combining shaking flask method and high performance liquid chromatography (HPLC) to detect the n-octanol/water partition coefficients of pulchinenosiden D, the equilibrium solubility of pulchinenosiden D in six organic solvents and different pH buffer solution were determined by HPLC analysis. n-Octanol/water partition coefficients of pulchinenosiden D in different pH were greater than zero, the equilibrium solubility of pulchinenosiden D was increased with increase the pH of the buffer solution. The maximum equilibrium solubility of pulchinenosiden D was 255.89 g x L(-1) in methanol, and minimum equilibrium solubility of pulchinenosiden D was 0.20 g x L(-1) in acetonitrile. Under gastrointestinal physiological conditions, pulchinenosiden D exists in molecular state and it has good absorption but poor water-solubility, so increasing the dissolution rate of pulchinenosiden D may enhance its bioavailability.

Thermodynamics of magnesian calcite solid-solutions at 25°C and 1 atm total pressure

USGS Publications Warehouse

Busenberg, Eurybiades; Plummer, Niel

1989-01-01

The stability of magnesian calcites was reexamined, and new results are presented for 28 natural inorganic, 12 biogenic, and 32 synthetic magnesian calcites. The magnesian calcite solid-solutions were separated into two groups on the basis of differences in stoichiometric solubility and other physical and chemical properties. Group I consists of solids of mainly metamorphic and hydrothermal origin, synthetic calcites prepared at high temperatures and pressures, and synthetic solids prepared at low temperature and very low calcite supersaturations () from artificial sea water or NaClMgCl2CaCl2solutions. Group I solids are essentially binary s of CaCO2 and MgCO2, and are thought to be relatively free of structural defects. Group II solid-solutions are of either biogenic origin or are synthetic magnesian calcites and protodolomites (0–20 and ∼ 45 mole percent MgCO3) prepared at high calcite supersaturations () from NaClNa2SO4MgCl2CaCl2 or NaClMgCl2CaCl2 solutions. Group II solid-solutions are treated as massively defective solids. The defects include substitution foreign ions (Na+ and SO42−) in the magnesian calcite lattice (point defects) and dislocations (~2 · 109 cm−2). Within each group, the excess free energy of mixing, GE, is described by the mixing model , where x is the mole fraction of the end-member Ca0.5Mg0.5CO3 in the solid-solution. The values of A0and A1 for Group I and II solids were evaluated at 25°C. The equilibrium constants of all the solids are closely described by the equation ln , where KC and KD are the equilibrium constants of calcite and Ca0.5Mg0.5CO3. Group I magnesian calcites were modeled as sub-regular solid-solutions between calcite and dolomite, and between calcite and “disordered dolomite”. Both models yield almost identical equilibrium constants for these magnesian calcites. The Group II magnesian calcites were modeled as sub-regular solid-solutions between defective calcite and protodolomite. Group I and II solid-solutions differ significantly in stability. The rate of crystal growth and the chemical composition of the aqueous solutions from which the solids were formed are the main factors controlling stoichiometric solubility of the magnesian calcites and the density of crystal defects. The literature on the occurrence and behavior of magnesian calcites in sea water and other aqueous solutions is also examined.

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 2. Light Lanthanides (Ce–Eu)

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

Mioduski, Tomasz; Gumiński, Cezary, E-mail: cegie@chem.uw.edu.pl; Zeng, Dewen, E-mail: dewen-zeng@hotmail.com

This is the second part of the volume devoted to the evaluation of experimental solubility data for rare earth metal (REM) fluorides in water as well as in aqueous ternary and multicomponent systems. Fluorides of Ce, Pr, Nd, Pm, Sm, and Eu (so-called light lanthanides), as the main solutes, are covered in the present part, which has thorough coverage of the experimental literature through the end of 2012. The experimentally unknown solubility value for PmF{sub 3} in water was predicted by an interpolation of the solubility values for NdF{sub 3} and SmF{sub 3} at 298 K. General features of themore » systems, such as the nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, pH, mixed solvent medium on the solubility, quality of the solubility results, and solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.« less

A New Method of Constructing a Drug-Polymer Temperature-Composition Phase Diagram Using Hot-Melt Extrusion.

PubMed

Tian, Yiwei; Jones, David S; Donnelly, Conor; Brannigan, Timothy; Li, Shu; Andrews, Gavin P

2018-04-02

Current experimental methodologies used to determine the thermodynamic solubility of an API within a polymer typically involves establishing the dissolution/melting end point of the crystalline API within a physical mixture or through the use of the glass transition temperature measurement of a demixed amorphous solid dispersion. The measurable "equilibrium" points for solubility are normally well above the glass transition temperature of the system, meaning extrapolation is required to predict the drug solubility at pharmaceutically relevant temperatures. In this manuscript, we argue that the presence of highly viscous polymers in these systems results in experimental data that exhibits an under or overestimated value relative to the true thermodynamic solubility. In previous work, we demonstrated the effects of experimental conditions and their impact on measured and predicted thermodynamic solubility points. In light of current understanding, we have developed a new method to limit error associated with viscosity effects for application in small-scale hot-melt extrusion (HME). In this study, HME was used to generate an intermediate (multiphase) system containing crystalline drug, amorphous drug/polymer-rich regions as well as drug that was molecularly dispersed in polymer. An extended annealing method was used together with high-speed differential scanning calorimetry to accurately determine the upper and lower boundaries of the thermodynamic solubility of a model drug-polymer system (felodipine and Soluplus). Compared to our previously published data, the current results confirmed our hypothesis that the prediction of the liquid-solid curve using dynamic determination of dissolution/melting end point of the crystalline API physical mixture presents an underestimation relative to the thermodynamic solubility point. With this proposed method, we were able to experimentally measure the upper and lower boundaries of the liquid-solid curve for the model system. The relationship between inverse temperature and drug-polymer solubility parameter (χ) remained linear at lower drug loadings. Significantly higher solubility and miscibility between the felodipine-Soluplus system were derived from the new χ values.

Semiconductor material and method for enhancing solubility of a dopant therein

DOEpatents

Sadigh, Babak; Lenosky, Thomas J.; Rubia, Tomas Diaz; Giles, Martin; Caturla, Maria-Jose; Ozolins, Vidvuds; Asta, Mark; Theiss, Silva; Foad, Majeed; Quong, Andrew

2003-09-09

A method for enhancing the equilibrium solubility of boron and indium in silicon. The method involves first-principles quantum mechanical calculations to determine the temperature dependence of the equilibrium solubility of two important p-type dopants in silicon, namely boron and indium, under various strain conditions. The equilibrium thermodynamic solubility of size-mismatched impurities, such as boron and indium in silicon, can be raised significantly if the silicon substrate is strained appropriately. For example, for boron, a 1% compressive strain raises the equilibrium solubility by 100% at 1100.degree. C.; and for indium, a 1% tensile strain at 1100.degree. C., corresponds to an enhancement of the solubility by 200%.

A Semiconductor Material And Method For Enhancing Solubility Of A Dopant Therein

DOEpatents

Sadigh, Babak; Lenosky, Thomas J.; Diaz de la Rubia, Tomas; Giles, Martin; Caturla, Maria-Jose; Ozolins, Vidvuds; Asta, Mark; Theiss, Silva; Foad, Majeed; Quong, Andrew

2005-03-29

A method for enhancing the equilibrium solubility of boron ad indium in silicon. The method involves first-principles quantum mechanical calculations to determine the temperature dependence of the equilibrium solubility of two important p-type dopants in silicon, namely boron and indium, under various strain conditions. The equilibrium thermodynamic solubility of size-mismatched impurities, such as boron and indium in silicon, can be raised significantly if the silicon substrate is strained appropriately. For example, for boron, a 1% compressive strain raises the equilibrium solubility by 100% at 1100.degree. C.; and for indium, a 1% tensile strain at 1100.degree. C., corresponds to an enhancement of the solubility by 200%.

Method for enhancing the solubility of boron and indium in silicon

DOEpatents

Sadigh, Babak; Lenosky, Thomas J.; Diaz de la Rubia, Tomas; Giles, Martin; Caturla, Maria-Jose; Ozolins, Vidvuds; Asta, Mark; Theiss, Silva; Foad, Majeed; Quong, Andrew

2002-01-01

A method for enhancing the equilibrium solubility of boron and indium in silicon. The method involves first-principles quantum mechanical calculations to determine the temperature dependence of the equilibrium solubility of two important p-type dopants in silicon, namely boron and indium, under various strain conditions. The equilibrium thermodynamic solubility of size-mismatched impurities, such as boron and indium in silicon, can be raised significantly if the silicon substrate is strained appropriately. For example, for boron, a 1% compressive strain raises the equilibrium solubility by 100% at 1100.degree. C.; and for indium, a 1% tensile strain at 1100.degree. C., corresponds to an enhancement of the solubility by 200%.

Enhanced oral bioavailability of glycyrrhetinic acid via nanocrystal formulation.

PubMed

Lei, Yaya; Kong, Yindi; Sui, Hong; Feng, Jun; Zhu, Rongyue; Wang, Wenping

2016-10-01

The purpose of this study was to prepare solid nanocrystals of glycyrrhetinic acid (GA) for improved oral bioavailability. The anti-solvent precipitation-ultrasonication method followed by freeze-drying was adopted for the preparation of GA nanocrystals. The physicochemical properties, drug dissolution and pharmacokinetic of the obtained nanocrystals were investigated. GA nanocrystals showed a mean particle size of 220 nm and shaped like short rods. The analysis results from differential scanning calorimetry and X-ray powder diffraction indicated that GA remained in crystalline state despite a huge size reduction. The equilibrium solubility and dissolution rate of GA nanocrystal were significantly improved in comparison with those of the coarse GA or the physical mixture. The bioavailability of GA nanocrystals in rats was 4.3-fold higher than that of the coarse GA after oral administration. With its rapid dissolution and absorption performance, the solid nanocrystal might be a more preferable formulation for oral administration of poorly soluble GA.

Pharmaceutical cocrystals: the coming wave of new drug substances.

PubMed

Brittain, Harry G

2013-02-01

Solid crystalline phases containing two cocrystallized components offer a new development pathway whereby one can potentially improve the physical characteristics (i.e., equilibrium solubility, dissolution rate, solid-state stability, etc.) of a drug substance that exhibits a profile that is less than desirable. In this commentary, the topic of pharmaceutical cocrystals will be briefly explored, and a short exposition of the solubility and dissolution rate advantages that have been realized in various systems will be provided. The Guidance for Industry document recently proposed by United States Food and Drug Administration will be outlined, and its requirements explained. Finally, the subset of pharmaceutical cocrystals that consist of a drug substance and a salt of that substance (termed a salt cocrystal) will be examined to illustrate this additional class of pharmaceutical cocrystals that may offer significant scientific and regulatory advantages. Copyright © 2012 Wiley Periodicals, Inc.

Ion Association versus Ion Interaction Models in Examining Electrolyte Solutions: Application to Calcium Hydroxide Solubility Equilibrium

ERIC Educational Resources Information Center

Menéndez, M. Isabel; Borge, Javier

2014-01-01

The heterogeneous equilibrium of the solubility of calcium hydroxide in water is used to predict both its solubility product from solubility and solubility values from solubility product when inert salts, in any concentration, are present. Accepting the necessity of including activity coefficients to treat the saturated solution of calcium…

The solubility of hydrogen in plutonium in the temperature range 475 to 825 degrees centigrade

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

Allen, T.H.

1991-01-01

The solubility of hydrogen (H) in plutonium metal (Pu) was measured in the temperature range of 475 to 825{degree}C for unalloyed Pu (UA) and in the temperature range of 475 to 625{degree}C for Pu containing two-weight-percent gallium (TWP). For TWP metal, in the temperature range 475 to 600{degree}C, the saturated solution has a maximum hydrogen to plutonium ration (H/Pu) of 0.00998 and the standard enthalpy of formation ({Delta}H{degree}{sub f(s)}) is (-0.128 {plus minus} 0.0123) kcal/mol. The phase boundary of the solid solution in equilibrium with plutonium dihydride (PuH{sub 2}) is temperature independent. In the temperature range 475 to 625{degree}C, UAmore » metal has a maximum solubility at H/Pu = 0.011. The phase boundary between the solid solution region and the metal+PuH{sub 2} two-phase region is temperature dependent. The solubility of hydrogen in UA metal was also measured in the temperature range 650 to 825{degree}C with {Delta}H{degree}{sub f(s)} = (-0.104 {plus minus} 0.0143) kcal/mol and {Delta}S{degree}{sub f(s)} = 0. The phase boundary is temperature dependent and the maximum hydrogen solubility has H/Pu = 0.0674 at 825{degree}C. 52 refs., 28 figs., 9 tabs.« less

Solubility limits in quaternary SnTe-based alloys [Metastability and solubility limits in quaternary SnTe-based alloys guided by combinatorial sputtering

DOE PAGES

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.; ...

2017-05-09

Here, the controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn 1–yMnyTe 1–xSe x phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y < 0.05 that are in good agreement with results obtained from bulk equilibrium synthesis experiments andmore » predict significantly higher spinodal limits. An experimental screening using sputtered combinatorial thin film sample libraries showed a remarkable increase in non-equilibrium solubility for x,y > 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn 1–yMn yTe 1–xSe x indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.« less

Thermodynamics of Pb17Li-bismuth interactions

NASA Astrophysics Data System (ADS)

Hubberstey, Peter; Sample, Tony

1994-09-01

Thermodynamic calculations of the PbBiLi ternary system have been completed to rationalise the formation of solid Li 3Bi on reaction of liquid Pb17Li with bismuth. At 723 K, the bismuth activity in equilibrium with liquid Pi17Li and solid Li 3Bi is calculated to be 9.50 × 10 -4; this can be correlated to a solubility of 2.09 × 10 -1 mol% Bi(2520 wppm). The corresponding bismuth activity in equilibrium with liquid Pb17Li and solid LiBi is 5.04 × 10 -2 (an extrapolated value as LiBi decomposes peritectically at 688 K). The minimum lithium content of PbLi alloys required to react with unit activity bismuth to form Li 3Bi at 723 K is calculated to be ˜ 1.8 mol% Li. The dominance of Li 3Bi in the PbBiLi system is attributed to its extreme stability as evidenced by both its high melting point (1418 K) and free energy of formation [ ΔGf0(Li 3Bi, c 723 K) = 212.8 kJ mol -1].

Cocrystal solubility product analysis - Dual concentration-pH mass action model not dependent on explicit solubility equations.

PubMed

Avdeef, Alex

2017-12-15

A novel general computational approach is described to address many aspects of cocrystal (CC) solubility product (K sp ) determination of drug substances. The CC analysis program, pDISOL-X, was developed and validated with published model systems of various acid-base combinations of active pharmaceutical ingredients (APIs) and coformers: (i) carbamazepine cocrystal systems with 4-aminobenzoic acid, cinnamic acid, saccharin, and salicylic acid, (ii) for indomethacin with saccharin, (iii) for nevirapine with maleic acid, saccharin, and salicylic acid, and (iv) for gabapentin with 3-hydroxybenzoic acid. In all systems but gabapentin, the coformer is much more soluble than the API. The model systems selected are those with available published dual concentration-pH data, one set for the API and one set for the coformer, generally measured at eutectic points (thermodynamically-stable three phases: solution, cocrystal, and crystalline API or coformer). The carbamazepine-cinnamic acid CC showed a substantial elevation in the API equilibrium concentration above pH5, consistent with the formation of a complex between carbamazepine and cinnamate anion. The analysis of the gabapentin:3-hydroxybenzoic acid 1:1 CC system indicated four zones of solid suspensions: coformer (pH<3.25), coformer and cocrystal eutectic (pH3.25-4.44), cocrystal (pH4.44-5.62), and API (pH>5.62). The general approach allows for testing of many possible equilibrium models, including those comprising drug-coformer complexation. The program calculates the ionic strength at each pH. From this, the equilibrium constants are adjusted for activity effects, based on the Stokes-Robinson hydration theory. The complete speciation analysis of the CC systems may provide useful insights into pH-sensitive dissolution effects that could potentially influence bioavailability. Copyright © 2017 Elsevier B.V. All rights reserved.

Soil solid-phase controls lead activity in soil solution.

PubMed

Badawy, S H; Helal, M I D; Chaudri, A M; Lawlor, K; McGrath, S P

2002-01-01

Lead pollution of the environment is synonymous with civilization. It has no known biological function, and is naturally present in soil, but its presence in food crops is deemed undesirable. The concern regarding Pb is mostly due to chronic human and animal health effects, rather then phytotoxicity. However, not much is known about the chemistry and speciation of Pb in soils. We determined the activity of Pb2+, in near neutral and alkaline soils, representative of alluvial, desertic and calcareous soils of Egypt, using the competitive chelation method. Lead activity ranged from 10(-6.73) to 10(-4.83) M, and was negatively correlated with soil and soil solution pH (R2 = -0.92, P < 0.01 and R2 = -0.89, P < 0.01, respectively). It could be predicted in soil solution from the equation: log(Pb2+) = 9.9 - 2pH. A solubility diagram for the various Pb minerals found in soil was constructed using published thermodynamic data obtained from the literature, and our measured Pb2+ activities compared with this information. The measured Pb2+ activities were undersaturated with regard to the solubility of PbSiO3 in equilibrium with SiO2 (soil). However, they were supersaturated with regard to the solubilities of the Pb carbonate minerals PbCO3 (cerussite) and Pb3(CO3)2(OH)2 in equilibrium with atmospheric CO2 and hydroxide Pb(OH)2. They were also supersaturated with regard to the solubilities of the Pb phosphate minerals Pb3(PO4)2, Pb5(PO4)3OH, and Pb4O(PO4)2 in equilibrium with tricalcium phosphate and CaCO3. The activity of Pb2+ was not regulated by any mineral of known solubility in our soils, but possibly by a mixture of Pb carbonate and phosphate minerals.

Residual waste from Hanford tanks 241-C-203 and 241-C-204. 2. Contaminant release model.

PubMed

Cantrell, Kirk J; Krupka, Kenneth M; Deutsch, William J; Lindberg, Michael J

2006-06-15

Release of U and 99Tc from residual sludge in Hanford waste tanks 241-C-203 and 241-C-204 atthe U.S. Department of Energy's (DOE) Hanford Site in southeastern Washington state was quantified by water-leaching, selective extractions, empirical solubility measurements, and thermodynamic modeling. A contaminant release model was developed based on these experimental results and solid-phase characterization results presented elsewhere. Uranium release was determined to be controlled by two phases and occurred in three stages. In the first stage, U release is controlled by the solubility of tejkaite, which is suppressed by high concentrations of sodium released from the dissolution of NaNO3 in the residual sludges. Equilibrium solubility calculations indicate the U released during this stage will have a maximum concentration of 0.021 M. When all the NaNO3 has dissolved from the sludge, the solubility of the remaining cejkaite will increase to 0.28 M. After cejkaite has completely dissolved, the majority of the remaining U is in the form of poorly crystalline Na2U2O7 [or clarkeite Na[(UO2)O(OH)](H20)0-1]. In contact with Hanford groundwater this phase is not stable, and becquerelite becomes the U solubility controlling phase, with a calculated equilibrium concentration of 1.2 x 10(-4) M. For Tc, a significant fraction of its concentration in the residual sludge was determined to be relatively insoluble (20 wt % for C-203 and 80 wt % for C-204). Because of the low concentrations of Tc in these sludge materials, the characterization studies did not identify any discrete Tc solids phases. Release of the soluble fraction of Tc was found to occur concomitantly with NO3-. It was postulated that a NaNO3-NaTcO4 solid solution could be responsible for this behavior. The Tc release concentrations for the soluble fraction were estimated to be 2.4 x 10-6 M for C-203 and 2.7 x 10(-5) M for C-204. Selective extraction results indicated that the recalcitrant fraction of Tc was associated with Fe oxides. Release of the recalcitrant fraction of Tc was assumed to be controlled by dissolution of Fe oxide in the form of ferrihydrite. Based on this assumption and measured values for the ratio of recalcitrant Tc to total Fe in each bulk sludge, the release concentration of the recalcitrant fraction of Tc was calculated to be 3.9 x 10(-12) M for C-203 and 10.0 x 10(-12) M for C-204.

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

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.

Here, the controlled decomposition of metastable alloys is an attractive route to form nanostructured thermoelectric materials with reduced thermal conductivity. The ternary SnTe–MnTe and SnTe–SnSe heterostructural alloys have been demonstrated as promising materials for thermoelectric applications. In this work, the quaternary Sn 1–yMnyTe 1–xSe x phase space serves as a relevant model system to explore how a combination of computational and combinatorial-growth methods can be used to study equilibrium and non-equilibrium solubility limits. Results from first principle calculations indicate low equilibrium solubility for x,y < 0.05 that are in good agreement with results obtained from bulk equilibrium synthesis experiments andmore » predict significantly higher spinodal limits. An experimental screening using sputtered combinatorial thin film sample libraries showed a remarkable increase in non-equilibrium solubility for x,y > 0.2. These theoretical and experimental results were used to guide the bulk synthesis of metastable alloys. The ability to reproduce the non-equilibrium solubility levels in bulk materials indicates that such theoretical calculations and combinatorial growth can inform bulk synthetic routes. Further, the large difference between equilibrium and non-equilibrium solubility limits in Sn 1–yMn yTe 1–xSe x indicates these metastable alloys are attractive in terms of nano-precipitate formation for potential thermoelectric applications.« less

The amorphous solid dispersion of the poorly soluble ABT-102 forms nano/microparticulate structures in aqueous medium: impact on solubility.

PubMed

Frank, Kerstin J; Westedt, Ulrich; Rosenblatt, Karin M; Hölig, Peter; Rosenberg, Jörg; Mägerlein, Markus; Fricker, Gert; Brandl, Martin

2012-01-01

Amorphous solid dispersions (ASDs) are a promising formulation approach for poorly soluble active pharmaceutical ingredients (APIs), because they ideally enhance both dissolution rate and solubility. However, the mechanism behind this is not understood in detail. In the present study, we investigated the supramolecular and the nano/microparticulate structures that emerge spontaneously upon dispersion of an ASD in aqueous medium and elucidated their influence on solubility. The ASD, prepared by hot melt extrusion, contained the poorly soluble ABT-102 (solubility in buffer, 0.05 μg/mL), a hydrophilic polymer, and three surfactants. The apparent solubility of ABT-102 from the ASD-formulation was enhanced up to 200 times in comparison to crystalline ABT-102. At the same time, the molecular solubility, as assessed by inverse equilibrium dialysis, was enhanced two times. Asymmetrical flow field-flow fractionation in combination with a multiangle light-scattering detector, an ultraviolet detector, and a refractometer enabled us to separate and identify the various supramolecular assemblies that were present in the aqueous dispersions of the API-free ASD (placebo) and of binary/ternary blends of the ingredients. Thus, the supramolecular assemblies with a molar mass between 20,000 and 90,000 could be assigned to the polyvinylpyrrolidone/vinyl acetate 64, while two other kinds of assemblies were assigned to different surfactant assemblies (micelles). The amount of ABT-102 remaining associated with each of the assemblies upon fractionation was quantified offline with high-performance liquid chromatography-ultraviolet-visible. The polymeric and the micellar fraction contributed to the substantial increase in apparent solubility of ABT-102. Furthermore, a microparticulate fraction was isolated by centrifugation and analyzed by scanning electron microscopy, X-ray scattering, and infrared spectroscopy. The microparticles were found to be amorphous and to contain two of the surfactants besides ABT-102 as the main component. The amorphous microparticles are assumed to be the origin of the observed increase in molecular solubility ("true" supersaturation).

Cocrystals to facilitate delivery of poorly soluble compounds beyond-rule-of-5.

PubMed

Kuminek, Gislaine; Cao, Fengjuan; Bahia de Oliveira da Rocha, Alanny; Gonçalves Cardoso, Simone; Rodríguez-Hornedo, Naír

2016-06-01

Besides enhancing aqueous solubilities, cocrystals have the ability to fine-tune solubility advantage over drug, supersaturation index, and bioavailability. This review presents important facts about cocrystals that set them apart from other solid-state forms of drugs, and a quantitative set of rules for the selection of additives and solution/formulation conditions that predict cocrystal solubility, supersaturation index, and transition points. Cocrystal eutectic constants are shown to be the most important cocrystal property that can be measured once a cocrystal is discovered, and simple relationships are presented that allow for prediction of cocrystal behavior as a function of pH and drug solubilizing agents. Cocrystal eutectic constant is a stability or supersatuation index that: (a) reflects how close or far from equilibrium a cocrystal is, (b) establishes transition points, and (c) provides a quantitative scale of cocrystal true solubility changes over drug. The benefit of this strategy is that a single measurement, that requires little material and time, provides a principled basis to tailor cocrystal supersaturation index by the rational selection of cocrystal formulation, dissolution, and processing conditions. Copyright © 2016 Elsevier B.V. All rights reserved.

IUPAC-NIST Solubility Data Series. 100. Rare Earth Metal Fluorides in Water and Aqueous Systems. Part 3. Heavy Lanthanides (Gd–Lu)

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

Mioduski, Tomasz; Gumiński, Cezary, E-mail: cegie@chem.uw.edu.pl; Zeng, Dewen, E-mail: dewen-zeng@hotmail.com

This is the third part of the volume devoted to solubility data for the rare earth metal (REM) fluorides in water and in aqueous ternary and multicomponent systems. It covers experimental results of trivalent fluorides of Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu (so-called heavy lanthanides), since no quantitative data on solubilities of TbF{sub 4} and YbF{sub 2} (the most stable compounds at these valencies) are available. The related literature has been covered through the end of 2014. Compilations of all available papers with the solubility data are introduced for each REM fluoride with a corresponding critical evaluation.more » Every such assessment contains a collection of all solubility results in aqueous solution, a selection of suggested solubility data, a solubility equation, and a brief discussion of the multicomponent systems. Only simple fluorides (no complexes or double salts) are treated as the input substances in this report. General features of the systems, such as nature of the equilibrium solid phases, solubility as a function of temperature, influence of ionic strength, solution pH, mixed solvent medium on the solubility, quality of the solubility results, and the solubility as a function of REM atomic number, have already been presented in Part 1 of the volume.« less

Effect of Extent of Supersaturation on the Evolution of Kinetic Solubility Profiles.

PubMed

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 precipitation kinetics, but rather on the critical supersaturation below which precipitation is not observed for a sufficiently long period.

Importance of reduced sulfur for the equilibrium chemistry and kinetics of Fe(II), Co(II) and Ni(II) supplemented to semi-continuous stirred tank biogas reactors fed with stillage.

PubMed

Shakeri Yekta, Sepehr; Lindmark, Amanda; Skyllberg, Ulf; Danielsson, Asa; Svensson, Bo H

2014-03-30

The objective of the present study was to assess major chemical reactions and chemical forms contributing to solubility and speciation of Fe(II), Co(II), and Ni(II) during anaerobic digestion of sulfur (S)-rich stillage in semi-continuous stirred tank biogas reactors (SCSTR). These metals are essential supplements for efficient and stable performance of stillage-fed SCSTR. In particular, the influence of reduced inorganic and organic S species on kinetics and thermodynamics of the metals and their partitioning between aqueous and solid phases were investigated. Solid phase S speciation was determined by use of S K-edge X-ray absorption near-edge spectroscopy. Results demonstrated that the solubility and speciation of supplemented Fe were controlled by precipitation of FeS(s) and formation of the aqueous complexes of Fe-sulfide and Fe-thiol. The relatively high solubility of Co (∼ 20% of total Co content) was attributed to the formation of compounds other than Co-sulfide and Co-thiol, presumably of microbial origin. Nickel had lower solubility than Co and its speciation was regulated by interactions with FeS(s) (e.g. co-precipitation, adsorption, and ion substitution) in addition to precipitation/dissolution of discrete NiS(s) phase and formation of aqueous Ni-sulfide complexes. Copyright © 2014 Elsevier B.V. All rights reserved.

End-Member Formulation of Solid Solutions and Reactive Transport

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

Lichtner, Peter C.

2015-09-01

A model for incorporating solid solutions into reactive transport equations is presented based on an end-member representation. Reactive transport equations are solved directly for the composition and bulk concentration of the solid solution. Reactions of a solid solution with an aqueous solution are formulated in terms of an overall stoichiometric reaction corresponding to a time-varying composition and exchange reactions, equivalent to reaction end-members. Reaction rates are treated kinetically using a transition state rate law for the overall reaction and a pseudo-kinetic rate law for exchange reactions. The composition of the solid solution at the onset of precipitation is assumed tomore » correspond to the least soluble composition, equivalent to the composition at equilibrium. The stoichiometric saturation determines if the solid solution is super-saturated with respect to the aqueous solution. The method is implemented for a simple prototype batch reactor using Mathematica for a binary solid solution. Finally, the sensitivity of the results on the kinetic rate constant for a binary solid solution is investigated for reaction of an initially stoichiometric solid phase with an undersaturated aqueous solution.« less

Solubility of NaCl in water by molecular simulation revisited.

PubMed

Aragones, J L; Sanz, E; Vega, C

2012-06-28

In this paper, the solubility of NaCl in water is evaluated by using computer simulations for three different force fields. The condition of chemical equilibrium (i.e., equal chemical potential of the salt in the solid and in the solution) is obtained at room temperature and pressure to determine the solubility of the salt. We used the same methodology that was described in our previous work [E. Sanz and C. Vega, J. Chem. Phys. 126, 014507 (2007)] although several modifications were introduced to improve the accuracy of the calculations. It is found that the predictions of the solubility are quite sensitive to the details of the force field used. Certain force fields underestimate the experimental solubility of NaCl in water by a factor of four, whereas the predictions of other force fields are within 20% of the experimental value. Direct coexistence molecular dynamic simulations were also performed to determine the solubility of the salt. Reasonable agreement was found between the solubility obtained from free energy calculations and that obtained from direct coexistence simulations. This work shows that the evaluation of the solubility of salts in water can now be performed in computer simulations. The solubility depends on the ion-ion, ion-water, and water-water interactions. For this reason, the prediction of the solubility can be quite useful in future work to develop force fields for ions in water.

Students’ misconceptions on solubility equilibrium

NASA Astrophysics Data System (ADS)

Setiowati, H.; Utomo, S. B.; Ashadi

2018-05-01

This study investigated the students’ misconceptions of the solubility equilibrium. The participants of the study consisted of 164 students who were in the science class of second year high school. Instrument used is two-tier diagnostic test consisting of 15 items. Responses were marked and coded into four categories: understanding, misconception, understand little without misconception, and not understanding. Semi-structured interviews were carried out with 45 students according to their written responses which reflected different perspectives, to obtain a more elaborated source of data. Data collected from multiple methods were analyzed qualitatively and quantitatively. Based on the data analysis showed that the students misconceptions in all areas in solubility equilibrium. They had more misconceptions such as in the relation of solubility and solubility product, common-ion effect and pH in solubility, and precipitation concept.

Chemical properties of ground water and their corrosion and encrustation effects on wells

USGS Publications Warehouse

Barnes, Ivan; Clarke, Frank Eldridge

1969-01-01

Well waters in Egypt, Nigeria, and West Pakistan were studied for their chemical properties and corrosive or encrusting behavior. From the chemical composition of the waters, reaction states with reference to equilibrium were tested for 29 possible coexisting oxides, carbonates, sulfides, and elements. Of the 29 solids considered, only calcite, CaCO3, and ferric hydroxide, Fe(OH)3, showed any correlation with the corrosiveness of the waters to mild steel (iron metal). All 39 of the waters tested were out of equilibrium with iron metal, but those waters in equilibrium or supersaturated with both calcite and ferric hydroxide were the least corrosive. Supersaturation with other solid phases apparently was unrelated to corrosion. A number of solids may form surface deposits in wells and lead to decreased yields by fouling well intakes (screens and gravel packs) or increasing friction losses in casings. Calcite, CaCO3; ferric hydroxide, Fe(OH)3; magnetite, Fe3O4; siderite, FeCO3; hausmannite, Mn304 (tetragonal); manganese spinel, Mn3O4 (isometric); three iron sulfides mackinawite, FeS (tetragonal); greigite, Fe3S4 (isometric); and smythite, Fe3S4 (rhombohedral)-copper hydroxide, Co(OH)2; and manganese hydroxide, Mn(OH)2, were all at least tentatively identified in the deposits sampled. Of geochemical interest is the demonstration that simple stable equilibrium models fail in nearly every case to predict compositions of water yielded by the wells studied. Only one stable phase (calcite) was found to exhibit behavior approximately predictable from stable equilibrium considerations. No other stable phase was found to behave as would be predicted from equilibrium considerations. All the solids found to precipitate (except calcite) are metastable in that they are not the least soluble phases possible in the systems studied. In terms of metastable equilibrium, siderite and ferric hydroxide behave approximately as would be predicted from equilibrium considerations, but both are metastable and the presence of neither would be anticipated if only the most stable phases were considered. The behaviors of none of the other solids would be predictable from either stable or metastable equilibrium considerations. An unanswered problem raised by the study reported here is how, or by what paths, truly stable phases form if first precipitates are generally metastable.The utility of the findings in well design and operation is in no way impaired by the general lack of equilibrium. Conditions leading to either corrosion (which is related to lack of supersaturation with protective phases), or encrustation (supersaturation with phases that were found to precipitate), or both, apparently can be identified. The application of the methods described can be of great importance in developing unexploited ground-water resources in that certain practical problems can be identified before extensive well construction and unnecessary well failure.

Solid dispersions enhance solubility, dissolution, and permeability of thalidomide.

PubMed

Barea, Silvana A; Mattos, Cristiane B; Cruz, Ariadne C C; Chaves, Vitor C; Pereira, Rafael N; Simões, Claudia M O; Kratz, Jadel M; Koester, Letícia S

2017-03-01

Thalidomide (THD) is a BCS class II drug with renewed and growing therapeutic applicability. Along with the low aqueous solubility, additional poor biopharmaceutical properties of the drug, i.e. chemical instability, high crystallinity, and polymorphism, lead to a slow and variable oral absorption. In this view, we developed solid dispersions (SDs) containing THD dispersed in different self-emulsifying carriers aiming at an enhanced absorption profile for the drug. THD was dispersed in lauroyl macrogol-32 glycerides (Gelucire ® 44/14) and α-tocopherol polyethylene glycol succinate (Kolliphor ® TPGS), in the presence or absence of the precipitation inhibitor polyvinylpyrrolidone K30 (PVP K30), by means of the solvent method. Physicochemical analysis revealed the formation of semicrystalline SDs. X-ray diffraction and infrared spectroscopy analyses suggest that the remaining crystalline fraction of the drug in the SDs did not undergo polymorphic transition. The impact of the solubility-enhancing formulations on the THD biopharmaceutical properties was evaluated by several in vitro techniques. The developed SDs were able to increase the apparent solubility of the drug (up to 2-3x the equilibrium solubility) for a least 4 h. Dissolution experiments (paddle method, 75 rpm) in different pHs showed that around 80% of drug dissolved after 120 min (versus 40% of pure crystalline drug). Additionally, we demonstrated the enhanced solubility obtained via SDs could be translated into increased flux in a parallel artificial membrane permeability assay (PAMPA). In summary, the results demonstrate that SDs could be considered an interesting and unexplored strategy to improve the biopharmaceutical properties of THD, since SDs of this important drug have yet to be reported.

Modeling the Hydrogen Solubility in Liquid Aluminum Alloys

NASA Astrophysics Data System (ADS)

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.

Phase Equilibria of Sn-Co-Cu Ternary System

NASA Astrophysics Data System (ADS)

Chen, Yu-Kai; Hsu, Chia-Ming; Chen, Sinn-Wen; Chen, Chih-Ming; Huang, Yu-Chih

2012-10-01

Sn-Co-Cu ternary alloys are promising lead-free solders, and isothermal sections of Sn-Co-Cu phase equilibria are fundamentally important for the alloys' development and applications. Sn-Co-Cu ternary alloys were prepared and equilibrated at 523 K, 1073 K, and 1273 K (250 °C, 800 °C, and 1000 °C), and the equilibrium phases were experimentally determined. In addition to the terminal solid solutions and binary intermetallic compounds, a new ternary compound, Sn3Co2Cu8, was found. The solubilities of Cu in the α-CoSn3 and CoSn2 phases at 523 K (250 °C) are 4.2 and 1.6 at. pct, respectively, while the Cu solubility in the α-Co3Sn2 phase is as high as 20.0 at. pct. The Cu solubility increases with temperature and is around 30.0 at. pct in the β-Co3Sn2 at 1073 K (800 °C). The Co solubility in the η-Cu6Sn5 phase is also significant and is 15.5 at. pct at 523 K (250 °C).

Synthesis and characterization of water-soluble hydroxybutenyl cyclomaltooligosaccharides (cyclodextrins).

PubMed

Buchanan, Charles M; Alderson, Susan R; Cleven, Curtis D; Dixon, Daniel W; Ivanyi, Robert; Lambert, Juanelle L; Lowman, Douglas W; Offerman, Rick J; Szejtli, Jozsef; Szente, Lajos

2002-03-15

We have examined the synthesis of hydroxybutenyl cyclomaltooligosaccharides (cyclodextrins) and the ability of these cyclodextrin ethers to form guest-host complexes with guest molecules. The hydroxybutenyl cyclodextrin ethers were prepared by a base-catalyzed reaction of 3,4-epoxy-1-butene with the parent cyclodextrins in an aqueous medium. Reaction byproducts were removed by nanofiltration before the hydroxybutenyl cyclodextrins were isolated by co-evaporation of water-EtOH. Hydroxybutenyl cyclodextrins containing no unsubstituted parent cyclodextrin typically have a degree of substitution of 2-4 and a molar substitution of 4-7. These hydroxybutenyl cyclodextrins are randomly substituted, amorphous solids. The hydroxybutenyl cyclodextrin ethers were found to be highly water soluble. Complexes of HBen-beta-CD with glibenclamide and ibuprofen were prepared and isolated. In both cases, the guest content of the complexes was large, and a significant increase in the solubility of the free drug was observed. Dissolution of the complexes in pH 1.4 water was very rapid, and significant increases in the solubility of the free drugs were observed. Significantly, after reaching equilibrium concentration, a decrease in the drug concentration over time was not observed.

Tungsten Speciation and Solubility in Munitions-Impacted Soils.

PubMed

Bostick, Benjamín C; Sun, Jing; Landis, Joshua D; Clausen, Jay L

2018-02-06

Considerable questions persist regarding tungsten geochemistry in natural systems, including which forms of tungsten are found in soils and how adsorption regulates dissolved tungsten concentrations. In this study, we examine tungsten speciation and solubility in a series of soils at firing ranges in which tungsten rounds were used. The metallic, mineral, and adsorbed forms of tungsten were characterized using X-ray absorption spectroscopy and X-ray microprobe, and desorption isotherms for tungsten in these soils were used to characterize its solid-solution partitioning behavior. Data revealed the complete and rapid oxidation of tungsten metal to hexavalent tungsten(VI) and the prevalence of adsorbed polymeric tungstates in the soils rather than discrete mineral phases. These polymeric complexes were only weakly retained in the soils, and porewaters in equilibrium with contaminated soils had 850 mg L -1 tungsten, considerably in excess of predicted solubility. We attribute the high solubility and limited adsorption of tungsten to the formation of polyoxometalates such as W 12 SiO 40 4- , an α-Keggin cluster, in soil solutions. Although more research is needed to confirm which of such polyoxometalates are present in soils, their formation may not only increase the solubility of tungsten but also facilitate its transport and influence its toxicity.

Si-Ge-metal ternary phase diagram calculations

NASA Technical Reports Server (NTRS)

Fleurial, J. P.; Borshchevsky, A.

1990-01-01

Solution crystal growth and doping conditions of Si-Ge alloys used for high-temperature thermoelectric generation are determined here. Liquid-phase epitaxy (LPE) has been successfully employed recently to obtain single-crystalline homogeneous layers of Si-Ge solid solutions from a liquid metal solvent. Knowledge of Si-Ge-metallic solvent ternary phase diagrams is essential for further single-crystal growth development. Consequently, a thermodynamic equilibrium model was used to calculate the phase diagrams of the Si-Ge-M systems, including solid solubilities, where M is Al, Ga, In, Sn, Pb, Sb, or Bi. Good agreement between calculated liquidus and solidus data and experimental DTA and microprobe results was obtained. The results are used to compare the suitability of the different systems for crystal growth (by LPE-type process).

Kinetics and capacities of phosphorus sorption to tertiary stage wastewater alum solids, and process implications for achieving low-level phosphorus effluents.

PubMed

Maher, Chris; Neethling, J B; Murthy, Sudhir; Pagilla, Krishna

2015-11-15

The role of adsorption and/or complexation in removal of reactive or unreactive effluent phosphorus by already formed chemical precipitates or complexes has been investigated. Potential operational efficiency gains resulting from age of chemically precipitated tertiary alum sludge and the recycle of sludge to the process stream was undertaken at the Iowa Hill Water Reclamation Facility which employs the DensaDeg(®) process (IDI, Richmond, VA) for tertiary chemical P removal to achieve a filtered final effluent total phosphorus concentration of <30 μg/L. The effect of sludge solids age was found to be insignificant over the solids retention time (SRT) of 2-8 days, indicating that the solids were unaffected by the aging effects of decreasing porosity and surface acidity. The bulk of solids inventory was retained in the clarifier blanket, providing no advantage in P removal from increased solids inventory at higher SRTs. When solids recycle was redirected from the traditional location of the flocculation reactor to a point just prior to chemical addition in the chemical mixing reactor, lower effluent soluble P concentrations at lower molar doses of aluminum were achieved. At laboratory scale, the "spent" or "waste" chemical alum sludge from P removal showed high capacity and rapid kinetics for P sorption from real wastewater effluents. Saturation concentrations were in the range of 8-29 mg soluble reactive P/g solids. Higher saturation concentrations were found at higher temperatures. Alum sludge produced without a coagulant aid polymer had a much higher capacity for P sorption than polymer containing alum sludge. The adsorption reaction reached equilibrium in less than 10 min with 50% or greater removal within the first minute. Copyright © 2015 Elsevier Ltd. All rights reserved.

Rapid Dissolution of Soluble Uranyl Phases in Arid, Mine-Impacted Catchments Near Church Rock, NM

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

deLemos, J.L.; Bostick, B.C.; Quicksall, A.N.

2009-05-14

We tested the hypothesis that runoff of uranium-bearing particles from mining waste disposal areas was a significant mechanism for redistribution of uranium in the northeastern part of the Upper Puerco River watershed (New Mexico). However, our results were not consistent with this hypothesis. Analysis of >100 sediment and suspended sediment samples collected adjacent to and downstream from uranium source areas indicated that uranium levels in the majority of the samples were not elevated above background. Samples collected within 50 m of a known waste disposal site were subjected to detailed geochemical characterization. Uranium in these samples was found to bemore » highly soluble; treatment with synthetic pore water for 24 h caused dissolution of 10-50% of total uranium in the samples. Equilibrium uranium concentrations in pore water were >4.0 mg/L and were sustained in repeated wetting events, effectively depleting soluble uranium from the solid phase. The dissolution rate of uranium appeared to be controlled by solid-phase diffusion of uranium from within uranium-bearing mineral particles. X-ray adsorption spectroscopy indicated the presence of a soluble uranyl silicate, and possibly a uranyl phosphate. These phases were exhausted in transported sediment suggesting that uranium was readily mobilized from sediments in the Upper Puerco watershed and transported in the dissolved load. These results could have significance for uranium risk assessment as well as mining waste management and cleanup efforts.« less

Rapid Dissolution of Soluble Uranyl Phases in Arid, Mine-Impacted Catchments near Church Rock, NM

PubMed Central

DELEMOS, JAMIE L.; BOSTICK, BENJAMIN C.; QUICKSALL, ANDREW N.; LANDIS, JOSHUA D.; GEORGE, CHRISTINE C.; SLAGOWSKI, NAOMI L.; ROCK, TOMMY; BRUGGE, DOUG; LEWIS, JOHNNYE; DURANT, JOHN L.

2008-01-01

We tested the hypothesis that runoff of uranium-bearing particles from mining waste disposal areas was a significant mechanism for redistribution of uranium in the northeastern part of the Upper Puerco River watershed (New Mexico). However, our results were not consistent with this hypothesis. Analysis of >100 sediment and suspended sediment samples collected adjacent to and downstream from uranium source areas indicated that uranium levels in the majority of the samples were not elevated above background. Samples collected within 50 m of a known waste disposal site were subjected to detailed geochemical characterization. Uranium in these samples was found to be highly soluble; treatment with synthetic pore water for 24 h caused dissolution of 10–50% of total uranium in the samples. Equilibrium uranium concentrations in pore water were >4.0 mg/L and were sustained in repeated wetting events, effectively depleting soluble uranium from the solid phase. The dissolution rate of uranium appeared to be controlled by solid-phase diffusion of uranium from within uranium-bearing mineral particles. X-ray adsorption spectroscopy indicated the presence of a soluble uranyl silicate, and possibly a uranyl phosphate. These phases were exhausted in transported sediment suggesting that uranium was readily mobilized from sediments in the Upper Puerco watershed and transported in the dissolved load. These results could have significance for uranium risk assessment as well as mining waste management and cleanup efforts. PMID:18589950

Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O

NASA Astrophysics Data System (ADS)

Pabalan, Roberto T.; Pitzer, Kenneth S.

1987-09-01

Mineral solubilities in binary and ternary electrolyte mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O are calculated to high temperatures using available thermodynamic data for solids and for aqueous electrolyte solutions. Activity and osmotic coefficients are derived from the ion-interaction model of Pitzer (1973, 1979) and co-workers, the parameters of which are evaluated from experimentally determined solution properties or from solubility data in binary and ternary mixtures. Excellent to good agreement with experimental solubilities for binary and ternary mixtures indicate that the model can be successfully used to predict mineral-solution equilibria to high temperatures. Although there are currently no theoretical forms for the temperature dependencies of the various model parameters, the solubility data in ternary mixtures can be adequately represented by constant values of the mixing term θ ij and values of ψ ijk which are either constant or have a simple temperature dependence. Since no additional parameters are needed to describe the thermodynamic properties of more complex electrolyte mixtures, the calculations can be extended to equilibrium studies relevant to natural systems. Examples of predicted solubilities are given for the quaternary system NaCl-KCl-MgCl 2-H 2O.

An isopiestic study of aqueous NaBr and KBr at 50 °C: Chemical equilibrium model of solution behavior and solubility in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems to high concentration and temperature

NASA Astrophysics Data System (ADS)

Christov, Christomir

2007-07-01

The isopiestic method has been used to determine the osmotic coefficients of the binary solutions NaBr-H 2O (from 0.745 to 5.953 mol kg -1) and KBr-H 2O (from 0.741 to 5.683 mol kg -1) at the temperature t = 50 °C. Sodium chloride solutions have been used as isopiestic reference standards. The isopiestic results obtained have been combined with all other experimental thermodynamic quantities available in literature (osmotic coefficients, water activities, bromide mineral's solubilities) to construct a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems from dilute to high solution concentration within the 0-300 °C temperature range. The Harvie and Weare [Harvie C., and Weare J. (1980) The prediction of mineral solubilities in naturalwaters: the Na-K-Mg-Ca-Cl-SO 4-H 2O system from zero to high concentration at 25 °C. Geochim. Cosmochim. Acta44, 981-997] solubility modeling approach, incorporating their implementation of the concentration-dependent specific interaction equations of Pitzer [Pitzer K. (1973) Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem.77, 268-277] is employed. The model for binary systems is validated by comparing activity coefficient predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solutions model due to data insufficiencies are discussed. This model expands the variable temperature sodium-potassium model of Greenberg and Moller [Greenberg J., and Moller N. (1989) The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO 4-H 2O system to high concentration from 0 to 250 °C. Geochim. Cosmochim. Acta53, 2503-2518] by evaluating Br - pure electrolyte and mixing solution parameters and the chemical potentials of three bromide solid phases: NaBr-2H 2O (cr), NaBr (cr) and KBr (cr).

Pourbaix Diagrams at Elevated Temperatures A Study of Zinc and Tin

NASA Astrophysics Data System (ADS)

Palazhchenko, Olga

Metals in industrial settings such as power plants are often subjected to high temperature and pressure aqueous environments, where failure to control corrosion compromises worker and environment safety. For instance, zircaloy (1.2-1.7 wt.% Sn) fuel rods are exposed to aqueous 250-310 °C coolant in CANDU reactors. The Pourbaix (EH-pH) diagram is a plot of electrochemical potential versus pH, which shows the domains of various metal species and by inference, corrosion susceptibility. Elevated temperature data for tin +II and tin +IV species were obtained using solid-aqueous phase equilibria with the respective oxides, in a batch vessel with in-situ pH measurement. Solubilities, determined via spectroscopic techniques, were used to calculate equilibrium constants and the Gibbs energies of Sn complexes for E-pH diagram construction. The SnOH3+ and Sn(OH )-5 species were incorporated, for the first time, into the 298.15 K and 358.15 K diagrams, with novel Go values determined at 358.15 K. Key words: Pourbaix diagrams, EH-pH, elevated temperatures, solubility, equilibrium, metal oxides, hydrolysis, redox potential, pH, thermochemical data, tin, zinc, zircaloy, corrosion, passivity.

Experimental investigation of the solubility of albite and jadeite in H 2O, with paragonite + quartz at 500 and 600 °C, and 1-2.25 GPa

NASA Astrophysics Data System (ADS)

Wohlers, Anke; Manning, Craig E.; Thompson, Alan B.

2011-05-01

The solubilities of the assemblages albite + paragonite + quartz and jadeite + paragonite + quartz in H 2O were determined at 500 and 600 °C, 1.0-2.25 GPa, using hydrothermal piston-cylinder methods. The three minerals are isobarically and isothermally invariant in the presence of H 2O, so fluid composition is uniquely determined at each pressure and temperature. A phase-bracketing approach was used to achieve accurate solubility determinations. Albite + quartz and jadeite + quartz dissolve incongruently in H 2O, yielding residual paragonite which could not be retrieved and weighed. Solution composition fixed by the three-mineral assemblage at a given pressure and temperature was therefore bracketed by adding NaSi 3O 6.5 glass in successive experiments, until no paragonite was observed in run products. Solubilities derived from experiments bounding the appearance of paragonite thus constrain the equilibrium fluid composition. Results indicate that, at a given pressure, Na, Al, and Si concentrations are higher at 600 °C than at 500 °C. At both 500 and 600 °C, solubilities of all three elements increase with pressure in the albite stability field, to a maximum at the jadeite-albite-quartz equilibrium. In the jadeite stability field, element concentrations decline with continued pressure increase. At the solubility maximum, Na, Al, and Si concentrations are, respectively, 0.16, 0.05, and 0.48 molal at 500 °C, and 0.45, 0.27, and 1.56 molal at 600 °C. Bulk solubilities are 3.3 and 10.3 wt% oxides, respectively. Observed element concentrations are everywhere greater than those predicted from extrapolated thermodynamic data for simple ions, monomers, ion pairs, and the silica dimer. The measurements therefore require the presence of additional, polymerized Na-Al-Si-bearing species in the solutions. The excess solubility is >50% at all conditions, indicating that polymeric structures are the predominant solutes in the P- T region studied. The solubility patterns likely arise from combination of the large solid volume change associated with the albite-jadeite-quartz equilibrium and the rise in Na-Al-Si polymerization with approach to the hydrothermal melting curves of albite + quartz and jadeite + quartz. Our results indicate that polymerization of Na-Al-Si solutes is a fundamental aspect of fluid-rock interaction at high pressure. In addition, the data suggest that high-pressure metamorphic isograds can impose unexpected controls on metasomatic mass transfer, that significant metasomatic mass transfer prior to melting should be considered in migmatitic terranes, and that polymeric complexes may be an important transport agent in subduction zones.

Stability of pharmaceutical salts in solid oral dosage forms.

PubMed

Nie, Haichen; Byrn, Stephen R; Zhou, Qi Tony

2017-08-01

Using pharmaceutical salts in solid dosage forms can raise stability concerns, especially salt dissociation which can adversely affect the product performance. Therefore, a thorough understanding of the salt instability encountered in solid-state formulations is imperative to ensure the product quality. The present article uses the fundamental theory of acid base, ionic equilibrium, relationship of pH and solubility as a starting point to illustrate and interpret the salt formation and salt disproportionation in pharmaceutical systems. The criteria of selecting the optimal salt form and the underlying theory of salt formation and disproportionation are reviewed in detail. Factors influencing salt stability in solid dosage forms are scrutinized and discussed with the case studies. In addition, both commonly used and innovative strategies for preventing salt dissociations in formulation, on storage and during manufacturing will be suggested herein. This article will provide formulation scientists and manufacturing engineers an insight into the mechanisms of salt disproportionation and salt formation, which can help them to avoid and solve the instability issues of pharmaceutical salts in the product design.

Ikaite solubility in seawater-derived brines at 1 atm and sub-zero temperatures to 265 K

NASA Astrophysics Data System (ADS)

Papadimitriou, Stathys; Kennedy, Hilary; Kennedy, Paul; Thomas, David N.

2013-05-01

The concentration-based (stoichiometric) equilibrium solubility product of ikaite (CaCO3·6H2O) in seawater and cryogenic seawater-derived brines was determined at 1 atm total pressure over the temperature range from -1.1 to -7.5 °C and the salinity range from 34 to 124 in temperature-salinity pairs representative of sea ice brines. The solubility measurements were obtained in solutions that were undersaturated and supersaturated with respect to ikaite by equilibration with CO2/N2 gas mixtures of known pCO2 (20-400 μatm). The solutions were then equilibrated with synthetic ikaite (seed) for up to 3 months in a closed system. Arrival of the solid-solution system at a long-term chemical equilibrium was indicated by attainment of constant chemical solution composition with respect to total dissolved calcium, total dissolved inorganic carbon, and total alkalinity. Using these measurements, the stoichiometric equilibrium solubility product of ikaite (Ksp,ikaite∗=[Ca][CO32-], in molkgsolution-2) was determined, with the carbonate ion concentration computed from the measured total alkalinity and total dissolved inorganic carbon concentrations. The computed carbonate ion concentration and, by extension, the Ksp,ikaite∗ are both contingent on solving the system of equations that describe the parameters of the CO2 system in seawater by extrapolation to the experimental salinity and temperature conditions. The results show that the pKsp,ikaite∗=-logKsp,ikaite∗ in seawater of salinity 34 at -1.1 °C was 5.362 ± 0.004 and that the pKsp,ikaite∗ in sea ice at the freezing point of brines of salinity greater than 34 can be described as a function of temperature (T, in K) by the equation, pKsp,ikaite∗=-15489.09608+623443.70216T-1+2355.14596lnT, in the temperature range of 265.15 K < T < 271.15 K (-8 °C < t < -2 °C). Brines of low pCO2 (20 μatm) yielded a much slower (>1 month) approach to chemical equilibrium when incubated without seeding ikaite crystals. Simple modeling indicated that ikaite should not precipitate from sea ice brines evolving under closed system conditions with respect to CO2 exchange. To facilitate ikaite precipitation, brine pCO2 reduction due to photosynthesis or CO2 degassing, or both, is necessary.

Solubility limits in quaternary SnTe-based alloys

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

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.

2017-01-01

A combined theoretical and experimental approach was used to determine the equilibrium as well as non-equilibrium solubility lines in the quaternary Sn 1-yMn yTe 1-xSe xalloy space, revealing a large area of accessible metastable phase space.

Mutations that alter the equilibrium between open and closed conformations of Escherichia coli maltose-binding protein impede its ability to enhance the solubility of passenger proteins

PubMed Central

Nallamsetty, Sreedevi; Waugh, David S.

2007-01-01

Certain highly soluble proteins, such as Escherichia coli maltose-binding protein (MBP), have the ability to enhance the solubility of their fusion partners, making them attractive vehicles for the production of recombinant proteins, yet the mechanism of solubility enhancement remains poorly understood. Here, we report that the solubility-enhancing properties of MBP are dramatically affected by amino acid substitutions that alter the equilibrium between its “open” and “closed” conformations. Our findings indicate that the solubility-enhancing activity of MBP is mediated by its open conformation and point to a likely role for the ligand-binding cleft in the mechanism of solubility enhancement. PMID:17964542

Statistical investigation of simulated intestinal fluid composition on the equilibrium solubility of biopharmaceutics classification system class II drugs.

PubMed

Khadra, Ibrahim; Zhou, Zhou; Dunn, Claire; Wilson, Clive G; Halbert, Gavin

2015-01-25

A drug's solubility and dissolution behaviour within the gastrointestinal tract is a key property for successful administration by the oral route and one of the key factors in the biopharmaceutics classification system. This property can be determined by investigating drug solubility in human intestinal fluid (HIF) but this is difficult to obtain and highly variable, which has led to the development of multiple simulated intestinal fluid (SIF) recipes. Using a statistical design of experiment (DoE) technique this paper has investigated the effects and interactions on equilibrium drug solubility of seven typical SIF components (sodium taurocholate, lecithin, sodium phosphate, sodium chloride, pH, pancreatin and sodium oleate) within concentration ranges relevant to human intestinal fluid values. A range of poorly soluble drugs with acidic (naproxen, indomethacin, phenytoin, and piroxicam), basic (aprepitant, carvedilol, zafirlukast, tadalafil) or neutral (fenofibrate, griseofulvin, felodipine and probucol) properties have been investigated. The equilibrium solubility results determined are comparable with literature studies of the drugs in either HIF or SIF indicating that the DoE is operating in the correct space. With the exception of pancreatin, all of the factors individually had a statistically significant influence on equilibrium solubility with variations in magnitude of effect between the acidic and basic or neutral compounds and drug specific interactions were evident. Interestingly for the neutral compounds pH was the factor with the second largest solubility effect. Around one third of all the possible factor combinations showed a significant influence on equilibrium solubility with variations in interaction significance and magnitude of effect between the acidic and basic or neutral compounds. The least number of significant media component interactions were noted for the acidic compounds with three and the greatest for the neutral compounds at seven, with again drug specific effects evident. This indicates that a drug's equilibrium solubility in SIF is influenced depending upon drug type by between eight to fourteen individual or combinations of media components with some of these drug specific. This illustrates the complex nature of these fluids and provides for individual drugs a visualisation of the possible solubility envelope within the gastrointestinal tract, which may be of importance for modelling in vivo behaviour. In addition the results indicate that the design of experiment approach can be employed to provide greater detail of drug solubility behaviour, possible drug specific interactions and influence of variations in gastrointestinal media components due to disease. The approach is also feasible and amenable to adaptation for high throughput screening of drug candidates. Copyright © 2014 Elsevier B.V. All rights reserved.

Solution equilibrium behind the room-temperature synthesis of nanocrystalline titanium dioxide.

PubMed

Seisenbaeva, Gulaim A; Daniel, Geoffrey; Nedelec, Jean-Marie; Kessler, Vadim G

2013-04-21

Formation of nanocrystalline and monodisperse TiO2 from a water soluble and stable precursor, ammonium oxo-lactato-titanate, (NH4)8Ti4O4(Lactate)8·4H2O, often referred to as TiBALDH or TALH, is demonstrated to be due to a coordination equilibrium. This compound, individual in the solid state, exists in solution in equilibrium with ammonium tris-lactato-titanate, (NH4)2Ti(Lactate)3 and uniform crystalline TiO2 nanoparticles (anatase) stabilized by surface-capping with lactate ligands. This equilibrium can be shifted towards nano-TiO2via application of a less polar solvent like methanol or ethanol, dilution of the solution, introduction of salts or raising the temperature, and reverted on addition of polar and strongly solvating media such as dimethyl sulfoxide, according to NMR. Aggregation and precipitation of the particles were followed by DLS and could be achieved by a decrease in their surface charge by adsorption of strongly hydrogen-bonding cations, e.g. in solutions of ammonia, ethanolamine or amino acid arginine or by addition of ethanol. The observed equilibrium may be involved in formation of nano-titania on the surface of plant roots exerting chelating organic carboxylate ligands and thus potentially influencing plant interactions.

Thermodynamics of phase-separating nanoalloys: Single particles and particle assemblies

NASA Astrophysics Data System (ADS)

Fèvre, Mathieu; Le Bouar, Yann; Finel, Alphonse

2018-05-01

The aim of this paper is to investigate the consequences of finite-size effects on the thermodynamics of nanoparticle assemblies and isolated particles. We consider a binary phase-separating alloy with a negligible atomic size mismatch, and equilibrium states are computed using off-lattice Monte Carlo simulations in several thermodynamic ensembles. First, a semi-grand-canonical ensemble is used to describe infinite assemblies of particles with the same size. When decreasing the particle size, we obtain a significant decrease of the solid/liquid transition temperatures as well as a growing asymmetry of the solid-state miscibility gap related to surface segregation effects. Second, a canonical ensemble is used to analyze the thermodynamic equilibrium of finite monodisperse particle assemblies. Using a general thermodynamic formulation, we show that a particle assembly may split into two subassemblies of identical particles. Moreover, if the overall average canonical concentration belongs to a discrete spectrum, the subassembly concentrations are equal to the semi-grand-canonical equilibrium ones. We also show that the equilibrium of a particle assembly with a prescribed size distribution combines a size effect and the fact that a given particle size assembly can adopt two configurations. Finally, we have considered the thermodynamics of an isolated particle to analyze whether a phase separation can be defined within a particle. When studying rather large nanoparticles, we found that the region in which a two-phase domain can be identified inside a particle is well below the bulk phase diagram, but the concentration of the homogeneous core remains very close to the bulk solubility limit.

Investigation of novel supersaturating drug delivery systems of chlorthalidone: The use of polymer-surfactant complex as an effective carrier in solid dispersions.

PubMed

França, Maria Terezinha; Nicolay Pereira, Rafael; Klüppel Riekes, Manoela; Munari Oliveira Pinto, Juliana; Stulzer, Hellen Karine

2018-01-01

Supersaturating drug delivery systems (SDDS), as solid dispersions (SDs), stand out among strategies to enhance bioavailability of poorly soluble drugs. After oral administration, their dissolution in gastrointestinal fluids often leads to supersaturation, which drives to a rapid and sustained absorption. Polymers and surfactants play important roles in SDs through inhibiting precipitation caused by transitions from amorphous into crystalline form, in supersaturated solutions, and also through improving SDs physical stability. Novel chlorthalidone SDs, a BCS IV drug, were developed using polymeric and non-polymeric carriers, specially a polymer-surfactant complex. SDs drug releases were evaluated using sink and non-sink conditions in water and biorelevant medium. Their physical stability was also monitored under different storage conditions. Polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (SOL), sodium lauryl sulfate (SLS) and a combination of both showed promising results in apparent solubility studies, and therefore they were selected to compose the spray dried SDs. Dissolution studies demonstrated the SOL-SLS complex potential for providing chlorthalidone fast release (>80% in 15min), producing and maintaining in vitro supersaturation. This formulation comprising high drug loading (75%) reached a high supersaturation degree under non-sink condition (up to 6-fold the equilibrium solubility) once maintained for 6h in biorelevant medium. In addition, this SD presented better physical stability when compared to the chlorthalidone neat amorphous. The SOL-SLS complex impacts positively on chlorthalidone release and physical stability, highlighting its potential as carrier in SDDS of a poorly soluble drug. Copyright © 2017. Published by Elsevier B.V.

Non-equilibrium induction of tin in germanium: towards direct bandgap Ge1−xSnx nanowires

PubMed Central

Biswas, Subhajit; Doherty, Jessica; Saladukha, Dzianis; Ramasse, Quentin; Majumdar, Dipanwita; Upmanyu, Moneesh; Singha, Achintya; Ochalski, Tomasz; Morris, Michael A.; Holmes, Justin D.

2016-01-01

The development of non-equilibrium group IV nanoscale alloys is critical to achieving new functionalities, such as the formation of a direct bandgap in a conventional indirect bandgap elemental semiconductor. Here, we describe the fabrication of uniform diameter, direct bandgap Ge1−xSnx alloy nanowires, with a Sn incorporation up to 9.2 at.%, far in excess of the equilibrium solubility of Sn in bulk Ge, through a conventional catalytic bottom-up growth paradigm using noble metal and metal alloy catalysts. Metal alloy catalysts permitted a greater inclusion of Sn in Ge nanowires compared with conventional Au catalysts, when used during vapour–liquid–solid growth. The addition of an annealing step close to the Ge-Sn eutectic temperature (230 °C) during cool-down, further facilitated the excessive dissolution of Sn in the nanowires. Sn was distributed throughout the Ge nanowire lattice with no metallic Sn segregation or precipitation at the surface or within the bulk of the nanowires. The non-equilibrium incorporation of Sn into the Ge nanowires can be understood in terms of a kinetic trapping model for impurity incorporation at the triple-phase boundary during growth. PMID:27095012

Non-equilibrium induction of tin in germanium: towards direct bandgap Ge1-xSnx nanowires

NASA Astrophysics Data System (ADS)

Biswas, Subhajit; Doherty, Jessica; Saladukha, Dzianis; Ramasse, Quentin; Majumdar, Dipanwita; Upmanyu, Moneesh; Singha, Achintya; Ochalski, Tomasz; Morris, Michael A.; Holmes, Justin D.

2016-04-01

The development of non-equilibrium group IV nanoscale alloys is critical to achieving new functionalities, such as the formation of a direct bandgap in a conventional indirect bandgap elemental semiconductor. Here, we describe the fabrication of uniform diameter, direct bandgap Ge1-xSnx alloy nanowires, with a Sn incorporation up to 9.2 at.%, far in excess of the equilibrium solubility of Sn in bulk Ge, through a conventional catalytic bottom-up growth paradigm using noble metal and metal alloy catalysts. Metal alloy catalysts permitted a greater inclusion of Sn in Ge nanowires compared with conventional Au catalysts, when used during vapour-liquid-solid growth. The addition of an annealing step close to the Ge-Sn eutectic temperature (230 °C) during cool-down, further facilitated the excessive dissolution of Sn in the nanowires. Sn was distributed throughout the Ge nanowire lattice with no metallic Sn segregation or precipitation at the surface or within the bulk of the nanowires. The non-equilibrium incorporation of Sn into the Ge nanowires can be understood in terms of a kinetic trapping model for impurity incorporation at the triple-phase boundary during growth.

Solubilities of Some Strong Electrolytes in the Hydrogen Peroxide-Water System. II. Rubidium and Cesium Nitrates

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

Everhard, Martin E.; Gross, Paul M.

1962-03-01

Solubilities of RbNO/sub 3/ and CsNO/sub 3/ were examined as well as the nature of the solid phases in equilibrium with these systems in order to study the possible role of cation size. The formation of hydroperoxidates and the increase in solibility of the salts with larger cations in hydrogen peroxide- rich solutions indicate preferential solvation of the ions by H/sub 2/O/sub 2/ rather than by H/sub 2/O. Conversely, the formation of hydrates and lower solubility in hydrogen peroxide-rich solutions of the smaller cation salts indicate preferential solvation of the ions by water. The deviation of the molal solubility, M',more » of the alkali nitrates in H/sub 2/O/sub 2/ from that in H/sub 2/O (M/sub H /sub 2/O/sub 2/) at ' =33.5r - 39.7 ( plus or minus 0.03 in M'), where r is the radius of the cation. CsNO/sub 3/, however, did not fall on the line, which probably is due to the lower charge density of the cesium ion. (P.C.H.)« less

Solution equilibrium behind the room-temperature synthesis of nanocrystalline titanium dioxide

NASA Astrophysics Data System (ADS)

Seisenbaeva, Gulaim A.; Daniel, Geoffrey; Nedelec, Jean-Marie; Kessler, Vadim G.

2013-03-01

Formation of nanocrystalline and monodisperse TiO2 from a water soluble and stable precursor, ammonium oxo-lactato-titanate, (NH4)8Ti4O4(Lactate)8.4H2O, often referred to as TiBALDH or TALH, is demonstrated to be due to a coordination equilibrium. This compound, individual in the solid state, exists in solution in equilibrium with ammonium tris-lactato-titanate, (NH4)2Ti(Lactate)3 and uniform crystalline TiO2 nanoparticles (anatase) stabilized by surface-capping with lactate ligands. This equilibrium can be shifted towards nano-TiO2via application of a less polar solvent like methanol or ethanol, dilution of the solution, introduction of salts or raising the temperature, and reverted on addition of polar and strongly solvating media such as dimethyl sulfoxide, according to NMR. Aggregation and precipitation of the particles were followed by DLS and could be achieved by a decrease in their surface charge by adsorption of strongly hydrogen-bonding cations, e.g. in solutions of ammonia, ethanolamine or amino acid arginine or by addition of ethanol. The observed equilibrium may be involved in formation of nano-titania on the surface of plant roots exerting chelating organic carboxylate ligands and thus potentially influencing plant interactions.Formation of nanocrystalline and monodisperse TiO2 from a water soluble and stable precursor, ammonium oxo-lactato-titanate, (NH4)8Ti4O4(Lactate)8.4H2O, often referred to as TiBALDH or TALH, is demonstrated to be due to a coordination equilibrium. This compound, individual in the solid state, exists in solution in equilibrium with ammonium tris-lactato-titanate, (NH4)2Ti(Lactate)3 and uniform crystalline TiO2 nanoparticles (anatase) stabilized by surface-capping with lactate ligands. This equilibrium can be shifted towards nano-TiO2via application of a less polar solvent like methanol or ethanol, dilution of the solution, introduction of salts or raising the temperature, and reverted on addition of polar and strongly solvating media such as dimethyl sulfoxide, according to NMR. Aggregation and precipitation of the particles were followed by DLS and could be achieved by a decrease in their surface charge by adsorption of strongly hydrogen-bonding cations, e.g. in solutions of ammonia, ethanolamine or amino acid arginine or by addition of ethanol. The observed equilibrium may be involved in formation of nano-titania on the surface of plant roots exerting chelating organic carboxylate ligands and thus potentially influencing plant interactions. Electronic supplementary information (ESI) available: Crystallographic data in cif and table format, detailed description of hydrogen bonding in (NH4)2[Ti(l-Lactate)3].3H2O, additional TEM images, DLS data on particle size in solutions and NanoSight data on particle size distribution, photos of produced TiO2 colloids, details of NMR experiments and a real-time movie demonstrating the equilibrium leading to TiO2 formation and re-dissolution in pH-neutral ammonium lactate solutions. CCDC 915222. For ESI and crystallographic data in CIF or other electronic format. see DOI: 10.1039/c3nr34068f

Solubility limits of dibutyl phosphoric acid in uranium-nitric acid solutions

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

Pierce, R.A.

2000-01-04

The Savannah River Site has enriched uranium (EU) solution that has been stored since being purified in its solvent extraction processes. The concentrations in solution are approximately 6 g/L U and 0.1 M nitric acid. Residual tributylphosphate in solution has slowly hydrolyzed to form dibutyl phosphoric acid (HDBP) at concentrations averaging 30--50 mg/L. Dibutyl phosphoric acid, in turn, is in equilibrium with (HDBP){sub 2} and DBP{sup {minus}}. Uranium can form compounds with the dibutylphosphate ion (DBP{sup {minus}}) which have limited solubility, thereby creating a nuclear criticality safety issue. Literature reports and earlier SRTC tests have shown that it is feasiblemore » to precipitate U-DBP solid during the storage and processing of EU solutions. As a result, a series of solubility experiments were run at nitric acid concentrations from 0--4.0 M HNO{sub 3}, uranium at 0--90 g/L, and temperatures from 0--30 C. The data shows temperature and nitric acid concentration dependence consistent with what would be expected. With respect to uranium concentration, U-DBP solubility passes through a minimum between 6 and 12 g/L U at the acid concentrations and temperatures studied. However, the minimum shows a slight shift toward lower uranium concentrations at lower nitric acid concentrations. The shifts in solubility are strongly dependent upon the overall ionic strength of the solution. The data also reveal a shift to higher DBP solubility above 0.5 M HNO{sub 3} for both 6 g/L and 12 g/L uranium solutions. Analysis of U-DBP solids from the tests identified distinct differences between precipitates from less than 0.5 M solutions and those from greater than 4 M acid. Analyses identified UO{sub 2}(DBP){sub 2} as the dominant compound present at low acid concentrations in accordance with literature reports. As the acid concentration increases, the crystalline UO{sub 2}(DBP){sub 2} shows molecular substitutions and an increase in amorphous content.« less

Solid-state NMR Study Reveals Collagen I Structural Modifications of Amino Acid Side Chains upon Fibrillogenesis*

PubMed Central

De Sa Peixoto, Paulo; Laurent, Guillaume; Azaïs, Thierry; Mosser, Gervaise

2013-01-01

In vivo, collagen I, the major structural protein in human body, is found assembled into fibrils. In the present work, we study a high concentrated collagen sample in its soluble, fibrillar, and denatured states using one and two dimensional {1H}-13C solid-state NMR spectroscopy. We interpret 13C chemical shift variations in terms of dihedral angle conformation changes. Our data show that fibrillogenesis increases the side chain and backbone structural complexity. Nevertheless, only three to five rotameric equilibria are found for each amino acid residue, indicating a relatively low structural heterogeneity of collagen upon fibrillogenesis. Using side chain statistical data, we calculate equilibrium constants for a great number of amino acid residues. Moreover, based on a 13C quantitative spectrum, we estimate the percentage of residues implicated in each equilibrium. Our data indicate that fibril formation greatly affects hydroxyproline and proline prolyl pucker ring conformation. Finally, we discuss the implication of these structural data and propose a model in which the attractive force of fibrillogenesis comes from a structural reorganization of 10 to 15% of the amino acids. These results allow us to further understand the self-assembling process and fibrillar structure of collagen. PMID:23341452

Thermodynamic evaluation of oxygen behavior in Ti powder deoxidized by Ca reductant

NASA Astrophysics Data System (ADS)

Kim, Sun-Joong; Oh, Jung-Min; Lim, Jae-Won

2016-07-01

To produce low oxygen Ti powder of less than 1000 mass ppm, commercial Ti powder was deoxidized by two types of Ca reductants: a solid Ca and a Ca vapor. Compared with the iso-oxygen partial pressure in the Ti-O binary phase diagram, the PO2 in the raw Ti powder increased with temperature compared to the reduction reaction of Ca. Therefore, the O2 content in the Ti powder decreased as the deoxidation temperature increased from 873 K, showing a local minima at 1273 K. The oxygen concentration at 1373 K was greater than that at 1273 K because the oxygen solubility of the Ti powder was increased by the equilibrium relation between Ca and CaO. On the basis of the thermodynamic assessment, the deoxidation of Ti powder can be improved by increasing the temperature and lowering the oxygen solubility with the saturation of CaO.

A Thermodynamic Description of the Adsorption of Simple Water-Soluble Peptoids to Silica.

PubMed

Calkins, Anna L; Yin, Jennifer; Rangel, Jacenda L; Landry, Madeleine R; Fuller, Amelia A; Stokes, Grace Y

2016-11-08

The first report of a water-soluble peptoid adsorbed to silica monitored by second harmonic generation (SHG) at the liquid/solid interface is presented here. The molecular insights gained from these studies will inform the design and preparation of novel peptoid coatings. Simple 6- and 15-residue peptoids were dissolved in phosphate buffered saline and adsorbed to bare silica surfaces. Equilibrium binding constants and relative surface concentrations of adsorbed peptoids were determined from fits to the Langmuir model. Complementary fluorescence spectroscopy studies were used to quantify the maximum surface excess. Binding constants, determined here by SHG, were comparable to those previously reported for cationic proteins and small molecules. Enthalpies and free energies of adsorption were determined to elucidate thermodynamic driving forces. Circular dichroism spectra confirm that minimal conformational changes occur when peptoids are adsorbed to silica while pH studies indicate that electrostatic interactions impact adsorption.

Glass-liquid phase separation in highly supersaturated aqueous solutions of telaprevir.

PubMed

Mosquera-Giraldo, Laura I; Taylor, Lynne S

2015-02-02

Amorphous solid dispersions are of great current interest because they can improve the delivery of poorly water-soluble compounds. It has been recently noted that the highly supersaturated solutions generated by dissolution of some ASDs can undergo a phase transition to a colloidal, disordered, drug-rich phase when the concentration exceeds the "amorphous solubility" of the drug. The purpose of this study was to investigate the phase behavior of supersaturated solutions of telaprevir, which is formulated as an amorphous solid dispersion in the commercial product. Different analytical techniques including proton nuclear magnetic resonance spectroscopy (NMR), ultraviolet spectroscopy (UV), fluorescence spectroscopy and flux measurements were used to evaluate the properties of aqueous supersaturated solutions of telaprevir. It was found that highly supersaturated solutions of telaprevir underwent glass-liquid phase separation (GLPS) when the concentration exceeded 90 μg/mL, forming a water-saturated colloidal, amorphous drug-rich phase with a glass transition temperature of 52 °C. From flux measurements, it was observed that the "free" drug concentration reached a maximum at the concentration where GLPS occurred, and did not increase further as the concentration was increased. This phase behavior, which results in a precipitate and a metastable equilibrium between a supersaturated solution and a drug-rich phase, is obviously important in the context of evaluating amorphous solid dispersion formulations and their crystallization routes.

First-line antituberculosis drug, pyrazinamide, its pharmaceutically relevant cocrystals and a salt.

PubMed

Sarmah, Kashyap Kumar; Rajbongshi, Trishna; Bhowmick, Sourav; Thakuria, Ranjit

2017-10-01

A few pyrazinamide (Pyz) cocrystals involving hydroxybenzoic/cinnamic acid derivatives [2,4-dihydroxybenzoic acid (24DHBA); 2,6-dihydroxybenzoic acid (26DHBA); 3,5-dihydroxybenzoic acid (35DHBA) and nutraceutical molecule ferulic acid (FRA)] and the first example of a molecular salt with p-toluenesulfonic acid (pTSA) have been prepared and characterized using various solid-state techniques. A high-temperature cocrystal polymorph of Pyz·FRA has been characterized from the endothermic peaks observed using differential scanning calorimetry. The presence of substituent groups carrying hydrogen bond donors or acceptors and their influence on supramolecular synthon formation has been investigated using a Cambridge Structural Database search. Equilibrium solubility of all the binary complexes of Pyz follows the order of their coformer solubility, i.e. Pyz + ·pTSA - > Pyz·35DHBA > Pyz > Pyz·26DHBA > Pyz·24DHBA > Pyz·FRA. A twofold enhancement in solubility of Pyz + ·pTSA - molecular salt compared with the parent drug suggests a potential drug formulation for the treatment of tuberculosis.

Connecting Solubility, Equilibrium, and Periodicity in a Green, Inquiry Experiment for the General Chemistry Laboratory

ERIC Educational Resources Information Center

Cacciatore, Kristen L.; Amado, Jose; Evans, Jason J.; Sevian, Hannah

2008-01-01

We present a novel first-year chemistry laboratory experiment that connects solubility, equilibrium, and chemical periodicity concepts. It employs a unique format that asks students to replicate experiments described in different sample lab reports, each lacking some essential information, rather than follow a scripted procedure. This structure is…

Influences of pH and CO2 on the formation of Metasilicate mineral water in Changbai Mountain, Northeast China

NASA Astrophysics Data System (ADS)

Yan, Baizhong; Xiao, Changlai; Liang, Xiujuan; Wu, Shili

2017-07-01

Mineral dissolution reactions actively participate in controlling the composition of mineral water. In this study, water soluble, acidic-alkaline and carbonated solution experiments were designed, and mineral reaction mechanisms were researched using chemical kinetics and the minimum free-energy method. The results showed that the release of metasilicate was controlled by pH, CO2, and rock characteristics. In the water soluble experiment, the release process of metasilicate in powdered rocks reached equilibrium after 40 days, while metasilicate in solid rocks took 170 days. The release process of metasilicate in solid rocks satisfied an asymptotic model, while in powdered rocks it accorded with the Stanford reaction kinetic model. In the acidic-alkaline experiment, metasilicate was released earlier under acidic conditions (2.46 < pH < 7) than under alkaline conditions (7 < pH < 10.61). The release process of metasilicate under acidic conditions reached equilibrium in 40 days, compared with 60 days for alkaline conditions. The addition of CO2 to the water solution was beneficial to the formation of metasilicate. Under neutral pH conditions, the reaction barely occurred. Under alkaline conditions, metasilicate was produced by the hydrolysis of metasilicate minerals. Under acidic and additional CO2 conditions, metasilicate formation was mainly via the reaction of H+, CO2, and metasilicate minerals. From these results, we concluded that the metasilicate mineral water from the Changbai Mountains, Jingyu County, is generated by a combination of the hydrolysis of metasilicate minerals and the reaction of H+, CO2, and metasilicate minerals. These results can contribute to a better development and protection of the mineral water resources in the Changbai Mountains.

Statistical investigation of simulated fed intestinal media composition on the equilibrium solubility of oral drugs.

PubMed

Zhou, Zhou; Dunn, Claire; Khadra, Ibrahim; Wilson, Clive G; Halbert, Gavin W

2017-03-01

Gastrointestinal fluid is a complex milieu and it is recognised that gut drug solubility is different to that observed in simple aqueous buffers. Simulated gastrointestinal media have been developed covering fasted and fed states to facilitate in vitro prediction of gut solubility and product dissolution. However, the combination of bile salts, phospholipids, fatty acids and proteins in an aqueous buffered system creates multiple phases and drug solubility is therefore a complex interaction between these components, which may create unique environments for each API. The impact on solubility can be assessed through a statistical design of experiment (DoE) approach, to determine the influence and relationships between factors. In this paper DoE has been applied to fed simulated gastrointestinal media consisting of eight components (pH, bile salt, lecithin, sodium oleate, monoglyceride, buffer, salt and pancreatin) using a two level D-optimal design with forty-four duplicate measurements and four centre points. The equilibrium solubility of a range of poorly soluble acidic (indomethacin, ibuprofen, phenytoin, valsartan, zafirlukast), basic (aprepitant, carvedilol, tadalafil, bromocriptine) and neutral (fenofibrate, felodipine, probucol, itraconazole) drugs was investigated. Results indicate that the DoE provides equilibrium solubility values that are comparable to literature results for other simulated fed gastrointestinal media systems or human intestinal fluid samples. For acidic drugs the influence of pH predominates but other significant factors related to oleate and bile salt or interactions between them are present. For basic drugs pH, oleate and bile salt have equal significance along with interactions between pH and oleate and lecithin and oleate. Neutral drugs show diverse effects of the media components particularly with regard to oleate, bile salt, pH and lecithin but the presence of monoglyceride, pancreatin and buffer have significant but smaller effects on solubility. There are fourteen significant interactions between factors mainly related to the surfactant components and pH, indicating that the solubility of neutral drugs in fed simulated media is complex. The results also indicate that the equilibrium solubility of each drug can exhibit individualistic behaviour associated with the drug's chemical structure, physicochemical properties and interaction with media components. The utility of DoE for fed simulated media has been demonstrated providing equilibrium solubility values comparable with similar in vitro systems whilst also providing greater information on the influence of media factors and their interactions. The determination of a drug's gastrointestinal solubility envelope provides useful limits that can potentially be applied to in silico modelling and in vivo experiments. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations: Theoretical manual, user`s guide, and related documentation (Version 7.0); Part 3

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

Wolery, T.J.

1992-09-14

EQ3NR is an aqueous solution speciation-solubility modeling code. It is part of the EQ3/6 software package for geochemical modeling. It computes the thermodynamic state of an aqueous solution by determining the distribution of chemical species, including simple ions, ion pairs, and complexes, using standard state thermodynamic data and various equations which describe the thermodynamic activity coefficients of these species. The input to the code describes the aqueous solution in terms of analytical data, including total (analytical) concentrations of dissolved components and such other parameters as the pH, pHCl, Eh, pe, and oxygen fugacity. The input may also include a desiredmore » electrical balancing adjustment and various constraints which impose equilibrium with special pure minerals, solid solution end-member components (of specified mole fractions), and gases (of specified fugacities). The code evaluates the degree of disequilibrium in terms of the saturation index (SI = 1og Q/K) and the thermodynamic affinity (A = {minus}2.303 RT log Q/K) for various reactions, such as mineral dissolution or oxidation-reduction in the aqueous solution itself. Individual values of Eh, pe, oxygen fugacity, and Ah (redox affinity) are computed for aqueous redox couples. Equilibrium fugacities are computed for gas species. The code is highly flexible in dealing with various parameters as either model inputs or outputs. The user can specify modification or substitution of equilibrium constants at run time by using options on the input file.« less

The effect of relative solubility on crystal purity

NASA Astrophysics Data System (ADS)

Givand, Jeffrey Christopher

This study establishes the relationship between impurity incorporation in a crystal by lattice substitution and the solubility of that impurity in solution. The model system studied was L-isoleucine crystals contaminated by the isomorphic impurity L-leucine. Upon crystallization from aqueous solution by cooling, leucine is concentrated in the isoleucine unit cell through lattice substitution mechanisms. Attempts to reduce the degree of leucine incorporation via adjustments of the rate at which supersaturation is generated yielded marginal success. This work demonstrates that incorporation of leucine in the crystal can be considerably suppressed by reducing the solubility of product relative to the solubility of impurity. Changes to the relative solubility of the impurity were accomplished by the addition of various electrolytes and organic co-solvents to the aqueous amino acid solutions. The solubilities of the two amino acids were measured and compared to their solubilities in pure water. Changes in the ratio of pure-component solubilities were directly related to changes in crystal purity. This thermodynamic quantity of relative solubility was shown to be a key factor in determining impurity uptake by lattice substitution. In addition to the experimental observations, a fundamental thermodynamic link between relative solubility and crystal purity is established through this research. First, the amino acid solubility data as a function of temperature in all solvent mixtures were accurately correlated using a thermodynamic model. The parameters from this model were then adapted to a novel solid-solution thermodynamic model to express the crystal purity in terms of equilibrium solution impurity concentration. After the determination of one system specific parameter, the model is able to predict the crystal purity in a new solvent in which the pure-component solubilities are known. The ability of an electrolyte or co-solvent to improve crystal purity from a given level can now be determined based on existing solubility and purity measurements and solubilities of the product and impurity in the new solvent mixture.

Thermodynamic equilibrium solubility measurements in simulated fluids by 96-well plate method in early drug discovery.

PubMed

Bharate, Sonali S; Vishwakarma, Ram A

2015-04-01

An early prediction of solubility in physiological media (PBS, SGF and SIF) is useful to predict qualitatively bioavailability and absorption of lead candidates. Despite of the availability of multiple solubility estimation methods, none of the reported method involves simplified fixed protocol for diverse set of compounds. Therefore, a simple and medium-throughput solubility estimation protocol is highly desirable during lead optimization stage. The present work introduces a rapid method for assessment of thermodynamic equilibrium solubility of compounds in aqueous media using 96-well microplate. The developed protocol is straightforward to set up and takes advantage of the sensitivity of UV spectroscopy. The compound, in stock solution in methanol, is introduced in microgram quantities into microplate wells followed by drying at an ambient temperature. Microplates were shaken upon addition of test media and the supernatant was analyzed by UV method. A plot of absorbance versus concentration of a sample provides saturation point, which is thermodynamic equilibrium solubility of a sample. The established protocol was validated using a large panel of commercially available drugs and with conventional miniaturized shake flask method (r(2)>0.84). Additionally, the statistically significant QSPR models were established using experimental solubility values of 52 compounds. Copyright © 2015 Elsevier Ltd. All rights reserved.

Characterization of two polymorphs of salmeterol xinafoate crystallized from supercritical fluids.

PubMed

Tong, H H; Shekunov, B Y; York, P; Chow, A H

2001-06-01

To characterize two polymorphs of salmeterol xinafoate (SX-I and SX-II) produced by supercritical fluid crystallization. SX-I and SX-II were crystallized as fine powders using Solution Enhanced Dispersion by Supercritical Fluids (SEDS). The two polymorphs and a reference micronized SX sample (MSX) were characterized using powder X-ray diffractometry (PXRD), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), aqueous solubility (and dissolution) determination at 5-40 degrees C, BET adsorption analysis, and inverse gas chromatography (IGC). Compared with SX-I, SX-II exhibited a lower enthalpy of fusion, a higher equilibrium solubility, a higher intrinsic dissolution rate, a lower enthalpy of solution (based on van't Hoff solubility plots), and a different FTIR spectrum (reflecting differences in intermolecular hydrogen bonding). Solubility ratio plot yielded a transition temperature (-99 degrees C) below the melting points of both polymorphs. MSX showed essentially the same crystal form as SX-I (confirmed by PXRD and FTIR), but a distinctly different thermal behaviour. Mild trituration of SX-I afforded a similar DSC profile to MSX while prolonged grinding of SX-I gave rise to an endotherm at -109 degrees C, corresponding to solid-solid transition of SX-I to SX-II. Surface analysis of MSX, SX-I, and SX-II by IGC revealed significant differences in surface free energy in terms of both dispersive (nonpolar) interactions and specific (polar) acid-base properties. The SEDS-processed SX-I and SX-II display high polymorphic purity and distinctly different physical and surface properties. The polymorphs are related enantiotropically with SX-I being the thermodynamically stable form at room temperature.

Comparison of the physicochemical properties of the N-(2-hydroxyethyl) pyrrolidine, diethylamine and sodium salt forms of diclofenac.

PubMed

O'Connor, K M; Corrigan, O I

2001-07-17

Non steroidal anti-inflammatory agents (NSAIDs) such as diclofenac have very low aqueous solubilities and consequently salt formation may be used to enhance solubility and dissolution rate. In this study, we examined the physicochemical properties of three diclofenac salts, diclofenac sodium (DNa), diclofenac N-(2-hydroxyethyl)pyrrolidine (DHEP) and diclofenac diethylamine (DDEA), and their different solid state forms to determine the influence of salt form on solubility, dissolution rate and membrane transport. The equilibrium solubility of DDEA at 25 degrees C was determined as 33 mM, lower than the solubilities of DHEP (273 mM) and DNa (66 mM) previously reported (Ledwidge and Corrigan, 1998). In addition to the dihydrate form of DHEP previously characterised, monohydrate forms of DHEP and DDEA were identified. Intrinsic dissolution rate studies were used to determine the solubility ratios of the hydrated and anhydrous forms. The monohydrate form of DHEP was found to be 1.8 times less soluble than the anhydrate, whereas DDEA anhydrate was approximately 1.7 times as soluble as the monohydrate form. On investigation of the pH-solubility profile (25 degrees C) of DDEA, appreciable supersaturation (76 mM) relative to the theoretical profile, was detected at the pH(max). This contrasts with values of >800 and 67 mM for DHEP and DNa, respectively. The transport of salt solutions through a porous membrane (Visking) was investigated. A linear relationship between concentration (mM) and rate of transport (mmol/h) was established for DNa and DHEP solutions. The mass transfer coefficient determined for DHEP was lower than that for the other two salts. Nevertheless, the maximum transport rate obtained for DHEP is almost six times higher than that obtained for DDEA.

Solubility of triuranyl diphosphate tetrahydrate (TDT) and Na autunite at 23 and 50 degrees C

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

Armstrong, Christopher R.; Felmy, Andrew R.; Clark, Sue B.

2010-11-01

In this report we present experimental solubility data for well-characterized triuranyl diphosphate tetrahydrate (TDT: (UO2)(3)(PO4)(2)center dot 4H(2)O) and Na autunite (Na[UO2PO4]center dot xH(2)O) at 23 and 50 degrees C in NaClO4-HClO4 solutions at pC(H+) = 2. Duplicate samples of TDT in 0.1, 0.5, 1.0, 2.0 and 5.0 in solutions were equilibrated at 23 and 50 degrees C. TDT solid was synthesized and characterized with ICP-OES, ATR-IR and powder XRD before and after solubility experiments. The pH of the suspensions were monitored throughout the experiments. Equilibrium was achieved from undersaturation with respect to TDT and oversaturation for Na autunite. Steady-state conditionsmore » were achieved in all cases within 82 d. TDT was unstable at ionic strengths above 0.1 m, where its complete conversion to Na autunite was observed. The ion-interaction model was used to interpret the experimental solubility data. The solubility product, log K-sp, for TDT was determined to be -49.7 and -51.3 at 23 and 50 degrees C respectively. log K for Na autunite was determined to be -24.4 (23 degrees C) and -24.1 +/- 0.2 (50 degrees C).« less

Thermodynamic model for solution behavior and solid-liquid equilibrium in Na-Al(III)-Fe(III)-Cr(III)-Cl-H2O system at 25°C

NASA Astrophysics Data System (ADS)

André, Laurent; Christov, Christomir; Lassin, Arnault; Azaroual, Mohamed

2018-03-01

The knowledge of the thermodynamic behavior of multicomponent aqueous electrolyte systems is of main interest in geo-, and environmental-sciences. The main objective of this study is the development of a high accuracy thermodynamic model for solution behavior, and highly soluble M(III)Cl3(s) (M= Al, Fe, Cr) minerals solubility in Na-Al(III)-Cr(III)-Fe(III)-Cl-H2O system at 25°C. Comprehensive thermodynamic models that accurately predict aluminium, chromium and iron aqueous chemistry and M(III) mineral solubilities as a function of pH, solution composition and concentration are critical for understanding many important geochemical and environmental processes involving these metals (e.g., mineral dissolution/alteration, rock formation, changes in rock permeability and fluid flow, soil formation, mass transport, toxic M(III) remediation). Such a model would also have many industrial applications (e.g., aluminium, chromium and iron production, and their corrosion, solve scaling problems in geothermal energy and oil production). Comparisons of solubility and activity calculations with the experimental data in binary and ternary systems indicate that model predictions are within the uncertainty of the data. Limitations of the model due to data insufficiencies are discussed. The solubility modeling approach, implemented to the Pitzer specific interaction equations is employed. The resulting parameterization was developed for the geochemical Pitzer formalism based PHREEQC database.

Solubility and Solubility Product Determination of a Sparingly Soluble Salt: A First-Level Laboratory Experiment

ERIC Educational Resources Information Center

Bonomo, Raffaele P.; Tabbi, Giovanni; Vagliasindi, Laura I.

2012-01-01

A simple experiment was devised to let students determine the solubility and solubility product, "K"[subscript sp], of calcium sulfate dihydrate in a first-level laboratory. The students experimentally work on an intriguing equilibrium law: the constancy of the product of the ion concentrations of a sparingly soluble salt. The determination of…

Aqueous solubility calculation for petroleum mixtures in soil using comprehensive two-dimensional gas chromatography analysis data.

PubMed

Mao, Debin; Lookman, Richard; Van De Weghe, Hendrik; Vanermen, Guido; De Brucker, Nicole; Diels, Ludo

2009-04-03

An assessment of aqueous solubility (leaching potential) of soil contaminations with petroleum hydrocarbons (TPH) is important in the context of the evaluation of (migration) risks and soil/groundwater remediation. Field measurements using monitoring wells often overestimate real TPH concentrations in case of presence of pure oil in the screened interval of the well. This paper presents a method to calculate TPH equilibrium concentrations in groundwater using soil analysis by high-performance liquid chromatography followed by comprehensive two-dimensional gas chromatography (HPLC-GCXGC). The oil in the soil sample is divided into 79 defined hydrocarbon fractions on two GCXGC color plots. To each of these fractions a representative water solubility is assigned. Overall equilibrium water solubility of the non-aqueous phase liquid (NAPL) present in the sample and the water phase's chemical composition (in terms of the 79 fractions defined) are then calculated using Raoult's law. The calculation method was validated using soil spiked with 13 different TPH mixtures and 1 field-contaminated soil. Measured water solubilities using a column recirculation equilibration experiment agreed well to calculated equilibrium concentrations and water phase TPH composition.

pH-Dependent Liquid-Liquid Phase Separation of Highly Supersaturated Solutions of Weakly Basic Drugs.

PubMed

Indulkar, Anura S; Box, Karl J; Taylor, Robert; Ruiz, Rebeca; Taylor, Lynne S

2015-07-06

Supersaturated solutions of poorly aqueous soluble drugs can be formed both in vivo and in vitro. For example, increases in pH during gastrointestinal transit can decrease the aqueous solubility of weakly basic drugs resulting in supersaturation, in particular when exiting the acidic stomach environment. Recently, it has been observed that highly supersaturated solutions of drugs with low aqueous solubility can undergo liquid-liquid phase separation (LLPS) prior to crystallization, forming a turbid solution such that the concentration of the drug in the continuous solution phase corresponds to the amorphous solubility while the colloidal phase is composed of a disordered drug-rich phase. Although it is well established that the equilibrium solubility of crystalline weakly basic drugs follows the Henderson-Hasselbalch relationship, the impact of pH on the LLPS phenomenon or the amorphous solubility has not been explored. In this work, the LLPS concentration of three weakly basic compounds-clotrimazole, nicardipine, and atazanavir-was determined as a function of pH using three different methods and was compared to the predicted amorphous solubility, which was calculated from the pH-dependent crystalline solubility and by estimating the free energy difference between the amorphous and crystalline forms. It was observed that, similar to crystalline solubility, the experimental amorphous solubility at any pH follows the Henderson-Hasselbalch relation and can be predicted if the amorphous solubility of the free base is known. Excellent agreement between the LLPS concentration and the predicted amorphous solubility was observed. Dissolution studies of amorphous drugs showed that the solution concentration can reach the corresponding LLPS concentration at that pH. Solid-state analysis of the precipitated material confirmed the amorphous nature. This work provides insight into the pH-dependent precipitation behavior of poorly water-soluble compounds and provides a fundamental basis with which to understand the performance of supersaturating dosage forms.

Dissolution of aragonite-strontianite solid solutions in nonstoichiometric Sr (HCO3)2-Ca (HCO3)2-CO2-H2O solutions

USGS Publications Warehouse

Plummer, Niel; Busenberg, E.; Glynn, P.D.; Blum, A.E.

1992-01-01

Synthetic strontianite-aragonite solid-solution minerals were dissolved in CO2-saturated non-stoichiometric solutions of Sr(HCO3)2 and Ca(HCO3)2 at 25??C. The results show that none of the dissolution reactions reach thermodynamic equilibrium. Congruent dissolution in Ca(HCO3)2 solutions either attains or closely approaches stoichiometric saturation with respect to the dissolving solid. In Sr(HCO3)2 solutions the reactions usually become incongruent, precipitating a Sr-rich phase before reaching stoichiometric saturation. Dissolution of mechanical mixtures of solids approaches stoichiometric saturation with respect to the least stable solid in the mixture. Surface uptake from subsaturated bulk solutions was observed in the initial minutes of dissolution. This surficial phase is 0-10 atomic layers thick in Sr(HCO3)2 solutions and 0-4 layers thick in Ca(HCO3)2 solutions, and subsequently dissolves and/or recrystallizes, usually within 6 min of reaction. The initial transient surface precipitation (recrystallization) process is followed by congruent dissolution of the original solid which proceeds to stoichiometric saturation, or until the precipitation of a more stable Sr-rich solid. The compositions of secondary precipitates do not correspond to thermodynamic equilibrium or stoichiometric saturation states. X-ray photoelectron spectroscopy (XPS) measurements indicate the formation of solid solutions on surfaces of aragonite and strontianite single crystals immersed in Sr(HCO3)2 and Ca(HCO3)2 solutions, respectively. In Sr(HCO3)2 solutions, the XPS signal from the outer ~ 60 A?? on aragonite indicates a composition of 16 mol% SrCO3 after only 2 min of contact, and 14-18 mol% SrCO3 after 3 weeks of contact. The strontianite surface averages approximately 22 mol% CaCO3 after 2 min of contact with Ca(HCO3)2 solution, and is 34-39 mol% CaCO3 after 3 weeks of contact. XPS analysis suggests the surface composition is zoned with somewhat greater enrichment in the outer ~25 A?? (as much as 26 mol% SrCO3 on aragonite and 44 mol% CaCO3 on strontianite). The results indicate rapid formation of a solid-solution surface phase from subsaturated aqueous solutions. The surface phase continually adjusts in composition in response to changes in composition of the bulk fluid as net dissolution proceeds. Dissolution rates of the endmembers are greatly reduced in nonstoichiometric solutions relative to dissolution rates observed in stoichiometric solutions. All solids dissolve more slowly in solutions spiked with the least soluble component ((Sr(HCO3)2)) than in solutions spiked with the more soluble component (Ca(HCO3)2), an effect that becomes increasingly significant as stoichiometric saturation is approached. It is proposed that the formation of a non-stoichiometric surface reactive zone significantly decreases dissolution rates. ?? 1992.

Physicochemical characterization of tacrolimus-loaded solid dispersion with sodium carboxylmethyl cellulose and sodium lauryl sulfate.

PubMed

Park, Young-Joon; Ryu, Dong-Sung; Li, Dong Xun; Quan, Qi Zhe; Oh, Dong Hoon; Kim, Jong Oh; Seo, Youn Gee; Lee, Young-Im; Yong, Chul Soon; Woo, Jong Soo; Choi, Han-Gon

2009-06-01

To develop a novel tacrolimus-loaded solid dispersion with improved solubility, various solid dispersions were prepared with various ratios of water, sodium lauryl sulfate, citric acid and carboxylmethylcellulose-Na using spray drying technique. The physicochemical properties of solid dispersions were investigated using scanning electron microscopy, differential scanning calorimetery and powder X-ray diffraction. Furthermore, their solubility and dissolution were evaluated compared to drug powder. The solid dispersion at the tacrolimus/CMC-Na/sodium lauryl sulfate/citric acid ratio of 3/24/3/0.2 significantly improved the drug solubility and dissolution compared to powder. The scanning electron microscopy result suggested that carriers might be attached to the surface of drug in this solid dispersion. Unlike traditional solid dispersion systems, the crystal form of drug in this solid dispersion could not be converted to amorphous form, which was confirmed by the analysis of DSC and powder X-ray diffraction. Thus, the solid dispersion system with water, sodium lauryl sulfate, citric acid and CMC-Na should be a potential candidate for delivering a poorly water-soluble tacrolimus with enhanced solubility and no convertible crystalline.

Significance of dissolved methane in effluents of anaerobically ...

EPA Pesticide Factsheets

The need for energy efficient Domestic Wastewater (DWW) treatment is increasing annually with population growth and expanding global energy demand. Anaerobic treatment of low strength DWW produces methane which can be used to as an energy product. Temperature sensitivity, low removal efficiencies (Chemical Oxygen Demand (COD), Suspended Solids (SS), and Nutrients), alkalinity demand, and potential greenhouse gas (GHG) emissions have limited its application to warmer climates. Although well designed anaerobic Membrane Bioreactors (AnMBRs) are able to effectively treat DWW at psychrophilic temperatures (10–30 °C), lower temperatures increase methane solubility leading to increased energy losses in the form of dissolved methane in the effluent. Estimates of dissolved methane losses are typically based on concentrations calculated using Henry's Law but advection limitations can lead to supersaturation of methane between 1.34 and 6.9 times equilibrium concentrations and 11–100% of generated methane being lost in the effluent. In well mixed systems such as AnMBRs which use biogas sparging to control membrane fouling, actual concentrations approach equilibrium values. Non-porous membranes have been used to recover up to 92.6% of dissolved methane and well suited for degassing effluents of Upflow Anaerobic Sludge Blanket (UASB) reactors which have considerable solids and organic contents and can cause pore wetting and clogging in microporous membrane modules. Micro

A partition-limited model for the plant uptake of organic contaminants from soil and water

USGS Publications Warehouse

Chiou, C.T.; Sheng, G.; Manes, M.

2001-01-01

In dealing with the passive transport of organic contaminants from soils to plants (including crops), a partition-limited model is proposed in which (i) the maximum (equilibrium) concentration of a contaminant in any location in the plant is determined by partition equilibrium with its concentration in the soil interstitial water, which in turn is determined essentially by the concentration in the soil organic matter (SOM) and (ii) the extent of approach to partition equilibrium, as measured by the ratio of the contaminant concentrations in plant water and soil interstitial water, ??pt (??? 1), depends on the transport rate of the contaminant in soil water into the plant and the volume of soil water solution that is required for the plant contaminant level to reach equilibrium with the external soil-water phase. Through reasonable estimates of plant organic-water compositions and of contaminant partition coefficients with various plant components, the model accounts for calculated values of ??pt in several published crop-contamination studies, including near-equilibrium values (i.e., ??pt ??? 1) for relatively water-soluble contaminants and lower values for much less soluble contaminants; the differences are attributed to the much higher partition coefficients of the less soluble compounds between plant lipids and plant water, which necessitates much larger volumes of the plant water transport for achieving the equilibrium capacities. The model analysis indicates that for plants with high water contents the plant-water phase acts as the major reservoir for highly water-soluble contaminants. By contrast, the lipid in a plant, even at small amounts, is usually the major reservoir for highly water-insoluble contaminants.

Development of a solid self-microemulsifying drug delivery system (SMEDDS) for solubility enhancement of naproxen.

PubMed

Čerpnjak, Katja; Zvonar, Alenka; Vrečer, Franc; Gašperlin, Mirjana

2015-01-01

Comparative evaluation of liquid and solid self-microemulsifying drug delivery systems (SMEDDS) as promising approaches for solubility enhancement. The aim of this work was to develop, characterize, and evaluate a solid SMEDDS prepared via spray-drying of a liquid SMEDDS based on Gelucire® 44/14 to improve the solubility and dissolution rate of naproxen. Various oils and co-surfactants in combination with Gelucire® 44/14 were evaluated during excipient selection study, solubility testing, and construction of (pseudo)ternary diagrams. The selected system was further evaluated for naproxen solubility, self-microemulsification ability, and in vitro dissolution of naproxen. In addition, its transformation into a solid SMEDDS by spray-drying using maltodextrin as a solid carrier was performed. Scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) were used to evaluate the physical characteristics of the solid SMEDDS obtained. The selected formulation of SMEDDS was comprised of Miglyol 812®, Peceol™, Gelucire® 44/14, and Solutol® HS 15. The liquid and solid SMEDDS formed a microemulsion after dilution with comparable average droplet size and exhibited uniform droplet size distribution. In the solid SMEDDS, liquid SMEDDS was adsorbed onto the surface of maltodextrin and formed smooth granular particles with the encapsulated drug predominantly in a dissolved state and partially in an amorphous state. Overall, incorporation of naproxen in SMEDDS, either liquid or solid, resulted in improved solubility and dissolution rate compared to pure naproxen. This study indicates that a liquid and solid SMEDDS is a strategy for solubility enhancement in the future development of orally delivered dosage forms.

Chloride removal from recycled cooling water using ultra-high lime with aluminum process.

PubMed

Abdel-Wahab, Ahmed; Batchelor, Bill

2002-01-01

Chloride is a deleterious ionic species in cooling water systems because it promotes corrosion, and most of the scale and corrosion inhibitors are sensitive to chloride concentration in the water. Chloride can be removed from cooling water by precipitation as calcium chloroaluminate [Ca4Al2Cl2(OH)12]. A set of equilibrium experiments and one kinetic experiment were conducted to evaluate chloride removal using the ultra-high lime with aluminum (UHLA) process and to characterize the equilibrium conditions of calcium chloroaluminate precipitation. A total of 48 batch-equilibrium experiments were conducted on a 30 mM NaCl solution over a range of values for lime dose (0 to 200 mM) and sodium aluminate dose (0 to 100 mM). Experimental results showed that the UHLA process can remove chloride and that the formation of a calcium chloroaluminate solid phase is a reasonable mechanism that is able to adequately describe experimental results. An average value of the ion activity product of 10(-94.75) was obtained and can be used as an estimate of the solubility product for Ca4Al2Cl2(OH)12.

Solubility Enhancement of a Poorly Water Soluble Drug by Forming Solid Dispersions using Mechanochemical Activation

PubMed Central

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 weight ratio of 1:1 of indomethacin and lactose were ground using a high speed vibrating ball mill. Particle size was determined by electron microscopy, the reduction of crystallinity was determined by calorimetry and transmission electron microscopy, infrared spectroscopy was used to find evidence of any interactions between the drug and the carrier and the determination of apparent solubility allowed for the corroboration of changes in solubility. Before grinding, scanning electron microscopy showed the drug and lactose to have an average particle size of around 50 and 30 μm, respectively. After high speed grinding, indomethacin and the mixture had a reduced average particle size of around 5 and 2 μm, respectively, showing a morphological change. The ground mixture produced a solid dispersion that had a loss of crystallinity that reached 81% after 30 min of grinding while the drug solubility of indomethacin within the solid dispersion increased by 2.76 fold as compared to the pure drug. Drug activation due to hydrogen bonds between the carboxylic group of the drug and the hydroxyl group of lactose as well as the decrease in crystallinity of the solid dispersion and the reduction of the particle size led to a better water solubility of indomethacin. PMID:23798775

Atmospheric Pressure Non-Equilibrium Plasma as a Green Tool to Crosslink Gelatin Nanofibers

NASA Astrophysics Data System (ADS)

Liguori, Anna; Bigi, Adriana; Colombo, Vittorio; Focarete, Maria Letizia; Gherardi, Matteo; Gualandi, Chiara; Oleari, Maria Chiara; Panzavolta, Silvia

2016-12-01

Electrospun gelatin nanofibers attract great interest as a natural biomaterial for cartilage and tendon repair despite their high solubility in aqueous solution, which makes them also difficult to crosslink by means of chemical agents. In this work, we explore the efficiency of non-equilibrium atmospheric pressure plasma in stabilizing gelatin nanofibers. We demonstrate that plasma represents an innovative, easy and environmentally friendly approach to successfully crosslink gelatin electrospun mats directly in the solid state. Plasma treated gelatin mats display increased structural stability and excellent retention of fibrous morphology after immersion in aqueous solution. This method can be successfully applied to induce crosslinking both in pure gelatin and genipin-containing gelatin electrospun nanofibers, the latter requiring an even shorter plasma exposure time. A complete characterization of the crosslinked nanofibres, including mechanical properties, morphological observations, stability in physiological solution and structural modifications, has been carried out in order to get insights on the occurring reactions triggered by plasma.

Equilibrium distribution of rare earth elements between molten KCl-LiCl eutectic salt and liquid cadmium

NASA Astrophysics Data System (ADS)

Sakata, Masahiro; Kurata, Masaki; Hijikata, Takatoshi; Inoue, Tadashi

1991-11-01

Distribution experiments for several rare earth elements (La, Ce, Pr, Nd and Y) between molten KCl-LiCl eutectic salt and liquid Cd were carried out at 450, 500 and 600°C. The material balance of rare earth elements after reaching the equilibrium and their distribution and chemical states in a Cd sample frozen after the experiment were examined. The results suggested the formation of solid intermetallic compounds at the lower concentrations of rare earth metals dissolved in liquid Cd than those solubilities measured in the binary alloy system. The distribution coefficients of rare earth elements between two phases (mole fraction in the Cd phase divided by mole fraction in the salt phase) were determined at each temperature. These distribution coefficients were explained satisfactorily by using the activity coefficients of chlorides and metals in salt and Cd. Both the activity coefficients of metal and chloride caused a much smaller distribution coefficient of Y relative to those of other elements.

Enhancement of solubility and dissolution of coenzyme Q10 using solid dispersion formulation.

PubMed

Nepal, Pushp R; Han, Hyo-Kyung; Choi, Hoo-Kyun

2010-01-04

This study aimed to develop a stable solid dispersion of Coenzyme Q(10) (CoQ(10)) with high aqueous solubility and dissolution rate. Among various carriers screened, poloxamer 407 was most effective to form a superior solid dispersion of CoQ(10) having significantly enhanced solubility. Particularly, solid dispersion of CoQ(10) with poloxamer 407 in the weight ratio of 1:5 prepared by melting method enhanced the solubility of CoQ(10) to the greatest extent. However, it exhibited poor stability and hence Aerosil 200 (colloidal silicon dioxide) was incorporated into the solid dispersion as an adsorbent to inhibit the recrystallization process. The solid dispersion of CoQ(10), poloxamer 407 and Aerosil 200 in the weight ratio of 1:5:6 exhibited improved stability with no significant change in solubility during the 1-month stability test. Moreover, the solid dispersion formulation containing Aerosil 200 significantly enhanced the extent of drug release (approx. 75% release) as well as the dissolution rate of CoQ(10). In conclusion, the present study has developed the stable solid dispersion formulation of CoQ(10) with poloxamer 407 and Aerosil 200 for the enhanced solubility and dissolution of CoQ(10), which could also offer some additional advantages including ease of preparation, good flowability and cost-effectiveness.

Chemical Equilibrium of Aluminate in Hanford Tank Waste Originating from Tanks 241-AN-105 and 241-AP-108

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

McCoskey, Jacob K.; Cooke, Gary A.; Herting, Daniel L.

The purposes of the study described in this document follow; Determine or estimate the thermodynamic equilibrium of gibbsite in contact with two real tank waste supernatant liquids through both dissolution of gibbsite (bottom-up approach) and precipitation of aluminum-bearing solids (top-down approach); determine or estimate the thermodynamic equilibrium of a mixture of gibbsite and real tank waste saltcake in contact with real tank waste supernatant liquid through both dissolution of gibbsite and precipitation of aluminum-bearing solids; and characterize the solids present after equilibrium and precipitation of aluminum-bearing solids.

Molecular implications of drug-polymer solubility in understanding the destabilization of solid dispersions by milling.

PubMed

Yang, Ziyi; Nollenberger, Kathrin; Albers, Jessica; Qi, Sheng

2014-07-07

The solubility of drugs in polymer matrixes has been recognized as one of the key factors governing the physical stability of solid dispersions. This study has explored the implications of drug solubility on the destabilization that occurs on milling, which is often used as an additional process for hot melt extruded (HME) solid dispersions. The theoretical drug solubility in the polymer was first predicted using various theoretical and experimental approaches. The destabilization effects of high-energy mechanical milling on the solid dispersions with drug loadings below and above the predicted solubility were then investigated using a range of thermal, microscopic, and spectroscopic techniques. Four model drug-polymer combinations were studied. The HME formulations with drug loading below the predicted solid solubility (undersaturated and true molecular dispersion) showed good stability against milling. In contrast, milling destabilized supersaturated HME dispersions via increasing molecular mobility and creating phase-separated, amorphous, drug-rich domains. However, these additional amorphous drug-rich domains created by milling show good stability under ambient conditions, though crystallization can be accelerated by additional heating. These results highlighted that the processing method used to prepare the solid dispersions may play a role in facilitating the stabilization of amorphous drug in supersaturated solid dispersions. The degree of supersaturation of the drug in the polymer showed significant impact on the destabilization behavior of milling on solid dispersions. An improved understanding of the destabilization behavior of solid dispersions upon milling can provide new insights into the processing related apparent solubility of drugs in polymers.

Preparation and physicochemical characterization of acyclovir cocrystals with improved dissolution properties.

PubMed

Bruni, Giovanna; Maietta, Mariarosa; Maggi, Lauretta; Mustarelli, Piercarlo; Ferrara, Chiara; Berbenni, Vittorio; Milanese, Chiara; Girella, Alessandro; Marini, Amedeo

2013-11-01

Acyclovir is a well-known antiviral agent. It can be administered in very high doses (from 200 to 1000 mg even three-four times daily). It has absorption problems mainly due to its poor solubility in water (about 0.2 g/100 mL at 25°C) and its oral bioavailability is approximately 15%-20% with a half-life of about 3 h. To improve acyclovir solubility and/or its dissolution properties, two cocrystals of this drug were successfully produced with glutaric acid (AGA1:1) and fumaric acid (AFA1:1) as conformers, using a cogrinding method. Their effective formation was investigated by a broad range of techniques: thermal analysis, Fourier transform infrared spectroscopy, X-ray powder diffraction, solid state nuclear magnetic resonance, and scanning electron microscopy coupled with energy dispersive X-ray spectrometry. The water solubility of the AGA1:1 cocrystal was not improved in comparison to acyclovir, while AFA1:1 showed a slight increased solubility at equilibrium. The main difference was detected in terms of intrinsic dissolution rates (IDR). The IDR of the new phases were much faster compared with acyclovir, particularly at neutral pH. AFA1:1 showed the most rapid dissolution behavior in water; within 10 min, the drug was released completely, while just 60% of acyclovir was dissolved in 1 h. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

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

Mehta, Vrajesh; Maillot, Fabien; Wang, Zheming

Uranyl phosphate solids are often found with uranium ores, and their low solubility makes them promising target phases for in situ remediation of uranium-contaminated subsurface environments. The products and solubility of uranium(VI) precipitated with phosphate can be affected by the pH, dissolved inorganic carbon (DIC) concentration, and co-solute composition (e.g. Na+/Ca2+) of the groundwater. Batch experiments were performed to study the effect of these parameters on the products and extent of uranium precipitation induced by phosphate addition. In the absence of co-solute cations, chernikovite [H3O(UO2)(PO4)•3H2O] precipitated despite uranyl orthophosphate [(UO2)3(PO4)2•4H2O] being thermodynamically more favorable under certain conditions. As determined usingmore » X-ray diffraction, electron microscopy, and laser induced fluorescence spectroscopy, the presence of Na+ or Ca2+ as a co-solute led to the precipitation of sodium autunite ([Na2(UO2)2(PO4)2] and autunite [Ca(UO2)2(PO4)2]), which are structurally similar to chernikovite. In the presence of sodium, the dissolved U(VI) concentrations were generally in agreement with equilibrium predictions of sodium autunite solubility. However, in the calcium-containing systems, the observed concentrations were below the predicted solubility of autunite, suggesting the possibility of uranium adsorption to or incorporation in a calcium phosphate precipitate in addition to the precipitation of autunite.« less

Dissolution-modulating mechanism of pH modifiers in solid dispersion containing weakly acidic or basic drugs with poor water solubility.

PubMed

Tran, Phuong Ha-Lien; Tran, Thao Truong-Dinh; Lee, Kyoung-Ho; Kim, Dong-Jin; Lee, Beom-Jin

2010-05-01

Although the solid dispersion method has been known to increase the dissolution rate of poorly water-soluble drugs by dispersing them in hydrophilic carriers, one obstacle of the solid dispersion method is its limited solubilization capacity, especially for pH-dependent soluble drugs. pH-modified solid dispersion, in which pH modifiers are incorporated, may be a useful method for increasing the dissolution rate of weakly acidic or basic drugs. Sufficient research, including the most recent reports, was undertaken in this review. How could the inclusion of the pH the pH modifiers in the solid dispersion system change drug structural behaviors, molecular interactions, microenvironmental pH, and/or release rate of pH modifiers, relating with the enhanced dissolution of weakly acidic or weakly basic drugs with poor water solubility? These questions have been investigated to determine the dissolution-modulating mechanism of pH modifiers in solid dispersion containing weakly acidic or basic drugs. It is believed that step-by-step mechanistic approaches could provide the ultimate solution for solubilizing several poorly water-soluble drugs with pH-dependent solubility from a solid dispersion system, as well as provide ideas for developing future dosage systems.

Solubility Control of Technetium Release from Saltstone by Tc02•xH20

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

Cantrell, Kirk J.; Williams, Benjamin D.

2013-11-12

Saltstone leaching experiments were conducted using a modified single-pass flow-through method under anoxic conditions. The analytical results of leachates collected from these experiments were evaluated using thermodynamic modeling to determine if the data were consistent with potential solubility controlling phases. The results demonstrate that technetium concentrations in water in contact with Saltstone under anoxic conditions is controlled by the solubility of TcO2•xH2O (likely TcO2•1.6H2O). In our system equilibrium solubility appears to have been reached within two weeks at a concentration of approximately 1.5 x 10-6 M. This concentration is likely to vary as the composition of Saltstone pore fluid evolvesmore » over time. As the pH goes from the initial high values (~12.5-13) to lower values, the solubility of technetium will decrease significantly. The thermodynamic data used to determine the solubility of TcO2•1.6H2O were taken from the tabulation of critically selected thermodynamic data determined by the Nuclear Energy Agency. Solid phase characterization to demonstrate the presence of TcO2•xH2O was not possible due to the low concentrations of technetium in our samples. Previous solid phase characterization studies with cementitious waste forms that were very similar to our Saltstone samples as well as reaction products derived from reductive immobilization of TcO4- by amorphous FeS clearly indicate the presence of TcO2 with varying degrees of hydration. Although, the presence of TcSx or other reduced technetium sulfide phases in our samples cannot be ruled out, release of technetium from Saltstone will be controlled by TcO2•1.6H2O because of its higher solubility. Our results clearly demonstrate that the release mechanism of technetium from Saltstone under reducing conditions is solubility controlled by TcO2•xH2O (likely TcO2•1.6H2O); however, distribution coefficients (Kds), that describe sorption and not solubility, were calculated for comparison with past literature values. After 84 days of reaction under anoxic conditions, the average Kd value for technetium was determined to be 610 mL/g. This value is similar to a value determined previously for a similar saltstone sample under reducing conditions at 56 days (712 ± 81 mL/g).« less

Comment on “Hydromagnesite solubility product and growth kinetics in aqueous solution from 25 to 75 °C” by Gautier, Q., Benezeth, P., Mavromatis, V., and Schott, J

DOE PAGES

Xiong, Yongliang

2016-04-16

Here, Gautier et al. (2014) recently published their determination of hydromagnesite solubility constant and hydromagnesite growth kinetics. Although their raw data appear to be of high quality, there is an oversight in their calculations of the hydromagnesite solubility constants given the solution compositions in their experiments. The oversight lies in the fact that they did not consider the constraint of simultaneous equilibrium with brucite. This oversight causes their newly calculated equilibrium constant for hydromagnesite to be discordant with the literature values (Königsberger et al., 1992 and Xiong, 2011).

Solubilities of crystalline drugs in polymers: an improved analytical method and comparison of solubilities of indomethacin and nifedipine in PVP, PVP/VA, and PVAc.

PubMed

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.

Enhancement of solubility and bioavailability of ambrisentan by solid dispersion using Daucus carota as a drug carrier: formulation, characterization, in vitro, and in vivo study.

PubMed

Deshmane, Subhash; Deshmane, Snehal; Shelke, Santosh; Biyani, Kailash

2018-06-01

Ambrisentan is an US FDA approved drug, it is the second oral endothelin A receptor antagonist known for the treatment of pulmonary arterial hypertension, but its oral administration is limited due to its poor water solubility. Hence, the objective of the investigation was focused on enhancement of solubility and bioavailability of ambrisentan by solid dispersion technique using natural Daucus carota extract as drug carrier. Drug carrier was evaluated for solubility, swelling index, viscosity, angle of repose, hydration capacity, and acute toxicity test (LD 50 ). Ambrisentan was studied for the saturation solubility, phase solubility, and Gibbs free energy change. Compatibility of drug and the natural carrier was confirmed by DSC, FTIR, and XRD. Solid dispersions were evaluated for drug content, solubility, morphology, in vitro, and in vivo study. Screening of the natural carrier showed the desirable properties like water solubility, less swelling index, less viscosity, and acute toxicity study revealed no any clinical symptoms of toxicity. Drug and carrier interaction study confirmed the compatibility to consider its use in the formulation. Formed particles were found to be spherical with smooth surface. In vitro studies revealed higher drug release from the solid dispersion than that of the physical mixture. Bioavailability study confirms the increased absorption and bioavailability by oral administration of solid dispersion. Hence, it can be concluded that the natural Daucus carota extract can be the better alternative source for the preparation of solid dispersion and/or other dosage forms for improving solubility and bioavailability.

Classification of solid dispersions: correlation to (i) stability and solubility (ii) preparation and characterization techniques.

PubMed

Meng, Fan; Gala, Urvi; Chauhan, Harsh

2015-01-01

Solid dispersion has been a topic of interest in recent years for its potential in improving oral bioavailability, especially for poorly water soluble drugs where dissolution could be the rate-limiting step of oral absorption. Understanding the physical state of the drug and polymers in solid dispersions is essential as it influences both the stability and solubility of these systems. This review emphasizes on the classification of solid dispersions based on the physical states of drug and polymer. Based on this classification, stability aspects such as crystallization tendency, glass transition temperature (Tg), drug polymer miscibility, molecular mobility, etc. and solubility aspects have been discussed. In addition, preparation and characterization methods for binary solid dispersions based on the classification have also been discussed.

AW-101 entrained solids - Solubility versus temperature

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

GJ Lumetta; RC Lettau; GF Piepel

This report describes the results of a test conducted by Battelle to assess the solubility of the solids entrained in the diluted AW-101 low-activity waste (LAW) sample. BNFL requested Battelle to dilute the AW-1-1 sample using de-ionized water to mimic expected plant operating conditions. BNFL further requested Battelle to assess the solubility of the solids present in the diluted AW-101 sample versus temperature conditions of 30, 40, and 50 C. BNFL requested these tests to assess the composition of the LAW supernatant and solids versus expected plant-operating conditions. The work was conducted according to test plan BNFL-TP-29953-7, Rev. 0, Determinationmore » of the Solubility of LAW Entrained Solids. The test went according to plan, with no deviations from the test plan.« less

Development of novel sibutramine base-loaded solid dispersion with gelatin and HPMC: physicochemical characterization and pharmacokinetics in beagle dogs.

PubMed

Lim, Hyun-Tae; Balakrishnan, Prabagar; Oh, Dong Hoon; Joe, Kwan Hyung; Kim, Young Ran; Hwang, Doo Hyung; Lee, Yong-Bok; Yong, Chul Soon; Choi, Han-Gon

2010-09-15

To develop a novel sibutramine base-loaded solid dispersion with enhanced solubility and bioavailability, various solid dispersions were prepared using a spray drying technique with hydrophilic polymers such as gelatin, HPMC and citric acid. Their solubility, thermal characteristics and crystallinity were investigated. The dissolution and pharmacokinetics of the sibutramine base-loaded solid dispersion were then compared with a sibutramine hydrochloride monohydrate-loaded commercial product (Reductil). The solid dispersions prepared with gelatin gave higher drug solubility than those prepared without gelatin, irrespective of the amount of polymer. The sibutramine base-loaded solid dispersions containing hydrophilic polymer and citric acid showed higher drug solubility compared to sibutramine base and sibutramine hydrochloride monohydrate. Among the formulations tested, the solid dispersion composed of sibutramine base/gelatin/HPMC/citric acid at the weight ratio of 1/0.8/0.2/0.5 gave the highest solubility of 5.03+/-0.24 mg/ml. Our DSC and powder X-ray diffraction results showed that the drug was present in an altered amorphous form in this solid dispersion. The difference factor (f(1)) values between solid dispersion and commercial product were 2.82, 6.65 and 6.31 at pH 1.2, 4.0 and 6.8, respectively. Furthermore, they had the similarity factor (f(2)) value of 65.68, 53.43 and 58.97 at pH 1.2, 4.0 and 6.8, respectively. Our results suggested that the solid dispersion and commercial product produced a similar correlation of dissolution profiles at all pH ranges. The AUC, C(max) and T(max) of the parent drug and metabolite I and II from the solid dispersion were not significantly different from those of the commercial product, suggesting that the solid dispersion might be bioequivalent to the commercial product in beagle dogs. Thus, the sibutramine base-loaded solid dispersion prepared with gelatin, HPMC and citric acid is a promising candidate for improving the solubility and bioavailability of the poorly water-soluble sibutramine base. Crown Copyright 2010. Published by Elsevier B.V. All rights reserved.

A Lab Experiment to Introduce Gas/Liquid Solubility

ERIC Educational Resources Information Center

Fonsecaa, I. M. A.; Almeida, J. P. B.; Fachada, H. C.

2008-01-01

A simplified version of a volumetric apparatus for gas/liquid solubility measurements is proposed. The procedure familiarizes undergraduate students with the experimental study of the solubility of a gas in a liquid and contributes to the understanding of this important phase equilibrium concept. The experimental results report the determination…

Enhanced solubility and bioavailability of sibutramine base by solid dispersion system with aqueous medium.

PubMed

Li, Dong Xun; Jang, Ki-Young; Kang, Wonku; Bae, Kyoungjin; Lee, Mann Hyung; Oh, Yu-Kyoung; Jee, Jun-Pil; Park, Young-Joon; Oh, Dong Hoon; Seo, Youn Gee; Kim, Young Ran; Kim, Jong Oh; Woo, Jong Soo; Yong, Chul Soon; Choi, Han-Gon

2010-01-01

To develop a novel sibutramine base-loaded solid dispersion with improved solubility bioavailability, various solid dispersions were prepared with water, hydroxypropylmethyl cellulose (HPMC), poloxamer and citric acid using spray-drying technique. The effect of HPMC, poloxamer and citric acid on the aqueous solubility of sibutramine was investigated. The physicochemical properties of solid dispersion were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and X-ray powder diffraction. The dissolution and pharmacokinetics in rats of solid dispersion were evaluated compared to the sibutramine hydrochloride monohydrate-loaded commercial product (Reductil). The sibutramine base-loaded solid dispersion gave two type forms. Like conventional solid dispersion system, one type appeared as a spherical shape with smooth surface, as the carriers and drug with relatively low melting point were soluble in water and formed it. The other appeared as an irregular form with relatively rough surface. Unlike conventional solid dispersion system, this type changed no crystalline form of drug. Our results suggested that this type was formed by attaching hydrophilic carriers to the surface of drug without crystal change, resulting from changing the hydrophobic drug to hydrophilic form. The sibutramine-loaded solid dispersion at the weight ratio of sibutramine base/HPMC/poloxamer/citric acid of 5/3/3/0.2 gave the maximum drug solubility of about 3 mg/ml. Furthermore, it showed the similar plasma concentration, area under the curve (AUC) and C(max) of parent drug, metabolite I and II to the commercial product, indicating that it might give the similar drug efficacy compared to the sibutramine hydrochloride monohydrate-loaded commercial product in rats. Thus, this solid dispersion system would be useful to deliver poorly water-soluble sibutramine base with enhanced bioavailability.

Thermodynamic Investigation of the Effect of Interface Curvature on the Solid-Liquid Equilibrium and Eutectic Point of Binary Mixtures.

PubMed

Liu, Fanghui; Zargarzadeh, Leila; Chung, Hyun-Joong; Elliott, Janet A W

2017-10-12

Thermodynamic phase behavior is affected by curved interfaces in micro- and nanoscale systems. For example, capillary freezing point depression is associated with the pressure difference between the solid and liquid phases caused by interface curvature. In this study, the thermal, mechanical, and chemical equilibrium conditions are derived for binary solid-liquid equilibrium with a curved solid-liquid interface due to confinement in a capillary. This derivation shows the equivalence of the most general forms of the Gibbs-Thomson and Ostwald-Freundlich equations. As an example, the effect of curvature on solid-liquid equilibrium is explained quantitatively for the water/glycerol system. Considering the effect of a curved solid-liquid interface, a complete solid-liquid phase diagram is developed over a range of concentrations for the water/glycerol system (including the freezing of pure water or precipitation of pure glycerol depending on the concentration of the solution). This phase diagram is compared with the traditional phase diagram in which the assumption of a flat solid-liquid interface is made. We show the extent to which nanoscale interface curvature can affect the composition-dependent freezing and precipitating processes, as well as the change in the eutectic point temperature and concentration with interface curvature. Understanding the effect of curvature on solid-liquid equilibrium in nanoscale capillaries has applications in the food industry, soil science, cryobiology, nanoporous materials, and various nanoscience fields.

Reactive solute transport in an acidic stream: Experimental pH increase and simulation of controls on pH, aluminum, and iron

USGS Publications Warehouse

Broshears, R.E.; Runkel, R.L.; Kimball, B.A.; McKnight, Diane M.; Bencala, K.E.

1996-01-01

Solute transport simulations quantitatively constrained hydrologic and geochemical hypotheses about field observations of a pH modification in an acid mine drainage stream. Carbonate chemistry, the formation of solid phases, and buffering interactions with the stream bed were important factors in explaining the behavior of pH, aluminum, and iron. The precipitation of microcrystalline gibbsite accounted for the behavior of aluminum; precipitation of Fe(OH)3 explained the general pattern of iron solubility. The dynamic experiment revealed limitations on assumptions that reactions were controlled only by equilibrium chemistry. Temporal variation in relative rates of photoreduction and oxidation influenced iron behavior. Kinetic limitations on ferrous iron oxidation and hydrous oxide precipitation and the effects of these limitations on field filtration were evident. Kinetic restraints also characterized interaction between the water column and the stream bed, including sorption and desorption of protons from iron oxides at the sediment-water interface and post-injection dissolution of the precipitated aluminum solid phase.

Recrystallization of fluconazole using the supercritical antisolvent (SAS) process.

PubMed

Park, Hee Jun; Kim, Min-Soo; Lee, Sibeum; Kim, Jeong-Soo; Woo, Jong-Soo; Park, Jeong-Sook; Hwang, Sung-Joo

2007-01-10

The supercritical antisolvent (SAS) process was used to modify solid state characteristics of fluconazole. Fluconazole was recrystallized at various temperatures (60-80 degrees C) and pressures (8-16MPa) using dichloromethane (DCM) as a solvent. Acetone and ethanol were also employed as solvents. The fluconazole polymorphs prepared by the SAS process were characterized by differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). Furthermore, the equilibrium solubility of the samples in aqueous solution was determined. Fluconazole anhydrate form I was obtained at low temperature (40 degrees C) and anhydrate form II was obtained at high temperature (80 degrees C). The variation of pressure during the SAS process may influence the preferred orientation. Anhydrate forms I and II were also obtained using various solvents. Therefore, it was shown that solid state characteristics of fluconazole, including the polymorphic form and preferred orientation, can be controlled by changing operating conditions of the SAS process such as temperature, pressure, and solvent.

Preparation of amorphous solid dispersions by rotary evaporation and KinetiSol Dispersing: approaches to enhance solubility of a poorly water-soluble gum extract.

PubMed

Bennett, Ryan C; Brough, Chris; Miller, Dave A; O'Donnell, Kevin P; Keen, Justin M; Hughey, Justin R; Williams, Robert O; McGinity, James W

2015-03-01

Acetyl-11-keto-β-boswellic acid (AKBA), a gum resin extract, possesses poor water-solubility that limits bioavailability and a high melting point making it difficult to successfully process into solid dispersions by fusion methods. The purpose of this study was to investigate solvent and thermal processing techniques for the preparation of amorphous solid dispersions (ASDs) exhibiting enhanced solubility, dissolution rates and bioavailability. Solid dispersions were successfully produced by rotary evaporation (RE) and KinetiSol® Dispersing (KSD). Solid state and chemical characterization revealed that ASD with good potency and purity were produced by both RE and KSD. Results of the RE studies demonstrated that AQOAT®-LF, AQOAT®-MF, Eudragit® L100-55 and Soluplus with the incorporation of dioctyl sulfosuccinate sodium provided substantial solubility enhancement. Non-sink dissolution analysis showed enhanced dissolution properties for KSD-processed solid dispersions in comparison to RE-processed solid dispersions. Variances in release performance were identified when different particle size fractions of KSD samples were analyzed. Selected RE samples varying in particle surface morphologies were placed under storage and exhibited crystalline growth following solid-state stability analysis at 12 months in comparison to stored KSD samples confirming amorphous instability for RE products. In vivo analysis of KSD-processed solid dispersions revealed significantly enhanced AKBA absorption in comparison to the neat, active substance.

Evaluation of the solubility constants of the hydrated solid phases in the H2O-Al2O3-SO3 ternary system

NASA Astrophysics Data System (ADS)

Teyssier, A.; Lagneau, V.; Schmitt, J. M.; Counioux, J. J.; Goutaudier, C.

2017-04-01

During the acid processing of aluminosilicate ores, the precipitation of a solid phase principally consisting of hydrated aluminium hydroxysulfates may be observed. The experimental study of the H2O-Al2O3-SO3 ternary system at 25 ∘C and 101 kPa enabled to describe the solid-liquid equilibra and to identify the nature, the composition and the solubility of the solid phases which may form during the acid leaching. To predict the appearance of these aluminium hydroxysulfates in more complex systems, their solubility constants were calculated by modelling the experimental solubility results, using a geochemical reaction modelling software, CHESS. A model for non-ideality correction, based on the B-dot equation, was used as it was suitable for the considered ion concentration range. The solubility constants of three out of four solid phases were calculated: 104.08 for jurbanite (Al(SO4)(OH).5H2O), 1028.09 for the solid T (Al8(SO4)5(OH)14.34H2O) and 1027.28 for the solid V (Al10(SO4)3(OH)24.20H2O). However the activity correction model was not suitable to determine the solubility constant of alunogen (Al2(SO4)3.15.8H2O), as the ion concentrations of the mixtures were too high and beyond the allowable limits of the model. Another ionic activity correction model, based on the Pitzer equation for example, must be applied to calculate the solubility constant of alunogen.

Multi-Phase Equilibrium and Solubilities of Aromatic Compounds and Inorganic Compounds in Sub- and Supercritical Water: A Review.

PubMed

Liu, Qinli; Ding, Xin; Du, Bowen; Fang, Tao

2017-11-02

Supercritical water oxidation (SCWO), as a novel and efficient technology, has been applied to wastewater treatment processes. The use of phase equilibrium data to optimize process parameters can offer a theoretical guidance for designing SCWO processes and reducing the equipment and operating costs. In this work, high-pressure phase equilibrium data for aromatic compounds+water systems and inorganic compounds+water systems are given. Moreover, thermodynamic models, equations of state (EOS) and empirical and semi-empirical approaches are summarized and evaluated. This paper also lists the existing problems of multi-phase equilibria and solubility studies on aromatic compounds and inorganic compounds in sub- and supercritical water.

Evidence of extended cation solubility in atomic layer deposited nanocrystalline BaTiO3 thin films and its strong impact on the electrical properties.

PubMed

Falmbigl, Matthias; Karateev, Igor A; Golovina, Iryna S; Plokhikh, Aleksandr V; Parker, Thomas C; Vasiliev, Alexander L; Spanier, Jonathan E

2018-06-22

Thin films of ≈50 nm thickness with Ba/Ti-ratios ranging from 0.8 to 1.06 were prepared by depositing alternating layers of Ba(OH)2 and TiO2. Annealing at 750 °C promoted the solid-solid transformation into polycrystalline BaTiO3 films containing a mixture of the perovskite and the hexagonal polymorphs with average crystallite sizes smaller than 14 nm and without impurity phases. This, together with an increase of the cubic lattice parameters for Ba-rich films, suggests an extended metastable solubility range for the perovskite-phase in these nanocrystalline thin films on both sides of the stoichiometric composition. Mapping of the cation distribution utilizing energy-filtered transmission electron microscopy corroborates defect accommodation within the BaTiO3 grains. While the cation off-stoichiometry in thermodynamic equilibrium is negligible for BaTiO3, the metastable extended solubility range in the thin films can be directly correlated to the low annealing temperature and nanocrystalline nature. The leakage current behavior can be explained by the formation of Schottky defects for nonstoichiometric films, and the cation ratio has a distinct impact on the dielectric properties: while excess-BaO has a marginal detrimental effect on the permittivity, the dielectric constant declines rapidly by more than 50% towards the Ti-rich side. The present findings highlight the importance of compositional control for the synthesis of nanocrystalline BaTiO3 thin films, in particular for low annealing and/or deposition temperatures. Our synthesis approach using alternating layers of Ba(OH)2 and TiO2 provides a route to precisely control the cation stoichiometry.

Development of a mathematical model for physical disintegration of flushable consumer products in wastewater systems.

PubMed

Karadagli, Fatih; McAvoy, Drew C; Rittmann, Bruce E

2009-05-01

The processes that flushable solid products may undergo after discharge to wastewater systems are (1) physical disintegration of solids resulting from turbulence, (2) direct dissolution of water-soluble components, (3) hydrolysis of solids to form soluble components, and (4) biodegradation of soluble and insoluble components. We develop a mathematical model for physical disintegration of flushable solid consumer products and test it with two different flushable products--product A, which has 40% water soluble-content, and product B, which has no water-soluble components. We present our modeling analysis of experimental results, from which we computed disintegration rate constants and fractional distribution coefficients for the disintegration of larger solids. The rate constants for solids of product A in units of (hour(-1)) are 0.45 for > 8-mm, 2.25 x 10(-2) for 4- to 8-mm, 0.9 x 10(-2) for 2- to 4-mm, and 1.26 x 10(-2) for 1- to 2-mm solids. The rate constants for solids of product B in units of hour(-1) are 1.8 for > 8-mm, 1.8 for 4- to 8-mm, 3.6 x 10(-1) for 2- to 4-mm, and 2.25 x 10(-3) for 1- to 2-mm solids. As indicated by the rate constants, larger solids disintegrate at a faster rate than smaller solids. In addition, product B disintegrated much faster and went mostly to the smallest size range, while product A disintegrated more slowly and was transferred to a range of intermediate solid sizes.

Enhancements and limits in drug membrane transport using supersaturated solutions of poorly water soluble drugs.

PubMed

Raina, Shweta A; Zhang, Geoff G Z; Alonzo, David E; Wu, Jianwei; Zhu, Donghua; Catron, Nathaniel D; Gao, Yi; Taylor, Lynne S

2014-09-01

Amorphous solid dispersions (ASDs) give rise to supersaturated solutions (solution concentration greater than equilibrium crystalline solubility). We have recently found that supersaturating dosage forms can exhibit the phenomenon of liquid-liquid phase separation (LLPS). Thus, the high supersaturation generated by dissolving ASDs can lead to a two-phase system wherein one phase is an initially nanodimensioned and drug-rich phase and the other is a drug-lean continuous aqueous phase. Herein, the membrane transport of supersaturated solutions, at concentrations above and below the LLPS concentration has been evaluated using a side-by-side diffusion cell. Measurements of solution concentration with time in the receiver cell yield the flux, which reflects the solute thermodynamic activity in the donor cell. As the nominal concentration of solute in the donor cell increases, a linear increase in flux was observed up to the concentration where LLPS occurred. Thereafter, the flux remained essentially constant. Both nifedipine and felodipine solutions exhibit such behavior as long as crystallization is absent. This suggests that there is an upper limit in passive membrane transport that is dictated by the LLPS concentration. These results have several important implications for drug delivery, especially for poorly soluble compounds requiring enabling formulation technologies. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association.

Solubility and transport of Cr(III) in a historically contaminated soil - Evidence of a rapidly reacting dimeric Cr(III) organic matter complex.

PubMed

Löv, Åsa; Sjöstedt, Carin; Larsbo, Mats; Persson, Ingmar; Gustafsson, Jon Petter; Cornelis, Geert; Kleja, Dan B

2017-12-01

Chromium is a common soil contaminant and, although it has been studied widely, questions about its speciation and dissolutions kinetics remain unanswered. We combined information from an irrigation experiment performed with intact soil columns with data from batch experiments to evaluate solubility and mobilization mechanisms of Cr(III) in a historically contaminated soil (>65 years). Particulate and colloidal Cr(III) forms dominated transport in this soil, but their concentrations were independent of irrigation intensity (2-20 mm h -1 ). Extended X-ray absorption fine structure (EXAFS) measurements indicated that Cr(III) associated with colloids and particles, and with the solid phase, mainly existed as dimeric hydrolyzed Cr(III) bound to natural organic matter. Dissolution kinetics of this species were fast (≤1 day) at low pH (<3) and slightly slower (≤5 days) at neutral pH. Furthermore, it proved possible to describe the solubility of the dimeric Cr(III) organic matter complex with a geochemical equilibrium model using only generic binding parameters, opening the way for use of geochemical models in risk assessments of Cr(III)-contaminated sites. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

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

Miller, D.J.; Pask, J.A.

The sintering of TiC-Ni particle compacts was studied with specific attention to effects of processing conditions. Densification was progressively inhibited with the increasing additions of free carbon to the system. These results are explained on the basis of changes in the eutectic reactions in the system, reduced solubility of TiC in the Ni-rich liquid, and decreased wetting of the solid by the liquid. Presintering hydrogen heat treatment reduced the carbon content of the TiC-Ni compacts and led to reduction in sintering rates and elevated temperatures of liquid-phase formation. Wetting experiments with hydrogen-treated materials showed a time-dependent wetting angle. These resultsmore » are discussed based on wetting theory and reactions predicted by the equilibrium ternary-phase diagram.« less

Solubility of (+/-)-ibuprofen and S (+)-ibuprofen in the presence of cosolvents and cyclodextrins.

PubMed

Nerurkar, Jayanti; Beach, J W; Park, M O; Jun, H W

2005-01-01

Aqueous solubility is an important parameter for the development of liquid formulations and in the determination of bioavailability of oral dosage forms. Ibuprofen (IB), a nonsteroidal anti-inflammatory drug, is a chiral molecule and is currently used clinically as a racemate (racIB). However, the S form of ibuprofen or S(+)-ibuprofen (SIB) is the biologically active isomer and is primarily responsible for the antiinflammatory activity. Phase solubility studies were carried out to compare the saturation solubilities of racIB and SIB in the presence of common pharmaceutical solvents such as glycerol, sorbitol solution, propylene glycol (PG), and polyethylene glycol (PEG 300) over the range of 20% to 80% v/v in aqueous based systems. The solubilities of the two compounds were also compared in the presence of cyclodextrins such as beta cyclodextrin (CD), hydroxypropyl beta cyclodextrin (HPCD), and beta cyclodextrin sulfobutyl ether sodium salt (CDSB) over the range of 5% to 25% w/v. Solubility determinations were carried at 25 degrees C and 37 degrees C. Cosolvents exponentially increased the solubility of both SIB and racIB, especially in the presence of PG and PEG 300. Glycerol was not very effective in increasing the aqueous solubilities of both compounds, whereas sorbitol solution had a minimal effect on their solubility. PG and PEG 300 increased the solubility of SIB by 400-fold and 1500-fold, respectively, whereas the rise in solubility for racIB was 193-fold and 700-fold, respectively, at 25 degrees C for the highest concentration of the cosolvents used (80% v/v). Of the two compounds studied, higher equilibrium solubilities were observed for SIB as compared with racIB. The derivatized cyclodextrins increased the aqueous solubility of racIB and SIB in a concentration-dependent manner giving AL type of phase diagrams. The phase solubility diagrams indicated the formation of soluble inclusion complexes between the drugs and HPCD and CDSB, which was of 1:1 stoichiometry. The addition of underivatized CD reduced the solubility of racIB and SIB via the formation of an insoluble complex. The S form formed more stable complexes with HPCD and CDSB as compared with raclB. The solubilization process is discussed in terms of solvent polarity and differential solid-state structure of raclB and SIB. The thermodynamic parameters for the solubilization process are presented.

C-104 high-level waste solids: Washing/leaching and solubility versus temperature studies

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

GJ Lumetta; DJ Bates; JP Bramson

This report describes the results of a test conducted by Battelle to assess the effects of inhibited water washing and caustic leaching on the composition of the C-104 HLW solids. The objective of this work was to determine the composition of the C-104 solids remaining after washing with 0.01 M NaOH or leaching with 3 M NaOH. Another objective of this test was to determine the solubility of the C-104 solids as a function of temperature. The work was conducted according to test plan BNFL-TP-29953-8, Rev. 0, ``Determination of the Solubility of HLW Sludge Solids.

Analysis and Thermodynamic Prediction of Hydrogen Solution in Solid and Liquid Multicomponent Aluminum Alloys

NASA Astrophysics Data System (ADS)

Anyalebechi, P. N.

Reported experimentally determined values of hydrogen solubility in liquid and solid Al-H and Al-H-X (where X = Cu, Si, Zn, Mg, Li, Fe or Ti) systems have been critically reviewed and analyzed in terms of Wagner's interaction parameter. An attempt has been made to use Wagner's interaction parameter and statistic linear regression models derived from reported hydrogen solubility limits for binary aluminum alloys to predict the hydrogen solubility limits in liquid and solid (commercial) multicomponent aluminum alloys. Reasons for the observed poor agreement between the predicted and experimentally determined hydrogen solubility limits are discussed.

Senior high school students’ need analysis of Three-Tier Multiple Choice (3TMC) diagnostic test about acid-base and solubility equilibrium

NASA Astrophysics Data System (ADS)

Ardiansah; Masykuri, M.; Rahardjo, S. B.

2018-05-01

Students’ conceptual understanding is the most important comprehension to obtain related comprehension. However, they held their own conception. With this need analysis, we will elicit student need of 3TMC diagnostic test to measure students’ conception about acid-base and solubility equilibrium. The research done by a mixed method using questionnaire analysis based on descriptive of quantitative and qualitative. The research subject was 96 students from 4 senior high schools and 4 chemistry teachers chosen by random sampling technique. Data gathering used a questionnaire with 10 questions for student and 28 questions for teachers. The results showed that 97% of students stated that the development this instrument is needed. In addition, there were several problems obtained in this questionnaire include learning activity, teacher’s test and guessing. In conclusion, this is necessary to develop the 3TMC instrument that can diagnose and measure the student’s conception in acid-base and solubility equilibrium.

Effect of Phosphate, Fluoride, and Nitrate on Gibbsite Dissolution Rate and Solubility

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

Herting, Daniel L.

2014-01-29

Laboratory tests have been completed with simulated tank waste samples to investigate the effects of phosphate, fluoride, and nitrate on the dissolution rate and equilibrium solubility of gibbsite in sodium hydroxide solution at 22 and 40{degrees}C. Results are compared to relevant literature data and to computer model predictions. The presence of sodium nitrate (3 M) caused a reduction in the rate of gibbsite dissolution in NaOH, but a modest increase in the equilibrium solubility of aluminum. The increase in solubility was not as large, though, as the increase predicted by the computer model. The presence of phosphate, either as sodiummore » phosphate or sodium fluoride phosphate, had a negligible effect on the rate of gibbsite dissolution, but caused a slight increase in aluminum solubility. The magnitude of the increased solubility, relative to the increase caused by sodium nitrate, suggests that the increase is due to ionic strength (or water activity) effects, rather than being associated with the specific ion involved. The computer model predicted that phosphate would cause a slight decrease in aluminum solubility, suggesting some Al-PO4 interaction. No evidence was found of such an interaction.« less

Solubilization of the poorly water soluble drug, telmisartan, using supercritical anti-solvent (SAS) process.

PubMed

Park, Junsung; Cho, Wonkyung; Cha, Kwang-Ho; Ahn, Junhyun; Han, Kang; Hwang, Sung-Joo

2013-01-30

Telmisartan is a biopharmaceutical classification system (BCS) class II drug that has extremely low water solubility but is freely soluble in highly alkalized solutions. Few organic solvents can dissolve telmisartan. This solubility problem is the main obstacle achieving the desired bioavailability. Because of its unique characteristics, the supercritical anti-solvent (SAS) process was used to BCS class II drug in a variety of ways including micronization, amorphization and solid dispersion. Solid dispersions were prepared using hydroxypropylmethylcellulose/polyvinylpyrrolidone (HPMC/PVP) at 1:0.5, 1:1, and 1:2 weight ratios of drug to polymer, and pure telmisartan was also treated using the SAS process. Processed samples were characterized for morphology, particle size, crystallinity, solubility, dissolution rate and polymorphic stability. After the SAS process, all samples were converted to the amorphous form and were confirmed to be hundreds nm in size. Solubility and dissolution rate were increased compared to the raw material. Solubility tended to increase with increases in the amount of polymer used. However, unlike the solubility results, the dissolution rate decreased with increases in polymer concentration due to gel layer formation of the polymer. Processed pure telmisartan showed the best drug release even though it had lower solubility compared to other solid dispersions; however, because there were no stabilizers in processed pure telmisartan, it recrystallized after 1 month under severe conditions, while the other solid dispersion samples remained amorphous form. We conclude that after controlling the formulation of solid dispersion, the SAS process could be a promising approach for improving the solubility and dissolution rate of telmisartan. Copyright © 2012 Elsevier B.V. All rights reserved.

Implementation of equilibrium aqueous speciation and solubility (EQ3 type) calculations into Cantera for electrolyte solutions.

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

Moffat, Harry K.; Jove-Colon, Carlos F.

2009-06-01

In this report, we summarize our work on developing a production level capability for modeling brine thermodynamic properties using the open-source code Cantera. This implementation into Cantera allows for the application of chemical thermodynamics to describe the interactions between a solid and an electrolyte solution at chemical equilibrium. The formulations to evaluate the thermodynamic properties of electrolytes are based on Pitzer's model to calculate molality-based activity coefficients using a real equation-of-state (EoS) for water. In addition, the thermodynamic properties of solutes at elevated temperature and pressures are computed using the revised Helgeson-Kirkham-Flowers (HKF) EoS for ionic and neutral aqueous species.more » The thermodynamic data parameters for the Pitzer formulation and HKF EoS are from the thermodynamic database compilation developed for the Yucca Mountain Project (YMP) used with the computer code EQ3/6. We describe the adopted equations and their implementation within Cantera and also provide several validated examples relevant to the calculations of extensive properties of electrolyte solutions.« less

Monodisperse ferrous phosphate colloids in an anoxic groundwater plume

USGS Publications Warehouse

Gschwend, Philip M.; Reynolds, Matthew D.

1987-01-01

Groundwater samples collected near a secondary-sewage infiltration site on Cape Cod, Massachusetts were examined for colloidal materials (10–1000 nm). In two wells the water contained a population of monodisperse 100-nm particles, detected using laser-light scattering and autocorrelation data processing. SEM and SEM-EDAX analysis of these colloidal materials collected on ultrafilters confirmed the laser light scattering result and revealed that these microparticles consisyed of primarily iron and phosphorus in a 1.86 Fe to 1.0 P stoichiometric ratio. Chemical analyses of the water samples, together with equilibrium solubility calculations, strongly suggest that the ion-activity product should exceed the solubility product of a 100-nm diameter predominantly vivianite-type (Fe3(PO4)2 · 8H2O) colloidal phase. In light of our results, we conclude that these microparticles were formed by sewage-derived phosphate combining with ferrous iron released from the aquifer solids, and that these colloids may be moving in the groundwater flow. Such a subsurface transport process could have major implications regarding the movement of particle-reactive pollutants traditionally viewed as non-mobile in groundwater.

Countercurrent extraction of soluble sugars from almond hulls and assessment of the bioenergy potential.

PubMed

Holtman, Kevin M; Offeman, Richard D; Franqui-Villanueva, Diana; Bayati, Andre K; Orts, William J

2015-03-11

Almond hulls contain considerable proportions (37% by dry weight) of water-soluble, fermentable sugars (sucrose, glucose, and fructose), which can be extracted for industrial purposes. The maximum optimal solids loading was determined to be 20% for sugar extraction, and the addition of 0.5% (w/v) pectinase aided in maintaining a sufficient free water volume for sugar recovery. A laboratory countercurrent extraction experiment utilizing a 1 h steep followed by three extraction (wash) stages produced a high-concentration (131 g/L fermentable sugar) syrup. Overall, sugar recovery efficiency was 88%. The inner stage washing efficiencies were compatible with solution equilibrium calculations, indicating that efficiency was high. The concentrated sugar syrup was fermented to ethanol at high efficiency (86% conversion), and ethanol concentrations in the broth were 7.4% (v/v). Thin stillage contained 233 g SCOD/L, which was converted to biomethane at an efficiency of 90% with a biomethane potential of 297 mL/g SCODdestroyed. Overall, results suggested that a minima of 49 gal (185 L) ethanol and 75 m(3) methane/t hulls (dry whole hull basis) are achievable.

An experimental study of the solubility and speciation of tantalum in fluoride-bearing aqueous solutions at elevated temperature

DOE PAGES

Timofeev, Alexander; Migdisov, Art. A.; Williams-Jones, A. E.

2016-10-27

Here, the solubility of Ta 2O 5 (solid) and the speciation of tantalum in HF-bearing aqueous solutions have been determined at temperatures of 100-250 °C and vapour-saturated water pressure. Tantalum is transported as the species Ta(OH) 5 0 at low HF concentration and pH ~1-3. At higher HF concentration, tantalum mobility is controlled by the species TaF 3(OH) 3- and TaF 5; the presence of TaF 5 0 is only evident at ≤150 °C. Equilibrium constants range from -17.4 ± 0.45 to -16.4 ± 0.12 for the formation of Ta(OH) 5 from crystalline Ta 2O 5 and from -8.24 ±more » 0.64 to -8.55 ± 0.68 for the formation of TaF 3(OH) 3- at 100 and 250 °C, respectively. For TaF 5 0, they were determined to be 0.13 at 100 °C and -0.35 at 150 °C.« less

QSPR analysis of the partitioning of vaporous chemicals in a water-gas phase system and the water solubility of liquid and solid chemicals on the basis of fragment and physicochemical similarity and hybot descriptors.

PubMed

Raevsky, O; Andreeva, E; Raevskaja, O; Skvortsov, V; Schaper, K

2005-01-01

QSPR analyses of the solubility in water of 558 vapors, 786 liquids and 2045 solid organic neutral chemicals and drugs are presented. Simultaneous consideration of H-bond acceptor and donor factors leads to a good description of the solubility of vapors and liquids. A volume-related term was found to have an essential negative contribution to the solubility of liquids. Consideration of polarizability, H-bond acceptor and donor factors and indicators for a few functional groups, as well as the experimental solubility values of structurally nearest neighbors yielded good correlations for liquids. The application of Yalkowsky's "General Solubility Equation" to 1063 solid chemicals and drugs resulted in a correlation of experimental vs calculated log S values with only modest statistical criteria. Two approaches to derive predictive models for solubility of solid chemicals and drugs were tested. The first approach was based on the QSPR for liquids together with indicator variables for different functional groups. Furthermore, a calculation of enthalpies for intermolecular complexes in crystal lattices, based on new H-bond potentials, was carried out for the better consideration of essential solubility- decreasing effects in the solid state, as compared with the liquid state. The second approach was based on a combination of similarity considerations and traditional QSPR. Both approaches lead to high quality predictions with average absolute errors on the level of experimental log S determination.

Sulfur Saturation Limits in Silicate Melts and their Implications for Core Formation Scenarios for Terrestrial Planets

NASA Technical Reports Server (NTRS)

Holzheid, Astrid; Grove, Timothy L.

2002-01-01

This study explores the controls of temperature, pressure, and silicate melt composition on S solubility in silicate liquids. The solubility of S in FeO-containing silicate melts in equilibrium with metal sulfide increases significantly with increasing temperature but decreases with increasing pressure. The silicate melt structure also exercises a control on S solubility. Increasing the degree of polymerization of the silicate melt structure lowers the S solubility in the silicate liquid. The new set of experimental data is used to expand the model of Mavrogenes and O'Neill(1999) for S solubility in silicate liquids by incorporating the influence of the silicate melt structure. The expected S solubility in the ascending magma is calculated using the expanded model. Because the negative pressure dependence of S solubility is more influential than the positive temperature dependence, decompression and adiabatic ascent of a formerly S-saturated silicate magma will lead to S undersaturation. A primitive magma that is S-saturated in its source region will, therefore, become S-undersaturated as it ascends to shallower depth. In order to precipitate magmatic sulfides, the magma must first cool and undergo fractional crystallization to reach S saturation. The S content in a metallic liquid that is in equilibrium with a magma ocean that contains approx. 200 ppm S (i.e., Earth's bulk mantle S content) ranges from 5.5 to 12 wt% S. This range of S values encompasses the amount of S (9 to 12 wt%) that would be present in the outer core if S is the light element. Thus, the Earth's proto-mantle could be in equilibrium (in terms of the preserved S abundance) with a core-forming metallic phase.

Solubility of noble gases in serpentine - Implications for meteoritic noble gas abundances

NASA Technical Reports Server (NTRS)

Zaikowski, A.; Schaeffer, O. A.

1979-01-01

An investigation of the solubilities of the noble gases from synthesis and solubility studies of the sheet silicate mineral serpentine in carbonaceous chondrites is presented. Hydrothermal synthesis and exchange experiments were made at 340C and 1 kbar with noble gas partial pressures from 2 times 10 to the -8th power to 0.1 atm. The measured distribution coefficients for noble gases are not sufficiently high to account for the trapped noble gases in carbonaceous chondrites by exchange in solar nebula if meteoritic minerals have comparable distribution coefficients. Also, serpentine gains and loses noble gases to approach equilibrium values with the terrestrial atmosphere, indicating that this exposure may have influenced the noble gas abundances in phyllosilicate minerals of these chondrites. The dispersion of K-Ar ages of carbonaceous chondrites could be the result of phyllosilicates approaching equilibrium solubility of atmospheric Ar-40.

A comparative study on the effects of amphiphilic and hydrophilic polymers on the release profiles of a poorly water-soluble drug.

PubMed

Irwan, Anastasia W; Berania, Jacqueline E; Liu, Xueming

2016-03-01

This paper reports the use of two crystalline polymers, an amphiphilic Pluronic® F-127 (PF-127) and a hydrophilic poly(ethylene glycol) (PEG6000) as drug delivery carriers for improving the drug release of a poorly water-soluble drug, fenofibrate (FEN), via micelle formation and formation of a solid dispersion (SD). In 10% PF-127 (aq.), FEN showed an equilibrium solubility of ca. 0.6 mg/mL, due to micelle formation. In contrast, in 10% PEG6000 (aq.), FEN only exhibited an equilibrium solubility of 0.0037 mg/mL. FEN-loaded micelles in PF-127 were prepared by direct dissolution and membrane dialysis. Both methods only yielded a highest drug loading (DL) of 0.5%. SDs of FEN in PF-127 and PEG6000, at DLs of 5-80%, were prepared by solvent evaporation. In-vitro dissolution testing showed that both micelles and SDs significantly improved FEN's release rate. The SDs of FEN in PF-127 showed significantly faster release than crystalline FEN, when the DL was as high as 50%, whereas SDs of PEG6000 showed similar enhancement in the release rate when the DL was not more than 20%. The DSC thermograms of SDs of PF-127 exhibited a single phase transition peak at ca. 55-57 °C when the DL was not more than 50%, whereas those in PEG6000 exhibited a similar peak at ca. 61-63 °C when the DL was not more than 35%. When the DL exceeded 50% for SDs of PF-127 and 35% for SDs of PEG6000, DSC thermograms showed two melting peaks for the carrier polymer and FEN, respectively. FT-IR studies revealed that PF-127 has a stronger hydrophobic-hydrophobic interaction with FEN than PEG6000. It is likely that both dispersion and micelle formation contributed to the stronger effect of PF-127 on enhancing the release rate of FEN in its SDs.

Enhanced solubility of piperine using hydrophilic carrier-based potent solid dispersion systems.

PubMed

Thenmozhi, Kathavarayan; Yoo, Young Je

2017-09-01

Piperine alkaloid, an important constituent of black pepper, exhibits numerous therapeutic properties, whereas its usage as a drug is limited due to its poor solubility in aqueous medium, which leads to poor bioavailability. Herein, a new method has been developed to improve the solubility of this drug based on the development of solid dispersions with improved dissolution rate using hydrophilic carriers such as sorbitol (Sor), polyethylene glycol (PEG) and polyvinyl pyrrolidone K30 (PVP) by solvent method. Physical mixtures of piperine and carriers were also prepared for comparison. The physicochemical properties of the prepared solid dispersions were examined using SEM, TEM, DSC, XRD and FT-IR. In vitro dissolution profile of the solid dispersions was recorded and compared with that of the pure piperine and physical mixtures. The effect of these carriers on the aqueous solubility of piperine has been investigated. The solid dispersions of piperine with Sor, PEG and PVP exhibited superior performance for the dissolution of piperine with a drug release of 70%, 76% and 89%, respectively after 2 h compared to physical mixtures and pure piperine, which could be due to its transformation from crystalline to amorphous form as well as the attachment of hydrophilic carriers to the surface of poorly water-soluble piperine. Results suggest that the piperine solid dispersions prepared with improved in vitro release exhibit potential advantage in delivering poorly water-soluble piperine as an oral supplement.

Crosslinked hydrogels-a promising class of insoluble solid molecular dispersion carriers for enhancing the delivery of poorly soluble drugs.

PubMed

Sun, Dajun D; Lee, Ping I

2014-02-01

Water-insoluble materials containing amorphous solid dispersions (ASD) are an emerging category of drug carriers which can effectively improve dissolution kinetics and kinetic solubility of poorly soluble drugs. ASDs based on water-insoluble crosslinked hydrogels have unique features in contrast to those based on conventional water-soluble and water-insoluble carriers. For example, solid molecular dispersions of poorly soluble drugs in poly(2-hydroxyethyl methacrylate) (PHEMA) can maintain a high level of supersaturation over a prolonged period of time via a feedback-controlled diffusion mechanism thus avoiding the initial surge of supersaturation followed by a sharp decline in drug concentration typically encountered with ASDs based on water-soluble polymers. The creation of both immediate- and controlled-release ASD dosage forms is also achievable with the PHEMA based hydrogels. So far, ASD systems based on glassy PHEMA have been shown to be very effective in retarding precipitation of amorphous drugs in the solid state to achieve a robust physical stability. This review summarizes recent research efforts in investigating the potential of developing crosslinked PHEMA hydrogels as a promising alternative to conventional water-soluble ASD carriers, and a related finding that the rate of supersaturation generation does affect the kinetic solubility profiles implications to hydrogel based ASDs.

Crosslinked hydrogels—a promising class of insoluble solid molecular dispersion carriers for enhancing the delivery of poorly soluble drugs

PubMed Central

Sun, Dajun D.; Lee, Ping I.

2014-01-01

Water-insoluble materials containing amorphous solid dispersions (ASD) are an emerging category of drug carriers which can effectively improve dissolution kinetics and kinetic solubility of poorly soluble drugs. ASDs based on water-insoluble crosslinked hydrogels have unique features in contrast to those based on conventional water-soluble and water-insoluble carriers. For example, solid molecular dispersions of poorly soluble drugs in poly(2-hydroxyethyl methacrylate) (PHEMA) can maintain a high level of supersaturation over a prolonged period of time via a feedback-controlled diffusion mechanism thus avoiding the initial surge of supersaturation followed by a sharp decline in drug concentration typically encountered with ASDs based on water-soluble polymers. The creation of both immediate- and controlled-release ASD dosage forms is also achievable with the PHEMA based hydrogels. So far, ASD systems based on glassy PHEMA have been shown to be very effective in retarding precipitation of amorphous drugs in the solid state to achieve a robust physical stability. This review summarizes recent research efforts in investigating the potential of developing crosslinked PHEMA hydrogels as a promising alternative to conventional water-soluble ASD carriers, and a related finding that the rate of supersaturation generation does affect the kinetic solubility profiles implications to hydrogel based ASDs. PMID:26579361

Modeling a distribution of point defects as misfitting inclusions in stressed solids

NASA Astrophysics Data System (ADS)

Cai, W.; Sills, R. B.; Barnett, D. M.; Nix, W. D.

2014-05-01

The chemical equilibrium distribution of point defects modeled as non-overlapping, spherical inclusions with purely positive dilatational eigenstrain in an isotropically elastic solid is derived. The compressive self-stress inside existing inclusions must be excluded from the stress dependence of the equilibrium concentration of the point defects, because it does no work when a new inclusion is introduced. On the other hand, a tensile image stress field must be included to satisfy the boundary conditions in a finite solid. Through the image stress, existing inclusions promote the introduction of additional inclusions. This is contrary to the prevailing approach in the literature in which the equilibrium point defect concentration depends on a homogenized stress field that includes the compressive self-stress. The shear stress field generated by the equilibrium distribution of such inclusions is proved to be proportional to the pre-existing stress field in the solid, provided that the magnitude of the latter is small, so that a solid containing an equilibrium concentration of point defects can be described by a set of effective elastic constants in the small-stress limit.

Drug-Drug Multicomponent Solid Forms: Cocrystal, Coamorphous and Eutectic of Three Poorly Soluble Antihypertensive Drugs Using Mechanochemical Approach.

PubMed

Haneef, Jamshed; Chadha, Renu

2017-08-01

The present study deals with the application of mechanochemical approach for the preparation of drug-drug multicomponent solid forms of three poorly soluble antihypertensive drugs (telmisartan, irbesartan and hydrochlorothiazide) using atenolol as a coformer. The resultant solid forms comprise of cocrystal (telmisartan-atenolol), coamorphous (irbesartan-atenolol) and eutectic (hydrochlorothiazide-atenolol). The study emphasizes that solid-state transformation of drug molecules into new forms is a result of the change in structural patterns, diminishing of dimers and creating new facile hydrogen bonding network based on structural resemblance. The propensity for heteromeric or homomeric interaction between two different drugs resulted into diverse solid forms (cocrystal/coamorphous/eutectics) and become one of the interesting aspects of this research work. Evaluation of these solid forms revealed an increase in solubility and dissolution leading to better antihypertensive activity in deoxycorticosterone acetate (DOCA) salt-induced animal model. Thus, development of these drug-drug multicomponent solid forms is a promising and viable approach to addressing the issue of poor solubility and could be of considerable interest in dual drug therapy for the treatment of hypertension.

Understanding the generation and maintenance of supersaturation during the dissolution of amorphous solid dispersions using modulated DSC and 1H NMR.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2018-01-30

In this study, the dissolution behaviour of dipyridamole (DPM) and cinnarizine (CNZ) spray-dried amorphous solid dispersions (ASDs) using polyvinyl pyrrolidone (PVP) and polyacrylic acid (PAA) as a carrier matrix were evaluated and compared. The drug concentrations achieved from the dissolution of PVP and PAA solid dispersions were significantly greater than the equilibrium solubility of crystalline DPM and CNZ in phosphate buffer pH 6.8 (PBS 6.8). The maximum drug concentration achieved by dissolution of PVP and PAA solid dispersions did not exceed the theoretically calculated apparent solubility of amorphous DPM and CNZ. However, the degree of supersaturation of DPM and CNZ increased considerably as the polymer weight fraction within the solid dispersion increased. In addition, the supersaturation profile of DPM and CNZ were studied in the presence and absence of the polymers. PAA was found to maintain a higher level of supersaturation compared to PVP. The enhanced drug solution concentration following dissolution of ASDs can be attributed to the reduced crystal growth rates of DPM and CNZ at an equivalent supersaturation. We have also shown that, for drugs having high crystallization tendency and weak drug-polymer interaction, the feasible way to increase dissolution might be increase the polymer weight fraction in the ASD. Solution 1 H NMR spectra were used to understand dissolution mechanism and to identify drug-polymer interaction. The change in electron densities of proton attached to different groups in DPM and CNZ suggested drug-polymer interaction in solution. The relative intensities of peak shift and nature of interaction between drug and polymer in different systems are different. These different effects suggest that DPM and CNZ interacts in a different way with PVP and PAA in solution which goes some way towards explaining the different polymeric effect, particularly in terms of inhibition of drug recrystallization and dissolution of DPM and CNZ ASDs. These results established that the different drug/polymer interactions in the solid state and in solution give rise to the variation in dissolution profile observed for different systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermodynamic approach to the paradox of diamond formation with simultaneous graphite etching in the low pressure synthesis of diamond

NASA Astrophysics Data System (ADS)

Hwang, Nong M.; Yoon, Duk Y.

1996-03-01

In spite of the critical handicap from the thermodynamic point of view, the atomic hydrogen hypothesis is strongly supported by experimental observations of diamond deposition with simultaneous graphite etching. Thermodynamic analysis of the CH system showed that at ˜ 1500 K, carbon solubility in the gas phase is minimal and thus, the equilibrium fraction of solid carbon is maximal. Depending on whether gas phase nucleation takes place or not, the driving force is for deposition or for etching of solid carbon below ˜ 1500 K for the input gas of the typical mixture of 1% CH 499% H 2. The previous observation of etching of the graphite substrate is not expected unless solid carbon precipitated in the gas phase. By rigorous thermodynamic analysis of the previous experimental observations of diamond deposition with simultaneous graphite etching, we suggested that the previous implicit assumption that diamond deposits by an atomic unit should be the weakest point leading to the thermodynamic paradox. The experimental observations could be successfully explained without violating thermodynamics by assuming that the diamond phase had nucleated in the gas phase as fine clusters.

Metal releases from a municipal solid waste incineration air pollution control residue mixed with compost.

PubMed

Van Praagh, M; Persson, K M

2008-08-01

The influence of 10 wt.% mature compost was tested on the heavy metal leachate emissions from a calcium-rich municipal solid waste incineration air pollution control residue (MSWI APC). Apart from elongated columns (500 and 1250 mm), an otherwise norm compliant European percolation test setup was used. More than 99% of the metals Al, As, Cd, Cr, Cu, Fe and Ni were left in the APC residue after leaching to a liquid-to-solid ratio (L/S) of 10. Apparent short-term effects of elevated leachate DOC concentrations on heavy metal releases were not detected. Zn and Pb leachate concentrations were one order of magnitude lower for L/S 5 and 10 from the pure APC residue column, which suggests a possible long-term effect of compost on the release of these elements. Prolonging the contact time between the pore water and the material resulted in elevated leachate concentrations at L/S 0.1 to L/S 1 by a factor of 2. Only Cr and Pb concentrations were at their maxima in the first leachates at L/S 0.1. Equilibrium speciation modelling with the PHREEQC code suggested portlandite (Ca(OH)2) to control Ca solubility and pH.

Phosphorus forms and extractability in dairy manure: a case study for Wisconsin on-farm anaerobic digesters.

PubMed

Güngör, Kerem; Karthikeyan, K G

2008-01-01

The effect of anaerobic digestion on phosphorus (P) forms and water P extractability was investigated using dairy manure samples from six full-scale on-farm anaerobic digesters in Wisconsin, USA. On an average, total dissolved P (TDP) constituted 12 +/- 4% of total P (TP) in the influent to the anaerobic digesters. Only 7 +/- 2% of the effluent was in a dissolved form. Dissolved unreactive P (DUP), comprising polyphosphates and organic P, dominated the dissolved P component in both the influent and effluent. In most cases, it appeared that the fraction of DUP mineralized during anaerobic digestion became subsequently associated with particulate-bound solids. Geochemical equilibrium modeling with Mineql+ indicated that dicalcium phosphate dihydrate, dicalcium phosphate anhydrous, octacalcium phosphate, newberyite, and struvite were the probable solid phases in both the digester influent and effluent samples. The water-extractable P (WEP) fraction in undigested manure ranged from 45% to 70% of TP, which reduced substantially after anaerobic digestion to 25% to 45% of TP. Anaerobic digestion of dairy manure appears capable of reducing the fraction of P that is immediately available by increasing the stability of the solid phases controlling P solubility.

Water-enhanced solvation of organics

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

Lee, Jane H.

1993-07-01

Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log γ s vs x w/x s curve. From graph shape Δ(log γ s) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid,more » propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement Δ(log γ acid)/Δ(x w/x acid) = -0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was -0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol and 2,3-butanediol did not level off at large water/solute mole ratio. Solutes investigated by solid-liquid equilibrium were citric acid, gallic acid, phenol, xylenols, 2-naphthol. Saturation concentration of citric acid in anhydrous butyl acetate increased from 0.0009 to 0.087 mol/L after 1.3 % (g/g) water co-dissolved into organic phase. Effect of water-enhanced solvation for citric acid is very large but very small for phenol and its derivatives.« less

Desorption of Arsenic from Drinking Water Distribution System Solids

EPA Science Inventory

Given the limited knowledge regarding the soluble release of arsenic from DWDS solids, the objectives of this research were to: 1) investigate the effect of pH on the dissolution/desorption of arsenic from DWDS solids, and 2) examine the effect of orthophosphate on the soluble re...

Effect of hydroxypropylcellulose and Tween 80 on physicochemical properties and bioavailability of ezetimibe-loaded solid dispersion.

PubMed

Rashid, Rehmana; Kim, Dong Wuk; Din, Fakhar Ud; Mustapha, Omer; Yousaf, Abid Mehmood; Park, Jong Hyuck; Kim, Jong Oh; Yong, Chul Soon; Choi, Han-Gon

2015-10-05

The purpose of this research was to evaluate the effect of the HPC (hydroxypropylcellulose) and Tween 80 on the physicochemical properties and oral bioavailability of ezetimibe-loaded solid dispersions. The binary solid dispersions were prepared with drug and various amounts of HPC. Likewise, ternary solid dispersions were prepared with different ratios of drug, HPC and Tween 80. Both types of solid dispersions were prepared using the solvent evaporation method. Their aqueous solubility, physicochemical properties, dissolution and oral bioavailability were investigated in comparison with the drug powder. All the solid dispersions significantly improved the drug solubility and dissolution. As the amount of HPC increased in the binary solid dispersions to 10-fold, the drug solubility and dissolution were increased accordingly. However, further increase in HPC did not result in significant differences among them. Similarly, up to 0.1-fold, Tween 80 increased the drug solubility in the ternary solid dispersions followed by no significant change. However, Tween 80 hardly affected the drug dissolution. The physicochemical analysis proved that the drug in binary and ternary solid dispersion was existed in the amorphous form. The particle-size measurements of these formulations were also not significantly different from each other, which showed that Tween 80 had no impact on physicochemical properties. The ezetimibe-loaded binary and ternary solid dispersions gave 1.6- and 1.8-fold increased oral bioavailability in rats, respectively, as compared to the drug powder; however, these values were not significantly different from each other. Thus, HPC greatly affected the solubility, dissolution and oral bioavailability of drug, but Tween 80 hardly did. Furthermore, this ezetimibe-loaded binary solid dispersion prepared only with HPC would be suggested as a potential formulation for oral administration of ezetimibe. Copyright © 2015 Elsevier Ltd. All rights reserved.

Porous Silica-Supported Solid Lipid Particles for Enhanced Solubilization of Poorly Soluble Drugs.

PubMed

Yasmin, Rokhsana; Rao, Shasha; Bremmell, Kristen E; Prestidge, Clive A

2016-07-01

Low dissolution of drugs in the intestinal fluid can limit their effectiveness in oral therapies. Here, a novel porous silica-supported solid lipid system was developed to optimize the oral delivery of drugs with limited aqueous solubility. Using lovastatin (LOV) as the model poorly water-soluble drug, two porous silica-supported solid lipid systems (SSL-A and SSL-S) were fabricated from solid lipid (glyceryl monostearate, GMS) and nanoporous silica particles Aerosil 380 (silica-A) and Syloid 244FP (silica-S) via immersion/solvent evaporation. SSL particles demonstrated significantly higher rate and extent of lipolysis in comparison with the pure solid lipid, depending on the lipid loading levels and the morphology. The highest lipid digestion was observed when silica-S was loaded with 34% (w/w) solid lipid, and differential scanning calorimeter (DSC) analysis confirmed the encapsulation of up to 2% (w/w) non-crystalline LOV in this optimal SSL-S formulation. Drug dissolution under non-digesting intestinal conditions revealed a three- to sixfold increase in dissolution efficiencies when compared to the unformulated drug and a LOV-lipid suspension. Furthermore, the SSL-S provided superior drug solubilization under simulated intestinal digesting condition in comparison with the drug-lipid suspension and drug-loaded silica. Therefore, solid lipid and nanoporous silica provides a synergistic effect on optimizing the solubilization of poorly water-soluble compound and the solid lipid-based porous carrier system provides a promising delivery approach to overcome the oral delivery challenges of poorly water-soluble drugs.

Aqueous fluid composition in CI chondritic materials: Chemical equilibrium assessments in closed systems

NASA Astrophysics Data System (ADS)

Zolotov, Mikhail Yu.

2012-08-01

Solids of nearly solar composition have interacted with aqueous fluids on carbonaceous asteroids, icy moons, and trans-neptunian objects. These processes altered mineralogy of accreted materials together with compositions of aqueous and gaseous phases. We evaluated chemistry of aqueous solutions coexisted with CI-type chondritic solids through calculations of chemical equilibria in closed water-rock-gas systems at different compositions of initial fluids, water/rock mass ratios (0.1-1000), temperatures (<350 °C), and pressures (<2 kbars). The calculations show that fluid compositions are mainly affected by solubilities of solids, the speciation of chlorine in initial water-rock mixtures, and the occurrence of Na-bearing secondary minerals such as saponite. The major species in modeled alkaline solutions are Na+, Cl-, CO32-,HCO3-, K+, OH-, H2, and CO2. Aqueous species of Mg, Fe, Ca, Mn, Al, Ni, Cr, S, and P are not abundant in these fluids owing to low solubility of corresponding solids. Typical NaCl type alkaline fluids coexist with saponite-bearing mineralogy that usually present in aqueously altered chondrites. A common occurrence of these fluids is consistent with the composition of grains emitted from Enceladus. Na-rich fluids with abundant CO32-,HCO3-, and OH- anions coexist with secondary mineralogy depleted in Na. The Na2CO3 and NaHCO3 type fluids could form via accretion of cometary ices. NaOH type fluids form in reduced environments and may locally occur on parent bodies of CR carbonaceous chondrites. Supposed melting of accreted HCl-bearing ices leads to early acidic fluids enriched in Mg, Fe and other metals, consistent with signs of low-pH alteration in chondrites. Neutralization of these solutions leads to alkaline Na-rich fluids. Sulfate species have negligible concentrations in closed systems, which remain reduced, especially at elevated pressures created by forming H2 gas. Hydrogen, CO2, and H2O dominate in the gaseous phase, though the abundance of methane cannot be fairly estimated.

A method of solid-solid phase equilibrium calculation by molecular dynamics

NASA Astrophysics Data System (ADS)

Karavaev, A. V.; Dremov, V. V.

2016-12-01

A method for evaluation of solid-solid phase equilibrium curves in molecular dynamics simulation for a given model of interatomic interaction is proposed. The method allows to calculate entropies of crystal phases and provides an accuracy comparable with that of the thermodynamic integration method by Frenkel and Ladd while it is much simpler in realization and less intense computationally. The accuracy of the proposed method was demonstrated in MD calculations of entropies for EAM potential for iron and for MEAM potential for beryllium. The bcc-hcp equilibrium curves for iron calculated for the EAM potential by the thermodynamic integration method and by the proposed one agree quite well.

The impact of antibacterial handsoap constituents on the dynamics of triclosan dissolution from dry sand.

PubMed

Koehler, Daniel A; Strevett, Keith A; Papelis, Charalambos; Kibbey, Tohren C G

2017-11-01

Triclosan has been widely used as an antibacterial agent in consumer and industrial products, and large quantities continue to be discharged to natural waters annually. The focus of this work was on studying the dynamics of triclosan dissolution following evaporative drying. Warm weather can cause the water in intermittent streams or the unsaturated zone to evaporate, causing nonvolatile compounds to form solid precipitates. Because dissolution of precipitates is a relatively slow process, the dynamics of dissolution following evaporation may play an important role in controlling the release of contaminants to the environment. The specific purpose of the work was to explore the effects of surfactant co-contaminants from an industrial antibiotic handsoap on the dissolution dynamics of triclosan. The work used a fiber optic-based optical cell to conduct stirred-batch dissolution experiments for sands coated with different mass loadings of triclosan. Results show that the presence of surfactants from the hand soap not only increase the apparent equilibrium solubility, but also increase the rate of approach to equilibrium. A model describing the dissolution process was developed, and was found to be consistent with experimental data. Results of the work suggest that even small solubility enhancement by surfactant co-contaminants may have a significant impact on dissolution dynamics. Because waters containing significant quantities of triclosan are also among those most likely to contain surfactant co-contaminants, it is likely that the release of triclosan to the environment following evaporation may be faster in many cases than would be predicted from experiments based on pure triclosan. Copyright © 2017 Elsevier Ltd. All rights reserved.

Metastable and equilibrium phase diagrams of unconjugated bilirubin IXα as functions of pH in model bile systems: Implications for pigment gallstone formation.

PubMed

Berman, Marvin D; Carey, Martin C

2015-01-01

Metastable and equilibrium phase diagrams for unconjugated bilirubin IXα (UCB) in bile are yet to be determined for understanding the physical chemistry of pigment gallstone formation. Also, UCB is a molecule of considerable biomedical importance because it is a potent antioxidant and an inhibitor of atherogenesis. We employed principally a titrimetric approach to obtain metastable and equilibrium UCB solubilities in model bile systems composed of taurine-conjugated bile salts, egg yolk lecithin (mixed long-chain phosphatidylcholines), and cholesterol as functions of total lipid concentration, biliary pH values, and CaCl2 plus NaCl concentrations. Metastable and equilibrium precipitation pH values were obtained, and average pKa values of the two carboxyl groups of UCB were calculated. Added lecithin and increased temperature decreased UCB solubility markedly, whereas increases in bile salt concentrations and molar levels of urea augmented solubility. A wide range of NaCl and cholesterol concentrations resulted in no specific effects, whereas added CaCl2 produced large decreases in UCB solubilities at alkaline pH values only. UV-visible absorption spectra were consistent with both hydrophobic and hydrophilic interactions between UCB and bile salts that were strongly influenced by pH. Reliable literature values for UCB compositions of native gallbladder biles revealed that biles from hemolytic mice and humans with black pigment gallstones are markedly supersaturated with UCB and exhibit more acidic pH values, whereas biles from nonstone control animals and patients with cholesterol gallstone are unsaturated with UCB. Copyright © 2015 the American Physiological Society.

Metastable and equilibrium phase diagrams of unconjugated bilirubin IXα as functions of pH in model bile systems: Implications for pigment gallstone formation

PubMed Central

Berman, Marvin D.

2014-01-01

Metastable and equilibrium phase diagrams for unconjugated bilirubin IXα (UCB) in bile are yet to be determined for understanding the physical chemistry of pigment gallstone formation. Also, UCB is a molecule of considerable biomedical importance because it is a potent antioxidant and an inhibitor of atherogenesis. We employed principally a titrimetric approach to obtain metastable and equilibrium UCB solubilities in model bile systems composed of taurine-conjugated bile salts, egg yolk lecithin (mixed long-chain phosphatidylcholines), and cholesterol as functions of total lipid concentration, biliary pH values, and CaCl2 plus NaCl concentrations. Metastable and equilibrium precipitation pH values were obtained, and average pKa values of the two carboxyl groups of UCB were calculated. Added lecithin and increased temperature decreased UCB solubility markedly, whereas increases in bile salt concentrations and molar levels of urea augmented solubility. A wide range of NaCl and cholesterol concentrations resulted in no specific effects, whereas added CaCl2 produced large decreases in UCB solubilities at alkaline pH values only. UV-visible absorption spectra were consistent with both hydrophobic and hydrophilic interactions between UCB and bile salts that were strongly influenced by pH. Reliable literature values for UCB compositions of native gallbladder biles revealed that biles from hemolytic mice and humans with black pigment gallstones are markedly supersaturated with UCB and exhibit more acidic pH values, whereas biles from nonstone control animals and patients with cholesterol gallstone are unsaturated with UCB. PMID:25359538

Transport and solubility of Hetero-disperse dry deposition particulate matter subject to urban source area rainfall-runoff processes

NASA Astrophysics Data System (ADS)

Ying, G.; Sansalone, J.

2010-03-01

SummaryWith respect to hydrologic processes, the impervious pavement interface significantly alters relationships between rainfall and runoff. Commensurate with alteration of hydrologic processes the pavement also facilitates transport and solubility of dry deposition particulate matter (PM) in runoff. This study examines dry depositional flux rates, granulometric modification by runoff transport, as well as generation of total dissolved solids (TDS), alkalinity and conductivity in source area runoff resulting from PM solubility. PM is collected from a paved source area transportation corridor (I-10) in Baton Rouge, Louisiana encompassing 17 dry deposition and 8 runoff events. The mass-based granulometric particle size distribution (PSD) is measured and modeled through a cumulative gamma function, while PM surface area distributions across the PSD follow a log-normal distribution. Dry deposition flux rates are modeled as separate first-order exponential functions of previous dry hours (PDH) for PM and suspended, settleable and sediment fractions. When trans-located from dry deposition into runoff, PSDs are modified, with a d50m decreasing from 331 to 14 μm after transport and 60 min of settling. Solubility experiments as a function of pH, contact time and particle size using source area rainfall generate constitutive models to reproduce pH, alkalinity, TDS and alkalinity for historical events. Equilibrium pH, alkalinity and TDS are strongly influenced by particle size and contact times. The constitutive leaching models are combined with measured PSDs from a series of rainfall-runoff events to demonstrate that the model results replicate alkalinity and TDS in runoff from the subject watershed. Results illustrate the granulometry of dry deposition PM, modification of PSDs along the drainage pathway, and the role of PM solubility for generation of TDS, alkalinity and conductivity in urban source area rainfall-runoff.

Thermal conductance at the interface between crystals using equilibrium and nonequilibrium molecular dynamics

NASA Astrophysics Data System (ADS)

Merabia, Samy; Termentzidis, Konstantinos

2012-09-01

In this article, we compare the results of nonequilibrium (NEMD) and equilibrium (EMD) molecular dynamics methods to compute the thermal conductance at the interface between solids. We propose to probe the thermal conductance using equilibrium simulations measuring the decay of the thermally induced energy fluctuations of each solid. We also show that NEMD and EMD give generally speaking inconsistent results for the thermal conductance: Green-Kubo simulations probe the Landauer conductance between two solids which assumes phonons on both sides of the interface to be at equilibrium. On the other hand, we show that NEMD give access to the out-of-equilibrium interfacial conductance consistent with the interfacial flux describing phonon transport in each solid. The difference may be large and reaches typically a factor 5 for interfaces between usual semiconductors. We analyze finite size effects for the two determinations of the interfacial thermal conductance, and show that the equilibrium simulations suffer from severe size effects as compared to NEMD. We also compare the predictions of the two above-mentioned methods—EMD and NEMD—regarding the interfacial conductance of a series of mass mismatched Lennard-Jones solids. We show that the Kapitza conductance obtained with EMD can be well described using the classical diffuse mismatch model (DMM). On the other hand, NEMD simulation results are consistent with an out-of-equilibrium generalization of the acoustic mismatch model (AMM). These considerations are important in rationalizing previous results obtained using molecular dynamics, and help in pinpointing the physical scattering mechanisms taking place at atomically perfect interfaces between solids, which is a prerequisite to understand interfacial heat transfer across real interfaces.

Development of solid dispersion systems of dapivirine to enhance its solubility.

PubMed

Gorajana, Adinarayana; Ying, Chan Chiew; Shuang, Yeen; Fong, Pooi; Tan, Zhi; Gupta, Jyoti; Talekar, Meghna; Sharma, Manisha; Garg, Sanjay

2013-06-01

Dapivirine, formerly known as TMC 120, is a poorly-water soluble anti-HIV drug, currently being developed as a vaginal microbicide. The clinical use of this drug has been limited due to its poor solubility. The aim of this study was to design solid dispersion systems of Dapivirine to improve its solubility. Solid dispersions were prepared by solvent and fusion methods. Dapivirine release from the solid dispersion system was determined by conducting in-vitro dissolution studies. The physicochemical characteristics of the drug and its formulation were studied using Differential Scanning Calorimetry (DSC), powder X-ray Diffraction (XRD), Fourier-transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). A significant improvement in drug dissolution rate was observed with the solid dispersion systems. XRD, SEM and DSC results indicated the transformation of pure Dapivirine which exists in crystalline form into an amorphous form in selected solid dispersion formulations. FTIR and HPLC analysis confirmed the absence of drug-excipient interactions. Solid dispersion systems can be used to improve the dissolution rate of Dapivirine. This improvement could be attributed to the reduction or absence of drug crystallinity, existence of drug particles in an amorphous form and improved wettability of the drug.

Solubility of carbon dioxide in aqueous mixtures of alkanolamines

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

Dawodu, O.F.; Meisen, A.

1994-07-01

The solubility of CO[sub 2] in water + N-methyldiethanolamine + monoethanolamine (MDEA + MEA) and water + N-methyldiethanolamine + diethanolamine (MDEA + DEA) are reported at two compositions of 3.4 M MDEA + 0.8 M MEA or DEA and 2.1 M MDEA + 2.1 M MEA or DEA at temperatures from 70 to 180 C and CO[sub 2] partial pressures from 100 to 3,850 kPa. The solubility of CO[sub 2] in the blends decreased with an increase in temperature but increased with an increase in CO[sub 2] partial pressure. At low partial pressures of CO[sub 2] and the same totalmore » amine concentration, the equilibrium CO[sub 2] loadings were in the order MDEA + MEA > MDEA + DEA > MDEA. However, at high CO[sub 2] partial pressures, the equilibrium CO[sub 2] loadings in the MDEA solutions were higher than those of the MDEA + MEA and MDEA + DEA blends of equal molar strengths due to the stoichiometric loading limitations of MEA and DEA. The nonadditivity of the equilibrium loadings for single amine systems highlights the need for independent measurements on amine blends.« less

The Solubility of Nickel Sulfate-6-Water: A General Chemistry Experiment.

ERIC Educational Resources Information Center

Pacer, Richard A.

1984-01-01

Background information, procedures used, and typical results are provided for a solubility experiment. Among the 12 objectives of the experiment are: acquiring understanding of the terms "saturated,""unsaturated," and "supersaturated;" learning meaning of the expression "to approach equilibrium;" gaining…

Mathematical model to analyze the dissolution behavior of metastable crystals or amorphous drug accompanied with a solid-liquid interface reaction.

PubMed

Hirai, Daiki; Iwao, Yasunori; Kimura, Shin-Ichiro; Noguchi, Shuji; Itai, Shigeru

2017-04-30

Metastable crystals and the amorphous state of poorly water-soluble drugs in solid dispersions (SDs), are subject to a solid-liquid interface reaction upon exposure to a solvent. The dissolution behavior during the solid-liquid interface reaction often shows that the concentration of drugs is supersaturated, with a high initial drug concentration compared with the solubility of stable crystals but finally approaching the latter solubility with time. However, a method for measuring the precipitation rate of stable crystals and/or the potential solubility of metastable crystals or amorphous drugs has not been established. In this study, a novel mathematical model that can represent the dissolution behavior of the solid-liquid interface reaction for metastable crystals or amorphous drug was developed and its validity was evaluated. The theory for this model was based on the Noyes-Whitney equation and assumes that the precipitation of stable crystals at the solid-liquid interface occurs through a first-order reaction. Moreover, two models were developed, one assuming that the surface area of the drug remains constant because of the presence of excess drug in the bulk and the other that the surface area changes in time-dependency because of agglomeration of the drug. SDs of Ibuprofen (IB)/polyvinylpyrrolidone (PVP) were prepared and their dissolution behaviors under non-sink conditions were fitted by the models to evaluate improvements in solubility. The model assuming time-dependent surface area showed good agreement with experimental values. Furthermore, by applying the model to the dissolution profile, parameters such as the precipitation rate and the potential solubility of the amorphous drug were successfully calculated. In addition, it was shown that the improvement in solubility with supersaturation was able to be evaluated quantitatively using this model. Therefore, this mathematical model would be a useful tool to quantitatively determine the supersaturation concentration of a metastable drug from solid dispersions. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermodynamic description of Tc(iv) solubility and hydrolysis in dilute to concentrated NaCl, MgCl2 and CaCl2 solutions.

PubMed

Yalçıntaş, Ezgi; Gaona, Xavier; Altmaier, Marcus; Dardenne, Kathy; Polly, Robert; Geckeis, Horst

2016-06-07

We present the first systematic investigation of Tc(iv) solubility, hydrolysis and speciation in dilute to concentrated NaCl, MgCl2 and CaCl2 systems, and comprehensive thermodynamic and activity models for the system Tc(4+)-H(+)-Na(+)-Mg(2+)-Ca(2+)-OH(-)-Cl(-)-H2O using both SIT and Pitzer approaches. The results are advancing the fundamental scientific understanding of Tc(iv) solution chemistry and are highly relevant in the applied context of nuclear waste disposal. The solubility of Tc(iv) was investigated in carbonate-free NaCl-NaOH (0.1-5.0 M), MgCl2 (0.25-4.5 M) and CaCl2 (0.25-4.5 M) solutions within 2 ≤ pHm≤ 14.5. Undersaturation solubility experiments were performed under an Ar atmosphere at T = 22 ± 2 °C. Strongly reducing conditions (pe + pHm≤ 2) were imposed with Na2S2O4, SnCl2 and Fe powder to stabilize technetium in the +IV redox state. The predominance of Tc(iv) in the aqueous phase was confirmed by solvent extraction and XANES/EXAFS spectroscopy. Solid phase characterization was accomplished after attaining thermodynamic equilibrium using XRD, SEM-EDS, XANES/EXAFS, TG-DTA and quantitative chemical analysis, and indicated that TcO2·0.6H2O(s) exerts solubility-control in all evaluated systems. The definition of the polyatomic Tc3O5(2+) species instead of TcO(2+) is favoured under acidic conditions, consistently with slope analysis (mTcvs. pHm) of the solubility data gained in this work and spectroscopic evidence previously reported in the literature. The additional formation of Tc(iv)-OH/O-Cl aqueous species in concentrated chloride media ([Cl(-)] = 9 M) and pHm≤ 4 is suggested by solubility and EXAFS data. The pH-independent behaviour of the solubility observed under weakly acidic to weakly alkaline pHm conditions can be explained with the equilibrium reaction TcO2·0.6H2O(s) + 0.4H2O(l) ⇔ TcO(OH)2(aq). Solubility data determined in dilute NaCl systems with pHm≥ 11 follow a well-defined slope of +1, consistent with the predominance of TcO(OH)3(-) previously selected by NEA-TDB. In concentrated MgCl2 and CaCl2 solutions with pHm≥ 8, the formation of the ternary Mg3[TcO(OH)5](3+) and Ca3[TcO(OH)5](3+) species is proposed based on the slope analysis of the solubility data, model calculations and previous observations for analogous An(iv) and Zr(iv) systems. The formation and stability of these hitherto unknown Tc(iv) species are supported by DFT calculations. Based on the newly generated experimental data and previous spectroscopic observations, new comprehensive chemical, thermodynamic and activity models (SIT, Pitzer) for these systems are derived.

21 CFR 177.1330 - Ionomeric resins.

Code of Federal Regulations, 2014 CFR

2014-04-01

... from a series of extraction times demonstrate equilibrium when the net chloroform-soluble extractives...)(i) and (2)(i) of this section. Should equilibrium not be demonstrated over the above time series... conditions of time and temperature characterizing the conditions of its intended use as determined from...

Characterization, dissolution and solubility of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 °C and pH 2-9.

PubMed

Zhu, Yinian; Huang, Bin; Zhu, Zongqiang; Liu, Huili; Huang, Yanhua; Zhao, Xin; Liang, Meina

2016-01-01

The interaction between Ca-HAP and Pb(2+) solution can result in the formation of a hydroxyapatite-hydroxypyromorphite solid solution [(PbxCa1-x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it's necessary to know the physicochemical properties of (PbxCa1-x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported. Dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb(2+) concentrations increased rapidly with time and reached a peak value after 240-720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00-0.80), the aqueous Pb(2+) concentrations increased quickly with time and reached a peak value after 1-12 h dissolution, and then decreased gradually and attained a stable state after 720-2160 h dissolution. The dissolution process of the solids with high XPb (0.89-1.00) was different from that of the solids with low XPb (0.00-0.80). The average K sp values were estimated to be 10(-80.77±0.20) (10(-80.57)-10(-80.96)) for hydroxypyromorphite [Pb5(PO4)3OH] and 10(-58.38±0.07) (10(-58.31)-10(-58.46)) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔG f (o) ) were determined to be -3796.71 and -6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1‒x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1-x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1-x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution. Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite-hydroxyapatite solid solution [(PbxCa1-x)5(PO4)3OH] at 25 ˚C and an initial pH of 2.00.

Derivation of Pitzer Interaction Parameters for an Aqueous Species Pair of Sodium and Iron(II)-Citrate Complex

NASA Astrophysics Data System (ADS)

Jang, J. H.; Nemer, M.

2015-12-01

The U.S. DOE Waste Isolation Pilot Plant (WIPP) is a deep underground repository for the permanent disposal of transuranic (TRU) radioactive waste. The WIPP is located in the Permian Delaware Basin near Carlsbad, New Mexico, U.S.A. The TRU waste includes, but is not limited to, iron-based alloys and the complexing agent, citric acid. Iron is also present from the steel used in the waste containers. The objective of this analysis is to derive the Pitzer activity coefficients for the pair of Na+ and FeCit- complex to expand current WIPP thermodynamic database. An aqueous model for the dissolution of Fe(OH)2(s) in a Na3Cit solution was fitted to the experimentally measured solubility data. The aqueous model consists of several chemical reactions and related Pitzer interaction parameters. Specifically, Pitzer interaction parameters for the Na+ and FeCit- pair (β(0), β(1), and Cφ) plus the stability constant for species of FeCit- were fitted to the experimental data. Anoxic gloveboxes were used to keep the oxygen level low (<1 ppm) throughout the experiments due to redox sensitivity. EQ3NR, a computer program for geochemical aqueous speciation-solubility calculations, packaged in EQ3/6 v.8.0a, calculates the aqueous speciation and saturation index using an aqueous model addressed in EQ3/6's database. The saturation index indicates how far the system is from equilibrium with respect to the solid of interest. Thus, the smaller the sum of squared saturation indices that the aqueous model calculates for the given number of experiments, the more closely the model attributes equilibrium to each individual experiment with respect to the solid of interest. The calculation of aqueous speciation and saturation indices was repeated by adjusting stability constant of FeCit-, β(0), β(1), and Cφ in the database until the values are found that make the sum of squared saturation indices the smallest for the given number of experiments. Results will be presented at the time of conference.

Phase Equilibrium Investigation on 2-Phenylethanol in Binary and Ternary Systems: Influence of High Pressure on Density and Solid-Liquid Phase Equilibrium.

PubMed

Domańska, Urszula; Królikowski, Marek; Wlazło, Michał; Więckowski, Mikołaj

2018-05-30

Ionic liquids (ILs) are important new solvents proposed for applications in different separation processes. Herein, an idea of possible use of high pressure in a general strategy of production of 2-phenylethanol (PEA) is discussed. In this work, we present the influence of pressure on the density in binary systems of {1-hexyl-1-methylpyrrolidynium bis{(trifluoromethyl)sulfonyl}imide, [HMPYR][NTf 2 ], or 1-dodecyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide, [DoMIM][NTf 2 ] + PEA} in a wide range of temperatures (298.15-348.15 K) and pressures (0.1-40 MPa). The densities at ambient and high pressures are measured to present the physicochemical properties of the ILs used in the process of separation of PEA from aqueous phase. The Tait equation was used for the correlation of density of one-component and two-component systems as a function of mole fraction, temperature, and pressure. The influence of pressure is not significant. These systems exhibit mainly negative molar excess volumes, V E . The solid-liquid phase equilibrium (SLE) of [DoMIM][NTf 2 ] in PEA at atmospheric pressure was measured and compared to the SLE high-pressure results. Additionally, the ternary liquid-liquid phase equilibrium (LLE) at ambient pressure in the {[DoMIM][NTf 2 ] (1) + PEA (2) + water (3)} at temperature T = 308.15 K was investigated. The solubility of water in the [DoMIM][NTf 2 ] is quite high in comparison with that measured by us earlier for ILs ( x 3 = 0.403) at T = 308.15 K, which results in not very successful average selectivity of extraction of PEA from the aqueous phase. The [DoMIM][NTf 2 ] has shown strong interaction with PEA without the immiscibility region. The ternary system revealed Treybal's type phase equilibrium in which two partially miscible binaries ([DoMIM][NTf 2 ] + water) and (PEA + water) exist. From the results of LLE in the ternary system, the selectivity and the solute distribution ratio of separation of water/PEA were calculated and compared to the results obtained for the ILs measured earlier by us. The popular NRTL model was used to correlate the experimental tie-lines in ternary LLE. These results may help in a new technological project of "in situ" extraction of PEA from aqueous phase during the biosynthesis.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer.

PubMed

Baker, Matthew B; Albertazzi, Lorenzo; Voets, Ilja K; Leenders, Christianus M A; Palmans, Anja R A; Pavan, Giovanni M; Meijer, E W

2015-02-20

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Consequences of chirality on the dynamics of a water-soluble supramolecular polymer

NASA Astrophysics Data System (ADS)

Baker, Matthew B.; Albertazzi, Lorenzo; Voets, Ilja K.; Leenders, Christianus M. A.; Palmans, Anja R. A.; Pavan, Giovanni M.; Meijer, E. W.

2015-02-01

The rational design of supramolecular polymers in water is imperative for their widespread use, but the design principles for these systems are not well understood. Herein, we employ a multi-scale (spatial and temporal) approach to differentiate two analogous water-soluble supramolecular polymers: one with and one without a stereogenic methyl. Initially aiming simply to understand the molecular behaviour of these systems in water, we find that while the fibres may look identical, the introduction of homochirality imparts a higher level of internal order to the supramolecular polymer. Although this increased order does not seem to affect the basic dimensions of the supramolecular fibres, the equilibrium dynamics of the polymers differ by almost an order of magnitude. This report represents the first observation of a structure/property relationship with regard to equilibrium dynamics in water-soluble supramolecular polymers.

Partially soluble organics as cloud condensation nuclei: Role of trace soluble and surface active species

NASA Astrophysics Data System (ADS)

Broekhuizen, K.; Kumar, P. Pradeep; Abbatt, J. P. D.

2004-01-01

The ability of partially soluble organic species to act as cloud condensation nuclei (CCN) has been studied. A Köhler model incorporating solute solubility and droplet surface tension describes the behavior of solid adipic and succinic acid particles, whereas solid azelaic acid activates much more efficiently that predicted. In addition, it was shown that trace levels of either sulfate or surface active species have a dramatic effect on the activation of adipic acid, a moderately soluble organic, as predicted by the full Köhler model. For internally mixed particles in the atmosphere, these effects will greatly enhance the role of organic aerosols as CCN.

Exploiting the Phenomenon of Liquid-Liquid Phase Separation for Enhanced and Sustained Membrane Transport of a Poorly Water-Soluble Drug.

PubMed

Indulkar, Anura S; Gao, Yi; Raina, Shweta A; Zhang, Geoff G Z; Taylor, Lynne S

2016-06-06

Recent studies on aqueous supersaturated lipophilic drug solutions prepared by methods including antisolvent addition, pH swing, or dissolution of amorphous solid dispersions (ASDs) have demonstrated that when crystallization is slow, these systems undergo liquid-liquid phase separation (LLPS) when the concentration of the drug in the medium exceeds its amorphous solubility. Following LLPS, a metastable equilibrium is formed where the concentration of drug in the continuous phase corresponds to the amorphous solubility while the dispersed phase is composed of a nanosized drug-rich phase. It has been reasoned that the drug-rich phase may act as a reservoir, enabling the rate of passive transport of the drug across a membrane to be maintained at the maximum value for an extended period of time. Herein, using clotrimazole as a model drug, and a flow-through diffusion cell, the reservoir effect is demonstrated. Supersaturated clotrimazole solutions at concentrations below the amorphous solubility show a linear relationship between the maximum flux and the initial concentration. Once the concentration exceeds the amorphous solubility, the maximum flux achieved reaches a plateau. However, the duration for which the high flux persists was found to be highly dependent on the number of drug-rich nanodroplets present in the donor compartment. Macroscopic amorphous particles of clotrimazole did not lead to the same reservoir effect observed with the nanodroplets formed through the process of LLPS. A first-principles mathematical model was developed which was able to fit the experimental receiver concentration-time profiles for concentration regimes both below and above amorphous solubility, providing support for the contention that the nanodroplet phase does not directly diffuse across the membrane but, instead, rapidly replenishes the drug in the aqueous phase that has been removed by transport across the membrane. This study provides important insight into the properties of supersaturated solutions and how these might in turn impact oral absorption through effects on passive membrane transport rates.

Experimental determination of carbon solubility in Fe-Ni-S melts

NASA Astrophysics Data System (ADS)

Zhang, Zhou; Hastings, Patrick; Von der Handt, Anette; Hirschmann, Marc M.

2018-03-01

To investigate the effect of metal/sulfide and Ni/Fe ratio on the C storage capacity of sulfide melts, we determine carbon solubility in Fe-Ni-S melts with various (Fe + Ni)/S and Ni/Fe via graphite-saturated high-pressure experiments from 2-7 GPa and 1200-1600 °C. Consistent with previous results, C solubility is high (4-6 wt.%) in metal-rich sulfide melts and diminishes with increasing S content. Melts with near M/S = 1 (XS > 0.4) have <0.5 wt.% C in equilibrium with graphite. C solubility is diminished modestly with increased Ni/Fe ratio, but the effect is most pronounced for S-poor melts, and becomes negligible in near-monosulfide compositions. Immiscibility between S-rich and C-rich melts is observed in Ni-poor compositions, but above ∼18 wt.% Ni there is complete miscibility. Because mantle sulfide compositions are expected to have high Ni concentrations, sulfide-carbide immiscibility is unlikely in natural mantle melts. An empirical parameterization of C solubility in Ni-Fe-S melts as a function of S and Ni contents allows estimation of the C storage capacity of sulfide in the mantle. Importantly, as the metal/sulfide (M/S) ratio of the melt increases, C storage increases both because C solubility increases and because the mass fraction of melt is enhanced by addition of metal from surrounding silicates. Under comparatively oxidized conditions where melts are near M/S = 1, as prevails at <250 km depth, bulk C storage is <3 ppm. In the deeper, more reduced mantle where M/S increases, up to 200 ppm C in typical mantle with 200 ± 100 ppm S can be stored in Fe-Ni-S melts. Thus, metal-rich sulfide melts are the principal host of carbon in the deep upper mantle and below. Residual carbon is present either as diamond or, if conditions are highly reduced and total C concentrations are low, solid alloy.

Membrane-entrapped microperoxidase as a 'solid-state' promoter in the electrochemistry of soluble metalloproteins.

PubMed Central

Brunori, M; Santucci, R; Campanella, L; Tranchida, G

1989-01-01

Immobilization of biological systems in solid matrices is presently of great interest, in view of the many potential advantages associated with both the higher stability of the immobilized macromolecules and the potential utilization for biotechnology. In the present paper the electrochemical behaviour of the undecapeptide from cytochrome c (called microperoxidase) tightly entrapped in cellulose triacetate membrane is reported; its utilization as 'solid-state' promoter in the electrochemistry of soluble metalloproteins is presented. The results obtained indicate that: (i) membrane-entrapped microperoxidase undergoes rapid reversible electron transfer at a glassy carbon electrode; (ii) the electrochemical process is diffusion-controlled; (iii) entrapped microperoxidase acts as 'solid-state' promoter in the electrochemistry of soluble cytochrome c and of azurin. PMID:2557833

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

Moto, Kenta; Sadoh, Taizoh; Miyao, Masanobu, E-mail: miyao@ed.kyushu-u.ac.jp

Crystalline GeSn-on-insulator structures with high Sn concentration (>8%), which exceeds thermal equilibrium solid-solubility (∼2%) of Sn in Ge, are essential to achieve high-speed thin film transistors and high-efficiency optical devices. We investigate non-thermal equilibrium growth of Ge{sub 1−x}Sn{sub x} (0 ≤ x ≤ 0.2) on quartz substrates by using pulsed laser annealing (PLA). The window of laser fluence enabling complete crystallization without film ablation is drastically expanded (∼5 times) by Sn doping above 5% into Ge. Substitutional Sn concentration in grown layers is found to be increased with decreasing irradiation pulse number. This phenomenon can be explained on the basis of significant thermal non-equilibriummore » growth achieved by higher cooling rate after PLA with a lower pulse number. As a result, GeSn crystals with substitutional Sn concentration of ∼12% are realized at pulse irradiation of single shot for the samples with the initial Sn concentration of 15%. Raman spectroscopy and electron microscopy measurements reveal the high quality of the grown layer. This technique will be useful to fabricate high-speed thin film transistors and high-efficiency optical devices on insulating substrates.« less

Cefuroxime axetil solid dispersion with polyglycolized glycerides for improved stability and bioavailability.

PubMed

Dhumal, Ravindra S; Biradar, Shailesh V; Aher, Suyog; Paradkar, Anant R

2009-06-01

Cefuroxime axetil (CA), a poorly soluble, broad spectrum cephalosporin ester prodrug, is hydrolysed by intestinal esterase prior to absorption, leading to poor and variable bioavailability. The objective was therefore to formulate a stable amorphous solid dispersion of the drug with enhanced solubility and stability against enzymatic degradation. Spray drying was used to obtain a solid dispersion of CA with Gelucire 50/13 and Aerosil 200 (SDCAGA), and a solid dispersion of CA with polyvinyl pyrrolidone (SDCAP); amorphous CA (ACA) was obtained by spray drying CA alone. The formulations were characterized by differential scanning calorimetry, X-ray powder diffraction, scanning electron microscopy and Fourier transform infrared spectroscopy studies, and compared for solubility, dissolution and bioavailability in rats. SDCAP and SDCAGA showed improved solubility and dissolution profiles owing to amorphization and formation of solid dispersions with hydrophilic carriers. The improved stability of amorphous CA in solid dispersions compared to ACA alone was attributed to hydrogen bonding interactions involving the amide of CA with the carbonyl of polyvinyl pyrrolidone in SDCAP, whereas in SDCAGA the interactions were at multiple sites involving the amide and carbonyl of CA with the carbonyl and hydroxyl of Gelucire 50/13. However, SDCAGA showed superior bioavailability compared to SDCAP, ACA and CA. Improvement in physical stability of solid dispersions was attributed to hydrogen bonding, while improvement in bioavailability of SDCAGA compared to SDCAP, in spite of comparable solubility and dissolution profile, may be attributed to Gelucire, which utilizes intestinal esterase for lipolysis, protecting the prodrug from enzymatic degradation to its non-absorbable base form.

In vitro characterization of a novel polymeric system for preparation of amorphous solid drug dispersions.

PubMed

Mahmoudi, Zahra N; Upadhye, Sampada B; Ferrizzi, David; Rajabi-Siahboomi, Ali R

2014-07-01

Preparation of amorphous solid dispersions using polymers is a commonly used formulation strategy for enhancing the solubility of poorly water-soluble drugs. However, often a single polymer may not bring about a significant enhancement in solubility or amorphous stability of a poorly water-soluble drug. This study describes application of a unique and novel binary polymeric blend in preparation of solid dispersions. The objective of this study was to investigate amorphous solid dispersions of glipizide, a BCS class II model drug, in a binary polymeric system of polyvinyl acetate phthalate (PVAP) and hypromellose (hydroxypropyl methylcellulose, HPMC). The solid dispersions were prepared using two different solvent methods: rotary evaporation (rotavap) and fluid bed drug layering on sugar spheres. The performance and physical stability of the dispersions were evaluated with non-sink dissolution testing, powder X-ray diffraction (PXRD), and modulated differential scanning calorimetry (mDSC). PXRD analysis demonstrated an amorphous state for glipizide, and mDSC showed no evidence of phase separation. Non-sink dissolution testing in pH 7.5 phosphate buffer indicated more than twofold increase in apparent solubility of the drug with PVAP-HPMC system. The glipizide solid dispersions demonstrated a high glass transition temperature (Tg) and acceptable chemical and physical stability during the stability period irrespective of the manufacturing process. In conclusion, the polymeric blend of PVAP-HPMC offers a unique formulation approach for developing amorphous solid dispersions with the flexibility towards the use of these polymers in different ratios and combined quantities depending on drug properties.

Tank 26F-2F Evaporator Study

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

Adu-Wusu, K.

2012-12-19

Tank 26F supernate sample was sent by Savannah River Remediation to Savannah River National Laboratory for evaporation test to help understand the underlying cause of the recent gravity drain line (GDL) pluggage during operation of the 2F Evaporator system. The supernate sample was characterized prior to the evaporation test. The evaporation test involved boiling the supernate in an open beaker until the density of the concentrate (evaporation product) was between 1.4 to 1.5 g/mL. It was followed by filtering and washing of the precipitated solids with deionized water. The concentrate supernate (or concentrate filtrate), the damp unwashed precipitated solids, andmore » the wash filtrates were characterized. All the precipitated solids dissolved during water washing. A semi-quantitative X-ray diffraction (XRD) analysis on the unwashed precipitated solids revealed their composition. All the compounds with the exception of silica (silicon oxide) are known to be readily soluble in water. Hence, their dissolution during water washing is not unexpected. Even though silica is a sparingly water-soluble compound, its dissolution is also not surprising. This stems from its small fraction in the solids as a whole and also its relative freshness. Assuming similar supernate characteristics, flushing the GDL with water (preferably warm) should facilitate dissolution and removal of future pluggage events as long as build up/aging of the sparingly soluble constituent (silica) is limited. On the other hand, since the amount of silica formed is relatively small, it is quite possible dissolution of the more soluble larger fraction will cause disintegration or fragmentation of the sparingly soluble smaller fraction (that may be embedded in the larger soluble solid mass) and allow its removal via suspension in the flushing water.« less

Comparison of a solid SMEDDS and solid dispersion for enhanced stability and bioavailability of clopidogrel napadisilate.

PubMed

Kim, Dong Wuk; Kwon, Min Seok; Yousaf, Abid Mehmood; Balakrishnan, Prabagar; Park, Jong Hyuck; Kim, Dong Shik; Lee, Beom-Jin; Park, Young Joon; Yong, Chul Soon; Kim, Jong Oh; Choi, Han-Gon

2014-12-19

The intention of this study was to compare the physicochemical properties, stability and bioavailability of a clopidogrel napadisilate (CN)-loaded solid dispersion (SD) and solid self-microemulsifying drug delivery system (solid SMEDDS). SD was prepared by a surface attached method using different ratios of Cremophor RH60 (surfactant) and HPMC (polymer), optimized based on their drug solubility. Liquid SMEDDS was composed of oil (peceol), a surfactant (Cremophor RH60) and a co-surfactant (Transcutol HP). A pseudo-ternary phase diagram was constructed to identify the emulsifying domain, and the optimized liquid SMEDDS was spray dried with an inert solid carrier (silicon dioxide), producing the solid SMEDDS. The physicochemical properties, solubility, dissolution, stability and pharmacokinetics were assessed and compared to clopidogrel napadisilate (CN) and bisulfate (CB) powders. In solid SMEDDS, liquid SMEDDS was absorbed or coated inside the pores of silicon dioxide. In SD, hydrophilic polymer and surfactants were adhered onto drug surface. The drug was in crystalline and molecularly dispersed form in SD and solid SMEDDS, respectively. Solid SMEDDS and SD greatly increased the solubility of CN but gave lower drug solubility compared to CB powder. These preparations significantly improved the dissolution of CN, but the latter more increased than the former. Stability under accelerated condition showed that they were more stable compared to CB powder, and SD was more stable than solid SMEDDS. They significantly increased the oral bioavailability of CN powder. Furthermore, SD showed significantly improved oral bioavailability compared to solid SMEDDS and CB powder. Thus, SD with excellent stability and bioavailability is recommended as an alternative for the clopidogrel-based oral formulation. Copyright © 2014 Elsevier Ltd. All rights reserved.

Preparation and characterization of solid dispersion freeze-dried efavirenz - polyvinylpyrrolidone K-30.

PubMed

Fitriani, Lili; Haqi, Alianshar; Zaini, Erizal

2016-01-01

The aim of this research is to prepare and characterize solid dispersion of efavirenz - polyvinylpyrrolidone (PVP) K-30 by freeze drying to increase its solubility. Solid dispersion of efavirenz - PVP K-30 was prepared by solvent evaporation method with ratio 2:1, 1:1, and 1:2 and dried using a freeze dryer. Characterizations were done by scanning electron microscopy (SEM), powder X-ray diffraction analysis, differential thermal analysis (DTA), and Fourier transform infrared (FT-IR) spectroscopy. Solubility test was carried out in CO2-free distilled water, and efavirenz assay was conducted using high-performance liquid chromatography with acetonitrile:acetic acid (80:20) as the mobile phases. Powder X-ray diffractogram showed a decrease in the peak intensity, which indicated the crystalline altered to amorphous phase. DTA thermal analysis showed a decrease in the melting point of the solid dispersion compared to intact efavirenz. SEM results indicated the changes in the morphology of the crystal into an amorphous form compared to pure components. FT-IR spectroscopy analysis showed a shift wavenumber of the spectrum efavirenz and PVP K-30. The solubility of solid dispersion at ratio 2:1, 1:1, and 1:2 was 6.777 μg/mL, 6.936 μg/mL, and 14,672 μg/mL, respectively, whereas the solubility of intact efavirenz was 0.250 μg/mL. In conclusion, the solubility of solid dispersion increased significantly (P < 0.05).

Adsorptive removal of pharmaceuticals from water by commercial and waste-based carbons.

PubMed

Calisto, Vânia; Ferreira, Catarina I A; Oliveira, João A B P; Otero, Marta; Esteves, Valdemar I

2015-04-01

This work describes the single adsorption of seven pharmaceuticals (carbamazepine, oxazepam, sulfamethoxazole, piroxicam, cetirizine, venlafaxine and paroxetine) from water onto a commercially available activated carbon and a non-activated carbon produced by pyrolysis of primary paper mill sludge. Kinetics and equilibrium adsorption studies were performed using a batch experimental approach. For all pharmaceuticals, both carbons presented fast kinetics (equilibrium times varying from less than 5 min to 120 min), mainly described by a pseudo-second order model. Equilibrium data were appropriately described by the Langmuir and Freundlich isotherm models, the last one giving slightly higher correlation coefficients. The fitted parameters obtained for both models were quite different for the seven pharmaceuticals under study. In order to evaluate the influence of water solubility, log Kow, pKa, polar surface area and number of hydrogen bond acceptors of pharmaceuticals on the adsorption parameters, multiple linear regression analysis was performed. The variability is mainly due to log Kow followed by water solubility, in the case of the waste-based carbon, and due to water solubility in the case of the commercial activated carbon. Copyright © 2015 Elsevier Ltd. All rights reserved.

Current trends and future perspectives of solid dispersions containing poorly water-soluble drugs.

PubMed

Vo, Chau Le-Ngoc; Park, Chulhun; Lee, Beom-Jin

2013-11-01

Over 40% of active pharmaceutical ingredients (API) in development pipelines are poorly water-soluble drugs which limit formulation approaches, clinical application and marketability because of their low dissolution and bioavailability. Solid dispersion has been considered one of the major advancements in overcoming these issues with several successfully marketed products. A number of key references that describe state-of-the-art technologies have been collected in this review, which addresses various pharmaceutical strategies and future visions for the solubilization of poorly water-soluble drugs according to the four generations of solid dispersions. This article reviews critical aspects and recent advances in formulation, preparation and characterization of solid dispersions as well as in-depth pharmaceutical solutions to overcome some problems and issues that limit the development and marketability of solid dispersion products. Copyright © 2013 Elsevier B.V. All rights reserved.

Dual Activity of Hydroxypropyl-β-Cyclodextrin and Water-Soluble Carriers on the Solubility of Carvedilol.

PubMed

Zoghbi, Abdelmoumin; Geng, Tianjiao; Wang, Bo

2017-11-01

Carvedilol (CAR) is a non-selective α and β blocker categorized as class II drug with low water solubility. Several recent studies have investigated ways to overcome this problem. The aim of the present study was to combine two of these methods: the inclusion complex using hydroxypropyl-β-cyclodextrin (HPβCD) with solid dispersion using two carriers: Poloxamer 188 (PLX) and Polyvinylpyrrolidone K-30 (PVP) to enhance the solubility, bioavailability, and the stability of CAR. Kneading method was used to prepare CAR-HPβCD inclusion complex (KD). The action of different carriers separately and in combination on Carvedilol solubility was investigated in three series. CAR-carrier and KD-carrier solid dispersions were prepared by solvent evaporation method. In vitro dissolution test was conducted in three different media: double-distilled water (DDW), simulative gastric fluid (SGF), and PBS pH 6.8 (PBS). The interactions between CAR, HPβCD, and different carriers were explored by Fourier transform infrared spectroscopy (FTIR), powder X-ray diffractometry (XRD), and differential scanning colorimetry (DSC). The results showed higher solubility of CAR in KD-PVP solid dispersions up to 70, 25, and 22 fold compared to pure CAR in DDW, SGF, and PBS, respectively. DSC and XRD analyses indicated an improved degree of transformation of CAR in KD-PVP solid dispersion from crystalline to amorphous state. This study provides a new successful combination of two polymers with the dual action of HPβCD and PLX/PVP on water solubility and bioavailability of CAR.

Influence of Physiological Gastrointestinal Surfactant Ratio on the Equilibrium Solubility of BCS Class II Drugs Investigated Using a Four Component Mixture Design

PubMed Central

2017-01-01

The absorption of poorly water-soluble drugs is influenced by the luminal gastrointestinal fluid content and composition, which control solubility. Simulated intestinal fluids have been introduced into dissolution testing including endogenous amphiphiles and digested lipids at physiological levels; however, in vivo individual variation exists in the concentrations of these components, which will alter drug absorption through an effect on solubility. The use of a factorial design of experiment and varying media by introducing different levels of bile, lecithin, and digested lipids has been previously reported, but here we investigate the solubility variation of poorly soluble drugs through more complex biorelevant amphiphile interactions. A four-component mixture design was conducted to understand the solubilization capacity and interactions of bile salt, lecithin, oleate, and monoglyceride with a constant total concentration (11.7 mM) but varying molar ratios. The equilibrium solubility of seven low solubility acidic (zafirlukast), basic (aprepitant, carvedilol), and neutral (fenofibrate, felodipine, griseofulvin, and spironolactone) drugs was investigated. Solubility results are comparable with literature values and also our own previously published design of experiment studies. Results indicate that solubilization is not a sum accumulation of individual amphiphile concentrations, but a drug specific effect through interactions of mixed amphiphile compositions with the drug. This is probably due to a combined interaction of drug characteristics; for example, lipophilicity, molecular shape, and ionization with amphiphile components, which can generate specific drug–micelle affinities. The proportion of each component can have a remarkable influence on solubility with, in some cases, the highest and lowest points close to each other. A single-point solubility measurement in a fixed composition simulated media or human intestinal fluid sample will therefore provide a value without knowledge of the surrounding solubility topography meaning that variability may be overlooked. This study has demonstrated how the amphiphile ratios influence drug solubility and highlights the importance of the envelope of physiological variation when simulating in vivo drug behavior. PMID:28749696

Comparative study on solid self-nanoemulsifying drug delivery and solid dispersion system for enhanced solubility and bioavailability of ezetimibe

PubMed Central

Rashid, Rehmana; Kim, Dong Wuk; Yousaf, Abid Mehmood; Mustapha, Omer; Din, Fakhar ud; Park, Jong Hyuck; Yong, Chul Soon; Oh, Yu-Kyoung; Youn, Yu Seok; Kim, Jong Oh; Choi, Han-Gon

2015-01-01

Background The objective of this study was to compare the physicochemical characteristics, solubility, dissolution, and oral bioavailability of an ezetimibe-loaded solid self-nanoemulsifying drug delivery system (SNEDDS), surface modified solid dispersion (SMSD), and solvent evaporated solid dispersion (SESD) to identify the best drug delivery system with the highest oral bioavailability. Methods For the liquid SNEDDS formulation, Capryol 90, Cremophor EL, and Tween 80 were selected as the oil, surfactant, and cosurfactant, respectively. The nanoemulsion-forming region was sketched using a pseudoternary phase diagram on the basis of reduced emulsion size. The optimized liquid SNEDDS was converted to solid SNEDDS by spray drying with silicon dioxide. Furthermore, SMSDs were prepared using the spray drying technique with various amounts of hydroxypropylcellulose and Tween 80, optimized on the basis of their drug solubility. The SESD formulation was prepared with the same composition of optimized SMSD. The aqueous solubility, dissolution, physicochemical properties, and pharmacokinetics of all of the formulations were investigated and compared with the drug powder. Results The drug existed in the crystalline form in SMSD, but was changed into an amorphous form in SNEDDS and SESD, giving particle sizes of approximately 24, 6, and 11 µm, respectively. All of these formulations significantly improved the aqueous solubility and dissolution in the order of solid SNEDDS ≥ SESD > SMSD, and showed a total higher plasma concentration than did the drug powder. Moreover, SESD gave a higher area under the drug concentration time curve from zero to infinity than did SNEDDS and SMSD, even if they were not significantly different, suggesting more improved oral bioavailability. Conclusion Among the various formulations tested in this study, the SESD system would be strongly recommended as a drug delivery system for the oral administration of ezetimibe with poor water solubility. PMID:26491288

Nanocrystal/sol-gel nanocomposites

DOEpatents

Klimov, Victor L.; Petruska, Melissa A.

2010-05-25

The present invention is directed to a process for preparing a solid composite having colloidal nanocrystals dispersed within a sol-gel matrix, the process including admixing colloidal nanocrystals with an amphiphilic polymer including hydrophilic groups selected from the group consisting of --COOH, --OH, --SO.sub.3H, --NH.sub.2, and --PO.sub.3H.sub.2 within a solvent to form an alcohol-soluble colloidal nanocrystal-polymer complex, admixing the alcohol-soluble colloidal nanocrystal-polymer complex and a sol-gel precursor material, and, forming the solid composite from the admixture. The present invention is also directed to the resultant solid composites and to the alcohol-soluble colloidal nanocrystal-polymer complexes.

Improving the dissolution rate of poorly water soluble drug by solid dispersion and solid solution: pros and cons.

PubMed

Chokshi, Rina J; Zia, Hossein; Sandhu, Harpreet K; Shah, Navnit H; Malick, Waseem A

2007-01-01

The solid dispersions with poloxamer 188 (P188) and solid solutions with polyvinylpyrrolidone K30 (PVPK30) were evaluated and compared in an effort to improve aqueous solubility and bioavailability of a model hydrophobic drug. All preparations were characterized by differential scanning calorimetry, powder X-ray diffraction, intrinsic dissolution rates, and contact angle measurements. Accelerated stability studies also were conducted to determine the effects of aging on the stability of various formulations. The selected solid dispersion and solid solution formulations were further evaluated in beagle dogs for in vivo testing. Solid dispersions were characterized to show that the drug retains its crystallinity and forms a two-phase system. Solid solutions were characterized to be an amorphous monophasic system with transition of crystalline drug to amorphous state. The evaluation of the intrinsic dissolution rates of various preparations indicated that the solid solutions have higher initial dissolution rates compared with solid dispersions. However, after storage at accelerated conditions, the dissolution rates of solid solutions were lower due to partial reversion to crystalline form. The drug in solid dispersion showed better bioavailability in comparison to solid solution. Therefore, considering physical stability and in vivo study results, the solid dispersion was the most suitable choice to improve dissolution rates and hence the bioavailability of the poorly water soluble drug.

Perspectives on Strategies Using Swellable Polymers in Solid Dispersions for Controlled Drug Release.

PubMed

Tran, Thao T D; Tran, Phuong H L

2017-01-01

Poorly water-soluble drugs, which commonly face the issue of poor absorption and low bioavailability, have been under ongoing research of many formulation scientists for the past few decades. Solid dispersion is one of the most effective strategies in concerns for improving bioavailability of poorly water-soluble drugs. Either application of solid dispersions in dissolution enhancement of poorly water-soluble drugs or the use of swellable polymers in controlled drug release has been reported in pharmaceutical designs widely. However, a review of strategies of using swellable polymers in solid dispersion to take a full advantage of these polymers as a current perspective in facilitating drug bioavailability enhancement is still missing. In this review, we aim to provide a summary of techniques used to formulate a swellable polymer in solid dispersion especially a description of a suitable fabrication method in design of a controlled release solid dispersion. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Solubility and Thermodynamics: An Introductory Experiment

NASA Astrophysics Data System (ADS)

Silberman, Robert G.

1996-05-01

This article describes a laboratory experiment suitable for high school or freshman chemistry students in which the solubility of potassium nitrate is determined at several different temperatures. The data collected is used to calculate the equilibrium constant, delta G, delta H, and delta S for dissolution reaction. The simplifying assumptions are noted in the article.

Hansen solubility parameters (HSP) for prescreening formulation of solid lipid nanoparticles (SLN): in vitro testing of curcumin-loaded SLN in MCF-7 and BT-474 cell lines.

PubMed

Doktorovova, Slavomira; Souto, Eliana B; Silva, Amélia M

2018-01-01

Curcumin, a phenolic compound from turmeric rhizome (Curcuma longa), has many interesting pharmacological effects, but shows very low aqueous solubility. Consequently, several drug delivery systems based on polymeric and lipid raw materials have been proposed to increase its bioavailability. Solid lipid nanoparticles (SLN), consisting of solid lipid matrix and a surfactant layer can load poorly water-soluble drugs, such as curcumin, deliver them at defined rates and enhance their intracellular uptake. In the present work, we demonstrate that, despite the drug's affinity to lipids frequently used in SLN production, the curcumin amount loaded in most SLN formulations may be too low to exhibit anticancer properties. The predictive curcumin solubility in solid lipids has been thoroughly analyzed by Hansen solubility parameters, in parallel with the lipid-screening solubility tests for a range of selected lipids. We identified the most suitable lipid materials for curcumin-loaded SLN, producing physicochemically stable particles with high encapsulation efficiency (>90%). Loading capacity of curcumin in SLN allowed preventing the cellular damage caused by cationic SLN on MCF-7 and BT-474 cells but was not sufficient to exhibit drug's anticancer properties. But curcumin-loaded SLN exhibited antioxidant properties, substantiating the conclusions that curcumin's effect in cancer cells is highly dose dependent.

A green analytical method using ultrasound in sample preparation for the flow injection determination of iron, manganese, and zinc in soluble solid samples by flame atomic absorption spectrometry.

PubMed

Yebra, M Carmen

2012-01-01

A simple and rapid analytical method was developed for the determination of iron, manganese, and zinc in soluble solid samples. The method is based on continuous ultrasonic water dissolution of the sample (5-30 mg) at room temperature followed by flow injection flame atomic absorption spectrometric determination. A good precision of the whole procedure (1.2-4.6%) and a sample throughput of ca. 25 samples h(-1) were obtained. The proposed green analytical method has been successfully applied for the determination of iron, manganese, and zinc in soluble solid food samples (soluble cocoa and soluble coffee) and pharmaceutical preparations (multivitamin tablets). The ranges of concentrations found were 21.4-25.61 μg g(-1) for iron, 5.74-18.30 μg g(-1) for manganese, and 33.27-57.90 μg g(-1) for zinc in soluble solid food samples and 3.75-9.90 μg g(-1) for iron, 0.47-5.05 μg g(-1) for manganese, and 1.55-15.12 μg g(-1) for zinc in multivitamin tablets. The accuracy of the proposed method was established by a comparison with the conventional wet acid digestion method using a paired t-test, indicating the absence of systematic errors.

Rare earth element variations resulting from inversion of pigeonite and subsolidus reequilibration in lunar ferroan anorthosites

USGS Publications Warehouse

James, O.B.; Floss, C.; McGee, J.J.

2002-01-01

We present results of a secondary ion mass spectrometry study of the rare earth elements (REEs) in the minerals of two samples of lunar ferroan anorthosite, and the results are applicable to studies of REEs in all igneous rocks, no matter what their planet of origin. Our pyroxene analyses are used to determine solid-solid REE distribution coefficients (D = CREE in low-Ca pyroxene/CREE in augite) in orthopyroxene-augite pairs derived by inversion of pigeonite. Our data and predictions from crystal-chemical considerations indicate that as primary pigeonite inverts to orthopyroxene plus augite and subsolidus reequilibration proceeds, the solid-solid Ds for orthopyroxene-augite pairs progressively decrease for all REEs; the decrease is greatest for the LREEs. The REE pattern of solid-solid Ds for inversion-derived pyroxene pairs is close to a straight line for Sm-Lu and turns upward for REEs lighter than Sm; the shape of this pattern is predicted by the shapes of the REE patterns for the individual minerals. Equilibrium liquids calculated for one sample from the compositions of primary phases, using measured or experimentally determined solid-liquid Ds, have chondrite-normalized REE patterns that are very slightly enriched in LREEs. The plagioclase equilibrium liquid is overall less rich in REEs than pyroxene equilibrium liquids, and the discrepancy probably arises because the calculated plagioclase equilibrium liquid represents a liquid earlier in the fractionation sequence than the pyroxene equilibrium liquids. "Equilibrium" liquids calculated from the compositions of inversion-derived pyroxenes or orthopyroxene derived by reaction of olivine are LREE depleted (in some cases substantially) in comparison with equilibrium liquids calculated from the compositions of primary phases. These discrepancies arise because the inversion-derived and reaction-derived pyroxenes did not crystallize directly from liquid, and the use of solid-liquid Ds is inappropriate. The LREE depletion of the calculated liquids is a relic of formation of these phases from primary LREE-depleted minerals. Thus, if one attempts to calculate the compositions of equilibrium liquids from pyroxene compositions, it is important to establish that the pyroxenes are primary. In addition, our data suggest that experimental studies have underestimated solid-liquid Ds for REEs in pigeonite and that REE contents of liquids calculated using these Ds are overestimates. Our results have implications for Sm-Nd age studies. Our work shows that if pigeonite inversion and/or subsolidus reequilibration between augite and orthopyroxene occured significantly after crystallization, and if pyroxene separates isolated for Sm-Nd studies do not have the bulk composition of the primary pyroxenes, then the Sm-Nd isochron age and ??Nd will be in error. Copyright ?? 2002 Elsevier Science Ltd.

Abiologic silicon isotope fractionation between aqueous Si and Fe(III)-Si gel in simulated Archean seawater: Implications for Si isotope records in Precambrian sedimentary rocks

NASA Astrophysics Data System (ADS)

Zheng, Xin-Yuan; Beard, Brian L.; Reddy, Thiruchelvi R.; Roden, Eric E.; Johnson, Clark M.

2016-08-01

Precambrian Si-rich sedimentary rocks, including cherts and banded iron formations (BIFs), record a >7‰ spread in 30Si/28Si ratios (δ30Si values), yet interpretation of this large variability has been hindered by the paucity of data on Si isotope exchange kinetics and equilibrium fractionation factors in systems that are pertinent to Precambrian marine conditions. Using the three-isotope method and an enriched 29Si tracer, a series of experiments were conducted to constrain Si isotope exchange kinetics and fractionation factors between amorphous Fe(III)-Si gel, a likely precursor to Precambrian jaspers and BIFs, and aqueous Si in artificial Archean seawater under anoxic conditions. Experiments were conducted at room temperature, and in the presence and absence of aqueous Fe(II) (Fe(II)aq). Results of this study demonstrate that Si solubility is significantly lower for Fe-Si gel than that of amorphous Si, indicating that seawater Si concentrations in the Precambrian may have been lower than previous estimates. The experiments reached ∼70-90% Si isotope exchange after a period of 53-126 days, and the highest extents of exchange were obtained where Fe(II)aq was present, suggesting that Fe(II)-Fe(III) electron-transfer and atom-exchange reactions catalyze Si isotope exchange through breakage of Fe-Si bonds. All experiments except one showed little change in the instantaneous solid-aqueous Si isotope fractionation factor with time, allowing extraction of equilibrium Si isotope fractionation factors through extrapolation to 100% isotope exchange. The equilibrium 30Si/28Si fractionation between Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -2.30 ± 0.25‰ (2σ) in the absence of Fe(II)aq. In the case where Fe(II)aq was present, which resulted in addition of ∼10% Fe(II) in the final solid, creating a mixed Fe(II)-Fe(III) Si gel, the equilibrium fractionation between Fe(II)-Fe(III)-Si gel and aqueous Si (Δ30Sigel-aqueous) is -3.23 ± 0.37‰ (2σ). Equilibrium Si isotope fractionation for Fe-Si gel systems is significantly larger in magnitude than estimates of a near-zero solid-aqueous fractionation factor between pure Si gel and aqueous Si, indicating a major influence of Fe atoms on Si-O bonds, and hence the isotopic properties, of Fe-Si gel. Larger Si isotope fractionation in the Fe(II)-bearing systems may be caused by incorporation of Fe(II) into the solid structure, which may further weaken Fe-Si bonds and thus change the Si isotope fractionation factor. The relatively large Si isotope fractionation for Fe-Si gel, relative to pure Si gel, provides a new explanation for the observed contrast in δ30Si values in the Precambrian BIFs and cherts, as well as an explanation for the relatively negative δ30Si values in BIFs, in contrast to previous proposals that the more negative δ30Si values in BIFs reflect hydrothermal sources of Si or sorption to Fe oxides/hydroxides.

Countercurrent extraction of soluble sugars from almond hulls and assessment of the bioenergy potential

USDA-ARS?s Scientific Manuscript database

Almond hulls contain considerable proportions (37 % by dry weight) of water soluble, fermentable sugars (sucrose, glucose, fructose) which can be extracted for industrial purposes. Optimization found that 20 % solids content was the maximum practical solids/liquor ratio for sugar extraction and tha...

Potassium application to table grape clusters after veraison increases soluble solids by enhancing berry water loss

USDA-ARS?s Scientific Manuscript database

Potassium salt solutions were applied twice to clusters of several table grapes cultivars, after the onset of veraison and three weeks later. Potassium bicarbonate, potassium sorbate, and glycine-complexed potassium, a commercial fertilizer product, increased soluble solids content consistently, whi...

Spatial assessment of soluble solid contents on apple slices using hyperspectral imaging

USDA-ARS?s Scientific Manuscript database

A partial least squares regression (PLSR) model to map internal soluble solids content (SSC) of apples using visible/near-infrared (VNIR) hyperspectral imaging was developed. The reflectance spectra of sliced apples were extracted from hyperspectral absorbance images obtained in the 400e1000 nm rang...

Comparison and fusion of four nondestructive sensors for predicting apple fruit firmness and soluble solids content

USDA-ARS?s Scientific Manuscript database

Four nondestructive technologies (i.e., acoustic firmness, bioyield firmness, visible/near-infrared (NIR) spectroscopy, and spectral scattering) have been developed in recent years for assessing the firmness and/or soluble solids content (SSC) of apples. Each of these technologies has its merits and...

Development of solid dispersions of artemisinin for transdermal delivery.

PubMed

Shahzad, Yasser; Sohail, Sadia; Arshad, Muhammad Sohail; Hussain, Talib; Shah, Syed Nisar Hussain

2013-11-30

Solid dispersions of the poorly soluble drug artemisinin were developed using polymer blends of polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) with the aim of enhancing solubility and in vitro permeation of artemisinin through skin. Formulations were characterised using a combination of molecular dynamics (MD) simulations, differential scanning calorimetry (DSC), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). Solubility of artemisinin was determined in two solvents: de-ionised water and phosphate buffered saline (PBS; pH 7.4), while in vitro drug permeation studies were carried out using rabbit skin as a model membrane. MD simulations revealed miscibility between the drug and polymers. DSC confirmed the molecular dispersion of the drug in the polymer blend. Decrease in crystallinity of artemisinin with respect to polymer content and the absence of specific drug-polymer interactions were confirmed using XRD and FT-IR, respectively. The solubility of artemisinin was dramatically enhanced for the solid dispersions, as was the permeation of artemisinin from saturated solid-dispersion vehicles relative to that from saturated solutions of the pure drug. The study suggests that high energy solid forms of artemisinin could possibly enable transdermal delivery of artemisinin. Copyright © 2013 Elsevier B.V. All rights reserved.

Bioavailability enhancement of a poorly water-soluble drug by solid dispersion in polyethylene glycol-polysorbate 80 mixture.

PubMed

Joshi, Hemant N; Tejwani, Ravindra W; Davidovich, Martha; Sahasrabudhe, Vaishali P; Jemal, Mohammed; Bathala, Mohinder S; Varia, Sailesh A; Serajuddin, Abu T M

2004-01-09

Oral bioavailability of a poorly water-soluble drug was greatly enhanced by using its solid dispersion in a surface-active carrier. The weakly basic drug (pK(a) approximately 5.5) had the highest solubility of 0.1mg/ml at pH 1.5, < 1 microg/ml aqueous solubility between pH 3.5 and 5.5 at 24+/-1 degrees C, and no detectable solubility (< 0.02 microg/ml) at pH greater than 5.5. Two solid dispersion formulations of the drug, one in Gelucire 44/14 and another one in a mixture of polyethylene glycol 3350 (PEG 3350) with polysorbate 80, were prepared by dissolving the drug in the molten carrier (65 degrees C) and filling the melt in hard gelatin capsules. From the two solid dispersion formulations, the PEG 3350-polysorbate 80 was selected for further development. The oral bioavailability of this formulation in dogs was compared with that of a capsule containing micronized drug blended with lactose and microcrystalline cellulose and a liquid solution in a mixture of PEG 400, polysorbate 80 and water. For intravenous administration, a solution in a mixture of propylene glycol, polysorbate 80 and water was used. Absolute oral bioavailability values from the capsule containing micronized drug, the capsule containing solid dispersion and the oral liquid were 1.7+/-1.0%, 35.8+/-5.2% and 59.6+/-21.4%, respectively. Thus, the solid dispersion provided a 21-fold increase in bioavailability of the drug as compared to the capsule containing micronized drug. A capsule formulation containing 25 mg of drug with a total fill weight of 600 mg was subsequently selected for further development. The selected solid dispersion formulation was physically and chemically stable under accelerated storage conditions for at least 6 months. It is hypothesized that polysorbate 80 ensures complete release of drug in a metastable finely dispersed state having a large surface area, which facilitates further solubilization by bile acids in the GI tract and the absorption into the enterocytes. Thus, the bioavailability of this poorly water-soluble drug was greatly enhanced by formulation as a solid dispersion in a surface-active carrier.

Correlation of Helium Solubility in Liquid Nitrogen

NASA Technical Reports Server (NTRS)

VanDresar, Neil T.; Zimmerli, Gregory A.

2012-01-01

A correlation has been developed for the equilibrium mole fraction of soluble gaseous helium in liquid nitrogen as a function of temperature and pressure. Experimental solubility data was compiled and provided by National Institute of Standards and Technology (NIST). Data from six sources was used to develop a correlation within the range of 0.5 to 9.9 MPa and 72.0 to 119.6 K. The relative standard deviation of the correlation is 6.9 percent.

The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-Ca-Cl-SO 4-H 2O system, to high temperature and concentration

NASA Astrophysics Data System (ADS)

Møller, Nancy

1988-04-01

This paper describes a chemical equilibrium model for the Na-Ca-Cl-SO 4-H 2O system which calculates solubilities from 25°C to 250°C and from zero to high concentration ( I ~ 18. m) within experimental uncertainty. The concentration and temperature dependence of the model were established by fitting available activity (solubility, osmotic and emf) data. A single ion complex, CaSO 04, which increases in strength with temperature, is included explicitly in the model. The validation of model accuracy by comparison to laboratory and field solubility data is included. Applications of the model are also given. Phase diagrams constructed for the Na-Ca-Cl-SO 4-H 2O system and predicted solubilities of anhydrite and hemihydrate in concentrated seawater at high temperature are in very good agreement with the data. Calculations of the temperature of gypsum-anhydrite coexistence as a function of water activity are compared to reported values, and are used to estimate the composition-temperature relation for gypsum-anhydrite transition in a natural brine evaporation. A preliminary model for barite solubility in sodium chloride solutions at high temperature (100°C to 250°C), based on this parameterization of the CaSO 4-NaCl-H 2O system, gives good agreement with the data.

Site specific solubility improvement using solid dispersions of HPMC-AS/HPC SSL--mixtures.

PubMed

Zecevic, Damir Elmar; Meier, Robin; Daniels, Rolf; Wagner, Karl-Gerhard

2014-07-01

Many upcoming drug candidates are pH-dependent poorly soluble weak bases in the pH range of the gastrointestinal tract. This often leads to a high in vivo variability and bioavailability issues. Aiming to overcome these limitations, the design of solid dispersions for site specific dissolution improvement or maintenance of a potent supersaturation over the entire gastro-intestinal pH-range, is proposed to assure a reliable drug therapy. Solid dispersions containing different ratios of Dipyridamole (DPD) or Griseofulvin (GRI) and the enteric polymer hydroxypropylmethylcellulose-acetate succinate (HPMC-AS) and the water soluble low-viscosity hydroxypropylcellulose (HPC-SSL) were prepared by hot melt extrusion (HME). The solid dispersions were evaluated for their solid state, dissolution characteristics applying a three pH-step dissolution method following an acidic to neutral pH transition and stability. The use of HPMC-AS in binary mixtures with DPD and GRI facilitated increased solubility and supersaturation at pH-controlled release of the preserved amorphous state of the dispersed drug, which even inverted the pH-dependent solubility profile of the weakly basic model drug (Dipyridamole). I.e. a potent site specific delivery system was created. With ternary solid dispersions of API, HPMC-AS and HPC-SSL, tailored release profiles with superior supersaturation over the applied pH-range could be obtained. At the same time, binary and ternary mixtures showed favorable stability properties at a temperature difference between glass transition temperature and the applied storage temperature of down to 16°C. Copyright © 2014 Elsevier B.V. All rights reserved.

State and solubility of cadmium as related to xenotic inorganic phases generated homogeneously in soils

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

Walker, W.J.

The state and solubility of cadmium in waste-treated soils was investigated. Three sets of experiments were designed to elucidate solid phase control of soil solution cadmium. First, the soil solution composition of two soils amended with either sludge or metal contaminated mulch was examined to determine the presence of anions capable of precipitating or co-precipitating cadmium. Results indicated that no known pure solid phases of cadmium developed but that high concentrations of phosphate, sulfate and carbonate apparently influenced cadmium solubility. Secondly, three soils were amended with 10 ug of cadmium as cadmium acetate/g of soil. Three different levels of glycerophosphate,more » cysteine and acetate were added to the soils and incubated at constant temperature and water content in order to release phosphate, sulfate and alkalinity under conditions conducive for homogeneous precipitation. Another set of treatments was prepared in the same fashion with an additional amendment of calcium carbonate to raise soil pH's to 7.0. In the presence of sulfate, cadmium solubility increased with no apparent solid phase formation. The addition of calcium carbonate shifted solid phase control to either calcium carbonate or calcium sulfate. The generation of alkalinity by acetate addition produced solid phase calcium carbonate which in turn controlled cadmium solubility through chemisorption of cadmium on calcite surfaces. In the presence of monobasic calcium phosphate, cadmium was interfacially adsorbed. In the presence of dibasic calcium phosphate, however, cadmium was homogeneously precipitated in the host crystal suggesting possible solid solution.« less

Formation of the racemic compound of ephedrine base from a physical mixture of its enantiomers in the solid, liquid, solution, or vapor state.

PubMed

Duddu, S P; Grant, D J

1992-08-01

Physical mixtures (conglomerates) of the two enantiomers of ephedrine base, each containing 0.5% (w/w) of water, were observed to be converted to the 1:1 racemic compound in the solid, liquid, solution, or vapor state. From a geometrically mixed racemic conglomerate of particle size 250-300 microns (50-60 mesh), the formation of the racemic compound follows second-order kinetics (first order with respect to each enantiomer), with a rate constant of 392 mol-1 hr-1 at 22 degrees C. The reaction appears to proceed via the vapor phase as indicated by the growth of the crystals of the racemic compound between diametrically separated crystals of the two enantiomers in a glass petri dish. The observed kinetics of conversion in the solid state are explained by a homogeneous reaction model via the vapor and/or liquid states. Formation of the racemic compound from the crystals of ephedrine enantiomers in the solution state may explain why Schmidt et al. (Pharm. Res. 5:391-395, 1988) observed a consistently lower aqueous solubility of the mixture than of the pure enantiomers. The solid phase in equilibrium with the solution at the end of the experiment was found to be the racemic compound, whose melting point and heat of fusion are higher than those of the enantiomers. An association reaction, of measurable rate, between the opposite enantiomers in a binary mixture in the solid, liquid, solution, or vapor state to form the racemic compound may be more common than is generally realized.

Improved intestinal absorption of a poorly water-soluble oral drug using mannitol microparticles containing a nanosolid drug dispersion.

PubMed

Nishino, Yukiko; Kubota, Aya; Kanazawa, Takanori; Takashima, Yuuki; Ozeki, Tetsuya; Okada, Hiroaki

2012-11-01

A nozzle for a spray dryer that can prepare microparticles of water-soluble carriers containing various nanoparticles in a single step was previously developed in our laboratory. To enhance the solubility and intestinal absorption of poorly water-soluble drugs, we used probucol (PBL) as a poorly water-soluble drug, mannitol (MAN) as a water-soluble carrier for the microparticles, and EUDRAGIT (EUD) as a polymer vehicle for the solid dispersion. PBL-EUD-acetone-methanol and aqueous MAN solutions were simultaneously supplied through different liquid passages of the spray nozzle and dried together. PBL-EUD solid dispersion was nanoprecipitated in the MAN solution using an antisolvent mechanism and rapidly dried by surrounding it with MAN. PBL in the dispersion vehicle was amorphous and had higher physical stability according to powder X-ray diffraction and differential scanning calorimetry analysis. The bioavailability of PBL in PBL-EUD S-100-MAN microparticles after oral administration in rats was markedly higher (14- and 6.2-fold, respectively) than that of the original PBL powder and PBL-MAN microparticles. These results demonstrate that the composite microparticles containing a nanosized solid dispersion of a poorly water-soluble drug prepared using the spray nozzle developed by us should be useful to increase the solubility and bioavailability of drugs after oral administration. Copyright © 2012 Wiley Periodicals, Inc.

Template-assisted mineral formation via an amorphous liquid phase precursor route

NASA Astrophysics Data System (ADS)

Amos, Fairland F.

The search for alternative routes to synthesize inorganic materials has led to the biomimetic route of producing ceramics. In this method, materials are manufactured at ambient temperatures and in aqueous solutions with soluble additives and insoluble matrix, similar to the biological strategy for the formation of minerals by living organisms. Using this approach, an anionic polypeptide additive was used to induce an amorphous liquid-phase precursor to either calcium carbonate or calcium phosphate. This precursor was then templated on either organic or inorganic substrates. Non-equilibrium morphologies, such as two-dimensional calcium carbonate films, one-dimensional calcium carbonate mesostructures and "molten" calcium phosphate spherulites were produced, which are not typical of the traditional (additive-free) solution grown crystals in the laboratory. In the study of calcium carbonate, the amorphous calcium carbonate mineral formed via the liquid-phase precursor, either underwent a dissolution-recrystallization event or a pseudo-solid-state transformation to produce different morphologies and polymorphs of the mineral. Discrete or aggregate calcite crystals were formed via the dissolution of the amorphous phase to allow the reprecipitation of the stable crystal. Non-equilibrium morphologies, e.g., films, mesotubules and mesowires were templated using organic and inorganic substrates and compartments. These structures were generated via an amorphous solid to crystalline solid transformation. Single crystalline tablets and mesowires of aragonite, which are reported to be found only in nature as skeletal structures of marine organisms, such as mollusk nacre and echinoderm teeth, were successfully synthesized. These biomimetic structures were grown via the polymer-induced liquid-phase precursor route in the presence of magnesium. Only low magnesium-bearing calcite was formed in the absence of the polymer. A similar approach of using a polymeric additive was implemented in calcium phosphate. Spherulitic crystals and films, seemingly formed from a molten state, were produced. These structures served as nucleating surfaces for the radial formation of calcium oxalate minerals. The composite calcium phosphate-calcium oxalate assemblies are similar to the core-shell structures found in certain kidney stones.

Metastable Phase Evolution in Oxide Systems

NASA Astrophysics Data System (ADS)

Levi, Carlos G.

2005-03-01

Multi-component ceramics are often synthesized by routes that facilitate mixing at the molecular scale and subsequently generate a solid product at low homologous temperatures. Examples include chemical and physical vapor deposition, thermal spray, and pyrolytic decomposition of precursor solutions. In these processes the solid evolves rapidly from a highly energized state, typically in a temperature regime wherein long-range diffusion is largely constrained and the equilibrium configuration can be kinetically suppressed. The resulting product may exhibit various forms of metastability such as amorphization, nanocrystallinity, extended solid solubility and alternate crystalline forms. The approach allows access to novel combinations of structure and composition with unprecedented defect structures that, if reasonably durable, could have properties of potential technological interest. Understanding phase selection and evolution is facilitated by having a suitable reference framework depicting the thermodynamic hierarchy of the phases available to the system under the relevant processing conditions. When transformations are partitionless the phase menu and hierarchy can be readily derived from the relative position of the T0 curves/surfaces for the different pairs of phases. The result is a phase hierarchy map, which is an analog of the phase diagram for partitionless equilibrium. Such maps can then be used to assess the kinetic effects on the selection of metastable states and their subsequent evolution. This presentation will discuss the evolution of metastable phases in oxides, with emphasis on systems involving fluorite phases and their ordered or distorted derivatives. The concepts will be illustrated primarily with zirconia-based systems, notably those of interest in thermal barrier coatings, fuel cells and ferroelectrics (ZrO2-MO3/2, where M = Y, Sc, the lanthanides and combinations thereof, as well as ZrO2-YO3/2-TiO2, ZrO2-TiO2-PbO, etc.). Of particular interest are the durabilities of metastable phases in systems that operate at high temperature, their decomposition paths and the implications to their functionality.

Dynamic fractionation of trace metals in soil and sediment samples using rotating coiled column extraction and sequential injection microcolumn extraction: a comparative study.

PubMed

Rosende, Maria; Savonina, Elena Yu; Fedotov, Petr S; Miró, Manuel; Cerdà, Víctor; Wennrich, Rainer

2009-09-15

Dynamic fractionation has been recognized as an appealing alternative to conventional equilibrium-based sequential extraction procedures (SEPs) for partitioning of trace elements (TE) in environmental solid samples. This paper reports the first attempt for harmonization of flow-through dynamic fractionation using two novel methods, the so-called sequential injection microcolumn (SIMC) extraction and rotating coiled column (RCC) extraction. In SIMC extraction, a column packed with the solid sample is clustered in a sequential injection system, while in RCC, the particulate matter is retained under the action of centrifugal forces. In both methods, the leachants are continuously pumped through the solid substrates by the use of either peristaltic or syringe pumps. A five-step SEP was selected for partitioning of Cu, Pb and Zn in water soluble/exchangeable, acid-soluble, easily reducible, easily oxidizable and moderately reducible fractions from 0.2 to 0.5 g samples at an extractant flow rate of 1.0 mL min(-1) prior to leachate analysis by inductively coupled plasma-atomic emission spectrometry. Similarities and discrepancies between both dynamic approaches were ascertained by fractionation of TE in certified reference materials, namely, SRM 2711 Montana Soil and GBW 07311 sediment, and two real soil samples as well. Notwithstanding the different extraction conditions set by both methods, similar trends of metal distribution were in generally found. The most critical parameters for reliable assessment of mobilizable pools of TE in worse-case scenarios are the size-distribution of sample particles, the density of particles, the content of organic matter and the concentration of major elements. For reference materials and a soil rich in organic matter, the extraction in RCC results in slightly higher recoveries of environmentally relevant fractions of TE, whereas SIMC leaching is more effective for calcareous soils.

The role of solid-solid phase transitions in mantle convection

NASA Astrophysics Data System (ADS)

Faccenda, Manuele; Dal Zilio, Luca

2017-01-01

With changing pressure and temperature conditions, downwelling and upwelling crustal and mantle rocks experience several solid-solid phase transitions that affect the mineral physical properties owing to structural changes in the crystal lattice and to the absorption or release of latent heat. Variations in density, together with phase boundary deflections related to the non-null reaction slope, generate important buoyancy forces that add to those induced by thermal perturbations. These buoyancy forces are proportional to the density contrast between reactant and product phases, their volume fraction, the slope and the sharpness of the reaction, and affect the style of mantle convection depending on the system composition. In a homogeneous pyrolitic mantle there is little tendency for layered convection, with slabs that may stagnate in the transition zone because of the positive buoyancy caused by post-spinel and post-ilmenite reactions, and hot plumes that are accelerated by phase transformations in the 600-800 km depth range. By adding chemical and mineralogical heterogeneities as on Earth, phase transitions introduce bulk rock and volatiles filtering effects that generate a compositional gradient throughout the entire mantle, with levels that are enriched or depleted in one or more of these components. Phase transitions often lead to mechanical softening or hardening that can be related to a different intrinsic mechanical behaviour and volatile solubility of the product phases, the heating or cooling associated with latent heat, and the transient grain size reduction in downwelling cold material. Strong variations in viscosity would enhance layered mantle convection, causing slab stagnation and plume ponding. At low temperatures and relatively dry conditions, reactions are delayed due to the sluggish kinetics, so that non-equilibrium phase aggregates can persist metastably beyond the equilibrium phase boundary. Survival of low-density metastable olivine, Ringwoodite, pyroxene and pyrope garnet in the transition zone and uppermost lower mantle produces positive buoyancy forces that decrease the subduction velocity and may lead to slab stagnation in the transition zone. The presence of deep metastable portions is still debated, and should not be associated a-priori with a completely dry slab as field observations suggest that heterogeneously hydrated oceanic plates could contain metastable dry portions surrounded by transformed wet rocks.

Studies on dissolution enhancement and mathematical modeling of drug release of a poorly water-soluble drug using water-soluble carriers.

PubMed

Ahuja, Naveen; Katare, Om Prakash; Singh, Bhupinder

2007-01-01

Role of various water-soluble carriers was studied for dissolution enhancement of a poorly soluble model drug, rofecoxib, using solid dispersion approach. Diverse carriers viz. polyethylene glycols (PEG 4000 and 6000), polyglycolized fatty acid ester (Gelucire 44/14), polyvinylpyrollidone K25 (PVP), poloxamers (Lutrol F127 and F68), polyols (mannitol, sorbitol), organic acid (citric acid) and hydrotropes (urea, nicotinamide) were investigated for the purpose. Phase-solubility studies revealed AL type of curves for each carrier, indicating linear increase in drug solubility with carrier concentration. The sign and magnitude of the thermodynamic parameter, Gibbs free energy of transfer, indicated spontaneity of solubilization process. All the solid dispersions showed dissolution improvement vis-à-vis pure drug to varying degrees, with citric acid, PVP and poloxamers as the most promising carriers. Mathematical modeling of in vitro dissolution data indicated the best fitting with Korsemeyer-Peppas model and the drug release kinetics primarily as Fickian diffusion. Solid state characterization of the drug-poloxamer binary system using XRD, FTIR, DSC and SEM techniques revealed distinct loss of drug crystallinity in the formulation, ostensibly accounting for enhancement in dissolution rate.

Le Chatelier's Principle: The Effect of Temperature on the Solubility of Solids in Liquids.

ERIC Educational Resources Information Center

Brice, L. K.

1983-01-01

Provides a rigorous but straightforward thermodynamic treatment of the temperature dependence of the solubility of solids in liquids that is suitable for presentation to undergraduates, suggesting how to approach the qualitative aspects of the subject for freshmen. Considers unsolvated/solvated solutes and Le Chatelier's principle. (JN)

7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

Code of Federal Regulations, 2013 CFR

2013-01-01

... 7 Agriculture 2 2013-01-01 2013-01-01 false Maximum anhydrous citric acid permissible for... Common Sweet Oranges (citrus Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for... following Table II together with the minimum ratio of total soluble solids to anhydrous citric acid: Table...

7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

Code of Federal Regulations, 2014 CFR

2014-01-01

... 7 Agriculture 2 2014-01-01 2014-01-01 false Maximum anhydrous citric acid permissible for... Common Sweet Oranges (citrus Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for... following Table II together with the minimum ratio of total soluble solids to anhydrous citric acid: Table...

7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

Code of Federal Regulations, 2012 CFR

2012-01-01

... 7 Agriculture 2 2012-01-01 2012-01-01 false Maximum anhydrous citric acid permissible for... Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble solids. For determining the grade of juice, the maximum permissible anhydrous citric acid content in...

7 CFR 51.1178 - Maximum anhydrous citric acid permissible for corresponding total soluble solids.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 7 Agriculture 2 2011-01-01 2011-01-01 false Maximum anhydrous citric acid permissible for... Sinensis (l) Osbeck) § 51.1178 Maximum anhydrous citric acid permissible for corresponding total soluble solids. For determining the grade of juice, the maximum permissible anhydrous citric acid content in...

Analysis of hyperspectral scattering profiles using a generalized Gaussian distribution function for prediction of apple firmness and soluble solids content

USDA-ARS?s Scientific Manuscript database

Hyperspectral scattering provides an effective means for characterizing light scattering in the fruit and is thus promising for noninvasive assessment of apple firmness and soluble solids content (SSC). A critical problem encountered in application of hyperspectral scattering technology is analyzing...

Measurement of moisture, soluble solids, and sucrose content and mechanical properties in sugar beet using portable visible and near-infrared spectroscopy

USDA-ARS?s Scientific Manuscript database

Visible and near-infrared spectroscopy, coupled with partial least squares regression, was used to predict the moisture, soluble solids and sucrose content and mechanical properties of sugar beet. Interactance spectra were acquired from both intact and sliced beets, using two portable spectrometers ...

Mineral scale management. Part II, Fundamental chemistry

Treesearch

Alan W. Rudie; Peter W. Hart

2006-01-01

The mineral scale that deposits in digesters and bleach plants is formed by a chemical precipitation process.As such, it is accurately modeled using the solubility product equilibrium constant. Although solubility product identifies the primary conditions that must be met for a scale problem to exist, the acid-base equilibria of the scaling anions often control where...

Fundamental chemistry of precipitation and mineral scale formation

Treesearch

Alan W. Rudie; Peter W. Hart

2005-01-01

The mineral scale that deposits in digesters and bleach plants is formed by a chemical precipitation process. As such, it is accurately described or modeled using the solubility product equilibrium constant. Although solubility product identifies the primary conditions that need to be met for a scale problem to exist, the acid base equilibria of the scaling anions...

Thermodynamic phase behavior of API/polymer solid dispersions.

PubMed

Prudic, Anke; Ji, Yuanhui; Sadowski, Gabriele

2014-07-07

To improve the bioavailability of poorly soluble active pharmaceutical ingredients (APIs), these materials are often integrated into a polymer matrix that acts as a carrier. The resulting mixture is called a solid dispersion. In this work, the phase behaviors of solid dispersions were investigated as a function of the API as well as of the type and molecular weight of the carrier polymer. Specifically, the solubility of artemisinin and indomethacin was measured in different poly(ethylene glycol)s (PEG 400, PEG 6000, and PEG 35000). The measured solubility data and the solubility of sulfonamides in poly(vinylpyrrolidone) (PVP) K10 and PEG 35000 were modeled using the perturbed-chain statistical associating fluid theory (PC-SAFT). The results show that PC-SAFT predictions are in a good accordance with the experimental data, and PC-SAFT can be used to predict the whole phase diagram of an API/polymer solid dispersion as a function of the kind of API and polymer and of the polymer's molecular weight. This remarkably simplifies the screening process for suitable API/polymer combinations.

Dissolution Failure of Solid Oral Drug Products in Field Alert Reports.

PubMed

Sun, Dajun; Hu, Meng; Browning, Mark; Friedman, Rick L; Jiang, Wenlei; Zhao, Liang; Wen, Hong

2017-05-01

From 2005 to 2014, 370 data entries of dissolution failures of solid oral drug products were assessed with respect to the solubility of drug substances, dosage forms [immediate release (IR) vs. modified release (MR)], and manufacturers (brand name vs. generic). The study results show that the solubility of drug substances does not play a significant role in dissolution failures; however, MR drug products fail dissolution tests more frequently than IR drug products. When multiple variables were analyzed simultaneously, poorly water-soluble IR drug products failed the most dissolution tests, followed by poorly soluble MR drug products and very soluble MR drug products. Interestingly, the generic drug products fail dissolution tests at an earlier time point during a stability study than the brand name drug products. Whether the dissolution failure of these solid oral drug products has any in vivo implication will require further pharmacokinetic, pharmacodynamic, clinical, and drug safety evaluation. Food and Drug Administration is currently conducting risk-based assessment using in-house dissolution testing, physiologically based pharmacokinetic modeling and simulation, and post-market surveillance tools. At the meantime, this interim report will outline a general scheme of monitoring dissolution failures of solid oral dosage forms as a pharmaceutical quality indicator. Published by Elsevier Inc.

Development of clinical dosage forms for a poorly water-soluble drug II: formulation and characterization of a novel solid microemulsion preconcentrate system for oral delivery of a poorly water-soluble drug.

PubMed

Li, Ping; Hynes, Sara R; Haefele, Thomas F; Pudipeddi, Madhu; Royce, Alan E; Serajuddin, Abu T M

2009-05-01

The solution of a poorly water-soluble drug in a liquid lipid-surfactant mixture, which served as a microemulsion preconcentrate, was converted into a solid form by incorporating it in a solid polyethylene glycol (PEG) matrix. The solid microemulsion preconcentrates thus formed consisted of Capmul PG8 (propylene glycol monocaprylate) as oil, Cremophor EL (polyoxyl 35 castor oil) as surfactant, and hydrophilic polymer PEG 3350 as solid matrix. The drug (aqueous solubility: 0.17 microg/mL at pH 1-8 and 25 degrees C) was dissolved in a melt of the mixture at 65-70 degrees C and then the hot solution was filled into hard gelatin capsules; the liquid gradually solidified upon cooling below 55 degrees C. The solid system was characterized by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), confocal Raman microscopy (CRM), and the dispersion testing in water. It was confirmed that a solid microemulsion preconcentrate is a two-phase system, where clusters of crystalline PEG 3350 formed the solid structure (m.p. 55-60 degrees C) and the liquid microemulsion preconcentrate dispersed in between PEG 3350 crystals as a separate phase. The drug remained dissolved in the liquid phase. In vitro release testing showed that the preconcentrate dispersed readily in water forming a microemulsion with the drug dissolved in the oil particles (<150 nm) and the presence of PEG 3350 did not interfere with the process of self-microemulsification.

Hydrogen dissolution in palladium: A resistometric study under pressure

NASA Astrophysics Data System (ADS)

Magnouche, A.; Fromageau, R.

1984-09-01

The hydrogen solubility in palladium in equilibrium with H2 gas has been measured, between room temperature and 540 °C, using a resistometric method, for pressures ranging between 0.01 and 10 MPa. In these conditions, the experimentally determined values of the solubility and of the dissolution enthalpy exhibit very close agreement with those obtained by other methods (calorimetry, volumetry, etc.), or after electrolytic charging. This good agreement demonstrates the validity of the resistometric method for determination of the solubility of hydrogen in metals.

Reactive extraction at liquid-liquid systems

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina

2018-01-01

The chapter summarizes the state of knowledge about a metal transport in two-phase system. The first part of this review focuses on the distribution law and main factors determination in classical solvent extraction (solubility and polarity of the solute, as well as inter- and intramolecules interaction. Next part of the chapter is devoted to the reactive solvent extraction and the molecular modeling requiring knowledge on type of extractants, complexation mechanisms, metals ions speciation and oxidation during complexes forming, and other parameters that enable to understand the extraction process. Also the kinetic data that is needed for proper modeling, simulation and design of processes needed for critical separations are discussed. Extraction at liquid-solid system using solvent impregnated resins is partially identical as in the case of the corresponding solvent extraction, therefore this subject was also presented in all aspects of separation process (equilibrium, mechanism, kinetics).

Investigation of phase diagrams and physical stability of drug-polymer solid dispersions.

PubMed

Lu, Jiannan; Shah, Sejal; Jo, Seongbong; Majumdar, Soumyajit; Gryczke, Andreas; Kolter, Karl; Langley, Nigel; Repka, Michael A

2015-01-01

Solid dispersion technology has been widely explored to improve the solubility and bioavailability of poorly water-soluble compounds. One of the critical drawbacks associated with this technology is the lack of physical stability, i.e. the solid dispersion would undergo recrystallization or phase separation thus limiting a product's shelf life. In the current study, the melting point depression method was utilized to construct a complete phase diagram for felodipine (FEL)-Soluplus® (SOL) and ketoconazole (KTZ)-Soluplus® (SOL) binary systems, respectively, based on the Flory-Huggins theory. The miscibility or solubility of the two compounds in SOL was also determined. The Flory-Huggins interaction parameter χ values of both systems were calculated as positive at room temperature (25 °C), indicating either compound was miscible with SOL. In addition, the glass transition temperatures of both solid dispersion systems were theoretically predicted using three empirical equations and compared with the practical values. Furthermore, the FEL-SOL solid dispersions were subjected to accelerated stability studies for up to 3 months.

Enhancement of carvedilol solubility by solid dispersion technique using cyclodextrins, water soluble polymers and hydroxyl acid.

PubMed

Yuvaraja, K; Khanam, Jasmina

2014-08-05

Aim of the present work is to enhance aqueous solubility of carvedilol (CV) by solid dispersion technique using wide variety of carriers such as: β-cyclodextrin (βCD), hydroxypropyl-β-cyclodextrin (HPβCD), tartaric acid (TA), polyvinyl pyrrolidone K-30 (PVP K-30) and poloxamer-407 (PLX-407). Various products of 'CV-solid dispersion' had been studied extensively in various pH conditions to check enhancement of solubility and dissolution characteristics of carvedilol. Any physical change upon interaction between CV and carriers was confirmed by instrumental analysis: XRD, DSC, FTIR and SEM. Negative change of Gibb's free energy and complexation constants (Kc, 75-240M(-1), for cyclodextrins and 1111-20,365M(-1), for PVP K-30 and PLX-407) were the evidence of stable nature of the binding between CV and carriers. 'Solubility enhancement factor' of ionized-CV was found high enough (340 times) with HPβCD in presence of TA. TA increases the binding efficiency of cyclodextrin and changing the pH of microenvironment in dissolution medium. In addition, ionization process was used to increase the apparent intrinsic solubility of drug. In vitro, dissolution time of CV was remarkably reduced in the solid dispersion system compared to that of pure drug. This may be attributed to increased wettability, dispersing ability and transformation of crystalline state of drug to amorphous one. Copyright © 2014 Elsevier B.V. All rights reserved.

A Green Analytical Method Using Ultrasound in Sample Preparation for the Flow Injection Determination of Iron, Manganese, and Zinc in Soluble Solid Samples by Flame Atomic Absorption Spectrometry

PubMed Central

Yebra, M. Carmen

2012-01-01

A simple and rapid analytical method was developed for the determination of iron, manganese, and zinc in soluble solid samples. The method is based on continuous ultrasonic water dissolution of the sample (5–30 mg) at room temperature followed by flow injection flame atomic absorption spectrometric determination. A good precision of the whole procedure (1.2–4.6%) and a sample throughput of ca. 25 samples h–1 were obtained. The proposed green analytical method has been successfully applied for the determination of iron, manganese, and zinc in soluble solid food samples (soluble cocoa and soluble coffee) and pharmaceutical preparations (multivitamin tablets). The ranges of concentrations found were 21.4–25.61 μg g−1 for iron, 5.74–18.30 μg g−1 for manganese, and 33.27–57.90 μg g−1 for zinc in soluble solid food samples and 3.75–9.90 μg g−1 for iron, 0.47–5.05 μg g−1 for manganese, and 1.55–15.12 μg g−1 for zinc in multivitamin tablets. The accuracy of the proposed method was established by a comparison with the conventional wet acid digestion method using a paired t-test, indicating the absence of systematic errors. PMID:22567553

Microscopic Structure and Solubility Predictions of Multifunctional Solids in Supercritical Carbon Dioxide: A Molecular Simulation Study.

PubMed

Noroozi, Javad; Paluch, Andrew S

2017-02-23

Molecular dynamics simulations were employed to both estimate the solubility of nonelectrolyte solids, such as acetanilide, acetaminophen, phenacetin, methylparaben, and lidocaine, in supercritical carbon dioxide and understand the underlying molecular-level driving forces. The solubility calculations involve the estimation of the solute's limiting activity coefficient, which may be computed using conventional staged free-energy calculations. For the case of lidocaine, wherein the infinite dilution approximation is not appropriate, we demonstrate how the activity coefficient at finite concentrations may be estimated without additional effort using the dilute solution approximation and how this may be used to further understand the solvation process. Combining with experimental pure-solid properties, namely, the normal melting point and enthalpy of fusion, solubilities were estimated. The results are in good quantitative agreement with available experimental data, suggesting that molecular simulations may be a powerful tool for understanding supercritical processes and the design of carbon dioxide-philic molecular systems. Structural analyses were performed to shed light on the microscopic details of the solvation of different functional groups by carbon dioxide and the observed solubility trends.

Supersaturation and crystallization: non-equilibrium dynamics of amorphous solid dispersions for oral drug delivery.

PubMed

Kawakami, Kohsaku

2017-06-01

Amorphous solid dispersions (ASDs) are one of the key formulation technologies that aid the development of poorly soluble candidates. However, their dynamic behaviors, including dissolution and crystallization processes, are still full of mystery. Further understanding of these processes should enhance their wider use. Areas covered: The first part of this review describes the current understanding of the dissolution of ASDs, where phase separation behavior is frequently involved and attempts to develop appropriate dissolution tests to achieve an in vitro-in vivo correlation are examined. The second part of this review discusses crystallization of the drug molecule with the eventual aim of establishing an accelerated testing protocol for predicting its physical stability. Expert opinion: The phase separation behavior from the supersaturated state during the dissolution test must be understood, and its relevance to the oral absorption behavior needs to be clarified. Research efforts should focus on the differences between the phase behavior in in vitro and in vivo situations. Initiation time of the crystallization was shown to be predicted only from storage and glass transition temperatures. This finding should encourage the establishment of testing protocol of the physical stability of ASDs.

Calculation of open and closed system elastic coefficients for multicomponent solids

NASA Astrophysics Data System (ADS)

Mishin, Y.

2015-06-01

Thermodynamic equilibrium in multicomponent solids subject to mechanical stresses is a complex nonlinear problem whose exact solution requires extensive computations. A few decades ago, Larché and Cahn proposed a linearized solution of the mechanochemical equilibrium problem by introducing the concept of open system elastic coefficients [Acta Metall. 21, 1051 (1973), 10.1016/0001-6160(73)90021-7]. Using the Ni-Al solid solution as a model system, we demonstrate that open system elastic coefficients can be readily computed by semigrand canonical Monte Carlo simulations in conjunction with the shape fluctuation approach. Such coefficients can be derived from a single simulation run, together with other thermodynamic properties needed for prediction of compositional fields in solid solutions containing defects. The proposed calculation approach enables streamlined solutions of mechanochemical equilibrium problems in complex alloys. Second order corrections to the linear theory are extended to multicomponent systems.

C-106 High-Level Waste Solids: Washing/Leaching and Solubility Versus Temperature Studies

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

GJ Lumetta; DJ Bates; PK Berry

This report describes the results of a test conducted by Battelle to assess the effects of inhibited water washing and caustic leaching on the composition of the Hanford tank C-106 high-level waste (HLW) solids. The objective of this work was to determine the composition of the C-106 solids remaining after washing with 0.01M NaOH or leaching with 3M NaOH. Another objective of this test was to determine the solubility of various C-106 components as a function of temperature. The work was conducted according to test plan BNFL-TP-29953-8,Rev. 0, Determination of the Solubility of HLW Sludge Solids. The test went accordingmore » to plan, with only minor deviations from the test plan. The deviations from the test plan are discussed in the experimental section.« less

The solubility of platinum in silicate melt under reducing conditions: Results from experiments without metal inclusions

NASA Astrophysics Data System (ADS)

Bennett, N. R.; Brenan, J. M.; Koga, K. T.

2014-05-01

The solubility of Pt in silicate melt was investigated at conditions of 2073-2573 K, 2 GPa and ˜IW -1.5 to +3.5. These are the first measurements of Pt solubility under conditions more reducing than the iron-wüstite buffer (IW) which are demonstrably free from contamination by metal-inclusions. Pt solubility increases with increasing temperature and decreasing oxygen fugacity. The ability of carbon to enhance Pt solubility under reducing conditions (3500 K. Under these conditions however, the estimated Pt/Os ratio is ˜40,000 times higher than that estimated for the PUM (Brandon et al., 2006). Instead, the PUM composition is generated most readily by metal-silicate equilibrium at more modest temperatures (˜3100 K), followed by a late accretion of chondritic material subsequent to core formation.

Enhanced electrodes for solid state gas sensors

DOEpatents

Garzon, Fernando H.; Brosha, Eric L.

2001-01-01

A solid state gas sensor generates an electrical potential between an equilibrium electrode and a second electrode indicative of a gas to be sensed. A solid electrolyte substrate has the second electrode mounted on a first portion of the electrolyte substrate and a composite equilibrium electrode including conterminous transition metal oxide and Pt components mounted on a second portion of the electrolyte substrate. The composite equilibrium electrode and the second electrode are electrically connected to generate an electrical potential indicative of the gas that is being sensed. In a particular embodiment of the present invention, the second electrode is a reference electrode that is exposed to a reference oxygen gas mixture so that the electrical potential is indicative of the oxygen in a gas stream.

Protein solubilities determined by a rapid technique and modification of that technique to a micro-method

NASA Technical Reports Server (NTRS)

Cacioppo, Elizabeth; Pusey, Marc Lee; Munson, Sibyl

1989-01-01

A simple, rapid method for determination of protein solubilities has been developed which is based upon maximization of the free solution volume to be brought into equilibrium. The tetragonal lysozome solubility diagram has been determined from pH 4.0 to 5.2 (0.1 M sodium acetate), 2-7 percent NaCl, 3-25 C, and portions of the orthorhombic solubility diagram using this technique. Both tetragonal and orthorhombic solubilities were found to increase smoothly with decreasing salt concentration and increasing temperature; no retrograde solubilities were observed. Using column volumes of 75, 300, and 900 microliters, identical tetragonal lysozyme solubility diagrams were obtained. Chymotrypsinogen solubilities have also been determined using this apparatus, being retrograde over the temperature range tested. It is noted that the primary limiting factor in reducing the crystalline volume is the minimum solution sample size needed to accurately quantitate the protein.

Foliar reflective film and water deficit increase anthocyanin to soluble solids ratio during berry ripening in Merlot

USDA-ARS?s Scientific Manuscript database

Elevated temperature can decrease the ratio of anthocyanins to soluble solids in red-skinned berries and warming trends in grape production regions have raised concern about color to alcohol balance in wines produced from fruit with altered ratios. In this study, we tested the effectiveness of a fol...

Integrated spectral and image analysis of hyperspectral scattering data for prediction of apple fruit firmness and soluble solids content

USDA-ARS?s Scientific Manuscript database

Spectral scattering is useful for assessing the firmness and soluble solids content (SSC) of apples. In previous research, mean reflectance extracted from the hyperspectral scattering profiles was used for this purpose since the method is simple and fast and also gives relatively good predictions. T...

Nondestructive determination of dry matter and soluble solids content in dehydrator onions and garlics using a handheld visible and near infrared instrument

USDA-ARS?s Scientific Manuscript database

A non-destructive method based on visible and near-infrared spectroscopy was investigated for determining the dry matter and soluble solids contents of dehydrator onions at the base, equatorial, and shoulder locations and of garlic cloves at the equatorial location. The interactance spectrum (400-10...

Using liquid and solid state NMR and photoluminescence to study the synthesis and solubility properties of amine capped silicon nanoparticles.

PubMed

Giuliani, J R; Harley, S J; Carter, R S; Power, P P; Augustine, M P

2007-08-01

Water soluble silicon nanoparticles were prepared by the reaction of bromine terminated silicon nanoparticles with 3-(dimethylamino)propyl lithium and characterized with liquid and solid state nuclear magnetic resonance (NMR) and photoluminescence (PL) spectroscopies. The surface site dependent 29Si chemical shifts and the nuclear spin relaxation rates from an assortment of 1H-29Si heteronuclear solid state NMR experiments for the amine coated reaction product are consistent with both the 1H and 13C liquid state NMR results and routine transmission electron microscopy, ultra-violet/visible, and Fourier transform infrared measurements. PL was used to demonstrate the pH dependent solubility properties of the amine passivated silicon nanoparticles.

Crystal Chemistry and Electrochemistry of Li xMn 1.5Ni 0.5O 4 Solid Solution Cathode Materials

DOE PAGES

Kan, Wang Hay; Kuppan, Saravanan; Cheng, Lei; ...

2017-07-19

For ordered high-voltage spinel LiMn 1.5Ni 0.5O 4 (LMNO) with the P4 32 1 symmetry, the two consecutive two-phase transformations at ~4.7 V (vs Li +/Li), involving three cubic phases of LMNO, Li 0.5Mn 1.5Ni 0.5O 4 (L 0.5MNO), and Mn 1.5Ni 0.5O 4 (MNO), have been well-established. Such a mechanism is traditionally associated with poor kinetics due to the slow movement of the phase boundaries and the large mechanical strain resulting from the volume changes among the phases, yet ordered LMNO has been shown to have excellent rate capability. In this paper, we show the ability of the phasesmore » to dissolve into each other and determine their solubility limit. We characterized the properties of the formed solid solutions and investigated the role of non-equilibrium single-phase redox processes during the charge and discharge of LMNO. Finally, by using an array of advanced analytical techniques, such as soft and hard X-ray spectroscopy, transmission X-ray microscopy, and neutron/X-ray diffraction, as well as bond valence sum analysis, the present study examines the metastable nature of solid-solution phases and provides new insights in enabling cathode materials that are thermodynamically unstable.« less

High throughput screening: an in silico solubility parameter approach for lipids and solvents in SLN preparations.

PubMed

Shah, Malay; Agrawal, Yadvendra

2013-01-01

The present paper describes an in silico solubility behavior of drug and lipids, an essential screening study in preparation of solid lipid nanoparticles (SLN). Ciprofloxacin HCl was selected as a model drug along with 11 lipids and 5 organic solvents. In silico miscibility study of drug/lipid/solvent was performed using Hansen solubility parameter approach calculated by group contribution method of Van Krevelen and Hoftyzer. Predicted solubility was validated by determining solubility of lipids in various solvent at different temperature range, while miscibility of drug in lipids was determined by apparent solubility study and partition experiment. The presence of oxygen and OH functionality increases the polarity and hydrogen bonding possibilities of the compound which has reflected the highest solubility parameter values for Geleol and Capmul MCM C8. Ethyl acetate, Geleol and Capmul MCM C8 was identified as suitable organic solvent, solid lipid and liquid lipid respectively based on a solubility parameter approach which was in agreement with the result of an apparent solubility study and partition coefficient. These works demonstrate the validity of solubility parameter approach and provide a feasible predictor to the rational selection of excipients in designing SLN formulation.

To evaluate the change in release from solid dispersion using sodium lauryl sulfate and model drug sulfathiazole.

PubMed

Dave, Rutesh H; Patel, Hardikkumar H; Donahue, Edward; Patel, Ashwinkumar D

2013-10-01

The solubility of drugs remains one of the most challenging aspects of formulation development. There are numerous ways to improve the solubility of drugs amongst which the most promising strategy is solid dispersion. Different ratios of sulfathiazole: PVP-K29/32: sodium lauryl sulfate (SLS) were prepared (1:1:0.1, 1:1:0.5, 1:1:1) and various methods were employed to characterize the prepared solid dispersions, namely modulated differential scanning calorimeter, X-ray powder diffraction, Fourier Transformed Infrared Spectroscopy and dissolution studies. Lack of crystallinity was observed in internal and external systems suggesting a loss of crystallinity, whereas the physical mixtures showed a characteristic peak of sulfathiazole. In vitro dissolution results clearly showed that the incorporation of a relatively small amount of surfactants (5, 20 or 33% w/w) into a solid dispersion can improve its dissolution rates compared to binary solid dispersion (SD) alone and pure sulfathiazole. In all ratios solid dispersion internal shows a higher dissolution rate compared to a physical mixture and solid dispersion external which suggests that the way that the surfactant is incorporated into the solid dispersion plays an important role in changing the solubility of a drug. The solubilization mechanism is mainly responsible for this higher dissolution rate when we incorporate the SLS in SD.

Orally Disintegrating Tablets Containing Melt Extruded Amorphous Solid Dispersion of Tacrolimus for Dissolution Enhancement.

PubMed

Ponnammal, Poovizhi; Kanaujia, Parijat; Yani, Yin; Ng, Wai Kiong; Tan, Reginald B H

2018-03-16

In order to improve the aqueous solubility and dissolution of Tacrolimus (TAC), amorphous solid dispersions of TAC were prepared by hot melt extrusion with three hydrophilic polymers, Polyvinylpyrrolidone vinyl acetate (PVP VA64), Soluplus ® and Hydroxypropyl Cellulose (HPC), at a drug loading of 10% w / w . Molecular modeling was used to determine the miscibility of the drug with the carrier polymers by calculating the Hansen Solubility Parameters. Powder X-ray diffraction and differential scanning calorimetry (DSC) studies of powdered solid dispersions revealed the conversion of crystalline TAC to amorphous form. Fourier transform Infrared (FTIR) spectroscopy results indicated formation of hydrogen bond between TAC and polymers leading to stabilization of TAC in amorphous form. The extrudates were found to be stable under accelerated storage conditions for 3 months with no re-crystallization, indicating that hot melt extrusion is suitable for producing stable amorphous solid dispersions of TAC in PVP VA64, Soluplus ® and HPC. Stable solid dispersions of amorphous TAC exhibited higher dissolution rate, with the solid dispersions releasing more than 80% drug in 15 min compared to the crystalline drug giving 5% drug release in two hours. These stable solid dispersions were incorporated into orally-disintegrating tablets in which the solid dispersion retained its solubility, dissolution and stability advantage.

Orally Disintegrating Tablets Containing Melt Extruded Amorphous Solid Dispersion of Tacrolimus for Dissolution Enhancement

PubMed Central

Ponnammal, Poovizhi; Kanaujia, Parijat; Ng, Wai Kiong; Tan, Reginald B. H.

2018-01-01

In order to improve the aqueous solubility and dissolution of Tacrolimus (TAC), amorphous solid dispersions of TAC were prepared by hot melt extrusion with three hydrophilic polymers, Polyvinylpyrrolidone vinyl acetate (PVP VA64), Soluplus® and Hydroxypropyl Cellulose (HPC), at a drug loading of 10% w/w. Molecular modeling was used to determine the miscibility of the drug with the carrier polymers by calculating the Hansen Solubility Parameters. Powder X-ray diffraction and differential scanning calorimetry (DSC) studies of powdered solid dispersions revealed the conversion of crystalline TAC to amorphous form. Fourier transform Infrared (FTIR) spectroscopy results indicated formation of hydrogen bond between TAC and polymers leading to stabilization of TAC in amorphous form. The extrudates were found to be stable under accelerated storage conditions for 3 months with no re-crystallization, indicating that hot melt extrusion is suitable for producing stable amorphous solid dispersions of TAC in PVP VA64, Soluplus® and HPC. Stable solid dispersions of amorphous TAC exhibited higher dissolution rate, with the solid dispersions releasing more than 80% drug in 15 min compared to the crystalline drug giving 5% drug release in two hours. These stable solid dispersions were incorporated into orally-disintegrating tablets in which the solid dispersion retained its solubility, dissolution and stability advantage. PMID:29547585

Thermal non-equilibrium in porous medium adjacent to vertical plate: ANN approach

NASA Astrophysics Data System (ADS)

Ahmed, N. J. Salman; Ahamed, K. S. Nazim; Al-Rashed, Abdullah A. A. A.; Kamangar, Sarfaraz; Athani, Abdulgaphur

2018-05-01

Thermal non-equilibrium in porous medium is a condition that refers to temperature discrepancy in solid matrix and fluid of porous medium. This type of flow is complex flow requiring complex set of partial differential equations that govern the flow behavior. The current work is undertaken to predict the thermal non-equilibrium behavior of porous medium adjacent to vertical plate using artificial neural network. A set of neurons in 3 layers are trained to predict the heat transfer characteristics. It is found that the thermal non-equilibrium heat transfer behavior in terms of Nusselt number of fluid as well as solid phase can be predicted accurately by using well-trained neural network.

Determining the Solubility Product of Fe(OH)[subscript 3]: An Equilibrium Study with Environmental Significance

ERIC Educational Resources Information Center

Meighan, Michelle; MacNeil, Joseph; Falconer, Renee

2008-01-01

The relationship between pH and the aqueous solubility of heavy metals is explored by considering the environmental impact of acidic mine drainage. Acid mine drainage is an important environmental concern in many areas of the United States. Associated with coal mining in the East and hard rock mining in the West, the acidity originates primarily…

Method to separate lignin-rich solid phase from acidic biomass suspension at an acidic pH

DOEpatents

Yasarla, Kumar Lakshmi Rakesh; Ramarao, Bandaru V; Amidon, Thomas

2017-09-05

A method of separating a lignin-rich solid phase from a solution suspension, by pretreating a lignocellulosic biomass with a pretreatment fluid having remove soluble components, colloidal material and primarily lignin containing particles; separating the pretreated lignocellulosic biomass from the pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles; flocculating the separated pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles using polyethylene oxide (i.e., PEO) or cationic Poly acrylamide (i.e., CPAM) as a flocculating agent; and filtering the flocculated separated pretreatment fluid with soluble components, colloidal material and primarily lignin containing particles to remove agglomerates.

Novel electrosprayed nanospherules for enhanced aqueous solubility and oral bioavailability of poorly water-soluble fenofibrate

PubMed Central

Yousaf, Abid Mehmood; Mustapha, Omer; Kim, Dong Wuk; Kim, Dong Shik; Kim, Kyeong Soo; Jin, Sung Giu; Yong, Chul Soon; Youn, Yu Seok; Oh, Yu-Kyoung; Kim, Jong Oh; Choi, Han-Gon

2016-01-01

Purpose The purpose of the present research was to develop a novel electrosprayed nanospherule providing the most optimized aqueous solubility and oral bioavailability for poorly water-soluble fenofibrate. Methods Numerous fenofibrate-loaded electrosprayed nanospherules were prepared with polyvinylpyrrolidone (PVP) and Labrafil® M 2125 as carriers using the electrospray technique, and the effect of the carriers on drug solubility and solvation was assessed. The solid state characterization of an optimized formulation was conducted by scanning electron microscopy, powder X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared spectroscopic analyses. Oral bioavailability in rats was also evaluated for the formulation of an optimized nanospherule in comparison with free drug and a conventional fenofibrate-loaded solid dispersion. Results All of the electrosprayed nanospherule formulations had remarkably enhanced aqueous solubility and dissolution compared with free drug. Moreover, Labrafil M 2125, a surfactant, had a positive influence on the solubility and dissolution of the drug in the electrosprayed nanospherule. Increases were observed as the PVP/drug ratio increased to 4:1, but higher ratios gave no significant increases. In particular, an electrosprayed nanospherule composed of fenofibrate, PVP, and Labrafil M 2125 at the weight ratio of 1:4:0.5 resulted in a particle size of <200 nm with the drug present in the amorphous state. It demonstrated the highest solubility (32.51±2.41 μg/mL), an excellent dissolution (~85% in 10 minutes), and an oral bioavailability ~2.5-fold better than that of the free drug. It showed similar oral bioavailability compared to the conventional solid dispersion. Conclusion Electrosprayed nanospherules, which provide improved solubility and bioavailability, are promising drug delivery tools for oral administration of poorly water-soluble fenofibrate. PMID:26834471

Novel electrosprayed nanospherules for enhanced aqueous solubility and oral bioavailability of poorly water-soluble fenofibrate.

PubMed

Yousaf, Abid Mehmood; Mustapha, Omer; Kim, Dong Wuk; Kim, Dong Shik; Kim, Kyeong Soo; Jin, Sung Giu; Yong, Chul Soon; Youn, Yu Seok; Oh, Yu-Kyoung; Kim, Jong Oh; Choi, Han-Gon

2016-01-01

The purpose of the present research was to develop a novel electrosprayed nanospherule providing the most optimized aqueous solubility and oral bioavailability for poorly water-soluble fenofibrate. Numerous fenofibrate-loaded electrosprayed nanospherules were prepared with polyvinylpyrrolidone (PVP) and Labrafil(®) M 2125 as carriers using the electrospray technique, and the effect of the carriers on drug solubility and solvation was assessed. The solid state characterization of an optimized formulation was conducted by scanning electron microscopy, powder X-ray diffraction, differential scanning calorimetry, and Fourier transform infrared spectroscopic analyses. Oral bioavailability in rats was also evaluated for the formulation of an optimized nanospherule in comparison with free drug and a conventional fenofibrate-loaded solid dispersion. All of the electrosprayed nanospherule formulations had remarkably enhanced aqueous solubility and dissolution compared with free drug. Moreover, Labrafil M 2125, a surfactant, had a positive influence on the solubility and dissolution of the drug in the electrosprayed nanospherule. Increases were observed as the PVP/drug ratio increased to 4:1, but higher ratios gave no significant increases. In particular, an electrosprayed nanospherule composed of fenofibrate, PVP, and Labrafil M 2125 at the weight ratio of 1:4:0.5 resulted in a particle size of <200 nm with the drug present in the amorphous state. It demonstrated the highest solubility (32.51±2.41 μg/mL), an excellent dissolution (~85% in 10 minutes), and an oral bioavailability ~2.5-fold better than that of the free drug. It showed similar oral bioavailability compared to the conventional solid dispersion. Electrosprayed nanospherules, which provide improved solubility and bioavailability, are promising drug delivery tools for oral administration of poorly water-soluble fenofibrate.

Insulin Particle Formation in Supersaturated Aqueous Solutions of Poly(Ethylene Glycol)

PubMed Central

Bromberg, Lev; Rashba-Step, Julia; Scott, Terrence

2005-01-01

Protein microspheres are of particular utility in the field of drug delivery. A novel, completely aqueous, process of microsphere fabrication has been devised based on controlled phase separation of protein from water-soluble polymers such as polyethylene glycols. The fabrication process results in the formation of spherical microparticles with narrow particle size distributions. Cooling of preheated human insulin-poly(ethylene glycol)-water solutions results in the facile formation of insulin particles. To map out the supersaturation conditions conducive to particle nucleation and growth, we determined the temperature- and concentration-dependent boundaries of an equilibrium liquid-solid phase separation. The kinetics of formation of microspheres were followed by dynamic and continuous-angle static light scattering techniques. The presence of PEG at a pH that was close to the protein's isoelectric point resulted in rapid nucleation and growth. The time elapsed from the moment of creation of a supersaturated solution and the detection of a solid phase in the system (the induction period, tind) ranged from tens to several hundreds of seconds. The dependence of tind on supersaturation could be described within the framework of classical nucleation theory, with the time needed for the formation of a critical nucleus (size <10 nm) being much longer than the time of the onset of particle growth. The growth was limited by cluster diffusion kinetics. The interfacial energies of the insulin particles were determined to be 3.2–3.4 and 2.2 mJ/m2 at equilibrium temperatures of 25 and 37°C, respectively. The insulin particles formed as a result of the process were monodisperse and uniformly spherical, in clear distinction to previously reported processes of microcrystalline insulin particle formation. PMID:16254391

An Initial Non-Equilibrium Porous-Media Model for CFD Simulation of Stirling Regenerators

NASA Technical Reports Server (NTRS)

Tew, Roy C.; Simon, Terry; Gedeon, David; Ibrahim, Mounir; Rong, Wei

2006-01-01

The objective of this paper is to define empirical parameters for an initial thermal non-equilibrium porous-media model for use in Computational Fluid Dynamics (CFD) codes for simulation of Stirling regenerators. The two codes currently used at Glenn Research Center for Stirling modeling are Fluent and CFD-ACE. The codes porous-media models are equilibrium models, which assume solid matrix and fluid are in thermal equilibrium. This is believed to be a poor assumption for Stirling regenerators; Stirling 1-D regenerator models, used in Stirling design, use non-equilibrium regenerator models and suggest regenerator matrix and gas average temperatures can differ by several degrees at a given axial location and time during the cycle. Experimentally based information was used to define: hydrodynamic dispersion, permeability, inertial coefficient, fluid effective thermal conductivity, and fluid-solid heat transfer coefficient. Solid effective thermal conductivity was also estimated. Determination of model parameters was based on planned use in a CFD model of Infinia's Stirling Technology Demonstration Converter (TDC), which uses a random-fiber regenerator matrix. Emphasis is on use of available data to define empirical parameters needed in a thermal non-equilibrium porous media model for Stirling regenerator simulation. Such a model has not yet been implemented by the authors or their associates.

Critical viewpoints on the methods of realizing the metal freezing points of the ITS-90

NASA Astrophysics Data System (ADS)

Ma, C. K.

1995-08-01

The time-honored method for realizing the freezing point tf of a metal (in practice necessarily a dilute alloy) is that of continuous, slow freezing where the plateau temperature (which is the result of solidifying material's being so pure that its phase-transition temperature is observably constant) is measured. The freezing point being an equilibrium temperature, Ancsin considers this method to be inappropriate in principle: equilibrium between the solid and liquid phases cannot be achieved while the solid is being cooled to dispose of the releasing latent heat and while it is accreting at the expense of the liquid. In place of the continuous freezing method he has employed the pulse-heating method (in which the sample is allowed to approach equilibrium after each heat pulse) in his study of Ag; his measurements suggest that freezing can produce non-negligible errors. Here we examine both methods and conclude that the freezing method, employing an inside solid-liquid interface thermally isolated by an outside interface, can provide realizations of the highest accuracy; in either method, perturbation, by inducing solid-liquid phase transition continuously or intermittently, is essential for detecting equilibrium thermally. The respective merits and disadvantages of these two methods and also of the inner-melt method are discussed. We conclude that in a freezing-point measurement what is being measured is in effect the however minutely varying phase transition, and nonconstitutional equilibrium, temperature ti at the solid-liquid interface. The objective is then to measure the ti that is the best measure of tf, which is, normally, the plateau temperature.

Improvement of solubility, dissolution and stability profile of artemether solid dispersions and self emulsified solid dispersions by solvent evaporation method.

PubMed

Tayyab Ansari, Muhammad; Arshad, Muhammad Sohail; Hussain, Altaf; Ahmad, Zeeshan

2016-12-08

The purpose of this study was to investigate changes in the water solubility of artemether; a poorly soluble drug used for the treatment of malaria. Different solid dispersions (SDs) of artemether were prepared using artemether and polyethylene glycol 6000 at ratio 12:88 (Group 1), self-emulsified solid dispersions (SESDs) containing artemether, polyethylene glycol 6000, cremophor-A-25, olive oil, hydroxypropylmethylcellulose and transcutol in the ratio 12:75:5:4:2:2, respectively (Group 2). SESDs were also prepared by substituting cremophor-A-25 in Group 2 with poloxamer 188 (noted as Group 3). Each of these preparations was formulated using physical mixing and the solvent evaporation method. Aqueous solubility of artemether improved 11-, 95- and 102-fold, while dissolution (in simulated gastric fluid) increased 3-, 13- and 14-fold, for formulation groups 1, 2 and 3, respectively. X-ray diffraction patterns of SDs indicated a decrease in peak intensities at 10° implying reduced artemether crystallinity. Scanning electron micrographs invariably revealed embedment of artemether by various excipients and a glassy appearance for solvent evaporated mixtures for all three formulation Groups. Our findings indicate improved hydrophilic interactions for drug particles yield greater solubility and dissolution in the following order for artemether formulating methods: solvent evaporation mixtures > physical mixtures > pure artemether.

Pulp extrusion at ultra-high consistencies : selection of water soluble polymers for process optimization

Treesearch

C. Tim Scott

2002-01-01

Pulp extrusion at ultra-high consistencies (20% to 40% solids) is a new process developed at USDA Forest Service, Forest Products Laboratory (FPL) to convert recovered papers, wastepaper, and papermill residuals into solid sheets or profiles for compression molding. This process requires adding a water-soluble polymer (WSP) to alter the rheological properties of the...

Solubility relations in the system sodium chloride-ferrous chloride-water between 25 and 70.degree.C at 1 atm

USGS Publications Warehouse

Chou, I.-Ming; Phan, L.D.

1985-01-01

Solubility relations in the ternary system NaCl-FeCl2-H2O have been determined by the visual polythermal method at 1 atm from 20 to 85??C along six composition lines. These she composition lines are defined by mixing FeCl2??4H2O with six aqueous NaCl solutions containing 5, 10, 11, 15, 20, and 25 wt % of NaCl, respectively. The solid phases encountered in these experiments were NaCl and FeCl2??4H2O. The maximum uncertainties in these measurements are ??0.02 wt % NaCl and ??0.15??C. The data along each composition line were regressed to a smooth curve when only one solid phase was stable. When two solids were stable along a composition line, the data were regressed to two smooth curves, the intersection of which indicated the point where the two solids coexisted. The maximum deviation of the measured solubilities from the smoothed curves is 0.14 wt % FeCl2. Isothermal solubilities of halite and FeCl2??4H2O were calculated from these smoothed curves at 25, 50, and 70 ??C.

Solubility of aluminum in the presence of hydroxide, fluoride, and sulfate

USGS Publications Warehouse

Roberson, Charles Elmer; Hem, John David

1969-01-01

The total concentration of aqueous dissolved species of aluminum that will be present in equilibrium with microcrystalline gibbsite at various levels of complexing ligand concentration are shown graphically. The graphs can be used to estimate aluminum solubility, at 25?C and 1 atmosphere total pressure, when the pH of the solution, its ionic strength, and the total sulfate and fluoride concentrations are known. The standard free energy of formation of cryolite calculated from solubility experiments is --745.4 ? 1.0 kcal per mole at 25?C. Diagrams are included showing the solubility of cryolite in terms of aluminum, fluoride, and sodium concentrations. The stability fields of cryolite and microcrystalline gibbsite and their solubilities also are shown on pH-[F] diagrams.

Reactive solute transport in streams: 1. Development of an equilibrium- based model

USGS Publications Warehouse

Runkel, Robert L.; Bencala, Kenneth E.; Broshears, Robert E.; Chapra, Steven C.

1996-01-01

An equilibrium-based solute transport model is developed for the simulation of trace metal fate and transport in streams. The model is formed by coupling a solute transport model with a chemical equilibrium submodel based on MINTEQ. The solute transport model considers the physical processes of advection, dispersion, lateral inflow, and transient storage, while the equilibrium submodel considers the speciation and complexation of aqueous species, precipitation/dissolution and sorption. Within the model, reactions in the water column may result in the formation of solid phases (precipitates and sorbed species) that are subject to downstream transport and settling processes. Solid phases on the streambed may also interact with the water column through dissolution and sorption/desorption reactions. Consideration of both mobile (water-borne) and immobile (streambed) solid phases requires a unique set of governing differential equations and solution techniques that are developed herein. The partial differential equations describing physical transport and the algebraic equations describing chemical equilibria are coupled using the sequential iteration approach.

Assessment of hupu gum for its carrier property in the design and evaluation of solid mixtures of poorly water soluble drug - rofecoxib.

PubMed

Vadlamudi, Harini Chowdary; Raju, Y Prasanna; Asuntha, G; Nair, Rahul; Murthy, K V Ramana; Vulava, Jayasri

2014-01-01

There are no reports about the pharmaceutical applications of hupu gum (HG). Hence the present study was undertaken to test its suitability in the dissolution enhancement of poorly water soluble drug. Rofecoxib (RFB) was taken as model drug. For comparison solid mixtures were prepared with carriers such as poly vinyl pyrrolidone (PVP), sodium starch glycollate (SSG) and guar gum (GG). Physical mixing (PM), co-grinding (CG), kneading (KT) and solvent evaporation (SE) techniques were used to prepare the solid mixtures, using all the carriers in different carrier and drug ratios. The solid mixtures were characterized by powder X-ray diffraction (XRD) and Fourier-transformed infrared spectroscopy (FTIR). There was a significant improvement in the dissolution rate of solid mixtures of HG, when compared with the solid mixtures of other carriers. There was an increase in dissolution rate with increase in concentration of HG upto 1:1 ratio of carrier and drug. No drug-carrier interaction was found by FTIR studies. XRD studies indicated reduction in crystallinity of the drug with increase in HG concentration. Hence HG could be a useful carrier for the dissolution enhancement of poorly water soluble drugs.

Extensive Diminution of Particle Size and Amorphization of a Crystalline Drug Attained by Eminent Technology of Solid Dispersion: A Comparative Study.

PubMed

Singh, Gurjeet; Sharma, Shailesh; Gupta, Ghanshyam Das

2017-07-01

The present study emphasized on the use of solid dispersion technology to triumph over the drawbacks associated with the highly effective antihypertensive drug telmisartan using different polymers (poloxamer 188 and locust bean gum) and methods (modified solvent evaporation and lyophilization). It is based on the comparison between selected polymers and methods for enhancing solubility through particle size reduction. The results showed different profiles for particle size, solubility, and dissolution of formulated amorphous systems depicting the great influence of polymer/method used. The resulting amorphous solid dispersions were characterized using x-ray diffraction (XRD), differential scanning calorimetry, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and particle size analysis. The optimized solid dispersion (TEL 19) prepared with modified locust bean gum using lyophilization technique showed reduced particle size of 184.5 ± 3.7 nm and utmost solubility of 702 ± 5.47 μg/mL in water, which is quite high as compared to the pure drug (≤1 μg/mL). This study showed that the appropriate selection of carrier may lead to the development of solid dispersion formulation with desired solubility and dissolution profiles. The optimized dispersion was later formulated into fast-dissolving tablets, and further optimization was done to obtain the tablets with desired properties.

Dissolution enhancement of efavirenz by solid dispersion and PEGylation techniques

PubMed Central

Madhavi, B. Bindu; Kusum, B.; Chatanya, CH. Krishna; Madhu, M. Naga; Harsha, V. Sri; Banji, David

2011-01-01

Background: Efavirenz is the preferred nonnucleotide reverse transcriptase inhibitor for first-line antiretroviral treatment in many countries. It is orally active and is specific for human immunodeficiency virus type 1. Its effectiveness can be attributed to its long half-life, which is 52–76 h after multiple doses. The drug is having poor water solubility. The formulation of poorly soluble drug for oral delivery will be one of the biggest challenges for formulation scientists in the research field. Among the available approaches, the solid dispersion technique has often proved to be the most commonly used method in improving dissolution and bioavailability of the drugs because of its simplicity and economy in preparation and evaluation. Materials and Methods: Solid dispersions were prepared by solvent evaporation and physical mixture methods by using polyethylene glycol as the hydrophilic carrier and PEGylated product was also prepared. The prepared products were evaluated for various parameters, such as polymer interaction, saturation solubility study, and drug release studies. The drug release data were analyzed by fitting it into various kinetic models. Results: There is an improvement in the dissolution from 16% to 70% with solid dispersion technology. Higuchi model was found to be the best fit model. Conclusion: Solid dispersion is the simple, efficient, and economic method to improve the dissolution of the poorly water-soluble drugs. PMID:23071917

Predicting the excess solubility of acetanilide, acetaminophen, phenacetin, benzocaine, and caffeine in binary water/ethanol mixtures via molecular simulation.

PubMed

Paluch, Andrew S; Parameswaran, Sreeja; Liu, Shuai; Kolavennu, Anasuya; Mobley, David L

2015-01-28

We present a general framework to predict the excess solubility of small molecular solids (such as pharmaceutical solids) in binary solvents via molecular simulation free energy calculations at infinite dilution with conventional molecular models. The present study used molecular dynamics with the General AMBER Force Field to predict the excess solubility of acetanilide, acetaminophen, phenacetin, benzocaine, and caffeine in binary water/ethanol solvents. The simulations are able to predict the existence of solubility enhancement and the results are in good agreement with available experimental data. The accuracy of the predictions in addition to the generality of the method suggests that molecular simulations may be a valuable design tool for solvent selection in drug development processes.

Predicting the excess solubility of acetanilide, acetaminophen, phenacetin, benzocaine, and caffeine in binary water/ethanol mixtures via molecular simulation

NASA Astrophysics Data System (ADS)

Paluch, Andrew S.; Parameswaran, Sreeja; Liu, Shuai; Kolavennu, Anasuya; Mobley, David L.

2015-01-01

We present a general framework to predict the excess solubility of small molecular solids (such as pharmaceutical solids) in binary solvents via molecular simulation free energy calculations at infinite dilution with conventional molecular models. The present study used molecular dynamics with the General AMBER Force Field to predict the excess solubility of acetanilide, acetaminophen, phenacetin, benzocaine, and caffeine in binary water/ethanol solvents. The simulations are able to predict the existence of solubility enhancement and the results are in good agreement with available experimental data. The accuracy of the predictions in addition to the generality of the method suggests that molecular simulations may be a valuable design tool for solvent selection in drug development processes.

Controlled release systems containing solid dispersions: strategies and mechanisms.

PubMed

Tran, Phuong Ha-Lien; Tran, Thao Truong-Dinh; Park, Jun Bom; Lee, Beom-Jin

2011-10-01

In addition to a number of highly soluble drugs, most new chemical entities under development are poorly water-soluble drugs generally characterized by an insufficient dissolution rate and a small absorption window, leading to the low bioavailability. Controlled-release (CR) formulations have several potential advantages over conventional dosage forms, such as providing a uniform and prolonged therapeutic effect to improve patient compliance, reducing the frequency of dosing, minimizing the number of side effects, and reducing the strength of the required dose while increasing the effectiveness of the drug. Solid dispersions (SD) can be used to enhance the dissolution rate of poorly water-soluble drugs and to sustain the drug release by choosing an appropriate carrier. Thus, a CR-SD comprises both functions of SD and CR for poorly water-soluble drugs. Such CR dosage forms containing SD provide an immediately available dose for an immediate action followed by a gradual and continuous release of subsequent doses to maintain the plasma concentration of poorly water-soluble drugs over an extended period of time. This review aims to summarize all currently known aspects of controlled release systems containing solid dispersions, focusing on the preparation methods, mechanisms of action and characterization of physicochemical properties of the system.

Solubility and dissolution performances of spray-dried solid dispersion of Efavirenz in Soluplus.

PubMed

Lavra, Zênia Maria Maciel; Pereira de Santana, Davi; Ré, Maria Inês

2017-01-01

Efavirenz (EFV), a first-line anti-HIV drug largely used as part of antiretroviral therapies, is practically insoluble in water and belongs to BCS class II (low solubility/high permeability). The aim of this study was to improve the solubility and dissolution performances of EFV by formulating an amorphous solid dispersion of the drug in polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (Soluplus ® ) using spray-drying technique. To this purpose, spray-dried dispersions of EFV in Soluplus ® at different mass ratios (1:1.25, 1:7, 1:10) were prepared and characterized using particle size measurements, SEM, XRD, DSC, FTIR and Raman microscopy mapping. Solubility and dissolution were determined in different media. Stability was studied at accelerated conditions (40 °C/75% RH) and ambient conditions for 12 months. DSC and XRD analyses confirmed the EFV amorphous state. FTIR spectroscopy analyses revealed possible drug-polymer molecular interaction. Solubility and dissolution rate of EFV was enhanced remarkably in the developed spray-dried solid dispersions, as a function of the polymer concentration. Spray-drying was concluded to be a proper technique to formulate a physically stable dispersion of amorphous EFV in Soluplus ® , when protected from moisture.

Use of the Flory-Huggins theory to predict the solubility of nifedipine and sulfamethoxazole in the triblock, graft copolymer Soluplus.

PubMed

Altamimi, Mohammad A; Neau, Steven H

2016-01-01

Drug dispersed in a polymer can improve bioavailability; dispersed amorphous drug undergoes recrystallization. Solid solutions eliminate amorphous regions, but require a measure of the solubility. Use the Flory-Huggins Theory to predict crystalline drugs solubility in the triblock, graft copolymer Soluplus® to provide a solid solution. Physical mixtures of the two drugs with similar melting points but different glass forming ability, sulfamethoxazole and nifedipine, were prepared with Soluplus® using a quick technique. Drug melting point depression (MPD) was measured using differential scanning calorimetry. The Flory-Huggins Theory allowed: (1) interaction parameter, χ, calculation using MPD data to provide a measure of drug-polymer interaction strength and (2) estimation of the free energy of mixing. A phase diagram was constructed with the MPD data and glass transition temperature (Tg) curves. The interaction parameters with Soluplus® and the free energy of mixing were estimated. Drug solubility was calculated by the intersection of solubility equations and that of MPD and Tg curves in the phase diagram. Negative interaction parameters indicated strong drug-polymer interactions. The phase diagram and solubility equations provided comparable solubility estimates for each drug in Soluplus®. Results using the onset of melting rather than the end of melting support the use of the onset of melting. The Flory-Huggins Theory indicates that Soluplus® interacts effectively with each drug, making solid solution formation feasible. The predicted solubility of the drugs in Soluplus® compared favorably across the methods and supports the use of the onset of melting.

Use of the Flory-Huggins theory to predict the solubility of nifedipine and sulfamethoxazole in the triblock, graft copolymer Soluplus.

PubMed

Altamimi, Mohammad A; Neau, Steven H

2016-03-01

Drug dispersed in a polymer can improve bioavailability; dispersed amorphous drug undergoes recrystallization. Solid solutions eliminate amorphous regions, but require a measure of the solubility. Use the Flory-Huggins Theory to predict crystalline drugs solubility in the triblock, graft copolymer Soluplus® to provide a solid solution. Physical mixtures of the two drugs with similar melting points but different glass forming ability, sulfamethoxazole and nifedipine, were prepared with Soluplus® using a quick technique. Drug melting point depression (MPD) was measured using differential scanning calorimetry. The Flory-Huggins Theory allowed: (1) interaction parameter, χ, calculation using MPD data to provide a measure of drug-polymer interaction strength and (2) estimation of the free energy of mixing. A phase diagram was constructed with the MPD data and glass transition temperature (T g ) curves. The interaction parameters with Soluplus® and the free energy of mixing were estimated. Drug solubility was calculated by the intersection of solubility equations and that of MPD and T g curves in the phase diagram. Negative interaction parameters indicated strong drug-polymer interactions. The phase diagram and solubility equations provided comparable solubility estimates for each drug in Soluplus®. Results using the onset of melting rather than the end of melting support the use of the onset of melting. The Flory-Huggins Theory indicates that Soluplus® interacts effectively with each drug, making solid solution formation feasible. The predicted solubility of the drugs in Soluplus® compared favorably across the methods and supports the use of the onset of melting.

Polymeric Amorphous Solid Dispersions: A Review of Amorphization, Crystallization, Stabilization, Solid-State Characterization, and Aqueous Solubilization of Biopharmaceutical Classification System Class II Drugs.

PubMed

Baghel, Shrawan; Cathcart, Helen; O'Reilly, Niall J

2016-09-01

Poor water solubility of many drugs has emerged as one of the major challenges in the pharmaceutical world. Polymer-based amorphous solid dispersions have been considered as the major advancement in overcoming limited aqueous solubility and oral absorption issues. The principle drawback of this approach is that they can lack necessary stability and revert to the crystalline form on storage. Significant upfront development is, therefore, required to generate stable amorphous formulations. A thorough understanding of the processes occurring at a molecular level is imperative for the rational design of amorphous solid dispersion products. This review attempts to address the critical molecular and thermodynamic aspects governing the physicochemical properties of such systems. A brief introduction to Biopharmaceutical Classification System, solid dispersions, glass transition, and solubility advantage of amorphous drugs is provided. The objective of this review is to weigh the current understanding of solid dispersion chemistry and to critically review the theoretical, technical, and molecular aspects of solid dispersions (amorphization and crystallization) and potential advantage of polymers (stabilization and solubilization) as inert, hydrophilic, pharmaceutical carrier matrices. In addition, different preformulation tools for the rational selection of polymers, state-of-the-art techniques for preparation and characterization of polymeric amorphous solid dispersions, and drug supersaturation in gastric media are also discussed. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Direct growth of high crystallinity graphene from water-soluble polymer powders

NASA Astrophysics Data System (ADS)

Chen, Qiao; Zhong, Yujia; Huang, Meirong; Zhao, Guoke; Zhen, Zhen; Zhu, Hongwei

2018-07-01

The use of solid-state carbon sources is effective to produce graphene by safe and low-cost chemical vapor deposition (CVD) process. Water-soluble polymers are generally environmentally friendly and have great potential on large-scale green production of graphene. Here, we systematically study the growth of graphene from water-soluble polymers on copper foils. Two different conversion ways are adopted to investigate the growth mechanism of graphene from water-soluble polymers. We find that the metal-binding functional group hydroxyl strongly influences the vaporization of water-soluble polymers on Cu foils, which hinders the formation of graphene films by rapid thermal treatment. In direct CVD process using water-soluble polymer powders as precursors, oxygenated functional groups in polymers can enhance the crystallinity of as-grown graphene in contrast to solid hydrocarbons without containing oxygen (e.g. polyethylene). Large and continuous graphene films of high quality are synthesized from polyvinyl alcohol and polyethylene glycol. Nitrogen doping in graphene can be easily realized by using nitrogen-containing water-soluble polymers (e.g. polyvinyl pyrrolidone).

Tutorial: Determination of thermal boundary resistance by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Liang, Zhi; Hu, Ming

2018-05-01

Due to the high surface-to-volume ratio of nanostructured components in microelectronics and other advanced devices, the thermal resistance at material interfaces can strongly affect the overall thermal behavior in these devices. Therefore, the thermal boundary resistance, R, must be taken into account in the thermal analysis of nanoscale structures and devices. This article is a tutorial on the determination of R and the analysis of interfacial thermal transport via molecular dynamics (MD) simulations. In addition to reviewing the commonly used equilibrium and non-equilibrium MD models for the determination of R, we also discuss several MD simulation methods which can be used to understand interfacial thermal transport behavior. To illustrate how these MD models work for various interfaces, we will show several examples of MD simulation results on thermal transport across solid-solid, solid-liquid, and solid-gas interfaces. The advantages and drawbacks of a few other MD models such as approach-to-equilibrium MD and first-principles MD are also discussed.

Thermodynamics of the formaldehyde-water and formaldehyde-ice systems for atmospheric applications.

PubMed

Barret, Manuel; Houdier, Stephan; Domine, Florent

2011-01-27

Formaldehyde (HCHO) is a species involved in numerous key atmospheric chemistry processes that can significantly impact the oxidative capacity of the atmosphere. Since gaseous HCHO is soluble in water, the water droplets of clouds and the ice crystals of snow exchange HCHO with the gas phase and the partitioning of HCHO between the air, water, and ice phases must be known to understand its chemistry. This study proposes thermodynamic formulations for the partitioning of HCHO between the gas phase and the ice and liquid water phases. A reanalysis of existing data on the vapor-liquid equilibrium has shown the inadequacy of the Henry's law formulation, and we instead propose the following equation to predict the mole fraction of HCHO in liquid water at equilibrium, X(HCHO,liq), as a function of the partial pressure P(HCHO) (Pa) and temperature T (K): X(HCHO,liq) = 1.700 × 10(-15) e((8014/T))(P(HCHO))(1.105). Given the paucity of data on the gas-ice equilibrium, the solubility of HCHO and the diffusion coefficient (D(HCHO)) in ice were measured by exposing large single ice crystals to low P(HCHO). Our recommended value for D(HCHO) over the temperature range 243-266 K is D(HCHO) = 6 × 10(-12) cm(2) s(-1). The solubility of HCHO in ice follows the relationship X(HCHO,ice) = 9.898 × 10(-13) e((4072/T))(P(HCHO))(0.803). Extrapolation of these data yields the P(HCHO) versus 1/T phase diagram for the H(2)O-HCHO system. The comparison of our results to existing data on the partitioning of HCHO between the snow and the atmosphere in the high arctic highlights the interplay between thermodynamic equilibrium and kinetics processes in natural systems.

Speciation and equilibrium relations of soluble aluminum in a headwater stream at base flow and during rain events

USGS Publications Warehouse

Burns, Douglas A.

1989-01-01

In a small watershed in the Shenandoah National Park, Virginia, the short-term dynamics of soluble aluminum in stream water sampled during rain events differed significantly from stream water sampled during base flow conditions. Three fractions of dissolved aluminum were measured. The inorganic monomeric fraction made up approximately two thirds of the total reactive aluminum at base flow, followed by the acid-soluble and organic monomeric fractions, respectively. Equilibrium modeling showed that hydroxide complexes were the most abundant form of inorganic monomeric aluminum followed by fluoride, free aluminum ion, and sulfate. The activity of inorganic monomeric aluminum at base flow appears to be in equilibrium with an Al(OH)3 phase with solubility intermediate between microcrystalline gibbsite and natural gibbsite. During two rain events, the concentration of all three aluminum fractions increased significantly. Available chemical evidence indicates that acidic soil water was the primary source of dissolved aluminum. As flow increased, the Al(OH)3 saturation index in the stream water increased significantly. The primary cause of the transient increase in the Al(OH)3 saturation index appears to have been the neutralization of excess H+ added by soil water through reaction with stream water HCO3− at a more rapid rate than excess inorganic monomeric aluminum could be removed from solution by hydroxide mineral precipitation. A soil water/stream water mixing model was developed based on measured changes of stream water alkalinity, silica concentration, and charge imbalance during the rain events. Model results indicate that a small amount of soil water (3–11%) was present in the stream at peak stage.

Amorphous ices explained in terms of nonequilibrium phase transitions in supercooled water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2013-03-01

We analyze the phase diagram of supercooled water out-of-equilibrium using concepts from space-time thermodynamics and the dynamic facilitation theory of the glass transition, together with molecular dynamics simulations. We find that when water is driven out-of-equilibrium, it can exist in multiple amorphous states. In contrast, we find that when water is at equilibrium, it can exist in only one liquid state. The amorphous non-equilibrium states are solids, distinguished from the liquid by their lack of mobility, and distinguished from each other by their different densities and local structure. This finding explains the experimentally observed polyamorphism of water as a class of nonequilibrium phenomena involving glasses of different densities. While the amorphous solids can be long lived, they are thermodynamically unstable. When allowed to relax to equilibrium, they crystallize with pathways that pass first through liquid state configurations and then to ordered ice.

Radionuclide solubility and speciation studies for the Yucca Mountain site characterization project

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

Nitsche, H.; Roberts, K.; Prussin, T.

1992-12-01

Yucca Mountain, Nevada, USA, is being investigated for its suitability as a potential site for a geologic nuclear waste repository. As part of the site characterization studies, actinide solubilities and speciations were studied at pH 6, 7, and 8.5 at 25{degrees}C in two different groundwaters from the vicinity of Yucca Mountain. The groundwaters differ substantially in total dissolved carbonate concentration, and to a lesser extent in ionic strength. In the waters with higher carbonate content, the solubilities of neptunium(V) decreased, whereas those americium(III) increased at 25{degrees}KC and decreased at 60{degrees}C. The solids formed were sodium neptunium carbonates and americium hydroxycarbonates.more » Plutonium solubilities did not significantly change with changing water composition because the solubility-controlling solids were mostly amorphous Pu(IV) polymers that contained only small amounts of carbonate.« less

Radionuclide solubility and speciation studies for the Yucca Mountain site characterization project

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

Nitsche, H.; Roberts, K.; Prussin, T.

1993-12-31

Yucca Mountain, Nevada, U.S.A., is being investigated for its suitability as a potential site for a geologic nuclear waste repository. As part of the site characterization studies, actinide solubilities and speciations were studied at pH 6, 7, and 8.5 at 25{degrees} and 60{degrees}C in two different groundwaters from the vicinity of Yucca Mountain. The groundwaters differ substantially in total dissolved carbonate concentration, and to a lesser extent in ionic strength. In the waters with higher carbonate content, the solubilities of neptunium(V) decreased, whereas those of americium (III) increased at 25{degrees}C and decreased at 60{degrees}C. The solids formed were sodium neptuniummore » carbonates and americium hydroxycarbonates. Plutonium solubilities did not significantly change with changing water composition because the solubility-controlling solids were mostly amorphous Pu(IV) polymers that contained only small amounts of carbonate.« less

Chemical Principls Exemplified

ERIC Educational Resources Information Center

Plumb, Robert C.

1973-01-01

Two topics are discussed: (1) Stomach Upset Caused by Aspirin, illustrating principles of acid-base equilibrium and solubility; (2) Physical Chemistry of the Drinking Duck, illustrating principles of phase equilibria and thermodynamics. (DF)

Solubility of oxygen in a seawater medium in equilibrium with a high-pressure oxy-helium atmosphere.

PubMed

Taylor, C D

1979-06-01

The molar oxygen concentration in a seawater medium in equilibrium with a high-pressure oxygen-helium atmosphere was measured directly in pressurized subsamples, using a modified version of the Winkler oxygen analysis. At a partial pressure of oxygen of 1 atm or less, its concentration in the aqueous phase was adequately described by Henry's Law at total pressures up to 600 atm. This phenomenon, which permits a straightforward determination of dissolved oxygen within hyperbaric systems, resulted from pressure-induced compensatory alterations in the Henry's Law variables rather than from a true obedience to the Ideal Gas Law. If the partial pressure of a gas contributes significantly to the hydrostatic pressure, Henry's Law is no longer adequate for determining its solubility within the compressed medium.

Experimental determination of solubilities of magnesium borates: Solubility constants of boracite [Mg 3B 7O 13Cl(cr)] and aksaite [MgB 6O 7(OH) 6 ·2H 2O(cr)

DOE PAGES

Xiong, Yongliang; Kirkes, Leslie Dawn; Knox, Jandi; ...

2018-02-03

In this work, solubility measurements regarding boracite [Mg 3B 7O 13Cl(cr)] and aksaite [MgB 6O 7(OH) 6·2H 2O(cr)] from the direction of supersaturation were conducted at 22.5 ± 0.5 °C. The equilibrium constant (log 10K 0) for boracite in terms of the following reaction, Mg 3B 7O 13Cl(cr) + 15H 2O(l) ⇌ 3Mg 2+ + 7B(OH) 4 – + Cl – + 2H + is determined as -29.49 ± 0.39 (2σ) in this study. The equilibrium constant for aksaite according to the following reaction, MgB 6O 7(OH) 6•2H 2O(cr) + 9H 2O(l) ⇌ Mg 2+ + 6B(OH) 4 – + 4H + is determined as -44.41 ± 0.41 (2σ) in this work. This work recommends a set of thermodynamic properties for aksaite at 25 °C and 1 bar as follows: ΔHmore » $$0\\atop{f}$$ =-6063.70 ± 4.85 kJ·mol -1, ΔG =-5492.55 ± 2.32 kJ·mol -1, and S 0 = 344.62 ± 1.85 J·mol -1·K -1. Among them, ΔG$$0\\atop{f}$$ is derived from the equilibrium constant for aksaite determined by this study; ΔH$$0\\atop{f}$$ is from the literature, determined by calorimetry; and S 0 is computed in the present work from ΔG$$0\\atop{f}$$ and ΔH$$0\\atop{f}$$. This investigation also recommends a set of thermodynamic properties for boracite at 25 °C and 1 bar as follows: ΔH$$0\\atop{f}$$ =-6575.02 ± 2.25 kJ·mol -1, ΔG$$0\\atop{f}$$ =-6178.35 ± 2.25 kJ·mol -1, and S 0 = 253.6 ± 0.5 J·mol -1·K -1. Among them, ΔG$$0\\atop{f}$$ is derived from the equilibrium constant for boracite determined by this study; S 0 is from the literature, determined by calorimetry; and ΔH$$0\\atop{f}$$ is computed in this work from ΔG$$0\\atop{f}$$ and S 0. The thermodynamic properties determined in this study can find applications in many fields. For instance, in the field of material science, boracite has many useful properties including ferroelectric and ferroelastic properties. The equilibrium constant of boracite determined in this work will provide guidance for economic synthesis of boracite in an aqueous medium. Similarly, in the field of nuclear waste management, iodide boracite [Mg 3B 7O 13I(cr)] is proposed as a waste form for radioactive 129I. Therefore, the solubility constant for chloride boracite [Mg 3B 7O 13Cl(cr)] will provide the guidance for the performance of iodide boracite in geological repositories. Boracite/aksaite themselves in geological repositories in salt formations may be solubility-controlling phase(s) for borate. Finally, solubility constants of boracite and aksaite will enable researchers to predict borate concentrations in equilibrium with boracite/aksaite in salt formations.« less

Experimental determination of solubilities of magnesium borates: Solubility constants of boracite [Mg 3B 7O 13Cl(cr)] and aksaite [MgB 6O 7(OH) 6 ·2H 2O(cr)

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

Xiong, Yongliang; Kirkes, Leslie Dawn; Knox, Jandi

In this work, solubility measurements regarding boracite [Mg 3B 7O 13Cl(cr)] and aksaite [MgB 6O 7(OH) 6·2H 2O(cr)] from the direction of supersaturation were conducted at 22.5 ± 0.5 °C. The equilibrium constant (log 10K 0) for boracite in terms of the following reaction, Mg 3B 7O 13Cl(cr) + 15H 2O(l) ⇌ 3Mg 2+ + 7B(OH) 4 – + Cl – + 2H + is determined as -29.49 ± 0.39 (2σ) in this study. The equilibrium constant for aksaite according to the following reaction, MgB 6O 7(OH) 6•2H 2O(cr) + 9H 2O(l) ⇌ Mg 2+ + 6B(OH) 4 – + 4H + is determined as -44.41 ± 0.41 (2σ) in this work. This work recommends a set of thermodynamic properties for aksaite at 25 °C and 1 bar as follows: ΔHmore » $$0\\atop{f}$$ =-6063.70 ± 4.85 kJ·mol -1, ΔG =-5492.55 ± 2.32 kJ·mol -1, and S 0 = 344.62 ± 1.85 J·mol -1·K -1. Among them, ΔG$$0\\atop{f}$$ is derived from the equilibrium constant for aksaite determined by this study; ΔH$$0\\atop{f}$$ is from the literature, determined by calorimetry; and S 0 is computed in the present work from ΔG$$0\\atop{f}$$ and ΔH$$0\\atop{f}$$. This investigation also recommends a set of thermodynamic properties for boracite at 25 °C and 1 bar as follows: ΔH$$0\\atop{f}$$ =-6575.02 ± 2.25 kJ·mol -1, ΔG$$0\\atop{f}$$ =-6178.35 ± 2.25 kJ·mol -1, and S 0 = 253.6 ± 0.5 J·mol -1·K -1. Among them, ΔG$$0\\atop{f}$$ is derived from the equilibrium constant for boracite determined by this study; S 0 is from the literature, determined by calorimetry; and ΔH$$0\\atop{f}$$ is computed in this work from ΔG$$0\\atop{f}$$ and S 0. The thermodynamic properties determined in this study can find applications in many fields. For instance, in the field of material science, boracite has many useful properties including ferroelectric and ferroelastic properties. The equilibrium constant of boracite determined in this work will provide guidance for economic synthesis of boracite in an aqueous medium. Similarly, in the field of nuclear waste management, iodide boracite [Mg 3B 7O 13I(cr)] is proposed as a waste form for radioactive 129I. Therefore, the solubility constant for chloride boracite [Mg 3B 7O 13Cl(cr)] will provide the guidance for the performance of iodide boracite in geological repositories. Boracite/aksaite themselves in geological repositories in salt formations may be solubility-controlling phase(s) for borate. Finally, solubility constants of boracite and aksaite will enable researchers to predict borate concentrations in equilibrium with boracite/aksaite in salt formations.« less

Solubility constants of hydroxyl sodalite at elevated temperatures evaluated from hydrothermal experiments: Applications to nuclear waste isolation

DOE PAGES

Xiong, Yongliang

2016-09-17

In this study, solubility constants of hydroxyl sodalite (ideal formula, Na 8[Al 6Si 6O 24][OH] 2·3H 2O) from 25°C to 100°C are obtained by applying a high temperature Al—Si Pitzer model to evaluate solubility data on hydroxyl sodalite in high ionic strength solutions at elevated temperatures. A validation test comparing model-independent experimental data to model predictions demonstrates that the solubility values produced by the model are in excellent agreement with the experimental data. In addition, the equilibrium constants obtained in this study have a wide range of applications, including synthesis of hydroxyl sodalite, de-silication in the Bayer process for extractionmore » of alumina, and the performance of proposed sodalite waste forms in geological repositories in various lithologies including salt formations. The thermodynamic calculations based on the equilibrium constants obtained in this work indicate that the solubility products in terms of m ΣAl×m ΣSi for hydroxyl sodalite are very low (e.g., ~10 -13 [mol·kg -1] 2 at 100°C) in brines characteristic of salt formations, implying that sodalite waste forms would perform very well in repositories located in salt formations. Finally, the information regarding the solubility behavior of hydroxyl sodalite obtained in this study provides guidance to investigate the performance of other pure end-members of sodalite such as chloride- and iodide-sodalite, which may be of interest for geological repositories in various media.« less

A novel osmotic pump-based controlled delivery system consisting of pH-modulated solid dispersion for poorly soluble drug flurbiprofen: in vitro and in vivo evaluation.

PubMed

Li, Shujuan; Wang, Xiaoyu; Wang, Yingying; Zhao, Qianqian; Zhang, Lina; Yang, Xinggang; Liu, Dandan; Pan, Weisan

2015-01-01

In this study, a novel controlled release osmotic pump capsule consisting of pH-modulated solid dispersion for poorly soluble drug flurbiprofen (FP) was developed to improve the solubility and oral bioavailability of FP and to minimize the fluctuation of plasma concentration. The pH-modulated solid dispersion containing FP, Kollidon® 12 PF and Na2CO3 at a weight ratio of 1/4.5/0.02 was prepared using the solvent evaporation method. The osmotic pump capsule was assembled by semi-permeable capsule shell of cellulose acetate (CA) prepared by the perfusion method. Then, the solid dispersion, penetration enhancer, and suspending agents were tableted and filled into the capsule. Central composite design-response surface methodology was used to evaluate the influence of factors on the responses. A second-order polynomial model and a multiple linear model were fitted to correlation coefficient of drug release profile and ultimate cumulative release in 12 h, respectively. The actual response values were in good accordance with the predicted ones. The optimized formulation showed a complete drug delivery and zero-order release rate. Beagle dogs were used to be conducted in the pharmacokinetic study. The in vivo study indicated that the relative bioavailability of the novel osmotic pump system was 133.99% compared with the commercial preparation. The novel controlled delivery system with combination of pH-modulated solid dispersion and osmotic pump system is not only a promising strategy to improve the solubility and oral bioavailability of poorly soluble ionizable drugs but also an effective way to reduce dosing frequency and minimize the plasma fluctuation.

Equilibrium and kinetic models for colloid release under transient solution chemistry conditions

USDA-ARS?s Scientific Manuscript database

We present continuum models to describe colloid release in the subsurface during transient physicochemical conditions. Our modeling approach relates the amount of colloid release to changes in the fraction of the solid surface area that contributes to retention. Equilibrium, kinetic, equilibrium and...

Theoretical Aspects of Differential Scanning Calorimetry as a Tool for the Studies of Equilibrium Thermodynamics in Pharmaceutical Solid Phase Transitions.

PubMed

Faroongsarng, Damrongsak

2016-06-01

Although differential scanning calorimetry (DSC) is a non-equilibrium technique, it has been used to gain energetic information that involves phase equilibria. DSC has been widely used to characterize the equilibrium melting parameters of small organic pharmaceutical compounds. An understanding of how DSC measures an equilibrium event could make for a better interpretation of the results. The aim of this mini-review was to provide a theoretical insight into the DSC measurement to obtain the equilibrium thermodynamics of a phase transition especially the melting process. It was demonstrated that the heat quantity obtained from the DSC thermogram (ΔH) was related to the thermodynamic enthalpy of the phase transition (ΔH (P) ) via: ΔH = ΔH (P) /(1 + K (- 1)) where K was the equilibrium constant. In melting, the solid and liquefied phases presumably coexist resulting in a null Gibbs free energy that produces an infinitely larger K. Thus, ΔH could be interpreted as ΔH (P). Issues of DSC investigations on melting behavior of crystalline solids including polymorphism, degradation impurity due to heating in situ, and eutectic melting were discussed. In addition, DSC has been a tool for determination of the impurity based on an ideal solution of the melt that is one of the official methods used to establish the reference standard.

Effects of solid dispersion and self-emulsifying formulations on the solubility, dissolution, permeability and pharmacokinetics of isorhamnetin, quercetin and kaempferol in total flavones of Hippophae rhamnoides L.

PubMed

Zhao, Guoying; Duan, Jingze; Xie, Yan; Lin, Guobei; Luo, Huilin; Li, Guowen; Yuan, Xiurong

2013-07-01

The aim of this study was to investigate the effects of solid dispersions (SD) and self-emulsifying (SE) formulations on the solubility and absorption properties of active components in total flavones of Hippophae rhamnoides L. (TFH). The solubility, dissolution rate, permeability and pharmacokinetics of isorhamnetin, quercetin and kaempferol in TFH SD/SE formulations and TFH were compared. The results showed that the solubility and dissolution rate of isorhamnetin, quercetin and kaempferol in SD/SE formulations were significantly enhanced compared to those in TFH, however, their intestinal permeability was comparable. The bioavailability of isorhamnetin, quercetin and kaempferol in rats remarkably increased after oral administration of TFH SD formulations compared to TFH, but there was no significant increase after oral administration of TFH SE formulations. The results of this study indicated the SD formulations on the improvement of pharmacokinetic properties of isorhamnetin, quercetin and kaempferol in TFH were much better than those of SE formulations. The improvement of pharmacokinetic properties of isorhamnetin, quercetin and kaempferol in TFH by SD formulations was probably ascribed to the enhancement of the solubility and dissolution of the three components, but was not relevant to the intestinal permeability. Therefore, as for herb extracts containing multiple components, especially for their major components with poor water solubility, solid dispersion formulations might have the better potential to enhance their bioavailability.

The Solid Phase Curing Time Effect of Asbuton with Texapon Emulsifier at the Optimum Bitumen Content

NASA Astrophysics Data System (ADS)

Sarwono, D.; Surya D, R.; Setyawan, A.; Djumari

2017-07-01

Buton asphalt (asbuton) could not be utilized optimally in Indonesia. Asbuton utilization rate was still low because the processed product of asbuton still have impracticable form in the term of use and also requiring high processing costs. This research aimed to obtain asphalt products from asbuton practical for be used through the extraction process and not requiring expensive processing cost. This research was done with experimental method in laboratory. The composition of emulsify asbuton were 5/20 grain, premium, texapon, HCl, and aquades. Solid phase was the mixture asbuton 5/20 grain and premium with 3 minutes mixing time. Liquid phase consisted texapon, HCl and aquades. The aging process was done after solid phase mixing process in order to reaction and tie of solid phase mixed become more optimal for high solubility level of asphalt production. Aging variable time were 30, 60, 90, 120, and 150 minutes. Solid and liquid phase was mixed for emulsify asbuton production, then extracted for 25 minutes. Solubility level of asphalt, water level, and asphalt characteristic was tested at extraction result of emulsify asbuton with most optimum ashphal level. The result of analysis tested data asphalt solubility level at extract asbuton resulted 94.77% on 120 minutes aging variable time. Water level test resulted water content reduction on emulsify asbuton more long time on occurring of aging solid phase. Examination of asphalt characteristic at extraction result of emulsify asbuton with optimum asphalt solubility level, obtain specimen that have rigid and strong texture in order that examination result have not sufficient ductility and penetration value.

Three-Phase Melting Curves in the Binary System of Carbon Dioxide and Water

NASA Astrophysics Data System (ADS)

Abramson, E. H.

2017-10-01

Invariant, three-phase melting curves, of ice VI in equilibrium with solid CO2, of ice VII in equilibrium with solid CO2, and of solid CO2 in simultaneous equilibrium with a majority aqueous and a majority CO2 fluid, were explored in the binary system of carbon dioxide and water. Diamond-anvil cells were used to develop pressures of 5 GPa. Water exhibits a large melting temperature depression (73°C less than its pure melting temperature of 253°C at 5 GPa) indicative of large concentrations of CO2 in the aqueous solution. The melting point of water-saturated CO2 does not show a measureable departure from that of the pure system at temperatures lower than ∼200°C and only 10°C at 5 GPa (from 327°C).

Surfactant Facilitated Spreading of Aqueous Drops on Hydrophobic Surfaces

NASA Technical Reports Server (NTRS)

Kumar, Nitin; Couzis, Alex; Maldarelli, Charles; Singh, Bhim S. (Technical Monitor)

2000-01-01

Microgravity technologies often require aqueous phases to spread over nonwetting hydrophobic solid/surfaces. At a hydrophobic surface, the air/hydrophobic solid tension is low, and the solid/aqueous tension is high. A large contact angle forms as the aqueous/air tension acts together with the solid/air tension to balance the large solid/aqueous tension. The aqueous phase, instead of spreading, is held in a meniscus by the large angle. Surfactants facilitate the wetting of water on hydrophobic surfaces by adsorbing on the water/air and hydrophobic solid/water interfaces and lowering the surface tensions of these interfaces. The tension reductions decrease the contact angle, which increases the equilibrium wetted area. Hydrocarbon surfactants (i.e. amphiphiles with a hydrophobic chain of methylene groups attached to a large polar group to give aqueous solubility) do not reduce significantly the contact angles of the very hydrophobic surfaces such as parafilm or polyethylene. Trisiloxane surfactants (amphiphiles with a hydrophobe consisting of methyl groups linked to a trisiloxane backbone in the form of a disk ((CH3)3-Si-O-Si-O-Si(CH3)3)) and an extended ethoxylate (-(OCH2CH2)n-) polar group in the form of a chain with seven or eight units) can significantly reduce the contact angle of water on a very hydrophobic surface and cause rapid and complete (or nearly complete) spreading (lermed superspreading). The overall goal of the research described in this proposal is to establish and verify a theory for how trisiloxanes cause superspreading, and then use this knowledge as a guide to developing more general hydrocarbon based surfactant systems which superspread and can be used in microgravity. We propose that the trisiloxane surfactants superspread when the siloxane adsorbs, the hydrophobic disk parts of the molecule adsorb onto the surface removing the surface water. Since the cross sectional area of the disk is larger than that of the extended ethoxylate chain, the disks can form a space filling mat on the surface which removes a significant amount of the surface water. The water adjacent to the hydrophobic solid surface is of high energy due to incomplete hydrogen bonding; its removal significantly lowers the tension and reduces the contact angle. Hydrocarbon surfactants cannot remove as much surface water because their large polar groups prevent the chains from cohering lengthwise. In our report last year we presented a poster describing the preparation of model very hydrophobic surfaces which are homogeneous and atomically smooth using self assembled monolayers of octadecyl trichlorosilane (OTS). In this poster we will use these surfaces as test substrates in developing hydrocarbon based surfactant systems which superspread. We studied a binary hydrocarbon surfactant systems consisting of a very soluble large polar group polyethylene oxide surfactant (C12E6 (CH3(CH2)11(OCH2CH2)6OH) and a long chain alcohol dodecanol. By mixing the alcohol with this soluble surfactant we have found that the contact angle of the mixed system on our test hydrophobic surfaces is very low. We hypothesize that the alcohol fills in the gaps between adjacent adsorbed chains of the large polar group surfactant. This filling in removes the surface water and effects the decrease in contact angle. We confirm this hypothesis by demonstrating that at the air/water interface the mixed layer forms condensed phases while the soluble large polar group surfactant by itself does not. We present drop impact experiments which demonstrate that the dodecanol/C12E6 mixture is effective in causing impacting drops to spread on the very hydrophobic model OTS surfaces.

Finite-deformation phase-field chemomechanics for multiphase, multicomponent solids

NASA Astrophysics Data System (ADS)

Svendsen, Bob; Shanthraj, Pratheek; Raabe, Dierk

2018-03-01

The purpose of this work is the development of a framework for the formulation of geometrically non-linear inelastic chemomechanical models for a mixture of multiple chemical components diffusing among multiple transforming solid phases. The focus here is on general model formulation. No specific model or application is pursued in this work. To this end, basic balance and constitutive relations from non-equilibrium thermodynamics and continuum mixture theory are combined with a phase-field-based description of multicomponent solid phases and their interfaces. Solid phase modeling is based in particular on a chemomechanical free energy and stress relaxation via the evolution of phase-specific concentration fields, order-parameter fields (e.g., related to chemical ordering, structural ordering, or defects), and local internal variables. At the mixture level, differences or contrasts in phase composition and phase local deformation in phase interface regions are treated as mixture internal variables. In this context, various phase interface models are considered. In the equilibrium limit, phase contrasts in composition and local deformation in the phase interface region are determined via bulk energy minimization. On the chemical side, the equilibrium limit of the current model formulation reduces to a multicomponent, multiphase, generalization of existing two-phase binary alloy interface equilibrium conditions (e.g., KKS). On the mechanical side, the equilibrium limit of one interface model considered represents a multiphase generalization of Reuss-Sachs conditions from mechanical homogenization theory. Analogously, other interface models considered represent generalizations of interface equilibrium conditions consistent with laminate and sharp-interface theory. In the last part of the work, selected existing models are formulated within the current framework as special cases and discussed in detail.

Barium isotope fractionation during witherite (BaCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; van Zuilen, Kirsten; Purgstaller, Bettina; Baldermann, Andre; Nägler, Thomas F.; Dietzel, Martin

2016-10-01

This study examines the behavior of Ba isotope fractionation between witherite and fluid during mineral dissolution, precipitation and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 10-2 M NaCl solution where the pH was adjusted by continuous bubbling of a water saturated gas phase of CO2 or atmospheric air. During witherite dissolution no Ba isotope fractionation was observed between solid and fluid. In contrast, during witherite precipitation, caused by a pH increase, a preferential uptake of the lighter 134Ba isotopomer in the solid phase was observed. In this case, the isotope fractionation factor αwitherite-fluid is calculated to be 0.99993 ± 0.00004 (or Δ137/134Bawitherite-fluid ≈ -0.07 ± 0.04‰, 2 sd). The most interesting feature of this study, however, is that after the attainment of chemical equilibrium, the Ba isotope composition of the aqueous phase is progressively becoming lighter, indicating a continuous exchange of Ba2+ ions between witherite and fluid. Mass balance calculations indicate that the detachment of Ba from the solid is not only restricted to the outer surface layer of the solid, but affects several (∼7 unit cells) subsurface layers of the crystal. This observation comes in excellent agreement with the concept of a dynamic system at chemical equilibrium in a mineral-fluid system, denoting that the time required for the achievement of isotopic equilibrium in the witherite-fluid system is longer compared to that observed for chemical equilibrium. Overall, these results indicate that the isotopic composition of Ba bearing carbonates in natural environments may be altered due to changes in fluid composition without a net dissolution/precipitation to be observed.

A miniature cell for gas solubility measurements in oils and bitumen.

PubMed

Foroughi, Hooman; Acosta, Edgar J; Kawaji, Masahiro

2011-03-01

A miniature cell has been designed and constructed to measure gas solubility in crude oils and bitumen. The cell was made of stainless steel with a total internal volume of 1.835 cc and only an oil sample of 0.4 cc was required for one set of measurements at different pressures. By using this small cell, the waiting time for reaching equilibrium was less than 10 min. The technique was validated by measuring CO(2) gas solubility in two bitumen samples. The results were compared and found to be in very good agreement with available data. The apparatus was also used to study the effect of ashphaltene on CO(2) solubility in bitumen. It was shown that ashphaltene had a negligible effect on CO(2) solubility in bitumen.

Soluble Molecularly Imprinted Nanorods for Homogeneous Molecular Recognition

NASA Astrophysics Data System (ADS)

Liang, Rongning; Wang, Tiantian; Zhang, Huan; Yao, Ruiqing; Qin, Wei

2018-03-01

Nowadays, it is still difficult for molecularly imprinted polymer (MIPs) to achieve homogeneous recognition since they cannot be easily dissolved in organic or aqueous phase. To address this issue, soluble molecularly imprinted nanorods have been synthesized by using soluble polyaniline doped with a functionalized organic protonic acid as the polymer matrix. By employing 1-naphthoic acid as a model, the proposed imprinted nanorods exhibit an excellent solubility and good homogeneous recognition ability. The imprinting factor for the soluble imprinted nanoroads is 6.8. The equilibrium dissociation constant and the apparent maximum number of the proposed imprinted nanorods are 248.5 μM and 22.1 μmol/g, respectively. We believe that such imprinted nanorods may provide an appealing substitute for natural receptors in homogeneous recognition related fields.

Enhancement of solubility and oral bioavailability of manidipine by formation of ternary solid dispersion with d-α-tocopherol polyethylene glycol 1000 succinate and copovidone.

PubMed

Chamsai, Benchawan; Limmatvapirat, Sontaya; Sungthongjeen, Srisagul; Sriamornsak, Pornsak

2017-12-01

Low bioavailability of oral manidipine (MDP) is due to its low water solubility. The objective of this study was to increase the solubility and bioavailability of MDP by fabricating ternary solid dispersion (tSD) with d-α-tocopherol polyethyleneglycol-1000-succinate and copovidone. In this study, solid ternary phase diagram was applied in order to check the homogeneity of tSD prepared by melting and solidifying with dry ice. The physicochemical properties of different formulations were determined by differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR) and hot stage microscopy. Their solubility, dissolution, stability and bioavailability were also investigated. The results demonstrated that tSD obtained from ternary phase diagram divided into homogeneous and non-homogeneous regions. In the homogenous region, the transparent characteristics of tSD was observed and considered as a glass solution, which have a higher MDP solubility than that in non-homogenous region. The hot stage microscopy, DSC and PXRD confirmed that solid dispersion was formed in which MDP was molecularly dispersed in the carriers, especially in the homogenous region of phase diagram. FTIR analysis demonstrated strong hydrogen bonding between amine groups of MDP and carbonyl groups of copovidone, which supported a higher solubility and dissolution of tSD. The pharmacokinetic study in Wistar rats showed that the tSD had the greatest effect on oral bioavailability. Immediate hypotensive effect of tSD was also observed in vivo. The improvement of stability, dissolution and oral bioavailability of MDP could be achieved by using tSD technique.

Liquid phase stabilization versus bubble formation at a nanoscale curved interface

NASA Astrophysics Data System (ADS)

Schiffbauer, Jarrod; Luo, Tengfei

2018-03-01

We investigate the nature of vapor bubble formation near a nanoscale-curved convex liquid-solid interface using two models: an equilibrium Gibbs model for homogenous nucleation, and a nonequilibrium dynamic van der Waals-diffuse-interface model for phase change in an initially cool liquid. Vapor bubble formation is shown to occur for sufficiently large radius of curvature and is suppressed for smaller radii. Solid-fluid interactions are accounted for and it is shown that liquid-vapor interfacial energy, and hence Laplace pressure, has limited influence over bubble formation. The dominant factor is the energetic cost of creating the solid-vapor interface from the existing solid-liquid interface, as demonstrated via both equilibrium and nonequilibrium arguments.

A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

PubMed

Bock, David C; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2013-06-01

Silver vanadium oxide (Ag 2 V 4 O 11 , SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag 2 VO 2 PO 4 , SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO 4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most phosphate salts, a lower material solubility of SVPO relative to SVO is anticipated. Thus, the first vanadium dissolution studies of SVPO in battery electrolyte solutions are described herein. The equilibrium solubility of SVPO was ~5 times less than SVO, with a rate constant of dissolution ~3.5 times less than that of SVO. The vanadium dissolution in SVO and SVPO can be adequately described with a diffusion layer model, as supported by the Noyes-Whitney equation. Cells prepared with vanadium-treated anodes displayed higher AC impedance and DC resistance relative to control anodes. These data support the premise that SVPO cells are likely to exhibit reduced cathode solubility and thus less affected by increased cell resistance due to cathode solubility compared to SVO based cells.

Soluble 1:1 complexes and insoluble 3:2 complexes - Understanding the phase-solubility diagram of hydrocortisone and γ-cyclodextrin.

PubMed

Schönbeck, Christian; Madsen, Tobias L; Peters, Günther H; Holm, René; Loftsson, Thorsteinn

2017-10-15

The molecular mechanisms underlying the drug-solubilizing properties of γ-cyclodextrin were explored using hydrocortisone as a model drug. The B S -type phase-solubility diagram of hydrocortisone with γ-cyclodextrin was thoroughly characterized by measuring the concentrations of hydrocortisone and γ-cyclodextrin in solution and the solid phase. The drug-solubilizer interaction was also studied by isothermal titration calorimetry from which a precise value of the 1:1 binding constant (K 11 =4.01mM -1 at 20°C) was obtained. The formation of water-soluble 1:1 complexes is responsible for the initial increase in hydrocortisone solubility while the precipitation of entities with a 3:2 ratio of γ-cyclodextrin:hydrocortisone is responsible for the plateau and the ensuing strong decrease in solubility once all solid hydrocortisone is used up. The complete phase-solubility diagram is well accounted for by a model employing the 1:1 binding constant and the solubility product of the precipitating 3:2 entity (K 32 S =5.51 mM 5 ). For such systems, a small surplus of γ-cyclodextrin above the optimum concentration may result in a significant decrease in drug solubility, and the implications for drug formulations are briefly discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Precipitation of Co(2+) carbonates from aqueous solution: insights on the amorphous to crystalline transformation.

NASA Astrophysics Data System (ADS)

González-López, Jorge; Fernández-González, Ángeles; Jiménez, Amalia

2016-04-01

Cobalt is toxic metal that is present only as a trace in the Earth crust. However, Co might concentrate on specific areas due to both natural and anthropogenic factors and thus, soils and groundwater can be contaminated. It is from this perspective that we are interested in the precipitation of cobalt carbonates, since co-precipitation with minerals phases is a well-known method for metal immobilization in the environment. In particular, the carbonates are widely used due to its reactivity and natural abundance. In order to evaluate the cobalt carbonate precipitation at room temperature, a simple experimental work was carried out in this work. The precipitation occurred via reaction of two common salts: 0.05M of CoCl2 and 0.05M of Na2CO3 in aqueous solution. After reaction, the precipitated solid was kept in the remaining water at 25 oC and under constant stirring for different aging times of 5 min, 1 and 5 hours, 1, 2, 4, 7, 30 and 60 days. In addition to the aging and precipitation experiments, we carried out experiments to determine the solubility of the solids. In these experiments each precipitate was dissolved in Milli-Q water until equilibrium was reached and then the aqueous solution was analyzed regarding Co2+ and total alkalinity. Furthermore, acid solution calorimetry of the products were attained. Finally, we modeled the results using the PHREEQC code. Solid and aqueous phase identification and characterization have been extensively reported in a previous work (González-López et al., 2015). The main results of our investigation were the initial precipitation of an amorphous cobalt carbonate that evolve towards a poorly crystalline cobalt hydroxide carbonate with aging treatment. Solubility of both phases have been calculated under two different approaches: precipitation and dissolution. Values of solubility from each approach were obtained with a general error due to differences in experiment conditions, for instance, ionic strength, temperature and water content. It was surprising the low solubility product (Ksp) of the new phase Co2CO3(OH)2 in the order of 10-30 and this could explain its appearance only after 7 days of aging. On the other hand, the high solubility product of amorphous is consistent with its instantaneous precipitation at the beginning of the reaction. Solution calorimetry shows a higher value of exothermic solution enthalpy for crystalline cobalt hydroxide carbonate and hence, the solubility result are confirmed. Although geochemical models indicated that aqueous solution was supersaturated with respect both phases, the sequence of obtained phases (first amorphous and next crystalline) indicate that the evolution of the saturation index has to be dropped with respect to amorphous phase with time. These results points towards a simultaneous dissolution of the amorphous and the precipitation of crystalline phase Co2CO3(OH)2 at the first stages of the reaction. González-López, J. ; Fernández-González, Á. ; Jiménez, A. (2015) Prepublication: Crystallization of nanostructured cobalt hydroxide carbonate at ambient conditions: a key precursor of Co3O4. DOI: http://dx.doi.org/10.1180/minmag.2015.079.7.02

Students' mental models on the solubility and solubility product concept

NASA Astrophysics Data System (ADS)

Rahmi, Chusnur; Katmiati, Siti; Wiji, Mulyani, Sri

2017-05-01

This study aims to obtain some information regarding profile of students' mental models on the solubility and solubility product concept. A descriptive qualitative method was the method employed in the study. The participants of the study were students XI grade of a senior high school in Bandung. To collect the data, diagnostic test on mental model-prediction, observation, explanation (TDM-POE) instrument was employed in the study. The results of the study revealed that on the concept of precipitation formation of a reaction, 30% of students were not able to explain the precipitation formation of a reaction either in submicroscopic or symbolic level although the microscopic have been shown; 26% of students were able to explain the precipitation formation of a reaction based on the relation of Qsp and Ksp, but they were not able to explain the interaction of particles that involved in the reaction and to calculate Qsp; 26% of students were able to explain the precipitation formation of a reaction based on the relation of Qsp and Ksp, and determine the particles involved, but they did not have the knowledge about the interactions occured and were uncapable of calculating Qsp; and 18% of students were able to explain the precipitation formation of a reaction based on the relation of Qsp and Ksp, and determine the interactions of the particles involved in the reactions but they were not able to calculate Qsp. On the effect of adding common ions and decreasing pH towards the solubility concept, 96% of students were not able to explain the effect of adding common ions and decreasing pH towards the solubility either in submicroscopic or symbolic level although the microscopic have been shown; while 4% of students were only able to explain the effect of adding common ions towards the solubility based on the chemical equilibrium shifts and predict the effect of decreasing pH towards the solubility. However, they were not able to calculate the solubility before and after adding common ions and explain it up to the submicroscopic level either based on the shift of equilibrium solubility or the comparison of solubility calculation results before and after decreasing pH. Overall, the present study showed that most students obtain incomplete mental model on the solubility and solubility product concept. From the findings, it is recommended for the teachers to improve students' learning activity.

Predicting the excess solubility of acetanilide, acetaminophen, phenacetin, benzocaine, and caffeine in binary water/ethanol mixtures via molecular simulation

PubMed Central

Paluch, Andrew S.; Parameswaran, Sreeja; Liu, Shuai; Kolavennu, Anasuya; Mobley, David L.

2015-01-01

We present a general framework to predict the excess solubility of small molecular solids (such as pharmaceutical solids) in binary solvents via molecular simulation free energy calculations at infinite dilution with conventional molecular models. The present study used molecular dynamics with the General AMBER Force Field to predict the excess solubility of acetanilide, acetaminophen, phenacetin, benzocaine, and caffeine in binary water/ethanol solvents. The simulations are able to predict the existence of solubility enhancement and the results are in good agreement with available experimental data. The accuracy of the predictions in addition to the generality of the method suggests that molecular simulations may be a valuable design tool for solvent selection in drug development processes. PMID:25637996

In Silico Determination of Gas Permeabilities by Non-Equilibrium Molecular Dynamics: CO2 and He through PIM-1

PubMed Central

Frentrup, Hendrik; Hart, Kyle E.; Colina, Coray M.; Müller, Erich A.

2015-01-01

We study the permeation dynamics of helium and carbon dioxide through an atomistically detailed model of a polymer of intrinsic microporosity, PIM-1, via non-equilibrium molecular dynamics (NEMD) simulations. This work presents the first explicit molecular modeling of gas permeation through a high free-volume polymer sample, and it demonstrates how permeability and solubility can be obtained coherently from a single simulation. Solubilities in particular can be obtained to a very high degree of confidence and within experimental inaccuracies. Furthermore, the simulations make it possible to obtain very specific information on the diffusion dynamics of penetrant molecules and yield detailed maps of gas occupancy, which are akin to a digital tomographic scan of the polymer network. In addition to determining permeability and solubility directly from NEMD simulations, the results shed light on the permeation mechanism of the penetrant gases, suggesting that the relative openness of the microporous topology promotes the anomalous diffusion of penetrant gases, which entails a deviation from the pore hopping mechanism usually observed in gas diffusion in polymers. PMID:25764366

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

Xiong, Yongliang

In this study, solubility constants of hydroxyl sodalite (ideal formula, Na 8[Al 6Si 6O 24][OH] 2·3H 2O) from 25°C to 100°C are obtained by applying a high temperature Al—Si Pitzer model to evaluate solubility data on hydroxyl sodalite in high ionic strength solutions at elevated temperatures. A validation test comparing model-independent experimental data to model predictions demonstrates that the solubility values produced by the model are in excellent agreement with the experimental data. In addition, the equilibrium constants obtained in this study have a wide range of applications, including synthesis of hydroxyl sodalite, de-silication in the Bayer process for extractionmore » of alumina, and the performance of proposed sodalite waste forms in geological repositories in various lithologies including salt formations. The thermodynamic calculations based on the equilibrium constants obtained in this work indicate that the solubility products in terms of m ΣAl×m ΣSi for hydroxyl sodalite are very low (e.g., ~10 -13 [mol·kg -1] 2 at 100°C) in brines characteristic of salt formations, implying that sodalite waste forms would perform very well in repositories located in salt formations. Finally, the information regarding the solubility behavior of hydroxyl sodalite obtained in this study provides guidance to investigate the performance of other pure end-members of sodalite such as chloride- and iodide-sodalite, which may be of interest for geological repositories in various media.« less

Surfactant-Free Solid Dispersions of Hydrophobic Drugs in an Amorphous Sugar Matrix Dried from an Organic Solvent.

PubMed

Takeda, Koji; Gotoda, Yuto; Hirota, Daichi; Hidaka, Fumihiro; Sato, Tomo; Matsuura, Tsutashi; Imanaka, Hiroyuki; Ishida, Naoyuki; Imamura, Koreyoshi

2017-03-06

The technique for homogeneously dispersing hydrophobic drugs in a water-soluble solid matrix (solid dispersion) is a subject that has been extensively investigated in the pharmaceutical industry. Herein, a novel technique for dispersing a solid, without the need to use a surfactant, is reported. A freeze-dried amorphous sugar sample was dissolved in an organic solvent, which contained a soluble model hydrophobic component. The suspension of the sugar and the model hydrophobic component was vacuum foam dried to give a solid powder. Four types of sugars and methanol were used as representative sugars and the organic medium. Four model drugs (indomethacin, ibuprofen, gliclazide, and nifedipine) were employed. Differential scanning calorimetry analyses indicated that the sugar and model drug (100:1) did not undergo segregation during the drying process. The dissolution of the hydrophobic drugs in water from the solid dispersion was then evaluated, and the results indicated that the C max and AUC 0-60 min of the hydrophobic drug in water were increased when the surfactant-free solid dispersion was used. Palatinose and/or α-maltose were superior to the other tested carbohydrates in increasing C max and AUC 0-60 min for all tested model drugs, and the model drug with a lower water solubility tended to exhibit a greater extent of over-dissolution.

Stability and Biological Activity Evaluation of Chlorantraniliprole Solid Nanodispersions Prepared by High Pressure Homogenization

PubMed Central

Cui, Bo; Feng, Lei; Wang, Chunxin; Yang, Dongsheng; Yu, Manli; Zeng, Zhanghua; Wang, Yan; Sun, Changjiao; Zhao, Xiang; Cui, Haixin

2016-01-01

Poorly water-soluble compounds are difficult to develop as pesticide products and face great challenges in water-based and environmentally friendly formulation development. In this study, high pressure homogenization combined with lyophilization was adopted to prepare the solid nanodispersions of chlorantraniliprole with poor solubility and high melting point. The mean particle sizes of the solid nanodispersions with different pesticide contents were all less than 75 nm, even when the content was up to 91.5%. For the 2.5% chlorantraniliprole solid nanodispersion with the mean particle size of 29 nm, the suspensibility and wetting time in water were 97.32% and 13 s, respectively. The re-dispersibility and wettability were superior to those of conventional water dispersible granules. The retention on the rice leaf of 18.7 mg/cm2 was 1.5 and 3 times that of commercial aqueous suspension concentrate and pure water. The bioassay result to diamondback moths indicated that the toxicity of the solid nanodispersion was 3.3 and 2.8 times that of technical and aqueous suspension concentrate, respectively. Moreover, the solid nanodispersion has the advantages of total avoidance of organic solvents, significant reduction of surfactants and feasibility of obtaining high concentration nanoformulations. The solid nanodispersion is an attractive candidate for improving pesticide solubility and efficacy, and its application in crop production will reduce both residues in food and environmental pollution of pesticide. PMID:27500828

Application of transglycosylated stevia and hesperidin as drug carriers to enhance biopharmaceutical properties of poorly-soluble artemisinin.

PubMed

Letchmanan, Kumaran; Shen, Shou-Cang; Ng, Wai Kiong; Tan, Reginald B H

2018-01-01

Biopharmaceutical properties of poorly water-soluble antimalarial drug, Artemisinin (ART), were improved by formulating amorphous solid dispersions with transglycosylated food additives (Hsp-G and Stevia-G) via co-spray drying. Both the formulated ART/Hsp-G and ART/Stevia-G showed superior dissolution properties with a burst release of more than 95% of drug within 5 min, whereas untreated ART dissolved only 4% in 5min. The supersaturation solubility of the formulated ART was enhanced by 2-fold as compared with untreated counterpart. The storage stability tests indicated that these formulations chemically stable at room temperature and under low humidity (<18% RH) conditions. However, high humidity (75% RH) induced re-crystallization and caused changes in the physical appearance of the solid dispersions. In addition, both the food additives and ART formulated samples showed low cytotoxicity to Caco-2 cell line suggesting their good biocompatibility. Thus, the formation of solid dispersions of ART with transglycosylated food additives is a potentially safe and effective approach to enhance the bioavailability of poorly water-soluble ART. Copyright © 2017 Elsevier B.V. All rights reserved.

Solid dispersions, part II: new strategies in manufacturing methods for dissolution rate enhancement of poorly water-soluble drugs.

PubMed

Bikiaris, Dimitrios N

2011-12-01

The absorption of poorly water-soluble drugs, when presented in the crystalline state to the gastrointestinal tract, is typically dissolution rate-limited, and according to BCS these drugs belong mainly to class II. Both dissolution kinetics and solubility are particle size dependent. Nowadays, various techniques are available to the pharmaceutical industry for dissolution rate enhancement of such drugs. Among such techniques, nanosuspensions and drug formulation in solid dispersions are those with the highest interest. This review discusses strategies undertaken over the last 10 years, which have been applied for the dissolution enhancement of poorly water-soluble drugs; such processes include melt mixing, electrospinning, microwave irradiation and the use of inorganic nanoparticles. Many problems in this field still need to be solved, mainly the use of toxic solvents, and for this reason the use of innovative new procedures and materials will increase over the coming years. Melt mixing remains extremely promising for the preparation of SDs and will probably become the most used method in the future for the preparation of solid drug dispersions.

Dust formation in LBV envelopes

NASA Astrophysics Data System (ADS)

Gail, H.-P.; Duschl, W. J.; Ferrarotti, A. S.; Weis, K.

2005-09-01

The condensation process for the peculiar element mixture of CNO cycle processed material in the pre-SN ejecta of massive stars is investigated. From thermodynamic equilibrium calculations it is shown that the most likely solids to be formed in CNO process equilibrated materials are solid FeSi, metallic Fe, and small quantities of forsterite (Mg2SiO4). Nucleation may be triggered by TiC. Some SiC may be formed by non-equilibrium condensation. As a case study for these substances the non-equilibrium dust condensation in the outflow is calculated for a simple stationary wind model which shows, that these dust species indeed can be formed in the ejecta.

Nonlinear Viscoelastic Mechanics of Cross-linked Rubbers

NASA Technical Reports Server (NTRS)

Freed, Alan D.; Leonov, Arkady I.; Gray, Hugh R. (Technical Monitor)

2002-01-01

The paper develops a general theory for finite rubber viscoelasticity, and specifies it in the form, convenient for solving problems important for rubber, tire and space industries. Based on the quasi-linear approach of non-equilibrium thermodynamics, a general nonlinear theory has been developed for arbitrary nonisothermal deformations of viscoelastic solids. In this theory, the constitutive equations are presented as the sum of known equilibrium (rubber elastic) and non-equilibrium (liquid polymer viscoelastic) terms. These equations are then simplified using several modeling arguments. Stability constraints for the proposed constitutive equations are also discussed. It is shown that only strong ellipticity criteria are applicable for assessing stability of the equations governing viscoelastic solids.

A Thermodynamic Theory of Solid Viscoelasticity. Part II:; Nonlinear Thermo-viscoelasticity

NASA Technical Reports Server (NTRS)

Freed, Alan D.; Leonov, Arkady I.; Gray, Hugh R. (Technical Monitor)

2002-01-01

This paper, second in the series of three papers, develops a general, nonlinear, non-isothermal, compressible theory for finite rubber viscoelasticity and specifies it in a form convenient for solving problems important to the rubber, tire, automobile, and air-space industries, among others. Based on the quasi-linear approach of non-equilibrium thermodynamics, a general nonlinear theory of differential type has been developed for arbitrary non-isothermal deformations of viscoelastic solids. In this theory, the constitutive equations were presented as the sum of a rubber elastic (equilibrium) and a liquid type viscoelastic (non-equilibrium) terms. These equations have then been simplified using several modeling and simplicity arguments.

Application of the Flory-Huggins theory to the solubility of solids in glyceryl trioleate

USGS Publications Warehouse

Chiou, Cary T.; Manes, Milton

1986-01-01

The conventional thermodynamic deviation for ideal solid–liquid solubilities is modified by substituting the Flory–Huggins model for Raoult's law. A comparison of published data for eleven solides in glyceryl trioleate with the predictions of the conventional and modified equations shows that the significantly higher athermal solubilities from the modified equation are in much better agreement with the experimental data. This suggests that discrepancies between the data and the predictions of the conventional model for ideal systems result from the inappropriate use of Raoult's law for systems with significant solute–solvent size disparity rather than from specific interactions.

Modeling multicomponent ion exchange equilibrium utilizing hydrous crystalline silicotitanates by a multiple interactive ion exchange site model

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

Zheng, Z.; Anthony, R.G.; Miller, J.E.

1997-06-01

An equilibrium multicomponent ion exchange model is presented for the ion exchange of group I metals by TAM-5, a hydrous crystalline silicotitanate. On the basis of the data from ion exchange and structure studies, the solid phase is represented as Na{sub 3}X instead of the usual form of NaX. By using this solid phase representation, the solid can be considered as an ideal phase. A set of model ion exchange reactions is proposed for ion exchange between H{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, and Cs{sup +}. The equilibrium constants for these reactions were estimated from experiments with simplemore » ion exchange systems. Bromley`s model for activity coefficients of electrolytic solutions was used to account for liquid phase nonideality. Bromley`s model parameters for CsOH at high ionic strength and for NO{sub 2}{sup {minus}} and Al(OH){sub 4}{sup {minus}} were estimated in order to apply the model for complex waste simulants. The equilibrium compositions and distribution coefficients of counterions were calculated for complex simulants typical of DOE wastes by solving the equilibrium equations for the model reactions and material balance equations. The predictions match the experimental results within 10% for all of these solutions.« less

Towards improved solubility of poorly water-soluble drugs: cryogenic co-grinding of piroxicam with carrier polymers.

PubMed

Penkina, Anna; Semjonov, Kristian; Hakola, Maija; Vuorinen, Sirpa; Repo, Timo; Yliruusi, Jouko; Aruväli, Jaan; Kogermann, Karin; Veski, Peep; Heinämäki, Jyrki

2016-01-01

Amorphous solid dispersions (SDs) open up exciting opportunities in formulating poorly water-soluble active pharmaceutical ingredients (APIs). In the present study, novel catalytic pretreated softwood cellulose (CPSC) and polyvinylpyrrolidone (PVP) were investigated as carrier polymers for preparing and stabilizing cryogenic co-ground SDs of poorly water-soluble piroxicam (PRX). CPSC was isolated from pine wood (Pinus sylvestris). Raman and Fourier transform infrared (FTIR) spectroscopy, X-ray powder diffraction (XRPD) and differential scanning calorimetry (DSC) were used for characterizing the solid-state changes and drug-polymer interactions. High-resolution scanning electron microscope (SEM) was used to analyze the particle size and surface morphology of starting materials and final cryogenic co-ground SDs. In addition, the molecular aspects of drug-polymer interactions and stabilization mechanisms are presented. The results showed that the carrier polymer influenced both the degree of amorphization of PRX and stabilization against crystallization. The cryogenic co-ground SDs prepared from PVP showed an enhanced dissolution rate of PRX, while the corresponding SDs prepared from CPSC exhibited a clear sustained release behavior. In conclusion, cryogenic co-grinding provides a versatile method for preparing amorphous SDs of poorly water-soluble APIs. The solid-state stability and dissolution behavior of such co-ground SDs are to a great extent dependent on the carrier polymer used.

Cocrystal of Ibuprofen⁻Nicotinamide: Solid-State Characterization and In Vivo Analgesic Activity Evaluation.

PubMed

Yuliandra, Yori; Zaini, Erizal; Syofyan, Syofyan; Pratiwi, Wenny; Putri, Lidiya Novita; Pratiwi, Yuti Sahra; Arifin, Helmi

2018-06-04

Ibuprofen is classified as a BCS class II drug which has low solubility and high permeability. We conducted the formation of the cocrystalline phase of ibuprofen with coformer nicotinamide to increase its solubility. The purpose of this study was to characterize the solid state of cocrystalline phase of ibuprofen-nicotinamide, determine the solubility, and evaluate its in vivo analgesic activity. The cocrystal of ibuprofen-nicotinamide was prepared by a slow evaporation method. The solid-state characterization was conducted by powder X-ray diffraction (PXRD) analysis, differential thermal analysis (DTA), and scanning electron microscopy (SEM). To investigate the in vivo analgesic activity, 28 male Swiss-Webster mice were injected with acetic acid 0.5% following oral administration of intact ibuprofen, physical mixture, and its cocrystalline phase with nicotinamide (equivalent to 26 mg/kg ibuprofen). The number of writhes was counted, and pain inhibition was calculated. All data were analyzed with one-way ANOVA followed by Duncan's Multiple Range Test (95% confidence interval). The results revealed that a new cocrystalline phase was successfully formed. The solubility testing showed that the cocrystal formation enhanced the solubility significantly as compared with the physical mixture and intact ibuprofen. A significant increase in the analgesic activity of cocrystal ibuprofen-nicotinamide was also confirmed.

Enhancement of solubility and antidiabetic effects of Repaglinide using spray drying technique in STZ-induced diabetic rats.

PubMed

Varshosaz, Jaleh; Minayian, Mohsen; Ahmadi, Mahdieh; Ghassami, Erfaneh

2017-09-01

The purpose of the study was to enhance the solubility of the poorly water-soluble drug, Repaglinide using spray drying based solid dispersion technique by different carriers including Eudragit E100, hydroxyl propyl cellulose Mw 80 000 and poly vinyl pyrollidone K30. Optimization of the best formulation was carried out according to drug solubility, release profile, particle size and angle of repose of the solid dispersions. The optimized sample was characterized using X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR). The morphology of the dispersions was studied by SEM. The blood glucose lowering effect of spray dried solid dispersions was studied in normal and streptozocin-induced diabetic rats. The results showed that Eudragit E100 in 1:3 ratio could enhance drug solubility by 100-fold. DSC studies indicated a marked change in melting point of the drug possibly due to strong hydrogen bonds between the drug and Eudragit, while FT-IR study did not show obvious interactions between them. According to XRPD results Repaglinide converted to an amorphous state in the spray dried dispersions. Spray dried Repaglinide reduced the blood glucose level significantly during the 8 h of obtaining blood samples in comparison with untreated drug (p < 0.05).

Development of novel ibuprofen-loaded solid dispersion with enhanced bioavailability using cycloamylose.

PubMed

Baek, Hyung Hee; Kim, Dae-Hwan; Kwon, So Young; Rho, Shin-Joung; Kim, Dong-Wuk; Choi, Han-Gon; Kim, Yong-Ro; Yong, Chul Soon

2012-03-01

To develop a novel ibuprofen-loaded solid dispersion with enhanced bioavailability using cycloamylose, it was prepared using spray-drying techniques with cycloamylose at a weight ratio of 1:1. The effect of cycloamylose on aqueous solubility of ibuprofen was investigated. The physicochemical properties of solid dispersions were investigated using scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and X-ray diffraction. The dissolution and bioavailability in rats were evaluated compared with ibuprofen powder. This ibuprofen-loaded solid dispersion improved about 14-fold drug solubility. Ibuprofen was present in an unchanged crystalline state, and cycloamylose played the simple role of a solubilizing agent in this solid dispersion. Moreover, the dispersion gave 2-fold higher AUC (area under the drug concentration-time curve) value compared with a ibuprofen powder, indicating that it improved the oral bioavailability of ibuprofen in rats. Thus, the solid dispersion may be useful to deliver ibuprofen with enhanced bioavailability without crystalline change.

Fuel spill identification using solid-phase extraction and solid-phase microextraction. 1. Aviation turbine fuels.

PubMed

Lavine, B K; Brzozowski, D M; Ritter, J; Moores, A J; Mayfield, H T

2001-12-01

The water-soluble fraction of aviation jet fuels is examined using solid-phase extraction and solid-phase microextraction. Gas chromatographic profiles of solid-phase extracts and solid-phase microextracts of the water-soluble fraction of kerosene- and nonkerosene-based jet fuels reveal that each jet fuel possesses a unique profile. Pattern recognition analysis reveals fingerprint patterns within the data characteristic of fuel type. By using a novel genetic algorithm (GA) that emulates human pattern recognition through machine learning, it is possible to identify features characteristic of the chromatographic profile of each fuel class. The pattern recognition GA identifies a set of features that optimize the separation of the fuel classes in a plot of the two largest principal components of the data. Because principal components maximize variance, the bulk of the information encoded by the selected features is primarily about the differences between the fuel classes.

Coupling microscopic and mesoscopic scales to simulate chemical equilibrium between a nanometric carbon cluster and detonation products fluid.

PubMed

Bourasseau, Emeric; Maillet, Jean-Bernard

2011-04-21

This paper presents a new method to obtain chemical equilibrium properties of detonation products mixtures including a solid carbon phase. In this work, the solid phase is modelled through a mesoparticle immersed in the fluid, such that the heterogeneous character of the mixture is explicitly taken into account. Inner properties of the clusters are taken from an equation of state obtained in a previous work, and interaction potential between the nanocluster and the fluid particles is derived from all-atoms simulations using the LCBOPII potential (Long range Carbon Bond Order Potential II). It appears that differences in chemical equilibrium results obtained with this method and the "composite ensemble method" (A. Hervouet et al., J. Phys. Chem. B, 2008, 112.), where fluid and solid phases are considered as non-interacting, are not significant, underlining the fact that considering the inhomogeneity of such system is crucial.

Optimizing solubility and permeability of a biopharmaceutics classification system (BCS) class 4 antibiotic drug using lipophilic fragments disturbing the crystal lattice.

PubMed

Tehler, Ulrika; Fagerberg, Jonas H; Svensson, Richard; Larhed, Mats; Artursson, Per; Bergström, Christel A S

2013-03-28

Esterification was used to simultaneously increase solubility and permeability of ciprofloxacin, a biopharmaceutics classification system (BCS) class 4 drug (low solubility/low permeability) with solid-state limited solubility. Molecular flexibility was increased to disturb the crystal lattice, lower the melting point, and thereby improve the solubility, whereas lipophilicity was increased to enhance the intestinal permeability. These structural changes resulted in BCS class 1 analogues (high solubility/high permeability) emphasizing that simple medicinal chemistry may improve both these properties.

Extraction of soluble substances from organic solid municipal waste to increase methane production.

PubMed

Campuzano, Rosalinda; González-Martínez, Simón

2015-02-01

This work deals with the analysis of the methane production from Mexico City's urban organic wastes after separating soluble from suspended substances. Water was used to extract soluble substances under three different water to waste ratios and after three extraction procedures. Methane production was measured at 35 °C during 21 days using a commercial methane potential testing device. Results indicate that volatile solids extraction increases with dilution rate to a maximum of 40% at 20 °C and to 43% at 93 °C. The extracts methane production increases with the dilution rate as a result of enhanced dissolved solids extraction. The combined (extract and bagasse) methane production reached, in 6 days, 66% of the total methane produced in 21 days. The highest methane production rates were measured during the first six days. Copyright © 2014 Elsevier Ltd. All rights reserved.

Fast Measurement of Soluble Solid Content in Mango Based on Visible and Infrared Spectroscopy Technique

NASA Astrophysics Data System (ADS)

Yu, Jiajia; He, Yong

Mango is a kind of popular tropical fruit, and the soluble solid content is an important in this study visible and short-wave near-infrared spectroscopy (VIS/SWNIR) technique was applied. For sake of investigating the feasibility of using VIS/SWNIR spectroscopy to measure the soluble solid content in mango, and validating the performance of selected sensitive bands, for the calibration set was formed by 135 mango samples, while the remaining 45 mango samples for the prediction set. The combination of partial least squares and backpropagation artificial neural networks (PLS-BP) was used to calculate the prediction model based on raw spectrum data. Based on PLS-BP, the determination coefficient for prediction (Rp) was 0.757 and root mean square and the process is simple and easy to operate. Compared with the Partial least squares (PLS) result, the performance of PLS-BP is better.

Developing a vacuum cooking equipment prototype to produce strawberry jam and optimization of vacuum cooking conditions.

PubMed

Okut, Dilara; Devseren, Esra; Koç, Mehmet; Ocak, Özgül Özdestan; Karataş, Haluk; Kaymak-Ertekin, Figen

2018-01-01

Purpose of this study was to develop prototype cooking equipment that can work at reduced pressure and to evaluate its performance for production of strawberry jam. The effect of vacuum cooking conditions on color soluble solid content, reducing sugars total sugars HMF and sensory properties were investigated. Also, the optimum vacuum cooking conditions for strawberry jam were optimized for Composite Rotatable Design. The optimum cooking temperature and time were determined targeting maximum soluble solid content and sensory attributes (consistency) and minimum Hue value and HMF content. The optimum vacuum cooking conditions determined were 74.4 °C temperature and 19.8 time. The soluble solid content strawberry jam made by vacuum process were similar to those prepared by traditional method. HMF contents of jams produced with vacuum cooking method were well within limit of standards.

Selection of optimum ionic liquid solvents for flavonoid and phenolic acids extraction

NASA Astrophysics Data System (ADS)

Rahman, N. R. A.; Yunus, N. A.; Mustaffa, A. A.

2017-06-01

Phytochemicals are important in improving human health with their functions as antioxidants, antimicrobials and anticancer agents. However, the quality of phytochemicals extract relies on the efficiency of extraction process. Ionic liquids (ILs) have become a research phenomenal as extraction solvent due to their unique properties such as unlimited range of ILs, non-volatile, strongly solvating and may become either polarity. In phytochemical extraction, the determination of the best solvent that can extract highest yield of solute (phytochemical) is very important. Therefore, this study is conducted to determine the best IL solvent to extract flavonoids and phenolic acids through a property prediction modeling approach. ILs were selected from the imidazolium-based anion for alkyl chains ranging from ethyl > octyl and cations consisting of Br, Cl, [PF6], BF4], [H2PO4], [SO4], [CF3SO3], [TF2N] and [HSO4]. This work are divided into several stages. In Stage 1, a Microsoft Excel-based database containing available solubility parameter values of phytochemicals and ILs including its prediction models and their parameters has been established. The database also includes available solubility data of phytochemicals in IL, and activity coefficient models, for solid-liquid phase equilibrium (SLE) calculations. In Stage 2, the solubility parameter values of the flavonoids (e.g. kaempferol, quercetin and myricetin) and phenolic acids (e.g. gallic acid and caffeic acid) are determined either directly from database or predicted using Stefanis and Marrero-Gani group contribution model for the phytochemicals. A cation-anion contribution model is used for IL. In Stage 3, the amount of phytochemicals extracted can be determined by using SLE relationship involving UNIFAC-IL model. For missing parameters (UNIFAC-IL), they are regressed using available solubility data. Finally, in Stage 4, the solvent candidates are ranked and five ILs, ([OMIM] [TF2N], [HeMIM] [TF2N], [HMIM] [TF2N], [HeMIM] [CF3SO3] and [HMIM] [CF3SO3]) were identified and selected.

An Introduction to the Understanding of Solubility.

ERIC Educational Resources Information Center

Letcher, Trevor M.; Battino, Rubin

2001-01-01

Explores different solubility processes and related issues, including the second law of thermodynamics and ideal mixtures, real liquids, intermolecular forces, and solids in liquids or gases in liquids. (Contains 22 references.) (ASK)

Intertextual learning strategy with guided inquiry on solubility equilibrium concept to improve the student’s scientific processing skills

NASA Astrophysics Data System (ADS)

Wardani, K. U.; Mulyani, S.; Wiji

2018-04-01

The aim of this study was to develop intertextual learning strategy with guided inquiry on solubility equilibrium concept to enhance student’s scientific processing skills. This study was conducted with consideration of some various studies which found that lack of student’s process skills in learning chemistry was caused by learning chemistry is just a concept. The method used in this study is a Research and Development to generate the intertextual learning strategy with guided inquiry. The instruments used in the form of sheets validation are used to determine the congruence of learning activities by step guided inquiry learning and scientific processing skills with aspects of learning activities. Validation results obtained that the learning activities conducted in line with aspects of indicators of the scientific processing skills.

Thermodynamic parameters of U (VI) sorption onto soils in aquatic systems.

PubMed

Kumar, Ajay; Rout, Sabyasachi; Ghosh, Malay; Singhal, Rakesh Kumar; Ravi, Pazhayath Mana

2013-01-01

The thermodynamic parameters viz. the standard free energy (∆Gº), Standard enthalpy change (∆Hº) and standard entropy change (∆Sº) were determined using the obtained values of distribution coefficient (kd) of U (VI) in two different types of soils (agricultural and undisturbed) by conducting a batch equilibrium experiment with aqueous media (groundwater and deionised water) at two different temperatures 25°C and 50°C. The obtained distribution coefficients (kd) values of U for undisturbed soil in groundwater showed about 75% higher than in agricultural soil at 25°C while in deionised water, these values were highly insignificant for both soils indicating that groundwater was observed to be more favorable for high surface sorption. At 50°C, the increased kd values in both soils revealed that solubility of U decreased with increasing temperature. Batch adsorption results indicated that U sorption onto soils was promoted at higher temperature and an endothermic and spontaneous interfacial process. The high positive values of ∆Sº for agricultural soil suggested a decrease in sorption capacity of U in that soil due to increased randomness at solid-solution interface. The low sorption onto agricultural soil may be due to presence of high amount of coarse particles in the form of sand (56%). Geochemical modeling predicted that mixed hydroxo-carbonato complexes of uranium were the most stable and abundant complexes in equilibrium solution during experimental.

Dissolution enhancement of atorvastatin calcium by co-grinding technique.

PubMed

Prabhu, Priyanka; Patravale, Vandana

2016-08-01

Atorvastatin calcium (AC) is a BCS class II drug which shows poor bioavailability due to inadequate dissolution. Solid dispersions present a promising option to enhance the solubility of poorly soluble drugs. Co-grinding with hydrophilic excipients is an easy and economical technique to improve the solubility of poorly soluble drugs and is free from usage of organic solvents. The aim of the present study was to explore novel carrier VBP-1 (organosulphur compound) for formulating a solid dispersion by using a simple, commercially viable co-grinding technique to enhance the dissolution of AC and to develop an oral formulation of the same. Composition of the solid dispersion was optimized based on the release profile in pH 1.2 buffer. The optimized solid dispersion was further characterized for flow properties, DSC, FTIR spectroscopy, XRD, contact angle, SEM studies and release profile in phosphate buffer pH 6.8. The developed solid dispersion gave similar release profile as the innovator formulation (Lipitor® tablets) in both pH 1.2 buffer and phosphate buffer pH 6.8. The developed solid dispersion was formulated into hard gelatin capsules (size 3). The developed capsules were found to give similar release as the innovator formulation in both pH 1.2 buffer and phosphate buffer pH 6.8. The developed capsules were found to be stable for a period of 6 months. Anti-hyperlipidemic efficacy studies in rats showed higher reduction in cholesterol and triglyceride levels by the developed capsules in comparison to pure AC. In conclusion, novel carrier VBP-1 was successfully employed to enhance the dissolution of AC using co-grinding technique.

Formation of phenytoin nanoparticles using rapid expansion of supercritical solution with solid cosolvent (RESS-SC) process.

PubMed

Thakur, Ranjit; Gupta, Ram B

2006-02-03

Nanoparticles are of significant importance in drug delivery. Rapid expansion of supercritical solution (RESS) process can produce pure and high-quality drug particles. However, due to extremely low solubility of polar drugs in supercritical CO(2) (sc CO(2)), RESS has limited commercial applicability. To overcome this major limitation, a modified process rapid expansion of supercritical solution with solid cosolvent (RESS-SC) is proposed which uses a solid cosolvent. Here, the new process is tested for phenytoin drug using menthol solid cosolvent. Phenytoin solubility in pure sc CO(2) is only 3 micromol/mol but when menthol solid cosolvent is used the solubility is enhanced to 1,302 micromol/mol, at 196 bar and 45 degrees C. This 400-fold increase in the solubility can be attributed to the interaction between phenytoin and menthol. Particle agglomeration in expansion zone is another major issue with conventional RESS process. In proposed RESS-SC process solid cosolvent hinders the particle growth resulting in the formation of small nanoparticles. For example, the average particle size of phenytoin in conventional RESS process is 200 nm whereas, with RESS-SC process, the average particle size is 120 nm, at 96 bar and 45 degrees C. Similarly at 196 bar and 45 degrees C, 105 nm average particles were obtained by RESS and 75 nm average particles were obtained in RESS-SC process. The particles obtained were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS) and differential scanning calorimetery (DSC) analyses. Phenytoin nanoparticle production rate in RESS-SC is about 400-fold more in comparison to that in RESS process.

Solubility of glucose isomerase in ammonium sulphate solutions

NASA Astrophysics Data System (ADS)

Chayen, N.; Akins, J.; Campbell-Smith, S.; Blow, D. M.

1988-07-01

In order to quantify protein crystallization techniques, a method for measuring protein solubility in high salt concentration has been developed. It is based on a sensitive protein concentration assay, using binding to Coomassie blue dye. The protein concentration in a supernatant from which glucose isomerase is crystallising has been studied as a function of time. Equilibrium is established in 3-5 weeks, and the protein concentration remaining in solution is defined as the solubility of the protein. The solubility of glucose isomerase has been determined as a function of ammonium sulphate concentration; its variation with pH in 1.50M ammonium sulphate has also been studied. A remarkable dependence on pH over the range of 5.5 to 6.5 has been observed.

The Lewis Chemical Equilibrium Program with parametric study capability

NASA Technical Reports Server (NTRS)

Sevigny, R.

1981-01-01

The program was developed to determine chemical equilibrium in complex systems. Using a free energy minimization technique, the program permits calculations such as: chemical equilibrium for assigned thermodynamic states; theoretical rocket performance for both equilibrium and frozen compositions during expansion; incident and reflected shock properties; and Chapman-Jouget detonation properties. It is shown that the same program can handle solid coal in an entrained flow coal gasification problem.

Enhancement of Ce/Cr Codopant Solubility and Chemical Homogeneity in TiO2 Nanoparticles through Sol-Gel versus Pechini Syntheses.

PubMed

Chen, Wen-Fan; Mofarah, Sajjad S; Hanaor, Dorian Amir Henry; Koshy, Pramod; Chen, Hsin-Kai; Jiang, Yue; Sorrell, Charles Christopher

2018-06-18

Ce/Cr codoped TiO 2 nanoparticles were synthesized using sol-gel and Pechini methods with heat treatment at 400 °C for 4 h. A conventional sol-gel process produced well-crystallized anatase, while Pechini synthesis yielded less-ordered mixed-phase anatase + rutile; this suggests that the latter method enhances Ce solubility and increases chemical homogeneity but destabilizes the TiO 2 lattice. Greater structural disruption from the decomposition of the Pechini precursor formed more open agglomerated morphologies, while the lower levels of structural disruption from pyrolysis of the dried sol-gel precursor resulted in denser agglomerates of lower surface areas. Codoping and associated destabilization of the lattice reduced the binding energies in both powders. Cr 4+ formation in sol-gel powders and Cr 6+ formation in Pechini powders suggest that these valence changes derive from synergistic electron exchange from intervalence and/or multivalence charge transfer. Since Ce is too large to allow either substitutional or interstitial solid solubility, the concept of integrated solubility is introduced, in which the Ti site and an adjacent interstice are occupied by the large Ce ion. The photocatalytic performance data show that codoping was detrimental owing to the effects of reduced crystallinity from lattice destabilization and surface area. Two regimes of mechanistic behavior are seen, which are attributed to the unsaturated solid solutions at lower codopant levels and supersaturated solid solutions at higher levels. The present work demonstrates that the Pechini method offers a processing technique that is superior to sol-gel because the former facilitates solid solubility and consequent chemical homogeneity.

Pharmaceutical Dispersion Techniques for Dissolution and Bioavailability Enhancement of Poorly Water-Soluble Drugs.

PubMed

Zhang, Xingwang; Xing, Huijie; Zhao, Yue; Ma, Zhiguo

2018-06-23

Over the past decades, a large number of drugs as well as drug candidates with poor dissolution characteristics have been witnessed, which invokes great interest in enabling formulation of these active ingredients. Poorly water-soluble drugs, especially biopharmaceutical classification system (BCS) II ones, are preferably designed as oral dosage forms if the dissolution limit can be broken through. Minimizing a drug’s size is an effective means to increase its dissolution and hence the bioavailability, which can be achieved by specialized dispersion techniques. This article reviews the most commonly used dispersion techniques for pharmaceutical processing that can practically enhance the dissolution and bioavailability of poorly water-soluble drugs. Major interests focus on solid dispersion, lipid-based dispersion (nanoencapsulation), and liquisolid dispersion (drug solubilized in a non-volatile solvent and dispersed in suitable solid excipients for tableting or capsulizing), covering the formulation development, preparative technique and potential applications for oral drug delivery. Otherwise, some other techniques that can increase the dispersibility of a drug such as co-precipitation, concomitant crystallization and inclusion complexation are also discussed. Various dispersion techniques provide a productive platform for addressing the formulation challenge of poorly water-soluble drugs. Solid dispersion and liquisolid dispersion are most likely to be successful in developing oral dosage forms. Lipid-based dispersion represents a promising approach to surmounting the bioavailability of low-permeable drugs, though the technique needs to traverse the obstacle from liquid to solid transformation. Novel dispersion techniques are highly encouraged to develop for formulation of poorly water-soluble drugs.

Solubility Database

National Institute of Standards and Technology Data Gateway

SRD 106 IUPAC-NIST Solubility Database (Web, free access)   These solubilities are compiled from 18 volumes (Click here for List) of the International Union for Pure and Applied Chemistry(IUPAC)-NIST Solubility Data Series. The database includes liquid-liquid, solid-liquid, and gas-liquid systems. Typical solvents and solutes include water, seawater, heavy water, inorganic compounds, and a variety of organic compounds such as hydrocarbons, halogenated hydrocarbons, alcohols, acids, esters and nitrogen compounds. There are over 67,500 solubility measurements and over 1800 references.

Significance of excipients to enhance the bioavailability of poorly water-soluble drugs in oral solid dosage forms: A Review

NASA Astrophysics Data System (ADS)

Vadlamudi, Manoj Kumar; Dhanaraj, Sangeetha

2017-11-01

Nowadays most of the drug substances are coming into the innovation pipeline with poor water solubility. Here, the influence of excipients will play a significant role to improve the dissolution of poorly aqueous soluble compounds. The drug substance needs to be dissolved in gastric fluids to get the better absorption and bioavailability of an orally administered drug. Dissolution is the rate-controlling stage for drugs which controls the rate and degree of absorption. Usually, poorly soluble oral administrated drugs show a slower dissolution rate, inconsistent and incomplete absorption which can lead to lower bioavailability. The low aqueous solubility of BCS class II and IV drugs is a major challenge in the drug development and delivery process. Several technologies have been used in an attempt to progress the bioavailability of poorly water-soluble drug compounds which include solid dispersions, lipid-based formulations, micronization, solvent evaporation, co-precipitation, ordered mixing, liquid-solid compacts, solvent deposition inclusion complexation, and steam aided granulation. In fact, most of the technologies require excipient as a carrier which plays a significant role in improving the bioavailability using Hypromellose acetate succinate, Cyclodextrin, Povidone, Copovidone, Hydroxypropyl cellulose, Hydroxypropyl methylcellulose, Crospovidone, Starch, Dimethylacetamide, Polyethylene glycol, Sodium lauryl sulfate, Polysorbate, Poloxamer. Mesoporous silica and so on. This review deliberates about the excipients significance on bioavailability enhancement of drug products in a single platform along with pragmatically proved applications so that user can able to select the right excipients as per the molecule.

Thermodynamics of reaction of praseodymium with gallium-indium eutectic alloy

NASA Astrophysics Data System (ADS)

Melchakov, S. Yu.; Ivanov, V. A.; Yamshchikov, L. F.; Volkovich, V. A.; Osipenko, A. G.; Kormilitsyn, M. V.

2013-06-01

Thermodynamic properties of Ga-In eutectic alloys saturated with praseodymium were determined for the first time employing the electromotive force method. The equilibrium potentials of the Pr-In alloys saturated with praseodymium (8.7-12.1 mol.% Pr) and Pr-Ga-In alloys (containing 0.0012-6.71 mol.% Pr) were measured between 573-1073 K. Pr-In alloy containing solid PrIn3 with known thermodynamic properties was used as the reference electrode when measuring the potentials of ternary Pr-In-Ga alloys. Activity, partial and excessive thermodynamic functions of praseodymium in alloys with indium and Ga-In eutectic were calculated. Activity (a), activity coefficients (γ) and solubility (X) of praseodymium in the studied temperature range can be expressed by the following equations: lgaα-Pr(In) = 4.425 - 11965/T ± 0.026. lgаα-Pr(Ga-In) = 5.866 - 14766/T ± 0.190. lgγα-Pr(Ga-In) = 2.351 - 9996/T ± 0.39. lgХPr(Ga-In) = 3.515 - 4770/T ± 0.20.

Influence of Secondary Interactions on the Structure, Sublimation Thermodynamics, and Solubility of Salicylate:4-Hydroxybenzamide Cocrystals. Combined Experimental and Theoretical Study.

PubMed

Manin, Alex N; Voronin, Alexander P; Shishkina, Anastasia V; Vener, Mikhail V; Churakov, Andrei V; Perlovich, German L

2015-08-20

Cocrystal screening of 4-hydroxybenzamide with a number of salicylates (salicylic acid, SA; 4-aminosalicylic acid, PASA; acetylsalicylic acid, ASA; and salicylsalicylic acid, SSA) was conducted to confirm the formation of two cocrystals, [SA+4-OHBZA] (1:1) and [PASA+4-OHBZA] (1:1). Their structures were determined using single-crystal X-ray diffraction, and the hydrogen-bond network topology was studied. Thermodynamic characteristics of salicylic acid cocrystal sublimation were obtained experimentally. It was proved that PASA cocrystallization with 4-OHBZA makes the drug more stable and prevents the irreversible process of decarboxylation of PASA resulting in formation of toxic 3-aminophenol. The pattern of non-covalent interactions in the cocrystals is described quantitatively using solid-state density functional theory followed by Bader analysis of the periodic electron density. It has been found that the total energy of secondary interactions between synthon atoms and the side hydroxyl group of the acid molecule in [SA+4-OHBZA] (1:1) and [PASA+4-OHBZA] (1:1) cocrystals is comparable to the energy of the primary acid-amide heterosynthon. The theoretical value of the sublimation enthalpy of [SA+4-OHBZA], 231 kJ/mol, agrees fairly well with the experimental one, 272 kJ/mol. The dissolution experiments with [SA+4-OHBZA] have proved that the relatively large cocrystal stability in relation to the stability of its components has a negative effect on the dissolution rate and equilibrium solubility. The [PASA+4-OHBZA] (1:1) cocrystal showed an enhancement of apparent solubility compared to that of the corresponding pure active pharmaceutical ingredient, while their intrinsic dissolution rates are comparable.

Design, Synthesis, and Chemical Processing of Hierarchical Ceramic Structures for Aerospace Applications

DTIC Science & Technology

1993-03-30

Massachusetts Institute of Technology, Cambridge, MA 02139I ABSTRACT polysilanes." Pyrolysis of these polymers usually The decomposition of polymeric SiC ...of soluble polymeric solids. Pyrolysis of these polymers in argon yielded The precursors were prepared by adding a TiC/A120 3 composite at 12501C...formation of soluble polymeric solids. Pyrolysis described an approach for synthesizing AI2O/ SiC of these polymers in argon yielded TiC/AI203

Total soluble solids from banana: evaluation and optimization of extraction parameters.

PubMed

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.

The Onset of Double Diffusive Convection in a Viscoelastic Fluid-Saturated Porous Layer with Non-Equilibrium Model

PubMed Central

Yang, Zhixin; Wang, Shaowei; Zhao, Moli; Li, Shucai; Zhang, Qiangyong

2013-01-01

The onset of double diffusive convection in a viscoelastic fluid-saturated porous layer is studied when the fluid and solid phase are not in local thermal equilibrium. The modified Darcy model is used for the momentum equation and a two-field model is used for energy equation each representing the fluid and solid phases separately. The effect of thermal non-equilibrium on the onset of double diffusive convection is discussed. The critical Rayleigh number and the corresponding wave number for the exchange of stability and over-stability are obtained, and the onset criterion for stationary and oscillatory convection is derived analytically and discussed numerically. PMID:24312193

The onset of double diffusive convection in a viscoelastic fluid-saturated porous layer with non-equilibrium model.

PubMed

Yang, Zhixin; Wang, Shaowei; Zhao, Moli; Li, Shucai; Zhang, Qiangyong

2013-01-01

The onset of double diffusive convection in a viscoelastic fluid-saturated porous layer is studied when the fluid and solid phase are not in local thermal equilibrium. The modified Darcy model is used for the momentum equation and a two-field model is used for energy equation each representing the fluid and solid phases separately. The effect of thermal non-equilibrium on the onset of double diffusive convection is discussed. The critical Rayleigh number and the corresponding wave number for the exchange of stability and over-stability are obtained, and the onset criterion for stationary and oscillatory convection is derived analytically and discussed numerically.

Simulation of the mobility of metal - EDTA complexes in groundwater: The influence of contaminant metals

USGS Publications Warehouse

Friedly, J.C.; Kent, D.B.; Davis, J.A.

2002-01-01

Reactive transport simulations were conducted to model chemical reactions between metal - EDTA (ethylenediaminetetraacetic acid) complexes during transport in a mildly acidic quartz - sand aquifer. Simulations were compared with the results of small-scale tracer tests wherein nickel-, zinc-, and calcium - EDTA complexes and free EDTA were injected into three distinct chemical zones of a plume of sewage-contaminated groundwater. One zone had a large mass of adsorbed, sewage-derived zinc; one zone had a large mass of adsorbed manganese resulting from mildly reducing conditions created bythe sewage plume; and one zone had significantly less adsorbed manganese and negligible zinc background. The chemical model assumed that the dissolution of iron(III) from metal - hydroxypolymer coatings on the aquifer sediments by the metal - EDTA complexes was kinetically restricted. All other reactions, including metal - EDTA complexation, zinc and manganese adsorption, and aluminum hydroxide dissolution were assumed to reach equilibrium on the time scale of transport; equilibrium constants were either taken from the literature or determined independently in the laboratory. A single iron(III) dissolution rate constant was used to fit the breakthrough curves observed in the zone with negligible zinc background. Simulation results agreed well with the experimental data in all three zones, which included temporal moments derived from breakthrough curves at different distances downgradient from the injections and spatial moments calculated from synoptic samplings conducted at different times. Results show that the tracer cloud was near equilibrium with respect to Fe in the sediment after 11 m of transport in the Zn-contaminated region but remained far from equilibrium in the other two zones. Sensitivity studies showed that the relative rate of iron(III) dissolution by the different metal - EDTA complexes was less important than the fact that these reactions are rate controlled. Results suggest that the published solubility for ferrihydrite reasonably approximates the Fe solubility of the hydroxypolymer coatings on the sediments. Aluminum may be somewhat more soluble than represented by the equilibrium constant for gibbsite, and its dissolution may be rate controlled when reacting with Ca - EDTA complexes.

Enhanced bioavailability of sirolimus via preparation of solid dispersion nanoparticles using a supercritical antisolvent process

PubMed Central

Kim, Min-Soo; Kim, Jeong-Soo; Park, Hee Jun; Cho, Won Kyung; Cha, Kwang-Ho; Hwang, Sung-Joo

2011-01-01

Background The aim of this study was to improve the physicochemical properties and bioavailability of poorly water-soluble sirolimus via preparation of a solid dispersion of nanoparticles using a supercritical antisolvent (SAS) process. Methods First, excipients for enhancing the stability and solubility of sirolimus were screened. Second, using the SAS process, solid dispersions of sirolimus-polyvinylpyrrolidone (PVP) K30 nanoparticles were prepared with or without surfactants such as sodium lauryl sulfate (SLS), tocopheryl propylene glycol succinate, Sucroester 15, Gelucire 50/13, and Myrj 52. A mean particle size of approximately 250 nm was obtained for PVP K30-sirolimus nanoparticles. Solid state characterization, kinetic solubility, powder dissolution, stability, and pharmacokinetics were analyzed in rats. Results X-ray diffraction, differential scanning calorimetry, and high-pressure liquid chromatography indicated that sirolimus existed in an anhydrous amorphous form within a solid dispersion of nanoparticles and that no degradation occurred after SAS processing. The improved supersaturation and dissolution of sirolimus as a solid dispersion of nanoparticles appeared to be well correlated with enhanced bioavailability of oral sirolimus in rats. With oral administration of a solid dispersion of PVP K30-SLS-sirolimus nanoparticles, the peak concentration and AUC0→12h of sirolimus were increased by approximately 18.3-fold and 15.2-fold, respectively. Conclusion The results of this study suggest that preparation of PVP K30-sirolimus-surfactant nanoparticles using the SAS process may be a promising approach for improving the bioavailability of sirolimus. PMID:22162657

Enhanced kinetic solubility profiles of indomethacin amorphous solid dispersions in poly(2-hydroxyethyl methacrylate) hydrogels.

PubMed

Sun, Dajun D; Ju, Tzu-chi Rob; Lee, Ping I

2012-05-01

The feasibility of forming solid molecular dispersions of poorly water-soluble drugs in crosslinked poly(2-hydroethyl methacrylate) (PHEMA) hydrogel has recently been reported by our group. The purpose of the present study is to investigate the extent of enhancement of kinetic solubility of amorphous solid dispersions (ASDs) of indomethacin (IND) in crosslinked PHEMA hydrogels as compared with those based on conventional water-soluble polymer carriers. Our results show that under non-sink conditions, the initial solubility enhancement is higher for ASDs based on polyvinylpyrrolidone (PVP) and hydroxypropylmethylcellulose acetate succinate (HMPCAS), but the ability to maintain this solubility enhancement at longer times is better for ASDs based on PHEMA over a period of 24h with the extent of solubility enhancement of IND ASDs in PHEMA falling between those in PVP and HPMCAS at 10.0% IND loading after 6h and outperforming those in PVP and HPMCAS at 32.9% IND loading after 8h. The observed kinetic solubility profiles reflect the fact that the amorphous IND is released from PHEMA by a different mechanism than those from water-soluble polymer carriers. In this case, the dissolution of IND ASD from water-soluble PVP and HPMCAS is almost instantaneous, resulting in an initial surge of IND concentration followed by a sharp decline due to the nucleation and crystallization events triggered by the rapid build-up of drug supersaturation. On the other hand, the dissolution of IND ASD from insoluble crosslinked PHEMA hydrogel beads is less rapid as it is regulated by a feedback-controlled diffusion mechanism, thus avoiding a sudden surge of supersaturation in the dissolution medium. The absence of an apparent decline in drug concentration during dissolution from IND-PHEMA ASD further reflects the diminished nucleation and crystallization events during IND dissolution from hydrogel-based solid molecular dispersions. Based on the XRD analyses, a threshold IND loading level of about 34% in PHEMA has been identified, above which amorphous to crystalline transition tends to occur. Also, by selecting the appropriate particle sizes, immediate to controlled release of IND from IND-PHEMA ASD can be readily achieved as the release rate increases with decreasing PHEMA bead size. Furthermore, a robust physical stability has been demonstrated in IND-PHEMA ASD with no drug precipitation for up to 8 months at IND loadings below 16.7% under direct open cup exposure to accelerated stability conditions (40°C/75% RH). Copyright © 2012 Elsevier B.V. All rights reserved.

Atomistic modelling of evaporation and explosive boiling of thin film liquid argon over internally recessed nanostructured surface

NASA Astrophysics Data System (ADS)

Hasan, Mohammad Nasim; Shavik, Sheikh Mohammad; Rabbi, Kazi Fazle; Haque, Mominul

2016-07-01

Molecular dynamics (MD) simulations have been carried out to investigate evaporation and explosive boiling phenomena of thin film liquid argon on nanostructured solid surface with emphasis on the effect of solid-liquid interfacial wettability. The nanostructured surface considered herein consists of trapezoidal internal recesses of the solid platinum wall. The wetting conditions of the solid surface were assumed such that it covers both the hydrophilic and hydrophobic conditions and hence effect of interfacial wettability on resulting evaporation and boiling phenomena was the main focus of this study. The initial configuration of the simulation domain comprised of a three phase system (solid platinum, liquid argon and vapor argon) on which equilibrium molecular dynamics (EMD) was performed to reach equilibrium state at 90 K. After equilibrium of the three-phase system was established, the wall was set to different temperatures (130 K and 250 K for the case of evaporation and explosive boiling respectively) to perform non-equilibrium molecular dynamics (NEMD). The variation of temperature and density as well as the variation of system pressure with respect to time were closely monitored for each case. The heat flux normal to the solid surface was also calculated to illustrate the effectiveness of heat transfer for hydrophilic and hydrophobic surfaces in cases of both nanostructured surface and flat surface. The results obtained show that both the wetting condition of the surface and the presence of internal recesses have significant effect on normal evaporation and explosive boiling of the thin liquid film. The heat transfer from solid to liquid in cases of surface with recesses are higher compared to flat surface without recesses. Also the surface with higher wettability (hydrophilic) provides more favorable conditions for boiling than the low-wetting surface (hydrophobic) and therefore, liquid argon responds quickly and shifts from liquid to vapor phase faster in case of hydrophilic surface. The heat transfer rate is also much higher in case of hydrophilic surface.

Solid dispersion of poorly water-soluble drugs: early promises, subsequent problems, and recent breakthroughs.

PubMed

Serajuddin, A T

1999-10-01

Although there was a great interest in solid dispersion systems during the past four decades to increase dissolution rate and bioavailability of poorly water-soluble drugs, their commercial use has been very limited, primarily because of manufacturing difficulties and stability problems. Solid dispersions of drugs were generally produced by melt or solvent evaporation methods. The materials, which were usually semisolid and waxy in nature, were hardened by cooling to very low temperatures. They were then pulverized, sieved, mixed with relatively large amounts of excipients, and encapsulated into hard gelatin capsules or compressed into tablets. These operations were difficult to scale up for the manufacture of dosage forms. The situation has, however, been changing in recent years because of the availability of surface-active and self-emulsifying carriers and the development of technologies to encapsulate solid dispersions directly into hard gelatin capsules as melts. Solid plugs are formed inside the capsules when the melts are cooled to room temperature. Because of surface activity of carriers used, complete dissolution of drug from such solid dispersions can be obtained without the need for pulverization, sieving, mixing with excipients, etc. Equipment is available for large-scale manufacturing of such capsules. Some practical limitations of dosage form development might be the inadequate solubility of drugs in carriers and the instability of drugs and carriers at elevated temperatures necessary to manufacture capsules.

Study on Enhanced Dissolution of Azilsartan-Loaded Solid Dispersion, Prepared by Combining Wet Milling and Spray-Drying Technologies.

PubMed

Lu, Tianshu; Sun, Yinghua; Ding, Dawei; Zhang, Qi; Fan, Rui; He, Zhonggui; Wang, Jing

2017-02-01

The purpose of this study was to develop a combination method of wet milling and spray-drying technologies to prepare the solid dispersion and improve the dissolution rate of poorly water-soluble drug candidates. Azilsartan (AZL) was selected as the model drug for its poor water solubility. In the study, AZL-loaded solid dispersion was prepared with polyethylene glycol 6000 (PEG6000) and hydroxypropyl cellulose with super low viscosity (HPC-SL) as stabilizers by using combination of wet grinding and spray-drying methods. The high AZL loading solid dispersion was then characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier transform infrared spectroscopy (FTIR). Besides, dissolution test was carried out by the paddle method and stability investigation was also conducted. As a result, the dissolution rate of the solid dispersion tablets was found to be greater than conventional tablets, but in close agreement with market tablets. Furthermore, the formulation was shown to be stable at 40 ± 2°C and 75 ± 5% for at least 6 months, owing to its decreased particle size, morphology, and its crystal form. It was concluded that the combination of wet milling and spray-drying approaches to prepare solid dispersion would be a prospective method to improve the dissolution rate of poorly water-soluble drugs.

Optimized formulation of solid self-microemulsifying sirolimus delivery systems

PubMed Central

Cho, Wonkyung; Kim, Min-Soo; Kim, Jeong-Soo; Park, Junsung; Park, Hee Jun; Cha, Kwang-Ho; Park, Jeong-Sook; Hwang, Sung-Joo

2013-01-01

Background The aim of this study was to develop an optimized solid self-microemulsifying drug delivery system (SMEDDS) formulation for sirolimus to enhance its solubility, stability, and bioavailability. Methods Excipients used for enhancing the solubility and stability of sirolimus were screened. A phase-separation test, visual observation for emulsifying efficiency, and droplet size analysis were performed. Ternary phase diagrams were constructed to optimize the liquid SMEDDS formulation. The selected liquid SMEDDS formulations were prepared into solid form. The dissolution profiles and pharmacokinetic profiles in rats were analyzed. Results In the results of the oil and cosolvent screening studies, Capryol™ Propylene glycol monocapry late (PGMC) and glycofurol exhibited the highest solubility of all oils and cosolvents, respectively. In the surfactant screening test, D-α-tocopheryl polyethylene glycol 1000 succinate (vitamin E TPGS) was determined to be the most effective stabilizer of sirolimus in pH 1.2 simulated gastric fluids. The optimal formulation determined by the construction of ternary phase diagrams was the T32 (Capryol™ PGMC:glycofurol:vitamin E TPGS = 30:30:40 weight ratio) formulation with a mean droplet size of 108.2 ± 11.4 nm. The solid SMEDDS formulations were prepared with Sucroester 15 and mannitol. The droplet size of the reconstituted solid SMEDDS showed no significant difference compared with the liquid SMEDDS. In the dissolution study, the release amounts of sirolimus from the SMEDDS formulation were significantly higher than the raw sirolimus powder. In addition, the solid SMEDDS formulation was in a more stable state than liquid SMEDDS in pH 1.2 simulated gastric fluids. The results of the pharmacokinetic study indicate that the SMEDDS formulation shows significantly greater bioavailability than the raw sirolimus powder or commercial product (Rapamune® oral solution). Conclusion The results of this study suggest the potential use of a solid SMEDDS formulation for the delivery of poorly water-soluble drugs, such as sirolimus, through oral administration. PMID:23641156

Maintenance of supersaturation I: indomethacin crystal growth kinetic modeling using an online second-derivative ultraviolet spectroscopic method.

PubMed

Patel, Dhaval D; Joguparthi, Vijay; Wang, Zeren; Anderson, Bradley D

2011-07-01

Formulations that produce supersaturated solutions after their oral administration have received increased attention as a means to improve bioavailability of poorly water-soluble drugs. Although it is widely recognized that excipients can prolong supersaturation, the mechanisms by which these beneficial effects are realized are generally unknown. Difficulties in separately measuring the kinetics of nucleation and crystal growth have limited progress in understanding the mechanisms by which excipients contribute to the supersaturation maintenance. This paper describes the crystal growth kinetic modeling of indomethacin, a poorly water-soluble drug, from supersaturated aqueous suspensions using a newly developed, online second-derivative ultraviolet spectroscopic method. The apparent indomethacin equilibrium solubility after crystal growth at a high degree of supersaturation (S=6) was approximately 55% higher than the indomethacin equilibrium solubility determined prior to growth, which was attributed to the deposition of a higher energy indomethacin form on the seed crystals. The indomethacin crystal growth kinetics (S=6) was of first order. By comparing the mass transfer coefficients from indomethacin dissolution and crystal growth, it was shown that the indomethacin crystal growth kinetics at S=6 was bulk diffusion controlled. The change in indomethacin seed crystal size distribution before and after crystal growth was determined and modeled using a mass-balance relationship. Copyright © 2011 Wiley-Liss, Inc. and the American Pharmacists Association

Enhanced solubility and intestinal absorption of candesartan cilexetil solid dispersions using everted rat intestinal sacs.

PubMed

Gurunath, S; Nanjwade, Baswaraj K; Patila, P A

2014-07-01

Candesartan cilexetil (CAN) is a poor aqueous soluble compound and a P-glycoprotein (P-gp) efflux pump substrate. These key factors are responsible for its incomplete intestinal absorption. In this study, we investigated to enhance the absorption of CAN by improving its solubility and inhibiting intestinal P-gp activity. A phase solubility method was used to evaluate the aqueous solubility of CAN in PVP K30 (0.2-2%). Gibbs free energy [Formula: see text] values were all negative. Solubility was enhanced by the freeze drying technique. The in vitro dissolution was evaluated using the USP paddle method. The interaction between drug and carrier was evaluated by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Differential scanning calorimetry (DSC) studies. Naringin was selected as P-gp inhibitor. Absorption studies were performed using the everted gut sac model from rat jejunum. The drug analysis was performed by HPLC. FTIR spectra revealed no interaction between drug and PVP K30. From XRD and DSC data, CAN was in the amorphous form, which explains the cumulative release of drug from its prepared systems. We noticed an enhancement of CAN absorption by improving its solubility and inhibiting the P-gp activity. The significant results (p < 0.05) were obtained for freeze dried solid dispersions in the presence of P-gp inhibitor than without naringin (15 mg/kg) with an absorption enhancement of 8-fold. Naringin, a natural flavonoid, has no undesirable side effects. Therefore, it could be employed as an excipient in the form of solid dispersions to increase CAN intestinal absorption and its oral bioavailability.

Enhanced solubility and intestinal absorption of candesartan cilexetil solid dispersions using everted rat intestinal sacs

PubMed Central

Gurunath, S.; Nanjwade, Baswaraj K.; Patila, P.A.

2013-01-01

Objective Candesartan cilexetil (CAN) is a poor aqueous soluble compound and a P-glycoprotein (P-gp) efflux pump substrate. These key factors are responsible for its incomplete intestinal absorption. Methods In this study, we investigated to enhance the absorption of CAN by improving its solubility and inhibiting intestinal P-gp activity. A phase solubility method was used to evaluate the aqueous solubility of CAN in PVP K30 (0.2–2%). Gibbs free energy (ΔGtro) values were all negative. Solubility was enhanced by the freeze drying technique. The in vitro dissolution was evaluated using the USP paddle method. The interaction between drug and carrier was evaluated by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Differential scanning calorimetry (DSC) studies. Naringin was selected as P-gp inhibitor. Absorption studies were performed using the everted gut sac model from rat jejunum. The drug analysis was performed by HPLC. Results FTIR spectra revealed no interaction between drug and PVP K30. From XRD and DSC data, CAN was in the amorphous form, which explains the cumulative release of drug from its prepared systems. We noticed an enhancement of CAN absorption by improving its solubility and inhibiting the P-gp activity. The significant results (p < 0.05) were obtained for freeze dried solid dispersions in the presence of P-gp inhibitor than without naringin (15 mg/kg) with an absorption enhancement of 8-fold. Conclusion Naringin, a natural flavonoid, has no undesirable side effects. Therefore, it could be employed as an excipient in the form of solid dispersions to increase CAN intestinal absorption and its oral bioavailability. PMID:25067902

23Na NUCLEAR MAGNETIC RESONANCE RELAXATION STUDIES OF SODIUM ION INTERACTION WITH SOLUBLE RNA*

PubMed Central

James, Thomas L.; Noggle, Joseph H.

1969-01-01

Interactions between 23Na+ and soluble RNA in aqueous solution are studied with the use of 23Na nuclear magnetic resonance. At low concentrations of NaCl, the interactions obey a simple equilibrium model with a formation constant log (Kf)3 = 2.8 ± 0.3. The relaxation rate of the bound sodium is found to be T1B-1 = 222 ± 19 sec-1 compared to that of free sodium T1F-1 = 17.5 sec-1. At high NaCl concentrations, the system deviates from the model, possibly owing to aggregation of the soluble RNA. PMID:5256995

Preparation and Evaluation of Solid Dispersion Tablets by a Simple and Manufacturable Wet Granulation Method Using Porous Calcium Silicate.

PubMed

Fujimoto, Yumi; Hirai, Nobuaki; Takatani-Nakase, Tomoka; Takahashi, Koichi

2016-01-01

The aim of this study was to prepare and evaluate solid dispersion tablets containing a poorly water-soluble drug using porous calcium silicate (PCS) by a wet granulation method. Nifedipine (NIF) was used as the model poorly water-soluble drug. Solid dispersion tablets were prepared with the wet granulation method using ethanol and water by a high-speed mixer granulator. The binder and disintegrant were selected from 7 and 4 candidates, respectively. The dissolution test was conducted using the JP 16 paddle method. The oral absorption of NIF was studied in fasted rats. Xylitol and crospovidone were selected as the binder and disintegrant, respectively. The dissolution rates of NIF from solid dispersion formulations were markedly enhanced compared with NIF powder and physical mixtures. Powder X-ray diffraction (PXRD) confirmed the reduced crystallinity of NIF in the solid dispersion formulations. Fourier transform infrared (FT-IR) showed the physical interaction between NIF and PCS in the solid dispersion formulations. NIF is present in an amorphous state in granules prepared by the wet granulation method using water. The area under the plasma concentration-time curve (AUC) and peak concentration (C(max)) values of NIF after dosing rats with the solid dispersion granules were significantly greater than those after dosing with NIF powder. The solid dispersion formulations of NIF prepared with PCS using the wet granulation method exhibited accelerated dissolution rates and superior oral bioavailability. This method is very simple, and may be applicable to the development of other poorly water-soluble drugs.

Nanocrystal/sol-gel nanocomposites

DOEpatents

Petruska, Melissa A [Los Alamos, NM; Klimov, Victor L [Los Alamos, NM

2007-06-05

The present invention is directed to solid composites including colloidal nanocrystals within a sol-gel host or matrix and to processes of forming such solid composites. The present invention is further directed to alcohol soluble colloidal nanocrystals useful in formation of sol-gel based solid composites.

Nanocrystal/sol-gel nanocomposites

DOEpatents

Petruska, Melissa A [Los Alamos, NM; Klimov, Victor L [Los Alamos, NM

2012-06-12

The present invention is directed to solid composites including colloidal nanocrystals within a sol-gel host or matrix and to processes of forming such solid composites. The present invention is further directed to alcohol soluble colloidal nanocrystals useful in formation of sol-gel based solid composites

Thermodynamic modeling of solid solutions between monosulfate and monochromate 3CaO Bullet Al{sub 2}O{sub 3} Bullet Ca[(CrO{sub 4}){sub x}(SO{sub 4}){sub 1-x}] Bullet nH{sub 2}O

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

Leisinger, Sabine M., E-mail: sabine.leisinger@eawag.ch; Institute of Biogeochemistry and Pollutant Dynamics, ETH, CH-8092 Zurich; Lothenbach, Barbara

2012-01-15

In hydrated cement paste AFm-phases are regarded to play an important role in the binding of the toxic contaminant chromate through isomorphic substitution with sulfate. Solid solutions formation can lower the solubility of the solids, thus reducing chromate leaching concentrations. Solid solutions between monosulfate and monochromate were synthesized and characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX) and inductive coupled plasma optical emission spectroscopy (ICP-OES). Based on the measured ion concentrations in solution total solubility products of the solid solution series were determined. For pure monochromate a logK = - 28.4more » {+-} 0.7 was determined. Results from solid and solution analysis showed that limited solid solutions exist. Based on XRD diffractograms a solid solution with a miscibility gap 0.15 < Crx < 0.85 with a dimensionless Guggenheim parameter of 2.43 was proposed.« less

Evolution of supersaturation of amorphous pharmaceuticals: the effect of rate of supersaturation generation.

PubMed

Sun, Dajun D; Lee, Ping I

2013-11-04

The combination of a rapidly dissolving and supersaturating "spring" with a precipitation retarding "parachute" has often been pursued as an effective formulation strategy for amorphous solid dispersions (ASDs) to enhance the rate and extent of oral absorption. However, the interplay between these two rate processes in achieving and maintaining supersaturation remains inadequately understood, and the effect of rate of supersaturation buildup on the overall time evolution of supersaturation during the dissolution of amorphous solids has not been explored. The objective of this study is to investigate the effect of supersaturation generation rate on the resulting kinetic solubility profiles of amorphous pharmaceuticals and to delineate the evolution of supersaturation from a mechanistic viewpoint. Experimental concentration-time curves under varying rates of supersaturation generation and recrystallization for model drugs, indomethacin (IND), naproxen (NAP) and piroxicam (PIR), were generated from infusing dissolved drug (e.g., in ethanol) into the dissolution medium and compared with that predicted from a comprehensive mechanistic model based on the classical nucleation theory taking into account both the particle growth and ripening processes. In the absence of any dissolved polymer to inhibit drug precipitation, both our experimental and predicted results show that the maximum achievable supersaturation (i.e., kinetic solubility) of the amorphous solids increases, the time to reach maximum decreases, and the rate of concentration decline in the de-supersaturation phase increases, with increasing rate of supersaturation generation (i.e., dissolution rate). Our mechanistic model also predicts the existence of an optimal supersaturation rate which maximizes the area under the curve (AUC) of the kinetic solubility concentration-time profile, which agrees well with experimental data. In the presence of a dissolved polymer from ASD dissolution, these observed trends also hold true except the de-supersaturation phase is more extended due to the crystallization inhibition effect. Since the observed kinetic solubility of nonequilibrium amorphous solids depends on the rate of supersaturation generation, our results also highlight the underlying difficulty in determining a reproducible solubility advantage for amorphous solids.

Molecular dynamics analysis of a equilibrium nanoscale droplet on a solid surface with periodic roughness

NASA Astrophysics Data System (ADS)

Furuta, Yuma; Surblys, Donatas; Yamaguchi, Yastaka

2016-11-01

Molecular dynamics simulations of the equilibrium wetting behavior of hemi-cylindrical argon droplets on solid surfaces with a periodic roughness were carried out. The rough solid surface is located at the bottom of the calculation cell with periodic boundary conditions in surface lateral directions and mirror boundary condition at the top boundary. Similar to on a smooth surface, the change of the cosine of the droplet contact angle was linearly correlated to the potential well depth of the inter-atomic interaction between liquid and solid on a surface with a short roughness period while the correlation was deviated on one with a long roughness period. To further investigate this feature, solid-liquid, solid-vapor interfacial free energies per unit projected area of solid surface were evaluated by using the thermodynamic integration method in independent quasi-one-dimensional simulation systems with a liquid-solid interface or vapor-solid interface on various rough solid surfaces at a constant pressure. The cosine of the apparent contact angles estimated from the density profile of the droplet systems corresponded well with ones calculated from Young's equation using the interfacial energies evaluated in the quasi-one dimensional systems.

Application of carrier and plasticizer to improve the dissolution and bioavailability of poorly water-soluble baicalein by hot melt extrusion.

PubMed

Zhang, Yilan; Luo, Rui; Chen, Yi; Ke, Xue; Hu, Danrong; Han, Miaomiao

2014-06-01

The objective of this study was to develop a suitable formulation for baicalein (a poorly water-soluble drug exhibiting high melting point) 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. The characteristic of solid dispersions prepared by HME was evaluated. The dissolution performance of the extrudates was compared to the pure drug and the physical mixtures. Physicochemical properties of the extrudates were characterized by differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier transform infrared spectroscopy (FTIR). Relative bioavailability after oral administration in beagle dogs was assessed. As a result, Kollidon VA64 and Eudragit EPO were selected as two carriers; Cremophor RH was used as the plasticizer. The dissolution of all the extrudates was significantly improved. DSC and PXRD results suggested that baicalein in the extrudates was amorphous. FTIR spectroscopy revealed the interaction between drug and polymers. After oral administration, the relative bioavailability of solid dispersions with VA64 and EPO was comparative, about 2.4- and 2.9-fold greater compared to the pure drug, respectively.

Biowaiver Monographs for Immediate-Release Solid Oral Dosage Forms: Folic Acid.

PubMed

Hofsäss, Martin A; Souza, Jacqueline de; Silva-Barcellos, Neila M; Bellavinha, Karime R; Abrahamsson, Bertil; Cristofoletti, Rodrigo; Groot, D W; Parr, Alan; Langguth, Peter; Polli, James E; Shah, Vinod P; Tajiri, Tomokazu; Mehta, Mehul U; Dressman, Jennifer B

2017-12-01

This work presents a review of literature and experimental data relevant to the possibility of waiving pharmacokinetic bioequivalence studies in human volunteers for approval of immediate-release solid oral pharmaceutical forms containing folic acid as the single active pharmaceutical ingredient. For dosage forms containing 5 mg folic acid, the highest dose strength on the World Health Organization Essential Medicines List, the dose/solubility ratio calculated from solubility studies was higher than 250 mL, corresponding to a classification as "not highly soluble." Small, physiological doses of folic acid (≤320 μg) seem to be absorbed completely via active transport, but permeability data for higher doses of 1-5 mg are inconclusive. Following a conservative approach, folic acid is classified as a Biopharmaceutics Classification System class IV compound until more reliable data become available. Commensurate with its solubility characteristics, the results of dissolution studies indicated that none of the folic acid products evaluated showed rapid dissolution in media at pH 1.2 or 4.5. Therefore, according to the current criteria of the Biopharmaceutics Classification System, the biowaiver approval procedure cannot be recommended for immediate-release solid oral dosage forms containing folic acid. Copyright © 2017 American Pharmacists Association®. All rights reserved.

Impact of polymer type on bioperformance and physical stability of hot melt extruded formulations of a poorly water soluble drug.

PubMed

Mitra, Amitava; Li, Li; Marsac, Patrick; Marks, Brian; Liu, Zhen; Brown, Chad

2016-05-30

Amorphous solid dispersion formulations have been widely used to enhance bioavailability of poorly soluble drugs. In these formulations, polymer is included to physically stabilize the amorphous drug by dispersing it in the polymeric carrier and thus forming a solid solution. The polymer can also maintain supersaturation and promote speciation during dissolution, thus enabling better absorption as compared to crystalline drug substance. In this paper, we report the use of hot melt extrusion (HME) to develop amorphous formulations of a poorly soluble compound (FaSSIF solubility=1μg/mL). The poor solubility of the compound and high dose (300mg) necessitated the use of amorphous formulation to achieve adequate bioperformance. The effect of using three different polymers (HPMCAS-HF, HPMCAS-LF and copovidone), on the dissolution, physical stability, and bioperformance of the formulations was demonstrated. In this particular case, HPMCAS-HF containing HME provided the highest bioavailability and also had better physical stability as compared to extrudates using HPMCAS-LF and copovidone. The data demonstrated that the polymer type can have significant impact on the formulation bioperformance and physical stability. Thus a thorough understanding of the polymer choice is imperative when designing an amorphous solid dispersion formulation, such that the formulation provides robust bioperformance and has adequate shelf life. Copyright © 2016 Elsevier B.V. All rights reserved.

Major Source of Error in QSPR Prediction of Intrinsic Thermodynamic Solubility of Drugs: Solid vs Nonsolid State Contributions?

PubMed

Abramov, Yuriy A

2015-06-01

The main purpose of this study is to define the major limiting factor in the accuracy of the quantitative structure-property relationship (QSPR) models of the thermodynamic intrinsic aqueous solubility of the drug-like compounds. For doing this, the thermodynamic intrinsic aqueous solubility property was suggested to be indirectly "measured" from the contributions of solid state, ΔGfus, and nonsolid state, ΔGmix, properties, which are estimated by the corresponding QSPR models. The QSPR models of ΔGfus and ΔGmix properties were built based on a set of drug-like compounds with available accurate measurements of fusion and thermodynamic solubility properties. For consistency ΔGfus and ΔGmix models were developed using similar algorithms and descriptor sets, and validated against the similar test compounds. Analysis of the relative performances of these two QSPR models clearly demonstrates that it is the solid state contribution which is the limiting factor in the accuracy and predictive power of the QSPR models of the thermodynamic intrinsic solubility. The performed analysis outlines a necessity of development of new descriptor sets for an accurate description of the long-range order (periodicity) phenomenon in the crystalline state. The proposed approach to the analysis of limitations and suggestions for improvement of QSPR-type models may be generalized to other applications in the pharmaceutical industry.

Structural Elucidation of Poloxamer 237 and Poloxamer 237/Praziquantel Solid Dispersions: Impact of Poly(Vinylpyrrolidone) over Drug Recrystallization and Dissolution.

PubMed

Orlandi, Silvina; Priotti, Josefina; Diogo, Hermínio P; Leonardi, Dario; Salomon, Claudio J; Nunes, Teresa G

2018-04-01

Praziquantel (PZQ) is the recommended, effective, and safe treatment against all forms of schistosomiasis. Solid dispersions (SDs) in water-soluble polymers have been reported to increase solubility and bioavailability of poorly water-soluble drugs like PZQ, generally due to the amorphous form stabilization. In this work, poloxamer (PLX) 237 and poly(vinylpyrrolidone) (PVP) K30 were evaluated as potential carriers to revert PZQ crystallization. Binary and ternary SDs were prepared by the solvent evaporation method. PZQ solubility increased similarly with PLX either as binary physical mixtures or SDs. Such unpredicted data correlated well with crystalline PZQ and PLX as detected by solid-state NMR (ssNMR) and differential scanning calorimetry in those samples. Ternary PVP/PLX/PZQ SDs showed both ssNMR broad and narrow superimposed signals, thus revealing the presence of amorphous and crystalline PZQ, respectively, and exhibited the highest PZQ dissolution efficiency (up to 82% at 180 min). SDs with PVP provided a promising way to enhance solubility and dissolution rate of PZQ since PLX alone did not prevent recrystallization of amorphous PZQ. Based on ssNMR data, novel evidences on PLX structure and molecular dynamics were also obtained. As shown for the first time using ssNMR, propylene glycol and ethylene glycol constitute the PLX amorphous and crystalline components, respectively.

Thermodynamic study of (anthracene + benzo[a]pyrene) solid mixtures

PubMed Central

Rice, James W.; Suuberg, Eric M.

2010-01-01

To characterize better the thermodynamic behavior of a binary polycyclic aromatic hydrocarbon mixture, thermochemical and vapor pressure experiments were used to examine the phase behavior of the {anthracene (1) + benzo[a]pyrene (2)} system. A solid-liquid phase diagram was mapped for the mixture. A eutectic point occurs at x1 = 0.26. The eutectic mixture is an amorphous solid that lacks organized crystal structure and melts between T = (414 and 420) K. For mixtures that contain 0.10 < x1 < 0.90, the enthalpy of fusion is dominated by that of the eutectic. Solid-vapor equilibrium studies show that mixtures of anthracene and benzo[a]pyrene at x1 < 0.10 sublime at the vapor pressure of pure benzo[a]pyrene. These results suggest that the solid-vapor equilibrium of benzo[a]pyrene is not significantly influenced by moderate levels of anthracene in the crystal structure. PMID:20814451

Measurement of Surface Tension of Solid Cu by Improved Multiphase Equilibrium

NASA Astrophysics Data System (ADS)

Nakamoto, Masashi; Liukkonen, Matti; Friman, Michael; Heikinheimo, Erkki; Hämäläinen, Marko; Holappa, Lauri

2008-08-01

The surface tension of solid Cu was measured with the multiphase equilibrium (MPE) method in a Pb-Cu system at 700 °C, 800 °C, and 900 °C. A special focus was on the measurement of angles involved in MPE. First, the effect of reading error in each angle measurement on the final result of surface tension of solid was simulated. It was found that the two groove measurements under atmosphere conditions are the primary sources of error in the surface tension of solid in the present system. Atomic force microscopy (AFM) was applied to these angle measurements as a new method with high accuracy. The obtained surface-tension values of solid Cu in the present work were 1587, 1610, and 1521 mN/m at 700 °C, 800 °C, and 900 °C, respectively, representing reasonable temperature dependence.

Nanoscale solid-state cooling: a review.

PubMed

Ziabari, Amirkoushyar; Zebarjadi, Mona; Vashaee, Daryoosh; Shakouri, Ali

2016-09-01

The recent developments in nanoscale solid-state cooling are reviewed. This includes both theoretical and experimental studies of different physical concepts, as well as nanostructured material design and device configurations. We primarily focus on thermoelectric, thermionic and thermo-magnetic coolers. Particular emphasis is given to the concepts based on metal-semiconductor superlattices, graded materials, non-equilibrium thermoelectric devices, Thomson coolers, and photon assisted Peltier coolers as promising methods for efficient solid-state cooling. Thermomagnetic effects such as magneto-Peltier and Nernst-Ettingshausen cooling are briefly described and recent advances and future trends in these areas are reviewed. The ongoing progress in solid-state cooling concepts such as spin-calorimetrics, electrocalorics, non-equilibrium/nonlinear Peltier devices, superconducting junctions and two-dimensional materials are also elucidated and practical achievements are reviewed. We explain the thermoreflectance thermal imaging microscopy and the transient Harman method as two unique techniques developed for characterization of thermoelectric microrefrigerators. The future prospects for solid-state cooling are briefly summarized.

Preparation and evaluation of solid dispersion of atorvastatin calcium with Soluplus® by spray drying technique.

PubMed

Ha, Eun-Sol; Baek, In-hwan; Cho, Wonkyung; Hwang, Sung-Joo; Kim, Min-Soo

2014-01-01

The aim of the present study was to investigate the effect of Soluplus® on the solubility of atorvastatin calcium and to develop a solid dispersion formulation that can improve the oral bioavailability of atorvastatin calcium. We demonstrated that Soluplus® increases the aqueous solubility of atorvastatin calcium. Several solid dispersion formulations of atorvastatin calcium with Soluplus® were prepared at various drug : carrier ratios by spray drying. Physicochemical analysis demonstrated that atorvastatin calcium is amorphous in each solid dispersion, and the 2 : 8 drug : carrier ratio provided the highest degree of sustained atorvastatin supersaturation. Pharmacokinetic analysis in rats revealed that the 2 : 8 dispersion significantly improved the oral bioavailability of atorvastatin. This study demonstrates that spray-dried Soluplus® solid dispersions can be an effective method for achieving higher atorvastatin plasma levels.

Solubilization of poorly water-soluble drugs using solid dispersions.

PubMed

Tran, Thao T-D; Tran, Phuong H-L; Khanh, Tran N; Van, Toi V; Lee, Beom-Jin

2013-08-01

Many new drugs have been discovered in pharmaceutical industry and exposed their surprised potential therapeutic effects. Unfortunately, these drugs possess low absorption and bioavailability since their solubility limitation in water. Solid dispersion (SD) is the current technique gaining so many attractions from scientists due to its effect on improving solubility and dissolution rate of poorly water-soluble drugs. A number of patents including the most recent inventions have been undertaken in this review to address various respects of this strategy in solubilization of poorly watersoluble drugs including type of carriers, preparation methods and view of technologies used to detect SD properties and mechanisms with the aim to accomplish a SD not only effective on enhanced bioavailability but also overcome difficulties associated with stability and production. Future prospects are as well discussed with an only hope that many developments and researches in this field will be successfully reached and contributed to commercial use for treatment as much as possible.

Transport relaxation processes in supercritical fluids

NASA Astrophysics Data System (ADS)

Jonas, J.

The technique for solubility measurements of solids in compressed supercritical fluids using NMR and theoretical analysis of experimental data on collision induced scattering were examined. Initial tests for a determination of solid solubilities in supercritical fluids without mixing were previously described and these preparations have continued. Super critical carbon dioxide dissolving naphthalene, for which solubility data is already available (M. McHugh, M.E. Paulaitis, J. Chem. Eng. Data, Vol. 25 (4), 1980) is being studied. This initial testing of the NMR technique for measuring solubilities in a well characterized system should prove very valuable for our later determinations with the proposed mixing probe. Systematic experimental studies of collision induced spectra in several supercritical fluids using both Raman and Rayleigh scattering are continued. The experimental work on SF6 and CH4 was finished and the experimental data testing of the various theoretical models for collision induced scattering is being analyzed.

Characterization of pH-fractionated humic acids with respect to their dissociation behaviour.

PubMed

Klučáková, Martina

2016-04-01

Humic acids were divided into several fractions using buffer solutions as extraction agents with different pH values. Two methods of fractionation were used. The first one was subsequent dissolution of bulk humic acids in buffers adjusted to different pH. The second one was sequential dissolution in buffers with increasing pH values. Experimental data were compared with hypothesis of partial solubility of humic acids in aqueous solutions. Behaviour of humic fractions obtained by sequential dissolution, original bulk sample and residual fractions obtained by subsequent dissolution at pH 10 and 12 agrees with the hypothesis. Results demonstrated that regardless the common mechanism, solubility and dissociation degree of various humic fractions may be very different and can be estimated using parameters of the model based on the proposed mechanism. Presented results suggest that dissolving of solid humic acids in water environment is more complex than conventional solubility behaviour of sparingly soluble solids.

Influence of a nonionic surfactant (Triton X-100) on contaminant distribution between water and several soil solids

USGS Publications Warehouse

Lee, J.-F.; Liao, P.-M.; Kuo, C.-C.; Yang, H.-T.; Chiou, C.T.

2000-01-01

The influence of a nonionic surfactant (Triton X-100) on the contaminant distribution coefficients in solid-water mixtures was determined for a number of relatively nonpolar compounds (contaminants) on several natural solids. The studied compounds consisted of BTEX (benzene, toluene, ethylbenzene, and p-xylene) and chlorinated pesticides (lindane, ??-BHC, and heptachlor epoxide), which span several orders of magnitude in water solubility (S(W)); the solid samples comprised a bentonite, a peat, and two other soils, which cover a wide range of solid organic matter (SOM) content. The applied surfactant concentrations (X) ranged from below the (nominal) CMC to 2-3 times the CMC. For relatively water-soluble BTEX compounds, the distribution coefficients with surfactant (K*(d)) all exceeded those without surfactant (K(d)); the K*(d)/K(d) ratios increased with increasing S(w) from p-xylene to benzene on each solid at a given X, with increasing X for each compound on a solid, and with decreasing solid SOM content for each compound over the range of X studied. For the less-soluble pesticides, the K*(d)/K(d) ratios exhibited a large increase with X for bentonite, a marginal change (increase or decrease) for a soil of 2.4% SOM, and a moderate-to-large decrease for two soils of 14.8% and 86.4% SOM. These unique observations were rationalized in terms of the properties of the compound, the amount of surfactant sorbed on the solid, the enhanced solubilization of the compound by surfactant in water, and the relative effects of the surfactant when adsorbed on minerals and when partitioned into SOM. (C) 2000 Academic Press.

Phase diagram of a crystalline protein: Determination of the solubility of concanavalin A by a microquantitation assay

NASA Astrophysics Data System (ADS)

Mikol, Vincent; Giegé, Richard

1989-09-01

A quick and miniature method has been devised for determining protein solubility and used to investigate the equilibrium solubility of concanavalin A from the Jack Bean with its crystals as a function of ammonium sulfate concentration, temperature and pH. The crystals were characterized by X-ray diffraction and their morphologies related to the corresponding solubilities. The protein solution concentration was estimated out of small crystallizing drops using a rapid and sensitive microassay. Measurements of protein quantity were carried out in 96-well microplates in an automatic spectrophotometer. The resulting phase diagram has permitted to analyse the solubility of concanavalin A, to estimate supersaturation and to devise readily new ways of crystal growth of this lectin, namely by pH and temperature variations. Moreover, the approach is proved to be a valuable tool to design crystallization experiments of new molecules and to improve and control protein crystal growth.

The global phase diagram of the Gay-Berne model

NASA Astrophysics Data System (ADS)

de Miguel, Enrique; Vega, Carlos

2002-10-01

The phase diagram of the Gay-Berne model with anisotropy parameters κ=3, κ'=5 has been evaluated by means of computer simulations. For a number of temperatures, NPT simulations were performed for the solid phase leading to the determination of the free energy of the solid at a reference density. Using the equation of state and free energies of the isotropic and nematic phases available in the existing literature the fluid-solid equilibrium was calculated for the temperatures selected. Taking these fluid-solid equilibrium results as the starting points, the fluid-solid equilibrium curve was determined for a wide range of temperatures using Gibbs-Duhem integration. At high temperatures the sequence of phases encountered on compression is isotropic to nematic, and then nematic to solid. For reduced temperatures below T=0.85 the sequence is from the isotropic phase directly to the solid state. In view of this we locate the isotropic-nematic-solid triple point at TINS=0.85. The present results suggest that the high-density phase designated smectic B in previous simulations of the model is in fact a molecular solid and not a smectic liquid crystal. It seems that no thermodynamically stable smectic phase appears for the Gay-Berne model with the choice of parameters used in this work. We locate the vapor-isotropic liquid-solid triple point at a temperature TVIS=0.445. Considering that the critical temperatures is Tc=0.473, the Gay-Berne model used in this work presents vapor-liquid separation over a rather narrow range of temperatures. It is suggested that the strong lateral attractive interactions present in the Gay-Berne model stabilizes the layers found in the solid phase. The large stability of the solid phase, particularly at low temperatures, would explain the unexpectedly small liquid range observed in the vapor-liquid region.

A Thermodynamic Model to Estimate the Formation of Complex Nitrides of Al x Mg(1- x)N in Silicon Steel

NASA Astrophysics Data System (ADS)

Luo, Yan; Zhang, Lifeng; Li, Ming; Sridhar, Seetharaman

2018-06-01

A complex nitride of Al x Mg(1- x)N was observed in silicon steels. A thermodynamic model was developed to predict the ferrite/nitride equilibrium in the Fe-Al-Mg-N alloy system, using published binary solubility products for stoichiometric phases. The model was used to estimate the solubility product of nitride compound, equilibrium ferrite, and nitride compositions, and the amounts of each phase, as a function of steel composition and temperature. In the current model, the molar ratio Al/(Al + Mg) in the complex nitride was great due to the low dissolved magnesium in steel. For a steel containing 0.52 wt pct Als, 10 ppm T.Mg., and 20 ppm T.N. at 1100 K (827 °C), the complex nitride was expressed by Al0.99496Mg0.00504N and the solubility product of this complex nitride was 2.95 × 10-7. In addition, the solution temperature of the complex nitride increased with increasing the nitrogen and aluminum in steel. The good agreement between the prediction and the detected precipitate compositions validated the current model.

Gas solubility in dilute solutions: A novel molecular thermodynamic perspective

NASA Astrophysics Data System (ADS)

Chialvo, Ariel A.

2018-05-01

We present an explicit molecular-based interpretation of the thermodynamic phase equilibrium underlying gas solubility in liquids, through rigorous links between the microstructure of the dilute systems and the relevant macroscopic quantities that characterize their solution thermodynamics. We apply the formal analysis to unravel and highlight the molecular-level nature of the approximations behind the widely used Krichevsky-Kasarnovsky [J. Am. Chem. Soc. 57, 2168 (1935)] and Krichevsky-Ilinskaya [Acta Physicochim. 20, 327 (1945)] equations for the modeling of gas solubility. Then, we implement a general molecular-based approach to gas solubility and illustrate it by studying Lennard-Jones binary systems whose microstructure and thermodynamic properties were consistently generated via integral equation calculations. Furthermore, guided by the molecular-based analysis, we propose a novel macroscopic modeling approach to gas solubility, emphasize some usually overlook modeling subtleties, and identify novel interdependences among relevant solubility quantities that can be used as either handy modeling constraints or tools for consistency tests.

Gas solubility in dilute solutions: A novel molecular thermodynamic perspective.

PubMed

Chialvo, Ariel A

2018-05-07

We present an explicit molecular-based interpretation of the thermodynamic phase equilibrium underlying gas solubility in liquids, through rigorous links between the microstructure of the dilute systems and the relevant macroscopic quantities that characterize their solution thermodynamics. We apply the formal analysis to unravel and highlight the molecular-level nature of the approximations behind the widely used Krichevsky-Kasarnovsky [J. Am. Chem. Soc. 57, 2168 (1935)] and Krichevsky-Ilinskaya [Acta Physicochim. 20, 327 (1945)] equations for the modeling of gas solubility. Then, we implement a general molecular-based approach to gas solubility and illustrate it by studying Lennard-Jones binary systems whose microstructure and thermodynamic properties were consistently generated via integral equation calculations. Furthermore, guided by the molecular-based analysis, we propose a novel macroscopic modeling approach to gas solubility, emphasize some usually overlook modeling subtleties, and identify novel interdependences among relevant solubility quantities that can be used as either handy modeling constraints or tools for consistency tests.

Development of solid-gas equilibrium propulsion system for small spacecraft

NASA Astrophysics Data System (ADS)

Chujo, Toshihiro; Mori, Osamu; Kubo, Yuki

2017-11-01

A phase equilibrium propulsion system is a kind of cold-gas jet in which the phase equilibrium state of the fuel is maintained in a tank and its vapor is ejected when a valve is opened. One such example is a gas-liquid equilibrium propulsion system that uses liquefied gas as fuel. This system was mounted on the IKAROS solar sail and has been demonstrated in orbit. The system has a higher storage efficiency and a lighter configuration than a high-pressure cold-gas jet because the vapor pressure is lower, and is suitable for small spacecraft. However, the system requires a gas-liquid separation device in order to avoid leakage of the liquid, which makes the system complex. As another example of a phase equilibrium propulsion system, we introduce a solid-gas equilibrium propulsion system, which uses a sublimable substance as fuel and ejects its vapor. This system has an even lower vapor pressure and does not require such a separation device, instead requiring only a filter to keep the solid inside the tank. Moreover, the system is much simpler and lighter, making it more suitable for small spacecraft, especially CubeSat-class spacecraft, and the low thrust of the system allows spacecraft motion to be controlled precisely. In addition, the thrust level can be controlled by controlling the temperature of the fuel, which changes the vapor pressure. The present paper introduces the concept of the proposed system, and describes ejection experiments and its evaluation. The basic function of the proposed system is demonstrated in order to verify its usefulness.

Characterization and evaluation of avermectin solid nanodispersion prepared by microprecipitation and lyophilisation techniques

PubMed Central

Wang, Chunxin; Zhao, Xiang; Yao, Junwei; Zeng, Zhanghua; Wang, Yan; Sun, Changjiao; Liu, Guoqiang; Cui, Haixin

2018-01-01

Poorly water-soluble and photosensitive pesticide compounds are difficult to formulate as solvent-free nanoformulations with high efficacy. A avermectin solid nanodispersion with a mean particle size of 188 nm was developed by microprecipitation and lyophilisation techniques. The suspensibility and wetting time of the solid nanodispersion in water were 99.8% and 13 s, respectively, superior to those of conventional water dispersible granules and wettable powders. The anti-photolysis performance of the nanoformulation was twice that of the technical material, and the biological activity against diamondback moths was more than 1.5 times that of the conventional solid formulations while taking LC 50 as the evaluation index. Moreover, the formulation composition substantially decreased the surfactant content and avoided organic solvents. Microprecipitation combined with lyophilisation is an easy and promising method to construct solid nanoformulations for pesticides with poor water solubility and environmental sensitivity. The application of the highly effective solid nanodispersion in crop production will have a great potential in reducing chemical residues and environmental pollution. PMID:29360866

Inert-Gas Condensed Co-W Nanoclusters: Formation, Structure and Magnetic Properties

NASA Astrophysics Data System (ADS)

Golkar-Fard, Farhad Reza

Rare-earth permanent magnets are used extensively in numerous technical applications, e.g. wind turbines, audio speakers, and hybrid/electric vehicles. The demand and production of rare-earth permanent magnets in the world has in the past decades increased significantly. However, the decrease in export of rare-earth elements from China in recent time has led to a renewed interest in developing rare-earth free permanent magnets. Elements such as Fe and Co have potential, due to their high magnetization, to be used as hosts in rare-earth free permanent magnets but a major challenge is to increase their magnetocrystalline anisotropy constant, K1, which largely drives the coercivity. Theoretical calculations indicate that dissolving the 5d transition metal W in Fe or Co increases the magnetocrystalline anisotropy. The challenge, though, is in creating a solid solution in hcp Co or bcc Fe, which under equilibrium conditions have negligible solubility. In this dissertation, the formation, structure, and magnetic properties of sub-10 nm Co-W clusters with W content ranging from 4 to 24 atomic percent were studied. Co-W alloy clusters with extended solubility of W in hcp Co were produced by inert gas condensation. The different processing conditions such as the cooling scheme and sputtering power were found to control the structural state of the as-deposited Co-W clusters. For clusters formed in the water-cooled formation chamber, the mean size and the fraction crystalline clusters increased with increasing power, while the fraction of crystalline clusters formed in the liquid nitrogen-cooled formation chamber was not as affected by the sputtering power. For the low W content clusters, the structural characterization revealed clusters predominantly single crystalline hcp Co(W) structure, a significant extension of W solubility when compared to the equilibrium solubility, but fcc Co(W) and Co3W structures were observed in very small and large clusters, respectively. At high W content, clusters with hcp Co(W), fcc Co(W) or Co3W structures were observed. The magnetic measurements at 10 K and 300 K revealed that the coercivity, saturation magnetization and magnetocrystalline anisotropy of the clusters formed in the water-cooled formation chamber were higher than for clusters formed in the liquid nitrogen-cooled formation chamber. The coercivity and magnetocrystalline anisotropy of the clusters increased as long as W was dissolved into the hcp Co structure. With increasing fraction of Co3W and fcc Co(W) clusters, as observed in the high-W content sample, the magnetic properties deteriorated significantly. The highest coercivity and magnetocrystalline anisotropy of 893 Oe and 3.9 x 106 ergs/cm3, respectively, was obtained at 10 K for the 5 at.% W clusters sputtered at 150 W in the water-cooled formation chamber.

Synergistic Effect of Hydrotrope and Surfactant on Solubility and Dissolution of Atorvastatin Calcium: Screening Factorial Design Followed by Ratio Optimization

PubMed Central

Patel, V. F.; Sarai, J.

2014-01-01

The present study was aimed at investigating the effect of hydrotrope and surfactant on poor solubility of atorvastatin calcium. Excipients screening followed by factorial design was performed to study effect of excipients and manufacturing methods on solubility of drug. Three independent factors (carrier, surfactant and manufacturing method) were evaluated at two levels using solubility as a dependant variable. Solid-state characterisation was performed using Fourier transform infrared spectroscopy and differential scanning calorimetry. Optimised complex were incorporated into orally disintegrating micro tablets and in vitro dissolution test was performed. Nicotinamide, Plasdone and sodium dodecyl sulphate were emerged as promising excipients from excipient screening. General regression analysis revealed only the type of carrier has significantly enhanced (P<0.05) the solubility of drug while other factors were found to be nonsignificant. Ratio optimisation trial revealed that drug to nicotinamide ratio is more critical in enhancing the solubility of drug (40 fold increases in solubility compared to pure drug) in comparison to drug-surfactant ratio; however the presence of surfactant deemed essential. Significantly higher rate and extent of dissolution was observed from solid dispersion complex and tablets compared to dissolution of pure drug (P<0.05). Study revealed hydrotrope and surfactant have synergistic effect on solubility and dissolution of atorvastatin calcium and this can be explored further. PMID:25593381

Estimation of medium effects on equilibrium constants in moderate and high ionic strength solutions at elevated temperatures by using specific interaction theory (SIT): Interaction coefficients involving Cl, OH- and Ac- up to 200°C and 400 bars

PubMed Central

Xiong, Yongliang

2006-01-01

In this study, a series of interaction coefficients of the Brønsted-Guggenheim-Scatchard specific interaction theory (SIT) have been estimated up to 200°C and 400 bars. The interaction coefficients involving Cl- estimated include ε(H+, Cl-), ε(Na+, Cl-), ε(Ag+, Cl-), ε(Na+, AgCl2 -), ε(Mg2+, Cl-), ε(Ca2+, Cl-), ε(Sr2+, Cl-), ε(Ba2+, Cl-), ε(Sm3+, Cl-), ε(Eu3+, Cl-), ε(Gd3+, Cl-), and ε(GdAc2+, Cl-). The interaction coefficients involving OH- estimated include ε(Li+, OH-), ε(K+, OH-), ε(Na+, OH-), ε(Cs+, OH-), ε(Sr2+, OH-), and ε(Ba2+, OH-). In addition, the interaction coefficients of ε(Na+, Ac-) and ε(Ca2+, Ac-) have also been estimated. The bulk of interaction coefficients presented in this study has been evaluated from the mean activity coefficients. A few of them have been estimated from the potentiometric and solubility studies. The above interaction coefficients are tested against both experimental mean activity coefficients and equilibrium quotients. Predicted mean activity coefficients are in satisfactory agreement with experimental data. Predicted equilibrium quotients are in very good agreement with experimental values. Based upon its relatively rapid attainment of equilibrium and the ease of determining magnesium concentrations, this study also proposes that the solubility of brucite can be used as a pH (pcH) buffer/sensor for experimental systems in NaCl solutions up to 200°C by employing the predicted solubility quotients of brucite in conjunction with the dissociation quotients of water and the first hydrolysis quotients of Mg2+, all in NaCl solutions. PMID:16759370

Novel Co(II) phthalocyanines of extended periphery and their water-soluble derivatives. Synthesis, spectral properties and catalytic activity

NASA Astrophysics Data System (ADS)

Filippova, Anna; Vashurin, Artur; Znoyko, Serafima; Kuzmin, Ilya; Razumov, Mikhail; Chernova, Alena; Shaposhnikov, Gennady; Koifman, Oscar

2017-12-01

Novel complexes of cobalt and copper with substituted phthalocyanines were synthesized and characterized. Their water-soluble derivatives were obtained by sulfonation under mild conditions and structurally proved. Aggregation equilibrium in water mediums was shown and influence of geometrical and electron parameters of macroheterocycle peripheral substituents on these processes was established. Catalytic activity upon liquid-phase oxidation of N,N-diethylcarbamodithiolate to thiuram E was studied. Kinetic parameters of substrate oxidation in presence of cobalt phthalocyanines were considered.

Experimental Liquidus Studies of the Pb-Cu-Si-O System in Equilibrium with Metallic Pb-Cu Alloys

NASA Astrophysics Data System (ADS)

Shevchenko, M.; Nicol, S.; Hayes, P. C.; Jak, E.

2018-03-01

Phase equilibria of the Pb-Cu-Si-O system have been investigated in the temperature range from 1073 K to 1673 K (800 °C to 1400 °C) for oxide liquid (slag) in equilibrium with solid Cu metal and/or liquid Pb-Cu alloy, and solid oxide phases: (a) quartz or tridymite (SiO2) and (b) cuprite (Cu2O). High-temperature equilibration on silica or copper substrates was performed, followed by quenching, and direct measurement of Pb, Cu, and Si concentrations in the liquid and solid phases using the electron probe X-ray microanalysis has been employed to accurately characterize the system in equilibrium with Cu or Pb-Cu metal. All results are projected onto the PbO-"CuO0.5"-SiO2 plane for presentation purposes. The present study is the first-ever systematic investigation of this system to describe the slag liquidus temperatures in the silica and cuprite primary phase fields.

On the kinetics of the pack - Aluminization process

NASA Technical Reports Server (NTRS)

Sivakumar, R.; Seigle, L. L.

1976-01-01

An investigation has been made of the aluminization of unalloyed Ni in fluoride-activated packs of varying Al activity. In packs of low Al activity, in which the ratio of Al to Ni was less than 50 at. pct, the specimen surface quickly came to equilibrium with the pack and remained close to equilibrium for the duration of normal coating runs. In these packs the kinetics of aluminization was controlled by diffusion in the solid. In packs of higher Al activity the surface of the specimen did not come to equilibrium with the pack and the kinetics of the process was governed by a combination of solid and gas diffusion rates. Under most conditions however, the surface composition was time-invariant and a steady-state appeared to exist at the pack-coating interface. By combining Levine and Caves' model for gaseous diffusion in pure-Al packs with calculations of solid diffusion rates some success has been achieved in explaining the results.

Solubility of jarosite solid solutions precipitated from acid mine waters, Iron Mountain, California

USGS Publications Warehouse

Alpers, Charles N.; Nordstrom, D. Kirk; Ball, J.W.

1989-01-01

Because of the common occurrence of 15 to 25 mole percent hydronium substitution on the alkali site in jarosites, it is necessary to consider the hydronium content of jarosites in any attempt at rigorous evaluation of jarosite solubility or of the saturation state of natural waters with respect to jarosite. A Gibbs free energy of 3293.5±2.1 kJ mol-1 is recommended for a jarosite solid solution of composition K.77Na.03(H3O).20Fe3(SO4)2(OH)6. Solubility determinations for a wider range of natural and synthetic jarosite solid solutions will be necessary to quantify the binary and ternary mixing parameters in the (K-Na-H3O) system. In the absence of such studies, molar volume data for endmember minerals indicate that the K-H3O substitution in jarosite is probably closer to ideal mixing than either the Na-K or Na-H3O substitution.

The Wettability of LaRC Colorless Polyimide Resins on Casting Surfaces

NASA Technical Reports Server (NTRS)

Miner, Gilda A.; Stoakley, Diane M.; St.Clair, Anne K.; Gierow, Paul A.; Bates, Kevin

1997-01-01

Two colorless polyimides developed at NASA Langley Research Center, LaRC -CP1 and LaRC -CP2, are noted for being optically transparent, resistant to radiation, and soluble in the imide form. These materials may be used to make transparent, thin polymer films for building large space reflector/collector inflatable antennas, solar arrays, radiometers, etc. Structures such as these require large area, seamless films produced via spin casting or spray coating the soluble imide on a variety of substrates. The ability of the soluble imide to wet and spread over the mandrel or casting substrate is needed information for processing these structures with minimum waste and reprocessing, thereby, reducing the production costs. The wettability of a liquid is reported as the contact angle of the solid/liquid system. This fairly simple measurement is complicated by the porosity and the amount of contamination of the solid substrate. This work investigates the effect of inherent viscosity, concentration of polyimide solids, and solvent type on the wettability of various curing surfaces.

Improvement of the dissolution rate of poorly soluble drugs by solid crystal suspensions.

PubMed

Thommes, Markus; Ely, David R; Carvajal, M Teresa; Pinal, Rodolfo

2011-06-06

We present a novel extrusion based approach where the dissolution rate of poorly soluble drugs (griseofulvin, phenytoin and spironolactone) is significantly accelerated. The drug and highly soluble mannitol are coprocessed in a hot melt extrusion operation. The obtained product is an intimate mixture of the crystalline drug and crystalline excipient, with up to 50% (w/w) drug load. The in vitro drug release from the obtained solid crystalline suspensions is over 2 orders of magnitude faster than that of the pure drug. Since the resulting product is crystalline, the accelerated dissolution rate does not bear the physical stability concerns inherent to amorphous formulations. This approach is useful in situations where the drug is not a good glass former or in cases where it is difficult to stabilize the amorphous drug. Being thermodynamically stable, the dissolution profile and the solid state properties of the product are maintained after storage at 40 °C, 75% RH for at least 90 days.

The Solubility of Diopside in Water at 10 to 15 kbar and 650 to 900 C

NASA Astrophysics Data System (ADS)

Macris, C. A.; Manning, C. E.

2005-12-01

Subduction zone fluids play a critical role in mass transfer and mantle-wedge metasomatism, yet little is known about their composition and chemical behavior. One way to better understand these important fluids is to investigate the solubility of minerals at subduction zone conditions. The solubility of diopside in H2O was measured at 10 to 15 kbar, 650 to 900 °C using a piston-cylinder apparatus with NaCl-graphite furnaces. A single gem-quality diopside crystal was placed in an inner Pt capsule, which then was perforated to allow fluid ingress and added with H2O to an outer Pt capsule, which was then sealed. The solubility was determined by the weight loss of the diopside crystals. All charges were carefully examined by SEM for composition and textural characteristics of quench material. SEM analysis revealed that in several experiments small diopside crystals nucleated and grew in the outer capsule or on the walls of the inner capsule due to fluid convection within the charge. These experiments yielded erroneously high solubilities and were omitted from final plots and equation calculations. Diopside was found to dissolve incongruently to forsterite + dissolved species at all conditions investigated. The forsterite occurs as euhedral crystals in pits etched from the diopside grain covering less than 5% of its surface. In addition, long thin wollastonite blades and a layer of SiO2 "mud" form upon quenching of the run. Experiments at 700 °C and varying times showed that diopside plus forsterite plus fluid reached equilibrium by 12 hours. The solubility of diopside + forsterite in H2O increases with increasing pressure and temperature. At 10 kbar, solubility increases from 0.004 molal at 650 °C to 0.012 molal at 900 °C. At 800 °C and 10 to 15 kbar, solubility increases from 0.008 to 0.015 molal. These preliminary data yield the equation: log mdi+fo = -0.7539 + -2135.7/T + 0.6355P, where T is in K and P is in GPa. Because temperature enhances solubility more than pressure in this system, we can predict that as a fluid moves from slab to wedge, which leads to decompression and heating, di+fo solubility will increase. The resulting fluid will be enriched in Ca and Si, but low in Mg. These results are consistent with theoretical predictions on the composition of fluids in equilibrium with eclogites (Manning 1998), experimental investigations on fluid compositions in equilibrium with high-pressure mantle rocks (Schneider and Eggler 1986; Ayers et al. 1997), and vein-mineral assemblages in blueschists and eclogites (e.g., Gao and Klemd 2001; Becker et al. 1999). Ayers J., Dittmer S.K., Layne G.D. (1997) Earth Planet. Sci. Lett. 150:381-398; Becker H., Jockum K.P., Carlson R.W. (1999) Chem. Geol. 160:291-308; Gao J., Klemd R. (2001) Contrib. Mineral. Petrol. 142:1-14; Manning C.E. (1998) Swiss Bull. Mineral. Petrol. 78:225-242; Schneider M.E., Eggler D.H. (1986) Geochim. Cosmochim. Acta 50:711-724

Comparison of HPMC based polymers performance as carriers for manufacture of solid dispersions using the melt extruder.

PubMed

Ghosh, Indrajit; Snyder, Jennifer; Vippagunta, Radha; Alvine, Marilyn; Vakil, Ronak; Tong, Wei-Qin; Vippagunta, Sudha

2011-10-31

Preparation of amorphous solid dispersions using hot-melt extrusion process for poorly water soluble compounds which degrade on melting remains a challenge due to exposure to high temperatures. The aim of this study was to develop a physically and chemically stable amorphous solid dispersion of a poorly water-soluble compound, NVS981, which is highly thermal sensitive and degrades upon melting at 165 °C. Hydroxypropyl Methyl Cellulose (HPMC) based polymers; HPMC 3cps, HPMC phthalate (HPMCP) and HPMC acetyl succinate (HPMCAS) were selected as carriers to prepare solid dispersions using hot melt extrusion because of their relatively low glass transition temperatures. The solid dispersions were compared for their ease of manufacturing, physical stability such as recrystallization potential, phase separation, molecular mobility and enhancement of drug dissolution. Two different drug loads of 20 and 50% (w/w) were studied in each polymer system. It was interesting to note that solid dispersions with 50% (w/w) drug load were easier to process in the melt extruder compared to 20% (w/w) drug load in all three carriers, which was attributed to the plasticizing behavior of the drug substance. Upon storage at accelerated stability conditions, no phase separation was observed in HPMC 3cps and HPMCAS solid dispersions at the lower and higher drug load, whereas for HPMCP, phase separation was observed at higher drug load after 3 months. The pharmaceutical performance of these solid dispersions was evaluated by studying drug dissolution in pH 6.8 phosphate buffer. Drug release from solid dispersion prepared from polymers used for enteric coating, i.e. HPMCP and HPMCAS was faster compared with the water soluble polymer HPMC 3cps. In conclusion, of the 3 polymers studied for preparing solid dispersions of thermally sensitive compound using hot melt extrusion, HPMCAS was found to be the most promising as it was easily processible and provided stable solid dispersions with enhanced dissolution. Copyright © 2011 Elsevier B.V. All rights reserved.

Experimental Determination of Solubilities of Sodium Polyborates In MgCl 2 Solutions: Solubility Constant of Di-Sodium Hexaborate Tetrahydrate, and Implications For the Diagenetic Formation of Ameghinite

DOE PAGES

Xiong, Yongliang; Kirkes, Leslie; KNOX, Jandi; ...

2017-11-01

In this paper, solubility measurements were conducted for sodium polyborates in MgCl 2 solutions at 22.5 ± 0.5 °C. According to solution chemistry and XRD patterns, di-sodium tetraborate decahydrate (borax) dissolves congruently, and is the sole solubility-controlling phase, in a 0.01 mol/kg MgCl 2 solution: Na 2B 4O 7•10H 2O(cr) ⇌ 2Na + + 4B(OH) 4 + 2H + + H 2O(l). However, in a 0.1 mol/kg MgCl 2 solution borax dissolves incongruently and is in equilibrium with di-sodium hexaborate tetrahydrate: 2Na 2B 6O 10•4H 2O(cr) + 2Na + + 23H 2O(l) ⇌ 3Na 2B 4O 7•10H 2O(cr) + 2Hmore » +. In this study, the equilibrium constant (log K 0) for Reaction 2 at 25 °C and infinite dilution was determined to be –16.44 ± 0.13 (2σ) based on the experimental data and the Pitzer model for calculations of activity coefficients of aqueous species. In accordance with the log K 0 for Reaction 1 from a previous publication from this research group, and log K 0 for Reaction 2 from this study, the equilibrium constant for dissolution of di-sodium hexaborate tetrahydrate at 25 °C and at infinite dilution, Na 2B 6O 10•4H 2O(cr) + 10H 2O(l) ⇌ 2Na + + 6B(OH) 4 - + 4H + was derived to be –45.42 ± 0.16 (2σ). The equilibrium constants determined in this study can find applications in many fields. For example, in the field of nuclear waste management, the formation of di-sodium hexaborate tetrahydrate in brines containing magnesium will decrease borate concentrations, making less borate available for interactions with Am(III). In the field of experimental investigations, based on the equilibrium constant for Reaction 2, the experimental systems can be controlled in terms of acidity around neutral pH by using the equilibrium assemblage of borax and di-sodium hexaborate tetrahydrate at 25 °C. As salt lakes and natural brines contain both borate and magnesium as well as sodium, the formation of sodium hexaborate tetrahydrate may influence the chemical evolution of salt lakes and natural brines. Di-sodium hexaborate tetrahydrate is a polymorph of the mineral ameghinite [chemical formula Na 2B 6O 10•4H 2O; structural formula NaB 3O 3(OH) 4 or Na 2B 6O 6(OH) 8]. Finally, di-sodium hexaborate tetrahydrate could be a precursor of ameghinite and could be transformed when borate deposits are subject to diagenesis.« less

Experimental Determination of Solubilities of Sodium Polyborates In MgCl 2 Solutions: Solubility Constant of Di-Sodium Hexaborate Tetrahydrate, and Implications For the Diagenetic Formation of Ameghinite

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

Xiong, Yongliang; Kirkes, Leslie; KNOX, Jandi

In this paper, solubility measurements were conducted for sodium polyborates in MgCl 2 solutions at 22.5 ± 0.5 °C. According to solution chemistry and XRD patterns, di-sodium tetraborate decahydrate (borax) dissolves congruently, and is the sole solubility-controlling phase, in a 0.01 mol/kg MgCl 2 solution: Na 2B 4O 7•10H 2O(cr) ⇌ 2Na + + 4B(OH) 4 + 2H + + H 2O(l). However, in a 0.1 mol/kg MgCl 2 solution borax dissolves incongruently and is in equilibrium with di-sodium hexaborate tetrahydrate: 2Na 2B 6O 10•4H 2O(cr) + 2Na + + 23H 2O(l) ⇌ 3Na 2B 4O 7•10H 2O(cr) + 2Hmore » +. In this study, the equilibrium constant (log K 0) for Reaction 2 at 25 °C and infinite dilution was determined to be –16.44 ± 0.13 (2σ) based on the experimental data and the Pitzer model for calculations of activity coefficients of aqueous species. In accordance with the log K 0 for Reaction 1 from a previous publication from this research group, and log K 0 for Reaction 2 from this study, the equilibrium constant for dissolution of di-sodium hexaborate tetrahydrate at 25 °C and at infinite dilution, Na 2B 6O 10•4H 2O(cr) + 10H 2O(l) ⇌ 2Na + + 6B(OH) 4 - + 4H + was derived to be –45.42 ± 0.16 (2σ). The equilibrium constants determined in this study can find applications in many fields. For example, in the field of nuclear waste management, the formation of di-sodium hexaborate tetrahydrate in brines containing magnesium will decrease borate concentrations, making less borate available for interactions with Am(III). In the field of experimental investigations, based on the equilibrium constant for Reaction 2, the experimental systems can be controlled in terms of acidity around neutral pH by using the equilibrium assemblage of borax and di-sodium hexaborate tetrahydrate at 25 °C. As salt lakes and natural brines contain both borate and magnesium as well as sodium, the formation of sodium hexaborate tetrahydrate may influence the chemical evolution of salt lakes and natural brines. Di-sodium hexaborate tetrahydrate is a polymorph of the mineral ameghinite [chemical formula Na 2B 6O 10•4H 2O; structural formula NaB 3O 3(OH) 4 or Na 2B 6O 6(OH) 8]. Finally, di-sodium hexaborate tetrahydrate could be a precursor of ameghinite and could be transformed when borate deposits are subject to diagenesis.« less

Drop dynamics on a thin film: Thin film rupture

NASA Astrophysics Data System (ADS)

Carlson, Andreas; Kim, Pilnam; Stone, Howard A.

2011-11-01

The spreading of a water drop on an oil film that covers a solid substrate is a common event in many industrial processes. We study in experiments the dynamics of a water drop on a thin silicone oil film and quantify its interaction with the solid substrate that supports the film. The oil film becomes unstable and ruptures for solids that are hydrophilic. We determine the ``waiting time,'' the time it takes the water drop to drain the silicone film. This timescale is found to highly depend on how well water wets the solid, illustrating the interplay between intermolecular and hydrodynamic forces in the phenomenon. A phase diagram for the thin film stability is extracted based on waters equilibrium contact angle on the solid, which shows that we can either promote or inhibit de-wetting. As water comes in direct contact with the solid, it spreads and peels off the silicone film. We show the influence of viscosity, equilibrium contact angle and film height on the opening radius of the hole formed as the solid de-wets.

Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

PubMed

Guan, Zixuan; Chen, Di; Chueh, William C

2017-08-30

The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

Sorption-desorption and biosorption of bisphenol A, triclosan, and 17α-ethinylestradiol to sewage sludge.

PubMed

Banihashemi, Bahman; Droste, Ronald L

2014-07-15

To better understand the fate of microconstituents (MCs) in an activated sludge (AS) system, sorption, biosorption, and desorption studies were investigated at μg/L range for 17α-ethinylestradiol (EE2), bisphenol A (BPA), and triclosan (TCS). Batch experiments with activated and deactivated sludge originating from continuous flow porous pot reactors operating at solid retention times (SRTs) of 5, 10, and 15 days were conducted in order to investigate the sorption kinetics and distinguish physicochemical sorption and biosorption. The effect of SRT and the biomass concentration on sorption kinetics were also studied. Selected MCs showed high sorption affinity to the non-viable biomass during the first 30 min of the experiment, which was gradually reduced until equilibrium was reached. Desorption results showed two distinct stages, a very rapid desorption within 20 min followed by a slow desorption stage. Biosorption study indicated that the soluble concentrations of target compounds decreased rapidly for selected MCs similar to the sorption study; however, the soluble and solid phase concentrations continued to decrease slowly during the length of the experiment which indicates the possible biodegradation of these compounds in both phases. Finally, mathematical models were applied to describe the sorption mechanism and Freundlich sorption isotherms with values of 1/n close to 1 were found to best fit the results which demonstrate that all tested concentrations result on the linear part of the Freundlich isotherm. Calculation of the Freundlich constant, KF and distribution coefficient, Kd exhibited the greater tendency of EE2 and TCS for sorption, compared to BPA. The results of this study indicated that the SRT had a clear effect on the sorption kinetics where the highest sorption rate constant was achieved for a SRT of 10 days for all three target substances. This could be due to change of the morphology of the biomass from reactors operating at different SRTs. Copyright © 2014 Elsevier B.V. All rights reserved.

The role of particle size of glyburide crystals in improving its oral absorption.

PubMed

Wang, Yongjun; Yang, Wenqian; Fu, Qiang; Guo, Zhibin; Sun, Bingjun; Liu, Wen; Liu, Yaxuan; Mu, Simeng; Guo, Mengran; Li, Jingru; Pu, Xiaohui; He, Zhonggui

2017-06-01

Currently, nanosizing is becoming increasingly prevalent as an efficient way for the improvement of oral drug absorption. This study mainly focuses on two points, namely the crystal properties, and the in vitro and in vivo characterizations of drug crystals during the nanosizing process. We used glyburide, an oral type 2 diabetes (T2D) medication, as our model drug. We sought to reduce the crystalline size of this drug and evaluate its absorption properties by comparing it with the original coarse drug because of previous reports about its gastrointestinal absorption insufficiency. Glyburide crystals, ranging from 237.6 to 4473 nm were prepared successfully by jet milling and media milling. The particle sizes and the crystal morphology were analyzed by characterization of the solid states, equilibrium solubility, and dissolution behavior. Additionally, pharmacokinetic study was performed in SD rats. The solid state results indicated a loss in crystallinity, amide-imidic acid interconversion, and partial amorphization during nanosizing. Further, in in vitro tests, nanocrystal formulations remarkably increased the solubility and dissolution of the drug (compared to microcrystals). In the in vivo test, reducing the particle size from 601.3 to 312.5 nm showed no improvement on the C max and AUC (0-36 h) values, while a profound slowing of the drug elimination occurred with reduction of particle size. Further reduction from 312.5 to 237.6 nm lead to a significant increase (p < 0.001) of the AUC (0-36 h) from 6857.8 ± 369.3 ng mL -1  h to 12,928.3 ± 1591.4 ng mL -1  h, respectively, in rats. Our present study confirmed that nanosizing has a tremendous impact on promoting the oral absorption of glyburide.

The effect of packaging methods (paper, active paper, and edible coating) on the characteristic of papaya MJ9 in ambient temperature storage

NASA Astrophysics Data System (ADS)

Suwanti, D.; Utami, R.; Kawiji; Praseptiangga, D.; Khasanah, L. U.

2018-01-01

Papaya is one of the export commodities that contain high vitamin C but having short shelf-life. One method that use to extend the shelf-life and maintain the quality of papaya is packaging. The aim of this study was to investigate the effect of the packaging methods (paper, active paper and edible coating) on the characteristics of papaya MJ9 (weight loss, firmness, total soluble solid (TSS), Total Titratable Acid (TTA), pH, vitamin C and total mold and yeast). The packaging methods were control (F1), wrapping paper (F2), wrapping active paper (F3), combination of edible coating and wrapping paper (F4), and combination of edible coating and wrapping active paper (F5). The result showed that paper packaging, edible coating and active paper packaging significantly affected the weight loss, firmness, total soluble solid, total titratable acids, pH, vitamin C, and total mold and yeast of papaya. The weight loss, total soluble solid and pH of packaged papaya was lower than that of control sample, however, the value of firmness and total titratable acid was higher than that of the control sample. Packaging can inhibit the increase of weight loss, total soluble solids and pH, and the decrease of firmness, total titratable acid, vitamin C and total mold and yeast. Based on the papaya characteristics, the selected packaging method was the combination of edible coating and wrapping active paper.

Solid-liquid phase equilibria in the ternary system (LiBO2 + Li2CO3 + H2O) at 288.15 and 298.15 K

NASA Astrophysics Data System (ADS)

Wang, Shi-qiang; Guo, Ya-fei; Yang, Jian-sen; Deng, Tian-long

2015-12-01

Experimental studies on the solubilities and physicochemical properties including density, refractive index and pH value in the ternary systems (LiBO2 + Li2CO3 + H2O) at 288.15 and 298.15 K were determined with the method of isothermal dissolution equilibrium. Based on the experimental results, the phase diagrams and their corresponding physicochemical properties versus composition diagram in the system were plotted. In the phase diagrams of the ternary system at 288.15 and 298.15 K, there are one eutectic point and two crystallization regions corresponding to lithium metaborate octahydrate (LiBO2 · 8H2O) and lithium carbonate (Li2CO3), respectively. This system at both temperatures belongs to hydrate type I, and neither double salt nor solid solution was found. A comparison of the phase diagrams for this ternary system at 288.15 and 298.15 K shows that the solid phase numbers and exist minerals are the same, and the area of crystallization region of Li2CO3 is increased obviously with the increasing temperature while that of LiBO2 · 8H2O is decreased. The physicochemical properties (density, pH value and refractive index) of the solutions of the ternary system at two temperatures changes regularly with the increasing lithium carbonate concentration. The calculated values of density and refractive index using empirical equations of the ternary system are in good agreement with the experimental values.

Solids mass flow determination

DOEpatents

Macko, Joseph E.

1981-01-01

Method and apparatus for determining the mass flow rate of solids mixed with a transport fluid to form a flowing mixture. A temperature differential is established between the solids and fluid. The temperature of the transport fluid prior to mixing, the temperature of the solids prior to mixing, and the equilibrium temperature of the mixture are monitored and correlated in a heat balance with the heat capacities of the solids and fluid to determine the solids mass flow rate.

Characterization, in Vivo and in Vitro Evaluation of Solid Dispersion of Curcumin Containing d-α-Tocopheryl Polyethylene Glycol 1000 Succinate and Mannitol.

PubMed

Song, Im-Sook; Cha, Jin-Sun; Choi, Min-Koo

2016-10-17

The aim of this study was to prepare a solid dispersion formulation of curcumin to enhance its solubility, dissolution rate, and oral bioavailability. The formulation was prepared with d-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) and mannitol using solvent evaporation and freeze-drying methods, which yielded a solid dispersion composed of curcumin, TPGS, and mannitol at a ratio of 1:10:15 ( w / w / w ). The solubility and dissolution rate of the curcumin solid dispersion markedly improved compared with those of curcumin powder and a physical mixture of curcumin, TPGS, and mannitol. About 90% of the curcumin was released from the solid dispersion formulation within 10 min. After administering the formulation orally to rats, higher plasma concentrations of curcumin were observed, with increases in the maximum plasma concentration (C max ) and area under the plasma concentration-time curve (AUC) of 86- and 65-fold, respectively, compared with those of curcumin powder. The solid dispersion formulation effectively increased intestinal permeability and inhibited P-gp function. These effects increased the anti-proliferative effect of curcumin in MDA-MB-231 breast cancer cells. Moreover, 2 h incubation with curcumin powder, solid dispersion formulation, and its physical mixture resulted in differential cytotoxic effect of paclitaxel in P-gp overexpressed LLC-PK1-P-gp and MDA-MB-231 cells through the inhibition of P-gp-mediated paclitaxel efflux. In conclusion, compared with curcumin, a solid dispersion formulation of curcumin with TPGS and mannitol could be a promising option for enhancing the oral bioavailability and efficacy of curcumin through increased solubility, dissolution rate, cell permeability, and P-gp modulation.

Determination of excipient based solubility increases using the CheqSol method.

PubMed

Etherson, Kelly; Halbert, Gavin; Elliott, Moira

2014-04-25

Aqueous solubility is an essential characteristic assessed during drug development to determine a compound's drug-likeness since solubility plays an important pharmaceutical role. However, nearly half of the drug candidates discovered today display poor water solubility; therefore methods have to be applied to increase solubility. Solubility determination using the CheqSol method is a novel rapid solubility screening technique for ionisable compounds. The aim of this study is to determine if the CheqSol method can be employed to determine solubility increases of four test drugs (ibuprofen, gliclazide, atenolol and propranolol) induced by non-ionising excipients such as hydroxypropyl-β-cyclodextrin and poloxamers 407 and 188. CheqSol assays were performed for the drugs alone or in combination with varying solubiliser concentrations. The measured intrinsic solubility of all four drugs increased with all the excipients tested in an excipient concentration dependent manner providing results consistent with previous literature. The results demonstrate that it may be possible to use this method to determine the solubility increases induced by non-ionic solubilising excipients with results that are comparable to standard equilibrium based solubility techniques. Since the technique is automated and requires only small drug quantities it may serve as a useful solubility or formulation screening tool providing more detailed physicochemical information than multiwell plate or similar visual systems. Copyright © 2014. Published by Elsevier B.V.

Development of novel fast-dissolving tacrolimus solid dispersion-loaded prolonged release tablet.

PubMed

Cho, Jung Hyun; Kim, Yong-Il; Kim, Dong-Wuk; Yousaf, Abid Mehmood; Kim, Jong Oh; Woo, Jong Soo; Yong, Chul Soon; Choi, Han-Gon

2014-04-11

The goal of this research was to develop a novel prolonged release tablet bioequivalent to the commercial sustained release capsule. A number of tacrolimus-loaded fast-dissolving solid dispersions containing various amounts of DOSS were prepared using the spray drying technique. Their solubility, dissolution and pharmacokinetics in rats were studied. DOSS increased drug solubility and dissolution in the solid dispersions. Compared with the drug powder, the solubility, dissolution and bioavailability of tacrolimus with the fast-dissolving solid dispersion containing tacrolimus/HP-β-CD/DOSS in the weight ratio of 5:40:4 were boosted by approximately 700-, 30- and 2-fold, respectively. Several tablet formulations were accomplished with this solid dispersion in combination with various ratios of HPMC/ethylcellulose. The release behaviour and pharmacokinetic studies in beagle dogs were assessed compared with the commercial prolonged release capsule. A decrease in HPMC/ethylcellulose ratios reduced the dissolution of tacrolimus from the tablets. Particularly, the tacrolimus-loaded prolonged release tablet consisting of fast-dissolving tacrolimus solid dispersion, HPMC, ethylcellulose and talc at the weight ratio of 20:66:112:2 exhibited a dissolution profile similar to that produced by the commercial prolonged release capsule. Furthermore, there were no significant differences in the AUC, Cmax, Tmax and MRT values between them in beagle dogs. Consequently, this tacrolimus-loaded prolonged release tablet might be bioequivalent to the tacrolimus-loaded commercial capsule. Copyright © 2013 Elsevier B.V. All rights reserved.

Strontium isotope fractionation during strontianite (SrCO3) dissolution, precipitation and at equilibrium

NASA Astrophysics Data System (ADS)

Mavromatis, Vasileios; Harrison, Anna L.; Eisenhauer, Anton; Dietzel, Martin

2017-12-01

In this study we examine the behavior of stable Sr isotopes between strontianite [SrCO3] and reactive fluid during mineral dissolution, precipitation, and at chemical equilibrium. Experiments were performed in batch reactors at 25 °C in 0.01 M NaCl solutions wherein the pH was adjusted by bubbling of a water saturated gas phase of pure CO2 or atmospheric air. The equilibrium Sr isotope fractionation between strontianite and fluid after dissolution of the solid under 1 atm CO2 atmosphere was estimated as Δ88/86SrSrCO3-fluid = δ88/86Sr SrCO3 - δ88/86Srfluid = -0.05 ± 0.01‰. On the other hand, during strontianite precipitation, an enrichment of the fluid phase in 88Sr, the heavy isotopomer, was observed. The evolution of the δ88/86Srfluid during strontianite precipitation can be modeled using a Rayleigh distillation approach and the estimated, kinetically driven, fractionation factor αSrCO3-fluid between solid and fluid is calculated to be 0.99985 ± 0.00003 corresponding to Δ88/86SrSrCO3-fluid = -0.15‰. The obtained results further support that under chemical equilibrium conditions between solid and fluid a continuous exchange of isotopes occurs until the system approaches isotopic equilibrium. This isotopic exchange is not limited to the outer surface layer of the strontianite crystal, but extends to ∼7-8 unit cells below the crystal surface. The behavior of Sr isotopes in this study is in excellent agreement with the concept of dynamic equilibrium and it suggests that the time needed for achievement of chemical equilibrium is generally shorter compared to that for isotopic equilibrium. Thus it is suggested that in natural Sr-bearing carbonates an isotopic change may still occur close to thermodynamic equilibrium, despite no observable change in aqueous elemental concentrations. As such, a secondary and ongoing change of Sr isotope signals in carbonate minerals caused by isotopic re-equilibration with fluids has to be considered in order to use Sr isotopes as environmental proxies in aquatic environments.

Atomistic modelling of evaporation and explosive boiling of thin film liquid argon over internally recessed nanostructured surface

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

Hasan, Mohammad Nasim, E-mail: nasim@me.buet.ac.bd.com; Shavik, Sheikh Mohammad, E-mail: shavik@me.buet.ac.bd.com; Rabbi, Kazi Fazle, E-mail: rabbi35.me10@gmail.com

2016-07-12

Molecular dynamics (MD) simulations have been carried out to investigate evaporation and explosive boiling phenomena of thin film liquid argon on nanostructured solid surface with emphasis on the effect of solid-liquid interfacial wettability. The nanostructured surface considered herein consists of trapezoidal internal recesses of the solid platinum wall. The wetting conditions of the solid surface were assumed such that it covers both the hydrophilic and hydrophobic conditions and hence effect of interfacial wettability on resulting evaporation and boiling phenomena was the main focus of this study. The initial configuration of the simulation domain comprised of a three phase system (solidmore » platinum, liquid argon and vapor argon) on which equilibrium molecular dynamics (EMD) was performed to reach equilibrium state at 90 K. After equilibrium of the three-phase system was established, the wall was set to different temperatures (130 K and 250 K for the case of evaporation and explosive boiling respectively) to perform non-equilibrium molecular dynamics (NEMD). The variation of temperature and density as well as the variation of system pressure with respect to time were closely monitored for each case. The heat flux normal to the solid surface was also calculated to illustrate the effectiveness of heat transfer for hydrophilic and hydrophobic surfaces in cases of both nanostructured surface and flat surface. The results obtained show that both the wetting condition of the surface and the presence of internal recesses have significant effect on normal evaporation and explosive boiling of the thin liquid film. The heat transfer from solid to liquid in cases of surface with recesses are higher compared to flat surface without recesses. Also the surface with higher wettability (hydrophilic) provides more favorable conditions for boiling than the low-wetting surface (hydrophobic) and therefore, liquid argon responds quickly and shifts from liquid to vapor phase faster in case of hydrophilic surface. The heat transfer rate is also much higher in case of hydrophilic surface.« less

Effect of aminoalkyl methacrylate copolymer E/HCl on in vivo absorption of poorly water-soluble drug.

PubMed

Yoshida, Takatsune; Kurimoto, Ippei; Yoshihara, Keiichi; Umejima, Hiroyuki; Ito, Naoki; Watanabe, Shunsuke; Sako, Kazuhiro; Kikuchi, Akihiko

2013-11-01

This study aimed to investigate in vivo absorption of tacrolimus formulated as a solid dispersion using Eudragit E®/HCl (E-SD). E-SD is an aminoalkyl methacrylate copolymer that can be dissolved under neutral pH conditions. E-SD was used alone as a solid dispersion carrier and/or was mixed with tacrolimus primarily dispersed with hydroxypropylmethylcellulose (HPMC). Tacrolimus was formulated with E-SD at several different ratios. Formulations with tacrolimus/E-SD ratio of 1/3 showed higher in vivo absorption, compared to tacrolimus dispersed in the excipients (primarily HPMC) found in commercially available tacrolimus capsules, using a rat in situ closed loop method. Good correlation was observed between in vitro drug solubility and in vivo drug absorption. In vitro solubility tests and rat oral absorption studies of tacrolimus/HPMC solid dispersion formulations were also conducted after mixing the HPMC dispersion with several ratios of E-SD. E-SD/tacrolimus/HPMC formulations yielded high in vitro drug solubility but comparatively low in vivo absorption. Dog oral absorption studies were conducted using capsules containing a formulation of tacrolimus/E-SD at a ratio of 1/5. The E-SD formulation-containing capsule showed higher in vivo drug absorption than tacrolimus dispersed in the standard HPMC capsule. These studies report enhancement of the in vivo absorption of a poorly water-soluble drug following dispersion with E-SD when compared to formulation in HPMC.

Evaluating the ready biodegradability of two poorly water-soluble substances: comparative approach of bioavailability improvement methods (BIMs).

PubMed

Sweetlove, Cyril; Chenèble, Jean-Charles; Barthel, Yves; Boualam, Marc; L'Haridon, Jacques; Thouand, Gérald

2016-09-01

Difficulties encountered in estimating the biodegradation of poorly water-soluble substances are often linked to their limited bioavailability to microorganisms. Many original bioavailability improvement methods (BIMs) have been described, but no global approach was proposed for a standardized comparison of these. The latter would be a valuable tool as part of a wider strategy for evaluating poorly water-soluble substances. The purpose of this study was to define an evaluation strategy following the assessment of different BIMs adapted to poorly water-soluble substances with ready biodegradability tests. The study was performed with two poorly water-soluble chemicals-a solid, anthraquinone, and a liquid, isodecyl neopentanoate-and five BIMs were compared to the direct addition method (reference method), i.e., (i) ultrasonic dispersion, (ii) adsorption onto silica gel, (iii) dispersion using an emulsifier, (iv) dispersion with silicone oil, and (v) dispersion with emulsifier and silicone oil. A two-phase evaluation strategy of solid and liquid chemicals was developed involving the selection of the most relevant BIMs for enhancing the biodegradability of tested substances. A description is given of a BIM classification ratio (R BIM), which enables a comparison to be made between the different test chemical sample preparation methods used in the various tests. Thereby, using this comparison, the BIMs giving rise to the greatest biodegradability were ultrasonic dispersion and dispersion with silicone oil or with silicone oil and emulsifier for the tested solid chemical, adsorption onto silica gel, and ultrasonic dispersion for the liquid one.

Chemical interactions of aluminum with aqueous silica at 25 degrees Celsius

USGS Publications Warehouse

Hem, John David; Roberson, C.E.; Lind, Carol J.; Polxer, W.L.

1973-01-01

Solutions containing from 10 -5 to 10 -2 moles per liter of aluminum and dissolved silica in various ratios were aged at pH levels between 4 and 10 at 25?C. A colloidal amorphous product having the composition of halloysite was produced in most solutions. It had a consistent and reversible equilibrium solubility equivalent to a standard free energy of formation of -8974 ? 1.0 kcal per mole for the formula A12Si2O5(OH)4. Some aging times were longer than 4 years, but most solutions gave consistent solubilities after only a few months of aging. Where silica concentrations were below about 10 -4 molar, microcrystalline gibbsite was formed below pH 6.0 and crystalline bayerite above pH 7.0, but only after much longer aging than was required for crystallization in silica-free solutions. Electron micrographs and diffraction patterns of the synthesized material indicate some crystallinity in the aluminosilicate, but no X-ray diffraction patterns could be obtained even in the material aged 4 years. Solubility relationships for solutions containing fluoride as well as silica and aluminum are explainable by using cryolite stabilities determined in previous work. Aluminum contents of 51 samples of water analyzed for other purposes are in reasonable agreement with the assumption of equilibrium with amorphous clay mineral species similar to the material synthesized in this work. Solubility calculations are summarized graphically for solutions of ionic strength of 0.01 and 0.10.

Solid dispersions of Myricetin with enhanced solubility: Formulation, characterization and crystal structure of stability-impeding Myricetin monohydrate crystals

NASA Astrophysics Data System (ADS)

Mureşan-Pop, M.; Pop, M. M.; Borodi, G.; Todea, M.; Nagy-Simon, T.; Simon, S.

2017-08-01

Three solid dispersion forms of Myricetin combined with the Polyvinylpyrrolidone were successfully prepared by spray drying method, and characterized by X-ray powder diffraction, thermal analysis, infrared spectroscopy and optical microscopy. Zeta potential measurements provided indications on solid dispersions stability in aqueous suspension related to their storage at elevated temperature and relative humidity, which depends on the Myricetin load. By increase of Myricetin load, the stability of the solid dispersion is impeded due to growth of Myricetin monohydrate crystals. The amorphous dispersions with 10% and 50% Myricetin load are stable and, compared to pure Myricetin, their aqueous solubility is enhanced by a factor of 47 and 13, respectively. The dispersion with 80% Myricetin load is unstable on storage, and this behavior acts in conjunction with the development of Myricetin monohydrate crystals. Single-crystal X-ray diffraction results obtained for Myricetin monohydrate reveal a structure of an infinite 2D network of hydrogen-bonded molecules involving all six hydroxyl groups of Myricetin. The water molecules are positioned in between the infinite chains, and contribute via H-bonds to robust crystal packing. The calculated needle-like morphology of monohydrate form is in agreement with the optical microscopy results. The study shows that the solid amorphous dispersions with up to 50% Myricetin load are a viable option for achieving substantial solubility improvement of Myricetin, and supports their potential use in pharmaceutical applications.

Biopharmaceutics classification of puerarin and comparison of perfusion approaches in rats.

PubMed

Li, Hewei; Dong, Ling; Liu, Yang; Wang, Guopeng; Wang, Gang; Qiao, Yanjiang

2014-05-15

The present study was conducted to characterize the biopharmaceutics classification system (BCS) category of puerarin in terms of intrinsic dissolution rate (IDR) and rat intestinal permeability and to investigate the poor intestinal absorption probably related to the drug metabolism in the gut wall of rats. Equilibrium solubility of puerarin was determined in various phosphate buffers and water, and IDR was estimated by measuring the dissolution of a non-disintegrating compact. Intestinal permeability (Peff and Pblood) of puerarin was determined using the technology of in situ single-pass intestinal perfusion (SPIP) and intestinal perfusion with venous sampling (IPVS) in fasted rats. Metabolism of puerarin in intestinal tissue was tested by S9 incubation in vitro. The aqueous solubility of puerarin in phosphate buffers and water was good with a maximum solubility of 7.56 mg/mL at pH 7.4. Obtained IDR values of puerarin were in the range of 0.360-1.088 mg/min/cm(2), with maximum and minimum IDR value of pH 7.4 and pH 4.0, respectively. The Peff was 1.252 × 10(-5)cm/s determined by SPIP and the Pblood was 0.068×10(-5)cm/s by IPVS in jejunum at puerarin 80 μg/mL. The metabolism rate of puerarin determined by the intestinal S9 fraction indicated that the gut wall metabolism of puerarin is one cause of poor absorption. According to the proposed classification of drugs and the results obtained from equilibrium solubility, IDR, Peff and Pblood, it is concluded that puerarin could be categorized IV drug of the BCS based on its low solubility and low intestinal permeability values. Copyright © 2014 Elsevier B.V. All rights reserved.

Solid state solubility of copper oxides in hydroxyapatite

NASA Astrophysics Data System (ADS)

Zykin, Mikhail A.; Vasiliev, Alexander V.; Trusov, Lev A.; Dinnebier, Robert E.; Jansen, Martin; Kazin, Pavel E.

2018-06-01

Samples containing copper oxide doped hydroxyapatite with the composition Ca10(PO4)6(CuxOH1-x-δ)2, x = 0.054 - 0.582, in the mixture with CuO/Cu2O were prepared by a solid-state high-temperature treatment at varying annealing temperatures and at different partial water vapor and oxygen pressures. The crystal structures of the apatite compounds were refined using powder X-ray diffraction patterns and the content of copper ions x in the apatite was determined. Copper ions enter exclusively into the apatite trigonal channels formally substituting protons of OH-groups and the hexagonal cell parameters grow approximately linearly with x, the channel volume mostly expanding while the remaining volume of the crystal lattice changing only slightly. The equilibrium copper content in the apatite increases drastically, by almost a factor of 10 with the annealing temperature rising from 800° to 1200°C. The reduction of the water partial pressure leads to a further increase of x, while the dependence of x on the oxygen partial pressure exhibits a maximum. The observed relations are consistent with the proposed chemical reactions implying the copper introduction is followed by the release of a considerable quantity of gaseous products - water and oxygen. The analysis of interatomic distances suggests that the maximum content of copper ions in the channel cannot exceed 2/3.

Phase diagrams and physicochemical properties of Li+,K+(Rb+)//borate-H2O systems at 323 K

NASA Astrophysics Data System (ADS)

Feng, Shan; Yu, Xudong; Cheng, Xinglong; Zeng, Ying

2017-11-01

The phase and physicochemical properties diagrams of Li+,K+(Rb+)//borate-H2O systems at 323 K were constructed using the experimentally measured solubilities, densities, and refractive indices. The Schreinemakers' wet residue method and the X-ray diffraction were used for the determination of the compositions of solid phase. Results show that these two systems belong to the hydrate I type, with no solid solution or double salt formation. The borate phases formed in our experiments are RbB5O6(OH)4 · 2H2O, Li2B4O5(OH)4 · H2O, and K2B4O5(OH)4 · 2H2O. Comparison between the stable phase diagrams of the studied system at 288, 323, and 348 K show that in this temperature range, the crystallization form of salts do not changed. With the increase in temperature, the crystallization field of Li2B4O5(OH)4 · H2O salt at 348 K is obviously larger than that at 288 K. In the Li+,K+(Rb+)//borate-H2O systems, the densities and refractive indices of the solutions (at equilibrium) increase along with the mass fraction of K2B4O7 (Rb2B4O7), and reach the maximum values at invariant point E.

Controlled poorly soluble drug release from solid self-microemulsifying formulations with high viscosity hydroxypropylmethylcellulose.

PubMed

Yi, Tao; Wan, Jiangling; Xu, Huibi; Yang, Xiangliang

2008-08-07

The objective of this work was the development of a controlled release system based on self-microemulsifying mixture aimed for oral delivery of poorly water-soluble drugs. HPMC-based particle formulations were prepared by spray drying containing a model drug (nimodipine) of low water solubility and hydroxypropylmethylcellulose (HPMC) of high viscosity. One type of formulations contained nimodipine mixed with HPMC and the other type of formulations contained HPMC and nimodipine dissolved in a self-microemulsifying system (SMES) consisting of ethyl oleate, Cremophor RH 40 and Labrasol. Based on investigation by transmission electron microscopy (TEM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and X-ray powder diffraction, differences were found in the particle structure between both types of formulations. In vitro release was performed and characterized by the power law. Nimodipine release from both types of formulations showed a controlled release profile and the two power law parameters, n and K, correlated to the viscosity of HPMC. The parameters were also influenced by the presence of SMES. For the controlled release solid SMES, oil droplets containing dissolved nimodipine diffused out of HPMC matrices following exposure to aqueous media. Thus, it is possible to control the in vitro release of poorly soluble drugs from solid oral dosage forms containing SMES.

Revealing facts behind spray dried solid dispersion technology used for solubility enhancement

PubMed Central

Patel, Bhavesh B.; Patel, Jayvadan K.; Chakraborty, Subhashis; Shukla, Dali

2013-01-01

Poor solubility and bioavailability of an existing or newly synthesized drug always pose challenge in the development of efficient pharmaceutical formulation. Numerous technologies can be used to improve the solubility and among them amorphous solid dispersion based spray drying technology can be successfully useful for development of product from lab scale to commercial scale with a wide range of powder characteristics. Current review deals with the importance of spray drying technology in drug delivery, basically for solubility and bioavailability enhancement. Role of additives, selection of polymer, effect of process and formulation parameters, scale up optimization, and IVIVC have been covered to gain the interest of readers about the technology. Design of experiment (DoE) to optimize the spray drying process has been covered in the review. A lot more research work is required to evaluate spray drying as a technology for screening the right polymer for solid dispersion, especially to overcome the issue related to drug re-crystallization and to achieve a stable product both in vitro and in vivo. Based on the recent FDA recommendation, the need of the hour is also to adopt Quality by Design approach in the manufacturing process to carefully optimize the spray drying technology for its smooth transfer from lab scale to commercial scale. PMID:27134535

A 5-day method for determination of soluble silicon concentrations in nonliquid fertilizer materials using a sodium carbonate-ammonium nitrate extractant followed by visible spectroscopy with heteropoly blue analysis: single-laboratory validation.

PubMed

Sebastian, Dennis; Rodrigues, Hugh; Kinsey, Charles; Korndörfer, Gaspar; Pereira, Hamilton; Buck, Guilherme; Datnoff, Lawrence; Miranda, Stephen; Provance-Bowley, Mary

2013-01-01

A 5-day method for determining the soluble silicon (Si) concentrations in nonliquid fertilizer products was developed using a sodium carbonate (Na2CO3)-ammonium nitrate (NH4NO3) extractant followed by visible spectroscopy with heteropoly blue analysis at 660 nm. The 5-Day Na2CO3-NH4NO3 Soluble Si Extraction Method can be applied to quantify the plant-available Si in solid fertilizer products at levels ranging from 0.2 to 8.4% Si with an LOD of 0.06%, and LOQ of 0.20%. This Si extraction method for fertilizers correlates well with plant uptake of Si (r2 = 0.96 for a range of solid fertilizers) and is applicable to solid Si fertilizer products including blended products and beneficial substances. Fertilizer materials can be processed as received using commercially available laboratory chemicals and materials at ambient laboratory temperatures. The single-laboratory validation of the 5-Day Na2CO3-NH4NO3 Soluble Si Extraction Method has been approved by The Association of American Plant Food Control Officials for testing nonliquid Si fertilizer products.

Revealing facts behind spray dried solid dispersion technology used for solubility enhancement.

PubMed

Patel, Bhavesh B; Patel, Jayvadan K; Chakraborty, Subhashis; Shukla, Dali

2015-09-01

Poor solubility and bioavailability of an existing or newly synthesized drug always pose challenge in the development of efficient pharmaceutical formulation. Numerous technologies can be used to improve the solubility and among them amorphous solid dispersion based spray drying technology can be successfully useful for development of product from lab scale to commercial scale with a wide range of powder characteristics. Current review deals with the importance of spray drying technology in drug delivery, basically for solubility and bioavailability enhancement. Role of additives, selection of polymer, effect of process and formulation parameters, scale up optimization, and IVIVC have been covered to gain the interest of readers about the technology. Design of experiment (DoE) to optimize the spray drying process has been covered in the review. A lot more research work is required to evaluate spray drying as a technology for screening the right polymer for solid dispersion, especially to overcome the issue related to drug re-crystallization and to achieve a stable product both in vitro and in vivo. Based on the recent FDA recommendation, the need of the hour is also to adopt Quality by Design approach in the manufacturing process to carefully optimize the spray drying technology for its smooth transfer from lab scale to commercial scale.

Near infrared spectral linearisation in quantifying soluble solids content of intact carambola.

PubMed

Omar, Ahmad Fairuz; MatJafri, Mohd Zubir

2013-04-12

This study presents a novel application of near infrared (NIR) spectral linearisation for measuring the soluble solids content (SSC) of carambola fruits. NIR spectra were measured using reflectance and interactance methods. In this study, only the interactance measurement technique successfully generated a reliable measurement result with a coefficient of determination of (R2) = 0.724 and a root mean square error of prediction for (RMSEP) = 0.461° Brix. The results from this technique produced a highly accurate and stable prediction model compared with multiple linear regression techniques.

Near Infrared Spectral Linearisation in Quantifying Soluble Solids Content of Intact Carambola

PubMed Central

Omar, Ahmad Fairuz; MatJafri, Mohd Zubir

2013-01-01

This study presents a novel application of near infrared (NIR) spectral linearisation for measuring the soluble solids content (SSC) of carambola fruits. NIR spectra were measured using reflectance and interactance methods. In this study, only the interactance measurement technique successfully generated a reliable measurement result with a coefficient of determination of (R2) = 0.724 and a root mean square error of prediction for (RMSEP) = 0.461° Brix. The results from this technique produced a highly accurate and stable prediction model compared with multiple linear regression techniques. PMID:23584118

Maturity assessment of compost from municipal solid waste through the study of enzyme activities and water-soluble fractions.

PubMed

Castaldi, Paola; Garau, Giovanni; Melis, Pietro

2008-01-01

In this work the dynamics of biochemical (enzymatic activities) and chemical (water-soluble fraction) parameters during 100 days of municipal solid wastes composting were studied to evaluate their suitability as tools for compost characterization. The hydrolase (protease, urease, cellulase, beta-glucosidase) and dehydrogenase activities were characterized by significant changes during the first 2 weeks of composting, because of the increase of easily decomposable organic compounds. After the 4th week a "maturation phase" was identified in which the enzymatic activities tended to gently decrease, suggesting the stabilisation of organic matter. Also the water-soluble fractions (water-soluble carbon, nitrogen, carbohydrates and phenols), which are involved in many degradation processes, showed major fluctuations during the first month of composting. The results obtained showed that the hydrolytic activities and the water-soluble fractions did not vary statistically during the last month of composting. Significant correlations between the enzymatic activities, as well as between enzyme activities and water-soluble fractions, were also highlighted. These results highlight the suitability of both enzymatic activities and water soluble fractions as suitable indicators of the state and evolution of the organic matter during composting. However, since in the literature the amount of each activity or fraction at the end of composting depends on the raw material used for composting, single point determinations appear inadequate for compost characterization. This emphasizes the importance of the characterization of the dynamics of enzymatic activities and water-soluble fractions during the process.

Methane and carbon at equilibrium in source rocks

PubMed Central

2013-01-01

Methane in source rocks may not exist exclusively as free gas. It could exist in equilibrium with carbon and higher hydrocarbons: CH4 + C < = > Hydrocarbon. Three lines of evidence support this possibility. 1) Shales ingest gas in amounts and selectivities consistent with gas-carbon equilibrium. There is a 50% increase in solid hydrocarbon mass when Fayetteville Shale is exposed to methane (450 psi) under moderate conditions (100°C): Rock-Eval S2 (mg g-1) 8.5 = > 12.5. All light hydrocarbons are ingested, but with high selectivity, consistent with competitive addition to receptor sites in a growing polymer. Mowry Shale ingests butane vigorously from argon, for example, but not from methane under the same conditions. 2) Production data for a well producing from Fayetteville Shale declines along the theoretical curve for withdrawing gas from higher hydrocarbons in equilibrium with carbon. 3) A new general gas-solid equilibrium model accounts for natural gas at thermodynamic equilibrium, and C6-C7 hydrocarbons constrained to invariant compositions. The results make a strong case for methane in equilibrium with carbon and higher hydrocarbons. If correct, the higher hydrocarbons in source rocks are gas reservoirs, raising the possibility of substantially more gas in shales than analytically apparent, and far more gas in shale deposits than currently recognized. PMID:24330266

Haste Makes Waste: The Interplay Between Dissolution and Precipitation of Supersaturating Formulations.

PubMed

Sun, Dajun D; Lee, Ping I

2015-11-01

Contrary to the early philosophy of supersaturating formulation design for oral solid dosage forms, current evidence shows that an exceedingly high rate of supersaturation generation could result in a suboptimal in vitro dissolution profile and subsequently could reduce the in vivo oral bioavailability of amorphous solid dispersions. In this commentary, we outline recent research efforts on the specific effects of the rate and extent of supersaturation generation on the overall kinetic solubility profiles of supersaturating formulations. Additional insights into an appropriate definition of sink versus nonsink dissolution conditions and the solubility advantage of amorphous pharmaceuticals are also highlighted. The interplay between dissolution and precipitation kinetics should be carefully considered in designing a suitable supersaturating formulation to best improve the dissolution behavior and oral bioavailability of poorly water-soluble drugs.

Enhancing the bioavailability of mebendazole by integrating the principles solid dispersion and nanocrystal techniques, for safe and effective management of human echinococcosis.

PubMed

Chaudhary, Sushant; Garg, Tarun; Rath, Goutam; Murthy, Rs Rayasa; Goyal, Amit K

2016-05-01

The method based on integrating the principles of solid dispersion and nanocrystal techniques was developed to prepare polymer crystals (PCs) of mebendazole (MBZ) and polyethylene glycol (PEG). Powder X-Ray diffraction (PXRD) of the PC crystals shows the required integrated crystalline and amorphous regions. The in vitro solubility studies showed a 32-fold increase in the solubility of the drug. Tests of dissolution of the PCs showed that the crystals have an enhanced dissolution rate in comparison to those in the MF. The results of the pharmacokinetic study showed a 2.12-fold increase in the bioavailability of the drug. Thus, the present study has proved the potential in enhancing solubility, dissolution, and bioavailability of the drug.

Extraction of effective solid-liquid interfacial free energies for full 3D solid crystallites from equilibrium MD simulations

DOE PAGES

Zepeda-Ruiz, L. A.; Sadigh, B.; Chernov, A. A.; ...

2017-11-21

Molecular dynamics simulations of an embedded atom copper system in the NPH ensemble are used to study the e ective solid-liquid interfacial free energy of quasispherical solid crystals within a liquid. This is within the larger context of MD simulations of this system undergoing solidi cation, where single individually-prepared crystallites of di erent sizes grow until they reach a thermodynamically stable nal state. The resulting equilibrium shapes possess the full structural details expected for solids with weakly anisotropic surface free energies (in these cases, ~5 % radial attening and rounded [111] octahedral faces). The simplifying assumption of sphericity and perfectmore » isotropy leads to an e ective interfacial free energy as appearing in the Gibbs-Thomson equation, which we determine to be ~179 erg/cm 2, roughly independent of crystal size for radii in the 50 - 250 A range. This quantity may be used in atomistically-informed models of solidi cation kinetics for this system.« less

Extraction of effective solid-liquid interfacial free energies for full 3D solid crystallites from equilibrium MD simulations

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

Zepeda-Ruiz, L. A.; Sadigh, B.; Chernov, A. A.

Molecular dynamics simulations of an embedded atom copper system in the NPH ensemble are used to study the e ective solid-liquid interfacial free energy of quasispherical solid crystals within a liquid. This is within the larger context of MD simulations of this system undergoing solidi cation, where single individually-prepared crystallites of di erent sizes grow until they reach a thermodynamically stable nal state. The resulting equilibrium shapes possess the full structural details expected for solids with weakly anisotropic surface free energies (in these cases, ~5 % radial attening and rounded [111] octahedral faces). The simplifying assumption of sphericity and perfectmore » isotropy leads to an e ective interfacial free energy as appearing in the Gibbs-Thomson equation, which we determine to be ~179 erg/cm 2, roughly independent of crystal size for radii in the 50 - 250 A range. This quantity may be used in atomistically-informed models of solidi cation kinetics for this system.« less

Spatial Control of Cell Transfection Using Soluble or Solid-Phase Redox Agents and a Redox-Active Ferrocenyl Lipid

PubMed Central

Aytar, Burcu S.; Muller, John P. E.; Kondo, Yukishige; Abbott, Nicholas L.; Lynn, David M.

2013-01-01

We report principles for active, user-defined control over the locations and timing with which DNA is expressed in cells. Our approach exploits unique properties of a ferrocenyl cationic lipid that is inactive when oxidized, but active when chemically reduced. We show that methods that exert spatial control over the administration of reducing agents can lead to local activation of lipoplexes and spatial control over gene expression. The versatility of this approach is demonstrated using both soluble and solid-phase reducing agents. These methods provide control over cell transfection, including methods for remote activation and the patterning of expression using solid-phase redox agents, that are difficult to achieve using conventional lipoplexes. PMID:23965341

Spatial control of cell transfection using soluble or solid-phase redox agents and a redox-active ferrocenyl lipid.

PubMed

Aytar, Burcu S; Muller, John P E; Kondo, Yukishige; Abbott, Nicholas L; Lynn, David M

2013-09-11

We report principles for active, user-defined control over the locations and timing with which DNA is expressed in cells. Our approach exploits unique properties of a ferrocenyl cationic lipid that is inactive when oxidized, but active when chemically reduced. We show that methods that exert spatial control over the administration of reducing agents can lead to local activation of lipoplexes and spatial control over gene expression. The versatility of this approach is demonstrated using both soluble and solid-phase reducing agents. These methods provide control over cell transfection, including methods for remote activation and the patterning of expression using solid-phase redox agents, that are difficult to achieve using conventional lipoplexes.

Heat Transfer and Fluid Transport of Supercritical CO 2 in Enhanced Geothermal System with Local Thermal Non-equilibrium Model

DOE PAGES

Zhang, Le; Luo, Feng; Xu, Ruina; ...

2014-12-31

The heat transfer and fluid transport of supercritical CO 2 in enhanced geothermal system (EGS) is studied numerically with local thermal non-equilibrium model, which accounts for the temperature difference between solid matrix and fluid components in porous media and uses two energy equations to describe heat transfer in the solid matrix and in the fluid, respectively. As compared with the previous results of our research group, the effect of local thermal non-equilibrium mainly depends on the volumetric heat transfer coefficient ah, which has a significant effect on the production temperature at reservoir outlet and thermal breakthrough time. The uniformity ofmore » volumetric heat transfer coefficient ah has little influence on the thermal breakthrough time, but the temperature difference become more obvious with time after thermal breakthrough with this simulation model. The thermal breakthrough time reduces and the effect of local thermal non-equilibrium becomes significant with decreasing ah.« less

The mechanisms of drug release from solid dispersions in water-soluble polymers.

PubMed

Craig, Duncan Q M

2002-01-14

Solid dispersions in water-soluble carriers have attracted considerable interest as a means of improving the dissolution rate, and hence possibly bioavailability, of a range of hydrophobic drugs. However, despite the publication of numerous original papers and reviews on the subject, the mechanisms underpinning the observed improvements in dissolution rate are not yet understood. In this review the current consensus with regard to the solid-state structure and dissolution properties of solid dispersions is critically assessed. In particular the theories of carrier- and drug-controlled dissolution are highlighted. A model is proposed whereby the release behaviour from the dispersions may be understood in terms of the dissolution or otherwise of the drug into the concentrated aqueous polymer layer adjacent to the solid surface, including a derivation of an expression to describe the release of intact particles from the dispersions. The implications of a deeper understanding of the dissolution mechanisms are discussed, with particular emphasis on optimising the choice of carrier and manufacturing method and the prediction of stability problems.

Capillary liquid chromatographic analysis of fat-soluble vitamins and beta-carotene in combination with in-tube solid-phase microextraction.

PubMed

Xu, Hui; Jia, Li

2009-01-01

A capillary liquid chromatography (CLC) system with UV/vis detection was coupled with an in-tube solid-phase microextraction (SPME) device for the analysis of fat-soluble vitamins and beta-carotene. A monolithic silica-ODS column was used as the extraction medium. An optical-fiber flow cell with a long light path in the UV/vis detector was utilized to further enhance the detection sensitivity. In the in-tube SPME/CLC system, the pre-condition of the extraction column and the effect of the injection volume were investigated. The detection limits (LOD) for the fat-soluble vitamins and beta-carotene were in the range from 1.9 to 173 ng/mL based on the signal-to-noise ratio of 3 (S/N=3). The relative standard deviations of migration time and peak area for each analyte were less than 5.0%. The method was applied to the analysis of fat-soluble vitamins and beta-carotene contents in corns.

Preparation and investigation of mefenamic acid - polyethylene glycol - sucrose ester solid dispersions.

PubMed

Fülöp, Ibolya; Gyéresi, Árpád; Kiss, Lóránd; Deli, Mária A; Croitoru, Mircea Dumitru; Szabó-Révész, Piroska; Aigner, Zoltán

2015-12-01

Mefenamic acid (MA) is a widely used non-steroidal antiinflammatory (NSAID) drug. The adverse effects typical of NSAIDs are also present in the case of MA, partly due to its low water solubility. The aim of this study was to increase the water solubility of MA in order to influence its absorption and bioavailability. Solid dispersions of MA were prepared by the melting method using polyethylene glycol 6000 and different types (laurate, D-1216; palmitate, P-1670; stearate, S-1670) and amounts of sucrose esters as carriers. The X-ray diffraction results show that MA crystals were not present in the products. Dissolution tests carried out in artificial intestinal juice showed that the product containing 10 % D-1216 increased water solubility about 3 times. The apparent permeability coefficient of MA across human Caco-2 intestinal epithelial cell layers was high and, despite the difference in solubility, there was no further increase in drug penetration in the presence of the applied additives.

Nootkatone encapsulation by cyclodextrins: Effect on water solubility and photostability.

PubMed

Kfoury, Miriana; Landy, David; Ruellan, Steven; Auezova, Lizette; Greige-Gerges, Hélène; Fourmentin, Sophie

2017-12-01

Nootkatone (NO) is a sesquiterpenoid volatile flavor, used in foods, cosmetics and pharmaceuticals, possessing also insect repellent activity. Its application is limited because of its low aqueous solubility and stability; this could be resolved by encapsulation in cyclodextrins (CDs). This study evaluated the encapsulation of NO by CDs using phase solubility studies, Isothermal Titration Calorimetry, Nuclear Magnetic Resonance spectroscopy and molecular modeling. Solid CD/NO inclusion complex was prepared and characterized for encapsulation efficiency and loading capacity using UV-Visible. Thermal properties were investigated by thermogravimetric-differential thermal analysis and release studies were performed using multiple headspace extraction. Formation constants (K f ) proved the formation of stable inclusion complexes. NO aqueous solubility, photo- and thermal stability were enhanced and the release could be insured from solid complex in aqueous solution. This suggests that CDs are promising carrier to improve NO properties and, consequently, to enlarge its use in foods, cosmetics, pharmaceuticals and agrochemicals preparations. Copyright © 2016 Elsevier Ltd. All rights reserved.

SU-G-IeP2-11: Measurement of Equilibrium Doses in Computed Tomography: Comparative Study of Ionization and Solid-State Dosimeters

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

Matsubara, K; Kobayashi, A; Koshida, K

Purpose: This study aimed to compare equilibrium doses in computed tomography (CT) obtained from ionization and solid-state dosimeters based on the approach presented in the American Association of Physicists in Medicine Report No. 111. The equilibrium doses were also compared with the CT dose index (CTDI) using a 10-cm pencil-type ionization chamber. Methods: A 0.6-cm{sup 3} ionization chamber (10X6-0.6CT) and a solid-state detector (CT Dose Profiler [CTDP]) were calibrated using 80–130 kVp X-ray beams (44.5–55.8 keV of effective energy) from a radiography X-ray machine against a reference ionization dosimeter. Three 16- or 32-cm diameter polymethyl methacrylate (PMMA) phantoms were assembledmore » consecutively on the CT table to obtain equilibrium doses. The 10X6-0.6CT and CTDP were each placed at the center and peripheral holes (12, 3, 6, and 9 o’clock) of the z-center. Central and mean peripheral equilibrium doses were obtained by scanning with longitudinal translation for a length less than the entire phantom length. CTDIs were also obtained with a 10-cm pencil-type ionization chamber (10X6-0.6CT) by scanning a 16- or 32-cm diameter PMMA phantom with one rotation of the X-ray tube. Results: The difference of calibration coefficients between 80 and 130 kVp was 21.1% for the CTDP and 0.7% for the 10X6-0.6CT. The equilibrium doses were higher than the CTDI. Especially at the peripheral positions and 80 kVp, the 10X6-0.6CT showed higher equilibrium doses than CTDP. However, the relation between the equilibrium dose for the 10X6-0.6CT and the CTDP differed depending on the phantom size, scanner type, measurement position, and selected acquisition parameters. Conclusion: The use of a 10-cm pencil-type ionization chamber causes underestimation of the equilibrium dose. The CTDP has a higher energy dependency than the 10X6-0.6CT. The obtained equilibrium doses are different between the 10X6-0.6CT and the CTDP depending on various conditions. This study was supported by JSPS KAKENHI Grant Number 15K09887.« less

Retardation of uranium and thorium by a cementitious backfill developed for radioactive waste disposal.

PubMed

Felipe-Sotelo, M; Hinchliff, J; Field, L P; Milodowski, A E; Preedy, O; Read, D

2017-07-01

The solubility of uranium and thorium has been measured under the conditions anticipated in a cementitious, geological disposal facility for low and intermediate level radioactive waste. Similar solubilities were obtained for thorium in all media, comprising NaOH, Ca(OH) 2 and water equilibrated with a cement designed as repository backfill (NRVB, Nirex Reference Vault Backfill). In contrast, the solubility of U(VI) was one order of magnitude higher in NaOH than in the remaining solutions. The presence of cellulose degradation products (CDP) results in a comparable solubility increase for both elements. Extended X-ray Absorption Fine Structure (EXAFS) data suggest that the solubility-limiting phase for uranium corresponds to a becquerelite-type solid whereas thermodynamic modelling predicts a poorly crystalline, hydrated calcium uranate phase. The solubility-limiting phase for thorium was ThO 2 of intermediate crystallinity. No breakthrough of either uranium or thorium was observed in diffusion experiments involving NRVB after three years. Nevertheless, backscattering electron microscopy and microfocus X-ray fluorescence confirmed that uranium had penetrated about 40 μm into the cement, implying active diffusion governed by slow dissolution-precipitation kinetics. Precise identification of the uranium solid proved difficult, displaying characteristics of both calcium uranate and becquerelite. Copyright © 2017 Elsevier Ltd. All rights reserved.

Experimental Solubility Approach to Determine PDMS-Water Partition Constants and PDMS Activity Coefficients.

PubMed

Grant, Sharon; Schacht, Veronika J; Escher, Beate I; Hawker, Darryl W; Gaus, Caroline

2016-03-15

Freely dissolved aqueous concentration and chemical activity are important determinants of contaminant transport, fate, and toxic potential. Both parameters are commonly quantified using Solid Phase Micro-Extraction (SPME) based on a sorptive polymer such as polydimethylsiloxane (PDMS). This method requires the PDMS-water partition constants, KPDMSw, or activity coefficient to be known. For superhydrophobic contaminants (log KOW >6), application of existing methods to measure these parameters is challenging, and independent measures to validate KPDMSw values would be beneficial. We developed a simple, rapid method to directly measure PDMS solubilities of solid contaminants, SPDMS(S), which together with literature thermodynamic properties was then used to estimate KPDMSw and activity coefficients in PDMS. PDMS solubility for the test compounds (log KOW 7.2-8.3) ranged over 3 orders of magnitude (4.1-5700 μM), and was dependent on compound class. For polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins (PCDDs), solubility-derived KPDMSw increased linearly with hydrophobicity, consistent with trends previously reported for less chlorinated congeners. In contrast, subcooled liquid PDMS solubilities, SPDMS(L), were approximately constant within a compound class. SPDMS(S) and KPDMSw can therefore be predicted for a compound class with reasonable robustness based solely on the class-specific SPDMS(L) and a particular congener's entropy of fusion, melting point, and aqueous solubility.

Lipid immiscibility and biophysical properties: Molecular order within and among unit cell volumes

USDA-ARS?s Scientific Manuscript database

Saturated and unsaturated fatty acids clearly have a discrete chemical structure in the solid state. In a saturated solution, the solid state and solution state are in chemical equilibrium. The lipid stearic acid packs in unit cell volumes in the liquid state as well as in the solid state. Normal...

Thermodynamic characterization of hydrogen interaction with iridium polyhydride complexes

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

Zidan, R.A.; Rocheleau, R.E.

1999-01-01

Hydrogen interaction with solid iridium complexes IrXH{sub 2}(PPr3{sup i}){sub 2} (X=Cl, I) was investigated. Gaseous hydrogen was found to react reversibly with solid chloro-iridium complex IrClH{sub 2}(PPr3{sup i}){sub 2} forming IrClH{sub 2}(PPr3{sup i}){sub 2}H{sub 2}. The relative partial molal enthalpy and entropy were obtained from equilibrium isotherms at different hydrogen concentrations. The decrease in entropy with increasing hydrogen concentration and the absence of plateaus in the equilibrium isotherms were consistent with a single phase solid solution with two chemical components. Hydrogen release from solid iodo-iridium complex IrIH{sub 2}(PPr3{sup i}){sub 2}H{sub 2} was not observed at temperatures up to 350 K,more » indicating stronger hydrogen bonding. {copyright} {ital 1999 Materials Research Society.}« less

Bench-Scale and Pilot-Scale Treatment Technologies for the Removal of Total Dissolved Solids from Coal Mine Water: A Review

EPA Science Inventory

Coal mine water (CMW) is typically treated to remove suspended solids, acidity, and soluble metals, but high concentrations of total dissolved solids (TDS) have been reported to impact the environment at several CMW discharge points. Consequently, various states have establishe...

Microparticles Containing Curcumin Solid Dispersion: Stability, Bioavailability and Anti-Inflammatory Activity.

PubMed

Teixeira, C C C; Mendonça, L M; Bergamaschi, M M; Queiroz, R H C; Souza, G E P; Antunes, L M G; Freitas, L A P

2016-04-01

This work aimed at improving the solubility of curcumin by the preparation of spray-dried ternary solid dispersions containing Gelucire®50/13-Aerosil® and quantifying the resulting in vivo oral bioavailability and anti-inflammatory activity. The solid dispersion containing 40% of curcumin was characterised by calorimetry, infrared spectroscopy and X-ray powder diffraction. The solubility and dissolution rate of curcumin in aqueous HCl or phosphate buffer improved up to 3600- and 7.3-fold, respectively. Accelerated stability test demonstrated that the solid dispersion was stable for 9 months. The pharmacokinetic study showed a 5.5-fold increase in curcumin in rat blood plasma when compared to unprocessed curcumin. The solid dispersion also provided enhanced anti-inflammatory activity in rat paw oedema. Finally, the solid dispersion proposed here is a promising way to enhance curcumin bioavailability at an industrial pharmaceutical perspective, since its preparation applies the spray drying, which is an easy to scale up technique. The findings herein stimulate further in vivo evaluations and clinical tests as a cancer and Alzheimer chemoprevention agent.

Preparation, characterization and in vitro evaluation of solid dispersions containing docetaxel.

PubMed

Chen, Jie; Qiu, Liyan; Hu, Minxin; Jin, Yi; Han, Jieru

2008-06-01

Solid dispersions using water-soluble carriers were studied for improving the dissolution of docetaxel, a poorly soluble compound. In order to obtain the most optimized formulation, we prepared many solid dispersions with different carriers, different solvents, or at a series of drug-to-carrier ratios, and compared their dissolution. The accumulative dissolution of docetaxel from poloxamer 188 was more excellent than that from PVP(k30) and glyceryl monostearate, and the dissolution of docetaxel from solid dispersion was markedly higher than that of pure docetaxel; meanwhile the increased dissolution was partly dependent on the ratios of docetaxel and poloxamer 188. The ethanol used to prepare solid dispersion is of more significant effect on the dissolution of docetaxel than that of acetone. The docetaxel/poloxamer 188 system was characterized by differential scanning calorimetry (DSC), X-ray diffractometry (XRD), and environmental scanning electron microscope (ESEM). The results of DSC, XRD, and ESEM analyses of docetaxel/poloxamer 188 system showed that there are intermolecular interactions between docetaxel and poloxamer, and the crystallinity of docetaxel disappeared. These results show that solid dispersion is a promising approach of developing docetaxel drug formulates.

Effect of adsorption on the surface tensions of solid-fluid interfaces.

PubMed

Ward, C A; Wu, Jiyu

2007-04-12

A method is proposed for determining the surface tensions of a solid in contact with either a liquid or a vapor. Only an equilibrium adsorption isotherm at the solid-vapor interface needs to be added to Gibbsian thermodynamics to obtain the expressions for the solid-vapor and the solid-liquid surface tensions, gamma[1](SV) and gamma[1](SL), respectively. An equilibrium adsorption isotherm relation is formulated that has the essential property of not predicting an infinite amount adsorbed when the pressure is equal to the saturation-vapor pressure. Five different solid-vapor systems from the literature are examined, and found to be well described by the new isotherm relation. The surface-tension expressions obtained from the isotherm relation are examined by determining the surface tension of the solid in the absence of adsorption, gamma[1](S0), a material property of a solid surface. The value of gamma[1](S0) can be determined by adsorbing different vapors on the same solid, determining the isotherm parameters in each case, and then from the expression for gamma[1](SV) taking the limit of the pressure vanishing to determine gamma[1](S0). From previously reported measurements of benzene and of n-hexane adsorbing on graphitized carbon, the same value of gamma[1](S0) is obtained.

Solid solubility, phase transitions, thermal expansion, and compressibility in Sc{sub 1−x}Al{sub x}F{sub 3}

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

Morelock, Cody R.; Gallington, Leighanne C.; Wilkinson, Angus P., E-mail: angus.wilkinson@chemistry.gatech.edu

2015-02-15

With the goal of thermal expansion control, the synthesis and properties of Sc{sub 1−x}Al{sub x}F{sub 3} were investigated. The solubility limit of AlF{sub 3} in ScF{sub 3} at ∼1340 K is ∼50%. Solid solutions (x≤0.50) were characterized by synchrotron powder diffraction at ambient pressure between 100 and 900 K and at pressures <0.414 GPa while heating from 298 to 523 K. A phase transition from cubic to rhombohedral is observed. The transition temperature increases smoothly with Al{sup 3+} content, approaching 500 K at the solid solubility limit, and also upon compression at fixed Al{sup 3+} content. The slope of themore » pressure–temperature phase boundary is ∼0.5 K MPa{sup −1}, which is steep relative to that for most symmetry-lowering phase transitions in perovskites. The volume coefficient of thermal expansion (CTE) for the rhombohedral phase is strongly positive, but the cubic-phase CTE varies from negative (x<0.15) to near-zero (x=0.15) to positive (x>0.20) between ∼600 and 800 K. The cubic solid solutions elastically stiffen on heating, while Al{sup 3+} substitution causes softening at a given temperature. - Graphical abstract: The cubic-phase coefficient of thermal expansion for Sc{sub 1−x}Al{sub x}F{sub 3}(solubility limit ∼50% at ∼1340 K) becomes more positive with increased Al{sup 3+} substitution, but the average isothermal bulk modulus decreases (elastic softening). - Highlights: • The solubility limit of AlF{sub 3} in ScF{sub 3} at ∼1340 K is ∼50%. • The phase transition temperature of Sc{sub 1−x}Al{sub x}F{sub 3} increases smoothly with x. • The cubic-phase volume CTE varies from negative to positive with increasing x. • The cubic solid solutions elastically stiffen on heating. • Al{sup 3+} substitution causes softening at a given temperature.« less

The major volume /density/ of solid oxygen in equilibrium with vapor

NASA Technical Reports Server (NTRS)

Roder, H. M.

1979-01-01

Data from the literature on the molar volume of solid oxygen have been compiled and critically analyzed. A correlated and thermodynamically consistent set of molar volumes, including the volume changes at the various solid phase transitions, is presented. Evidence for the existence of a delta-solid phase is reviewed. Uncertainties in the data and in the recommended set of values are discussed.

Reactive solute transport in streams: 2. Simulation of a pH modification experiment

USGS Publications Warehouse

Runkel, Robert L.; McKnight, Diane M.; Bencala, Kenneth E.; Chapra, Steven C.

1996-01-01

We present an application of an equilibrium-based solute transport model to a pH-modification experiment conducted on the Snake River, an acidic, metal-rich stream located in the Rocky Mountains of Colorado. During the experiment, instream pH decreased from 4.2 to 3.2, causing a marked increase in dissolved iron concentrations. Model application requires specification of several parameters that are estimated using tracer techniques, mass balance calculations, and geochemical data. Two basic questions are addressed through model application: (1) What are the processes responsible for the observed increase in dissolved iron concentrations? (2) Can the identified processes be represented within the equilibrium-based transport model? Simulation results indicate that the increase in iron was due to the dissolution of hydrous iron oxides and the photoreduction of ferric iron. Dissolution from the streambed is represented by considering a trace compartment consisting of freshly precipitated hydrous iron oxide and an abundant compartment consisting of aged precipitates that are less soluble. Spatial variability in the solubility of hydrous iron oxide is attributed to heterogeneity in the streambed sediments, temperature effects, and/or variability in the effects of photoreduction. Solubility products estimated via simulation fall within a narrow range (pKsp from 40.2 to 40.8) relative to the 6 order of magnitude variation reported for laboratory experiments (pKsp from 37.3 to 43.3). Results also support the use of an equilibrium-based transport model as the predominate features of the iron and pH profiles are reproduced. The model provides a valuable tool for quantifying the nature and extent of pH-dependent processes within the context of hydrologic transport.

Reactive Solute Transport in Streams: 2. Simulation of a pH Modification Experiment

NASA Astrophysics Data System (ADS)

Runkel, Robert L.; McKnight, Diane M.; Bencala, Kenneth E.; Chapra, Steven C.

1996-02-01

We present an application of an equilibrium-based solute transport model to a pH-modification experiment conducted on the Snake River, an acidic, metal-rich stream located in the Rocky Mountains of Colorado. During the experiment, instream pH decreased from 4.2 to 3.2, causing a marked increase in dissolved iron concentrations. Model application requires specification of several parameters that are estimated using tracer techniques, mass balance calculations, and geochemical data. Two basic questions are addressed through model application: (1) What are the processes responsible for the observed increase in dissolved iron concentrations? (2) Can the identified processes be represented within the equilibrium-based transport model? Simulation results indicate that the increase in iron was due to the dissolution of hydrous iron oxides and the photoreduction of ferric iron. Dissolution from the streambed is represented by considering a trace compartment consisting of freshly precipitated hydrous iron oxide and an abundant compartment consisting of aged precipitates that are less soluble. Spatial variability in the solubility of hydrous iron oxide is attributed to heterogeneity in the streambed sediments, temperature effects, and/or variability in the effects of photoreduction. Solubility products estimated via simulation fall within a narrow range (pKsp from 40.2 to 40.8) relative to the 6 order of magnitude variation reported for laboratory experiments (pKsp from 37.3 to 43.3). Results also support the use of an equilibrium-based transport model as the predominate features of the iron and pH profiles are reproduced. The model provides a valuable tool for quantifying the nature and extent of pH-dependent processes within the context of hydrologic transport.

The Importance of Kinetics and Redox in the Biogeochemical Cycling of Iron in the Surface Ocean

PubMed Central

Croot, Peter L.; Heller, Maija I.

2012-01-01

It is now well established that Iron (Fe) is a limiting element in many regions of the open ocean. Our current understanding of the key processes which control iron distribution in the open ocean have been largely based on thermodynamic measurements performed under the assumption of equilibrium conditions. Using this equilibrium approach, researchers have been able to detect and quantify organic complexing ligands in seawater and examine their role in increasing the overall solubility of iron. Our current knowledge about iron bioavailability to phytoplankton and bacteria is also based heavily on carefully controlled laboratory studies where it is assumed the chemical species are in equilibrium in line with the free ion association model and/or its successor the biotic ligand model. Similarly most field work on iron biogeochemistry generally consists of a single profile which is in essence a “snap-shot” in time of the system under investigation. However it is well known that the surface ocean is an extremely dynamic environment and it is unlikely if thermodynamic equilibrium between all the iron species present is ever truly achieved. In sunlit waters this is mostly due to the daily passage of the sun across the sky leading to photoredox processes which alter Fe speciation by cycling between redox states and between inorganic and organic species. Episodic deposition events, dry and wet, are also important perturbations to iron cycling as they bring in new iron to the system and alter the equilibrium between iron species and phases. Here we utilize new field data collected in the open ocean on the complexation kinetics of iron in the surface ocean to identify the important role of weak iron binding ligands (i.e., those that cannot maintain iron in solution indefinitely at seawater pH: αFeL < αFe′) in allowing transient increases in iron solubility in response to iron deposition events. Experiments with the thermal O2- source SOTS-1 also indicate the short term impact of this species on iron solubility also with relevance to the euphotic zone. This data highlights the roles of kinetics, redox, and weaker iron binding ligands in the biogeochemical cycling of iron in the ocean. PMID:22723797

Experimental measurement and thermodynamic modeling of the solubility of carbon dioxide in aqueous blends of monoethanolamine and diethanolamine

NASA Astrophysics Data System (ADS)

Suleman, Humbul; Maulud, Abdulhalim Shah; Man, Zakaria

2017-12-01

In this study, the solubilities of carbon dioxide in aqueous mixtures of monoethanolamine (MEA) and diethanolamine (DEA) were determined using a high pressure vapor-liquid equilibrium apparatus. The carbon dioxide loadings (mole of CO2/mole of amine mixture) were reported for a wide range of temperature (303.15, 323.15, 343.15 K) and pressure (100 - 4100 kPa). The carbon dioxide solubility shows an increase with increase in pressure and amine concentration and a decrease with increase in temperature in the aqueous blends of MEA and DEA. At carbon dioxide loadings above 1.0, the carbon dioxide solubility becomes a weak function of pressure and follows the general trend of carbon dioxide solubility in aqueous alkanolamines. The new experimental data points determined in this study were correlated by using a recently developed, enhanced Kent-Eisenberg model. An average absolute relative error of 9.4 % was observed between the model results and experimental data, indicating good correlative capability of the thermodynamic model.

Alcohol dose dumping: The influence of ethanol on hot-melt extruded pellets comprising solid lipids.

PubMed

Jedinger, N; Schrank, S; Mohr, S; Feichtinger, A; Khinast, J; Roblegg, E

2015-05-01

The objective of the present study was to investigate interactions between alcohol and hot-melt extruded pellets and the resulting drug release behavior. The pellets were composed of vegetable calcium stearate as matrix carrier and paracetamol or codeine phosphate as model drugs. Two solid lipids (Compritol® and Precirol®) were incorporated into the matrix to form robust/compact pellets. The drug release characteristics were a strong function of the API solubility, the addition of solid lipids, the dissolution media composition (i.e., alcohol concentration) and correspondingly, the pellet wettability. Pellets comprising paracetamol, which is highly soluble in ethanol, showed alcohol dose dumping regardless of the matrix composition. The wettability increased with increasing ethanol concentrations due to higher paracetamol solubilities yielding increased dissolution rates. For pellets containing codeine phosphate, which has a lower solubility in ethanol than in acidic media, the wettability was a function of the matrix composition. Dose dumping occurred for formulations comprising solid lipids as they showed increased wettabilities with increasing ethanol concentrations. In contrast, pellets comprising calcium stearate as single matrix component showed robustness in alcoholic media due to wettabilities that were not affected by the addition of ethanol. The results clearly indicate that the physico-chemical properties of the drug and the matrix systems are crucial for the design of ethanol-resistant dosage forms. Moreover, hydrophobic calcium stearate can be considered a suitable matrix system that minimizes the risk of ethanol-induced dose dumping for certain API's. Copyright © 2015 Elsevier B.V. All rights reserved.

The determination of solubility and diffusion coefficient for solids in liquids by an inverse measurement technique using cylinders of amorphous glucose as a model compound

NASA Astrophysics Data System (ADS)

Hu, Chengyao; Huang, Pei

2011-05-01

The importance of sugar and sugar-containing materials is well recognized nowadays, owing to their application in industrial processes, particularly in the food, pharmaceutical and cosmetic industries. Because of the large numbers of those compounds involved and the relatively small number of solubility and/or diffusion coefficient data for each compound available, it is highly desirable to measure the solubility and/or diffusion coefficient as efficiently as possible and to be able to improve the accuracy of the methods used. In this work, a new technique was developed for the measurement of the diffusion coefficient of a stationary solid solute in a stagnant solvent which simultaneously measures solubility based on an inverse measurement problem algorithm with the real-time dissolved amount profile as a function of time. This study differs from established techniques in both the experimental method and the data analysis. The experimental method was developed in which the dissolved amount of solid solute in quiescent solvent was investigated using a continuous weighing technique. In the data analysis, the hybrid genetic algorithm is used to minimize an objective function containing a calculated and a measured dissolved amount with time. This is measured on a cylindrical sample of amorphous glucose in methanol or ethanol. The calculated dissolved amount, that is a function of the unknown physical properties of the solid solute in the solvent, is calculated by the solution of the two-dimensional nonlinear inverse natural convection problem. The estimated values of the solubility of amorphous glucose in methanol and ethanol at 293 K were respectively 32.1 g/100 g methanol and 1.48 g/100 g ethanol, in agreement with the literature values, and support the validity of the simultaneously measured diffusion coefficient. These results show the efficiency and the stability of the developed technique to simultaneously estimate the solubility and diffusion coefficient. Also the influence of the solution density change and the initial concentration conditions on the dissolved amount was investigated by the numerical results using the estimated parameters. It is found that the theoretical assumption to simplify the inverse measurement problem algorithm is reasonable for low solubility.

Use of polynomial expressions to describe the bioconcentration of hydrophobic chemicals by fish

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

Connell, D.W.; Hawker, D.W.

1988-12-01

For the bioconcentration of hydrophobic chemicals by fish, relationships have been previously established between uptake rate constants (k1) and the octanol/water partition coefficient (Kow), and also between the clearance rate constant (k2) and Kow. These have been refined and extended on the basis of data for chlorinated hydrocarbons, and closely related compounds including polychlorinated dibenzodioxins, that covered a wider range of hydrophobicity (2.5 less than log Kow less than 9.5). This has allowed the development of new relationships between log Kow and various factors, including the bioconcentration factor (as log KB), equilibrium time (as log teq), and maximum biotic concentrationmore » (as log CB), which include extremely hydrophobic compounds previously not taken into account. The shape of the curves generated by these equations are in qualitative agreement with theoretical prediction and are described by polynomial expressions which are generally approximately linear over the more limited range of log Kow values used to develop previous relationships. The influences of factors such as hydrophobicity, aqueous solubility, molecular weight, lipid solubility, and also exposure time were considered. Decreasing lipid solubilities of extremely hydrophobic chemicals were found to result in increasing clearance rate constants, as well decreasing equilibrium times and bioconcentration factors.« less

Pore scale study of multiphase multicomponent reactive transport during CO 2 dissolution trapping

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

Chen, Li; Wang, Mengyi; Kang, Qinjun

Solubility trapping is crucial for permanent CO 2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO 2-water two-phase flow, multicomponent (CO 2(aq), H +, HCO 3 –, CO 3 2 – and OH –) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO 2(aq) concentration, scCO 2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is requiredmore » by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Lastly, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO 2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.« less

Molecular-dynamics evaluation of fluid-phase equilibrium properties by a novel free-energy perturbation approach: Application to gas solubility and vapor pressure of liquid hexane

NASA Astrophysics Data System (ADS)

Kuwajima, Satoru; Kikuchi, Hiroaki; Fukuda, Mitsuhiro

2006-03-01

A novel free-energy perturbation method is developed for the computation of the free energy of transferring a molecule between fluid phases. The methodology consists in drawing a free-energy profile of the target molecule moving across a binary-phase structure built in the computer. The novelty of the method lies in the difference of the definition of the free-energy profile from the common definition. As an important element of the method, the process of making a correction to the transfer free energy with respect to the cutoff of intermolecular forces is elucidated. In order to examine the performance of the method in the application to fluid-phase equilibrium properties, molecular-dynamics computations are carried out for the evaluation of gas solubility and vapor pressure of liquid n-hexane at 298.15K. The gas species treated are methane, ethane, propane, and n-butane, with the gas solubility expressed as Henry's constant. It is shown that the method works fine and calculated results are generally in good agreement with experiments. It is found that the cutoff correction is strikingly large, constituting a dominant part of the calculated transfer free energy at the cutoff of 8Å.

Pore scale study of multiphase multicomponent reactive transport during CO 2 dissolution trapping

DOE PAGES

Chen, Li; Wang, Mengyi; Kang, Qinjun; ...

2018-04-26

Solubility trapping is crucial for permanent CO 2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO 2-water two-phase flow, multicomponent (CO 2(aq), H +, HCO 3 –, CO 3 2 – and OH –) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO 2(aq) concentration, scCO 2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is requiredmore » by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Lastly, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO 2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.« less

Pore scale study of multiphase multicomponent reactive transport during CO2 dissolution trapping

NASA Astrophysics Data System (ADS)

Chen, Li; Wang, Mengyi; Kang, Qinjun; Tao, Wenquan

2018-06-01

Solubility trapping is crucial for permanent CO2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO2-water two-phase flow, multicomponent (CO2(aq), H+, HCO3-, CO32- and OH-) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO2(aq) concentration, scCO2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is required by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Finally, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.

Sediment Equilibrium and Diffusive Fluxes in Relation to Phosphorus Dynamics in the Turbid Minnesota River

DTIC Science & Technology

2009-01-01

extractable P and K in a sandy clay loam soil under continuous corn ( Zea mays L .). Can J Soil Sci 75:361-367. Zhang, T. Q., A. F. MacKenzie, B. C...diffusive P flux from deposited sediment stored in river channels may also play a role in soluble P control. Ranges in equilibrium partitioning between...largest plants in the State of Minnesota, discharge (average discharge = 1.8 m3 s-1) at effluent P concentrations of 1.5 mg L -1 or less. A 538-megawatt

Cooperativity and specificity of association of a designed transmembrane peptide.

PubMed Central

Gratkowski, Holly; Dai, Qing-Hong; Wand, A Joshua; DeGrado, William F; Lear, James D

2002-01-01

Thermodynamics studies aimed at quantitatively characterizing free energy effects of amino acid substitutions are not restricted to two state systems, but do require knowing the number of states involved in the equilibrium under consideration. Using analytical ultracentrifugation and NMR methods, we show here that a membrane-soluble peptide, MS1, designed by modifying the sequence of the water-soluble coiled-coil GCN4-P1, exhibits a reversible monomer-dimer-trimer association in detergent micelles with a greater degree of cooperativity in C14-betaine than in dodecyl phosphocholine detergents. PMID:12202385

Improved modeling of two-dimensional transitions in dense phases on crystalline surfaces. Krypton–graphite system

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

Ustinov, E. A., E-mail: eustinov@mail.wplus.net

This paper presents a refined technique to describe two-dimensional phase transitions in dense fluids adsorbed on a crystalline surface. Prediction of parameters of 2D liquid–solid equilibrium is known to be an extremely challenging problem, which is mainly due to a small difference in thermodynamic functions of coexisting phases and lack of accuracy of numerical experiments in case of their high density. This is a serious limitation of various attempts to circumvent this problem. To improve this situation, a new methodology based on the kinetic Monte Carlo method was applied. The methodology involves analysis of equilibrium gas–liquid and gas–solid systems undergoingmore » an external potential, which allows gradual shifting parameters of the phase coexistence. The interrelation of the chemical potential and tangential pressure for each system is then treated with the Gibbs–Duhem equation to obtain the point of intersection corresponding to the liquid/solid–solid equilibrium coexistence. The methodology is demonstrated on the krypton–graphite system below and above the 2D critical temperature. Using experimental data on the liquid–solid and the commensurate–incommensurate transitions in the krypton monolayer derived from adsorption isotherms, the Kr–graphite Lennard–Jones parameters have been corrected resulting in a higher periodic potential modulation.« less

Preparation and in vitro/in vivo characterization of porous sublingual tablets containing ternary kneaded solid system of vinpocetine with î-cyclodextrin and hydroxy Acid.

PubMed

Aburahma, Mona H; El-Laithy, Hanan M; Hamza, Yassin El-Said

2010-01-01

The demand for sublingual tablets has been growing during the previous decades especially for drugs with extensive hepatic first-pass metabolism. Vinpocetine, a widely used neurotropic agent, has low oral bioavailability due to its poor aqueous solubility and marked first-pass metabolism. Accordingly, the aim of this work was to develop tablets for the sublingual delivery of vinpocetine. Initially, the feasibility of improving vinpocetineâs poor aqueous solubility by preparing kneaded solid systems of the drug with Î-Cyclodextrin and hydroxy acids (citric acid and tartaric acid) was assessed. The solid system with improved solubility and dissolution properties was incorporated into porous tablets that rapidly disintegrate permitting fast release of vinpocetine into the sublingual cavity. The pores were induced into these tablets by directly compressing the tabletsâ excipients with a sublimable material, either camphor or menthol, which was eventually sublimated leaving pores. The obtained results demonstrated that the tablets prepared using camphor attained sufficient mechanical strength for practical use together with rapid disintegration and dissolution. In vivo absorption study performed in rabbits indicated that the sublingual administration of the proposed porous tablets containing vinpocetine solid system with Î-Cyclodextrin and tartaric acid could be useful for therapeutic application.

Preparation and In Vitro/In Vivo Characterization of Porous Sublingual Tablets Containing Ternary Kneaded Solid System of Vinpocetine with β-Cyclodextrin and Hydroxy Acid

PubMed Central

Aburahma, Mona H.; El-Laithy, Hanan M.; Hamza, Yassin El-Said

2010-01-01

The demand for sublingual tablets has been growing during the previous decades especially for drugs with extensive hepatic first-pass metabolism. Vinpocetine, a widely used neurotropic agent, has low oral bioavailability due to its poor aqueous solubility and marked first-pass metabolism. Accordingly, the aim of this work was to develop tablets for the sublingual delivery of vinpocetine. Initially, the feasibility of improving vinpocetine’s poor aqueous solubility by preparing kneaded solid systems of the drug with β-Cyclodextrin and hydroxy acids (citric acid and tartaric acid) was assessed. The solid system with improved solubility and dissolution properties was incorporated into porous tablets that rapidly disintegrate permitting fast release of vinpocetine into the sublingual cavity. The pores were induced into these tablets by directly compressing the tablets’ excipients with a sublimable material, either camphor or menthol, which was eventually sublimated leaving pores. The obtained results demonstrated that the tablets prepared using camphor attained sufficient mechanical strength for practical use together with rapid disintegration and dissolution. In vivo absorption study performed in rabbits indicated that the sublingual administration of the proposed porous tablets containing vinpocetine solid system with β-Cyclodextrin and tartaric acid could be useful for therapeutic application. PMID:21179352

High-throughput 96-well solvent mediated sonic blending synthesis and on-plate solid/solution stability characterization of pharmaceutical cocrystals.

PubMed

Luu, Van; Jona, Janan; Stanton, Mary K; Peterson, Matthew L; Morrison, Henry G; Nagapudi, Karthik; Tan, Helming

2013-01-30

A 96-well high-throughput cocrystal screening workflow has been developed consisting of solvent-mediated sonic blending synthesis and on-plate solid/solution stability characterization by XRPD. A strategy of cocrystallization screening in selected blend solvents including water mixtures is proposed to not only manipulate solubility of the cocrystal components but also differentiate physical stability of the cocrystal products. Caffeine-oxalic acid and theophylline-oxalic acid cocrystals were prepared and evaluated in relation to saturation levels of the cocrystal components and stability of the cocrystal products in anhydrous and hydrous solvents. AMG 517 was screened with a number of coformers, and solid/solution stability of the resulting cocrystals on the 96-well plate was investigated. A stability trend was observed and confirmed that cocrystals comprised of lower aqueous solubility coformers tended to be more stable in water. Furthermore, cocrystals which could be isolated under hydrous solvent blending condition exhibited superior physical stability to those which could only be obtained under anhydrous condition. This integrated HTS workflow provides an efficient route in an API-sparing approach to screen and identify cocrystal candidates with proper solubility and solid/solution stability properties. Copyright © 2012 Elsevier B.V. All rights reserved.

Hydrothermal pre-treatment of oil palm empty fruit bunch into fermentable sugars

NASA Astrophysics Data System (ADS)

Muhd Ali, M. D.; Tamunaidu, P.; Nor Aslan, A. K. H.; Morad, N. A.; Sugiura, N.; Goto, M.; Zhang, Z.

2016-06-01

Presently oil palm empty fruit bunch (OPEFB) is one of the solid waste which is produced daily whereby it is usually left at plantation site to act as organic fertilizer for the plants to ensure the sustainability of fresh fruit bunch. The major drawback in biomass conversion technology is the difficulty of degrading the material in a short period of time. A pre-treatment step is required to break the lignocellulosic biomass to easily accessible carbon sources for further use in the production of fuels and fine chemicals. Therefore, this study investigated the effect of hydrothermal pre-treatment under different reaction temperatures (100 - 250°C), reaction time (10 - 40 min), solid to solvent ratio of (1:10 - 1:20 w/v) and particle size (0.15 - 1.00 mm) on the solubilization of OPEFB to produce soluble fermentable sugars. The maximum soluble sugars of 68.18 mg glucose per gram of OPEFB were achieved at 175°C of reaction temperature, 20 min of reaction time, 1:15 w/v of solid to solvent ratio for 30 mm of particle size. Results suggest that reaction temperature, reaction time, the amount of solid to solvent ratio and size of the particle are crucial parameters for hydrothermal pretreatment, in achieving a high yield of soluble fermentable sugars.

The "high solubility" definition of the current FDA Guidance on Biopharmaceutical Classification System may be too strict for acidic drugs.

PubMed

Yazdanian, Mehran; Briggs, Katherine; Jankovsky, Corinne; Hawi, Amale

2004-02-01

The purpose of this study was to assess if the definition of high solubility as proposed in the FDA Guidance on Biopharmaceutical Classification System (BCS) is too strict for highly permeable acidic drugs. The solubility and permeability values of 20 (18 acidic and 2 non-acidic) nonsteroidal anti-inflammatory drugs (NSAID) were determined. The NSAIDs were grouped into three different sets having acetic acid, propionic acid, or other acidic moieties such as fenamate, oxicam, and salicylate. Two nonacidic NSAIDs (celecoxib and rofecoxib) were also included for comparison purposes. Equilibrium solubility values were determined at pH 1.2, 5.0, 7.4, and in biorelevant media simulating fed intestinal fluid at pH 5.0. For a select number of acids, we also measured solubility values in media simulating gastric and fasted intestinal fluids. Permeability classification was established relative to that of reference drugs in the Caco-2 cell permeability model. Permeability coefficients for all drugs were measured at concentrations corresponding to the lowest and highest marketed dose strengths dissolved in 250 ml volume, and their potential interaction with cellular efflux pumps was investigated. All NSAIDs with different acidic functional groups were classified as highly permeable based on their Caco-2 cell permeability. Only ketorolac appeared to have a potential for interaction with cellular efflux pumps. Solubility classification was based on comparison of equilibrium solubility at pH 1.2, 5.0. and 7.4 relative to marketed dose strengths in 250 ml. The pKa values for the acidic NSAIDs studied were between 3.5 and 5.1. and, as expected, their solubility increased dramatically at pH 7.4 compared to pH 1.2. Only three NSAIDs, ketorolac, ketoprofen. and acetyl salicylic acid, meet the current criteria for high solubility over the entire pH range. However, with the exception of ibuprofen, oxaprozin, and mefenamic acid, the remaining compounds can be classified as Class I drugs (high solubility-high permeability) relative to solubility at pH 7.4. The use of bio-relevant media simulating gastric and intestinal milieu for solubility measurements or increasing the dose volume to 500 ml did not provide for a better boundary for solubility classification. Based on the current definition of solubility, 15 of the 18 acidic NSAIDs in this study will be classified as Class II compounds as the solubility criteria applies to the entire pH range of 1.2 to 7.4, although the low solubility criteria does not hold true over the entire pH range. Whence, of the 18 acidic drugs, 15 can be classified as Class I based on the pH 7.4 solubility alone. This finding is intriguing because these drugs exhibit Class I behavior as their absorption does not seem to be dissolution or solubility limited. It could then be argued that for acidic drugs, the boundaries for solubility are too restrictive. Solubility at pH > 5 (pH in duodenum) may be more appropriate because most compounds are mainly absorbed in the intestinal region. Consideration for an intermediate solubility classification for highly permeable ionizable compounds that reflects physiological conditions seems warranted.

Solid/liquid extraction equilibria of phenolic compounds with trioctylphosphine oxide impregnated in polymeric membranes.

PubMed

Praveen, Prashant; Loh, Kai-Chee

2016-06-01

Trioctylphosphine oxide based extractant impregnated membranes (EIM) were used for extraction of phenol and its methyl, hydroxyl and chloride substituted derivatives. The distribution coefficients of the phenols varied from 2 to 234, in the order of 1-napthol > p-chlorophenol > m-cresol > p-cresol > o-cresol > phenol > catechol > pyrogallol > hydroquinone, when initial phenols loadings was varied in 100-2000 mg/L. An extraction model, based on the law of mass action, was formulated to predict the equilibrium distribution of the phenols. The model was in excellent agreement (R(2) > 0.97) with the experimental results at low phenols concentrations (<800 mg/L). At higher phenols loadings though, Langmuir isotherm was better suited for equilibrium prediction (R(2) > 0.95), which signified high mass transfer resistance in the EIMs. Examination of the effects of ring substitution on equilibrium, and bivariate statistical analysis between the amounts of phenols extracted into the EIMs and factors affecting phenols interaction with TOPO, indicated the dominant role of hydrophobicity in equilibrium determination. These results improve understanding of the solid/liquid equilibrium process between phenols and the EIMs, and these will be useful in designing phenol recovery process from wastewater. Copyright © 2016 Elsevier Ltd. All rights reserved.

Visualizing Chemistry: Investigations for Teachers.

ERIC Educational Resources Information Center

Ealy, Julie B.; Ealy, James L., Jr.

This book contains 101 investigations for chemistry classrooms. Topics include: (1) Physical Properties; (2) Reactions of Some Elements; (3) Reactions Involving Gases; (4) Energy Changes; (5) Solutions and Solubility; (6) Transition Metals and Complex Ions; (7) Kinetics and Equilibrium; (8) Acids and Bases; (9) Oxidation-Reduction; (10)…

Temperature Dependence of Errors in Parameters Derived from Van't Hoff Studies.

ERIC Educational Resources Information Center

Dec, Steven F.; Gill, Stanley J.

1985-01-01

The method of Clarke and Glew is broadly applicable to studies of the temperature dependence of equilibrium constant measurements. The method is described and examples of its use in comparing calorimetric results and temperature dependent gas solubility studies are provided. (JN)

The Chemistry Involved in the Preparation of a Paint Pigment: An Experiment for the Freshman Laboratory

ERIC Educational Resources Information Center

Daines, Terri L.; Morse, Karen W.

1976-01-01

Describes an experiment that demonstrates the following principles and reactions: amphoterism, oxidation-reduction, equilibrium dependence on pH, solubility, and polymerization. The experiment involves the oxidation of chromium and the precipitation of a chromate salt. (MLH)

Fugacity and concentration gradients in a gravity field

NASA Technical Reports Server (NTRS)

May, C. E.

1986-01-01

Equations are reviewed which show that at equilibrium fugacity and concentration gradients can exist in gravitational fields. At equilibrium, the logarithm of the ratio of the fugacities of a species at two different locations in a gravitational field is proportional to the difference in the heights of the two locations and the molecular weight of the species. An analogous relation holds for the concentration ratios in a multicomponent system. The ratio is calculated for a variety of examples. The kinetics for the general process are derived, and the time required to approach equilibrium is calculated for several systems. The following special topics are discussed: ionic solutions, polymers, multiphase systems, hydrostatic pressure, osmotic pressure, and solubility gradients in a gravity field.

Student certainty answering misconception question: study of Three-Tier Multiple-Choice Diagnostic Test in Acid-Base and Solubility Equilibrium

NASA Astrophysics Data System (ADS)

Ardiansah; Masykuri, M.; Rahardjo, S. B.

2018-04-01

Students’ concept comprehension in three-tier multiple-choice diagnostic test related to student confidence level. The confidence level related to certainty and student’s self-efficacy. The purpose of this research was to find out students’ certainty in misconception test. This research was quantitative-qualitative research method counting students’ confidence level. The research participants were 484 students that were studying acid-base and equilibrium solubility subject. Data was collected using three-tier multiple-choice (3TMC) with thirty questions and students’ questionnaire. The findings showed that #6 item gives the highest misconception percentage and high student confidence about the counting of ultra-dilute solution’s pH. Other findings were that 1) the student tendency chosen the misconception answer is to increase over item number, 2) student certainty decreased in terms of answering the 3TMC, and 3) student self-efficacy and achievement were related each other in the research. The findings suggest some implications and limitations for further research.

Fluorides and non-fluoride remineralization systems.

PubMed

Amaechi, Bennett T; van Loveren, Cor

2013-01-01

Caries develops when the equilibrium between de- and remineralization is unbalanced favoring demineralization. De- and remineralization occur depending on the degree of saturation of the interstitial fluids with respect to the tooth mineral. This equilibrium is positively influenced when fluoride, calcium and phosphate ions are added favoring remineralization. In addition, when fluoride is present, it will be incorporated into the newly formed mineral which is then less soluble. Toothpastes may contain fluoride and calcium ions separately or together in various compounds (remineralization systems) and may therefore reduce demineralization and promote remineralization. Formulating all these compounds in one paste may be challenging due to possible premature calcium-fluoride interactions and the low solubility of CaF2. There is a large amount of clinical evidence supporting the potent caries preventive effect of fluoride toothpastes indisputably. The amount of clinical evidence of the effectiveness of the other remineralization systems is far less convincing. Evidence is lacking for head to head comparisons of the various remineralization systems. Copyright © 2013 S. Karger AG, Basel.

Validity of Scientific Based Chemistry Android Module to Empower Science Process Skills (SPS) in Solubility Equilibrium

NASA Astrophysics Data System (ADS)

Antrakusuma, B.; Masykuri, M.; Ulfa, M.

2018-04-01

Evolution of Android technology can be applied to chemistry learning, one of the complex chemistry concept was solubility equilibrium. this concept required the science process skills (SPS). This study aims to: 1) Characteristic scientific based chemistry Android module to empowering SPS, and 2) Validity of the module based on content validity and feasibility test. This research uses a Research and Development approach (RnD). Research subjects were 135 s1tudents and three teachers at three high schools in Boyolali, Central of Java. Content validity of the module was tested by seven experts using Aiken’s V technique, and the module feasibility was tested to students and teachers in each school. Characteristics of chemistry module can be accessed using the Android device. The result of validation of the module contents got V = 0.89 (Valid), and the results of the feasibility test Obtained 81.63% (by the student) and 73.98% (by the teacher) indicates this module got good criteria.

Gaseous Sulfate Solubility in Glass: Experimental Method

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

Bliss, Mary

2013-11-30

Sulfate solubility in glass is a key parameter in many commercial glasses and nuclear waste glasses. This report summarizes key publications specific to sulfate solubility experimental methods and the underlying physical chemistry calculations. The published methods and experimental data are used to verify the calculations in this report and are expanded to a range of current technical interest. The calculations and experimental methods described in this report will guide several experiments on sulfate solubility and saturation for the Hanford Waste Treatment Plant Enhanced Waste Glass Models effort. There are several tables of sulfate gas equilibrium values at high temperature tomore » guide experimental gas mixing and to achieve desired SO3 levels. This report also describes the necessary equipment and best practices to perform sulfate saturation experiments for molten glasses. Results and findings will be published when experimental work is finished and this report is validated from the data obtained.« less

Thermodynamic and kinetic theory of nucleation, deliquescence and efflorescence transitions in the ensemble of droplets on soluble particles.

PubMed

Shchekin, Alexander K; Shabaev, Ilya V; Hellmuth, Olaf

2013-02-07

Thermodynamic and kinetic peculiarities of nucleation, deliquescence and efflorescence transitions in the ensemble of droplets formed on soluble condensation nuclei from a solvent vapor have been considered. The interplay of the effects of solubility and the size of condensation nuclei has been analyzed. Activation barriers for the deliquescence and phase transitions and for the reverse efflorescence transition have been determined as functions of the relative humidity of the vapor-gas atmosphere, initial size, and solubility of condensation nuclei. It has been demonstrated that, upon variations in the relative humidity of the atmosphere, the crossover in thermodynamically stable and unstable variables of the droplet state takes place. The physical meaning of stable and unstable variables has been clarified. The kinetic equations for establishing equilibrium and steady distributions of binary droplets have been solved. The specific times for relaxation, deliquescence and efflorescence transitions have been calculated.

Mineralogical controls on aluminum and magnesium in uranium mill tailings: Key Lake, Saskatchewan, Canada.

PubMed

Gomez, M A; Hendry, M J; Koshinsky, J; Essilfie-Dughan, J; Paikaray, S; Chen, J

2013-07-16

The mineralogy and evolution of Al and Mg in U mill tailings are poorly understood. Elemental analyses (ICP-MS) of both solid and aqueous phases show that precipitation of large masses of secondary Al and Mg mineral phases occurs throughout the raffinate neutralization process (pH 1-11) at the Key Lake U mill, Saskatchewan, Canada. Data from a suite of analytical methods (ICP-MS, EMPA, laboratory- and synchrotron-based XRD, ATR-IR, Raman, TEM, EDX, ED) and equilibrium thermodynamic modeling showed that nanoparticle-sized, spongy, porous, Mg-Al hydrotalcite is the dominant mineralogical control on Al and Mg in the neutralized raffinate (pH ≥ 6.7). The presence of this secondary Mg-Al hydrotalcite in mineral samples of both fresh and 15-year-old tailings indicates that the Mg-Al hydrotalcite is geochemically stable, even after >16 years in the oxic tailings body. Data shows an association between the Mg-Al hydrotalcite and both As and Ni and point to this Mg-Al hydrotalcite exerting a mineralogical control on the solubility of these contaminants.

Thermodynamic and kinetic modelling of fuel oxidation behaviour in operating defective fuel

NASA Astrophysics Data System (ADS)

Lewis, operating defective fuel B. J.; Thompson, W. T.; Akbari, F.; Thompson, D. M.; Thurgood, C.; Higgs, J.

2004-07-01

A theoretical treatment has been developed to predict the fuel oxidation behaviour in operating defective nuclear fuel elements. The equilibrium stoichiometry deviation in the hyper-stoichiometric fuel has been derived from thermodynamic considerations using a self-consistent set of thermodynamic properties for the U-O system, which emphasizes replication of solubilities and three-phase invariant conditions displayed in the U-O binary phase diagram. The kinetics model accounts for multi-phase transport including interstitial oxygen diffusion in the solid and gas-phase transport of hydrogen and steam in the fuel cracks. The fuel oxidation model is further coupled to a heat conduction model to account for the feedback effect of a reduced thermal conductivity in the hyper-stoichiometric fuel. A numerical solution has been developed using a finite-element technique with the FEMLAB software package. The model has been compared to available data from several in-reactor X-2 loop experiments with defective fuel conducted at the Chalk River Laboratories. The model has also been benchmarked against an O/U profile measurement for a spent defective fuel element discharged from a commercial reactor.

Active package for wild strawberry fruit (Fragaria vesca L.).

PubMed

Almenar, Eva; Del Valle, Valeria; Catala, Ramón; Gavara, Rafael

2007-03-21

An antimicrobial active package has been developed to improve the safety and quality of wild strawberries, as well as extending their shelf life. The fruits were packed in equilibrium-modified atmosphere packaging (EMAP), and the effect on Botrytis cinerea growth and on the quality parameters of the fruit by the addition of different amounts of 2-nonanone, an antifungal volatile compound naturally present in strawberries, was investigated during storage at 10 and 22 degrees C. The temperature of 10 degrees C was chosen as the temperature used at points of sale, and 22 degrees C was chosen as the control temperature. Fungal growth was inhibited in all cases, possibly due to the synergistic effect of high CO2 partial pressures and the presence of the antifungal compound. Weight, soluble solids, titrable acidity, and anthocyanin losses were retarded by the presence of 2-nonanone. This effect was more pronounced as the 2-nonanone concentration was increased at both temperatures. Therefore, an active package that releases 2-nonanone inhibits fungal decay and delays the senescence of highly perishable wild strawberry fruit.

Catalysis and chemical mechanisms of calcite dissolution in seawater.

PubMed

Subhas, Adam V; Adkins, Jess F; Rollins, Nick E; Naviaux, John; Erez, Jonathan; Berelson, William M

2017-07-18

Near-equilibrium calcite dissolution in seawater contributes significantly to the regulation of atmospheric [Formula: see text] on 1,000-y timescales. Despite many studies on far-from-equilibrium dissolution, little is known about the detailed mechanisms responsible for calcite dissolution in seawater. In this paper, we dissolve 13 C-labeled calcites in natural seawater. We show that the time-evolving enrichment of [Formula: see text] in solution is a direct measure of both dissolution and precipitation reactions across a large range of saturation states. Secondary Ion Mass Spectrometer profiles into the 13 C-labeled solids confirm the presence of precipitated material even in undersaturated conditions. The close balance of precipitation and dissolution near equilibrium can alter the chemical composition of calcite deeper than one monolayer into the crystal. This balance of dissolution-precipitation shifts significantly toward a dissolution-dominated mechanism below about [Formula: see text] Finally, we show that the enzyme carbonic anhydrase (CA) increases the dissolution rate across all saturation states, and the effect is most pronounced close to equilibrium. This finding suggests that the rate of hydration of [Formula: see text] is a rate-limiting step for calcite dissolution in seawater. We then interpret our dissolution data in a framework that incorporates both solution chemistry and geometric constraints on the calcite solid. Near equilibrium, this framework demonstrates a lowered free energy barrier at the solid-solution interface in the presence of CA. This framework also indicates a significant change in dissolution mechanism at [Formula: see text], which we interpret as the onset of homogeneous etch pit nucleation.

Nature of diffraction fringes originating in the core of core-shell nanoparticle Cu/SiO2 and formation mechanism of the structures

NASA Astrophysics Data System (ADS)

Radnaev, A. R.; Kalashnikov, S. V.; Nomoev, A. V.

2016-05-01

This article is devoted to the analysis of the reasons for the occurrence of diffraction fringes in the cores of the core-shell nanoparticles Cu/SiO2. Moiré and diffraction fringes are observed while studying the nanoparticle cores under a transmission electron microscope. The formation of diffraction fringes is closely connected to the mechanism of nanoparticle formation under study and appears to be its consequence, letting us develop a hypothesis of metastable phase formation in nanoparticle cores. In our opinion, the emergence of diffraction fringes in cores of copper is connected to clasterisation in solid solution oversaturated with silicon α-Cu with the diffused interphase state. Only copper and oxygen (oxygen is presented as oxides in such types of copper as M0 - up to 0.01%; and M1 - up to 0.03%), Copper and silicon with oxygen in a stoichiometric proportion that is only sufficient for silicon dioxide formation (SiO2), Copper and silicon with oxygen in an amount that is sufficient not only for silicon dioxide formation, but also for the dissolution of silicon in the α-Cu solid solution, The amount of silicon in the alloy is not sufficient for the total fixation of oxygen contained in copper, Copper, oxygen and silicon whose contamination is greater than 8 wt.%. In the first case, the top-cut of oxygen in α-Cu solid solution is 0.03% at the temperature of 1066 °C. At slow cooling, secondary recrystallisation leads to the formation of equilibrium Cu2O on the line of the ultimate solubility (Figure 1a - line of maximum solubility of oxygen in copper). In the case of fast cooling fixation of oversaturated, single-phase, non-equilibrium α-Cu, solid solution (heat-treated) takes place, which contains saluted oxygen in an interstice crystal lattice of copper.Room temperature for nonferrous alloys (metals) is sufficient for the diffusive mobility of atoms, but insufficient for the formation of an equilibrium phase and stable phase of Cu2O. This is why diffusion of oxygen atoms in certain areas (clusters) with their increased diffusion of oxygen atoms in certain areas (clusters) with their increased number has been suggested [4]. At the same time, there is a boundary between the stable phase of α-Cu and 'pre-precipitations' containing oxygen, but not having the full value oxide: red copper ore, Cu2O (Figure 1b - solvus of suggested metastable phase). In this case, diffraction fringes can be treated as 'pre-precipitations' in the form of Guinier-Preston zones with diffuse interfaces and a stable α-Cu phase.In the second case, all oxygen and silicon after condensation and crystallisation are fixed in the form of amorphous SiO2 on the core surface of copper. As far as there are no atoms of saluted oxygen or silicon in copper, there are no conditions for the formation of non-equilibrium structures. Consequently, the diffraction pattern of nanoparticle cores is not observed (Figure 2a).In the third case, in the presence of quite a large amount of silicon in the stoichiometric drop, the process of copper oxide formation is not possible, because all the oxygen is used for the production of silicon dioxide since the sensitivity of oxygen to silicon is higher than to copper. This can be explained by the difference in Gibbs energy for the oxidising reaction of components. At the temperature of 25 °C it is 29.0 J/(g mol) - for copper, and 80.8 J/(g mol) for silicon. Silicon dioxide occurring due to the oxygen content in copper will be displaced on the surface of the drop in the form of ash, forming the SiO2 shell [24]. The reason lies in the lower specific density of silicon (approximately 2.2 g/cm3) compared to copper (8.92 g/cm3). This is why, in our case, it is appropriate to study the system where there is no influence of oxygen on the crystallisation of the Cu-Si system [5]. In the cores of such nanoparticles, prominent diffraction fringes can be observed in the α-Cu core (Figure 3b).Analysis of the Cu-Si phase diagram (Figure 3) shows that the maximum solubility of silicon α-Cu at the temperature 552 °C comprises 4.65 wt.% Si. This part of the Cu-Si phase diagram containing up to 8 wt.% silicon represents a classical example of the well-studied phase diagram of Al-Cu components, with the formation of Guinier-Preston zones in the quenched aluminium alloy [25].Single-phase solid solution of silicon α-Cu is fixed at fast cooling in our case. During its formation, cooling and natural ageing of the nanoparticle core, and redistribution of silicon into certain areas, takes place, forming metastable clusters in the matrix with high silicon content. They seem to be 'pre-precipitations' of the γ-phase of copper, though they really are not. In our opinion, diffraction fringes observed in these particles appear to be metastable phases according to Guinier-Preston zone type, i.e. α-Cu area with excessive silicon content.For nonferrous alloys, room temperature is sufficient for diffusive mobility of atoms of the saluted component [19]. Clusters are formed both at the time of cooling and in the long-term process (i.e. natural ageing). Provided that it is not a new phase, but rather the area of the initial matrix α-Cu solid solution enriched with dissolved silicon, such areas may be treated as Guinier-Preston zones. In contrast to intermediate phases with qualitatively new structures, characterised by their own lattices, Guinier-Preston zones have the same lattice as the matrix solution, but are deformed because of the difference in the atomic diameters of the solute and solvent. There is no clear boundary between the zone and solid solution by which it is surrounded. Compared to concentration fluctuations that appear continuously and are diffused by thermal motion, Guinier-Preston zones are stable for a long time (at low temperatures, for an intermediate amount of time). Experiments have shown that, with the increase of ageing duration, zone sizes are also increased. Furthermore, larger zones grow due to dissolution of the smaller ones, i.e. the same way as in coagulation of crystal grains in the solid state (i.e. collective crystallisation) [19]. The number of the zones at the given ageing temperature does not depend on the alloy composition.In some alloys, Guinier-Preston zones appear immediately after heat treatment or even during the cooling after heat treatment. At the same time, intermediate phases and stable phases appear after the incubation interval. All these facts show that Guinier-Preston zones are different to intermediate and stable phases. This is why Guinier-Preston zones are often called 'pre-precipitations' to differentiate them from real precipitations of intermediate and stable phases with a qualitatively new structure [19].Unlike such a structured approach that treats Guinier-Preston zones as 'pre-precipitations' from a thermodynamic point of view, they can be treated as independent stable phases, intermediate between the matrix solution and the stable phase. Consequently, these zones can be treated as the second phase that is in metastable equilibrium with the matrix solution.Moreover, a Guinier-Preston zone in the dual Cu-Si system with limited solubility of silicon in solid state can have its own line limit of solubility km (Figure 3). Metastable phases with a high content of silicon in the α-Cu matrix crystalline lattice appear below this line.Provided that the Guinier-Preston zone is treated as a phase, at the moment of its origin, the change of the free energy of the alloy is as follows: ΔU = -ΔUtot + ΔUsurf + ΔUel (Utot - total energy of the system, Usurf - surface energy of the crystal, Uel - elastic energy component). Because of the coherence property of the zone and the matrix, the ΔUsurf component can be neglected as its value is very small. Then, at relatively high oversaturation, the energy barrier for the origin of the Guinier-Preston zone should be relatively small, which explains the occurrence of clusters immediately after heat treatment or even at the moment of cooling and following natural ageing.The fact that Guinier-Preston zones can easily appear throughout the whole volume of the matrix solid solution and give the structure of equable decay with high density is of high practical value for us (Figure 2b).Thus, diffraction fringes in copper cores of core-shell nanoparticles should be treated as the second metastable phase, which is in equilibrium with the matrix solid solution. Similar to the exfoliation curve km in the solid solution α-Cu, the solvus curve for γ-Cu with intermediate 'pre-precipitations' can be built. The structure of the boundary with the matrix differentiates Guinier-Preston zones from other intermediate phases. These zones are fully coherent extractions, which is why their boundary with the matrix is poorly defined.As the rate accuracy of basal spacing with the method of electronic diffraction does not exceed 1 Å, according to the data it is not possible to evaluate accurately the change dα-Cu in diffraction fringes of the nanoparticle core; phase nonuniformity of structures has been suggested [26]. This is why it is necessary to treat such structures as solid solutions of α-Cu matrix, with the presence of metastable phases with the deformed crystal lattice.In the fourth case, formation of core-shell nanoparticle Cu/SiO2 happens much like in the third case, but due to the fact the amount of silicon is insufficient for the total fixation of oxygen and copper, a transition zone containing Cu2O is formed. Moiré in such particles are observed at the possible placing of double diffraction from two or more crystals of solid solution α-Cu (Figure 4a) [3]. The nanoparticle according to SAED analysis is very much like a 'sandwich': core α-Cu (Figure 4b, basal spacing d(111) ≈ 2.0 Å, corresponding to the tabular data for Cu), transition zone - copper oxide Cu2O (Figure 5a, basal spacing d(111) ≈ 2.4 Å) and shell - amorphous silicon dioxide, according to the EDAX data, the content of oxygen in this area is greater than 12% [11]. High copper oxide (CuO) was discovered only on the surface of the nanoparticle shell SiO2 (Figure 5b, basal spacing d(111) ≈ 2.5 Å).In the fifth case, when the silicon content is from 8.3-8.5 wt.% to 13 wt.%, copper with silicon in solid state at room temperature forms a continuous series of solid solutions of copper α, γ, ɛ and η. Silicon containing more than 13 wt.% copper undergoes eutectic decomposition only at (η″ + Si) [5]; structurally, such a solution contains eutectics in eutectics. In the obtained powder of nanoparticles, there are no modifications of solid solutions of copper, except for α-Cu.

Simple Derivation of the Maxwell Stress Tensor and Electrostrictive Effects in Crystals

ERIC Educational Resources Information Center

Juretschke, H. J.

1977-01-01

Shows that local equilibrium and energy considerations in an elastic dielectric crystal lead to a simple derivation of the Maxwell stress tensor in anisotropic dielectric solids. The resulting equilibrium stress-strain relations are applied to determine the deformations of a charged parallel plate capacitor. (MLH)

PULMONARY INJURY AND INFLAMMATION FROM REPEATED EXPOSURE TO SOLUBLE COMPONENTS AND SOLID PARTICULATE MATTER (PM)

EPA Science Inventory

Pulmonary injury from acute exposures to PM and the role of soluble versus insoluble PM have received considerable attention; however, their long-term impacts are less well understood. This study compared pulmonary injury and inflammatory responses from repeated exposure to solub...

Rapid, Efficient Determination of Recrystallization Solvents at the Microscale Level.

ERIC Educational Resources Information Center

Craig, Rhoda E. R.

1989-01-01

Presents a procedure used in sophomore level organic chemistry which has been particularly useful for organic qualitative analysis. Uses a nine-well spotplate and one-two mg of solid and three-four drops of eight different solvents. Solubility is checked at different temperatures. Provides a solubility table. (MVL)

Significance of dissolved methane in effluents of anaerobically treated low strength wastewater and potential for recovery as an energy product: A review.

PubMed

Crone, Brian C; Garland, Jay L; Sorial, George A; Vane, Leland M

2016-11-01

The need for energy efficient Domestic Wastewater (DWW) treatment is increasing annually with population growth and expanding global energy demand. Anaerobic treatment of low strength DWW produces methane which can be used to as an energy product. Temperature sensitivity, low removal efficiencies (Chemical Oxygen Demand (COD), Suspended Solids (SS), and Nutrients), alkalinity demand, and potential greenhouse gas (GHG) emissions have limited its application to warmer climates. Although well designed anaerobic Membrane Bioreactors (AnMBRs) are able to effectively treat DWW at psychrophilic temperatures (10-30 °C), lower temperatures increase methane solubility leading to increased energy losses in the form of dissolved methane in the effluent. Estimates of dissolved methane losses are typically based on concentrations calculated using Henry's Law but advection limitations can lead to supersaturation of methane between 1.34 and 6.9 times equilibrium concentrations and 11-100% of generated methane being lost in the effluent. In well mixed systems such as AnMBRs which use biogas sparging to control membrane fouling, actual concentrations approach equilibrium values. Non-porous membranes have been used to recover up to 92.6% of dissolved methane and well suited for degassing effluents of Upflow Anaerobic Sludge Blanket (UASB) reactors which have considerable solids and organic contents and can cause pore wetting and clogging in microporous membrane modules. Microporous membranes can recover up to 98.9% of dissolved methane in AnMBR effluents which have low COD and SS concentrations. Sequential Down-flow Hanging Sponge (DHS) reactors have been used to recover between 57 and 88% of dissolved methane from Upflow Anaerobic Sludge Blanket (UASB) reactor effluent at concentrations of greater than 30% and oxidize the rest for a 99% removal of total dissolved methane. They can also remove 90% of suspended solids and COD in UASB effluents and produce a high quality effluent. In situ degassing can increase process stability, COD removal, biomass retention, and headspace methane concentrations. A model for estimating energy consumption associated with membrane-based dissolved methane recovery predicts that recovered dissolved and headspace methane may provide all the energy required for operation of an anaerobic system treating DWW at psychrophilic temperatures. Copyright © 2016 Elsevier Ltd. All rights reserved.

SOME RARE-EARTH ALLOY SYSTEMS. I. La-Gd, La-Y, Gd-Y

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

Spedding, F.H.; Valletta, R.M.; Daane, A.H.

The La-Y, La--Gd, and Gd--Y alloy systems were examined by conventional metallurgical research techniques. As would be expected from the similarity of the parent metals, the Gd--Y system exhibits complete solid solubility across the system in both the alpha and beta regions, with nearly perfect behavior indicated by the essentially linear plots of lattice constants and other related data, The La--Y and La--Gd systems show complete solid solubility in the high temperature bcc region, with limited solubility in the room temperature forms. In the central region of these two systems at room temperature, an ordered phase with the samarium structuremore » is observed, Some correlation of structure and lattice constants of this phase with the properties of the related pure metals is observed. (auth)« less

A New Extrudable Form of Hypromellose: AFFINISOL™ HPMC HME.

PubMed

Huang, Siyuan; O'Donnell, Kevin P; Keen, Justin M; Rickard, Mark A; McGinity, James W; Williams, Robert O

2016-02-01

Hypromellose is a hydrophilic polymer widely used in immediate- and modified-release oral pharmaceutical dosage forms. However, currently available grades of hypromellose are difficult, if not impossible, to process by hot melt extrusion (HME) because of their high glass transition temperature, high melt viscosity, and low degradation temperature. To overcome these challenges, a modified grade of hypromellose, AFFINISOL™ HPMC HME, was recently introduced. It has a significantly lower glass transition temperature and melt viscosity as compared to other available grades of hypromellose. The objective of this paper is to assess the extrudability and performance of AFFINISOL™ HPMC HME (100LV and 4M) as compared to other widely used polymers in HME, including HPMC 2910 100cP (the currently available hypromellose), Soluplus®, Kollidon® VA 64, and EUDRAGIT® E PO. Formulations containing polymer and carbamazepine (CBZ) were extruded on a co-rotating 16-mm twin-screw extruder, and the effect of temperature, screw speed, and feed rate was investigated. The performance of the solid dispersions was evaluated based on Flory-Huggins modeling and characterized by differential scanning calorimetry (DSC), X-ray powder diffraction (XRD), Raman spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, and dissolution. All formulations extruded well except for HPMC 2910 100cP, which resulted in over-torqueing the extruder (machine overloading because the motor cannot provide efficient energy to rotate the shaft). Among the HME extrudates, only the EUDRAGIT® E PO formulation was crystalline as confirmed by DSC, XRD, and Raman, which agreed with predictions from Flory-Huggins modeling. Dissolution testing was conducted under both sink and non-sink conditions. Sink dissolution testing in neutral media revealed that amorphous CBZ in the HME extrudates completely dissolved within 15 min, which was much more rapid than the time for complete dissolution of bulk CBZ (60 min) and EUDRAGIT® E PO solid dispersion (more than 6 h). Non-sink dissolution in acidic media testing revealed that only CBZ contained in the AFFINISOL™ HPMC HME, and EUDRAGIT® E PO solid dispersions rapidly supersaturated after 15 min, reaching a twofold drug concentration compared to the CBZ equilibrium solubility. In summary, AFFINISOL™ HPMC HME 100LV and AFFINISOL™ HPMC HME 4M are useful in the pharmaceutical HME process to increase wetting and dissolution properties of poorly water-soluble drugs like CBZ.

The Iron-Iron Carbide Phase Diagram: A Practical Guide to Some Descriptive Solid State Chemistry.

ERIC Educational Resources Information Center

Long, Gary J.; Leighly, H. P., Jr.

1982-01-01

Discusses the solid state chemistry of iron and steel in terms of the iron-iron carbide phase diagram. Suggests that this is an excellent way of introducing the phase diagram (equilibrium diagram) to undergraduate students while at the same time introducing the descriptive solid state chemistry of iron and steel. (Author/JN)

Differences in fluorescence characteristics and bioavailability of water-soluble organic matter (WSOM) in sediments and suspended solids in Lihu Lake, China.

PubMed

Wang, Wenwen; Wang, Shuhang; Jiang, Xia; Zheng, Binghui; Zhao, Li; Zhang, Bo; Chen, Junyi

2018-05-01

The spectral characteristics, spatial distribution, and bioavailability of water-soluble organic matter (WSOM) in suspended solids and surface sediments of Lihu Lake, China, were investigated through excitation-emission matrix spectra and parallel factor analysis. The average content of dissolved organic carbon (DOC) in the sediments reached 643.28 ± 58.34 mg C/kg and that in suspended solids was 714.87 ± 69.24 mg C/kg. The fluorescence intensity of WSOM totaled 90.87 ± 5.65 and 115.42 ± 8.02 RU/g for the sediments and suspended solids, respectively. The DOC and fluorescence intensity of the WSOM showed an increasing trend moving from the west to the east of the lake. The WSOM in sediments and suspended solids contained two humic-like (C1 and C2) and one tryptophan-like (C3) components. These components had different fluorescent peaks and relative proportions. In the sediments, the relative proportions of C1, C2, and C3 were 33.71% ± 0.71, 26.83% ± 0.68, and 39.50% ± 0.71%, respectively. Meanwhile, C1 (35.77 ± 0.84%), C2 (34.07 ± 0.61%), and C3 (30.16 ± 0.75%) had similar relative percentages in suspended solids. The sediments had a lower humification index (3.02 ± 0.08) than the suspended solids (4.04 ± 0.15). Exchangeable nitrogen for the sediments and suspended solids was dominated by exchangeable ammonium nitrogen and soluble organic nitrogen, respectively. WSOM plays an important role in migration and transformation of nitrogen in sediments and suspended solids. The sediment-derived WSOM exhibited higher lability and biological activity than did the suspended solid-derived WSOM. The relative ratio of the intensity of protein-like fluorescent component to that of the humic-like one can be used as a reference index to evaluate the lability and biological activity of WSOM in sediments and suspended solids.

Studies on copper alloys containing chromium on the copper side phase diagram

NASA Technical Reports Server (NTRS)

Doi, T.

1984-01-01

Specimens were prepared from vacuum melted alloys of high purity vacuum melted copper and electrolytic chromium. The liquidus and eutectic point were determined by thermal analysis. The eutectic temperature is 1974.8 F and its composition is 1.28 wt% of chromium. The determination of solid solubility of chromium in copper was made by microscopic observation and electrical resistivity measurement. The solubility of chromium in solid copper is 0.6 wt% at 1050 F, 0.4 wt% at 1000 F, 0.25 wt% at 950 F, 0.17 wt% at 900 F, and 0.30 wt% at 840 F.

Kinetics of the isothermal decomposition of zirconium hydride: terminal solid solubility for precipitation and dissolution

NASA Astrophysics Data System (ADS)

Denisov, E. A.; Kompaniets, T. N.; Voyt, A. P.

2018-05-01

The hydrogen permeation technique in the surface-limited regime (SLR) was first used to study the isothermal decomposition of zirconium hydride. It is shown that under isothermal conditions, the hydrogen terminal solid solubility in the α-phase for hydride precipitation (TSSp) and dissolution (TSSd) differ only by 6%, in contrast to the 20-30% indicated in the available literature. It is demonstrated that even the minimum heating/cooling rate (1 C/min) used in the traditional methods of studying TSSp and TSSd is too high to exclude the effect of kinetics on the results obtained.