Nonideality in diffusion of ionic and hydrophobic solutes and pair dynamics in water-acetone mixtures of varying composition.

PubMed

Gupta, Rini; Chandra, Amalendu

2007-07-14

We have performed a series of molecular dynamics simulations of water-acetone mixtures containing either an ionic solute or a neutral hydrophobic solute to study the extent of nonideality in the dynamics of these solutes with variation of composition of the mixtures. The diffusion coefficients of the charged solutes, both cationic and anionic, are found to change nonmonotonically with the composition of the mixtures showing strong nonideality of their dynamics. Also, the extent of nonideality in the diffusion of these charged solutes is found to be similar to the nonideality that is observed for the diffusion and orientational relaxation of water and acetone molecules in these mixtures which show a somewhat similar changes in the solvation characteristics of charged and dipolar solutes with changes of composition of water-acetone mixtures. The diffusion of the hydrophobic solute, however, shows a monotonic increase with increase of acetone concentration showing its different solvation characteristics as compared to the charged and dipolar solutes. The links between the nonideality in diffusion and solvation structures are further confirmed through calculations of the relevant solute-solvent and solvent-solvent radial distribution functions for both ionic and hydrophobic solutes. We have also calculated various pair dynamical properties such as the relaxation of water-water and acetone-water hydrogen bonds and residence dynamics of water molecules in water and acetone hydration shells. The lifetimes of both water-water and acetone-water hydrogen bonds and also the residence times of water molecules are found to increase steadily with increase in acetone concentration. No maximum or minimum was found in the composition dependence of these pair dynamical quantities. The lifetimes of water-water hydrogen bonds are always found to be longer than that of acetone-water hydrogen bonds in these mixtures. The residence times of water molecules are also found to follow a similar trend.

Solvent controlled intramolecular electron transfer in mixtures of 1-butyl-3-methylimidizolium tetrafluoroborate and acetonitrile

NASA Astrophysics Data System (ADS)

Rumble, Christopher A.; Maroncelli, Mark

2018-05-01

Time-resolved emission techniques were used to study the excited-state intramolecular electron transfer of 9-(4-biphenyl)-10-methylacridinium (BPAc+) in mixtures of 1-butyl-3-methylimidizolium tetrafluoroborate ([Im41][BF4])+ acetonitrile (ACN), a mixture previously shown to be of nearly constant polarity and nearly ideal mixing behavior. Reaction times (τrxn) track solvation times (τsolv) as a function of mixture composition over a range of more than 3 orders of magnitude in τsolv. This same correlation extends to a variety of neat dipolar solvents and ionic liquids. Reaction times are ˜2-fold larger than τsolv over most of the range studied but appear to reach a limiting value of ˜3 ps in the fastest solvents.

Effects of solvent concentration and composition on protein dynamics: 13C MAS NMR studies of elastin in glycerol-water mixtures.

PubMed

Demuth, Dominik; Haase, Nils; Malzacher, Daniel; Vogel, Michael

2015-08-01

We use (13)C CP MAS NMR to investigate the dependence of elastin dynamics on the concentration and composition of the solvent at various temperatures. For elastin in pure glycerol, line-shape analysis shows that larger-scale fluctuations of the protein backbone require a minimum glycerol concentration of ~0.6 g/g at ambient temperature, while smaller-scale fluctuations are activated at lower solvation levels of ~0.2 g/g. Immersing elastin in various glycerol-water mixtures, we observe at room temperature that the protein mobility is higher for lower glycerol fractions in the solvent and, thus, lower solvent viscosity. When decreasing the temperature, the elastin spectra approach the line shape for the rigid protein at 245 K for all studied samples, indicating that the protein ceases to be mobile on the experimental time scale of ~10(-5) s. Our findings yield evidence for a strong coupling between elastin fluctuations and solvent dynamics and, hence, such interaction is not restricted to the case of protein-water mixtures. Spectral resolution of different carbon species reveals that the protein-solvent couplings can, however, be different for side chain and backbone units. We discuss these results against the background of the slaving model for protein dynamics. Copyright © 2015 Elsevier B.V. All rights reserved.

Method for forming thin composite solid electrolyte film for lithium batteries

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan (Inventor); Attia, Alan I. (Inventor)

1994-01-01

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a co-solvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Pressurized solvent extraction of pure food grade starch

USDA-ARS?s Scientific Manuscript database

A commercial pressurized solvent extractor was used to remove lipid and non-lipid material from cornstarch using n-propanol/water and ethanol/water mixtures. Yields and chemical composition of the extract fractions were determined. Cornstarch samples were characterized using pasting properties and...

The solvent dependent shift of the amide I band of a fully solvated peptide in methanol/water mixtures as a local probe for the solvent composition in the peptide/solvent interface

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

Gnanakaran, S

2008-01-01

We determine the shift and line-shape of the amide I band of a model AK-peptide from molecular dynamics (MD) simulations of the peptide dissolved in methanol/water mixtures with varying composition. The IR-spectra are determined from a transition dipole coupling exciton model. A simplified empirical model Hamiltonian is employed, taking both the effect of hydrogen bonding, as well as intramolecular vibrational coupling into account. We consider a single isolated AK-peptide in a mostly helical conformation, while the solvent is represented by 2600 methanol or water molecules, simulated for a pressure of 1 bar and a temperature of 300 K. Over themore » course of the simulations minor reversible conformational changes at the termini are observed, which are found to only slightly affect the calculated spectral properties. Over the entire composition range, varying from pure water to the pure methanol solvent, a monotonous blue-shift of the IR amide I band of about 8 wavenumbers is observed. The shift is found to be caused by two counter-compensating effects: An intramolecular red-shift of about 1.2 wavenumbers, due to stronger intramolecular hydrogen-bonding in a methanol-rich environment. Dominating, however, is the intermolecular solvent-dependent blue-shift of about 10 wavenumbers, being attributed to the less effective hydrogen bond donor capabilities of methanol compared to water. The importance of solvent-contribution to the IR-shift, as well as the significantly different hydrogen formation capabilities of water and methanol make the amide I band sensitive to composition changes in the local environment close the peptide/solvent interface. This allows, in principle, an experimental determination of the composition of the solvent in close proximity to the peptide surface. For the AK-peptide case they observe at low methanol concentrations a significantly enhanced methanol concentration at the peptide/solvent-interface, supposedly promoted by the partially hydrophobic character of the AK-peptide's solvent accessible surface.« less

Study of molecular interactions in binary mixtures of 2-chloro-4'methoxy benzoin with various solvents through ultrasonic speed measurements

NASA Astrophysics Data System (ADS)

Thanuja, B.; Kanakam, C.; Nithya, G.

2013-12-01

Density ( ρ) and ultrasonic velocity ( U), for binary mixtures of 2-chloro-4'-methoxy benzoin with ethanol, chloroform, acetonitrile, benzene and 1,4-dioxane of different compositions have been measured at 298 K and explanation of solute solvent interactions and effect of polarity of the solvent on type of interactions are presented in this paper. From the above data, adiabatic compressibility ( β), intermolecular free length ( L f ) and relative association ( R A ) have been calculated. Other useful parameters such as excess density, excess velocity, excess intermolecular freelength and excess adiabatic compressibility have also been calculated. These parameters have been used to study the nature and extent of intermolecular interactions between component molecules in present binary mixtures.

Thermodynamics of DL-alanine solvation in water-dimethylsulfoxide mixtures at 298.15 K

NASA Astrophysics Data System (ADS)

Roy, S.; Mahali, K.; Mondal, S.; Dolui, B. K.

2015-04-01

In this study we mainly discuss the transfer Gibbs free energy Δ G {/t 0}( i) and Δ S {/t 0}( i)entropy of DL-alanine at 298.15 K and consequently the involved chemical transfer free energy (Δ G {/t,ch 0}( i)) and entropy ( TΔ S {/t,ch 0}( i)) in aqueous mixtures of dimethylsulfoxide are discussed to clarify the solvation chemistry of DL-alanine. For the evaluation of these energy terms, solubility of this amino acid has been measured by formol titrimetry at five equidistant temperatures i.e., from 288.15 to 308.15 K in different composition of this mixed solvent system. The various solvent parameters as well as thermodynamic parameters like molar volume, density, dipole moment and solvent diameter of this solvent system have also been reported here. The chemical effects of the transfer Gibbs energies (Δ G {/t,ch 0}( i)) and entropies of transfer ( TΔ S {/t,ch 0}( i)) have been obtained after elimination of cavity effect and dipole-dipole interaction effects from the total transfer energies. Here the chemical contribution of transfer energetics of DL-alanine is mainly guided by the composite effects of increased dispersion interaction, basicity effect and decreased acidity, hydrogen bonding effects, hydrophilic hydration and hydrophobic hydration of aqueous DMSO mixtures as compared to that of reference solvent, water.

Simulation of macromolecule self-assembly in solution: A multiscale approach

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

Lavino, Alessio D., E-mail: alessiodomenico.lavino@studenti.polito.it; Barresi, Antonello A., E-mail: antonello.barresi@polito.it; Marchisio, Daniele L., E-mail: daniele.marchisio@polito.it

2015-12-17

One of the most common processes to produce polymer nanoparticles is to induce self-assembly by using the solvent-displacement method, in which the polymer is dissolved in a “good” solvent and the solution is then mixed with an “anti-solvent”. The polymer ability to self-assemble in solution is therefore determined by its structural and transport properties in solutions of the pure solvents and at the intermediate compositions. In this work, we focus on poly-ε-caprolactone (PCL) which is a biocompatible polymer that finds widespread application in the pharmaceutical and biomedical fields, performing simulation at three different scales using three different computational tools: fullmore » atomistic molecular dynamics (MD), population balance modeling (PBM) and computational fluid dynamics (CFD). Simulations consider PCL chains of different molecular weight in solution of pure acetone (good solvent), of pure water (anti-solvent) and their mixtures, and mixing at different rates and initial concentrations in a confined impinging jets mixer (CIJM). Our MD simulations reveal that the nano-structuring of one of the solvents in the mixture leads to an unexpected identical polymer structure irrespectively of the concentration of the two solvents. In particular, although in pure solvents the behavior of the polymer is, as expected, very different, at intermediate compositions, the PCL chain shows properties very similar to those found in pure acetone as a result of the clustering of the acetone molecules in the vicinity of the polymer chain. We derive an analytical expression to predict the polymer structural properties in solution at different solvent compositions and use it to formulate an aggregation kernel to describe the self-assembly in the CIJM via PBM and CFD. Simulations are eventually validated against experiments.« less

Comparative physicochemical properties of hydrocortisone-PVP composites prepared using supercritical carbon dioxide by the GAS anti-solvent recrystallization process, by coprecipitation and by spray drying.

PubMed

Corrigan, Owen I; Crean, Abina M

2002-10-01

Hydrocortisone-PVP composites were successfully prepared using the supercritical fluid gas anti-solvent method (GAS). Analysis by differential scanning calorimetry DSC and powder X-ray diffraction (XRD) indicated that these systems were more crystalline than corresponding systems prepared by spray drying. These systems, prepared by the GAS method were more similar in physicochemical properties to coprecipitates prepared by conventional solvent evaporation. Compressed composites of hydrocortisone-PVP systems, prepared by the GAS method, had dissolution rates lower than those of corresponding systems prepared by the other processing methods but equivalent to those of corresponding physical mixtures.

Method for forming thin composite solid electrolyte film for lithium batteries

NASA Technical Reports Server (NTRS)

Attia, Alan I. (Inventor); Nagasubramanian, Ganesan (Inventor)

1997-01-01

A composite solid electrolyte film is formed by dissolving a lithium salt such as lithium iodide in a mixture of a first solvent which is a cosolvent for the lithium salt and a binder polymer such as polyethylene oxide and a second solvent which is a solvent for the binder polymer and has poor solubility for the lithium salt. Reinforcing filler such as alumina particles are then added to form a suspension followed by the slow addition of binder polymer. The binder polymer does not agglomerate the alumina particles. The suspension is cast into a uniform film.

Automatized sspKa measurements of dihydrogen phosphate and Tris(hydroxymethyl) aminomethane in acetonitrile/water mixtures from 20 to 60°C.

PubMed

Acquaviva, A; Tascon, M; Padró, J M; Gagliardi, L G; Castells, C B

2014-09-01

We measured pKa values of Tris(hydroxymethyl)aminomethane and dihydrogen phosphate; both are commonly used to prepare buffers for reverse-phase liquid chromatography (RPLC), in acetonitrile/water mixtures from 0% to 70% (v/v) (64.6% (w/w)) acetonitrile and at 20, 30, 40, 50, and 60°C. The procedure is based on potentiometric measurements of pH of buffer solutions of variable solvent compositions using a glass electrode and a novel automated system. The method consists in the controlled additions of small volumes of a thermostated solution from an automatic buret into another isothermal solution containing exactly the same buffer-component concentrations, but a different solvent composition. The continuous changes in the solvent composition induce changes in the potentials. Thus, only two sequences of additions are needed: increasing the amount of acetonitrile from pure water and decreasing the content of acetonitrile from 70% (v/v) (64.6% (w/w)). In the procedure with homemade apparatus, times for additions, stirring, homogenization, and data acquisition are entirely controlled by software programmed for this specific routine. This rapid, fully automated method was applied to acquire more than 40 potential data covering the whole composition range (at each temperature) in about two hours and allowed a systematic study of the effect of temperature and acetonitrile composition on acid-base equilibria of two widely used substances to control pH close to 7. The experimental pKa results were fitted to empirical functions between pKa and temperature and acetonitrile composition. These equations allowed predictions of pKa to estimate the pH of mixtures at any composition and temperature, which would be very useful, for instance, during chromatographic method development. Copyright © 2014 Elsevier B.V. All rights reserved.

N,N'-DICYCLOHEXYL-N"-ISOTRIDECYLGUANIDINE AS SUPPRESSOR FOR THE NEXT GENERATION CAUSTIC SIDE SOLVENT EXTRACTION (NG-CSSX) PROCESS

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

Duncan, Nathan C; Roach, Benjamin D; Williams, Neil J

2012-01-01

ABSTRACT The purity, concentration, and source of the N,N'-dicyclohexyl-N"-isotridecylguanidine (DCiTG) suppressor (guanidine) used in the NG-CSSX process were found to influence solvent performance. As the starting isotridecanol used in the preparation of DCiTG is comprised of a mixture of branched-chain aliphatic alcohols, varying in composition with manufacturer, the resulting DCiTG itself is a mixture. Thus, it is necessary to address how the solvent performance will be affected by the different preparations of the DCiTG solvent component. In this study, four preparations of DCiTG from three sources were analyzed and evaluated for purity and performance, both in the absence and presencemore » of an anionic surfactant impurity.« less

Electro-responsivity of ionic liquid boundary layers in a polar solvent revealed by neutron reflectance

NASA Astrophysics Data System (ADS)

Pilkington, Georgia A.; Harris, Kathryn; Bergendal, Erik; Reddy, Akepati Bhaskar; Palsson, Gunnar K.; Vorobiev, Alexei; Antzutkin, Oleg. N.; Glavatskih, Sergei; Rutland, Mark W.

2018-05-01

Using neutron reflectivity, the electro-responsive structuring of the non-halogenated ionic liquid (IL) trihexyl(tetradecyl)phosphonium-bis(mandelato)borate, [P6,6,6,14][BMB], has been studied at a gold electrode surface in a polar solvent. For a 20% w/w IL mixture, contrast matched to the gold surface, distinct Kiessig fringes were observed for all potentials studied, indicative of a boundary layer of different composition to that of the bulk IL-solvent mixture. With applied potential, the amplitudes of the fringes from the gold-boundary layer interface varied systematically. These changes are attributable to the differing ratios of cations and anions in the boundary layer, leading to a greater or diminished contrast with the gold electrode, depending on the individual ion scattering length densities. Such electro-responsive changes were also evident in the reflectivities measured for the pure IL and a less concentrated (5% w/w) IL-solvent mixture at the same applied potentials, but gave rise to less pronounced changes. These measurements, therefore, demonstrate the enhanced sensitivity achieved by contrast matching the bulk solution and that the structure of the IL boundary layers formed in mixtures is strongly influenced by the bulk concentration. Together these results represent an important step in characterising IL boundary layers in IL-solvent mixtures and provide clear evidence of electro-responsive structuring of IL ions in their solutions with applied potential.

Optimisation of the recovery of carotenoids from tomato processing wastes: application on textile dyeing and assessment of its antioxidant activity.

PubMed

Baaka, Noureddine; El Ksibi, Imen; Mhenni, Mohamed Farouk

2017-01-01

The present study has been focused on the extraction of natural pigments from tomato industry waste. At first, different solvents and solvents mixture were compared to determine which one is the best for extracting carotenoids compounds from tomato by-products. A mixture of hexane and acetone gave the highest carotenoids extraction yield among the others examined. The extraction conditions were optimised using a five-level-five-factor central composite design. Under optimal conditions, solvent solid ratio 90, hexane percentage in the solvent mixture 60, extraction duration 50, number of extractions 4 and extraction temperature 35 °C, the yield of carotenoids was 80.7 μg/g. The coloured extract of tomato by-products was applied on textile fabrics to investigate the dyeing characteristics and antioxidant activities. The results indicate that extract can be applied on textile fabrics (wool, silk and polyamide) to produce coloured clothing with acceptable antioxidant properties.

Process of making carbon-carbon composites

NASA Technical Reports Server (NTRS)

Kowbel, Witold (Inventor); Withers, James C. (Inventor); Bruce, Calvin (Inventor); Vaidyanathan, Ranji (Inventor); Loutfy, Raouf O. (Inventor)

2000-01-01

A carbon composite structure, for example, an automotive engine piston, is made by preparing a matrix including of a mixture of non crystalline carbon particulate soluble in an organic solvent and a binder that has a liquid phase. The non crystalline particulate also contains residual carbon hydrogen bonding. An uncured structure is formed by combining the matrix mixture, for example, carbon fibers such as graphite dispersed in the mixture and/or graphite cloth imbedded in the mixture. The uncured structure is cured by pyrolyzing it in an inert atmosphere such as argon. Advantageously, the graphite reinforcement material is whiskered prior to combining it with the matrix mixture by a novel method involving passing a gaseous metal suboxide over the graphite surface.

Influence of solvent composition on the performance of carbodiimide cross-linked gelatin carriers for retinal sheet delivery.

PubMed

Lai, Jui-Yang

2013-09-01

Gelatin is a protein molecule that displays bioaffinity and provides a template to guide retinal pigment epithelial (RPE) cell organization and growth. We have recently demonstrated that the carbodiimide cross-linked gelatin membranes can be used as retinal sheet carriers. The purpose of this work was to further determine the role of solvent composition in the tissue delivery performance of chemically modified biopolymer matrices. The gelatin molecules were treated with 1-ethyl-3-(3-dimethyl aminopropyl) carbodiimide (EDC) in the presence of binary ethanol/water mixtures with varying ethanol concentrations (70-95 vol%) to obtain the carriers with different cross-linking efficiencies and mechanical properties. Results of melting point measurements and in vitro degradation tests showed that when the cross-linking index reached a high level of around 45 %, the EDC cross-linked gelatin materials have sufficient thermal stability and resistance to enzymatic degradation, indicating their suitability for the development of carriers for retinal sheet delivery. Irrespective of the solvent composition, the chemically modified gelatin samples are compatible toward human RPE cells without causing toxicity and inflammation. In particular, the membrane carriers prepared by the cross-linking in the presence of solvent mixtures containing 80-90 vol% of ethanol have no impact on the proliferative capacity of ARPE-19 cultures and possess good efficiency in transferring and encapsulating the retinal tissues. It is concluded that, except for cell viability and pro-inflammatory cytokine expression, the retinal sheet delivery performance strongly depends on the solvent composition for EDC cross-linking of gelatin molecules.

Communication: Control of chemical reactions using electric field gradients.

PubMed

Deshmukh, Shivaraj D; Tsori, Yoav

2016-05-21

We examine theoretically a new idea for spatial and temporal control of chemical reactions. When chemical reactions take place in a mixture of solvents, an external electric field can alter the local mixture composition, thereby accelerating or decelerating the rate of reaction. The spatial distribution of electric field strength can be non-trivial and depends on the arrangement of the electrodes producing it. In the absence of electric field, the mixture is homogeneous and the reaction takes place uniformly in the reactor volume. When an electric field is applied, the solvents separate and the reactants are concentrated in the same phase or separate to different phases, depending on their relative miscibility in the solvents, and this can have a large effect on the kinetics of the reaction. This method could provide an alternative way to control runaway reactions and to increase the reaction rate without using catalysts.

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

Deshmukh, Shivaraj D.; Tsori, Yoav, E-mail: tsori@bgu.ac.il

We examine theoretically a new idea for spatial and temporal control of chemical reactions. When chemical reactions take place in a mixture of solvents, an external electric field can alter the local mixture composition, thereby accelerating or decelerating the rate of reaction. The spatial distribution of electric field strength can be non-trivial and depends on the arrangement of the electrodes producing it. In the absence of electric field, the mixture is homogeneous and the reaction takes place uniformly in the reactor volume. When an electric field is applied, the solvents separate and the reactants are concentrated in the same phasemore » or separate to different phases, depending on their relative miscibility in the solvents, and this can have a large effect on the kinetics of the reaction. This method could provide an alternative way to control runaway reactions and to increase the reaction rate without using catalysts.« less

A thermodynamic study of complexation process between N, N'-dipyridoxylidene(1,4-butanediamine) and Cd2+ in some binary mixed solvents using conductometry

NASA Astrophysics Data System (ADS)

Ebrahimpoor, Sonia; Khoshnood, Razieh Sanavi; Beyramabadi, S. Ali

2016-12-01

Complexation of the Cd2+ ion with N, N'-dipyridoxylidene(1,4-butanediamine) Schiff base was studied in pure solvents including acetonitrile (AN), ethanol (EtOH), methanol (MeOH), tetrahydrofuran (THF), dimethylformamide (DMF), water (H2O), and various binary solvent mixtures of acetonitrile-ethanol (AN-EtOH), acetonitrile-methanol (AN-MeOH), acetonitrile-tetrahydrofuran (AN-THF), acetonitrile-dimethylformamide (AN-DMF), and acetonitrile-water (AN-H2O) systems at different temperatures using the conductometric method. The conductance data show that the stoichiometry of complex is 1: 1 [ML] in all solvent systems. A non-linear behavior was observed for changes of log K f of [Cd( N, N'-dipyridoxylidene(1,4-butanediamine)] complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions. The results show that the thermodynamics of complexation reaction is affected by the nature and composition of the mixed solvents.

Fabricating porous materials using interpenetrating inorganic-organic composite gels

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

Seo, Dong-Kyun; Volosin, Alex

Porous materials are fabricated using interpenetrating inorganic-organic composite gels. A mixture or precursor solution including an inorganic gel precursor, an organic polymer gel precursor, and a solvent is treated to form an inorganic wet gel including the organic polymer gel precursor and the solvent. The inorganic wet gel is then treated to form a composite wet gel including an organic polymer network in the body of the inorganic wet gel, producing an interpenetrating inorganic-organic composite gel. The composite wet gel is dried to form a composite material including the organic polymer network and an inorganic network component. The composite materialmore » can be treated further to form a porous composite material, a porous polymer or polymer composite, a porous metal oxide, and other porous materials.« less

Waste gas storage

NASA Technical Reports Server (NTRS)

Vickers, Brian D. (Inventor)

1994-01-01

Method for storing a waste gas mixture comprised of nitrogen, oxygen, carbon dioxide, and inert gases, the gas mixture containing corrosive contaminants including inorganic acids and bases and organic solvents, and derived from space station operations. The gas mixture is stored under pressure in a vessel formed of a filament wound composite overwrap on a metal liner, the metal liner being pre-stressed in compression by the overwrap, thereby avoiding any tensile stress in the liner, and preventing stress corrosion cracking of the liner during gas mixture storage.

Structural and thermodynamic properties of the Cm III ion solvated by water and methanol

DOE PAGES

Kelley, Morgan P.; Yang, Ping; Clark, Sue B.; ...

2016-04-27

The geometric and electronic structures of the 9-coordinate Cm 3+ ion solvated with both water and methanol are systematically investigated in the gas phase at each possible solvent-shell composition and configuration using density functional theory and second-order Møller–Plesset perturbation theory. Ab initio molecular dynamics simulations are employed to assess the effects of second and third solvent shells on the gas-phase structure. The ion–solvent dissociation energy for methanol is greater than that of water, potentially because of increased charge donation to the ion made possible by the electron-rich methyl group. Further, the ion–solvent dissociation energy and the ion–solvent distance are shownmore » to be dependent on the solvent-shell composition. Furthermore, this has implications for solvent exchange, which is generally the rate-limiting step in complexation reactions utilized in the separation of curium from complex metal mixtures that derive from the advanced nuclear fuel cycle.« less

Thermodynamic properties of deep eutectic solvent and ionic liquid mixtures at temperatures from 293.15 K to 343.15 K

NASA Astrophysics Data System (ADS)

Achsah, R. S.; Shyam, S.; Mayuri, N.; Anantharaj, R.

2018-04-01

Deep eutectic solvents (DES) and ionic liquids (ILs) have their applications in various fields of research and in industries due to their attractive physiochemical properties. In this study, the combined thermodynamic properties of DES (choline chloride-glycerol) + IL1 (1-butyl-3-methylimiazolium acetate) and DES(choline chloride-glycerol) + IL2 (1-ethyl-3-methylimadzolium ethyl sulphate) have been studied. The thermodynamic properties such as excess molar volume, partial molar volume, excess partial molar volume and apparent molar volume were calculated for different mole fractions ranging from 0 to 1 and varying temperatures from 293.15 K to 343.15 K. In order to know the solvent properties of DESs and ILs mixtures at different temperatures and their molecular interactions to enhance the solvent performance and process efficiency at fixed composition and temperature the thermodynamic properties were analyzed.

The solvation of L-serine in mixtures of water with some aprotic solvents at 298.15 K

NASA Astrophysics Data System (ADS)

Mezhevoi, I. N.; Badelin, V. G.

2009-03-01

The integral enthalpies of solution Δsol H m of L-serine in mixtures of water with acetonitrile, 1,4-dioxane, dimethylsulfoxide (DMSO), and acetone were measured by solution calorimetry at organic component concentrations up to 0.31 mole fractions. The standard enthalpies of solution (Δsol H°), transfer (Δtr H°), and solvation (Δsolv H°) of L-serine from water into mixed solvents were calculated. The dependences of Δsol H°, Δsolv H°, and Δtr H° on the composition of aqueous-organic solvents contained extrema. The calculated enthalpy coefficients of pair interactions of the amino acid with cosolvent molecules were positive and increased in the series acetonitrile, 1,4-dioxane, DMSO, acetone. The results obtained were interpreted from the point of view of various types of interactions in solutions and the influence of the nature of organic solvents on the thermochemical characteristics of solutions.

Morphology and transport in biodegradable polymer compositions based on poly(3-hydroxybutyrate) and polyamide 54C

NASA Astrophysics Data System (ADS)

Zhul'Kina, A. L.; Ivantsova, E. L.; Filatova, A. G.; Kosenko, R. Yu.; Gumargalieva, K. Z.; Iordanskii, A. L.

2009-05-01

Complex investigation of the equilibrium sorption of water, diffusive transport of antiseptic, and morphology of mixed compositions based on polyoxybutirate and polyamide resin 54C has been performed to develop and analyze new biodegradable polymer compositions for controlled release of medicinal substances. Samples of mixtures were prepared by two methods: pressing under pressure and solvent evaporation from a polymer solution. The samples were compared and their morphology was analyzed by scanning electron microscopy. It is shown that the component ratio in the obtained mixtures affects their morphological, transport, and sorption characteristics.

Morphology and transport in biodegradable polymer compositions based on poly(3-hydroxybutyrate) and polyamide 54C

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

Zhul'kina, A. L.; Ivantsova, E. L.; Filatova, A. G.

2009-05-15

Complex investigation of the equilibrium sorption of water, diffusive transport of antiseptic, and morphology of mixed compositions based on polyoxybutirate and polyamide resin 54C has been performed to develop and analyze new biodegradable polymer compositions for controlled release of medicinal substances. Samples of mixtures were prepared by two methods: pressing under pressure and solvent evaporation from a polymer solution. The samples were compared and their morphology was analyzed by scanning electron microscopy. It is shown that the component ratio in the obtained mixtures affects their morphological, transport, and sorption characteristics.

Enthalpy characteristics of L-proline dissolution in certain water-organic mixtures at 298.15 K

NASA Astrophysics Data System (ADS)

Badelin, V. G.; Smirnov, V. I.

2017-01-01

A thermochemical study of the processes of L-proline dissolution in aqueous solutions of acetonitrile, 1,4-dioxane, acetone, dimethyl sulfoxide, nitromethane and tetrahydrofuran at T = 298.15 K in the range of organic solvent concentrations x2 = 0-0.25 mole fractions is performed. Standard values of the enthalpies of solution and transfer of L-proline from water to mixed solvent, and the enthalpy coefficients of pairwise interactions between L-proline and molecules of organic solvents, are calculated. The effect the composition of a water-organic mixture and the structure of organic solvents have on the enthalpy characteristics of L-proline dissolution and transfer is examined. The effect the energy properties of intermolecular interactions between components of a mixed solvent has on the intermolecular interactions between L-proline and molecules of cosolvent is estimated. The correlation between the enthalpy characteristics of L-proline dissolution and electron-donor properties of organic cosolvent in aqueous solutions is determined.

Elastomer toughened polyimide adhesives. [bonding metal and composite material structures for aircraft and spacecraft

NASA Technical Reports Server (NTRS)

St.clair, A. K.; St.clair, T. L. (Inventor)

1985-01-01

A rubber-toughened, addition-type polyimide composition is disclosed which has excellent high temperature bonding characteristics in the fully cured state and improved peel strength and adhesive fracture resistance physical property characteristics. The process for making the improved adhesive involves preparing the rubber-containing amic acid prepolymer by chemically reacting an amine-terminated elastomer and an aromatic diamine with an aromatic dianhydride with which a reactive chain stopper anhydride has been mixed, and utilizing solvent or mixture of solvents for the reaction.

Properties of sugar-based low-melting mixtures

NASA Astrophysics Data System (ADS)

Fischer, Veronika; Kunz, Werner

2014-05-01

Physico-chemical properties of ternary sugar-based low-melting mixtures were determined. Choline chloride, urea and glucose or sorbitol, serving as sugars, were blended in various compositions. The refractive index, density, viscosity, decomposition temperatures and glass transition temperatures were measured. Further, the influence of temperature and water content was investigated. The results show that the mixtures are liquid below room temperature and the viscosity and density are dependent on the temperature and composition. Moreover, the viscosity decreases with increasing water content. These mixtures are biodegradable, low toxic, non-volatile, non-reactive with water and can be accomplished with low-cost materials. In consideration of these advantages and a melting point below room temperature, these low-melting mixtures can be a good alternative to ionic liquids as well as environmentally unfriendly and toxic solvents.

Solvent coarsening around colloids driven by temperature gradients

NASA Astrophysics Data System (ADS)

Roy, Sutapa; Dietrich, Siegfried; Maciolek, Anna

2018-04-01

Using mesoscopic numerical simulations and analytical theory, we investigate the coarsening of the solvent structure around a colloidal particle emerging after a temperature quench of the colloid surface. Qualitative differences in the coarsening mechanisms are found, depending on the composition of the binary liquid mixture forming the solvent and on the adsorption preferences of the colloid. For an adsorptionwise neutral colloid, the phase next to its surface alternates as a function of time. This behavior sets in on the scale of the relaxation time of the solvent and is absent for colloids with strong adsorption preferences. A Janus colloid, with a small temperature difference between its two hemispheres, reveals an asymmetric structure formation and surface enrichment around it, even if the solvent is within its one-phase region and if the temperature of the colloid is above the critical demixing temperature Tc of the solvent. Our phenomenological model turns out to capture recent experimental findings according to which, upon laser illumination of a Janus colloid and due to the ensuing temperature gradient between its two hemispheres, the surrounding binary liquid mixture develops a concentration gradient.

Effect of Tunable Surface Potential on the Structure of Spin-Cast Polymeric Blend Films

NASA Astrophysics Data System (ADS)

Hawker, C.; Huang, E.; Russell, T. P.

1998-03-01

The demixing of binary polymeric mixtures has been studied with various surface potentials. This was performed by spin casting polystyrene/poly(methyl methacrylate) mixtures on to silicon substrates that had been modified with an end-grafted random copolymer brush layer. The composition of the random copolymer brush, containing the same monomeric components as the homopolymers can be varied in a precise manner over the entire concentration range. Atomic force and optical microscopy were used to study the morphology formed during spin casting and after annealing. Further insight into the structure was gained by rinsing these films with preferential solvents to remove one of the constituents and by performing the microscopy measurements. Finally, x-ray photoelectron spectroscopy, XPS, was used to elucidate the composition of the film near the air/polymer interface. Our data show that the resulting thin film structure depends strongly on the composition of the end grafted random copolymer film. Furthermore, the effect of thickness, solvent used in casting, and annealing conditions will be addressed.

Modeling water partition in composite gels of BSA with gelatin following high pressure treatment.

PubMed

Semasaka, Carine; Mhaske, Pranita; Buckow, Roman; Kasapis, Stefan

2018-11-01

Changes in the structural properties of hydrogels made with gelatin and bovine serum albumin mixtures were recorded following exposure to high pressure at 300 MPa for 15 min at 10 and 80 °C. Dynamic oscillation, SEM, FTIR and blending law modelling were utilised to rationalise results. Pressurization at the low temperature end yielded continuous gelatin networks supporting discontinuous BSA inclusions, whereas an inverted dispersion was formed at the high temperature end with the continuous BSA network suspending the discontinuous gelatin inclusions. Lewis and Nielsen equations followed the mechanical properties of the composites thus arguing that solvent partition between the two phases was always in favour of the polymer forming the continuous network. As far as we are aware, this is the first attempt to elucidate the solvent partition in pressurised hydrogel composites using blending law theory. Outcomes were contrasted with earlier work where binary mixtures were subjected only to thermal treatment. Copyright © 2018. Published by Elsevier Ltd.

Environmentally Friendly Cleaners for Removing Tar from Metal Surfaces

DTIC Science & Technology

2009-04-01

treatment plants that handle phosphate type solu- tions. The terms used by commercial vendors such as environmentally friendly, all natural, green, and...solvents used in relation to diesel fuel, and the procedure can also rank solvents quantitatively. Sacco (2004) has studied the blending of two plant ...other bituminous materials from industrial equipment surfaces. The composition is a mixture of a carrier monocyclic monoterpene and a nonionic

Effect of the composition of a solution on the enthalpies of solvation of piperidine in methanol-acetonitrile and dimethylsulfoxide-acetonitrile mixed solvents

NASA Astrophysics Data System (ADS)

Kuz'mina, I. A.; Volkova, M. A.; Sitnikova, K. A.; Sharnin, V. A.

2014-01-01

Heat effects of dissolution of piperidine (ppd) are measured by calorimetry at 298.15 K over the range of composition of acetonitrile-methanol (AN-MeOH) mixed solvents. Based on the Δsol H ○(ppd)AN-MeOH values obtained using the literature data on Δsol H ○ (ppd) in acetonitrile-dimethylsulfoxide (AN-DMSO) mixed solvents and the vaporization enthalpy of ppd, the enthalpies of solvation of amine in AN-MeOH and AN-DMSO binary mixtures are calculated. A rise in the exothermicity of solvation of piperidine is observed upon the transition from AN to DMSO and MeOH, due mainly to the enhanced solvation of the amino group of ppd as a result of changes in the acid-base properties of the mixed solvent.

Molecular simulations of electrolyte structure and dynamics in lithium-sulfur battery solvents

NASA Astrophysics Data System (ADS)

Park, Chanbum; Kanduč, Matej; Chudoba, Richard; Ronneburg, Arne; Risse, Sebastian; Ballauff, Matthias; Dzubiella, Joachim

2018-01-01

The performance of modern lithium-sulfur (Li/S) battery systems critically depends on the electrolyte and solvent compositions. For fundamental molecular insights and rational guidance of experimental developments, efficient and sufficiently accurate molecular simulations are thus in urgent need. Here, we construct a molecular dynamics (MD) computer simulation model of representative state-of-the art electrolyte-solvent systems for Li/S batteries constituted by lithium-bis(trifluoromethane)sulfonimide (LiTFSI) and LiNO3 electrolytes in mixtures of the organic solvents 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL). We benchmark and verify our simulations by comparing structural and dynamic features with various available experimental reference systems and demonstrate their applicability for a wide range of electrolyte-solvent compositions. For the state-of-the-art battery solvent, we finally calculate and discuss the detailed composition of the first lithium solvation shell, the temperature dependence of lithium diffusion, as well as the electrolyte conductivities and lithium transference numbers. Our model will serve as a basis for efficient future predictions of electrolyte structure and transport in complex electrode confinements for the optimization of modern Li/S batteries (and related devices).

Preparation, isolation, and characterization of cutin monomers and oligomers from tomato peels.

PubMed

Osman, S F; Irwin, P; Fett, W F; O'Connor, J V; Parris, N

1999-02-01

Cutin in tomato peels was depolymerized in methanolic base to yield cutin monomers or a mixture of cutin oligomers. These products were isolated by typical solvent extraction methods or by precipitation, and the isolates were characterized by chromatographic and spectroscopic analyses. It was determined that the compositions of the isolates from both isolation procedures were similar, although solvent extraction gave higher yields. However, the precipitation method, which is easy to carry out and avoids the use of undesirable organic solvents, may be preferable in commercial processes for recovering these compounds.

Synergetic Effects of Alcohol/Water Mixing on the Catalytic Reductive Fractionation of Poplar Wood

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

Renders, Tom; Van den Bosch, Sander; Vangeel, Thijs

One of the foremost challenges in lignocellulose conversion encompasses the integration of effective lignin valorization in current carbohydrate-oriented biorefinery schemes. Catalytic reductive fractionation (CRF) of lignocellulose offers a technology to simultaneously produce lignin-derived platform chemicals and a carbohydrate-enriched pulp via the combined action of lignin solvolysis and metal-catalyzed hydrogenolysis. Herein, the solvent (composition) plays a crucial role. In this contribution, we study the influence of alcohol/water mixtures by processing poplar sawdust in varying MeOH/water and EtOH/water blends. The results show particular effects that strongly depend on the applied water concentration. Low water concentrations enhance the removal of lignin from themore » biomass, while the majority of the carbohydrates are left untouched (scenario A). Contrarily, high water concentrations favor the solubilization of both hemicellulose and lignin, resulting in a more pure cellulosic residue (scenario B). For both scenarios, an evaluation was made to determine the most optimal solvent composition, based on two earlier introduced empirical efficiency descriptors (denoted LFDE and LFFE). According to these measures, 30 (A) and 70 vol % water (B) showed to be the optimal balance for both MeOH/water and EtOH/water mixtures. This successful implementation of alcohol/water mixtures allows operation under milder processing conditions in comparison to pure alcohol solvents, which is advantageous from an industrial point of view.« less

Change in the Gibbs energy of 18-crown-6 ether transfer from methanol to methanol-acetonitrile mixtures at 298 K

NASA Astrophysics Data System (ADS)

Kuz'mina, I. A.; Usacheva, T. R.; Kuz'mina, K. I.; Volkova, M. A.; Sharnin, V. A.

2015-01-01

The Gibbs energies of the transfer of 18-crown-6 ether from methanol to its mixtures with acetonitrile (χAN = 0.0-1.0 mole fraction) are determined by means of interphase distribution at 298 K. The effect the solvent composition has on the thermodynamic characteristics of the solvation of 18-crown-6 ether is analyzed. An increase in the content of acetonitrile in the mixed solvent enhances the solvation of crown ether due to changes in the energy of the solution. Resolvation of the macrocycle is assumed to be complete at acetonitrile concentrations higher than 0.6 mole fraction.

Advanced dielectric continuum model of preferential solvation

NASA Astrophysics Data System (ADS)

Basilevsky, Mikhail; Odinokov, Alexey; Nikitina, Ekaterina; Grigoriev, Fedor; Petrov, Nikolai; Alfimov, Mikhail

2009-01-01

A continuum model for solvation effects in binary solvent mixtures is formulated in terms of the density functional theory. The presence of two variables, namely, the dimensionless solvent composition y and the dimensionless total solvent density z, is an essential feature of binary systems. Their coupling, hidden in the structure of the local dielectric permittivity function, is postulated at the phenomenological level. Local equilibrium conditions are derived by a variation in the free energy functional expressed in terms of the composition and density variables. They appear as a pair of coupled equations defining y and z as spatial distributions. We consider the simplest spherically symmetric case of the Born-type ion immersed in the benzene/dimethylsulfoxide (DMSO) solvent mixture. The profiles of y(R ) and z(R ) along the radius R, which measures the distance from the ion center, are found in molecular dynamics (MD) simulations. It is shown that for a given solute ion z(R ) does not depend significantly on the composition variable y. A simplified solution is then obtained by inserting z(R ), found in the MD simulation for the pure DMSO, in the single equation which defines y(R ). In this way composition dependences of the main solvation effects are investigated. The local density augmentation appears as a peak of z(R ) at the ion boundary. It is responsible for the fine solvation effects missing when the ordinary solvation theories, in which z =1, are applied. These phenomena, studied for negative ions, reproduce consistently the simulation results. For positive ions the simulation shows that z ≫1 (z =5-6 at the maximum of the z peak), which means that an extremely dense solvation shell is formed. In such a situation the continuum description fails to be valid within a consistent parametrization.

Analysis of non-phthalates plasticizers on porous graphitic carbon by supercritical fluid chromatography using evaporative light scattering detection.

PubMed

Vaccher, Claude; Decaudin, Bertrand; Sautou, Valérie; Lecoeur, Marie

2014-09-12

The analysis of several plasticizers, widely used in the production of medical devices, was investigated on porous graphitic carbon (PGC) stationary phase in supercritical fluid chromatography (SFC) with an evaporative light scattering detector (ELSD). Due to strong interaction of compounds with the PGC support, solvents of strong eluotropic strength were added to the CO2 supercritical fluid. The effect of alkyl chain (pentane, hexane, heptane) and chlorinated (CH2Cl2, CHCl3, CCl4) solvents was studied on the retention and on the ELSD detection of plasticizers. A co-solvent mixture composed of CHCl3/heptane, eluted under gradient mode, allowed a significant improvement of the ELSD response compared to the use of each solvent individually. Then, a central composite design (CCD) was implemented to optimize both the separation and the detection of plasticizers. The parameters involved were the outlet pressure, the gradient slope, the co-solvent composition and the drift tube temperature of the ELSD. After optimization, baseline separation of plasticizers was achieved in 7min and best signal-to-noise ratios were obtained with outlet pressure and drift tube temperature of ELSD set at 200bar and 31°C, respectively. The co-solvent mixture was also composed of CHCl3/heptane (35/65 v/v) and a gradient from 15 to 60% of co-solvent in 2.2min was employed. The results demonstrated that CCD is a powerful tool for the optimization of SFC/ELSD method and the response surface model analysis can provide statistical understandings of the significant factors required to achieve optimal separation and ELSD sensitivity. Copyright © 2014 Elsevier B.V. All rights reserved.

Supercritical extraction of lycopene from tomato industrial wastes with ethane.

PubMed

Nobre, Beatriz P; Gouveia, Luisa; Matos, Patricia G S; Cristino, Ana F; Palavra, António F; Mendes, Rui L

2012-07-11

Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO₂ and a near critical mixture of ethane and propane). The recovery of all-E-lycopene increased with pressure, decreased with the increase of the particle size in the initial stages of the extraction and was not practically affected by the solvent superficial velocity. The effect of the temperature was more complex. When the temperature increased from 40 to 60 °C the recovery of all-E-lycopene increased from 80 to 90%. However, for a further increase to 80 °C, the recovery remained almost the same, indicating that some E-Z isomerization could have occurred, as well as some degradation of lycopene. The recovery of all-E-lycopene was almost the same for feed samples with different all-E-lycopene content. Furthermore, when a batch with a higher all-E-lycopene content was used, supercritical ethane and a near critical mixture of ethane and propane showed to be better solvents than supercritical CO₂ leading to a faster extraction with a higher recovery of the carotenoid.

Electrolytes for Low-Temperature Operation of Li-CFx Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Whitacre, Jay F.; Bugga, Ratnakumar V.; Prakash, G. K. Surya; Bhalla, Pooja; Smith, Kiah

2009-01-01

A report describes a study of electrolyte compositions selected as candidates for improving the low-temperature performances of primary electrochemical cells that contain lithium anodes and fluorinated carbonaceous (CFx) cathodes. This study complements the developments reported in Additive for Low-Temperature Operation of Li-(CF)n Cells (NPO- 43579) and Li/CFx Cells Optimized for Low-Temperature Operation (NPO- 43585), which appear elsewhere in this issue of NASA Tech Briefs. Similar to lithium-based electrolytes described in several previous NASA Tech Briefs articles, each of these electrolytes consisted of a lithium salt dissolved in a nonaqueous solvent mixture. Each such mixture consisted of two or more of the following ingredients: propylene carbonate (PC); 1,2-dimethoxyethane (DME); trifluoropropylene carbonate; bis(2,2,2-trifluoroethyl) ether; diethyl carbonate; dimethyl carbonate; and ethyl methyl carbonate. The report describes the physical and chemical principles underlying the selection of the compositions (which were not optimized) and presents results of preliminary tests made to determine effects of the compositions upon the low-temperature capabilities of Li-CFx cells, relative to a baseline composition of LiBF4 at a concentration of 1.0 M in a solvent comprising equal volume parts of PC and DME.

From nicotinate-containing layered double hydroxides (LDHs) to NAD coenzyme-LDH nanocomposites - Syntheses and structural characterization by various spectroscopic methods

NASA Astrophysics Data System (ADS)

Muráth, Szabolcs; Dudás, Csilla; Kukovecz, Ákos; Kónya, Zoltán; Sipos, Pál; Pálinkó, István

2017-07-01

The syntheses of nicotinate anion- and NAD coenzyme-layered double hydroxide (LDH) composites were performed with the aim of having the organic component among the layers. In-house prepared CaAl-LDHs were the host materials. Intercalation was attempted by direct ion exchange or by the dehydration-rehydration method applying aqueous solvent mixtures (containing ethanol, propanol, acetone, N,N-dimethylformamide). For structural characterization, beside X-ray diffractometry, X-ray photoelectron and IR spectroscopies, transmission and scanning electron microscopies as well as energy-dispersive X-ray analysis were used. Molecular modelling served for the visualization of the arrangements of the intercalated ions among the layers of the LDH samples. Although not all the intercalation methods and solvent mixtures led to intercalated composite materials, successful ones could be identified. The combination of spectroscopic methods helped in proposing sensible spatial arrangements for the intercalated anions. The NAD-CaAl-LDH composite proved to be an active catalyst in the oxidation of hydroquinone to 1,4-bezoquinoe in the presence of H2O2.

Microchip electrospray: improvements in spray and signal stability during gradient elution by an inverted postcolumn makeup flow.

PubMed

Jung, Stephanie; Effelsberg, Uwe; Tallarek, Ulrich

2011-12-01

Dynamic changes in mobile phase composition during high-performance liquid chromatography (HPLC) gradient elution coupled to mass spectrometry (MS) sensitively affect electrospray modes. We investigate the impact of the eluent composition on spray stability and MS response by infusion and injection experiments with a small tetrapeptide in water-acetonitrile mixtures. The employed HPLC/electrospray (ESI)-MS configuration uses a microchip equipped with an enrichment column, a separation column, and a makeup flow (MUF) channel. One nano pump is connected to the separation column, while a second one delivers solvent of exactly inverted composition to the MUF channel. Both solvent streams are united behind the separation column, before the ESI tip, such that the resulting electrosprayed solution always has identical composition during a gradient elution. Analyte peak parameters without and with MUF compensation are determined and discussed with respect to the electrospray mode and eluent composition. The postcolumn MUF significantly improves spray and signal stability over the entire solvent gradient, without compromising the performance of the HPLC separation column. It can also be conveniently implemented on microchip platforms.

Oak (Quercus frainetto Ten.) honeydew honey--approach to screening of volatile organic composition and antioxidant capacity (DPPH and FRAP assay).

PubMed

Jerković, Igor; Marijanović, Zvonimir

2010-05-25

Two samples of oak honeydew honey were investigated. Headspace solid-phase microextraction (HS-SPME) combined with GC and GC/MS enabled identification of the most volatile organic headspace compounds being dominated by terpenes(mainly cis- and trans-linalool oxides). The volatile and less-volatile organic composition of the samples was obtained by ultrasonic assisted extraction (USE) with two solvents (1:2 (v/v) pentane -diethyl ether mixture and dichloromethane) followed by GC and GC/MS analysis. Shikimic pathway derivatives are of particular interest with respect to the botanical origin of honey and the most abundant was phenylacetic acid (up to 16.4%). Antiradical activity (DPPH assay) of the honeydew samples was 4.5 and 5.1 mmol TEAC/kg. Ultrasonic solvent extracts showed several dozen times higher antiradical capacity in comparison to the honeydew. Antioxidant capacity (FRAP assay) of honeydew samples was 4.8 and 16.1 mmol Fe(2+)/kg, while the solvent mixture extracts showed antioxidant activity of 374.5 and 955.9 Fe(2+)/kg, respectively, and the dichloromethane extracts 127.3 and 101.5 mmol Fe(2+)/kg.

Microcalorimetric study of thermal unfolding of lysozyme in water/glycerol mixtures: An analysis by solvent exchange model

NASA Astrophysics Data System (ADS)

Spinozzi, Francesco; Ortore, Maria Grazia; Sinibaldi, Raffaele; Mariani, Paolo; Esposito, Alessandro; Cinelli, Stefania; Onori, Giuseppe

2008-07-01

Folded protein stabilization or destabilization induced by cosolvent in mixed aqueous solutions has been studied by differential scanning microcalorimetry and related to difference in preferential solvation of native and denatured states. In particular, the thermal denaturation of a model system formed by lysozyme dissolved in water in the presence of the stabilizing cosolvent glycerol has been considered. Transition temperatures and enthalpies, heat capacity, and standard free energy changes have been determined when applying a two-state denaturation model to microcalorimetric data. Thermodynamic parameters show an unexpected, not linear, trend as a function of solvent composition; in particular, the lysozyme thermodynamic stability shows a maximum centered at water molar fraction of about 0.6. Using a thermodynamic hydration model based on the exchange equilibrium between glycerol and water molecules from the protein solvation layer to the bulk, the contribution of protein-solvent interactions to the unfolding free energy and the changes of this contribution with solvent composition have been derived. The preferential solvation data indicate that lysozyme unfolding involves an increase in the solvation surface, with a small reduction of the protein-preferential hydration. Moreover, the derived changes in the excess solvation numbers at denaturation show that only few solvent molecules are responsible for the variation of lysozyme stability in relation to the solvent composition.

Morphology of molecular soy protein fractions in binary composite gels.

PubMed

Kasapis, Stefan; Tay, Sok Li

2009-08-04

We investigate the structural properties of gels of binary mixtures of the three major soy protein fractions: 11S, 7S, and 2S. Gels are formed at 25 degrees C in the presence of glucono-delta-lactone and studied using a combination of dynamic rheology and scanning electron microscopy. The theological data was then modeled using a blending-law approach that yields insights into the solvent distribution between the gelled protein fractions and first-order reaction kinetics that follow the gelation process of the single fractions and their mixtures. Gelled mixtures of 11S and 7S yielded enhanced network strength with increasing solid content; in these gels, 50% more solvent partitioned into the 11S phase as compared to that in the 7S phase. In contrast, the addition of small-molecular-weight counterpart 2S to either 11S or 7S results in a catastrophic drop in the values of the overall strength of the mixture. The unexpected phase behavior has been rationalized on the basis of the high water-holding capacity of 2S; 450% more solvent partitions preferentially into the 2S phase as compared to that in the 11S phase. As the concentration of 2S is increased relative to that of 11S or 7S, it becomes the dominant phase and entraps the polymeric segments of 11S (or 7S), thus preventing them from becoming the structural knots of the gel. In addition to the solvent distribution in the gel, the rates of gelation differ markedly between 11S and 2S (with the 11S rate of gelation being up to 2 orders of magnitude greater); a fixed 11S concentration, the rate of gelation decreases with increasing amounts of 2S, further confirming that the latter essentially becomes the dominant phase in the composite gel.

Supercritical CO2 foamed polycaprolactone scaffolds for controlled delivery of 5-fluorouracil, nicotinamide and triflusal.

PubMed

Salerno, Aurelio; Saurina, Javier; Domingo, Concepción

2015-12-30

The manufacture of porous polycaprolactone (PCL) scaffolds containing three different drugs, namely 5-fluorouracil, nicotinamide and triflusal, was investigated in this work with the aim of obtaining bioactive systems with controlled drug delivery capabilities. The scaffolds were prepared by means of a supercritical CO2 (scCO2) foaming technique by optimizing the drug loading process. This was achieved by dissolving the drugs in organic solvents miscible with scCO2 and by mixing these drug/solvent solutions with PCL powder. The as prepared mixtures were further compressed to eliminate air bubbles and finally processed by the scCO2 foaming technique. ScCO2 saturation and foaming conditions were optimized to create the porosity within the samples and to allow for the concomitant removal of the organic solvents. Physical and chemical properties of porous scaffolds, as well as drug content and delivery profiles, were studied by HPLC. The results of this study demonstrated that the composition of the starting PCL/drug/solvent mixtures affected polymer crystallization, scaffold morphology and pore structure features. Furthermore, it was found that drug loading efficiency depended on both initial solution composition and drug solubility in scCO2. Nevertheless, in the case of highly scCO2-soluble drugs, such as triflusal, loading efficiency was improved by adding a proper amount of free drug inside of the pressure vessel. The drug delivery study indicated that release profiles depended mainly upon scaffolds composition and pore structure features. Copyright © 2015 Elsevier B.V. All rights reserved.

Membrane formation in liquids by adding an antagonistic salt

NASA Astrophysics Data System (ADS)

Sadakane, Koichiro; Seto, Hideki

2018-03-01

Antagonistic salts are composed of hydrophilic and hydrophobic ions. In a binary mixture, such as water and organic solvent, these ion pairs preferentially dissolve to those phases, respectively, and there is a coupling between the charge density and the composition. The heterogeneous distribution of ions forms a large electric double layer at the interface between these solvents. This reduces the interfacial tension between water and organic solvent, and stabilizes an ordered structure, such as a membrane. These phenomena have been extensively studied from both theoretical and experimental point of view. In addition, the numerical simulations can reproduce such ordered structures.

Elastomer toughened polyimide adhesives

NASA Technical Reports Server (NTRS)

St.clair, A. K.; St.clair, T. L. (Inventor)

1983-01-01

A rubber-toughened addition-type polyimide composition is disclosed which has excellent high temperature bonding characteristics in the fully cured state, and improved peel strength and adhesive fracture resistance physical property characteristics. The process for making the improved adhesive involves preparing the rubber containing amic acid prepolymer by chemically reacting an amine-terminated elastomer and an aromatic diamine with an aromatic dianhydride with which a reactive chain stopper anhydride was mixed, and utilizing solvent or mixture of solvents for the reaction.

One-pot low-temperature green synthesis of magnetic graphene nanocomposite for the selective reduction of nitrobenzene

NASA Astrophysics Data System (ADS)

Haridas, Vijayasree; Sugunan, Sankaran; Narayanan, Binitha N.

2018-06-01

In the present study, a green one-pot low-temperature method is adopted for the synthesis of a novel magnetic graphene nanocomposite catalyst. Graphene preparation is performed without employing any oxidizing agents or corrosive chemicals, under mild sonication in isopropyl alcohol - water mixture. Monolayered nanoplatelets of graphene are obtained in the green solvent mixture and the composite material is found to be ferromagnetic in nature, obvious from the vibrating sample magnetometric measurements. Fe in the nanocomposite exists in two different forms i.e., α-Fe2O3 and α-FeOOH, as evident from the material characterization results. The graphene nanocomposite is found to be highly efficient in the selective reduction of nitrobenzene to aniline under solvent free reaction conditions and magnetic separation of this fine nanomaterial from the reaction mixture is successfully carried out. The catalyst is efficiently reusable till five repeated cycles.

Tuning Organic Carbon Dioxide Absorbents for Carbonation and Decarbonation

PubMed Central

Rajamanickam, Ramachandran; Kim, Hyungsoo; Park, Ji-Woong

2015-01-01

The reaction of carbon dioxide with a mixture of a superbase and alcohol affords a superbase alkylcarbonate salt via a process that can be reversed at elevated temperatures. To utilize the unique chemistry of superbases for carbon capture technology, it is essential to facilitate carbonation and decarbonation at desired temperatures in an easily controllable manner. Here, we demonstrate that the thermal stabilities of the alkylcarbonate salts of superbases in organic solutions can be tuned by adjusting the compositions of hydroxylic solvent and polar aprotic solvent mixtures, thereby enabling the best possible performances to be obtained from the various carbon dioxide capture agents based on these materials. The findings provides valuable insights into the design and optimization of organic carbon dioxide absorbents. PMID:26033537

Technique for the polymerization of monomers for PPQ/graphite fiber composites

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Delvigs, P.; Vannucci, R. D.

1973-01-01

Impregnation of fiber prior to appreciable polymerization completely eliminates impregnation problems encountered with use of high viscosity high molecular weight polyphenylquinoxalines (PPQ) solutions. Major part of polymerization of reactant mixture is conducted on fiber during solvent removal and final curing stages.

Biofoam II

DOEpatents

Morrison, R.L.

1994-11-01

Biofoam is a rigid, microcellular organic foam made from organic materials derived from natural products and biological organisms. Starting materials include agar, agarose, gelatin, algin, alginates, gellan gum, and microcrystalline cellulose. The organic material is dissolved in a polar solvent, typically water, and the mixture is gelled. The water in the gel pores is replaced at least once with another solvent to reduce the pore size of the final biofoam. The solvent in the gel pores may be replaced several times. After the final replacement of solvent, the gel is frozen and freeze-dried to form a biofoam. Translucent biofoams are formed by selecting a final solvent that forms very small crystals. A variety of crystalline, fibrous, amorphous, or metallic additives may be incorporated into the foam structure to produce lightweight composite materials with enhanced strength and insulating properties. 1 fig.

Biofoam II

DOEpatents

Morrison, Robert L.

1994-01-01

Biofoam is a rigid, microcellular organic foam made from organic materials derived from natural products and biological organisms. Starting materials include agar, agarose, gelatin, algin, alginates, gellan gum, and microcrystalline cellulose. The organic material is dissolved in a polar solvent, typically water, and the mixture is gelled. The water in the gel pores is replaced at least once with another solvent to reduce the pore size of the final biofoam. The solvent in the gel pores may be replaced several times. After the final replacement of solvent, the gel is frozen and freeze-dried to form a biofoam. Translucent biofoams are formed by selecting a final solvent that forms very small crystals. A variety of crystalline, fibrous, amorphous, or metallic additives may be incorporated into the foam structure to produce lightweight composite materials with enhanced strength and insulating properties.

Electrolyte for stable cycling of high-energy lithium sulfur redox flow batteries

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

Xiao, Jie; Liu, Jun; Pan, Huilin

A device comprising: a lithium sulfur redox flow battery comprising an electrolyte composition comprising: (i) a dissolved Li 2S x electroactive salt, wherein x.gtoreq.4; (ii) a solvent selected from dimethyl sulfoxide, tetrahydrofuran, or a mixture thereof; and (iii) a supporting salt at a concentration of at least 2 M, as measured by moles of supporting salt divided by the volume of the solvent without considering the volume change of the electrolyte after dissolving the supporting salt.

Physicochemical properties of binary solutions of propylene carbonate-acetonitrile in the range of 253.15-313.15 K

NASA Astrophysics Data System (ADS)

Tyunina, E. Yu.; Chekunova, M. D.

2017-05-01

The density, dynamic viscosity, and dielectric constant of propylene carbonate solutions with acetonitrile are measured over the composition of a mixed solvent at temperatures of 253.15, 273.15, 293.15, and 313.15 K. The molar volume, molar viscosity, and molar capacity of a mixture of propylene carbonate-acetonitrile and an excess amount of it are calculated. The effect the temperature and composition of the mixture have on the excess molar properties is discussed. A linear correlation is observed between the values of the molar fluidity, capacity, polarization, and molar volume of the studied system.

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2010 CFR

2010-07-01

... Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Averageboiling point * (degrees F) Criteria Reactivityfactor 1 80-205 Alkanes... + Dry Point) / 2 (b) Aromatic Hydrocarbon Solvents ...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2011 CFR

2011-07-01

... Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Averageboiling point * (degrees F) Criteria Reactivityfactor 1 80-205 Alkanes... + Dry Point) / 2 (b) Aromatic Hydrocarbon Solvents ...

Thermodynamic study of complex formation between Ce3+ and cryptand 222 in some binary mixed nonaqueous solvents

NASA Astrophysics Data System (ADS)

Rounaghi, G. H.; Dolatshahi, S.; Tarahomi, S.

2014-12-01

The stoichiometry, stability and the thermodynamic parameters of complex formation between cerium(III) cation and cryptand 222 (4,7,13,16,21,24-hexaoxa-1,10-diazabycyclo[8.8.8]-hexacosane) were studied by conductometric titration method in some binary solvent mixtures of dimethylformamide (DMF), 1,2-dichloroethane (DCE), ethyl acetate (EtOAc) and methyl acetate (MeOAc) with methanol (MeOH), at 288, 298, 308, and 318 K. A model based on 1: 1 stoichiometry has been used to analyze the conductivity data. The data have been fitted according to a non-linear least-squares analysis that provide the stability constant, K f, for the cation-ligand inclusion complex. The results revealed that the stability order of [Ce(cryptand 222)]3+ complex changes with the nature and composition of the solvent system. A non-linear relationship was observed between the stability constant (log K f) of [Ce(cryptand 222)]3+ complex versus the composition of the binary mixed solvent. Standard thermodynamic values were obtained from temperature dependence of the stability constant of the complex, show that the studied complexation process is mainly entropy governed and are influenced by the nature and composition of the binary mixed solvent solutions.

Effects of Temperature and Steam Environment on Fatigue Behavior of Three SIC/SIC Ceramic Matrix Composites

DTIC Science & Technology

2008-09-01

Infiltration (CVI), Chemical Vapor Deposition (CVD) and polymer impregnation/ pyrolysis (PIP) [5:20, 32]. The SiC fibers currently... composite was infiltrated with a mixture of polymer , filler particles and solvent. During pyrolysis under nitrogen at temperatures > 1000 °C, the...using polymer infiltration and pyrolysis (PIP) method. Polymer infiltration and pyrolysis processing method allows near-net-shape molding and

Separation of n-hexane/acetone mixtures by pervaporation using high density polyethylene/ethylene propylene diene terpolymer rubber blend membranes.

PubMed

Kumar, P V Anil; Anilkumar, S; Varughese, K T; Thomas, Sabu

2012-01-15

Polymer membranes were prepared by blending high density polyethylene (HDPE) with ethylene propylene diene terpolymer rubber (EPDM). These blend membranes were evaluated for the selective separation of n-hexane from acetone. The flux and selectivity of the membranes were determined both as a function of the blend composition and feed mixture composition. Results showed that polymer blending method could be very useful to develop new membranes with improved selectivity. Pervaporation properties could be optimized by adjusting the blend composition. The effects of blend ratio, feed composition, and penetrant size on the pervaporation process were analyzed. The permeation properties have been explained on the basis of interaction between the membrane and solvents and blend morphology. Flux increases with increasing alkane content in the feed composition. Copyright © 2011 Elsevier B.V. All rights reserved.

Qualitative and quantitative evaluation of solvent systems for countercurrent separation.

PubMed

Friesen, J Brent; Ahmed, Sana; Pauli, Guido F

2015-01-16

Rational solvent system selection for countercurrent chromatography and centrifugal partition chromatography technology (collectively known as countercurrent separation) studies continues to be a scientific challenge as the fundamental questions of comparing polarity range and selectivity within a solvent system family and between putative orthogonal solvent systems remain unanswered. The current emphasis on metabolomic investigations and analysis of complex mixtures necessitates the use of successive orthogonal countercurrent separation (CS) steps as part of complex fractionation protocols. Addressing the broad range of metabolite polarities demands development of new CS solvent systems with appropriate composition, polarity (π), selectivity (σ), and suitability. In this study, a mixture of twenty commercially available natural products, called the GUESSmix, was utilized to evaluate both solvent system polarity and selectively characteristics. Comparisons of GUESSmix analyte partition coefficient (K) values give rise to a measure of solvent system polarity range called the GUESSmix polarity index (GUPI). Solvatochromic dye and electrical permittivity measurements were also evaluated in quantitatively assessing solvent system polarity. The relative selectivity of solvent systems were evaluated with the GUESSmix by calculating the pairwise resolution (αip), the number of analytes found in the sweet spot (Nsw), and the pairwise resolution of those sweet spot analytes (αsw). The combination of these parameters allowed for both intra- and inter-family comparison of solvent system selectivity. Finally, 2-dimensional reciprocal shifted symmetry plots (ReSS(2)) were created to visually compare both the polarities and selectivities of solvent system pairs. This study helps to pave the way to the development of new solvent systems that are amenable to successive orthogonal CS protocols employed in metabolomic studies. Copyright © 2014 Elsevier B.V. All rights reserved.

The development of novel Nexar block copolymer/Ultem composite membranes for C2-C4 alcohols dehydration via pervaporation.

PubMed

Zuo, Jian; Shi, Gui Min; Wei, Shawn; Chung, Tai-Shung

2014-08-27

Novel composite membranes comprising sulfonated styrenic Nexar pentablock copolymers were developed by dip-coating on poly(ether imide) hollow fibers for pervaporation dehydration of C2-C4 alcohols. The advantages of using block copolymers as the selective layer are (1) their effectiveness to synergize the physicochemical properties of different chemical and structural moieties and (2) tunable nanoscale morphology and nanostructure via molecular engineering. To achieve high-performance composite membranes, the effects of coating time, ion exchange capacity (IEC) of the copolymer, and solvent systems for coating were investigated. It is revealed that a minimum coating time of 30 s is needed for the formation of a continuous and less-defective top layer. A higher IEC value results in a membrane with a higher flux and lower separation factor because of enhanced hydrophilicity and stretched chain conformation. Moreover, the composite membranes prepared from hexane/ethanol mixtures show higher separation factors and lower fluxes than those from the hexane solvent owing to microdomain segregation induced by ethanol and a smooth and dense top selective layer. These hypotheses were verified by atomic force microscopy and positron annihilation spectroscopy. The newly developed composite membranes demonstrate impressive separation performance with fluxes exceeding 2 kg/m(2) h and separation factors more than 200 for isopropyl alcohol and n-butanol dehydration from 85/15 wt % alcohol/water feed mixtures at 50 °C.

Determination of zearalenone and its metabolites in endometrial cancer by coupled separation techniques.

PubMed

Gadzała-Kopciuch, Renata; Cendrowski, Krzysztof; Cesarz, Anna; Kiełbasa, Paweł; Buszewski, Bogusław

2011-10-01

This study presents a selective method of isolation of zearalenone (ZON) and its metabolite, α-zearalenol (α-ZOL), in neoplastically changed human tissue by accelerated solvent and ultrasonic extractions using a mixture of acetonitrile/water (84/16% v/v) as the extraction solvent. Extraction effectiveness was determined through the selection of parameters (composition of the solvent mixture, temperature, pressure, number of cycles) with tissue contamination at the level of nanograms per gram. The produced acetonitrile/water extracts were purified, and analytes were enriched in columns packed with homemade molecularly imprinted polymers. Purified extracts were determined by liquid chromatography (LC) coupled with different detection systems (diode array detection--DAD and mass spectrometry--MS) involving the Ascentis RP-Amide as a stationary phase and gradient elution. The combination of UE-MISPE-LC (ultrasonic extraction--molecularly imprinted solid-phase extraction--liquid chromatography) produced high (R≈95-98%) and repeatable (RSD<3%) recovery values for ZON and α-ZOL. © The Author(s) 2011. This article is published with open access at Springerlink.com

Effects of water-alcohol binary solvents on the thermochemical characteristics of L-tryptophane dissolution at 298.15 K

NASA Astrophysics Data System (ADS)

Badelin, V. G.; Smirnov, V. I.

2013-01-01

The enthalpies of L-tryptophane solution in water-methanol, water-ethanol, water-1-propanol, and water-2-propanol mixtures at alcohol concentrations of x 2 = 0-0.4 mole fractions were measured by calorimetry. The standard enthalpies of L-tryptophane solution (Δsol H ∘) and transfer (Δtr H ∘) from water to the binary solvent were calculated. The influence of the composition of the water-alcohol mixture and the structure and properties of L-tryptophane on the enthalpy characteristics of the latter was considered. The enthalpy coefficients of pair interactions ( h xy ) of L-tryptophane with alcohol molecules were calculated. The coefficients were positive and increased in the series: methanol (MeOH), ethanol (EtOH), 1-propanol (1-PrOH), and 2-propanol (2-PrOH). The solution and transfer enthalpies of L-tryptophane were compared with those of aliphatic amino acids (glycine, L-threonine, DL-alanine, L-valine, and L-phenylalanine) in similar binary solvents.

Solvent-assisted morphology confinement of a nickel sulfide nanostructure and its application for non-enzymatic glucose sensor.

PubMed

Kim, Soochan; Lee, Sang Ha; Cho, Misuk; Lee, Youngkwan

2016-11-15

Morphology-controlled synthesis of nickel sulfide (Ni3S2) was performed directly on Ni foam using thioacetamide as a sulfur ion source. Various morphologies of nickel sulfide were fabricated using a hydrothermal process by adjusting the solvent composition of ethanol and water. In the water-dominant condition, a dendrite structure was obtained; otherwise, a flaky structure was achieved. A hierarchical cauliflower-like structure was obtained at a solvent mixture composition of 1:1 and was used as non-enzymatic glucose sensor. The hierarchical Ni3S2 electrode showed a high level of electro-catalytic activity toward the oxidation of glucose (16,460μAmM(-1)cm(-2)) over a wide range of detection (0.0005-3mM) and a low detection limit (0.82μM) with excellent selectivity in the presence of several electroactive species. Copyright © 2016 Elsevier B.V. All rights reserved.

Dielectric and physiochemical study of binary mixture of nitrobenzene with toluene

NASA Astrophysics Data System (ADS)

Mohod, Ajay G.; Deshmukh, S. D.; Pattebahadur, K. L.; Undre, P. B.; Patil, S. S.; Khirade, P. W.

2018-05-01

This paper presents the study of binary mixture of Nitrobenzene (NB) with Toluene (TOL) for eleven different concentrations at room temperature. The determined Dielectric Constant (ɛ0) Density (ρ) and Refractive index (nD) values of binary mixture are used to calculate the excess properties i.e. Excess Dielectric Constant (ɛ0E), Excess Molar Volume (VmE), Excess Refractive Index (nDE) and Excess Molar Refraction (RmE) of mixture over the entire composition range and fitted to the Redlich-Kister equation. The Kirkwood Correlation Factor (geff) and other parameters were used to discuss the information about the orientation of dipoles and the solute-solvent interaction of binary mixture at molecular level over the entire range of concentration.

Optimization of soy isoflavone extraction with different solvents using the simplex-centroid mixture design.

PubMed

Yoshiara, Luciane Yuri; Madeira, Tiago Bervelieri; Delaroza, Fernanda; da Silva, Josemeyre Bonifácio; Ida, Elza Iouko

2012-12-01

The objective of this study was to optimize the extraction of different isoflavone forms (glycosidic, malonyl-glycosidic, aglycone and total) from defatted cotyledon soy flour using the simplex-centroid experimental design with four solvents of varying polarity (water, acetone, ethanol and acetonitrile). The obtained extracts were then analysed by high-performance liquid chromatography. The profile of the different soy isoflavones forms varied with different extractions solvents. Varying the solvent or mixture used, the extraction of different isoflavones was optimized using the centroid-simplex mixture design. The special cubic model best fitted to the four solvents and its combination for soy isoflavones extraction. For glycosidic isoflavones extraction, the polar ternary mixture (water, acetone and acetonitrile) achieved the best extraction; malonyl-glycosidic forms were better extracted with mixtures of water, acetone and ethanol. Aglycone isoflavones, water and acetone mixture were best extracted and total isoflavones, the best solvents were ternary mixture of water, acetone and ethanol.

Polymer formulations for gettering hydrogen

DOEpatents

Shepodd, Timothy J.; Even, Jr., William R.

2000-01-01

A novel method for preparing a hydrogenation composition comprising organic polymer molecules having carbon--carbon double bonds, for removing hydrogen from the atmosphere within enclosed spaces and particularly from atmospheres within enclosed spaces that contain air, water vapor, oxygen, carbon dioxide or ammonia. The organic polymers molecules containing carbon--carbon double bonds throughout their structures, preferably polybutadiene, polyisoprene and derivatives thereof, intimately mixed with an insoluble noble metal catalyst composition. High molecular weight polymers may be added to the organic polymer/catalyst mixture in order to improve their high temperature performance. The hydrogenation composition is prepared by dispersing the polymers in a suitable solvent, forming thereby a solution suspension, flash-freezing droplets of the solution in a liquid cryogen, freeze-drying the frozen droplets to remove frozen solvent incorporated in the droplets, and recovering the dried powder thus formed.

Investigation of novel sol-gel hydrophobic surfaces for desorption electrospray ionization-mass spectrometry analysis.

PubMed

Penna, Andrea; Elviri, Lisa; Careri, Maria; Mangia, Alessandro; Predieri, Giovanni

2011-05-01

Sol-gel-based materials were synthesized, characterized and finally tested as solid supports for desorption electrospray ionization-mass spectrometry (DESI-MS) analysis of a mixture of compounds of different polarity. Films with thickness in the 2-4 μm range were obtained by a dip-coating process using tetraethoxysilane (TEOS) and octyltriethoxysilane (OTES) as sol-gel precursors. Three types of surface with different hydrophobic character were obtained by varying the TEOS/OTES ratio in the sol-gel mixture. Each coating was characterized by atomic force microscopy investigations, gaining insight into homogeneity, smoothness and thickness of the obtained films. To study hydrophobicity of each surface, surface free energy measurements were performed. Different DESI-MS responses were observed when different solvent mixture deposition procedures and solvent spray compositions were investigated. Results were finally compared to those obtained by using commercial polytetrafluoroethylene-coated slides. It was found that surface free energy plays an important role in the desorption/ionization process as a function of the polarity of analytes.

Impact of swelling characteristics on the permselective ...

EPA Pesticide Factsheets

The removal of water from organic solvents and biofuels, including lower alcohols (i.e., methanol, ethanol, propanol, and butanol), is necessary for the production, blending, and reuse of those organic compounds. Water forms an azeotrope with many hydrophilic solvents, complicating the separation of water/solvent mixtures. The use of water-selective membranes in a pervaporation or vapor permeation process enables the removal of water from the solvents, even when an azeotrope is present. Common hydrophilic polymer membranes often swell in water, resulting in permeabilities and selectivities that are dependent on the water content of the feed mixture. Recent work has shown the benefit of overcoating a hydrophilic water-permselective membrane with a non-swelling perfluoropolymer film [1,2]. The perfluoropolymer layer reduces the activity of water the hydrophilic polymer layer experiences, thereby reducing swelling in that layer and increasing the water selectivity of the multi-layer membrane relative to the selectivity of the base hydrophilic polymer, usually at the expense of permeability. In this work, the effect of overcoating the hydrophilic layer with polymer films of various swelling characteristics was modelled. Top layers that swell in the solvent offer some advantages, particularly with regard to the water permeance of the multi-layer composite. 1. Huang, Y.; Baker, R. W.; Wijmans, J. G. Perfluoro-coated hydrophilic membranes with improved selectivity. In

Understanding Solvent Manipulation of Morphology in Bulk-Heterojunction Organic Solar Cells.

PubMed

Chen, Yuxia; Zhan, Chuanlang; Yao, Jiannian

2016-10-06

Film morphology greatly influences the performance of bulk-heterojunction (BHJ)-structure-based solar cells. It is known that an interpenetrating bicontinuous network with nanoscale-separated donor and acceptor phases for charge transfer, an ordered molecular packing for exciton diffusion and charge transport, and a vertical compositionally graded structure for charge collection are prerequisites for achieving highly efficient BHJ organic solar cells (OSCs). Therefore, control of the morphology to obtain an ideal structure is a key problem. For this solution-processing BHJ system, the solvent participates fully in film processing. Its involvement is critical in modifying the nanostructure of BHJ films. In this review, we discuss the effects of solvent-related methods on the morphology of BHJ films, including selection of the casting solvent, solvent mixture, solvent vapor annealing, and solvent soaking. On the basis of a discussion on interaction strength and time between solvent and active materials, we believe that the solvent-morphology-performance relationship will be clearer and that solvent selection as a means to manipulate the morphology of BHJ films will be more rational. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards more thermally stable Li-ion battery electrolytes with salts and solvents sharing nitrile functionality

NASA Astrophysics Data System (ADS)

Kerner, Manfred; Lim, Du-Hyun; Jeschke, Steffen; Rydholm, Tomas; Ahn, Jou-Hyeon; Scheers, Johan

2016-11-01

The overall safety of Li-ion batteries is compromised by the state-of-the-art electrolytes; the thermally unstable lithium salt, lithium hexafluorophosphate (LiPF6), and flammable carbonate solvent mixtures. The problem is best addressed by new electrolyte compositions with thermally robust salts in low flammability solvents. In this work we introduce electrolytes with either of two lithium nitrile salts, lithium 4,5-dicyano-1,2,3-triazolate (LiDCTA) or lithium 4,5-dicyano-2-trifluoromethylimidazolide (LiTDI), in solvent mixtures with high flashpoint adiponitrile (ADN), as the main component. With sulfolane (SL) and ethylene carbonate (EC) as co-solvents the liquid temperature range of the electrolytes are extended to lower temperatures without lowering the flashpoint, but at the expense of high viscosities and moderate ionic conductivities. The anodic stabilities of the electrolytes are sufficient for LiFePO4 cathodes and can be charged/discharged for 20 cycles in Li/LiFePO4 cells with coulombic efficiencies exceeding 99% at best. The excellent thermal stabilities of the electrolytes with the solvent combination ADN:SL are promising for future electrochemical investigations at elevated temperatures (> 60 °C) to compensate the moderate transport properties and rate capability. The electrolytes with EC as a co-solvent, however, release CO2 by decomposition of EC in presence of a lithium salt, which potentially makes EC unsuitable for any application targeting higher operating temperatures.

Comparison of yield, composition, and antioxidant activity of turmeric (Curcuma longa L.) extracts obtained using various techniques.

PubMed

Braga, Mara E M; Leal, Patrícia F; Carvalho, João E; Meireles, M Angela A

2003-10-22

Turmeric extracts were obtained from two lots of raw material (M and S) using various techniques: hydrodistillation, low pressure solvent extraction, Soxhlet, and supercritical extraction using carbon dioxide and cosolvents. The solvents and cosolvents tested were ethanol, isopropyl alcohol, and their mixture in equal proportions. The composition of the extracts was determined by gas chromatography-flame ionization detection (GC-FID) and UV. The largest yield (27%, weight) was obtained in the Soxhlet extraction (turmeric (S), ethanol = 1:100); the lowest yield was detected in the hydrodistillation process (2.1%). For the supercritical extraction, the best cosolvent was a mixture of ethanol and isopropyl alcohol. Sixty percent of the light fraction of the extracts consisted of ar-turmerone, (Z)-gamma-atlantone, and (E)-gamma-atlantone, except for the Soxhlet extracts (1:100, ethanol), for which only ar-turmeronol and (Z)-alpha-atlantone were detected. The maximum amount of curcuminoids (8.43%) was obtained using Soxhlet extraction (ethanol/isopropyl alcohol). The Soxhlet and low pressure extract exhibited the strongest antioxidant activities.

Electric Double Layer Composed of an Antagonistic Salt in an Aqueous Mixture: Local Charge Separation and Surface Phase Transition

NASA Astrophysics Data System (ADS)

Yabunaka, Shunsuke; Onuki, Akira

2017-09-01

We examine an electric double layer containing an antagonistic salt in an aqueous mixture, where the cations are small and hydrophilic but the anions are large and hydrophobic. In this situation, a strong coupling arises between the charge density and the solvent composition. As a result, the anions are trapped in an oil-rich adsorption layer on a hydrophobic wall. We then vary the surface charge density σ on the wall. For σ >0 the anions remain accumulated, but for σ <0 the cations are attracted to the wall with increasing |σ |. Furthermore, the electric potential drop Ψ (σ ) is nonmonotonic when the solvent interaction parameter χ (T ) exceeds a critical value χc determined by the composition and the ion density in the bulk. This leads to a first-order phase transition between two kinds of electric double layers with different σ and common Ψ . In equilibrium such two-layer regions can coexist. The steric effect due to finite ion sizes is crucial in these phenomena.

Study of complexation process between 4'-nitrobenzo-15-crown-5 and yttrium(III) cation in binary mixed non-aqueous solvents using conductometric method

NASA Astrophysics Data System (ADS)

Habibi, N.; Rounaghi, G. H.; Mohajeri, M.

2012-12-01

The complexation reaction of macrocyclic ligand (4'-nitrobenzo-15C5) with Y3+ cation was studied in acetonitrile-methanol (AN-MeOH), acetonitrile-ethanol (AN-EtOH), acetonitrile-dimethylformamide (AN-DMF) and ethylacetate-methanol (EtOAc-MeOH) binary mixtures at different temperatures using conductometry method. The conductivity data show that in all solvent systems, the stoichiometry of the complex formed between 4'-nitrobenzo-15C5 and Y3+ cation is 1: 1 (ML). The stability order of (4'-nitrobenzo-15C5). Y3+ complex in pure non-aqueous solvents at 25°C was found to be: EtOAc > EtOH > AN ≈ DMF > MeOH, and in the case of most compositions of the binary mixed solvents at 25°C it was: AN≈MeOH ≈ AN-EtOH > AN-DMF > EtOAc-MeOH. But the results indicate that the sequence of the stability of the complex in the binary mixed solutions changes with temperature. A non-linear behavior was observed for changes of log K f of (4'-nitrobenzo-15C5 · Y3+) complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions and also the hetero-selective solvation of the species involved in the complexation reaction. The values of thermodynamic parameters (Δ H {c/ℴ} and Δ S {c/ℴ}) for formation of the complex were obtained from temperature dependent of the stability constant using the van't Hoff plots. The results represent that in most cases, the complex is both enthalpy and entropy stabilized and the values and also the sign of thermodynamic parameters are influenced by the nature and composition of the mixed solvents.

Conformational Changes of the Alanine Dipeptide in Water-Ethanol Binary Mixtures.

PubMed

Almeida, Glauco G; Cordeiro, João M M; Martín, M Elena; Aguilar, Manuel A

2016-04-12

Experimental work developed in the last years has evidenced the capacity of alcohols and polyalcohols to modify the energy landscape of peptides and proteins. However, the mechanism underlying this effect is not clear. Taking as a model system the alanine dipeptide (AD) we perform a QM/MM study in water, ethanol, and a 40-60% in volume water-ethanol mixture. The AD molecule was described at the MP2/aug-cc-pVDZ level. In polar solution, only αR and PPII conformers contribute in an appreciable way to the conformational equilibrium. The final in solution αR-PPII free energy difference is determined from the interplay between the internal energy of the dipeptide and the solute-solvent interaction free energy. Internal energy favors the formation of PPII, whereas, on the contrary, solute-solvent interaction is favorable to αR, so any factor that decreases the solute-solvent interaction free energy will increase the PPII population. The addition of ethanol increases the stability of the PPII conformer. Our results point to the presence of preferential solvation in this system, the composition of the first solvation shell in the binary mixture being dominated by water molecules. Remarkably, this fact does not affect the differential conformational stability that is controlled by long-range interactions. From the analysis of solvent density maps it is concluded that, in the water-ethanol mixture, ethanol molecules are more likely found around the alanine side chain and the carbonyl group, but while in PPII ethanol molecules interact mainly with the carbonyl group of the N-terminal end, in C5 the interaction is with the carbonyl group of the C-terminal end. In αR, ethanol interacts with both carbonyl groups.

Multiprobe Spectroscopic Inverstigation of Molecular-level Behavior within Aqueous 1-Butyl-3-methylimidazolium Tetrafluoroborate

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

Sarkar, Abhra; Ali, Maroof; Baker, Gary A

2009-01-01

In this work, an array of molecular-level solvent featuressincluding solute-solvent/solvent-solvent interactions, dipolarity, heterogeneity, dynamics, probe accessibility, and diffusionswere investigated across the entire composition of ambient mixtures containing the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate, [bmim][BF4], and pH 7.0 phosphate buffer, based on results assembled for nine different molecular probes utilized in a range of spectroscopic modes. These studies uncovered interesting and unusual solvatochromic probe behavior within this benchmark mixture. Solvatochromic absorbance probessa watersoluble betaine dye (betaine dye 33), N,N-diethyl-4-nitroaniline, and 4-nitroanilineswere employed to determine ET (a blend of dipolarity/polarizability and hydrogen bond donor contributions) and the Kamlet-Taft indices * (dipolarity/polarizability), R (hydrogenmore » bond donor acidity), and (hydrogen bond acceptor basicity) characterizing the [bmim][BF4] + phosphate buffer system. These parameters each showed a marked deviation from ideality, suggesting selective solvation of the individual probe solutes by [bmim][BF4]. Similar conclusions were derived from the responses of the fluorescent polarity-sensitive probes pyrene and pyrene-1-carboxaldehyde. Importantly, the fluorescent microfluidity probe 1,3-bis(1-pyrenyl)propane senses a microviscosity within the mixture that significantly exceeds expectations derived from simple interpolation of the behavior in the neat solvents. On the basis of results from this probe, a correlation between microviscosity and bulk viscosity was established; pronounced solvent-solvent hydrogen-bonding interactions were implicit in this behavior. The greatest deviation from ideal additive behavior for the probes studied herein was consistently observed to occur in the buffer-rich regime. Nitromethane-based fluorescence quenching of pyrene within the [bmim][BF4] + phosphate buffer system showed unusual compliance with a sphere-of-action quenching model, a further manifestation of the microheterogeneity of the system. Fluorescence correlation spectroscopic results for both small (BODIPY FL) and macromolecular (Texas Red-10 kDa dextran conjugate) diffusional probes provide additional evidence in support of microphase segregation inherent to aqueous [bmim][BF4].« less

Design of spray dried insulin microparticles to bypass deposition in the extrathoracic region and maximize total lung dose.

PubMed

Ung, Keith T; Rao, Nagaraja; Weers, Jeffry G; Huang, Daniel; Chan, Hak-Kim

2016-09-25

Inhaled drugs all too often deliver only a fraction of the emitted dose to the target lung site due to deposition in the extrathoracic region (i.e., mouth and throat), which can lead to increased variation in lung exposure, and in some instances increases in local and systemic side effects. For aerosol medications, improved targeting to the lungs may be achieved by tailoring the micromeritic properties of the particles (e.g., size, density, rugosity) to minimize deposition in the mouth-throat and maximize the total lung dose. This study evaluated a co-solvent spray drying approach to modulate particle morphology and dose delivery characteristics of engineered powder formulations of insulin microparticles. The binary co-solvent system studied included water as the primary solvent mixed with an organic co-solvent, e.g., ethanol. Factors such as the relative rate of evaporation of each component of a binary co-solvent mixture, and insulin solubility in each component were considered in selecting feedstock compositions. A water-ethanol co-solvent mixture with a composition range considered suitable for modulating particle shell formation during drying was selected for experimental investigation. An Alberta Idealized Throat model was used to evaluate the in vitro total lung dose of a series of spray dried insulin formulations engineered with different bulk powder properties and delivered with two prototype inhalers that fluidize and disperse powder using different principles. The in vitro total lung dose of insulin microparticles was improved and favored for powders with low bulk density and small primary particle size, with reduction of deposition in the extrathoracic region. The results demonstrated that a total lung dose >95% of the delivered dose can be achieved with engineered particles, indicating a high degree of lung targeting, almost completely bypassing deposition in the mouth-throat. Copyright © 2016 Elsevier B.V. All rights reserved.

Enzymatic synthesis of ethyl esters from waste oil using mixtures of lipases in a plug-flow packed-bed continuous reactor.

PubMed

Kathiele Poppe, Jakeline; Matte, Carla Roberta; Olave de Freitas, Vitória; Fernandez-Lafuente, Roberto; Rodrigues, Rafael C; Záchia Ayub, Marco Antônio

2018-04-30

This work describes the continuous synthesis of ethyl esters via enzymatic catalysis on a packed-bed continuous reactor, using mixtures of immobilized lipases (combi-lipases) of Candida antarctica (CALB), Thermomyces lanuginosus (TLL), and Rhizomucor miehei (RML). The influence of the addition of glass beads to the reactor bed, evaluation of the use of different solvents, and flow rate on reaction conditions were studied. All experiments were conducted using the best combination of lipases according to the fatty acid composition of the waste oil (combi-lipase composition: 40% of TLL, 35% of CALB, and 25% of RML), and soybean oil (combi-lipase composition: 22.5% of TLL, 50% of CALB, and 27.5% of RML). The best general reaction conditions were found to be using tert-butanol as solvent, and the flow rate of 0.08 mL min -1 . The combi-lipase reactors operating at steady state for over 30 days (720 h), kept conversion yields of approximately 50%, with average productivity of 1.94 g ethyl esters g substrate -1 h -1 , regardless of the type of oil in use. This article is protected by copyright. All rights reserved. © 2018 American Institute of Chemical Engineers.

Solvent sensitivity of protein unfolding: dynamical study of chicken villin headpiece subdomain in water-ethanol binary mixture.

PubMed

Ghosh, Rikhia; Roy, Susmita; Bagchi, Biman

2013-12-12

We carry out a series of long atomistic molecular dynamics simulations to study the unfolding of a small protein, chicken villin headpiece (HP-36), in water-ethanol (EtOH) binary mixture. The prime objective of this work is to explore the sensitivity of protein unfolding dynamics toward increasing concentration of the cosolvent and unravel essential features of intermediates formed in search of a dynamical pathway toward unfolding. In water-ethanol binary mixtures, HP-36 is found to unfold partially, under ambient conditions, that otherwise requires temperature as high as ∼600 K to denature in pure aqueous solvent. However, an interesting course of pathway is observed to be followed in the process, guided by the formation of unique intermediates. The first step of unfolding is essentially the separation of the cluster formed by three hydrophobic (phenylalanine) residues, namely, Phe-7, Phe-11, and Phe-18, which constitute the hydrophobic core, thereby initiating melting of helix-2 of the protein. The initial steps are similar to temperature-induced unfolding as well as chemical unfolding using DMSO as cosolvent. Subsequent unfolding steps follow a unique path. As water-ethanol shows composition-dependent anomalies, so do the details of unfolding dynamics. With an increase in cosolvent concentration, different partially unfolded intermediates are found to be formed. This is reflected in a remarkable nonmonotonic composition dependence of several order parameters, including fraction of native contacts and protein-solvent interaction energy. The emergence of such partially unfolded states can be attributed to the preferential solvation of the hydrophobic residues by the ethyl groups of ethanol. We further quantify the local dynamics of unfolding by using a Marcus-type theory.

Paclitaxel-loaded poly(lactide-co-glycolide)/poly(ethylene vinyl acetate) composite for stent coating by ultrasonic atomizing spray.

PubMed

Yuk, Soon Hong; Oh, Keun Sang; Park, Jinah; Kim, Soon-Joong; Kim, Jung Ho; Kwon, Il Keun

2012-04-01

The mixture of poly(lactide-co-glycolide) (PLGA) and poly(ethylene vinyl acetate) (PEVA) forms a homogeneous liquid in an organic solvent such as tetrahydrofuran, and a phase-separated PLGA/PEVA composite can be prepared from it by evaporating the organic solvent. Exploiting this phenomenon, we designed a novel method of preparing a drug-loaded PLGA/PEVA composite and used it for coating drug-eluting stents (DESs). Paclitaxel (PTX), an anticancer drug, was chosen as a model drug. PLGA acts as a microdepot for PTX, and PEVA provides mechanical strength to the coating material. The presence of PLGA in the PLGA/PEVA composite suppressed PTX crystallization in the coating material, and PTX showed a sustained release rate over more than 30 days. The mechanical strength of the PLGA/PEVA composite was better than that of PEVA used as a control. After coating the stent with a PLGA/PEVA composite using ultrasonic atomizing spray, the morphology of the coated material was observed by scanning electron microscopy, and the release pattern of PTX was measured by high-performance liquid chromatography.

Paclitaxel-loaded poly(lactide-co-glycolide)/poly(ethylene vinyl acetate) composite for stent coating by ultrasonic atomizing spray

PubMed Central

Yuk, Soon Hong; Oh, Keun Sang; Park, Jinah; Kim, Soon-Joong; Kim, Jung Ho; Kwon, Il Keun

2012-01-01

The mixture of poly(lactide-co-glycolide) (PLGA) and poly(ethylene vinyl acetate) (PEVA) forms a homogeneous liquid in an organic solvent such as tetrahydrofuran, and a phase-separated PLGA/PEVA composite can be prepared from it by evaporating the organic solvent. Exploiting this phenomenon, we designed a novel method of preparing a drug-loaded PLGA/PEVA composite and used it for coating drug-eluting stents (DESs). Paclitaxel (PTX), an anticancer drug, was chosen as a model drug. PLGA acts as a microdepot for PTX, and PEVA provides mechanical strength to the coating material. The presence of PLGA in the PLGA/PEVA composite suppressed PTX crystallization in the coating material, and PTX showed a sustained release rate over more than 30 days. The mechanical strength of the PLGA/PEVA composite was better than that of PEVA used as a control. After coating the stent with a PLGA/PEVA composite using ultrasonic atomizing spray, the morphology of the coated material was observed by scanning electron microscopy, and the release pattern of PTX was measured by high-performance liquid chromatography. PMID:27877483

Paclitaxel-loaded poly(lactide-co-glycolide)/poly(ethylene vinyl acetate) composite for stent coating by ultrasonic atomizing spray

NASA Astrophysics Data System (ADS)

Yuk, Soon Hong; Oh, Keun Sang; Park, Jinah; Kim, Soon-Joong; Kim, Jung Ho; Kwon, Il Keun

2012-04-01

The mixture of poly(lactide-co-glycolide) (PLGA) and poly(ethylene vinyl acetate) (PEVA) forms a homogeneous liquid in an organic solvent such as tetrahydrofuran, and a phase-separated PLGA/PEVA composite can be prepared from it by evaporating the organic solvent. Exploiting this phenomenon, we designed a novel method of preparing a drug-loaded PLGA/PEVA composite and used it for coating drug-eluting stents (DESs). Paclitaxel (PTX), an anticancer drug, was chosen as a model drug. PLGA acts as a microdepot for PTX, and PEVA provides mechanical strength to the coating material. The presence of PLGA in the PLGA/PEVA composite suppressed PTX crystallization in the coating material, and PTX showed a sustained release rate over more than 30 days. The mechanical strength of the PLGA/PEVA composite was better than that of PEVA used as a control. After coating the stent with a PLGA/PEVA composite using ultrasonic atomizing spray, the morphology of the coated material was observed by scanning electron microscopy, and the release pattern of PTX was measured by high-performance liquid chromatography.

Enzyme-polymer composites with high biocatalytic activity and stability

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

Kim, Jungbae; Kosto, Timothy J.; Manimala, Joseph C.

2004-08-22

We have applied vacuum-spraying and electrospinning to incorporate an enzyme into a polymer matrix, creating a novel and highly active biocatalytic composite. As a unique technical approach, enzymes were co-dissolved in toluene with polymers, and the solvent was then rapidly removed by injecting the mixture into a vacuum chamber or by electrospinning. Subsequent crosslinking of the enzyme with glutaraldehyde resulted in stable entrapped enzyme within the polymeric matrices. For example, an amorphous composite of alpha-chymotrypsin and polyethylene showed no significant loss of enzymatic activity in aqueous buffer for one month. Nanofibers of alpha-chymotrypsin and polystyrene also showed no decrease inmore » activity for more than two weeks. The normalized activity of amorphous composite in organic solvents was 3-13 times higher than that of native alpha-chymotrypsin. The activity of nanofibers was 5-7 times higher than that of amorphous composite in aqueous buffer solution. The composites of alpha-chymotrypsin and polymers demonstrate the feasibility of obtaining a wide variety of active and stable biocatalytic materials with many combinations of enzymes and polymers.« less

Improvement in bioavailability of transdermally applied flurbiprofen using tulsi (Ocimum sanctum) and turpentine oil.

PubMed

Charoo, Naseem Ahmad; Shamsher, Areeg Anwer Ali; Kohli, Kanchan; Pillai, Krishna; Rahman, Ziyaur

2008-09-01

Penetration enhancing potential of tulsi and turpentine oil on transdermal delivery of flurbiprofen, a potent non-steroidal anti-inflammatory agent, was investigated. The transdermal permeation rate of flurbiprofen across the rat abdominal skin from binary solvent mixture composition of propylene glycol (PG):isopropyl alcohol (IPA) (30:70%, v/v) was 98.88 microg/cm(2)/h, significantly higher than other binary solvent mixtures. The corresponding steady state plasma concentration, 0.71 microg/ml, was much lower than required steady state plasma concentration of 3-5 microg/ml. Hence influence of tulsi and turpentine oil in the optimized binary solvent mixture along with the increased drug load on the flurbiprofen permeation was evaluated. The magnitude of the flux enhancement factor with turpentine oil and tulsi oil was 2.4 and 2.0 respectively at 5% (v/v) concentration beyond which there was no significant increase in the flux. Addition of 2% (w/v) hydroxypropyl methylcellulose (HPMC), as a thickening agent, resulted in desired consistency for the fabrication of patch with insignificant effect on permeation rate of flurbiprofen. The reservoir type of transdermal patch formulation, fabricated by encapsulating the flurbiprofen reservoir solution within a shallow compartment moulded from polyester backing film and microporous ethyl vinyl acetate membrane, did not modulate the skin permeation of flurbiprofen through rat skin in case of turpentine formulations whereas flux of formulations with tulsi oil was significantly altered. The influence of penetration enhancer and solvents on the anatomical structure of the rat skin was studied. Enhancement properties exhibited by turpentine oil and tulsi oil in optimized binary solvent mixture were superior as compared to solvent treated and normal control groups with negligible skin irritation. The fabricated transdermal patches were found to be stable. The bioavailability of flurbiprofen with reference to orally administered flurbiprofen in albino rats was found to increase by 2.97, 3.80 and 5.56 times with transdermal patch formulation without enhancer, tulsi and turpentine oil formulations, respectively. The results were confirmed by pharmacodynamic studies in rat edema inflammation model.

Theory of competitive solvation of polymers by two solvents and entropy-enthalpy compensation in the solvation free energy upon dilution with the second solvent.

PubMed

Dudowicz, Jacek; Freed, Karl F; Douglas, Jack F

2015-06-07

We develop a statistical mechanical lattice theory for polymer solvation by a pair of relatively low molar mass solvents that compete for binding to the polymer backbone. A theory for the equilibrium mixture of solvated polymer clusters {AiBCj} and free unassociated molecules A, B, and C is formulated in the spirit of Flory-Huggins mean-field approximation. This theoretical framework enables us to derive expressions for the boundaries for phase stability (spinodals) and other basic properties of these polymer solutions: the internal energy U, entropy S, specific heat CV, extent of solvation Φsolv, average degree of solvation 〈Nsolv〉, and second osmotic virial coefficient B2 as functions of temperature and the composition of the mixture. Our theory predicts many new phenomena, but the current paper applies the theory to describe the entropy-enthalpy compensation in the free energy of polymer solvation, a phenomenon observed for many years without theoretical explanation and with significant relevance to liquid chromatography and other polymer separation methods.

In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition

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

Bai, W.; Yager, K. G.; Ross, C. A.

The room-temperature solvent vapor annealing of polystyrene-b-polydimethylsiloxane (PS-b-PDMS) block copolymer films was studied in situ by grazing incidence small-angle X-ray scattering. Films of cylinder-forming PS-b-PDMS with molecular weight 16 kg/mol and 12.2 kg/mol, annealed under vapors of toluene:heptane with varying composition, exhibited swelling-ratio-dependent evolution of microdomain spacing and orientation. In a vapor made from a toluene:heptane 5:1 volumetric ratio liquid mixture, or from pure toluene, cylindrical microdomains reoriented from majority out-of-plane to in-plane during annealing, while drying led to shrinkage along the film normal and a large distortion of the hexagonal lattice of in-plane cylinders. As a result, annealing undermore » vapor from a toluene:heptane 1:5 volumetric ratio liquid produced a non-bulk lamellar structure in the 16 kg/mol PS-b-PDMS.« less

In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition

DOE PAGES

Bai, W.; Yager, K. G.; Ross, C. A.

2016-08-19

The room-temperature solvent vapor annealing of polystyrene-b-polydimethylsiloxane (PS-b-PDMS) block copolymer films was studied in situ by grazing incidence small-angle X-ray scattering. Films of cylinder-forming PS-b-PDMS with molecular weight 16 kg/mol and 12.2 kg/mol, annealed under vapors of toluene:heptane with varying composition, exhibited swelling-ratio-dependent evolution of microdomain spacing and orientation. In a vapor made from a toluene:heptane 5:1 volumetric ratio liquid mixture, or from pure toluene, cylindrical microdomains reoriented from majority out-of-plane to in-plane during annealing, while drying led to shrinkage along the film normal and a large distortion of the hexagonal lattice of in-plane cylinders. As a result, annealing undermore » vapor from a toluene:heptane 1:5 volumetric ratio liquid produced a non-bulk lamellar structure in the 16 kg/mol PS-b-PDMS.« less

Self-assembly of nanocomposite materials

DOEpatents

Brinker, C. Jeffrey; Sellinger, Alan; Lu, Yunfeng

2001-01-01

A method of making a nanocomposite self-assembly is provided where at least one hydrophilic compound, at least one hydrophobic compound, and at least one amphiphilic surfactant are mixed in an aqueous solvent with the solvent subsequently evaporated to form a self-assembled liquid crystalline mesophase material. Upon polymerization of the hydrophilic and hydrophobic compounds, a robust nanocomposite self-assembled material is formed. Importantly, in the reaction mixture, the amphiphilic surfactant has an initial concentration below the critical micelle concentration to allow formation of the liquid-phase micellar mesophase material. A variety of nanocomposite structures can be formed, depending upon the solvent evaporazation process, including layered mesophases, tubular mesophases, and a hierarchical composite coating composed of an isotropic worm-like micellar overlayer bonded to an oriented, nanolaminated underlayer.

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 5 2011-07-01 2011-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Boiling range (degrees F) Criteria Reactivityfactor 21 280-290 Aromatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 5 2010-07-01 2010-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Hydrocarbon Solvent Mixtures Bin Boiling range (degrees F) Criteria Reactivityfactor 21 280-290 Aromatic...

Controlled crosslinking of trimethylolpropane trimethacrylate for preparation of organic monolithic columns for capillary liquid chromatography.

PubMed

Gama, Mariana R; Aggarwal, Pankaj; Lee, Milton L; Bottoli, Carla B G

2017-11-01

Organic monolithic columns based on single crosslinking of trimethylolpropane trimethacrylate (TRIM) monomer were prepared in a single step by living/controlled free-radical polymerization. Full optimization of the preparation, such as using different percentages of TRIM and different amounts of radical promoter as well as various porogen solvents were explored. The resulting monolithic columns were characterized by scanning electronic microscopy and nitrogen sorption for structure morphology studies and surface area measurements, respectively. Using capillary liquid chromatography, 150 μm i.d. columns were applied to separate a mixture of small hydrophobic molecules. The results indicated that column performance is highly sensitive to the type and the amount of porogen solvents used in the polymerization mixture composition. Good resolution factors and methylene selectivity were obtained, indicating the promising potential of this material for capillary liquid chromatography separations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microphase Separation in Oil-Water Mixtures Containing Hydrophilic and Hydrophobic Ions

NASA Astrophysics Data System (ADS)

Tasios, Nikos; Samin, Sela; van Roij, René; Dijkstra, Marjolein

2017-11-01

We develop a lattice-based Monte Carlo simulation method for charged mixtures capable of treating dielectric heterogeneities. Using this method, we study oil-water mixtures containing an antagonistic salt, with hydrophilic cations and hydrophobic anions. Our simulations reveal several phases with a spatially modulated solvent composition, in which the ions partition between water-rich and water-poor regions according to their affinity. In addition to the recently observed lamellar phase, we find tubular and droplet phases, reminiscent of those found in block copolymers and surfactant systems. Interestingly, these structures stem from ion-mediated interactions, which allows for tuning of the phase behavior via the concentrations, the ionic properties, and the temperature.

Solvent systems with n-hexane and/or cyclohexane in countercurrent chromatography--Physico-chemical parameters and their impact on the separation of alkyl hydroxybenzoates.

PubMed

Englert, Michael; Vetter, Walter

2014-05-16

Countercurrent chromatography (CCC) is an efficient preparative separation technique based on the liquid-liquid distribution of compounds between two phases of a biphasic liquid system. The crucial parameter for the successful application is the selection of the solvent system. Especially for nonpolar analytes the selection options are limited. On the search for a suitable solvent system for the separation of an alkyl hydroxybenzoate homologous series, we noted that the substitution of cyclohexane with n-hexane was accompanied with unexpected differences in partitioning coefficients of the individual analytes. In this study, we investigated the influence of the subsequent substitution of n-hexane with cyclohexane in the n-hexane/cyclohexane/tert-butylmethylether/methanol/water solvent system family. Exact phase compositions and polarity, viscosity and density differences were determined to characterize the different mixtures containing n-hexane and/or cyclohexane. Findings were confirmed by performing CCC separations with different mixtures, which led to baseline resolution for positional isomers when increasing the amount of cyclohexane while the resolution between two pairs of structural isomers decreased. With the new methodology described, structurally similar compounds could be resolved by choosing a certain ratio of n-hexane to cyclohexane. Copyright © 2014 Elsevier B.V. All rights reserved.

Unravelling the Composition Dependent Anomalies of Pair Hydrophobicity in Water-Ethanol Binary Mixtures.

PubMed

Halder, Ritaban; Jana, Biman

2018-06-05

Aqueous binary mixtures have received immense attention in recent years because of their extensive application in several biological and industrial processes. Water-ethanol binary mixture serves as a unique system because it exhibits composition dependent alteration of dynamic and thermodynamic properties. Our present work demonstrates how different compositions of water-ethanol binary mixtures affect the pair hydrophobicity of different hydrophobes. Pair hydrophobicity is measured by the depth of the first minimum (contact minima) of potential of mean force (PMF) profile between two hydrophobes. The pair hydrophobicity is found to be increased with addition of ethanol to water up to mole fraction of 0.10 and decreased with further addition of ethanol. This observation is shown to be true for three different pairs of hydrophobes. Decomposition of PMF into enthalpic and entropic contribution indicates a switch from entropic to enthalpic stabilization of the contact minimum upon addition of ethanol to water. The gain in mixing enthalpy of the binary solvent system upon association of two hydrophobes is found to be the determining factor for the stabilization of contact minimum. Several static/dynamics quantities (average composition fluctuations, diffusion coefficients, fluctuations in total dipole moment, propensity of ethyl-ethyl association, etc) of the ethanol-water binary mixture also show irregularities around xEtOH =0.10-0.15. We have also discovered that the hydrogen bonding pattern of ethanol rather than water reveals a change in trend near the similar composition range. As the anomalous behaviour of the physical/dynamical properties along with the pair hydrophobicity in aqueous binary mixture of amphiphilic solutes is common phenomena, our results may provide a general viewpoint on these aspects.

Composition and Process for Retarding the Premature Aging of PMR Monomer Solutions and PMR Prepegs

NASA Technical Reports Server (NTRS)

Alston, William B. (Inventor); Gahn, Gloria S. (Inventor)

2000-01-01

Polyimides are derived from solutions of at least one low-boiling organic solvent, e.g. isopropanol containing a mixture of polyimide-forming monomers. The monomeric solutions have an extended shelf life at ambient (room) temperatures as high as 80 C, and consist essentially of a mixture of monoalkyl ester-acids, alkyl diester-diacids and aromatic polyamines wherein the alkyl radicals of the esteracids are derived from lower molecular weight aliphatic secondary alcohols having 3 to 5 carbon atoms per molecule such as isopropanol, secondary butanol, 2-methyl-3-butanol, 2 pentanol or 3-pentanol. The solutions of the polyimide-forming monomers have a substantially improved shelf-life and are particularly useful in the aerospace and aeronautical industry for the preparation of polyimide reinforced fiber composites such as the polyimide cured carbon composites used in jet engines, missiles, and for other high temperature applications.

Preferential solvation of Brooker's merocyanine in binary solvent mixtures composed of formamides and hydroxylic solvents.

PubMed

Bevilaqua, Tharly; da Silva, Domingas C; Machado, Vanderlei G

2004-03-01

The ET polarity values of 4-[(1-methyl-4(1H)-pyridinylidene)-ethylidene]-2,5-cyclohexadien-1-one (Brooker's merocyanine) were collected in mixed-solvent systems comprising a formamide [N,N-dimethylformamide (DMF), N-methylformamide (NMF) or formamide (FA)] and a hydroxylic (water, methanol, ethanol, propan-2-ol or butan-1-ol) solvent. Binary mixtures involving DMF and the other formamides (NMF and FA) as well as NMF and FA were also studied. These data were employed in the investigation of the preferential solvation (PS) of the probe. Each solvent system was analyzed in terms of both solute-solvent and solvent-solvent interactions. These latter interactions were responsible for the synergism observed in many binary mixtures. This synergistic behaviour was observed for DMF-propan-2-ol, DMF-butan-1-ol, FA-methanol, FA-ethanol and for the mixtures of the alcohols with NMF. All data were successfully fitted to a model based on solvent-exchange equilibria, which allowed the separation of the different contributions of the solvent species in the solvation shell of the dye. The results suggest that both hydrogen bonding and solvophobic interactions contribute to the formation of the solvent complexes responsible for the observed synergistic effects in the PS of the dye.

Composition of sulla (Hedysarum coronarium L.) honey solvent extractives determined by GC/MS: norisoprenoids and other volatile organic compounds.

PubMed

Jerković, Igor; Tuberoso, Carlo I G; Tuberso, Carlo I G; Gugić, Mirko; Bubalo, Dragan

2010-09-09

Samples of unifloral sulla (Hedysarum coronarum L.) honey from Sardinia (Italy) were analysed. To investigate the chemical composition of the honey volatiles two solvent systems were used for ultrasonic solvent extraction (USE): 1) a 1:2 (v/v) pentane and diethyl ether mixture and 2) dichloromethane. All the extracts were analysed by GC and GC/MS. These procedures have permitted the identification of 56 compounds that include norisoprenoids, benzene derivatives, aliphatic compounds and Maillard reaction products. Norisoprenoids were the major compounds in both extracts, dominated by vomifoliol (5.3-11.2%; 9.6-14.0%) followed by minor percentages of other norisoprenoids such as α-isophorone, 4-ketoisophorone, 3-oxo-α-ionol or 3-oxo-α-ionone. Other abundant single compounds in the extracts were 3-hydroxy-4-phenylbutan-2-one (0.8-5.4%; 0.6-5.7%) and methyl syringate (3.0-5.7%; 2.2-4.1%). The composition of the volatiles and semi-volatiles in the obtained extracts suggests that sulla honey is quite distinctive relative to the other honeys that have been chemically studied by GC/MS, but no specific markers of the honey botanical origin were found.

Experimental consideration of capillary chromatography based on tube radial distribution of ternary mixture carrier solvents under laminar flow conditions.

PubMed

Jinno, Naoya; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2011-01-01

A capillary chromatography system has been developed based on the tube radial distribution of the carrier solvents using an open capillary tube and a water-acetonitrile-ethyl acetate mixture carrier solution. This tube radial distribution chromatography (TRDC) system works under laminar flow conditions. In this study, a phase diagram for the ternary mixture carrier solvents of water, acetonitrile, and ethyl acetate was constructed. The phase diagram that included a boundary curve between homogeneous and heterogeneous solutions was considered together with the component ratios of the solvents in the homogeneous carrier solutions required for the TRDC system. It was found that the TRDC system performed well with homogeneous solutions having component ratios of the solvents that were positioned near the homogeneous-heterogeneous solution boundary of the phase diagram. For preparing the carrier solutions of water-hydrophilic/hydrophobic organic solvents for the TRDC system, we used for the first time methanol, ethanol, 1,4-dioxane, and 1-propanol, instead of acetonitrile (hydrophilic organic solvent), as well as chloroform and 1-butanol, instead of ethyl acetate (hydrophobic organic solvent). The homogeneous ternary mixture carrier solutions were prepared near the homogeneous-heterogeneous solution boundary. Analyte mixtures of 2,6-naphthalenedisulfonic acid and 1-naphthol were separated with the TRDC system using these homogeneous ternary mixture carrier solutions. The pressure change in the capillary tube under laminar flow conditions might alter the carrier solution from homogeneous in the batch vessel to heterogeneous, thus affecting the tube radial distribution of the solvents in the capillary tube.

Observation of CO2 and solvent adduct ions during negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric analysis of monohydric alcohols.

PubMed

Zhou, Xibin; Zhang, Yahe; Zhao, Suoqi; Hsu, Chang Samuel; Shi, Quan

2013-12-15

Monohydric alcohols are common in natural products, bio-oils, and medicine. We have found that monohydric alcohols can form O3 (ions containing three oxygen atoms) and O4 adduct ions in negative electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), which would significantly affect the composition analysis of alcohols, especially in a complex mixture. It is necessary to study the reaction pathways and the method to eliminate or reduce the 'artifact' adducts. Octadecanol, cholesterol, squalanol and two complex monohydric alcohol mixtures were selected as model compounds. These samples were subjected to negative ion ESI FT-ICR MS analysis. The composition and formation mechanism of adducts were studied by the ultrahigh-resolution accurate mass measurement for elemental composition, along with the MS(2) isolation and collision-induced dissociation (CID) experiments for structural determination. The reaction pathway of O3 adduct formation is the coupling of a monohydric alcohol ion with a CO2 to form a stable O3 ionic species by likely a covalent bond (source of CO2 is not clear). The O4 species are formed by O3 ionic species adducted with an alcohol molecule of the solvent, such as methanol or ethanol, by likely a hydrogen bond. These adduct ions could be eliminated or reduced by increasing collision energy. However, excessive collision energy would fragment monohydric alcohol ions. The formation mechanisms of O3 and O4 adducts from monohydric alcohols in negative ion ESI FT-ICR MS were proposed. The solvent adduction effects can be eliminated or reduced by optimizing the collision energy of CID in FT-ICR MS. Copyright © 2013 John Wiley & Sons, Ltd.

Nanoscale Morphology of PTB7 Based Organic Photovoltaics as a Function of Fullerene Size

DOE PAGES

Roehling, John D.; Baran, Derya; Sit, Joseph; ...

2016-08-08

High efficiency polymer:fullerene photovoltaic device layers self-assemble with hierarchical features from ångströms to 100’s of nanometers. The feature size, shape, composition, orientation, and order all contribute to device efficiency and are simultaneously difficult to study due to poor contrast between carbon based materials. This study seeks to increase device efficiency and simplify morphology measurements by replacing the typical fullerene acceptor with endohedral fullerene Lu 3N@PC 80BEH. The metal atoms give excellent scattering contrast for electron beam and x-ray experiments. Additionally, Lu 3N@PC 80BEH has a lower electron affinity than standard fullerenes, which can raise the open circuit voltage of photovoltaicmore » devices. Electron microscopy techniques are used to produce a detailed account of morphology evolution in mixtures of Lu 3N@PC 80BEH with the record breaking donor polymer, PTB7 and coated using solvent mixtures. We demonstrate that common solvent additives like 1,8-diiodooctane or chloronapthalene do not improve the morphology of endohedral fullerene devices as expected. The poor device performance is attributed to the lack of mutual miscibility between this particular polymer:fullerene combination and to co-crystallization of Lu 3N@PC 80BEH with 1,8-diiodooctane. This negative result explains why solvent additives mixtures are not necessarily a morphology cure-all.« less

Nanoscale Morphology of PTB7 Based Organic Photovoltaics as a Function of Fullerene Size

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

Roehling, John D.; Baran, Derya; Sit, Joseph

High efficiency polymer:fullerene photovoltaic device layers self-assemble with hierarchical features from ångströms to 100’s of nanometers. The feature size, shape, composition, orientation, and order all contribute to device efficiency and are simultaneously difficult to study due to poor contrast between carbon based materials. This study seeks to increase device efficiency and simplify morphology measurements by replacing the typical fullerene acceptor with endohedral fullerene Lu 3N@PC 80BEH. The metal atoms give excellent scattering contrast for electron beam and x-ray experiments. Additionally, Lu 3N@PC 80BEH has a lower electron affinity than standard fullerenes, which can raise the open circuit voltage of photovoltaicmore » devices. Electron microscopy techniques are used to produce a detailed account of morphology evolution in mixtures of Lu 3N@PC 80BEH with the record breaking donor polymer, PTB7 and coated using solvent mixtures. We demonstrate that common solvent additives like 1,8-diiodooctane or chloronapthalene do not improve the morphology of endohedral fullerene devices as expected. The poor device performance is attributed to the lack of mutual miscibility between this particular polymer:fullerene combination and to co-crystallization of Lu 3N@PC 80BEH with 1,8-diiodooctane. This negative result explains why solvent additives mixtures are not necessarily a morphology cure-all.« less

Molecular Dynamics Simulations of the Initial-State Predict Product Distributions of Dediazoniation of Aryldiazonium in Binary Solvents.

PubMed

Cruz, Gustavo N; Lima, Filipe S; Dias, Luís G; El Seoud, Omar A; Horinek, Dominik; Chaimovich, Hernan; Cuccovia, Iolanda M

2015-09-04

The dediazoniation of aryldiazonium salts in mixed solvents proceeds by a borderline SN1 and SN2 pathway, and product distribution should be proportional to the composition of the solvation shell of the carbon attached to the -N2 group (ipso carbon). The rates of dediazoniation of 2,4,6-trimethylbenzenediazonium in water, methanol, ethanol, propanol, and acetonitrile were similar, but measured product distributions were noticeably dependent on the nature of the water/cosolvent mixture. Here we demonstrated that solvent distribution in the first solvation shell of the ipso carbon, calculated from classical molecular dynamics simulations, is equal to the measured product distribution. Furthermore, we showed that regardless of the charge distribution of the initial state, i.e., whether the positive charge is smeared over the molecule or localized on phenyl moiety, the solvent distribution around the reaction center is nearly the same.

Heat, Moisture and Chemical Resistant Polyimide Compositions and Methods for Making and Using Them

NASA Technical Reports Server (NTRS)

Pater, Ruth H. (Inventor)

2004-01-01

Polyimides having a desired combination of high thermo-oxidative stability, low moisture absorption and excellent chemical and corrosion resistance are prepared by reacting a mixture of compounds including (a) 3,3',4,4'- benzophenonetetracarboxylic dianhydride (BTDA), (b) 3,4'- oxydianiline (3,4'-ODA), and (c) 5-norbornene-2,3- dicarboxylic anhydride (NA) in a high boiling, aprotic solvent to give 5 to 35% by weight of polyamic acid solution. The ratio of (a), (b), and (c) is selected to afford a family of polyimides having different molecular weights and properties. The mixture first forms a polyamic acid precursor. Upon heating at or above 300 C, the polyamic acids form polyimides, which are particularly suitable for use as a high temperature coating, adhesive, thin film, or composite matrix resin.

Palladium-catalyzed hydrodehalogenation of 1,2,4,5-tetrachlorobenzene in water-ethanol mixtures.

PubMed

Wee, Hun-Young; Cunningham, Jeffrey A

2008-06-30

Palladium-catalyzed hydrodehalogenation (HDH) was applied for destroying 1,2,4,5-tetrachlorobenzene (TeCB) in mixtures of water and ethanol. This investigation was performed as a critical step in the development of a new technology for clean-up of soil contaminated by halogenated hydrophobic organic contaminants. The main goals of the investigation were to demonstrate the feasibility of the technology, to determine the effect of the solvent composition (water:ethanol ratio), and to develop a model for the kinetics of the dehalogenation process. All experiments were conducted in a batch reactor at ambient temperature under mild hydrogen pressure. The experimental results are all consistent with a Langmuir-Hinshelwood model for heterogeneous catalysis. Major findings that can be interpreted within the Langmuir-Hinshelwood framework include: (1) the rate of hydrodehalogenation depends strongly on the solvent composition, increasing as the water fraction of the solvent increases; (2) the HDH rate increases as the catalyst concentration in the reactor increases; (3) when enough catalyst is present, the HDH reaction appears to follow first-order kinetics, but the kinetics appear to be zero-order at low catalyst concentrations. TeCB is converted rapidly and quantitatively to benzene, with only trace concentrations of 1,2,4-trichlorobenzene appearing as a reactive intermediate. The results obtained here have important implications for the further development of the proposed soil remediation technology, and may also be important for the treatment of other hazardous waste streams.

Solvatochromic fluorescence characteristics of cinnamoyl pyrone derivatives

NASA Astrophysics Data System (ADS)

Benosmane, Nadjib; Boutemeur, Baya; Hamdi, Safouane M.; Hamdi, Maamar; Silva, Artur S. M.

2017-12-01

The solvatochromic fluorescence behavior of cinnamoyl pyrone derivatives has been studied in several polar and non-polar solvents. The fluorescence spectra of these compounds exhibit red shift from its absorption spectra and present an excellent correlation with solvent polarity. Cinnamoyl pyrones show a significant spectral shift in fluorescence emission as a function of water composition in binary aqueous solutions mixture. This change is due to the specific intermolecular hydrogen bonding of cinnamoyl pyrones with a molecules of water, due to the deactivation of the lowest excited singlet state of these compounds. The relative quantum yields are calculated. It is found that the quantum yields of the cinnamoyl pyrones vary with the change in the solvent polarity indicating the dependency of fluorescence properties on the solvent nature. It has been observed that the addition of water and pH medium can affect the fluorescence properties of cinnamoyl pyrones in ethanol. This study exhibited that due to the solvent sensitive emission, cinnamoyl pyrone derivatives are a good compound to be used as fluorescence probes.

Molecular mechanism of the adsorption process of an iodide anion into liquid-vapor interfaces of water-methanol mixtures

NASA Astrophysics Data System (ADS)

Annapureddy, Harsha V. R.; Dang, Liem X.

2012-12-01

To enhance our understanding of the molecular mechanism of ion adsorption to the interface of mixtures, we systematically carried out a free energy calculations study involving the transport of an iodide anion across the interface of a water-methanol mixture. Many body affects are taken into account to describe the interactions among the species. The surface propensities of I- at interfaces of pure water and methanol are well understood. In contrast, detailed knowledge of the molecular level adsorption process of I- at aqueous mixture interfaces has not been reported. In this paper, we explore how this phenomenon will be affected for mixed solvents with varying compositions of water and methanol. Our potential of mean force study as function of varying compositions indicated that I- adsorption free energies decrease from pure water to pure methanol but not linearly with the concentration of methanol. We analyze the computed density profiles and hydration numbers as a function of concentrations and ion positions with respect to the interface to further explain the observed phenomenon.

A non-ideal model for predicting the effect of dissolved salt on the flash point of solvent mixtures.

PubMed

Liaw, Horng-Jang; Wang, Tzu-Ai

2007-03-06

Flash point is one of the major quantities used to characterize the fire and explosion hazard of liquids. Herein, a liquid with dissolved salt is presented in a salt-distillation process for separating close-boiling or azeotropic systems. The addition of salts to a liquid may reduce fire and explosion hazard. In this study, we have modified a previously proposed model for predicting the flash point of miscible mixtures to extend its application to solvent/salt mixtures. This modified model was verified by comparison with the experimental data for organic solvent/salt and aqueous-organic solvent/salt mixtures to confirm its efficacy in terms of prediction of the flash points of these mixtures. The experimental results confirm marked increases in liquid flash point increment with addition of inorganic salts relative to supplementation with equivalent quantities of water. Based on this evidence, it appears reasonable to suggest potential application for the model in assessment of the fire and explosion hazard for solvent/salt mixtures and, further, that addition of inorganic salts may prove useful for hazard reduction in flammable liquids.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G.; Eckert, Charles A.; Liotta, Charles L.; Heldebrant, David J.

2013-08-20

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G [Kingston, CA; Eckert, Charles A [Atlanta, GA; Liotta, Charles L [Atlanta, GA; Heldebrant, David J [Richland, WA

2011-07-19

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G; Eckert, Charles A; Liotta, Charles L; Heldebrant, David J

2014-04-29

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Hybrid Composite Using Natural Filler and Multi-Walled Carbon Nanotubes (MWCNTs)

NASA Astrophysics Data System (ADS)

Nabinejad, Omid; Sujan, D.; Rahman, Muhammad Ekhlasur; Liew, Willey Yun Hsien; Davies, Ian J.

2017-12-01

This paper presents an experimental study on the development of hybrid composites comprising of multi-walled carbon nanotubes (MWCNTs) and natural filler (oil palm shell (OPS) powder) within unsaturated polyester (UP) matrix. The results revealed that the dispersion of pristine MWCNTs in the polymer matrix was strongly enhanced through use of the solvent mixing method assisted by ultrasonication. Four different solvents were investigated, namely, ethanol, methanol, styrene and acetone. The best compatibility with minimum side effects on the curing of the polyester resin was exhibited by the styrene solvent and this produced the maximum tensile and flexural properties of the resulting nanocomposites. A relatively small amount of pristine MWCNTs well dispersed within the natural filler polyester composite was found to be capable of improving mechanical properties of hybrid composite. However, increasing the MWCNT amount resulted in increased void content within the matrix due to an associated rapid increase in viscosity of the mixture during processing. Due to this phenomenon, the maximum tensile and flexural strengths of the hybrid composites were achieved at MWCNT contents of 0.2 to 0.4 phr and then declined for higher MWCNT amounts. The flexural modulus also experienced its peak at 0.4 phr MWCNT content whereas the tensile modulus exhibited a general decrease with increasing MWCNT content. Thermal stability analysis using TGA under an oxidative atmosphere showed that adding MWCNTs shifted the endset degradation temperature of the hybrid composite to a higher temperature.

Batch extracting process using magneticparticle held solvents

DOEpatents

Nunez, Luis; Vandergrift, George F.

1995-01-01

A process for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents.

Solvent Extraction of Rare Earth Elements from a Nitric Acid Leach Solution of Apatite by Mixtures of Tributyl Phosphate and Di-(2-ethylhexyl) Phosphoric Acid

NASA Astrophysics Data System (ADS)

Ferdowsi, Ali; Yoozbashizadeh, Hossein

2017-12-01

Solvent extraction of rare earths from nitrate leach liquor of apatite using mixtures of tributyl phosphate (TBP) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) was studied. The effects of nitrate and hydrogen ion concentration of the aqueous phase as well as the composition and concentration of extractants in the organic phase on the extraction behavior of lanthanum, cerium, neodymium, and yttrium were investigated. The distribution ratio of REEs increases by increasing the nitrate concentration in aqueous phase and concentration of extractants in organic phase, but the hydrogen ion concentration in aqueous phase has a decreasing effect. Yttrium as a heavy rare earth is more sensitive to these parameters than light rare earth elements. Although the composition of organic phase has a minor effect on the extraction of light rare earths, the percent of extraction of yttrium decreases dramatically by increasing the TBP content of organic phase. Mixtures of TBP and D2EHPA can show either synergism or antagonism extraction depending on the concentration and composition of extractants in organic phase. The best condition for separating rare earth elements in groups of heavy and light REEs can be achieved at high nitrate concentration, low H+ concentration, and high concentration of D2EHPA in organic phase. Separation of Ce and La by TBP and D2EHPA is practically impossible in the studied conditions; however, low nitrate concentration and high hydrogen ion concentration in aqueous phase and low concentration of extractants in organic phase favor the separation of Nd from other light rare earth elements.

Preparation and characterization of biodegradable magnetic carriers by single emulsion-solvent evaporation

NASA Astrophysics Data System (ADS)

Liu, Xianqiao; Kaminski, Michael D.; Riffle, Judy S.; Chen, Haitao; Torno, Michael; Finck, Martha R.; Taylor, LaToyia; Rosengart, Axel J.

2007-04-01

This paper describes a single emulsion-solvent evaporation protocol to prepare PEGylated biodegradable/biocompatible magnetic carriers by utilizing hydrophobic magnetite and a mixture of poly( D,L lactide-co-glycolide) (PLGA) and poly(lactic acid-block-polyethylene glycol) (PLA-PEG) (26:1 by mass) polymers. We characterized the magnetic microspheres in terms of morphology, composite microstructure, size and size distribution, and magnetic properties. Results show that the preparation produces magnetic microspheres with a good spherical morphology, small size (mean diameter of 1.2-1.5 μm) by means of large size distributions, and magnetizations up to 20-30 emu/g of microspheres.

Lipase-catalyzed synthesis of xylitol monoesters: solvent engineering approach.

PubMed

Castillo, E; Pezzotti, F; Navarro, A; López-Munguía, A

2003-05-08

A solvent engineering strategy was applied to the lipase-catalyzed synthesis of xylitol-oleic acid monoesters. The different esterification degrees for this polyhydroxylated molecule were examined in different organic solvent mixtures. In this context, conditions for high selectivity towards monooleoyl xylitol synthesis were enhanced from 6 mol% in pure n-hexane to 73 mol% in 2-methyl-2-propanol/dimethylsulfoxide (DMSO) 80:20 (v/v). On the contrary, the highest production of di- and trioleoyl xylitol, corresponding to 94 mol%, was achieved in n-hexane. Changes in polarity of the reaction medium and in the molecular interactions between solvents and reactants were correlated with the activity coefficients of products. Based on experimental results and calculated thermodynamic activities, the effect of different binary mixtures of solvents on the selective production of xylitol esters is reported. From this analysis, it is concluded that in the more polar conditions (100% dimethylsulfoxide (DMSO)), the synthesis of xylitol monoesters is favored. However, these conditions are unfavorable in terms of enzyme stability. As an alternative, binary mixtures of solvents were proposed. Each mixture of solvents was characterized in terms of the quantitative polarity parameter E(T)(30) and related with the activity coefficients of xylitol esters. To our knowledge, the characterization of solvent mixtures in terms of this polarity parameter and its relationship with the selectivity of the process has not been previously reported.

Top-down approach for nanophase reconstruction in bulk heterojunction solar cells.

PubMed

Kong, Jaemin; Hwang, In-Wook; Lee, Kwanghee

2014-09-01

"Top-Down" nanophase reconstruction via a post-additive soaking process is first presented with various BHJ binary composites. By simply rinsing as-cast BHJ films with a solvent mixture containing a few traces of a nanophase-control reagent such as 1,8-diiodooctane, oversized fullerene-rich clusters (>100 nm in dia-meter) in the BHJ film are instataneously disassembled and entirely reorganized into finely intermixed donor/acceptor nanophases (ca. 10 nm) with a 3D compositional homogeneity, without surface segregation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Organosolv extraction of lignin from hydrolyzed almond shells and application of the delta-value theory.

PubMed

Quesada-Medina, Joaquín; López-Cremades, Francisco Javier; Olivares-Carrillo, Pilar

2010-11-01

The solubility of lignin from hydrolyzed almond (Prunus amygdalus) shells in different acetone, ethanol and dioxane-water mixtures and conditions (extraction time and temperature) was studied. The concept of the solubility parameter (delta-value) was applied to explain the effect of organic solvent concentration on lignin solubility. The organic solvent-water mixture that led to the highest lignin extraction was composed of a 75% vol. of organic solvent for all the solvent series investigated (acetone, ethanol and dioxane). Moreover, the best lignin extraction conditions were a temperature of 210 degrees C and an extraction time of 40 min for the acetone and ethanol series, and 25 min for the dioxane series. The delta-value of the hydrolyzed almond shell lignin [14.60 (cal/cm(3))(1/2)] and that of the organic solvent-water mixtures was calculated. The experimental delignification capacity of the aqueous organic solvents clearly reflected the proximity of their delta-value to that of lignin. The hydrogen-bonding capacity of the solvent-water mixtures was also taken into account. Copyright 2010 Elsevier Ltd. All rights reserved.

Excess protons in water-acetone mixtures. II. A conductivity study.

PubMed

Semino, Rocío; Longinotti, M Paula

2013-10-28

In the present work we complement a previous simulation study [R. Semino and D. Laria, J. Chem. Phys. 136, 194503 (2012)] on the disruption of the proton transfer mechanism in water by the addition of an aprotic solvent, such as acetone. We provide experimental measurements of the mobility of protons in aqueous-acetone mixtures in a wide composition range, for water molar fractions, xw, between 0.05 and 1.00. Furthermore, new molecular dynamics simulation results are presented for rich acetone mixtures, which provide further insight into the proton transport mechanism in water-non-protic solvent mixtures. The proton mobility was analyzed between xw 0.05 and 1.00 and compared to molecular dynamics simulation data. Results show two qualitative changes in the proton transport composition dependence at xw ∼ 0.25 and 0.8. At xw < 0.25 the ratio of the infinite dilution molar conductivities of HCl and LiCl, Λ(0)(HCl).Λ(0)(LiCl)(-1), is approximately constant and equal to one, since the proton diffusion is vehicular and equal to that of Li(+). At xw ∼ 0.25, proton mobility starts to differ from that of Li(+) indicating that above this concentration the Grotthuss transport mechanism starts to be possible. Molecular dynamics simulation results showed that at this threshold concentration the probability of interconversion between two Eigen structures starts to be non-negligible. At xw ∼ 0.8, the infinite molar conductivity of HCl concentration dependence qualitatively changes. This result is in excellent agreement with the analysis presented in the previous simulation work and it has been ascribed to the interchange of water and acetone molecules in the second solvation shell of the hydronium ion.

Solvent isotope-induced equilibrium perturbation for isocitrate lyase.

PubMed

Quartararo, Christine E; Hadi, Timin; Cahill, Sean M; Blanchard, John S

2013-12-23

Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacterium's life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage ((D₂O)V = 2.0 ± 0.1, and (D₂O)[V/K(isocitrate)] = 2.2 ± 0.3) arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of the succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate, and succinate prepared in D₂O would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by ¹H NMR spectroscopy shows a clear equilibrium perturbation in D₂O. The final equilibrium isotopic composition of reactants in D₂O revealed dideuterated succinate, protiated glyoxylate, and monodeuterated isocitrate, with the transient appearance and disappearance of monodeuterated succinate. A model for the equilibrium perturbation of substrate species and their time-dependent isotopic composition is presented.

Selective extraction of high-value phenolic compounds from distillation wastewater of basil (Ocimum basilicum L.) by pressurized liquid extraction.

PubMed

Pagano, Imma; Sánchez-Camargo, Andrea Del Pilar; Mendiola, Jose Antonio; Campone, Luca; Cifuentes, Alejandro; Rastrelli, Luca; Ibañez, Elena

2018-01-31

During the essential oil steam distillation from aromatic herbs, huge amounts of distillation wastewaters (DWWs) are generated. These by-products represent an exceptionally rich source of phenolic compounds such as rosmarinic acid (RA) and caffeic acid (CA). Herein, the alternative use of dried basil DWWs (dDWWs) to perform a selective extraction of RA and CA by pressurized liquid extraction (PLE) employing bio-based solvent was studied. To select the most suitable solvent for PLE, the theoretical modelling of Hansen solubility parameters (HSP) was carried out. This approach allows reducing the list of candidate to two solvents: ethanol and ethyl lactate. Due to the composition of the sample, mixtures of water with those solvents were also tested. An enriched PLE extract in RA (23.90 ± 2.06 mg/g extract) with an extraction efficiency of 75.89 ± 16.03% employing a water-ethanol mixture 25:75 (% v/v) at 50°C was obtained. In the case of CA, a PLE extract with 2.42 ± 0.04 mg/g extract, having an extraction efficiency of 13.86 ± 4.96% using ethanol absolute at 50°C was achieved. DWWs are proposed as new promising sources of natural additives and/or functional ingredients for cosmetic, nutraceutical, and food applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Batch extracting process using magnetic particle held solvents

DOEpatents

Nunez, L.; Vandergrift, G.F.

1995-11-21

A process is described for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents. 5 figs.

Insecticide solvents: interference with insecticidal action.

PubMed

Brattsten, L B; Wilkinson, C F

1977-06-10

Several commercial solvent mixtures commonly used as insecticide carriers in spray formulations increase by more than threefold the microsomal N-demethylation of p-chloro N-methylaniline in midgut preparations of southern army-worm (Spodoptera eridania) larvae exposed orally to the test solvents. Under laboratory conditions, the same solvent mixtures exhibit a protective action against the in vivo toxicity of the insecticide carbaryl to the larvae. The data are discussed with respect to possible solvent-insecticide interactions occurring under field conditions and, more broadly, to potential toxicological hazards of these solvents to humans.

Nitriding kinetics of Si-SiC powder mixtures as simulations of reaction bonded Si3N4-SiC composites

NASA Technical Reports Server (NTRS)

Lightfoot, A.; Sheldon, B. W.; Flint, J. H.; Haggerty, J. S.

1989-01-01

The nitriding kinetics of Si and Si plus SiC powder mixtures were studied to simulate the fabrication of RBSN-SiC ceramic matrix composites. Very clean, assynthesized, and solvent-exposed powders were studied; C-rich and Si-rich SiC 0.04-0.05 micron diameter powders were mixed in varying concentrations with SiH4-derived 0.2-0.3 micron diameter Si powder. Complete nitridation is achieved with C-rich SiC powders in 140 min at 1250 C, and in the centers of Si-rich SiC powders in 15 min. The effects on the incubation periods, fast reaction periods, and slow reaction periods that characterize these nitriding processes were studied to explain unusual reverse reaction gradients and other effects of contamination.

Maximum workplace concentration values and carcinogenicity classification for mixtures.

PubMed Central

Bartsch, R; Forderkunz, S; Reuter, U; Sterzl-Eckert, H; Greim, H

1998-01-01

In Germany, the Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area (MAK Commission) generally sets maximum workplace concentration values (i.e., a proposed occupational exposure level [OEL]) for single substances, not for mixtures. For mixtures containing substances with a genotoxic and carcinogenic potential, the commission considered it scientifically inappropriate to establish a safe threshold. This approach is currently under discussion. Carcinogenic mixtures are categorized according to either the carcinogenicity of the mixture or the classification of the carcinogenic substances included. In regulating exposure to mixtures, an approach similar to that used by the American Conference of Governmental Hygienists is proposed: For components with the same target organ and mode of action or interfering metabolism, synergistic effects must be expected and the respective OELs must be lowered. However, if there is proof that the components act independently, the OELs of the individual compounds are not considered to be modified. In the view of the commission, calculating OELs for solvent mixtures according to their liquid phase composition is not justified, and the setting of scientifically based OELs for complex mixtures is not possible. PMID:9860883

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

Aines, Roger D; Spadaccini, Christopher M; Stolaroff, Joshuah K

Method and apparatus for separating a target substance from a fluid or mixture. Capsules having a coating and stripping solvents encapsulated in the capsules are provided. The coating is permeable to the target substance. The capsules having a coating and stripping solvents encapsulated in the capsules are exposed to the fluid or mixture. The target substance migrates through the coating and is taken up by the stripping solvents. The target substance is separated from the fluid or mixture by driving off the target substance from the capsules.

Chemical mixtures in untreated water from public-supply wells in the U.S. — Occurrence, composition, and potential toxicity

USGS Publications Warehouse

Toccalino, Patricia L.; Norman, Julia E.; Scott, Jonathon C.

2012-01-01

Chemical mixtures are prevalent in groundwater used for public water supply, but little is known about their potential health effects. As part of a large-scale ambient groundwater study, we evaluated chemical mixtures across multiple chemical classes, and included more chemical contaminants than in previous studies of mixtures in public-supply wells. We (1) assessed the occurrence of chemical mixtures in untreated source-water samples from public-supply wells, (2) determined the composition of the most frequently occurring mixtures, and (3) characterized the potential toxicity of mixtures using a new screening approach. The U.S. Geological Survey collected one untreated water sample from each of 383 public wells distributed across 35 states, and analyzed the samples for as many as 91 chemical contaminants. Concentrations of mixture components were compared to individual human-health benchmarks; the potential toxicity of mixtures was characterized by addition of benchmark-normalized component concentrations. Most samples (84%) contained mixtures of two or more contaminants, each at concentrations greater than one-tenth of individual benchmarks. The chemical mixtures that most frequently occurred and had the greatest potential toxicity primarily were composed of trace elements (including arsenic, strontium, or uranium), radon, or nitrate. Herbicides, disinfection by-products, and solvents were the most common organic contaminants in mixtures. The sum of benchmark-normalized concentrations was greater than 1 for 58% of samples, suggesting that there could be potential for mixtures toxicity in more than half of the public-well samples. Our findings can be used to help set priorities for groundwater monitoring and suggest future research directions for drinking-water treatment studies and for toxicity assessments of chemical mixtures in water resources.

Kinetic model for astaxanthin aggregation in water-methanol mixtures

NASA Astrophysics Data System (ADS)

Giovannetti, Rita; Alibabaei, Leila; Pucciarelli, Filippo

2009-07-01

The aggregation of astaxanthin in hydrated methanol was kinetically studied in the temperature range from 10 °C to 50 °C, at different astaxanthin concentrations and solvent composition. A kinetic model for the formation and transformation of astaxanthin aggregated has been proposed. Spectrophotometric studies showed that monomeric astaxanthin decayed to H-aggregates that after-wards formed J-aggregates when water content was 50% and the temperature lower than 20 °C; at higher temperatures, very stable J-aggregates were formed directly. Monomer formed very stable H-aggregates when the water content was greater than 60%; in these conditions H-aggregates decayed into J-aggregates only when the temperature was at least 50 °C. Through these findings it was possible to establish that the aggregation reactions took place through a two steps consecutive reaction with first order kinetic constants and that the values of these depended on the solvent composition and temperature.

Ultrasonic Removal of Mucilage for Pressurized Liquid Extraction of Omega-3 Rich Oil from Chia Seeds (Salvia hispanica L.).

PubMed

Castejón, Natalia; Luna, Pilar; Señoráns, Francisco J

2017-03-29

Chia (Salvia hispanica L.) seeds contain an important amount of edible oil rich in omega-3 fatty acids. Fast and alternative extraction techniques based on polar solvents, such as ethanol or water, have become relevant for oil extraction in recent years. However, chia seeds also contain a large amount of soluble fiber or mucilage, which makes difficult an oil extraction process with polar solvents. For that reason, the aim of this study was to develop a gentle extraction method for mucilage in order to extract chia oil with polar solvents using pressurized liquids and compare with organic solvent extraction. The proposed mucilage extraction method, using an ultrasonic probe and only water, was optimized at mild conditions (50 °C and sonication 3 min) to guarantee the omega-3 oil quality. Chia oil extraction was performed using pressurized liquid extraction (PLE) with different solvents and their mixtures at five different extraction temperatures (60, 90, 120, 150, and 200 °C). Optimal PLE conditions were achieved with ethyl acetate or hexane at 90 °C in only 10 min of static extraction time (chia oil yield up to 30.93%). In addition, chia oils extracted with nonpolar and polar solvents by PLE were analyzed by gas chromatography-mass spectrometry (GC-MS) to evaluate fatty acid composition at different extraction conditions. Chia oil contained ∼65% of α-linolenic acid regardless of mucilage extraction method, solvent, or temperature used. Furthermore, tocopherols and tocotrienols were also analyzed by HPLC in the extracted chia oils. The mucilage removal allowed the subsequent extraction of the chia oil with polar or nonpolar solvents by PLE producing chia oil with the same fatty acid and tocopherol composition as traditional extraction.

Oxidation behavior of multiwall carbon nanotubes with different diameters and morphology

NASA Astrophysics Data System (ADS)

Mazov, Ilya; Kuznetsov, Vladimir L.; Simonova, Irina A.; Stadnichenko, Andrey I.; Ishchenko, Arkady V.; Romanenko, Anatoly I.; Tkachev, Evgeniy N.; Anikeeva, Olga B.

2012-06-01

Multiwall carbon nanotubes (MWNT) with three medium diameters (20-22, 9-13, and 6-8 nm) and different morphology were chemically oxidized using concentrated nitric acid, mixture of nitric and sulfuric acids ("mélange" solution) and mixture of sulfuric acid and hydrogen peroxide ("piranha" solution). Influence of MWNT type and structure as well as type of oxidizer on the surface composition and structure of nanotubes after oxidation was investigated. Acid-base titration, X-ray photoelectron spectroscopy and thermal gravimetric analysis were used for quantitative and qualitative investigation of surface group composition of initial and oxidized nanotubes. Amount of oxygen-containing groups on the surface of oxidized MWNT depends on the type of initial MWNT. It was found that ratio of different oxygen containing groups is less dependent on the type of oxidizer. Electrophysical properties of initial and oxidized nanotubes were investigated in temperature range 4-293 K and main types of electrical conductivity were determined. It was shown that oxidation results in decrease in electrical conductivity of all samples with simultaneous change in the conductivity mechanism. Dispersive behavior of initial and oxidized nanotubes in different commonly used solvents was investigated. It was shown that oxidation leads to the improvement of sedimentation stability of MWNT in polar solvents.

Influence of Polar Organic Solvents in an Ionic Liquid Containing Lithium Bis(fluorosulfonyl)amide: Effect on the Cation-Anion Interaction, Lithium Ion Battery Performance, and Solid Electrolyte Interphase.

PubMed

Lahiri, Abhishek; Li, Guozhu; Olschewski, Mark; Endres, Frank

2016-12-14

Ionic liquid-organic solvent mixtures have recently been investigated as potential battery electrolytes. However, contradictory results with these mixtures have been shown for battery performance. In this manuscript, we studied the influence of the addition of polar organic solvents into the ionic liquid electrolyte 1 M lithium bis(fluorosulfonyl)amide (LiFSI)-1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)amide ([Py 1,4 ]FSI) and tested it for lithium ion battery applications. From infrared and Raman spectroscopy, clear changes in the lithium solvation and cation-anion interactions in the ionic liquid were observed on addition of organic solvents. From the lithiation/delithiation studies on electrodeposited Ge, the storage capacity for the ionic liquid-highly polar organic solvent (acetonitrile) mixture was found to be the highest at low C-rates (0.425 C) compared to using an ionic liquid alone and ionic liquid-less polar solvent (dimethyl carbonate) mixtures. Furthermore, XPS and AFM were used to evaluate the solid electrolyte interphase (SEI) and to correlate its stability with Li storage capacity.

Study on Solution Properties of Binary Mixtures of Some Industrially Important Solvents with Cyclohexylamine and Cyclohexanone at 298.15 K

NASA Astrophysics Data System (ADS)

Roy, Mahendra Nath; Das, Rajesh Kumar; Chanda, Riju

2010-03-01

Densities and viscosities were measured for the binary mixtures of cyclohexylamine and cyclohexanone with butyl acetate, butanone, butylamine, tert-butylamine, and 2-butoxyethanol at 298.15 K over the entire composition range. From density data, the values of the excess molar volume ( V E) have been calculated. The experimental viscosity data were correlated by means of the equation of Grunberg-Nissan. The density and viscosity data have been analyzed in terms of some semiempirical viscosity models. The results are discussed in terms of molecular interactions and structural effects. The excess molar volume is found to be either negative or positive depending on the molecular interactions and the nature of the liquid mixtures and is discussed in terms of molecular interactions and structural changes.

Universal adsorption at the vapor-liquid interface near the consolute point

NASA Technical Reports Server (NTRS)

Schmidt, James W.

1990-01-01

The ellipticity of the vapor-liquid interface above mixtures of methylcyclohexane (C7H14) and perfluoromethylcyclohexane (C7F14) has been measured near the consolute point T(c) = 318.6 K. The data are consistent with a model of the interface that combines a short-ranged density-vs height profile in the vapor phase with a much longer-ranged composition-versus-height profile in the liquid. The value of the free parameter produced by fitting the model to the data is consistent with results from two other simple mixtures and a mixture of a polymer and solvent. This experiment combines precision ellipsometry of the vapor-liquid interface with in situ measurements of refractive indices of the liquid phases, and it precisely locates the consolute point.

Degradation of palm oil empty fruit bunch (EFB) into bio-oil in sub-and supercritical solvents

NASA Astrophysics Data System (ADS)

Sarwono, Rakhman; Pusfitasari, Eka Dian

2017-01-01

Hydrothemal Liquefaction (HTL) of empty fruit bunch (EFB) of palm oil in different solvents (water, ethanol and hexane) were comparatively investigated. Experiments were carried out in an autoclave in different EFB loading of 9%, 11%, and 13%. The temperature operation was 350 oC, without any catalysts and reaction time of 5 hours. The efficiency of above solvents in terms of conversion rate, soluble liquid and carbon products were found in this experiments. The water solvent gave higher conversion rate of 35 - 36.5 %, while hexane gave conversion of 17 - 25.25 %, and ethanol gave the lower conversion rate of 12.65 - 30.3%, respectively. Increasing the EFB load decreased the conversion rate for ethanol and hexane solvents, for water there are no significant change in the conversion rate. The bio-oil as soluble liquid produced were in order of water, ethanol, and hexane solvents, respectively. The chemical properties of bio-oil products were significantly affected by the type of liquefaction solvent. The compositional of bio-oil consists of mostly of a mixture of organic acids, ketones, and esters. The hexane and ethanol solvents resulted mostly organic acids. In water solvent resulted 2-pentanone, 4-hydroxy-4-methyl and others substances. According to the bio-oil results, organic solvents resulted higher HHV compared to water solvent. The higher heating value (HHV) of the carbon products were also comparatively, ethanol solvent resulted soluble liquid with higher HHV compared to the water solvent.

Lid opening and conformational stability of T1 Lipase is mediated by increasing chain length polar solvents

PubMed Central

Mohamad Ali, Mohd Shukuri; Salleh, Abu Bakar; Rahman, Raja Noor Zaliha Raja Abd; Normi, Yahaya M.; Mohd Shariff, Fairolniza

2017-01-01

The dynamics and conformational landscape of proteins in organic solvents are events of potential interest in nonaqueous process catalysis. Conformational changes, folding transitions, and stability often correspond to structural rearrangements that alter contacts between solvent molecules and amino acid residues. However, in nonaqueous enzymology, organic solvents limit stability and further application of proteins. In the present study, molecular dynamics (MD) of a thermostable Geobacillus zalihae T1 lipase was performed in different chain length polar organic solvents (methanol, ethanol, propanol, butanol, and pentanol) and water mixture systems to a concentration of 50%. On the basis of the MD results, the structural deviations of the backbone atoms elucidated the dynamic effects of water/organic solvent mixtures on the equilibrium state of the protein simulations in decreasing solvent polarity. The results show that the solvent mixture gives rise to deviations in enzyme structure from the native one simulated in water. The drop in the flexibility in H2O, MtOH, EtOH and PrOH simulation mixtures shows that greater motions of residues were influenced in BtOH and PtOH simulation mixtures. Comparing the root mean square fluctuations value with the accessible solvent area (SASA) for every residue showed an almost correspondingly high SASA value of residues to high flexibility and low SASA value to low flexibility. The study further revealed that the organic solvents influenced the formation of more hydrogen bonds in MtOH, EtOH and PrOH and thus, it is assumed that increased intraprotein hydrogen bonding is ultimately correlated to the stability of the protein. However, the solvent accessibility analysis showed that in all solvent systems, hydrophobic residues were exposed and polar residues tended to be buried away from the solvent. Distance variation of the tetrahedral intermediate packing of the active pocket was not conserved in organic solvent systems, which could lead to weaknesses in the catalytic H-bond network and most likely a drop in catalytic activity. The conformational variation of the lid domain caused by the solvent molecules influenced its gradual opening. Formation of additional hydrogen bonds and hydrophobic interactions indicates that the contribution of the cooperative network of interactions could retain the stability of the protein in some solvent systems. Time-correlated atomic motions were used to characterize the correlations between the motions of the atoms from atomic coordinates. The resulting cross-correlation map revealed that the organic solvent mixtures performed functional, concerted, correlated motions in regions of residues of the lid domain to other residues. These observations suggest that varying lengths of polar organic solvents play a significant role in introducing dynamic conformational diversity in proteins in a decreasing order of polarity. PMID:28533982

Method to prepare Semtex

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

Alcaraz, A; Dougan, A

This procedure requires the binder and uncoated RDX be prepared in separate steps, see Figure 1: (1) The binder and dye are mixed by agitation with a water-insoluble organic solvent (e.g., toluene), I; (2) The RDX/PETN is agitated thoroughly with water, II; (3) The binder solution I is added to the RDX/water mixture at II with thorough mixing to form a slurry III; (4) In the next step the solvent is distilled off at IV leaving resulting granules; (5) The next step is followed by filtration at V, which may be done by vacuum; (6) The composition is then driedmore » at VI to a dough-like consistency.« less

Solvent influence on complex formation between Cd2+ and 2-hydroxy-1,4-naphthoquinone in binary mixed nonaqueous solvents at 15-45°C

NASA Astrophysics Data System (ADS)

Farazandeh, R.; Rounaghi, G. H.; Ebrahimi, M.; Basafa, S.

2017-04-01

The complexation reaction of Cd2+ cation with 2-hydroxy-1,4-naphthoquinone (HNQ) was studied in acetonitrile (AN), 2-PrOH, ethyl acetate (EtOAc), EtOH, dimethylformamide (DMF) and in binary solutions AN-2-PrOH, AN-DMF, AN-EtOH, and AN-EtOAc using conductometric method at 15-45°C. The conductance data show that the stoichiometry of the Cd2+ complex with HNQ in all solvent systems is 1 : 1. In the pure solvents the stability of the complex changes in the order AN > 2-PrOH > EtOH > DMF. The stability of the complex at 25°C in the studied mixtures changes in the following order : AN-EtOAc > AN-2-PrOH > AN-EtOH > AN-DMF. These orders are affected by the nature and composition of the solvent systems and by the temperature. From the temperature dependence data, the thermodynamic functions values (Δ H° and Δ S°) for the complex formation were calculated.

Assessment of time to pregnancy and spontaneous abortion status following occupational exposure to organic solvents mixture.

PubMed

Attarchi, Mir Saeed; Ashouri, Monir; Labbafinejad, Yasser; Mohammadi, Saber

2012-04-01

Due to increasing usage of chemicals in various industries, occupational exposure of women with these materials is unavoidable. Nowadays, some studies indicate adverse effects of exposure to these chemicals, especially organic solvents on the reproductive system of females. This study aimed to assess the relationship between spontaneous abortion and occupational exposure to organic solvents mixture in pharmaceutical industry. This study was carried out in a pharmaceutical factory located in the suburb of Tehran in 2010. During the study, married women who were working in the factory laboratory units and had exposure to mixed organic solvents were compared with married women who were working in the packing units of the factory without occupational exposure to organic solvents in terms of spontaneous abortion frequency and duration of pregnancy using statistical methods. In this study, the frequency of spontaneous abortion in employees with and without exposure to organic solvents mixture was 10.7 and 2.9% respectively. This study showed that even after adjustment for confounding factors, there was a significant correlation between spontaneous abortion and occupational exposure to organic solvents mixture and this correlation increased with increasing levels of exposure to organic solvents. Also, a significant correlation was observed between occupational exposure to mixed organic solvents and waiting time to become pregnant (TTP). Furthermore, this study showed that even after adjustment for confounding variables, shift workers were significantly more affected by spontaneous abortion compared to daytime workers (P < 0.001). Also, in our study, synergistic effect between shift working and occupational exposure to organic solvents mixture on spontaneous abortion was seen. According to the results of this study, since there is probability of spontaneous abortion resulting from occupational exposure to various chemicals including organic solvents, recommendation to review the status of occupational exposure of workers can be helpful in improving fertility consultations and reproductive health.

Thermodynamics of cosolvent action: phenacetin, salicylic acid and probenecid.

PubMed

Peña, M A; Escalera, B; Reíllo, A; Sánchez, A B; Bustamante, P

2009-03-01

The solubility of phenacetin, salicylic acid, and probenecid in ethanol-water and ethanol-ethyl acetate mixtures at several temperatures (15-40 degrees C) was measured. The solubility profiles are related to medium polarity changes. The apparent thermodynamic magnitudes and enthalpy-entropy relationships are related to the cosolvent action. Salicylic acid and probenecid show a single peak against the solubility parameter delta(1) of both solvent mixtures, at 40% (delta(1) = 21.70 MPa(1/2)) and 30% (delta(1) = 20.91 MPa(1/2)) ethanol in ethyl acetate, respectively. Phenacetin displays two peaks at 60% ethanol in ethyl acetate (23.30 MPa(1/2)) and 90% ethanol in water (delta(1) = 28.64 MPa(1/2)). The apparent enthalpies of solution display a maximum at 30% (phenacetin and salicylic acid) and 40% (probenecid) ethanol in water, respectively. Two different mechanisms, entropy at low ethanol ratios, and enthalpy at high ethanol ratios control the solubility enhancement in the aqueous mixture. In the nonaqueous mixture (ethanol-ethyl acetate) enthalpy is the driving force throughout the whole solvent composition for salicylic acid and phenacetin. For probenecid, the dominant mechanism shifts from entropy to enthalpy as the ethanol in ethyl acetate concentration increases. The enthalpy-entropy compensation plots corroborate the different mechanisms involved in the solubility enhancement by cosolvents. (c) 2008 Wiley-Liss, Inc. and the American Pharmacists Association

Composite gel polymer electrolyte for lithium ion batteries

NASA Astrophysics Data System (ADS)

Naderi, Roya

Composite gel polymer electrolyte (CGPE) films, consisting of poly (vinylidene fluoride-hexafluoropropylene) (PVdF-HFP) as the membrane, DMF and PC as solvent and plasticizing agent, mixture of charge modified TiO2 and SiO 2 nano particles as ionic conductors, and LiClO4+LiPF 6 as lithium salts were fabricated. Following the work done by Li et al., CGPE was coated on an O2-plasma treated trilayer polypropylene-polyethylene-polypropylene membrane separator using solution casting technique in order to improve the adhesive properties of gel polymer electrolyte to the separator membrane and its respective ionic conductivity due to decreasing the bulk resistance. In acidic CGPE with, the mixture of acid treated TiO2 and neutral SiO2 nano particles played the role of the charge modified nano fillers with enhanced hydroxyl groups. Likely, the mixture of neutral TiO 2 nano particles with basic SiO2 prepared through the hydrolization of tetraethyl orthosilicate (TEOS) provided a more basic environment due to the residues of NH4OH (Ammonium hydroxide) catalyst. The O2 plasma treated separator was coated with the solution of PVDF-HFP: modified nano fillers: Organic solvents with the mixture ratio of 0.1:0.01:1. After the evaporation of the organic solvents, the dried coated separator was soaked in PC-LiClO4+LiPF6 in EC: DMC:DEC (4:2:4 in volume) solution (300% wt. of PVDF-HFP) to form the final CGPE. Lim et al. has reported the enhanced ionic conductivity of 9.78*10-5 Scm-1 in an acidic composite polystyrene-Al2O3 solid electrolyte system with compared to that of basic and neutral in which the ionic conductivity undergoes an ion hopping process in solid interface rather than a segmental movement of ions through the plasticized polymer chain . Half-cells with graphite anode and Li metal as reference electrode were then assembled and the electrochemical measurements and morphology examinations were successfully carried out. Half cells demonstrated a considerable change in their electrochemical performance upon the enhancement of acidic properties of the CGPE, gaining the reversible specific capacity of 314 mAh.g-1 in acidic CGPE vs. 247 mAh.g-1 in basic CGPE C/20 after 33 cycles. The CGPE exhibited submicron pore size while the ionic conductivities were in order of 10-3 and 10-5 Scm-1 with and without modified nano-fillers respectively.

Method of analysis of polymerizable monomeric species in a complex mixture

DOEpatents

Hermes, Robert E

2014-03-18

Method of selective quantitation of a polymerizable monomeric species in a well spacer fluid, said method comprising the steps of adding at least one solvent having a refractive index of less than about 1.33 to a sample of the complex mixture to produce a solvent phase, and measuring the refractive index of the solvent phase.

Step-wise supercritical extraction of carbonaceous residua

DOEpatents

Warzinski, Robert P.

1987-01-01

A method of fractionating a mixture containing high boiling carbonaceous material and normally solid mineral matter includes processing with a plurality of different supercritical solvents. The mixture is treated with a first solvent of high critical temperature and solvent capacity to extract a large fraction as solute. The solute is released as liquid from solvent and successively treated with other supercritical solvents of different critical values to extract fractions of differing properties. Fractionation can be supplemented by solute reflux over a temperature gradient, pressure let down in steps and extractions at varying temperature and pressure values.

Solvent Isotope-induced Equilibrium Perturbation for Isocitrate Lyase

PubMed Central

Quartararo, Christine E.; Hadi, Timin; Cahill, Sean M.; Blanchard, John S.

2014-01-01

Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacteria’s life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage of D2OV = 2.0 ± 0.1 and D2O[V/Kisocitrate] = 2.2 ± 0.3 arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate and succinate prepared in D2O, would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of NMR spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by 1H NMR spectroscopy shows a clear equilibrium perturbation in D2O. The final equilibrium isotopic composition of reactants in D2O revealed di-deuterated succinate, protiated glyoxylate, and mono-deuterated isocitrate, with the transient appearance and disappearance of mono-deuterated succinate. A model for the equilibrium perturbation of substrate species, and their time-dependent isotopic composition is presented. PMID:24261638

Solvent extraction of diatomite

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

Williams, W.

1984-07-24

There is provided a method of extracting hydrocarbons from a diatomite ore. The particle size of the ore is first reduced to form a processed ore. The processed ore is then mixed with a substantially irregular granular material to form an unstratified ore mixture having increased permeability to an extracting solvent. The unstratified ore mixture is then permeated with an extracting solvent to obtain a hydrocarbon-solvent stream from which hydrocarbons are subsequently separated. The irregular granular material may be sand.

Evaluation of the performance and response of the bacharach TLV sniffer and H-Nu photoionization gas analyzer to common hydrocarbon solvents.

PubMed

Chelton, C F; Zakraysek, N; Lautner, G M; Confer, R G

1983-10-01

Two direct reading instruments, the H-Nu PI 101 photoionization analyzer and the J.W. Bacharach TLV Sniffer, were evaluated under laboratory conditions to determine their performance characteristics when challenged by vapors of common hydrocarbon solvent mixtures. Each instrument was evaluated against the manufacturer's recommended test solvent for rise time, fall time, noise, span drift, zero drift, position sensitivity, battery life, and recharge time. The precision, accuracy, and operating linear range were also determined for the test solvents and some petroleum solvent mixtures which are common refinery products. For these latter mixtures, correction factors are presented which allow for an improved estimate of ambient concentrations when monitoring with each of these instruments. All tests except operating humidity range were performed by challenging each instrument with a known concentration of hydrocarbon generated by evaporating calculated liquid volumes into a static chamber. Humidity tests were performed using a dynamic dilution apparatus generating a fixed concentration of hydrocarbon while relative humidity was varied. Concentrations in both systems were verified by gas injection into gas chromatograph. Each instrument performed well when challenged by manufacturers' recommended test solvents. Humidity was shown to influence each instrument's readings. Also, the instruments were shown to have application as monitors of airborne concentrations of common hydrocarbon solvent mixtures.

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

Xu, Wu; Xiao, Jie; Zhang, Jian

The selection and optimization of non-aqueous electrolytes for ambient operations of lithium/air batteries has been studied. Organic solvents with low volatility and low moisture absorption are necessary to minimize the change of electrolyte compositions and the reaction between lithium anode and water during discharge process. It is critical to make the electrolytes with high polarity so that it can reduce wetting and flooding of carbon based air electrode and lead to improved battery performance. For ambient operations, the viscosity, ionic conductivity, and oxygen solubility of the electrolyte are less important than the polarity of organic solvents once the electrolyte hasmore » reasonable viscosity, conductivity, and oxygen solubility. It has been found that PC/EC mixture is the best solvent system and LiTFSI is the most feasible salt for ambient operations of Li/air batteries. Battery performance is not very sensitive to PC/EC ratio or salt concentration.« less

Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

PubMed Central

Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

2016-01-01

Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

Sacrificial component fabrication for optimised production of micro-vascular polymer composite

NASA Astrophysics Data System (ADS)

Dalton, B.; Dixon, D.; McIlhagger, A.; Archer, E.

2015-02-01

Smart functional materials are a viable future goal for advanced applications in aerospace, space and medical applications. In this work micro-vascular polymer composite systems have been developed using sacrificial fibres produced from catalyst loaded Poly(lactic acid). The sacrificial fibres have been produced via a published technique which treated PLA in a solvent catalyst mixture of 60% Trifluoroethanol, 40% H2O dispersed with 10 wt% tin (II) oxalate catalyst. A second process of polymer extrusion of PLA using graded fill contents of tin (II) oxalate has also been developed for the up scaled production of fibres as an alternative to solution treatment. Thermal analysis (TGA) was used to compare sacrificial fibre specimens. PLA fibres produced via the polymer extrusion method outperformed solution treated fibres displaying a lower degradation onset temperature (average 25°C lower), higher degradation rates (observed through a derivative curve comparison) and lower residual catalyst content (0.67% solvent treated fibre against 0.16% extruded fibre). The continuous extrusion process is solvent free and is suitable for high volume production. This work has been carried out to fully understand the fabrication issues with sacrificial components.

Unusual solvatochromic absorbance probe behaviour within mixtures of poly(ethylene glycol)-400 + ionic liquid, [bmim][Tf2N

NASA Astrophysics Data System (ADS)

Ali, Anwar; Ali, Maroof; Malik, Nisar Ahmad; Uzair, Sahar

2014-03-01

The potentially green solvents made up of ionic liquids (ILs) and poly(ethylene glycols) may have wide range of the applications in many chemical and biochemical fields. In the present work, solvatochromic absorbance probe behaviour is used to assess the physicochemical properties of the mixtures composed of PEG-400 + IL, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [bmim][Tf2N]. Lowest energy intramolecular charge-transfer absorbance maxima of a betaine dye, i.e., ETN , indicates the dipolarity/polarizability and/or hydrogen-bond donating (HBD) acidity of the [bmim][Tf2N] + PEG-400 mixtures to be even higher than that of neat [bmim][Tf2N], the solution component with higher dipolarity/polarizability and/or HBD acidity. Dipolarity/polarizability (π∗) obtained separately from the electronic absorbance response of probe N,N-diethyl-4-nitroaniline, and the HBD acidity (α) of PEG-400 + [bmim][Tf2N] mixtures are also observed to be anomalously high. A comparative study of the PEG + IL mixtures has also been done with PEG-400 + molecular organic solvents (protic polar [methanol], aprotic polar [N,N-dimethylformamide], and non polar, [benzene]) mixtures, but these mixtures do not show this type of unusual behaviour. A four-parameter simplified combined nearly ideal binary solvent/Redlich-Kister (CNIBS/R-K) equation is shown to satisfactorily predict the solvatochromic parameters within PEG-400 + different solvent mixtures.

Coal liquefaction process using pretreatment with a binary solvent mixture

DOEpatents

Miller, R.N.

1986-10-14

An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300 C before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil. 1 fig.

Homopolymer Micelles in Heterogeneous Solvent Mixtures

PubMed Central

Basu, Subhadeep; Vutukuri, Dharma Rao

2008-01-01

Amphiphilic homopolymers containing a hydrophilic and a hydrophobic functionality in each monomer unit have been shown to form polar or apolar containers depending on the solvent environment. When presented with a mixture of solvents, these polymeric containers are capable of releasing certain guest molecules. The fundamental mechanism behind these properties is investigated and the utility of these assemblies in separations has been demonstrated with an example. PMID:16316219

Coal liquefaction process using pretreatment with a binary solvent mixture

DOEpatents

Miller, Robert N.

1986-01-01

An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300.degree. C. before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil.

High throughput method to characterize acid-base properties of insoluble drug candidates in water.

PubMed

Benito, D E; Acquaviva, A; Castells, C B; Gagliardi, L G

2018-05-30

In drug design experimental characterization of acidic groups in candidate molecules is one of the more important steps prior to the in-vivo studies. Potentiometry combined with Yasuda-Shedlovsky extrapolation is one of the more important strategy to study drug candidates with low solubility in water, although, it requires a large number of sequences to determine pK a values at different solvent-mixture compositions to, finally, obtain the pK a in water (pwwK a ) by extrapolation. We have recently proposed a method which requires only two sequences of additions to study the effect of organic solvent content in liquid chromatography mobile phases on the acidity of the buffer compounds usually dissolved in it along wide ranges of compositions. In this work we propose to apply this method to study thermodynamic pwwK a of drug candidates with low solubilities in pure water. Using methanol/water solvent mixtures we study six pharmaceutical drugs at 25 °C. Four of them: ibuprofen, salicylic acid, atenolol and labetalol, were chosen as members of carboxylic, amine and phenol families, respectively. Since these compounds have known pwwK a values, they were used to validate the procedure, the accuracy of Yasuda-Shedlovsky and other empirical models to fit the behaviors, and to obtain pwwK a by extrapolation. Finally, the method is applied to determine unknown thermodynamic pwwK a values of two pharmaceutical drugs: atorvastatin calcium and the two dissociation constants of ethambutol. The procedure proved to be simple, very fast and accurate in all of the studied cases. Copyright © 2018 Elsevier B.V. All rights reserved.

In situ synthesis of molecularly imprinted nanoparticles in porous support membranes using high-viscosity polymerization solvents.

PubMed

Renkecz, Tibor; László, Krisztina; Horváth, Viola

2012-06-01

There is a growing need in membrane separations for novel membrane materials providing selective retention. Molecularly imprinted polymers (MIPs) are promising candidates for membrane functionalization. In this work, a novel approach is described to prepare composite membrane adsorbers incorporating molecularly imprinted microparticles or nanoparticles into commercially available macroporous filtration membranes. The polymerization is carried out in highly viscous polymerization solvents, and the particles are formed in situ in the pores of the support membrane. MIP particle composite membranes selective for terbutylazine were prepared and characterized by scanning electron microscopy and N₂ porosimetry. By varying the polymerization solvent microparticles or nanoparticles with diameters ranging from several hundred nanometers to 1 µm could be embedded into the support. The permeability of the membranes was in the range of 1000 to 20,000 Lm⁻²  hr⁻¹  bar⁻¹. The imprinted composite membranes showed high MIP/NIP (nonimprinted polymer) selectivity for the template in organic media both in equilibrium-rebinding measurements and in filtration experiments. The solid phase extraction of a mixture of the template, its analogs, and a nonrelated compound demonstrated MIP/NIP selectivity and substance selectivity of the new molecularly imprinted membrane. The synthesis technique offers a potential for the cost-effective production of selective membrane adsorbers with high capacity and high throughput. Copyright © 2012 John Wiley & Sons, Ltd.

PREDICTION OF THE SOLUBILITY OF HYDROPHOBIC COMPOUNDS IN NONIDEAL SOLVENT MIXTURES

EPA Science Inventory

The solubility of hydrophobic organic chemicals (HOCs) in partially-miscible solvent mixtures was investigated. In agreement with previous findings, it was observed that there is a limited domain in which nonideality effects are important; appreciable concentrations of partially-...

Method for molding ceramic powders

DOEpatents

Janney, Mark A.

1990-01-01

A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant for the metal-containing powder, and a monomer solution. The monomer solution includes at least one multifunctional monomer, a free-radical initiator, and an organic solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product may be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, whereafter the product may be sintered.

Method for molding ceramic powders

DOEpatents

Janney, M.A.

1990-01-16

A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant for the metal-containing powder, and a monomer solution. The monomer solution includes at least one multifunctional monomer, a free-radical initiator, and an organic solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product may be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, where after the product may be sintered.

Evaluation of solvent effect on the extraction of phenolic compounds and antioxidant capacities from the berries: application of principal component analysis.

PubMed

Boeing, Joana Schuelter; Barizão, Erica Oliveira; E Silva, Beatriz Costa; Montanher, Paula Fernandes; de Cinque Almeida, Vitor; Visentainer, Jesuí Vergilio

2014-01-01

This study evaluated the effect of the solvent on the extraction of antioxidant compounds from black mulberry (Morus nigra), blackberry (Rubus ulmifolius) and strawberry (Fragaria x ananassa). Different extracts of each berry were evaluated from the determination of total phenolic content, anthocyanin content and antioxidant capacity, and data were applied to the principal component analysis (PCA) to gain an overview of the effect of the solvent in extraction method. For all the berries analyzed, acetone/water (70/30, v/v) solvent mixture was more efficient solvent in the extracting of phenolic compounds, and methanol/water/acetic acid (70/29.5/0.5, v/v/v) showed the best values for anthocyanin content. Mixtures of ethanol/water (50/50, v/v), acetone water/acetic acid (70/29.5/0.5, v/v/v) and acetone/water (50/50, v/v) presented the highest antioxidant capacities for black mulberries, blackberries and strawberries, respectively. Antioxidants extractions are extremely affected by the solvent combination used. In addition, the obtained extracts with the organic solvent-water mixtures were distinguished from the extracts obtained with pure organic solvents, through the PCA analysis.

Solvent-dependent gating motions of an extremophilic lipase from Pseudomonas aeruginosa

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

Johnson, Quentin R.; Nellas, Ricky B.; Shen, Tongye

2012-07-25

Understanding how organic solvent-stable proteins can function in anhydrous and often complex solutions is essential for the study of the interaction of protein and molecular immiscible interfaces and the design of efficient industrial enzymes in nonaqueous solvents. Using an extremophilic lipase from Pseudomonas aeruginosa as an example, we investigated the conformational dynamics of an organic solvent-tolerant enzyme in complex solvent milieux. Four 100-ns molecular dynamics simulations of the lipase were performed in solvent systems: water, hexane, and two mixtures of hexane and water, 5% and 95% (w/w) hexane. Our results show a solvent-dependent structural change of the protein, especially inmore » the region that regulates the admission of the substrate. We observed that the lipase is much less flexible in hexane than in aqueous solution or at the immiscible interface. Quantified by the size of the accessible channel, the lipase in water has a closed-gate conformation and no access to the active site, while in the hexane-containing systems, the lipase is at various degrees of open-gate state, with the immiscible interface setup being in the widely open conformation ensembles. Furthermore, the composition of explicit solvents in the access channel showed a significant influence on the conformational dynamics of the protein. Interestingly, the slowest step (bottleneck) of the hexane-induced conformational switch seems to be correlated with the slow dehydration dynamics of the channel.« less

Catalytic conversion of cellulose to fuels and chemicals using boronic acids

DOEpatents

Raines, Ronald; Caes, Benjamin; Palte, Michael

2015-10-20

Methods and catalyst compositions for formation of furans from carbohydrates. A carbohydrate substrate is heating in the presence of a 2-substituted phenylboronic acid (or salt or hydrate thereof) and optionally a magnesium or calcium halide salt. The reaction is carried out in a polar aprotic solvent other than an ionic liquid, an ionic liquid or a mixture thereof. Additional of a selected amount of water to the reaction can enhance the yield of furans.

The ultrasound-assisted oxidative scission of monoenic fatty acids by ruthenium tetroxide catalysis: influence of the mixture of solvents.

PubMed

Rup, Sandrine; Zimmermann, François; Meux, Eric; Schneider, Michel; Sindt, Michele; Oget, Nicolas

2009-02-01

Carboxylic acids and diacids were synthesized from monoenic fatty acids by using RuO4 catalysis, under ultrasonic irradiation, in various mixtures of solvents. Ultrasound associated with Aliquat 336 have promoted in water, the quantitative oxidative cleavage of the CH=CH bond of oleic acid. A design of experiment (DOE) shows that the optimal mixture of solvents (H2O/MeCN, ratio 1/1, 2.2% RuCl3/4.1 eq. NaIO4) gives 81% azelaic acid and 97% pelargonic acid. With the binary heterogeneous mixture H2O/AcOEt, the oxidation of the oleic acid leads to a third product, the alpha-dione 9,10-dioxostearic acid.

Process for producing an activated carbon adsorbent with integral heat transfer apparatus

NASA Technical Reports Server (NTRS)

Jones, Jack A. (Inventor); Yavrouian, Andre H. (Inventor)

1996-01-01

A process for producing an integral adsorbent-heat exchanger apparatus useful in ammonia refrigerant heat pump systems. In one embodiment, the process wets an activated carbon particles-solvent mixture with a binder-solvent mixture, presses the binder wetted activated carbon mixture on a metal tube surface and thereafter pyrolyzes the mixture to form a bonded activated carbon matrix adjoined to the tube surface. The integral apparatus can be easily and inexpensively produced by the process in large quantities.

Effects of solvents on the synthesis of CuInSe2 nanoparticles for thin film solar cells.

PubMed

Lee, Jaehyeong; Lee, Soo-Ho; Hahn, Jae-Sub; Sun, Ho-Jung; Park, Gyungse; Shim, Joongpyo

2014-12-01

Chalcopyrite CuInSe2 (CIS) nanoparticles were synthesized in oleic acid, 1-octadecene, oleyl amine and tetraethylene glycol at temperature above 200 degrees C. Depending on the solvent used and reaction temperature, the obtained nanoparticles had different shapes, sizes, chemical compositions, and crystal and thermal properties. CIS powders synthesized in oleic acid, 1-octadecene and oleyl amine above 200 degrees C exhibited chalcopyrite structure. On the other hand, powders prepared in tetraethylene glycol contained a mixture of CIS and CuSe compounds. The CIS powder obtained in oleyl amine had a high thermal stability over 500 degrees C. CIS thin films prepared from nanoparticles were heat-treated in order to observe changes in their property. After 10 min heat-treatment at 500 degrees C, their crystal structure and chemical composition were slightly changed, and their band gap energies were ca. 1.01 eV except in the case of powders prepared in tetraethylene glycol.

Magnetic Fe-Co films electroplated in a deep-eutectic-solvent-based plating bath

NASA Astrophysics Data System (ADS)

Yanai, T.; Shiraishi, K.; Watanabe, Y.; Ohgai, T.; Nakano, M.; Suzuki, K.; Fukunaga, H.

2015-05-01

We fabricated Fe-Co films from a deep eutectic solvent (DES)-based plating bath and investigated magnetic properties of the plated films. The plating baths were obtained by stirring the mixture of choline chloride, ethylene glycol, FeCl2.4H2O, and CoCl2.6H2O. The composition of the plated films depended on the amount of FeCl2.4H2O in the plating bath, and Fe content of the films was varied from 0 to 100 at. %. Depending on the Fe content, the saturation magnetization and the coercivity of the films varied. The Fe76Co24 film shows high saturation magnetization and smooth surface, and the change in the saturation magnetization shows good agreement with the expected change by the Slater-Pauling curve. High current efficiency (>90%) could be obtained in the wide film composition. From these results, we concluded that the DES-based plating bath is one of effective baths for the Fe-Co films with high current efficiency.

1H NMR-based metabolomics reveals interactive effects between the carrier solvent methanol and a pharmaceutical mixture in an amphibian developmental bioassay with Limnodynastes peronii.

PubMed

Melvin, Steven D; Jones, Oliver A H; Carroll, Anthony R; Leusch, Frederic D L

2018-05-01

Organic carrier solvents are used in aquatic toxicity testing to improve chemical solubility and facilitate the exploration of dose-response relationships. Both water- and solvent-control groups are normally included in these scenarios to ensure that the solvent itself has no effect on the test organism, but this fails to consider possible interactive effects between carrier solvents and contaminants of interest. We explored this topic by exposing Limnodynastes peronii tadpoles to a mixture of common water-soluble pharmaceuticals (diclofenac, metformin and valproic acid) in the presence and absence of the carrier solvent methanol, according to standard developmental bioassay methodology. Nuclear Magnetic Resonance (NMR) spectroscopy was applied as a platform for untargeted metabolomics, to compare broad sub-lethal hepatotoxicity in solvent- and solvent-free exposure scenarios. Considerable interactive effects were identified between the pharmaceutical mixture and a typical dose of methanol (0.003%). Specifically, pronounced differences were observed between the solvent- and solvent-free exposure groups for leucine, acetate, glutamine, citrate, glycogen, tyrosine, arginine, purine nucleotides and an unidentified metabolite at 6.53 ppm. Various other metabolites exhibited similar disparity related to the use of carrier solvent, but the interactions were non-significant. These results raise important questions about the use of carrier solvents for chemical exposures in aquatic ecotoxicology, and particularly for studies interested in sub-lethal mechanistic information and/or biomarker discovery. Copyright © 2018 Elsevier Ltd. All rights reserved.

Flexible energetic materials and related methods

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

Heaps, Ronald J.

Energetic compositions and methods of forming components from the compositions are provided. In one embodiment, a composition includes aluminum, molybdenum trioxide, potassium perchlorate, and a binder. In one embodiment, the binder may include a silicone material. The materials may be mixed with a solvent, such as xylene, de-aired, shaped and cured to provide a self-supporting structure. In one embodiment, one or more reinforcement members may be added to provide additional strength to the structure. For example, a weave or mat of carbon fiber material may be added to the mixture prior to curing. In one embodiment, blade casting techniques maymore » be used to form a structure. In another embodiment, a structure may be formed using 3-dimensional printing techniques.« less

Effect of Hydroxyl Concentration on Chemical Sensitivity of Polyvinyl Alcohol/Carbon-Black Composite Chemiresistors

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

Hughes, Robert C.; Patel, Sanjay V.; Yelton, W. Graham

1999-05-19

The sensitivity and selectivity of polyvinyl alcohol (PVA) / carbon black composite films have been found to vary depending upon the hydroxylation percentage ("-OH") of the polymer. These chemiresistors made from PVA films whose polymer backbone is 88% hydroxylated (PVA88) have a high sensitivity to water, while chemiresistors made from PVA75 have a higher sensitivity to methanol. The minor differences in polymer composition result in films with different Hildebrand volubility parameters. The relative responses of several different PVA-based chemiresistors to solvents with different volubility parameters are presented. In addition, polyvinyl acetate (PVAC) films with PVA88 are used in an arraymore » to distinguish the responses to methanol-water mixtures.« less

PARIS II: Computer Aided Solvent Design for Pollution Prevention

EPA Science Inventory

This product is a summary of U.S. EPA researchers' work developing the solvent substitution software tool PARIS II (Program for Assisting the Replacement of Industrial Solvents, version 2.0). PARIS II finds less toxic solvents or solvent mixtures to replace more toxic solvents co...

Extraction of aucubin from seeds of Eucommia ulmoides Oliv. using supercritical carbon dioxide.

PubMed

Li, Hui; Hu, Jiangyu; Ouyang, Hui; Li, Yanan; Shi, Hui; Ma, Chengjin; Zhang, Yongkang

2009-01-01

Supercritical CO2 was used as solvent for the extraction of aucubin from the seeds of Eucommia ulmoides Oliv. The co-solvent composition was tested and extraction conditions were optimized. Results showed that the best co-solvent was a water-ethanol mixture (1 + 3, v/v), and the highest yield was obtained when the extraction was performed under 26 MPa at extraction and separation temperatures of 55 and 30 degrees C for 120 min, using 6 mL co-solvent/g material at a CO2 flow rate of 20 L/h. In a comparison of the supercritical CO2 and Soxhlet extraction methods, the Soxhlet method needed 3 h to extract 10 g material, whereas the supercritical CO2 extraction technique needed only 2 h to extract 100 g material, thus showing a high extraction capability. The supercritical CO2 extraction produced a higher yield, with a lower cost for the extraction. Owing to the advantages of low extraction temperature, high yield, and ease of separating the product from the solvent, supercritical CO2 extraction is likely to be developed into an ideal technique for the extraction of aucubin, a compound with thermal instability, from the seeds of this plant.

Water dispersible microbicidal cellulose acetate phthalate film

PubMed Central

Neurath, A Robert; Strick, Nathan; Li, Yun-Yao

2003-01-01

Background Cellulose acetate phthalate (CAP) has been used for several decades in the pharmaceutical industry for enteric film coating of oral tablets and capsules. Micronized CAP, available commercially as "Aquateric" and containing additional ingredients required for micronization, used for tablet coating from water dispersions, was shown to adsorb and inactivate the human immunodeficiency virus (HIV-1), herpesviruses (HSV) and other sexually transmitted disease (STD) pathogens. Earlier studies indicate that a gel formulation of micronized CAP has a potential as a topical microbicide for prevention of STDs including the acquired immunodeficiency syndrome (AIDS). The objective of endeavors described here was to develop a water dispersible CAP film amenable to inexpensive industrial mass production. Methods CAP and hydroxypropyl cellulose (HPC) were dissolved in different organic solvent mixtures, poured into dishes, and the solvents evaporated. Graded quantities of a resulting selected film were mixed for 5 min at 37°C with HIV-1, HSV and other STD pathogens, respectively. Residual infectivity of the treated viruses and bacteria was determined. Results The prerequisites for producing CAP films which are soft, flexible and dispersible in water, resulting in smooth gels, are combining CAP with HPC (other cellulose derivatives are unsuitable), and casting from organic solvent mixtures containing ≈50 to ≈65% ethanol (EtOH). The films are ≈100 µ thick and have a textured surface with alternating protrusions and depressions revealed by scanning electron microscopy. The films, before complete conversion into a gel, rapidly inactivated HIV-1 and HSV and reduced the infectivity of non-viral STD pathogens >1,000-fold. Conclusions Soft pliable CAP-HPC composite films can be generated by casting from organic solvent mixtures containing EtOH. The films rapidly reduce the infectivity of several STD pathogens, including HIV-1. They are converted into gels and thus do not have to be removed following application and use. In addition to their potential as topical microbicides, the films have promise for mucosal delivery of pharmaceuticals other than CAP. PMID:14617380

Influence of solvents on species crossover and capacity decay in non-aqueous vanadium redox flow batteries: Characterization of acetonitrile and 1, 3 dioxolane solvent mixture

NASA Astrophysics Data System (ADS)

Bamgbopa, Musbaudeen O.; Almheiri, Saif

2017-02-01

The importance of the choice of solvent in a non-aqueous redox flow battery (NARFB) cannot be overemphasized. Several studies demonstrated the influence of the solvent on electrolyte performance in terms of reaction rates, energy/power densities, and efficiencies. In this work, we investigate capacity decay as a direct consequence of varying reactant crossover rates through membranes in different solvent environments. Specifically, we demonstrate the superiority of an 84/16 vol% acetonitrile/1,3 dioxolane solvent mixture over pure acetonitrile in terms of energy efficiency (up to 89%) and capacity retention for vanadium NARFBs - while incorporating a Nafion 115 membrane. The permeability of Nafion to the vanadium acetylacetonate active species is an order of magnitude lower when pure acetonitrile is replaced by the solvent mixture. A method to estimate relative membrane permeability is formulated from numerical analysis of self-discharge experimental data. Furthermore, tests on a modified Nafion/SiO2 membrane, which generally offered low species permeability, also show that different solvents alter membrane permeability. Elemental and morphological analyses of cycled Nafion and NafionSi membranes in different solvent environments indicate that different crossover rates induced by the choice of solvent during cycling are due to changes in the membrane microstructure, intrinsic permeability, swelling rates, and chemical stability.

Evaluation of different solvent mixtures in esterifiable lipids extraction from microalgae Botryococcus braunii for biodiesel production.

PubMed

Hidalgo, Pamela; Ciudad, Gustavo; Navia, Rodrigo

2016-02-01

Non-polar and polar solvents as well as their mixtures were tested for the extraction of microalgae lipids and thus, to evaluate their effect on total and esterifiable lipids extraction yields with potential to be converted to biodiesel. The obtained results show an increase in lipids and esterifiable lipids extraction yields when non-polar and polar solvent mixtures were used. The higher esterifiable lipids extraction yield was 19.2%wt (based on dry biomass) using a chloroform-methanol mixture (75%v/v of methanol), corresponding to a 98.9%wt esterifiable lipids extraction. In addition, esterifiable lipids extraction yield of 18.9%wt (based on dry biomass) was obtained when a petroleum ether-methanol mixture (75%v/v of methanol) was used, corresponding to a 96.9%wt esterifiable lipids extraction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synergism and antagonism in extracting local anesthetics from aqueous media with mixtures of solvents

NASA Astrophysics Data System (ADS)

Sukhanov, P. T.; Chibisova, T. V.; Korenman, Ya. I.

2014-12-01

The extraction of local anesthetics from aqueous media with mixtures of solvent is examined and its synergistic and antagonistic effects are determined. Synergism parameters, separation factors, constants for the formation of anesthetic complexes, and solvate numbers are calculated.

Enzymatic synthesis of 6-O-glucosyl-poly(3-hydroxyalkanoate) in organic solvents and their binary mixture.

PubMed

Gumel, A M; Annuar, M S M; Heidelberg, T

2013-04-01

The effects of organic solvents and their binary mixture in the glucose functionalization of bacterial poly-3-hydroxyalkanoates catalyzed by Lecitase™ Ultra were studied. Equal volume binary mixture of DMSO and chloroform with moderate polarity was more effective for the enzyme catalyzed synthesis of the carbohydrate polymer at ≈38.2 (±0.8)% reactant conversion as compared to the mono-phasic and other binary solvents studied. The apparent reaction rate constant as a function of medium water activity (aw) was observed to increase with increasing solvent polarity, with optimum aw of 0.2, 0.4 and 0.7 (±0.1) observed in hydrophilic DMSO, binary mixture DMSO:isooctane and hydrophobic isooctane, respectively. Molecular sieve loading between 13 to 15gL(-1) (±0.2) and reaction temperature between 40 to 50°C were found optimal. Functionalized PHA polymer showed potential characteristics and biodegradability. Copyright © 2012 Elsevier B.V. All rights reserved.

Desolventizing of soybean oil/azeotrope mixtures using ceramic membranes.

PubMed

de Melo, Jonas R M; Tiggeman, Lidia; Rezzadori, Katia; Steffens, Juliana; Palliga, Marshall; Oliveira, J Vladimir; Di Luccio, Marco; Tres, Marcus V

2017-08-01

This work investigates the use of ceramic membranes with different molecular weight cut-offs (MWCOs: 5, 10 and 20 kDa) to desolventize azeotropic solvent mixtures (ethanol/n-hexane and isopropyl alcohol/n-hexane) from soybean oil/azeotrope micelles. Results show that a decrease in the MWCO of a membrane and an increase in the solvent mass ratio in the mixture resulted in a significant reduction in the permeate flux. The 20 kDa membrane presented the highest permeate flux, 80 and 60 kg/m 2 h for the soybean oil/n-hexane/isopropyl alcohol and soybean oil/n-hexane/ethanol azeotropes, respectively, for an oil to solvent ratio of 1:3 (w/w). The highest oil retention was found using the n-hexane/isopropyl alcohol azeotrope, around 25% in the membrane with the lowest MWCO, that is, 5 kDa. It is shown that the azeotropic mixtures provided intermediate characteristics compared to the original pure solvent behavior.

Solubility and conversion of carbamazepine polymorphs in supercritical carbon dioxide.

PubMed

Bettini, R; Bonassi, L; Castoro, V; Rossi, A; Zema, L; Gazzaniga, A; Giordano, F

2001-06-01

The aim of this work was to investigate whether mixtures of carbamazepine polymorphs could be processed in supercritical (SC) CO(2) in order to obtain the pure stable crystalline phase. To accomplish this goal the solubility of carbamazepine polymorphs I and III in supercritical CO(2) was first assessed using a low solvent flux dynamic method. Mixtures of Form I and Form III were processed in dynamic or static conditions in SC-CO(2). Differential scanning calorimetry, Fourier transformed infrared spectroscopy, and powder X-ray diffractometry were used to analyse solid samples in terms of polymorph composition. It was found that Form I and Form III of carbamazepine have different solubility in supercritical CO(2) at 55 degrees C above 300 bar. Due to the transformation of the metastable form, conversion of Form I into Form III can be carried out on a binary mixture of the two polymorphs by treating the mixture at 55 degrees C and 350 bar, under both static and dynamic conditions, via its solubilization in supercritical CO(2).

Solvent effects on the polar network of ionic liquid solutions

NASA Astrophysics Data System (ADS)

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

2015-05-01

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

Method for molding ceramic powders using a water-based gel casting

DOEpatents

Janney, Mark A.; Omatete, Ogbemi O.

1991-07-02

A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant, and a monomer solution. The monomer solution includes at least one monofunctional monomer and at least one difunctional monomer, a free-radical initiator, and a aqueous solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product any be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, whereafter the product may be sintered.

Method for molding ceramic powders using a water-based gel casting process

DOEpatents

Jenny, Mark A.; Omalete, Ogbemi O.

1992-09-08

A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant, and a monomer solution. The monomer solution includes at least one monofunctional monomer and at least one difunctional monomer, a free-radical initiator, and a aqueous solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product may be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, whereafter the product may be sintered.

In-pore exchange and diffusion of carbonate solvent mixtures in nanoporous carbon

DOE PAGES

Alam, Todd M.; Osborn Popp, Thomas M.

2016-06-04

High resolution magic angle spinning (HRMAS) 1H NMR spectroscopy has been used to resolve different surface and in-pore solvent environments of ethylene carbonate (EC) and dimethyl carbonate (DMC) mixtures absorbed within nanoporous carbon (NPC). Two dimensional (2D) 1H HRMAS NMR exchange measurements revealed that the inhomogeneous broadened in-pore resonances have pore-to-pore exchange rates on the millisecond timescale. Pulsed-field gradient (PFG) NMR diffusometry revealed the in-pore self-diffusion constants for both EC and DMC were reduced by up to a factor of five with respect to the diffusion in the non-absorbed solvent mixtures.

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

PubMed

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

2015-08-07

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

Identification of isopropylbiphenyl, alkyl diphenylmethanes, diisopropylnaphthalene, linear alkyl benzenes and other polychlorinated biphenyl replacement compounds in effluents, sediments and fish in the Fox River System, Wisconsin

USGS Publications Warehouse

Peterman, Paul H.; Delfino, Joseph J.

1990-01-01

Five polychlorinated biphenyl replacement dye solvents and a diluent present in carbonless copy paper were identified by gas chromatography/mass spectrometry in the following matrices: effluents from a de-inking–recycling paper mill and a municipal wastewater treatment plant receiving wastewaters from a carbonless copy paper manufacturing plant; sediments; and fish collected near both discharges in the Fox River System, Wisconsin. An isopropylbiphenyl dye solvent mixture included mono-, di- and triisopropylbiphenyls. Also identified were two dye solvent mixtures marketed under the trade name Santosol. Santosol 100 comprised ethyl-diphenylmethanes (DPMs), benzyl-ethyl-DPMs, and dibenzyl-ethyl-DPMs. Similarly, Santosol 150 comprised dimethyl-DPMs, benzyl-dimethyl-DPMs, and dibenzyl-dimethyl-DPMs. Diisopropylnaphthalenes, widely used as a dye solvent in Japan, were identified for the first time in the US environment. sec-Butylbiphenyls and di-sec-butylbiphenyls, likely constituents of a sec-butylbiphenyl dye solvent mixture, were tentatively identified. Linear alkyl benzenes (C10 to C13-LABs) constituted the Alkylate 215 diluent mixture. Although known to occur as minor constituents in linear alkyl sulfonate detergents, LAB residues have not been previously attributed to commercial use of LABs.

Solvent selection and optimization of α-chymotrypsin-catalyzed synthesis of N-Ac-Phe-Tyr-NH2 using mixture design and response surface methodology.

PubMed

Hu, Shih-Hao; Kuo, Chia-Hung; Chang, Chieh-Ming J; Liu, Yung-Chuan; Chiang, Wen-Dee; Shieh, Chwen-Jen

2012-01-01

A peptide, N-Ac-Phe-Tyr-NH(2) , with angiotensin I-converting enzyme (ACE) inhibitor activity was synthesized by an α-chymotrypsin-catalyzed condensation reaction of N-acetyl phenylalanine ethyl ester (N-Ac-Phe-OEt) and tyrosinamide (Tyr-NH(2) ). Three kinds of solvents: a Tris-HCl buffer (80 mM, pH 9.0), dimethylsulfoxide (DMSO), and acetonitrile were employed in this study. The optimum reaction solvent component was determined by simplex centroid mixture design. The synthesis efficiency was enhanced in an organic-aqueous solvent (Tris-HCl buffer: DMSO: acetonitrile = 2:1:1) in which 73.55% of the yield of N-Ac-Phe-Tyr-NH(2) could be achieved. Furthermore, the effect of reaction parameters on the yield was evaluated by response surface methodology (RSM) using a central composite rotatable design (CCRD). Based on a ridge max analysis, the optimum condition for this peptide synthesis included a reaction time of 7.4 min, a reaction temperature of 28.1°C, an enzyme activity of 98.9 U, and a substrate molar ratio (Phe:Tyr) of 1:2.8. The predicted and the actual (experimental) yields were 87.6 and 85.5%, respectively. The experimental design and RSM performed well in the optimization of synthesis of N-Ac-Phe-Tyr-NH(2) , so it is expected to be an effective method for obtaining a good yield of enzymatic peptide. © 2012 American Institute of Chemical Engineers Biotechnol. Prog., 2012. Copyright © 2012 American Institute of Chemical Engineers (AIChE).

Molecular Dynamics Study of the Solution Structure, Clustering, and Diffusion of Four Aqueous Alkanolamines.

PubMed

Melnikov, Sergey M; Stein, Matthias

2018-03-15

CO 2 sequestration from anthropogenic resources is a challenge to the design of environmental processes at a large scale. Reversible chemical absorption by amine-based solvents is one of the most efficient methods of CO 2 removal. Molecular simulation techniques are very useful tools to investigate CO 2 binding by aqueous alkanolamine molecules for further technological application. In the present work, we have performed detailed atomistic molecular dynamics simulations of aqueous solutions of three prototype amines: monoethanolamine (MEA) as a standard, 3-aminopropanol (MPA), 2-methylaminoethanol (MMEA), and 4-diethylamino-2-butanol (DEAB) as potential novel CO 2 absorptive solvents. Solvent densities, radial distribution functions, cluster size distributions, hydrogen-bonding statistics, and diffusion coefficients for a full range of mixture compositions have been obtained. The solvent densities and diffusion coefficients from simulations are in good agreement with those in the experiment. In aqueous solution, MEA, MPA, and MMEA molecules prefer to be fully solvated by water molecules, whereas DEAB molecules tend to self-aggregate. In a range from 30/70-50/50 (w/w) alkanolamine/water mixtures, they form a bicontinuous phase (both alkanolamine and water are organized in two mutually percolating clusters). Among the studied aqueous alkanolamine solutions, the diffusion coefficients decrease in the following order MEA > MPA = MMEA > DEAB. With an increase of water content, the diffusion coefficients increase for all studied alkanolamines. The presented results are a first step for process-scale simulation and provide important qualitative and quantitative information for the design and engineering of efficient new CO 2 removal processes.

3D printing biodegradable scaffolds with chitosan materials for tissue engineering

NASA Astrophysics Data System (ADS)

Bardakova, K. N.; Demina, T. S.; Grebenik, E. A.; Minaev, N. V.; Akopova, T. A.; Bagratashvili, V. N.; Timashev, P. S.

2018-04-01

Chitosan-g-oligo (L,L-lactide) copolymer was synthesized through a solvent-free reaction in an extruder. Three-dimensional scaffolds based on photosensitive composition contained the synthetized copolymer were formed by two-photon polymerization. The optimum ratio of components, methods of preparation of photopolymerizable mixtures, parameters of the laser structuring and procedure of washing from unbound crosslinkers have been optimized. Chitosan scaffolds were non-cytotoxic and might therefore be a suitable candidate for treating spinal cord injuries and other neuronal degenerative diseases.

A deeper insight into an intriguing acetonitrile-water binary mixture: synergistic effect, dynamic Stokes shift, fluorescence correlation spectroscopy, and NMR studies.

PubMed

Koley, Somnath; Ghosh, Subhadip

2016-11-30

An insight study reveals the strong synergistic solvation behaviours from reporter dye molecules within the acetonitrile (ACN)-water (WT) binary mixture. Synergism of a binary mixture refers to some unique changes of the physical and thermodynamic properties of the solvent mixture, originating from the interactions among its cosolvents, which are absent within the pure cosolvents. Synergistic solvation of a binary mixture is likely to be fundamental for greater stabilization of an excited state solute dipole; at least to some extent greater as compared to one stabilized by any of its cosolvents alone. A dynamic Stokes shift due to the solvation of an excited dipole in the ACN-WT binary mixture is found to be highly relevant to the ground state physical properties of the solute molecule (polarity, hydrophilicity, acidity, etc.). Largely different solvation times in the ACN-WT mixture are observed from different dye molecules with widely varying polarities. However, earlier study shows that dye molecules, irrespective of their varying polarities, exhibit very similar solvation times within a pure solvent (J. Phys. Chem. B, 2014, 118, 7577-7785). On further study with fluorescence correlation spectroscopy (FCS) we observed that, unlike the translational diffusion coefficient (D t ) of a dye molecule within a pure solvent, which remains the same irrespective of the location of the dye molecule inside the solvent, a broad distribution among the D t values of a dye molecule is obtained from different locations within the ACN-WT binary mixture. Lastly our 1 H NMR study in the ACN-WT binary mixture shows the existence of strong hydrogen bond interactions among the cosolvents in the ACN-WT mixture.

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

Sakurada, I.; Okada, T.; Hutakeyama, S.

Experiments on radioinduced graft copolymerization of binary mixtures such as butadiene -- styrene, butadiene-acrylonitrile, styrene-- acrylonitrile and some other systems onto cellulose and PVA (polyvinyl alcohol) fibers were carried out with the use of methanol as a solvent. A very marked maximum of graft was observed in every case at a certain composition of the comonomer mixture. It seemed that such a marked maximum was closely connected with popcorn polymerization for the case of butadiene-- styrene, but popcorn polymerization was not a necessary condition for the appearance of the maximum. Only a combined effect of swelling of the gel, formationmore » of radicals in the gel, homocopolymerization, and some other unknown factors is considered likely to lead to a very high degree of grafting. (auth)« less

Structural transformations, composition anomalies and a dramatic collapse of linear polymer chains in dilute ethanol-water mixtures.

PubMed

Banerjee, Saikat; Ghosh, Rikhia; Bagchi, Biman

2012-03-29

Water-ethanol mixtures exhibit many interesting anomalies, such as negative excess partial molar volume of ethanol, excess sound absorption coefficient at low concentrations, and positive deviation from Raoult's law for vapor pressure, to mention a few. These anomalies have been attributed to different, often contradictory origins, but a quantitative understanding is still lacking. We show by computer simulation and theoretical analyses that these anomalies arise from the sudden emergence of a bicontinuous phase that occurs at a relatively low ethanol concentration of x(eth) ≈ 0.06-0.10 (that amounts to a volume fraction of 0.17-0.26, which is a significant range!). The bicontinuous phase is formed by aggregation of ethanol molecules, resulting in a weak phase transition whose nature is elucidated. We find that the microheterogeneous structure of the mixture gives rise to a pronounced nonmonotonic composition dependence of local compressibility and nonmonotonic dependence in the peak value of the radial distribution function of ethyl groups. A multidimensional free energy surface of pair association is shown to provide a molecular explanation of the known negative excess partial volume of ethanol in terms of parallel orientation and hence better packing of the ethyl groups in the mixture due to hydrophobic interactions. The energy distribution of the ethanol molecules indicates additional energy decay channels that explain the excess sound attenuation coefficient in aqueous alcohol mixtures. We studied the dependence of the solvation of a linear polymer chain on the composition of the water-ethanol solvent. We find that there is a sudden collapse of the polymer at x(eth) ≈ 0.05-a phenomenon which we attribute to the formation of the microheterogeneous structures in the binary mixture at low ethanol concentrations. Together with recent single molecule pulling experiments, these results provide new insight into the behavior of polymer chain and foreign solutes, such as enzymes, in aqueous binary mixtures.

Transparent ceramics and methods of preparation thereof

DOEpatents

Hollingsworth, Joel P.; Kuntz, Joshua D.; Seeley, Zachary M.; Soules, Thomas F.

2012-12-25

A method for forming a transparent ceramic preform in one embodiment includes forming a suspension of oxide particles in a solvent, wherein the suspension includes a dispersant, with the proviso that the suspension does not include a gelling agent; and uniformly curing the suspension for forming a preform of gelled suspension. A method according to another embodiment includes creating a mixture of inorganic particles, a solvent and a dispersant, the inorganic particles having a mean diameter of less than about 2000 nm; agitating the mixture; adding the mixture to a mold; and curing the mixture in the mold for gelling the mixture, with the proviso that no gelling agent is added to the mixture.

Ultrasonic studies of intermolecular interactions in binary mixtures of 4-methoxy benzoin with various solvents: Excess molar functions of ultrasonic parameters at different concentrations and in different solvents.

PubMed

Thanuja, B; Nithya, G; Kanagam, Charles C

2012-11-01

Density (ρ), ultrasonic velocity (U), for the binary mixtures of 4-methoxy benzoin (4MB) with ethanol, chloroform, acetonitrile, benzene, and di-oxane were measured at 298K. The solute-solvent interactions and the effect of the polarity of the solvent on the type of intermolecular interactions are discussed here. From the above data, adiabatic compressibility (β), intermolecular free length (L(f)), acoustic impedance (Z), apparent molar volume (Ø), relative association (RA) have been calculated. Other useful parameters such as excess density, excess velocity and excess adiabatic compressibility have also been calculated. These parameters were used to study the nature and extent of intermolecular interactions between component molecules in the binary mixtures. Copyright © 2012 Elsevier B.V. All rights reserved.

Experimental Limiting Oxygen Concentrations for Nine Organic Solvents at Temperatures and Pressures Relevant to Aerobic Oxidations in the Pharmaceutical Industry

PubMed Central

2015-01-01

Applications of aerobic oxidation methods in pharmaceutical manufacturing are limited in part because mixtures of oxygen gas and organic solvents often create the potential for a flammable atmosphere. To address this issue, limiting oxygen concentration (LOC) values, which define the minimum partial pressure of oxygen that supports a combustible mixture, have been measured for nine commonly used organic solvents at elevated temperatures and pressures. The solvents include acetic acid, N-methylpyrrolidone, dimethyl sulfoxide, tert-amyl alcohol, ethyl acetate, 2-methyltetrahydrofuran, methanol, acetonitrile, and toluene. The data obtained from these studies help define safe operating conditions for the use of oxygen with organic solvents. PMID:26622165

Multiscale structure, interfacial cohesion, adsorbed layers, miscibility and properties in dense polymer-particle mixtures

NASA Astrophysics Data System (ADS)

Schweizer, Ken

2012-02-01

A major goal in polymer nanocomposite research is to understand and predict how the chemical and physical nature of individual polymers and nanoparticles, and thermodynamic state (temperature, composition, solvent dilution, filler loading), determine bulk assembly, miscibility and properties. Microscopic PRISM theory provides a route to this goal for equilibrium disordered mixtures. A major prediction is that by manipulating the net polymer-particle interfacial attraction, miscibility is realizable via the formation of thin thermodynamically stable adsorbed layers, which, however, are destroyed by entropic depletion and bridging attraction effects if interface cohesion is too weak or strong, respectively. This and related issues are quantitatively explored for miscible mixtures of hydrocarbon polymers, silica nanospheres, and solvent using x-ray scattering, neutron scattering and rheology. Under melt conditions, quantitative agreement between theory and silica scattering experiments is achieved under both steric stabilization and weak depletion conditions. Using contrast matching neutron scattering to characterize the collective structure factors of polymers, particles and their interface, the existence and size of adsorbed polymer layers, and their consequences on microstructure, is determined. Failure of the incompressible RPA, accuracy of PRISM theory, the nm thickness of adsorbed layers, and qualitative sensitivity of the bulk modulus to interfacial cohesion and particle size are demonstrated for concentrated PEO-silica-ethanol nanocomposites. Temperature-dependent complexity is discovered when water is the solvent, and nonequilibrium effects emerge for adsorbing entangled polymers that strongly impact structure. By varying polymer chemistry, the effect of polymer-particle attraction on the intrinsic viscosity is explored with striking non-classical effects observed. This work was performed in collaboration with S.Y.Kim, L.M.Hall, C.Zukoski and B.Anderson.

COMPARISON OF SORPTION ENERGTICS FOR HYDROPHOBIC ORGANIC CHEMICALS BY SYNTHETIC AND NATURAL SORBENTS FROM METHANOL/WATER SOLVENT MIXTURES

EPA Science Inventory

Reversed-phase liquid chromatography (RPLC) was used to investigate the thermodynamics and mechanisms of hydrophobic organic chemical (HOC) retention from methanol/water solvent mixtures. The enthalpy-entropy compensation model was used to infer that the hydro- phobic sorptive me...

Tube radial distribution phenomenon with a two-phase separation solution of a fluorocarbon and hydrocarbon organic solvent mixture in a capillary tube and metal compounds separation.

PubMed

Kitaguchi, Koichi; Hanamura, Naoya; Murata, Masaharu; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2014-01-01

A fluorocarbon and hydrocarbon organic solvent mixture is known as a temperature-induced phase-separation solution. When a mixed solution of tetradecafluorohexane as a fluorocarbon organic solvent and hexane as a hydrocarbon organic solvent (e.g., 71:29 volume ratio) was delivered in a capillary tube that was controlled at 10°C, the tube radial distribution phenomenon (TRDP) of the solvents was clearly observed through fluorescence images of the dye, perylene, dissolved in the mixed solution. The homogeneous mixed solution (single phase) changed to a heterogeneous solution (two phases) with inner tetradecafluorohexane and outer hexane phases in the tube under laminar flow conditions, generating the dynamic liquid-liquid interface. We also tried to apply TRDP to a separation technique for metal compounds. A model analyte mixture, copper(II) and hematin, was separated through the capillary tube, and detected with a chemiluminescence detector in this order within 4 min.

40 CFR 148.10 - Waste specific prohibitions-solvent wastes.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 22 2010-07-01 2010-07-01 false Waste specific prohibitions-solvent wastes. 148.10 Section 148.10 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER... injection unless the solvent waste is a solvent-water mixture or solvent-containing sludge containing less...

FINDING SOLVENT REPLACEMENTS TO REDUCE THE POTENTIAL ENVIRONMENTAL IMPACT OF INDUSTRIAL WASTES

EPA Science Inventory

The United States Environmental Protection Agency has developed a solvent substitution software tool PARIS II (Program for Assisting the Replacement of Industrial Solvents, version 2.0). The purpose of this tool is to find less toxic solvents or solvent mixtures which may functi...

Induced liquid-crystalline ordering in solutions of stiff and flexible amphiphilic macromolecules: Effect of mixture composition

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

Glagolev, Mikhail K.; Vasilevskaya, Valentina V., E-mail: vvvas@polly.phys.msu.ru; Khokhlov, Alexei R.

Impact of mixture composition on self-organization in concentrated solutions of stiff helical and flexible macromolecules was studied by means of molecular dynamics simulation. The macromolecules were composed of identical amphiphilic monomer units but a fraction f of macromolecules had stiff helical backbones and the remaining chains were flexible. In poor solvents the compacted flexible macromolecules coexist with bundles or filament clusters from few intertwined stiff helical macromolecules. The increase of relative content f of helical macromolecules leads to increase of the length of helical clusters, to alignment of clusters with each other, and then to liquid-crystalline-like ordering along a singlemore » direction. The formation of filament clusters causes segregation of helical and flexible macromolecules and the alignment of the filaments induces effective liquid-like ordering of flexible macromolecules. A visual analysis and calculation of order parameter relaying the anisotropy of diffraction allow concluding that transition from disordered to liquid-crystalline state proceeds sharply at relatively low content of stiff components.« less

Photoinduced electron transfer in an imidazolium ionic liquid and in its binary mixtures with water, methanol, and 2-propanol: appearance of Marcus-type of inversion.

PubMed

Sarkar, Souravi; Mandal, Sarthak; Ghatak, Chiranjib; Rao, Vishal Govind; Ghosh, Surajit; Sarkar, Nilmoni

2012-02-02

The photoinduced electron transfer (PET) reaction has been investigated in a room temperature imidazolium ionic liquid (RTIL), 1-ethyl-3-methylimidazolium ethyl sulfate ([Emim][EtSO(4)]) and also in [Emim][EtSO(4)]-co-solvents mixtures from N,N-dimethyl aniline (DMA) to different Coumarin dyes using steady state and time-resolved fluorescence quenching measurements. We have used water and methanol and 2-propanol as the cosolvents of RTILs for the PET study. On going from neat ionic liquid to the RTIL-co-solvents mixtures the electron transfer rate has been largely enhanced. In neat RTIL as well as in [Emim][EtSO(4)]-co-solvents mixtures, a Marcus type of inversion in the PET rate have been observed.

Thermodynamic of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar; Chu, Jhih-Wei

2013-04-01

Biomass contains abundant amounts of cellulose as crystalline microfibrils. A limiting step to using cellulose as an alternative energy source, however, is the hydrolysis of the biomass and subsequent transformation into fuels. Cellulose is insoluble in most solvents including organic solvents and water, but it is soluble in some ionic liquids like BMIM-Cl. This project aims to find alternative solvents that are less expensive and are more environmentally benign than the ionic liquids. All-atom molecular dynamics simulations were performed on dissociated glucan chains separated by multiple (4-5) solvation shells, in the presence of several novel solvents and solvent mixtures. The solubility of the chains in each solvent was indicated by contacts calculations after the equilibration of the molecular dynamics. It was discovered that pyridine and imidazole acted as the best solvents because their aromatic electronic structure was able to effectively disrupt the inter-sheet interactions among the glucan chains in the axial direction, and because perturbation of the solvent interactions in the presence of glucan chains was minimal.

Thermodynamic of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar

2013-03-01

Biomass contains abundant amounts of cellulose as crystalline microfibrils. A limiting step to using cellulose as an alternative energy source, however, is the hydrolysis of the biomass and subsequent transformation into fuels. Cellulose is insoluble in most solvents including organic solvents and water, but it is soluble in some ionic liquids like BMIM-Cl. This project aims to find alternative solvents that are less expensive and are more environmentally benign than the ionic liquids. All-atom molecular dynamics simulations were performed on dissociated glucan chains separated by multiple (4-5) solvation shells, in the presence of several novel solvents and solvent mixtures. The solubility of the chains in each solvent was indicated by contacts calculations after the equilibration of the molecular dynamics. It was discovered that pyridine and imidazole acted as the best solvents because their aromatic electronic structure was able to effectively disrupt the inter-sheet interactions among the glucan chains in the axial direction, and because perturbation of the solvent interactions in the presence of glucan chains was minimal.

Thermodynamics of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar; Chu, Jhih-Wei

2012-10-01

Biomass contains abundant amounts of cellulose as crystalline microfibrils. A limiting step to using cellulose as an alternative energy source, however, is the hydrolysis of the biomass and subsequent transformation into fuels. Cellulose is insoluble in most solvents including organic solvents and water, but it is soluble in some ionic liquids like BMIM-Cl. This project aims to find alternative solvents that are less expensive and are more environmentally benign than the ionic liquids. All-atom molecular dynamics simulations were performed on dissociated glucan chains separated by multiple (4-5) solvation shells, in the presence of several novel solvents and solvent mixtures. The solubility of the chains in each solvent was indicated by contacts calculations after the equilibration of the molecular dynamics. It was discovered that pyridine and imidazole acted as the best solvents because their aromatic electronic structure was able to effectively disrupt the inter-sheet interactions among the glucan chains in the axial direction, and because perturbation of the solvent interactions in the presence of glucan chains was minimal.

Thermodynamic of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar

2012-11-01

Biomass contains abundant amounts of cellulose as crystalline microfibrils. A limiting step to using cellulose as an alternative energy source, however, is the hydrolysis of the biomass and subsequent transformation into fuels. Cellulose is insoluble in most solvents including organic solvents and water, but it is soluble in some ionic liquids like BMIM-Cl. This project aims to find alternative solvents that are less expensive and are more environmentally benign than the ionic liquids. All-atom molecular dynamics simulations were performed on dissociated glucan chains separated by multiple (4-5) solvation shells, in the presence of several novel solvents and solvent mixtures. The solubility of the chains in each solvent was indicated by contacts calculations after the equilibration of the molecular dynamics. It was discovered that pyridine and imidazole acted as the best solvents because their aromatic electronic structure was able to effectively disrupt the inter-sheet interactions among the glucan chains in the axial direction, and because perturbation of the solvent interactions in the presence of glucan chains was minimal.

Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2007-03-27

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2004-06-22

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Highly efficient organosolv fractionation of cornstalk into cellulose and lignin in organic acids.

PubMed

Shui, Tao; Feng, Shanghuan; Yuan, Zhongshun; Kuboki, Takashi; Xu, Chunbao Charles

2016-10-01

In this study, effects of fractionation solvents, catalysts, temperatures and residence time on yields, purity and chemical composition of the products were investigated at the solid/solvent ratio of 1:5 (g/g). It was revealed that mixture of acetic acid/formic acid/water at the ratio of 3:6:1 (v/v/v) resulted in crude cellulose and lignin products of relatively high purity. The use of HCl catalyst contributed to a high crude cellulose yield, while H2SO4 showed an adverse effect on cellulose yield. However, both of these acidic catalysts contributed to much lower hemicellulose contents in the resulted crude cellulose products compared with those obtained without a catalyst. Fractionation at 90°C for 180min in mixed solvents of acetic acid/formic acid/water (3:6:1, v/v/v) with or without catalyst produced crude cellulose with very low residual lignin contents (<4%). Copyright © 2016. Published by Elsevier Ltd.

Direct Immersion Annealing of Thin Block Copolymer Films.

PubMed

Modi, Arvind; Bhaway, Sarang M; Vogt, Bryan D; Douglas, Jack F; Al-Enizi, Abdullah; Elzatahry, Ahmed; Sharma, Ashutosh; Karim, Alamgir

2015-10-07

We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene-poly(methyl methacrylate) (PS-PMMA) system: rapid short-range order, optimal long-range order, and a film instability regime. Kinetic studies in the "optimal long-range order" processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering.

Direct Immersion Annealing of Thin Block Copolymer Films

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

Modi, Arvind; Bhaway, Sarang M.; Vogt, Bryan D.

2015-09-09

We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene–poly(methyl methacrylate) (PS–PMMA) system: rapid short-range order, optimal long-range order, and a film instability regime. Kinetic studies in themore » “optimal long-range order” processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering.« less

Chemical composition and antibacterial activity of Cordia verbenacea extracts obtained by different methods.

PubMed

Michielin, Eliane M Z; Salvador, Ana A; Riehl, Carlos A S; Smânia, Artur; Smânia, Elza F A; Ferreira, Sandra R S

2009-12-01

The present study describes the chemical composition and the antibacterial activity of extracts from Cordia verbenacea DC (Borraginaceae), a traditional medicinal plant that grows widely along the southeastern coast of Brazil. The extracts were obtained using different extraction techniques: high-pressure operations and low-pressure methods. The high-pressure technique was applied to obtain C. verbenacea extracts using pure CO(2) and CO(2) with co-solvent at pressures up to 30MPa and temperatures of 30, 40 and 50 degrees C. Organic solvents such as n-hexane, ethyl acetate, ethanol, acetone and dichloromethane were used to obtain extracts by low-pressure processes. The antibacterial activity of the extracts was also subjected to screening against four strains of bacteria using the agar dilution method. The extraction yields were up to 5.0% w/w and up to 8.6% w/w for supercritical fluid extraction with pure CO(2) and with ethyl acetate as co-solvent, respectively, while the low-pressure extraction indicates yields up to 24.0% w/w in the soxhlet extraction using water and aqueous mixture with 50% ethanol as solvents. The inhibitory activity of the extracts in gram-positive bacteria was significantly higher than in gram-negative. The quantification and the identification of the extracts recovered were accomplished using GC/MS analysis. The most important components identified in the extract were artemetin, beta-sitosterol, alpha-humulene and beta-caryophyllene, among others.

Physicochemical properties of betaine monohydrate-carboxylic acid mixtures

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

System and method for treatment of a flue gas

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

Spiry, Irina Pavlovna; Wood, Benjamin Rue; Singh, Surinder Prabhjot

A method for treatment of a flue gas involves feeding the flue gas and a lean solvent to an absorber. The method further involves reacting the flue gas with the lean solvent within the absorber to generate a clean flue gas and a rich solvent. The method also involves feeding the clean flue gas from the absorber and water from a source, to a wash tower to separate a stripped portion of the lean solvent from the clean flue gas to generate a washed clean flue gas and a mixture of the water and the stripped portion of the leanmore » solvent. The method further involves treating at least a portion of the mixture of the water and the stripped portion of the lean solvent via a separation system to separate the water from the stripped portion of the lean solvent.« less

Method of synthesis of proton conducting materials

DOEpatents

Garzon, Fernando Henry; Einsla, Melinda Lou; Mukundan, Rangachary

2010-06-15

A method of producing a proton conducting material, comprising adding a pyrophosphate salt to a solvent to produce a dissolved pyrophosphate salt; adding an inorganic acid salt to a solvent to produce a dissolved inorganic acid salt; adding the dissolved inorganic acid salt to the dissolved pyrophosphate salt to produce a mixture; substantially evaporating the solvent from the mixture to produce a precipitate; and calcining the precipitate at a temperature of from about 400.degree. C. to about 1200.degree. C.

Supercritical-Fluid Extraction of Oil From Tar Sands

NASA Technical Reports Server (NTRS)

Compton, L. E.

1982-01-01

New supercritical solvent mixtures have been laboratory-tested for extraction of oil from tar sands. Mixture is circulated through sand at high pressure and at a temperature above critical point, dissolving organic matter into the compressed gas. Extract is recovered from sand residues. Low-temperature super-critical solvents reduce energy consumption and waste-disposal problems.

Flash-point prediction for binary partially miscible mixtures of flammable solvents.

PubMed

Liaw, Horng-Jang; Lu, Wen-Hung; Gerbaud, Vincent; Chen, Chan-Cheng

2008-05-30

Flash point is the most important variable used to characterize fire and explosion hazard of liquids. Herein, partially miscible mixtures are presented within the context of liquid-liquid extraction processes. This paper describes development of a model for predicting the flash point of binary partially miscible mixtures of flammable solvents. To confirm the predictive efficacy of the derived flash points, the model was verified by comparing the predicted values with the experimental data for the studied mixtures: methanol+octane; methanol+decane; acetone+decane; methanol+2,2,4-trimethylpentane; and, ethanol+tetradecane. Our results reveal that immiscibility in the two liquid phases should not be ignored in the prediction of flash point. Overall, the predictive results of this proposed model describe the experimental data well. Based on this evidence, therefore, it appears reasonable to suggest potential application for our model in assessment of fire and explosion hazards, and development of inherently safer designs for chemical processes containing binary partially miscible mixtures of flammable solvents.

Colloidal infrared reflective and transparent conductive aluminum-doped zinc oxide nanocrystals

DOEpatents

Buonsanti, Raffaella; Milliron, Delia J

2015-02-24

The present invention provides a method of preparing aluminum-doped zinc oxide (AZO) nanocrystals. In an exemplary embodiment, the method includes (1) injecting a precursor mixture of a zinc precursor, an aluminum precursor, an amine, and a fatty acid in a solution of a vicinal diol in a non-coordinating solvent, thereby resulting in a reaction mixture, (2) precipitating the nanocrystals from the reaction mixture, thereby resulting in a final precipitate, and (3) dissolving the final precipitate in an apolar solvent. The present invention also provides a dispersion. In an exemplary embodiment, the dispersion includes (1) nanocrystals that are well separated from each other, where the nanocrystals are coated with surfactants and (2) an apolar solvent where the nanocrystals are suspended in the apolar solvent. The present invention also provides a film. In an exemplary embodiment, the film includes (1) a substrate and (2) nanocrystals that are evenly distributed on the substrate.

Raman bandshape analysis on CH and CSC stretching modes of dimethyl sulfoxide in liquid binary mixture: comparative study with quantum-chemical calculations.

PubMed

Upadhyay, Ganesh; Gomti Devi, Th

2014-12-10

The interacting nature of dimethyl sulfoxide (DMSO) in binary mixtures has been carried out on CH and CSC stretching modes of vibration using chloroform (CLF), chloroform-d (CLFd), acetonitrile (ACN) and acetonitrile-d3 (ACNd) solvents. Peak frequencies of both the stretching modes show blue shift with the increase in solvent concentration. Variation of Raman bandwidth with the solvent concentration was discussed using different mechanisms. Ab initio calculation for geometry optimization and vibrational wavenumber calculation have been performed on monomer and dimer structures of DMSO to explain the experimentally observed Raman spectra. Theoretically calculated values are found in good agreement with the experimental results. Vibrational and reorientational relaxation times have been studied corresponding to solvent concentrations to elucidate the interacting mechanisms of binary mixtures. Copyright © 2014 Elsevier B.V. All rights reserved.

Columnar to nematic mesophase transition in mixtures of rhodium or copper soaps with hydrocarbon solvents

NASA Astrophysics Data System (ADS)

Ibn-Elhaj, M.; Guillon, D.; Skoulios, A.; Giroud-Godquin, A. M.; Marchon, J.-C.

1992-12-01

This paper describes observations of the mesomorphic behaviour of mixtures of rhodium eicosanoate or copper dodecanoate with solvents such as toluene, decahydronaphthalene, and (+) camphene. The mesophase found with these compounds at high temperatures turns from columnar to nematic when the weight fraction of the solvent (toluene, decahydronaphthalene is increased beyond a value of about 50%. The binary phase diagram of the copper compound with toluene was experimentally determined using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction. The novel feature of the nematic phase is that the basic physical object which align parallel to the nematic director are not individual molecules, but columns of molecules (one-dimensional supramolecular assemblies) which have lost the long-range lateral positional order characteristic of the columnar mesophase. These observations are discussed on the grounds of recent theoretical calculations. Cholesteric-like textures are observed for mixtures of rhodium eicosanoate with the chiral solvent (+) camphene.

Self-assembly and omniphobic property of fluorinated unit end-functionalized poly(methyl methacrylate)

NASA Astrophysics Data System (ADS)

Junyan, Liang; Pingdi, Xu; Jingxian, Bao; Ling, He; Nan, Zhu

2018-03-01

The self-assembly behavior of fluorinated unit end-functionalized poly(methyl methacrylate) (PDFHM-ef-PMMA) in solution and its influence on the surface microstructure, elemental composition and omniphobic property of cast film was investigated in this work. Specifically, three mixed solutions of tetrahydrofuran (THF)/methanol (MeOH), THF/H2O and THF/H2O/MeOH in various compositions were employed separately as the selective solvents. In THF/MeOH solution, the aggregate morphologies of PDFHM-ef-PMMA changed gradually from core-shell spheres to worm, and then to elliptical vesicles as MeOH content increased. In THF/H2O solution, spherical and bowl-shaped aggregates with significantly larger sizes than those in THF/MeOH solution were favored despite lower H2O content. The further addition of MeOH to THF/H2O mixture could reduce the size of aggregate but hardly change original aggregate morphology. During the film formation process, those self-assembled aggregates in THF/MeOH solution fused with one another to form a smooth surface. When such surface was fully covered by fluorinated segments, the outstanding hexadecane and water slide-off properties and ink-resistant property required for antifouling application were demonstrated. Instead, the aggregates formed in THF/H2O/MeOH mixture were subjected to secondary aggregation of PDFHM-ef-PMMA chains during solvent evaporation, leading to the formation of a particulate film with poor adhesion towards glass plate and hexadecane-repellent property.

Molecular dynamics study of unfolding of lysozyme in water and its mixtures with dimethyl sulfoxide.

PubMed

Sedov, Igor A; Magsumov, Timur I

2017-09-01

All-atom explicit solvent molecular dynamics was used to study the process of unfolding of hen egg white lysozyme in water and mixtures of water with dimethyl sulfoxide at different compositions. We have determined the kinetic parameters of unfolding at a constant temperature 450K. For each run, the time of disruption of the tertiary structure of lysozyme t u was defined as the moment when a certain structural criterion computed from the trajectory reaches its critical value. A good agreement is observed between the results obtained using several different criteria. The secondary structure according to DSSP calculations is found to be partially unfolded to the moment of disruption of tertiary structure, but some of its elements keep for a long time after that. The values of t u averaged over ten 30ns-long trajectories for each solvent composition are shown to decrease very rapidly with addition of dimethyl sulfoxide, and rather small amounts of dimethyl sulfoxide are found to change the pathway of unfolding. In pure water, despite the loss of tertiary contacts and disruption of secondary structure elements, the protein preserves its compact globular state at least over 130ns of simulation, while even at 5mol percents of dimethyl sulfoxide it loses its compactness within 30ns. The proposed methodology is a generally applicable tool to quantify the rate of protein unfolding in simulation studies. Copyright © 2017 Elsevier Inc. All rights reserved.

Innovative aspects of protein stability in ionic liquid mixtures.

PubMed

Kumar, Awanish; Venkatesu, Pannuru

2018-06-01

Mixtures of ionic liquids (ILs) have attracted our attention because of their extraordinary performances in extraction technologies and in absorbing large amount of CO 2 gas. It has been observed that when two or more ILs are mixed in different proportions, a new solvent is obtained which is much better than that of each component of ILs from which the mixture is obtained. Within a mixture of ILs, several unidentified interactions occur among several ions which give rise to unique solvent properties to the mixture. Herein, in this review, we have highlighted the utilization of the advantageous properties of the IL mixtures in protein stability studies. This approach is exceptional and opens new directions to the use of ILs in biotechnology.

Experimental limiting oxygen concentrations for nine organic solvents at temperatures and pressures relevant to aerobic oxidations in the pharmaceutical industry

DOE PAGES

Osterberg, Paul M.; Niemeier, Jeffry K.; Welch, Christopher J.; ...

2014-12-06

Applications of aerobic oxidation methods in pharmaceutical manufacturing are limited in part because mixtures of oxygen gas and organic solvents often create the potential for a flammable atmosphere. To address this issue, limiting oxygen concentration (LOC) values, which define the minimum partial pressure of oxygen that supports a combustible mixture, have been measured for nine commonly used organic solvents at elevated temperatures and pressures. The solvents include acetic acid, N-methylpyrrolidone, dimethyl sulfoxide, tert-amyl alcohol, ethyl acetate, 2-methyltetrahydrofuran, methanol, acetonitrile, and toluene. Furthermore, the data obtained from these studies help define safe operating conditions for the use of oxygen with organicmore » solvents.« less

Method for separating mono- and di-octylphenyl phosphoric acid esters

DOEpatents

Arnold, Jr., Wesley D.

1977-01-01

A method for separating mono-octylphenyl phosphoric acid ester and di-octylphenyl phosphoric acid ester from a mixture thereof comprises reacting the ester mixture with a source of lithium or sodium ions to form a mixture of the phosphate salts; contacting the salt mixture with an organic solvent which causes the dioctylphenyl phosphate salt to be dissolved in the organic solvent phase and the mono-octylphenyl phosphate salt to exist in a solid phase; separating the phases; recovering the phosphate salts from their respective phases; and acidifying the recovered salts to form the original phosphoric acid esters.

Exacerbation of noise-induced hearing loss by co-exposure to workplace chemicals.

PubMed

Sliwinska-Kowalska, Mariola; Zamyslowska-Szmytke, Ewa; Szymczak, Wieslaw; Kotylo, Piotr; Fiszer, Marta; Wesolowski, Wiktor; Pawlaczyk-Luszczynska, Malgorzata

2005-05-01

: Numerous organic solvents applied in industry, like toluene, styrene, xylene and n-hexane have been demonstrated to impair hearing in animals. However, the effects of exposure to a given organic solvent and the interaction of noise and solvents on hearing in humans are still not fully recognized. : The study was aimed to assess the effects of occupational exposure to solvents alone or in combination with noise on hearing in 1117 employees of yacht, ship, plastic, shoe, and paint and lacquer industry. These persons were exposed either to the mixture of organic solvents with xylene as the main component, or predominantly to styrene, or to the mixture of n-hexane and toluene. Detailed questionnaire data and pure-tone audiometry were compared with data of the reference group that included white collar workers, exposed neither to solvents nor noise and metal factory workers exposed to noise only. In all statistics, the confounding factors were recognized as gender, age, exposure to noise, and other variables occurring at a different rate in study and reference group. : Odds ratio (OR) of hearing loss related with the particular exposure to chemicals was 2.4 (95%CI 1.59-3.74) in case of solvent mixture, 3.9 (95%CI 2.4-6.2) in case of styrene and 5.3 (95%CI 2.6-10.9) in case of n-hexane and toluene exposure. The odds of developing hearing loss substantially increased in the case of combined exposure to organic solvents and noise as compared to isolated exposure to each of these hazards. The highest OR (over 20-fold) was demonstrated in subgroups of subjects exposed simultaneously to noise and two ototoxic solvents (i.e. styrene and toluene or n-hexane and toluene). The mean hearing thresholds were significantly higher in the solvent-exposed groups than in the reference group. The differences in thresholds were observed at high frequencies in the solvent mixture- and n-hexane + toluene-exposed groups and at all frequencies in the styrene-exposed group. A positive linear relationship existed between exposure to solvents and hearing thresholds at high frequencies. : The results of the study provide the epidemiological evidence that exposure to organic solvents in humans is associated with an increased risk of hearing loss. The simultaneous exposure to organic solvents and noise seems to enhance the hearing deficit if compared with isolated exposures.

Treatment System for Removing Halogenated Compounds from Contaminated Sources

NASA Technical Reports Server (NTRS)

Clausen, Christian A. (Inventor); Yestrebsky, Cherie L. (Inventor); Quinn, Jacqueline W. (Inventor)

2015-01-01

A treatment system and a method for removal of at least one halogenated compound, such as PCBs, found in contaminated systems are provided. The treatment system includes a polymer blanket for receiving at least one non-polar solvent. The halogenated compound permeates into or through a wall of the polymer blanket where it is solubilized with at least one non-polar solvent received by said polymer blanket forming a halogenated solvent mixture. This treatment system and method provides for the in situ removal of halogenated compounds from the contaminated system. In one embodiment, the halogenated solvent mixture is subjected to subsequent processes which destroy and/or degrade the halogenated compound.

Solvent Dependent Dynamics of Salicylidene Aniline in Binary Mixtures of Supercritical CO2 with 1-Propanol or Cyclohexane.

PubMed

Kieda, Ryan D; Dunkelberger, Adam D; Case, Amanda S; Crim, F Fleming

2017-02-02

The role of different solvent environments in determining the behavior of molecules in solution is a fundamental aspect of chemical reactivity. We present an approach for exploring the influence of solvent properties on condensed-phase dynamics using ultrafast transient absorption spectroscopy in supercritical CO 2 . Using supercritical CO 2 permits adjustment of the density, by varying the temperature and pressure, whereas varying the concentration or identity of a second solvent, the cosolvent, in a binary mixture allows for adjustments of the degree of interaction between the solute and the solvent. Salicylidene aniline, a prototypical excited-state intramolecular proton-transfer system, is the subject of this study. In this system, the decay rate of the transient absorption signal decreases as the fraction of the cosolvent (for both 1-propanol and cyclohexane) increases. The decay rate also decreases with an increase in the viscosity of the mixture, but the effect is much larger for the 1-propanol cosolvent than for cyclohexane. These observations illustrate that the decay rate of the photoexcited salicylidene aniline depends on more than just the solvent viscosity, suggesting that properties such as polarity also play a role in the dynamics.

Effects of intermolecular forces and backbone architecture on the phase behavior of fluorocopolymer-supercritical fluid mixtures

NASA Astrophysics Data System (ADS)

Mertdogan, Cynthia Asli

The impact of polymer backbone architecture on fluorocopolymer solubility in supercritical fluid (SCF) solvents is studied by systematically varying the chemical type of the repeat units in the main chain. The fluorocopolymers investigated include nonpolar copolymers of tetrafluoroethylene with 19 mol% hexafluoropropylene (FEPsb{19}) and 48 mol% hexafluoropropylene (FEPsb{48}) and a polar copolymer of vinylidene fluoride with 22 mol% hexafluoropropylene (Fluorelsp°ler ). The solvents are methodically varied from nonpolar perfluoroalkanes and SFsb6 to polar fluorocarbons and COsb2. Low molecular weight solvents are used to facilitate in interpreting the intermolecular forces that control fluorocopolymer solubility, although pressures in excess of 2,500 bar are sometimes needed to dissolve the fluorocopolymers in these simple solvents. Polarity effects, which vary inversely with temperature, are moderated by operating over a large temperature range from 0 to 300sp° C. A variable-volume view cell, capable of operating to high temperatures and high pressures, was designed and implemented to meet these extreme operating conditions. Increasing the polarizability of nonpolar solvents reduces the pressures required to dissolve FEPsb{19} by as much as 1,500 bar going from perfluoromethane to perfluoropropane. However, in polar solvents, the pressures required for FEPsb{19} solubility rise dramatically as the temperature is decreased due to the increase in polar, solvent-solvent interactions that do not favor the solubility of a nonpolar copolymer. Replacing semi-crystalline FEPsb{19} with amorphous FEPsb{48} yields the same trends in phase behavior. Therefore, crystallinity does not control the shape of these fluorocopolymer-SCF cloud-point curves. Adding a cosolvent to the solution can dramatically lower the pressures needed to dissolve the copolymer. Introducing the "cosolvent" directly into the polymer backbone by changing copolymer architecture is another method of modifying fluorocopolymer solubility as seen with the results for Fluorel-SCF mixtures compared to those for FEPsb{19}-SCF mixtures. A supercritical fractionation of FEPsb{19} provides information on the impact of molecular weight and end-group content on fluorocopolymer solubility. Challenges remain for modeling fluorocopolymer-solvent mixtures. The Sanchez-Lacombe equation cannot capture the characteristics of FEPsb{19}-SCF solvent phase behavior unless two empirical mixture parameters, one of which varies with temperature, are used.

Adsorption of sophorolipid biosurfactants on their own and mixed with sodium dodecyl benzene sulfonate, at the air/water interface.

PubMed

Chen, Minglei; Dong, Chuchuan; Penfold, Jeff; Thomas, Robert K; Smyth, Thomas J P; Perfumo, Amedea; Marchant, Roger; Banat, Ibrahim M; Stevenson, Paul; Parry, Alyn; Tucker, Ian; Campbell, Richard A

2011-07-19

The adsorption of the lactonic (LS) and acidic (AS) forms of sophorolipid and their mixtures with the anionic surfactant sodium dodecyl benzene sulfonate (LAS) has been measured at the air/water interface by neutron reflectivity, NR. The AS and LS sophorolipids adsorb with Langmuir-like adsorption isotherms. The more hydrophobic LS is more surface active than the AS, with a lower critical micellar concentration, CMC, and stronger surface adsorption, with an area/molecule ∼70 Å(2) compared with 85 Å(2) for the AS. The acidic sophorolipid shows a maximum in its adsorption at the CMC which appears to be associated with a mixture of different isomeric forms. The binary LS/AS and LS/LAS mixtures show a strong surface partitioning in favor of the more surface active and hydrophobic LS component but are nevertheless consistent with ideal mixing at the interface. In contrast, the surface composition of the AS/LAS mixture is much closer to the solution composition, but the surface mixing is nonideal and can be accounted for by regular solution theory, RST. In the AS/LS/LAS ternary mixtures, the surface adsorption is dominated by the sophorolipid, and especially the LS component, in a way that is not consistent with the observations for the binary mixtures. The extreme partitioning in favor of the sophorolipid for the LAS/LS/AS (1:2) mixtures is attributed to a reduction in the packing constraints at the surface due to the AS component. Measurements of the surface structure reveal a compact monolayer for LS and a narrow solvent region for LS, LS/AS, and LS/LAS mixtures, consistent with the more hydrophobic nature of the LS component. The results highlight the importance of the relative packing constraints on the adsorption of multicomponent mixtures, and the impact of the lactonic form of the sophorolipid on the adsorption of the sophorolipid/LAS mixtures.

Program for Assisting the Replacement of Industrial Solvents PARIS III User’s Guide

EPA Science Inventory

PARIS III is a third generation Windows-based computer software to assist the design of less harmful solvent replacements by estimating values of the solvent properties that characterize the static, dynamic, performance, and environmental behavior of the original solvent mixture ...

Substitution of carcinogenic solvent dichloromethane for the extraction of volatile compounds in a fat-free model food system.

PubMed

Cayot, Nathalie; Lafarge, Céline; Bou-Maroun, Elias; Cayot, Philippe

2016-07-22

Dichloromethane is known as a very efficient solvent, but, as other halogenated solvents, is recognized as a hazardous product (CMR substance). The objective of the present work is to propose substitution solvent for the extraction of volatile compounds. The most important physico-chemical parameters in the choice of an appropriate extraction solvent of volatile compounds are reviewed. Various solvents are selected on this basis and on their hazard characteristics. The selected solvents, safer than dichloromethane, are compared using the extraction efficiency of volatile compounds from a model food product able to interact with volatile compounds. Volatile compounds with different hydrophobicity are used. High extraction yields were positively correlated with high boiling points and high Log Kow values of volatile compounds. Mixtures of solvents such as azeotrope propan-2-one/cyclopentane, azeotrope ethyl acetate/ethanol, and mixture ethyl acetate/ethanol (3:1, v/v) gave higher extraction yields than those obtained with dichloromethane. Copyright © 2016 Elsevier B.V. All rights reserved.

Renewable Gasoline, Solvents, and Fuel Additives from 2,3-Butanediol.

PubMed

Harvey, Benjamin G; Merriman, Walter W; Quintana, Roxanne L

2016-07-21

2,3-Butanediol (2,3-BD) is a renewable alcohol that can be prepared in high yield from biomass sugars. 2,3-BD was selectively dehydrated in a solvent-free process to a complex mixture of 2-ethyl-2,4,5-trimethyl-1,3-dioxolanes and 4,5-dimethyl-2isopropyl dioxolanes with the heterogeneous acid catalyst Amberlyst-15. The purified dioxolane mixture exhibited an anti-knock index of 90.5, comparable to high octane gasoline, and a volumetric net heat of combustion 34 % higher than ethanol. The solubility of the dioxolane mixture in water was only 0.8 g per 100 mL, nearly an order of magnitude lower than the common gasoline oxygenate methyl tert-butyl ether. The dioxolane mixture has potential applications as a sustainable gasoline blending component, diesel oxygenate, and industrial solvent. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Continuous process for singlet oxygenation of hydrophobic substrates in microemulsion using a pervaporation membrane.

PubMed

Caron, Laurent; Nardello, Véronique; Mugge, José; Hoving, Erik; Alsters, Paul L; Aubry, Jean-Marie

2005-02-15

Chemically generated singlet oxygen (1O2, 1Deltag) is able to oxidize a great deal of hydrophobic substrates from molybdate-catalyzed hydrogen peroxide decomposition, provided a suitable reaction medium such as a microemulsion system is used. However, high substrate concentrations or poorly reactive organics require large amounts of H2O2 that generate high amounts of water and thus destabilize the system. We report results obtained on combining dark singlet oxygenation of hydrophobic substrates in microemulsions with a pervaporation membrane process. To avoid composition alterations after addition of H2O2 during the peroxidation, the reaction mixture circulates through a ceramic membrane module that enables a partial and selective dewatering of the microemulsion. Optimization phase diagrams of sodium molybdate/water/alcohol/anionic surfactant/organic solvent have been elaborated to maximize the catalyst concentration and therefore the reaction rate. The membrane selectivity towards the mixture constituents has been investigated showing that a high retention is observed for the catalyst, for organic solvents and hydrophobic substrates, but not for n-propanol (cosurfactant) and water. The efficiency of such a process is illustrated with the peroxidation of a poorly reactive substrate, viz., beta-pinene.

Process to prepare stable trifluorostyrene containing compounds grafted to base polymers using a solvent/water mixture

DOEpatents

Roelofs, Mark Gerrit; Yang, Zhen-Yu; Han, Amy Qi

2010-06-15

A fluorinated ion exchange polymer is prepared by grafting at least one grafting monomer derived from trifluorostyrene on to at least one base polymer in a organic solvent/water mixture. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

Development of a process for the extraction of {sup 137}Cs from acidic HLLW based on crown-calix extractant use of di-alkylamide modifier

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

Alexova, J.; Sirova, M.; Rais, J.

2008-07-01

Within the framework of the ARTIST project of total fuel retreatment with ecological mixtures of solvents and extractants containing only C, H, O, and N atoms, a process segment of extraction of {sup 137}Cs from acidic stream was developed. The process with 25,27-Bis(1-octyloxy)calix[4]arene-crown- 6, DOC[4]C6, dissolved at its 0.01 M concentration in a mixture of 90 vol % 1-octanol and 10% dihexyl octanamide, DHOA was proposed as a viable variant due to its good multicycle performance, even with irradiated solvent, and due to the good chemical stability of the chosen combination of solvent mixture. (authors)

Method of filtering a target compound from a first solvent that is above its critical density

DOEpatents

Phelps, Max R [Richland, WA; Yonker, Clement R [Kennewick, WA; Fulton, John L [Richland, WA; Bowman, Lawrence E [Richland, WA

2001-07-24

The present invention is a method of separating a first compound having a macromolecular structure from a mixture. The first solvent is a fluid that is a gas at standard temperature and pressure and is at a density greater than a critical density of the fluid. A macromolecular structure containing a first compound is dissolved therein as a mixture. The mixture is contacted onto a selective barrier and the first solvent passed through the selective barrier thereby retaining the first compound, followed by recovering the first compound. By using a fluid that is a gas at standard temperature and pressure at a density greater than its critical density, separation without depressurization is fast and efficient.

Determination of solvents permeating through chemical protective clothing with a microsensor array.

PubMed

Park, J; Zellers, E T

2000-08-01

The performance of a novel prototype instrument in determining solvents and solvent mixtures permeating through samples of chemical protective clothing (CPC) materials was evaluated. The instrument contains a mini-preconcentrator and an array of three polymer-coated surface-acoustic-wave (SAW) microsensors whose collective response patterns are used to discriminate among multiple permeants. Permeation tests were performed with a 2.54 cm diameter test cell in an open-loop configuration on samples of common glove materials challenged with four individual solvents, three binary mixtures, and two ternary mixtures. Breakthrough times, defined as the times required for the permeation rate to reach a value of 1 microg cm(-2) min(-1), determined by the instrument were within 3 min of those determined in parallel by manual sampling and gas chromatographic analysis. Permeating solvents were recognized (identified) from their response patterns in 59 out of 64 measurements (92%) and their vapor concentrations were quantified to an accuracy of +/- 31% (typically +/- 10%). These results demonstrate the potential for such instrumentation to provide semi-automated field or bench-top screening of CPC permeation resistance.

Photoimageable composition

DOEpatents

Simison, Kelby Liv; Dentinger, Paul

2003-11-11

The use of selected buffering amines in a photoimageable composition prevents process bias which with conventional photoresists causes designed features to be distorted, especially in corners and high resolution features. It is believed that the amines react with the catalysts, e.g., photoacids, generated to create an inert salt. The presence of the amines also increases resolution. Suitable photoimageable compositions includes: (a) a multifunctional polymeric epoxy resin that is dissolved in an organic solvent wherein the epoxy resin comprises oligomers of bisphenol A that is quantitatively protected by glycidyl ether and wherein the oligomers have an average functionality that ranges from about 3 to 12; (b) a photoactive compound; and (c) an amine that is selected from the group consisting of triisobutylamine, 1,8-bis(dimethylamino)naphthalene (also known as PROTON SPONGET.TM.), 2,2'-diazabicyclo[2.2.2] octane and mixtures thereof. The photoimageable composition is particularly suited for producing high aspect ratio metal microstructures.

Quantitative assessments of the distinct contributions of polypeptide backbone amides versus sidechain groups to chain expansion via chemical denaturation

PubMed Central

Holehouse, Alex S.; Garai, Kanchan; Lyle, Nicholas; Vitalis, Andreas; Pappu, Rohit V.

2015-01-01

In aqueous solutions with high concentrations of chemical denaturants such as urea and guanidinium chloride (GdmCl) proteins expand to populate heterogeneous conformational ensembles. These denaturing environments are thought to be good solvents for generic protein sequences because properties of conformational distributions align with those of canonical random coils. Previous studies showed that water is a poor solvent for polypeptide backbones and therefore backbones form collapsed globular structures in aqueous solvents. Here, we ask if polypeptide backbones can intrinsically undergo the requisite chain expansion in aqueous solutions with high concentrations of urea and GdmCl. We answer this question using a combination of molecular dynamics simulations and fluorescence correlation spectroscopy. We find that the degree of backbone expansion is minimal in aqueous solutions with high concentrations denaturants. Instead, polypeptide backbones sample conformations that are denaturant-specific mixtures of coils and globules, with a persistent preference for globules. Therefore, typical denaturing environments cannot be classified as good solvents for polypeptide backbones. How then do generic protein sequences expand in denaturing environments? To answer this question, we investigated the effects of sidechains using simulations of two archetypal sequences with amino acid compositions that are mixtures of charged, hydrophobic, and polar groups. We find that sidechains lower the effective concentration of backbone amides in water leading to an intrinsic expansion of polypeptide backbones in the absence of denaturants. Additional dilution of the effective concentration of backbone amides is achieved through preferential interactions with denaturants. These effects lead to conformational statistics in denaturing environments that are congruent with those of canonical random coils. Our results highlight the role of sidechain-mediated interactions as determinants of the conformational properties of unfolded states in water and in influencing chain expansion upon denaturation. PMID:25664638

Combined effects of exposure to occupational noise and mixed organic solvents on blood pressure in car manufacturing company workers.

PubMed

Attarchi, Mirsaeed; Golabadi, Majid; Labbafinejad, Yasser; Mohammadi, Saber

2013-02-01

Recent studies suggest that occupational exposures such as noise and organic solvents may affect blood pressure. The aim of this study was to investigate interaction of noise and mixed organic solvents on blood pressure. Four hundred seventy-one workers of a car manufacturing plant were divided into four groups: group one or G1 workers exposed to noise and mixed organic solvents in the permitted limit or control group, G3 exposed to noise only, G2 exposed to solvents only, and G4 workers exposed to noise and mixed organic solvents at higher than the permitted limit or co-exposure group. Biological interaction of two variables on hypertension was calculated using the synergistic index. The workers of co-exposure group (G4), noise only group (G3), and solvents only group (G2) had significantly higher mean values of SBP and DBP than workers of control group (G1) or office workers (P < 0.05). Also logistic regression analysis showed a significant association between hypertension and exposure to noise and mixture of organic solvents. Odds ratio for hypertension in the co-exposure group and the noise only and solvents only exposed groups was 14.22, 9.43, and 4.38, respectively, compared to control group. In this study, the estimated synergism index was 1.11. Our results indicate that exposure to noise or a mixture of organic solvents may be associated with the prevalence of hypertension in car manufacturing company workers and co-exposure to noise and a mixture of solvents has an additive effect in this regard. Therefore appropriate preventive programs in these workers recommended. Copyright © 2012 Wiley Periodicals, Inc.

Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2006-07-11

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2002-01-01

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Statistical mixture design selective extraction of compounds with antioxidant activity and total polyphenol content from Trichilia catigua.

PubMed

Lonni, Audrey Alesandra Stinghen Garcia; Longhini, Renata; Lopes, Gisely Cristiny; de Mello, João Carlos Palazzo; Scarminio, Ieda Spacino

2012-03-16

Statistical design mixtures of water, methanol, acetone and ethanol were used to extract material from Trichilia catigua (Meliaceae) barks to study the effects of different solvents and their mixtures on its yield, total polyphenol content and antioxidant activity. The experimental results and their response surface models showed that quaternary mixtures with approximately equal proportions of all four solvents provided the highest yields, total polyphenol contents and antioxidant activities of the crude extracts followed by ternary design mixtures. Principal component and hierarchical clustering analysis of the HPLC-DAD spectra of the chromatographic peaks of 1:1:1:1 water-methanol-acetone-ethanol mixture extracts indicate the presence of cinchonains, gallic acid derivatives, natural polyphenols, flavanoids, catechins, and epicatechins. Copyright © 2011 Elsevier B.V. All rights reserved.

Composite fabrication and polymer modification using neoteric solvents

NASA Astrophysics Data System (ADS)

Eastman, Scott A.

This thesis is divided into two research initiatives: The fabrication and study of bulk, co-continuous, cellulosic-polymer composites with the aid of supercritical CO2 (SC CO2); and the study of poly(vinyl alcohol) (PVOH) modification and surface activity in ionic liquids. The first part of this thesis utilizes the tunable solubility, gas-like diffusivity, and omniphilic wettability of SC CO2 to incorporate and subsequently polymerize silicone and poly(enemer) prepolymer mixtures throughout various cellulosic substrates. Chapters two and three investigate the mechanical properties of these composites and demonstrate that nearly every resulting composite demonstrates an improved flexural modulus and energy release rate upon splitting. Fire resistance of these composites was also investigated and indicates that the heat release rate, total heat released, and char yield were significantly improved upon for all silicone composites compared to the untreated cellulosic material. Chapter four looks specifically at aspen-silicone composites for thermo-oxidative studies under applied loads in order to study the effect of silicone incorporation on the failure kinetics of aspen. The aspen-silicone composites tested under these conditions demonstrated significantly longer lifetimes under the same loading and heating conditions compared with untreated aspen. The second part of this thesis focuses on studying ionic liquids as potentially useful solvents and reaction media for poly(vinyl alcohol). Two ionic liquids (1-Butyl-3-methylimidizolium chloride and tributylethylphosphonium diethylphosphate) were found to readily dissolve PVOH. More importantly, we have demonstrated that these solvents can be used as inert reaction media for PVOH modification. Both ionic liquids were found to facilitate the quantitative esterification of PVOH, while only the phosphonium ionic liquid supports the quantitative urethanation of the polymer. In an attempt to tune the surface properties of ionic liquid/polymer solutions, PVOH was also partially esterified with low surface energy substituents. Both surface tension and surface composition of the ionic liquid/polymer solutions can be manipulated by the stoichiometric addition of low surface energy acid chlorides. This work on the modification of PVOH can be directly applied to the modification of polysaccharides such as cellulose which could have important implications from a sustainability and energy standpoint.

Online sample concentration and analysis of drugs of abuse in human urine by micelle to solvent stacking in capillary zone electrophoresis.

PubMed

Aturki, Zeineb; Fanali, Salvatore; Rocco, Anna

2016-10-01

A sensitive and rapid CZE-UV method was developed to determine drugs and their metabolites' presence in human urine. Ten drugs of abuse were analyzed including four amphetamines, cocaine, cocaethylene, heroin, morphine, 6-monoacetylmorphine, and 4-methylmethcathinone. An MSS (micelle to solvent stacking) approach was evaluated to enhance method sensitivity. This method considers composition of the micellar sample solution matrix and the injection time. Several analytical conditions influencing the resolution of the drugs mixture as pH and buffer concentration, organic solvent content, were also investigated. The base-line separation of all studied analytes in the same run was achieved within 18 min in an uncoated fused silica capillary (50 μm id × 60 cm) using a background solution containing 50 mM phosphate buffer pH 2.5 and 30% ACN v/v. Other experimental parameters such as applied voltage and capillary temperature were set up at 20 kV and 20°C, respectively. LOD values ranging between 15 and 75 ng/mL for all studied compounds were obtained. From a comparison with conventional CZE, the proposed method provides an increase of sensitivity (39- to 55-fold enhancement factor). Under optimal MSS-CZE conditions, good linearity was achieved (R 2 ≤ 0.9998). The method was finally applied to the analysis of urine samples spiked with a standard mixture after a sample pretreatment, reaching satisfactory recovery values. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Siloxane containing addition polyimides

NASA Technical Reports Server (NTRS)

Maudgal, S.; St. Clair, T. L.

1984-01-01

Addition polyimide oligomers have been synthesized from bis(gamma-aminopropyl) tetramethyldisiloxane and 3, 3', 4, 4'-benzophenonetetracarboxylic dianhydride using a variety of latent crosslinking groups as endcappers. The prepolymers were isolated and characterized for solubility (in amide, chlorinated and ether solvents), melt flow and cure properties. The most promising systems, maleimide and acetylene terminated prepolymers, were selected for detailed study. Graphite cloth reinforced composites were prepared and properties compared with those of graphite/Kerimid 601, a commercially available bismaleimide. Mixtures of the maleimide terminated system with Kerimid 601, in varying proportions, were also studied.

Sprayable low density ablator and application process

NASA Technical Reports Server (NTRS)

Sharpe, M. H.; Hill, W. E.; Simpson, W. G.; Carter, J. M.; Brown, E. L.; King, H. M.; Schuerer, P. H.; Webb, D. D. (Inventor)

1978-01-01

A sprayable, low density ablative composition is described consisting esentially of: (1) 100 parts by weight of a mixture of 25-65% by weight of phenolic microballoons, 0-20% by weight of glass microballoons, 4-10% by weight of glass fibers, 25-45% by weight of an epoxy-modified polyurethane resin, 2-4% by weight of a bentonite dispersing aid, and 1-2% by weight of an alcohol activator for the bentonite; (2) 1-10 parts by weight of an aromatic amine curing agent; and (3) 200-400 parts by weight of a solvent.

Mixed organic compound-ionic liquid electrolytes for lithium battery electrolyte systems

NASA Astrophysics Data System (ADS)

Montanino, M.; Moreno, M.; Carewska, M.; Maresca, G.; Simonetti, E.; Lo Presti, R.; Alessandrini, F.; Appetecchi, G. B.

2014-12-01

The thermal, transport, rheological and flammability properties of electrolyte mixtures, proposed for safer lithium-ion battery systems, were investigated as a function of the mole composition. The blends were composed of a lithium salt (LiTFSI), organic solvents (namely EC, DEC) and an ionic liquid (PYR13TFSI). The main goal is to combine the fast ion transport properties of the organic compounds with the safe issues of the non-flammable and non-volatile ionic liquids. Preliminary tests in batteries have evidenced cycling performance approaching that observed in commercial organic electrolytes.

Status review of PMR polyimides. [Polymerization of Monomer Reactants

NASA Technical Reports Server (NTRS)

Serafini, T. T.

1979-01-01

In the NASA developed PMR (polymerization of monomer reactants) the reinforcing fibers are impregnated with a solution containing a mixture of monomers dissolved in a low boiling point alkyl alcohol solvent, with the monomers reacting in situ at elevated temperatures to form a thermo-oxidatively stable polyimide matrix. The current status of first and second generation PMR polyimides is reviewed, considering synthesis and properties, processing, and applications. It is concluded that the PMR approach offers various significant advantages, especially superior high temperature properties and processing versatility, to fabricators and users of polyimide/fiber composites.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1983-09-20

A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

Googin, John M.; Napier, John M.; Travaglini, Michael A.

1983-01-01

A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

DOEpatents

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1982-03-31

A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contracting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible polyhydroxy compound, such as, water, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds in the low polar or nonpolar solvent by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered for recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 2 tables.

Separation of nitrogen heterocyclic compounds from model coal tar fraction by solvent extraction

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

Kim, S.J.; Chun, Y.J.

2005-07-01

The separation of four kinds of nitrogen heterocyclic compounds (NHCs) from a model mixture comprising NHCs (indole (In), quinoline (Q), iso-quinoline (iQ), quinaldine (Qu)), three kinds of bicyclic aromatic compounds (BACs; 1-methyl-naphthalene (IMN), 2-methyl naphthalene (2MN), dimethylnaphthalene (DMN)), biphenyl (Bp) and phenyl ether (Pe) was examined by a solvent extraction. The model mixture used as a raw material of this work was prepared according to the components and compositions contained in coal tar fraction (the temperature ranges of fraction: 240-265{sup o}C). An aqueous solution of methanol, ethanol, iso-propyl alcohol, N,N-dimethyl acetamide, DMF, formamide, N-methylformamide/methanol, and formamide/methanol were used as solvents.more » An aqueous solution of formamide was found suitable for separating NHCs contained in coal tar fraction based on distribution coefficient and selectivity. The effect of operation factors on separating NHCs was investigated by the distribution equilibrium using an aqueous solution of formamide. Increasing the operation temperature and the volume ratio of solvent to feed at initial (S/F)(o) resulted in improving the distribution coefficients of each NHC, but increasing the volume fraction of water in the solvent at initial (y(w,O)) resulted in deteriorating the distribution coefficients of each NHC. With increasing y(w,O) and (S/F)(o), the selectivities of each NHC in reference to DMN increased. Increase in operation temperature resulted in decrease in selectivities of each NHC in reference to DMN. At an experimental condition fixed, the sequence of the distribution coefficient and selectivity in reference to DMN for each NHC was In {gt} iQ {gt} Q {gt} Qu, and also the sequence of the distribution coefficient for each BAC was IMN {gt} 2MN {gt} DMN. The sequence of the distribution coefficient for entire compounds analyzed by this work was In {gt} iQ {gt} Q {gt} Qu {gt} BP {gt} 1MN {gt} 2MN {gt} Pe {gt} DMN.« less

Particle size-controllable microwave-assisted solvothermal synthesis of the high-voltage cathode material LiCoPO4 using water/ethylene glycol solvent blends

NASA Astrophysics Data System (ADS)

Ludwig, Jennifer; Haering, Dominik; Doeff, Marca M.; Nilges, Tom

2017-03-01

Particle size-tuned platelets of the high-voltage cathode material LiCoPO4 for Li-ion batteries have been synthesized by a simple one-step microwave-assisted solvothermal process using an array of water/ethylene glycol (EG) solvent mixtures. Particle size control was achieved by altering the concentration of the EG co-solvent in the mixture between 0 and 100 vol%, with amounts of 0-80 vol% EG producing single phase, olivine-type LiCoPO4. The particle sizes of the olivine materials were significantly reduced from about 1.2 μm × 1.2 μm × 500 nm (0 vol% EG) to 200 nm × 100 nm × 50 nm (80 vol% EG) with increasing EG content, while specific surface areas increased from 2 to 13 m2 g-1. The particle size reduction could mainly be attributed to the modified viscosities of the solvent blends. Owing to the soft template effect of EG, the crystals exhibited the smallest dimensions along the [010] direction of the Li diffusion pathways in the olivine crystal structure, resulting in enhanced lithium diffusion properties. The relationship between the synthesis, crystal properties and electrochemical performance was further elucidated, indicating that the electrochemical performances of the as-prepared materials mainly depend on the solvent composition and the respective particle size range. LiCoPO4 products obtained from reaction media with low and high EG contents exhibited good electrochemical performances (initial discharge capacities of 87-124 mAh g-1 at 0.1 C), whereas materials made from medium EG concentrations (40-60 vol% EG) showed the highest capacities and gravimetric energy densities (up to 137 mAh g-1 and 658 Wh kg-1 at 0.1 C), excellent rate capabilities, and cycle life.

Total milk fat extraction and quantification of polar and neutral lipids of cow, goat, and ewe milk by using a pressurized liquid system and chromatographic techniques.

PubMed

Castro-Gómez, M P; Rodriguez-Alcalá, L M; Calvo, M V; Romero, J; Mendiola, J A; Ibañez, E; Fontecha, J

2014-11-01

Although milk polar lipids such as phospholipids and sphingolipids located in the milk fat globule membrane constitute 0.1 to 1% of the total milk fat, those lipid fractions are gaining increasing interest because of their potential beneficial effects on human health and technological properties. In this context, the accurate quantification of the milk polar lipids is crucial for comparison of different milk species, products, or dairy treatments. Although the official International Organization for Standardization-International Dairy Federation method for milk lipid extraction gives satisfactory results for neutral lipids, it has important disadvantages in terms of polar lipid losses. Other methods using mixtures of solvents such as chloroform:methanol are highly efficient for extracting polar lipids but are also associated with low sample throughput, long time, and large solvent consumption. As an alternative, we have optimized the milk fat extraction yield by using a pressurized liquid extraction (PLE) method at different temperatures and times in comparison with those traditional lipid extraction procedures using 2:1 chloroform:methanol as a mixture of solvents. Comparison of classical extraction methods with the developed PLE procedure were carried out using raw whole milk from different species (cows, ewes, and goats) and considering fat yield, fatty acid methyl ester composition, triacylglyceride species, cholesterol content, and lipid class compositions, with special attention to polar lipids such as phospholipids and sphingolipids. The developed PLE procedure was validated for milk fat extraction and the results show that this method performs a complete or close to complete extraction of all lipid classes and in less time than the official and Folch methods. In conclusion, the PLE method optimized in this study could be an alternative to carry out milk fat extraction as a routine method. Copyright © 2014 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Viscosity minima in binary mixtures of ionic liquids + molecular solvents.

PubMed

Tariq, M; Shimizu, K; Esperança, J M S S; Canongia Lopes, J N; Rebelo, L P N

2015-05-28

The viscosity (η) of four binary mixtures (ionic liquids plus molecular solvents, ILs+MSs) was measured in the 283.15 < T/K < 363.15 temperature range. Different IL/MS combinations were selected in such a way that the corresponding η(T) functions exhibit crossover temperatures at which both pure components present identical viscosity values. Consequently, most of the obtained mixture isotherms, η(x), exhibit clear viscosity minima in the studied T-x range. The results are interpreted using auxiliary molecular dynamics (MD) simulation data in order to correlate the observed η(T,x) trends with the interactions in each mixture, including the balance between electrostatic forces and hydrogen bonding.

"Dry-column" chromatography of plant pigments

NASA Technical Reports Server (NTRS)

Woeller, F. H.; Lehwalt, M. F.; Oyama, V. I.

1973-01-01

Separation of plant pigments which can be accomplished on thin-layer silica plates with mixture of petroleum ether, halocarbon, acetone, and polar solvent can be readily translated into dry-column technique that yields reproducible chromatograms after elution in fashion of liquid chromatography with fluorimeter as detector. Best solvent system was found to be mixture of petroleum ether, dichloromethane, acetone, and ethyl acetate.

Probing effect of solvent concentration on glass transition and sub-T{sub g} structural relaxation in polymer solvent mixtures: The case of polystyrene-toluene system

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

Pierleoni, Davide; Minelli, Matteo; Doghieri, Ferruccio

A novel experimental method for the analysis of volume relaxation induced by solvents in glassy polymers is presented. A gravimetric technique is used to evaluate the isothermal solvent mass uptake at controlled increasing/decreasing solvent pressure at constant rate. Fundamental properties of the solvent/polymer system can be obtained directly, and models can be applied, combining both nonequilibrium thermodynamics and mechanics of volume relaxation contribution. The fundamental case of polystyrene and toluene mixtures are thus accounted for, and various experimental conditions have been explored, varying the temperature, and spanning over different pressure increase/decrease rates. The results obtained allowed to evaluate the isothermalmore » second order transition induced by solvent sorption, as well as the determination of the effect of the pressure rate. Therefore, this work proposes a new standard for the characterization and the understanding of the relaxational behavior of glassy polymers.« less

Solubility Limits in Lennard-Jones Mixtures: Effects of Disparate Molecule Geometries.

PubMed

Dyer, Kippi M; Perkyns, John S; Pettitt, B Montgomery

2015-07-23

In order to better understand general effects of the size and energy disparities between macromolecules and solvent molecules in solution, especially for macromolecular constructs self-assembled from smaller molecules, we use the first- and second-order exact bridge diagram extensions of the HNC integral equation theory to investigate single-component, binary, ternary, and quaternary mixtures of Lennard-Jones fluids. For pure fluids, we find that the HNCH3 bridge function integral equation (i.e., exact to third order in density) is necessary to quantitatively predict the pure gas and pure liquid sides of the coexistence region of the phase diagram of the Lennard-Jones fluid. For the mixtures, we find that the HNCH2 bridge function integral equation is sufficient to qualitatively predict solubility in the binary, ternary, and quaternary mixtures, up to the nominal solubility limit. The results, as limiting cases, should be useful to several problems, including accurate phase diagram predictions for complex mixtures, design of self-assembling nanostructures via solvent controls, and the solvent contributions to the conformational behavior of macromolecules in complex fluids.

REMEDIATION OF CONTAMINATED SOILS BY SOLVENT FLUSHING

EPA Science Inventory

Solvent flushing is a potential technique for remediating a waste disposal/spill site contaminated with organic chemicals. This technique involves the injection of a solvent mixture (e.g., water plus alcohols) that enhances contaminant solubility, reduces the retardation factor, ...

Photonic Crystal Based Sensor for Organic Solvents and for Solvent-Water Mixtures

PubMed Central

Fenzl, Christoph; Hirsch, Thomas; Wolfbeis, Otto S.

2012-01-01

Monodisperse polystyrene nanoparticles with a diameter of 173 nm were incorporated into a polydimethylsiloxane matrix where they display an iridescent color that can be attributed to the photonic crystal effect. The film is of violet color if placed in plain water, but turns to red in the presence of the non-polar solvent n-hexane. Several solvents were studied in some detail. We show that such films are capable of monitoring the water content of ethanol/water mixtures, where only 1% (v/v) of water leads to a shift of the peak wavelength of reflected light by 5 nm. The method also can be applied to determine, both visually and instrumentally, the fraction of methanol in ethanol/methanol mixtures. Here, a fraction of 1% of methanol (v/v) results in a wavelength shift of 2 nm. The reflected wavelength is not influenced by temperature changes nor impeded by photobleaching. The signal changes are fully reversible and response times are <1 s. PMID:23235441

Characterization of secondary organic aerosol generated from ozonolysis of α-pinene mixtures

NASA Astrophysics Data System (ADS)

Amin, Hardik S.; Hatfield, Meagan L.; Huff Hartz, Kara E.

2013-03-01

In the atmosphere, multiple volatile organic compounds (VOCs) co-exist, and they can be oxidized concurrently and generate secondary organic aerosol (SOA). In this work, SOA is formed by the oxidation (in presence of excess ozone) of mixtures containing α-pinene and other VOCs. The VOC mixtures were made so their composition approached a commercially-available α-pinene-based essential oil, Siberian fir needle oil. The SOA products were sampled using filters, solvent extracted and analyzed by gas chromatography/mass spectrometry with trimethylsilyl derivatization. The individual product yields for SOA generated from α-pinene changed upon the addition of other VOCs. An increase in concentration of non-reactive VOCs (bornyl acetate, camphene, and borneol) lead to a decrease in individual product yields of characteristic α-pinene SOA products. Although these experiments were carried out under higher VOC and ozone concentrations in comparison to the atmosphere, this work suggests that the role of non-reactive VOCs should be explored in SOA products formation.

Development of dispersive liquid-liquid microextraction technique using ternary solvents mixture followed by heating for the rapid and sensitive analysis of phthalate esters and di(2-ethylhexyl) adipate.

PubMed

Farajzadeh, Mir Ali; Khoshmaram, Leila

2015-01-30

In this study, for the first time, a dispersive liquid-liquid microextraction technique using a ternary solvent mixture is reported. In order to extract five phthalate esters and di(2-ethylhexyl) adipate with different polarities from aqueous samples, a simplex centroid experimental design method was used to select an optimal mixture of ternary solvents prior to gas chromatographyflame ionization detection. In this work, dimethyl formamide as a disperser solvent containing dichloromethane, chloroform, and carbon tetrachloride as a ternary extraction solvent mixture is injected into sample solution and a cloudy solution is formed. After centrifuging, 250μL of the obtained sedimented phase was transferred into another tube and 5μL DMF was added to it. Then, the tube was heated in a water bath at 75°C for 5min in order to evaporate the main portion of the extraction solvents. Finally, 2μL of the remained phase is injected into the separation system. Under the optimum extraction conditions, the method shows wide linear ranges and low limits of detection and quantification between 0.03-0.15 and 0.09-0.55μgL(-1), respectively. Enrichment factors and extraction recoveries are in the ranges of 980-4500 and 20-90%, respectively. The method is successfully applied in the determination of the target analytes in mineral water, soda, lemon juice, vinegar, dough, and yogurt packed in plastic packages. Copyright © 2014 Elsevier B.V. All rights reserved.

Fact or artifact: the representativeness of ESI-MS for complex natural organic mixtures.

PubMed

Novotny, Nicole R; Capley, Erin N; Stenson, Alexandra C

2014-04-01

Because mass spectrometers provide their own dispersion and resolution of analytes, electrospray ionization mass spectrometry (ESI-MS) has become a workhorse for the characterization of complex mixtures from aerosols to crude oil. Unfortunately, ESI mass spectra commonly contain multimers, adducts and fragments. For the characterization of complex mixtures of unknown initial composition, this presents a significant concern. Mixed-multimer formation could potentially lead to results that bare no resemblance to the original mixture. Conversely, ESI-MS has continually reflected subtle differences between natural organic matter mixtures that are in agreement with prediction or theory. Knowing the real limitations of the technique is therefore critical to avoiding both over-interpretation and unwarranted skepticism. Here, data were collected on four mass spectrometers under a battery of conditions. Results indicate that formation of unrepresentative ions cannot entirely be ruled out, but non-covalent multimers do not appear to make a major contribution to typical natural organic matter spectra based on collision-induced dissociation results. Multimers also appear notably reduced when a cooling gas is present in the accumulation region of the mass spectrometer. For less complex mixtures, the choice of spray solvent can make a difference, but generally spectrum cleanliness (i.e. representativeness) comes at the price of increased selectivity. Copyright © 2014 John Wiley & Sons, Ltd.

Hydrogen bonding donation of N-methylformamide with dimethylsulfoxide and water

NASA Astrophysics Data System (ADS)

Borges, Alexandre; Cordeiro, João M. M.

2013-04-01

20% N-methylformamide (NMF) mixtures with water and with dimethylsulfoxide (DMSO) have been studied. A comparison between the hydrogen bonding (H-bond) donation of N-methylformamide with both solvents in the mixtures is presented. Results of radial distribution functions, pair distribution energies, molecular dipole moment correlation, and geometry of the H-bonded species in each case are shown. The results indicate that the NMF - solvent H-bond is significantly stronger with DMSO than with water. The solvation shell is best organized in the DMSO mixture than in the aqueous one.

Process for making ultra-fine ceramic particles

DOEpatents

Stangle, Gregory C.; Venkatachari, Koththavasal R.; Ostrander, Steven P.; Schulze, Walter A.

1995-01-01

A process for producing ultra-fine ceramic particles in which droplets are formed from a ceramic precursor mixture containing a metal cation, a nitrogen-containing fuel, a solvent, and an anion capable of participating in an anionic oxidation-reduction reaction with the nitrogen containing fuel. The nitrogen-containing fuel contains at least three nitrogen atoms, at least one oxygen atom, and at least one carbon atom. The ceramic precursor mixture is dried to remove at least 85 weight percent of the solvent, and the dried mixture is then ignited to form a combusted powder.

Experimental investigation on the minimum ignition temperature of hybrid mixtures of dusts and gases or solvents.

PubMed

Addai, Emmanuel Kwasi; Gabel, Dieter; Krause, Ulrich

2016-01-15

Investigations on the minimum ignition temperatures (MIT) of hybrid mixtures of dusts with gases or solvents were performed in the modified Godbert-Greenwald (GG) furnace. Five combustible dusts and six flammable gases (three ideal and three real) were used. The test protocol was according to EN 50281-2-1 for dust-air mixtures whereas in the case of gases, solvents and hybrid mixtures this standard was used with slight modification. The experimental results demonstrated a significant decrease of the MIT of gas, solvent or dust and an increase in the likelihood of explosion when a small amount of dust, which was either below the minimum explosion concentration or not ignitable by itself, was mixed with gas and vice versa. For example, the MIT of toluene decreased from 540°C to 455°C when small amount of lycopodium was added. It was also confirmed that a hybrid mixture explosion is possible even when both dust and vapour or gas concentrations are respectively lower than their minimum explosion concentration (MEC) and lower explosion limit (LEL). Another example is CN4, the MEC of which of 304 g/m(3) decreased to 37 g/m(3) when propane was added, even though the concentrations of the gas was below its LEL. Copyright © 2015 Elsevier B.V. All rights reserved.

Continuous bio-catalytic conversion of sugar mixture to acetone-butanol-ethanol by immobilized Clostridium acetobutylicum DSM 792.

PubMed

Survase, Shrikant A; van Heiningen, Adriaan; Granström, Tom

2012-03-01

Continuous production of acetone, n-butanol, and ethanol (ABE) was carried out using immobilized cells of Clostridium acetobutylicum DSM 792 using glucose and sugar mixture as a substrate. Among various lignocellulosic materials screened as a support matrix, coconut fibers and wood pulp fibers were found to be promising in batch experiments. With a motive of promoting wood-based bio-refinery concept, wood pulp was used as a cell holding material. Glucose and sugar mixture (glucose, mannose, galactose, arabinose, and xylose) comparable to lignocellulose hydrolysate was used as a substrate for continuous production of ABE. We report the best solvent productivity among wild-type strains using column reactor. The maximum total solvent concentration of 14.32 g L(-1) was obtained at a dilution rate of 0.22 h(-1) with glucose as a substrate compared to 12.64 g L(-1) at 0.5 h(-1) dilution rate with sugar mixture. The maximum solvent productivity (13.66 g L(-1) h(-1)) was obtained at a dilution rate of 1.9 h(-1) with glucose as a substrate whereas solvent productivity (12.14 g L(-1) h(-1)) was obtained at a dilution rate of 1.5 h(-1) with sugar mixture. The immobilized column reactor with wood pulp can become an efficient technology to be integrated with existing pulp mills to convert them into wood-based bio-refineries.

An improved processible acetylene-terminated polyimide for composites

NASA Technical Reports Server (NTRS)

Landis, A. L.; Naselow, A. B.

1985-01-01

The newest member of a family of thermosetting acetylene-substituted polyimide oligomers is HR600P. This oligomer is the isoimide version of the oligomer known as HR600P and Thermid 600. Although both types of material yield the same heat resistant end products after cure, HR600P has much superior processing characteristics. This attributed to its lower melting temperature (160 + or - 10 C, 320 + or - 20 F) in contrast to 202 C (396 F) for Thermid MC-600, its longer gel time at its processing temperature (16 to 30 minutes bvs 3 minutes), and its excellent solubility in low boiling solvents such as tetrahydrofuran, glymes, or 4:1 methyl ethyl ketone/toluene mixtures. These advantages provide more acceptable coating and impregnation procedures, allow for more complete removal at lower temperatures, provide a longer pot life or working time, and allow composite structure fabrication in conventional autoclaves used for epoxy composite curing. The excellent processing characteristics of HR600P allow its use in large area laminated structures, structural composites, and molding compositions.

Dissolution thermodynamics and solubility of silymarin in PEG 400-water mixtures at different temperatures.

PubMed

Shakeel, Faiyaz; Anwer, Md Khalid

2015-01-01

An isothermal method was used to measure the solubility of silymarin in binary polyethylene glycol 400 (PEG 400) + water co-solvent mixtures at temperatures T = 298.15-333.15 K and pressure p = 0.1 MPa. Apelblat and Yalkowsky models were used to correlate experimental solubility data. The mole fraction solubility of silymarin was found to increase with increasing the temperature and mass fraction of PEG 400 in co-solvent mixtures. The root mean square deviations were observed in the range of 0.48-5.32% and 1.50-9.65% for the Apelblat equation and Yalkowsky model, respectively. The highest and lowest mole fraction solubility of silymarin was observed in pure PEG 400 (0.243 at 298.15 K) and water (1.46 × 10(-5) at 298.15 K). Finally, thermodynamic parameters were determined by Van't Hoff and Krug analysis, which indicated an endothermic and spontaneous dissolution of silymarin in all co-solvent mixtures.

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2B Table 2B to Subpart E of Part 59—Reactivity Factors for Aliphatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 6 2014-07-01 2014-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2C Table 2C to Subpart E of Part 59—Reactivity Factors for Aromatic...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2B Table 2B to Subpart E of Part 59—Reactivity Factors for Aliphatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 6 2013-07-01 2013-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2C Table 2C to Subpart E of Part 59—Reactivity Factors for Aromatic...

40 CFR Table 2b to Subpart E of... - Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Reactivity Factors for Aliphatic Hydrocarbon Solvent Mixtures 2B Table 2B to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2B Table 2B to Subpart E of Part 59—Reactivity Factors for Aliphatic...

40 CFR Table 2c to Subpart E of... - Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 6 2012-07-01 2012-07-01 false Reactivity Factors for Aromatic Hydrocarbon Solvent Mixtures 2C Table 2C to Subpart E of Part 59 Protection of Environment ENVIRONMENTAL... Coatings Pt. 59, Subpt. E, Table 2C Table 2C to Subpart E of Part 59—Reactivity Factors for Aromatic...

TiO2 Processed by pressurized hot solvents as a novel photocatalyst for photocatalytic reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Reli, Martin; Kobielusz, Marcin; Matějová, Lenka; Daniš, Stanislav; Macyk, Wojciech; Obalová, Lucie; Kuśtrowski, Piotr; Rokicińska, Anna; Kočí, Kamila

2017-01-01

Anatase-brookite TiO2 photocatalysts were prepared by the sol-gel process controlled within reverse micelles and processing by pressurized hot solvents-water/methanol/water (TiO2(M)) and water/ethanol/water (TiO2(E)), as an unconventional alternative to common calcination. The main goal of this work was to prepare anatase-brookite mixtures by processing by two different alcohols (methanol and ethanol) and evaluate the influence of the alcohol on the photocatalytic activity. Prepared photocatalysts were characterized by organic elemental analysis, nitrogen physisorption, XRD, UV-vis, photoelectrochemical and spectroelectrochemical measurements and XPS. The prepared photocatalysts efficiency was tested on the photocatalytic reduction of carbon dioxide and compared with commercial TiO2 Evonik P25. Both prepared nanocomposites were more efficient towards methane production but Evonik P25 was the most efficient towards hydrogen generated through water splitting. The higher performance of anatase-brookite mixture towards methane production can be explained by (i) a higher photocatalytic activity of brookite than rutile; (ii) a large surface area of anatase-brookite composites enabling better carbon dioxide adsorption; (iii) the photoinduced electron transfer from the brookite conduction band to the anatase conduction band. On the other hand, a higher production of hydrogen in the presence of Evonik P25 is caused by a better charge separation in anatase-rutile than anatase-brookite phase compositions. TiO2(M) appeared more active than TiO2(E) in the photocatalytic reduction of carbon dioxide due to a lower density of defects created in the crystal lattice.

Supercritical antisolvent co-precipitation of rifampicin and ethyl cellulose.

PubMed

Djerafi, Rania; Swanepoel, Andri; Crampon, Christelle; Kalombo, Lonji; Labuschagne, Philip; Badens, Elisabeth; Masmoudi, Yasmine

2017-05-01

Rifampicin-loaded submicron-sized particles were prepared through supercritical anti-solvent process using ethyl cellulose as polymeric encapsulating excipient. Ethyl acetate and a mixture of ethyl acetate/dimethyl sulfoxide (70/30 and 85/15) were used as solvents for both drug and polymeric excipient. When ethyl acetate was used, rifampicin was crystallized separately without being embedded within the ethyl cellulose matrix while by using the ethyl acetate/dimethyl sulfoxide mixture, reduced crystallinity of the active ingredient was observed and a simultaneous precipitation of ethyl cellulose and drug was achieved. The effect of solvent/CO 2 molar ratio and polymer/drug mass ratio on the co-precipitates morphology and drug loading was investigated. Using the solvent mixture, co-precipitates with particle sizes ranging between 190 and 230nm were obtained with drug loading and drug precipitation yield from respectively 8.5 to 38.5 and 42.4 to 77.2% when decreasing the ethyl cellulose/rifampicin ratio. Results show that the solvent nature and the initial drug concentrations affect morphology and drug precipitation yield of the formulations. In vitro dissolution studies revealed that the release profile of rifampicin was sustained when co-precipitation was carried out with the solvent mixture. It was demonstrated that the drug to polymer ratio influenced amorphous content of the SAS co-precipitates. Differential scanning calorimetry thermograms and infrared spectra revealed that there is neither interaction between rifampicin and the polymer nor degradation of rifampicin during co-precipitation. In addition, stability stress tests on SAS co-precipitates were carried out at 75% relative humidity and room temperature in order to evaluate their physical stability. SAS co-precipitates were X-ray amorphous and remained stable after 6months of storage. The SAS co-precipitation process using a mixture of ethyl acetate/dimethyl sulfoxide demonstrates that this strategy can be successful for controlling rifampicin delivery. Copyright © 2017 Elsevier B.V. All rights reserved.

Solvent-induced changes in PEDOT:PSS films for organic electrochemical transistors

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

Zhang, Shiming; Kumar, Prajwal; Nouas, Amel Sarah

2015-01-01

Organic electrochemical transistors based on the conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) (PEDOT:PSS) are of interest for several bioelectronic applications. In this letter, we investigate the changes induced by immersion of PEDOT:PSS films, processed by spin coating from different mixtures, in water and other solvents of different polarities. We found that the film thickness decreases upon immersion in polar solvents, while the electrical conductivity remains unchanged. The decrease in film thickness is minimized via the addition of a cross-linking agent to the mixture used for the spin coating of the films.

High pressure liquid chromatographic gradient mixer

DOEpatents

Daughton, Christian G.; Sakaji, Richard H.

1985-01-01

A gradient mixer which effects the continuous mixing of any two miscible solvents without excessive decay or dispersion of the resultant isocratic effluent or of a linear or exponential gradient. The two solvents are fed under low or high pressure by means of two high performance liquid chromatographic pumps. The mixer comprises a series of ultra-low dead volume stainless steel tubes and low dead volume chambers. The two solvent streams impinge head-on at high fluxes. This initial nonhomogeneous mixture is then passed through a chamber packed with spirally-wound wires which cause turbulent mixing thereby homogenizing the mixture with minimum "band-broadening".

High-pressure liquid chromatographic gradient mixer

DOEpatents

Daughton, C.G.; Sakaji, R.H.

1982-09-08

A gradient mixer effects the continuous mixing of any two miscible solvents without excessive decay or dispersion of the resultant isocratic effluent or of a linear or exponential gradient. The two solvents are fed under low or high pressure by means of two high performance liquid chromatographic pumps. The mixer comprises a series of ultra-low dead volume stainless steel tubes and low dead volume chambers. The two solvent streams impinge head-on at high fluxes. This initial nonhomogeneous mixture is then passed through a chamber packed with spirally-wound wires which cause turbulent mixing thereby homogenizing the mixture with minimum band-broadening.

Halogenated solvent remediation

DOEpatents

Sorenson, Jr., Kent S.

2008-11-11

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. An illustrative method includes adding an electron donor for microbe-mediated anaerobic reductive dehalogenation of the halogenated solvents, which electron donor enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative electron donors include C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof, of which lactic acid, salts of lactic acid--such as sodium lactate, lactate esters, and mixtures thereof are particularly illustrative. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the electron donor.

Comparison Pore Aggregate Levels After Extraction With Solvents Pertamax Plus And Gasoline

NASA Astrophysics Data System (ADS)

Anggraini, Muthia

2017-12-01

Loss of asphalt content extraction results become problems in Field Work For implementing parties. The use of solvents with high octane (pertamax plus) for the extraction, dissolving the asphalt more than gasoline. By comparing the levels of aggregate pores after using solvent extraction pertamax plus compared to gasoline could answer that pertamax plus more solvent dissolves the bitumen compared to gasoline. This study aims to obtain comparative levels of porous aggregate mix AC-WC after using solvent extraction pertamax plus compared to gasoline. This study uses the aggregate that has been extracted from the production of asphalt mixtures, when finisher and after compaction field. The method used is the assay of coarse and fine aggregate pores, extraction of bitumen content to separate the aggregate with bitumen. Results of testing the total absorption after extraction using a solvent preta max plus in the production of asphalt mixtures 0.80%, while gasoline solvent 0.67% deviation occurs 0.13%. In the finisher after the solvent extraction preta max plus 0.77%, while 0.67% gasoline solvent occurs deviation of 0.1%. At the core after extraction and solvent pertamax plus 0.71%, while gasoline solvent 0.60% 0.11% deviation occurs. The total water absorption after extraction using a solvent pertamax plus greater than gasoline. This proves that the solvent dissolves pertamax plus more asphalt than gasoline.

Effects of Solvent Composition on Liquid Range, Glass Transition, and Conductivity of Electrolytes of a (Li, Cs)PF 6 Salt in EC-PC-EMC Solvents

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

Ding, Michael S.; Li, Qiuyan; Li, Xing

Electrolytes of 1 M LiPF 6 (lithium hexafluorophosphate) and 0.05 M CsPF 6 (cesium hexafluorophosphate) in EC-PC-EMC (ethylene carbonate-propylene carbonate-ethyl methyl carbonate) solvents of varying solvent compositions were studied for the effects of solvent composition on the lower limit of liquid range, viscosity (as reflected by the glass transition temperature), and electrolytic conductivity. In addition, a ternary phase diagram of EC-PC-EMC was constructed and crystallization temperatures of EC and EMC were calculated to assist the interpretation and understanding of the change of liquid range with solvent composition. A function based on Vogel-Fulcher-Tammann equation was fitted to the conductivity data inmore » their entirety and plotted as conductivity surfaces in solvent composition space for more direct and clear comparisons and discussions. Changes of viscosity and dielectric constant of the solvents with their composition, in relation to those of the solvent components, were found to be underlying many of the processes studied.« less

Using a low melting solvent mixture to extract value from wood biomass

NASA Astrophysics Data System (ADS)

Hiltunen, Jaakko; Kuutti, Lauri; Rovio, Stella; Puhakka, Eini; Virtanen, Tommi; Ohra-Aho, Taina; Vuoti, Sauli

2016-09-01

Green chemistry, sustainability and eco-efficiency are guiding the development of the next generation of industrial chemical processes. The use of non-edible lignocellulosic biomass as a source of chemicals and fuels has recently raised interest due to the need for an alternative to fossil resources. Valorisation mainly focuses on cellulose, which has been used for various industrial scale applications for decades. However, creating an economically more viable value chain would require the exploitation of the other main components, hemicellulose and lignin. Here, we present a new low melting mixture composition based in boric acid and choline chloride, and demonstrate its efficiency in the fractionation of wood-based biomass for the production of non-condensed lignin, suitable for further use in the search for sustainable industrial applications, and for the selective conversion of hemicelluloses into valuable platform chemicals.

Supercritical fluid extraction. Principles and practice

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

McHugh, M.A.; Krukonis, V.J.

This book is a presentation of the fundamentals and application of super-critical fluid solvents (SCF). The authors cover virtually every facet of SCF technology: the history of SCF extraction, its underlying thermodynamic principles, process principles, industrial applications, and analysis of SCF research and development efforts. The thermodynamic principles governing SCF extraction are covered in depth. The often complex three-dimensional pressure-temperature composition (PTx) phase diagrams for SCF-solute mixtures are constructed in a coherent step-by-step manner using the more familiar two-dimensional Px diagrams. The experimental techniques used to obtain high pressure phase behavior information are described in detail and the advantages andmore » disadvantages of each technique are explained. Finally, the equations used to model SCF-solute mixtures are developed, and modeling results are presented to highlight the correlational strengths of a cubic equation of state.« less

Solvatochromic probe behavior within choline chloride-based deep eutectic solvents: effect of temperature and water.

PubMed

Pandey, Ashish; Pandey, Siddharth

2014-12-18

Deep eutectic solvents (DESs) have shown potential as promising environmentally friendly alternatives to conventional solvents. Many common and popular DESs are obtained by simply mixing a salt and a H-bond donor. Properties of such a DES depend on its constituents. Change in temperature and addition of water, a benign cosolvent, can change the physicochemical properties of DESs. The effect of changing temperature and addition of water on solvatochromic probe behavior within three DESs formed from choline chloride combined with 1,2-ethanediol, glycerol, and urea, respectively, in 1:2 mol ratios termed ethaline, glyceline, and reline is presented. Increase in temperature results in reduced H-bond donating acidity of the DESs. Dipolarity/polarizability and H-bond accepting basicity do not change with changing temperature of the DESs. The response of the fluorescence probe pyrene also indicates a decrease in the polarity of the DESs as temperature is increased. Addition of water to DES results in increased dipolarity/polarizability and a decrease in H-bond accepting basicity. Except for pyrene, solvatochromic probes exhibit responses close to those predicted from ideal-additive behavior with slight preferential solvation by DES within the aqueous mixtures. Pyrene response reveals significant preferential solvation by DES and/or the presence of solvent-solvent interactions, especially within aqueous mixtures of ethaline and glyceline, the DESs constituted of H-bond donors with hydroxyl functionalities. FTIR absorbance and Raman spectroscopic measurements of aqueous DES mixtures support the outcomes from solvatochromic probe responses. Aqueous mixtures of ethaline and glyceline possess relatively more interspecies H-bonds as compared to aqueous mixtures of reline, where interstitial accommodation of water within the reline molecular network appears to dominate.

Nonhazardous solvent composition and method for cleaning metal surfaces

DOEpatents

Googin, John M.; Simandl, Ronald F.; Thompson, Lisa M.

1993-01-01

A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140.degree. F. and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140.degree. F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

Nonhazardous solvent composition and method for cleaning metal surfaces

DOEpatents

Googin, J.M.; Simandl, R.F.; Thompson, L.M.

1993-05-04

A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140 F and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140 F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

A neurological evaluation of workers exposed to mixtures of organic solvents.

PubMed Central

Maizlish, N A; Fine, L J; Albers, J W; Whitehead, L; Langolf, G D

1987-01-01

Workers with long term exposure to mixtures of organic solvents below regulatory limits have been reported to experience mild, but clinically detectable, sensory or sensorimotor polyneuropathies. In conjuction with a cross sectional study of behavioural performance a clinical neurological evaluation was conducted among printers and spray painters to examine dose response relations. All 240 subjects completed an occupational history and symptom questionnaire and underwent a clinical neurological examination. On average, subjects had been employed on their current job for six years. Classification of solvent exposure for each subject was based on exposed versus non-exposed job titles and observations during an industrial hygiene walk-through or on the measured concentration of solvents in full shift personal air samples. The average full shift solvent concentration was 302 ppm for printing plant workers and 6-13 ppm for workers at other plants. Isopropanol and hexane were the major constituents. Neurological abnormalities consistent with mild polyneuropathy were found in 16% of subjects; none was clinically significant. Exposed/non-exposed comparisons showed slightly higher frequency of symptoms in the exposed subjects which was not related to solvent level. Subjects categorised as exposed during the walk- through survey also had poorer vibratory sensation measured at the foot and diminished ankle reflexes. In multiple linear regression models, however, controlling for age, sex, alcohol intake, and examiner, no significant (p less than 0.05) relation was found between solvent concentration and poor neurological function except for two point discrimination measured at the foot. This investigation has not provided evidence for dose related adverse neurological effects from exposure to moderately low levels of solvent mixtures for a relatively short duration, although this may be due to the shortness of exposure duration, the type of solvent exposure, or to selection factors. PMID:3814530

Metal Cationization Extractive Electrospray Ionization Mass Spectrometry of Compounds Containing Multiple Oxygens

NASA Astrophysics Data System (ADS)

Swanson, Kenneth D.; Spencer, Sandra E.; Glish, Gary L.

2017-06-01

Extractive electrospray ionization is an ambient ionization technique that allows real-time sampling of liquid samples, including organic aerosols. Similar to electrospray ionization, the composition of the electrospray solvent used in extractive electrospray ionization can easily be altered to form metal cationized molecules during ionization simply by adding a metal salt to the electrospray solvent. An increase in sensitivity is observed for some molecules that are lithium, sodium, or silver cationized compared with the protonated molecule formed in extractive electrospray ionization with an acid additive. Tandem mass spectrometry of metal cationized molecules can also significantly improve the ability to identify a compound. Tandem mass spectrometry of lithium and silver cationized molecules can result in an increase in the number and uniqueness of dissociation pathways relative to [M + H]+. These results highlight the potential for extractive electrospray ionization with metal cationization in analyzing complex aerosol mixtures. [Figure not available: see fulltext.

Surfactant/Supercritical Fluid Cleaning of Contaminated Substrates

NASA Technical Reports Server (NTRS)

White, Gary L.

1997-01-01

CFC's and halogenated hydrocarbon solvents have been the solvents of choice to degrease and otherwise clean precision metal parts to allow proper function. Recent regulations have, however, rendered most of these solvents unacceptable for these purposes. New processes which are being used or which have been proposed to replace these solvents usually either fail to remove water soluble contaminants or produce significant aqueous wastes which must then be disposed of. In this work, a new method for cleaning surfaces will be investigated. Solubility of typical contaminants such as lubricating greases and phosphatizing bath residues will be studied in several surfactant/supercritical fluid solutions. The effect of temperature, pressure, and the composition of the cleaning mixture on the solubility of oily, polar, and ionic contaminants will be investigated. A reverse micellar solution in a supercritical light hydrocarbon solvent will be used to clean samples of industrial wastes. A reverse micellar solution is one where water is dissolved into a non-polar solvent with the aid of a surfactant. The solution will be capable of dissolving both water-soluble contaminants and oil soluble contaminants. Once the contaminants have been dissolved into the solution they will be separated from the light hydrocarbon and precipitated by a relatively small pressure drop and the supercritical solvent will be available for recycle for reuse. The process will be compared to the efficacy of supercritical CO2 cleaning by attempting to clean the same types of substrates and machining wastes with the same contaminants using supercritical CO2. It is anticipated that the supercritical CO2 process will not be capable of removing ionic residues.

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

Cao, Siqin; Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon; Sheong, Fu Kit

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

Biodegradation Kinetics of 1,4-Dioxane in Chlorinated Solvent Mixtures.

PubMed

Zhang, Shu; Gedalanga, Phillip B; Mahendra, Shaily

2016-09-06

This study investigated the impacts of individual chlorinated solvents and their mixtures on aerobic 1,4-dioxane biodegradation by Pseudonocardia dioxanivorans CB1190. The established association of these co-occurring compounds suggests important considerations for their respective biodegradation processes. Our kinetics and mechanistic studies demonstrated that individual solvents inhibited biodegradation of 1,4-dioxane in the following order: 1,1-dichloroethene (1,1-DCE) > cis-1,2-diochloroethene (cDCE) > trichloroethene (TCE) > 1,1,1-trichloroethane (TCA). The presence of 5 mg L(-1) 1,1-DCE completely inhibited 1,4-dioxane biodegradation. Subsequently, we determined that 1,1-DCE was the strongest inhibitor of 1,4-dioxane biodegradation by bacterial pure cultures exposed to chlorinated solvent mixtures as well as in environmental samples collected from a site contaminated with chlorinated solvents and 1,4-dioxane. Inhibition of 1,4-dioxane biodegradation rates by chlorinated solvents was attributed to delayed ATP production and down-regulation of both 1,4-dioxane monooxygenase (dxmB) and aldehyde dehydrogenase (aldH) genes. Moreover, increasing concentrations of 1,1-DCE and cis-1,2-DCE to 50 mg L(-1) respectively increased 5.0-fold and 3.5-fold the expression of the uspA gene encoding a universal stress protein. In situ natural attenuation or enhanced biodegradation of 1,4-dioxane is being considered for contaminated groundwater and industrial wastewater, so these results will have implications for selecting 1,4-dioxane bioremediation strategies at sites where chlorinated solvents are present as co-contaminants.

Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture

NASA Astrophysics Data System (ADS)

Kasai, Yukako; Yoshida, Norio; Nakano, Haruyuki

2015-05-01

The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol-1. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol-1. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

RECOVERY OF METAL VALUES FROM AQUEOUS SOLUTIONS BY SOLVENT EXTRACTION

DOEpatents

Moore, R.L.

1959-09-01

An organic solvent mixure is described for extracting actinides from aqueous solutions; the solvent mixture consists of from 10 to 25% by volume of tributyl phosphate and the remainder a chlorine-fluorine-substituted saturated hydrocarbon having two carbon atoms in the molecule.

Structural anomaly and dynamic heterogeneity in cycloether/water binary mixtures: Signatures from composition dependent dynamic fluorescence measurements and computer simulations

NASA Astrophysics Data System (ADS)

Indra, Sandipa; Guchhait, Biswajit; Biswas, Ranjit

2016-03-01

We have performed steady state UV-visible absorption and time-resolved fluorescence measurements and computer simulations to explore the cosolvent mole fraction induced changes in structural and dynamical properties of water/dioxane (Diox) and water/tetrahydrofuran (THF) binary mixtures. Diox is a quadrupolar solvent whereas THF is a dipolar one although both are cyclic molecules and represent cycloethers. The focus here is on whether these cycloethers can induce stiffening and transition of water H-bond network structure and, if they do, whether such structural modification differentiates the chemical nature (dipolar or quadrupolar) of the cosolvent molecules. Composition dependent measured fluorescence lifetimes and rotation times of a dissolved dipolar solute (Coumarin 153, C153) suggest cycloether mole-fraction (XTHF/Diox) induced structural transition for both of these aqueous binary mixtures in the 0.1 ≤ XTHF/Diox ≤ 0.2 regime with no specific dependence on the chemical nature. Interestingly, absorption measurements reveal stiffening of water H-bond structure in the presence of both the cycloethers at a nearly equal mole-fraction, XTHF/Diox ˜ 0.05. Measurements near the critical solution temperature or concentration indicate no role for the solution criticality on the anomalous structural changes. Evidences for cycloether aggregation at very dilute concentrations have been found. Simulated radial distribution functions reflect abrupt changes in respective peak heights at those mixture compositions around which fluorescence measurements revealed structural transition. Simulated water coordination numbers (for a dissolved C153) and number of H-bonds also exhibit minima around these cosolvent concentrations. In addition, several dynamic heterogeneity parameters have been simulated for both the mixtures to explore the effects of structural transition and chemical nature of cosolvent on heterogeneous dynamics of these systems. Simulated four-point dynamic susceptibility suggests formation of clusters inducing local heterogeneity in the solution structure.

Collapse in two good solvents, swelling in two poor solvents: defying the laws of polymer solubility?

NASA Astrophysics Data System (ADS)

Mukherji, Debashish; Marques, Carlos M.; Kremer, Kurt

2018-01-01

In this work we discuss two mirror but distinct phenomena of polymer paradoxical properties in mixed solvents: co-non-solvency and co-solvency. When a polymer collapses in a mixture of two miscible good solvents the phenomenon is known as co-non-solvency, while co-solvency is a phenomenon that is associated with the swelling of a polymer in poor solvent mixtures. A typical example of co-non-solvency is provided by poly(N-isopropylacrylamide) in aqueous alcohol, while poly(methyl methacrylate) in aqueous alcohol shows co-solvency. We discuss these two phenomena to compare their microscopic origins and show that both can be understood within generic universal concepts. A broad range of polymers is therefore expected to exhibit these phenomena where specific chemical details play a lesser role than the appropriate combination of interactions between the trio of molecular components.

Use of solvent mixtures for total lipid extraction of Chlorella vulgaris and gas chromatography FAME analysis.

PubMed

Moradi-Kheibari, Narges; Ahmadzadeh, Hossein; Hosseini, Majid

2017-09-01

Lipid extraction is the bottleneck step for algae-based biodiesel production. Herein, 12 solvent mixture systems (mixtures of three non-polar and two polar organic solvents) were examined to evaluate their effects on the total lipid yield from Chlorella vulgaris (C. vulgaris). Moreover, the extraction yields of three solvent systems with maximum extraction efficiency of esterifiable lipids were determined by acidic transesterification and GC-FID analysis. Three solvent systems, which resulted in a higher extraction yield, were further subjected to fatty acid methyl ester (FAME) analysis. The total lipid extraction yields (based on dry biomass) were (38.57 ± 1.51), (25.33 ± 0.58), and (25.17 ± 1.14) %, for chloroform-methanol (1:2) (C1M2), hexane-methanol (1:2) (H1M2), and chloroform-methanol (2:1) (C2M1), respectively. The extraction efficiency of C1M2 was approximately 1.5 times higher than H1M2 and C2M1, whereas the FAME profile of extracted lipids by H1M2 and C1M2 were almost identical. Moreover, the esterifiable lipid extraction yields of (18.14 ± 2.60), (16.66 ± 0.35), and (13.22 ± 0.31) % (based on dry biomass) were obtained for C1M2, H1M2, and C2M1 solvent mixture systems, respectively. The biodiesel fuel properties produced from C. vulgaris were empirically predicted and compared to that of the EN 14214 and ASTM 6751 standard specifications.

URANIUM SEPARATION PROCESS

DOEpatents

Hyde, E.K.; Katzin, L.I.; Wolf, M.J.

1959-07-14

The separation of uranium from a mixture of uranium and thorium by organic solvent extraction from an aqueous solution is described. The uranium is separrted from an aqueous mixture of uranium and thorium nitrates 3 N in nitric acid and containing salting out agents such as ammonium nitrate, so as to bring ihe total nitrate ion concentration to a maximum of about 8 N by contacting the mixture with an immiscible aliphatic oxygen containing organic solvent such as diethyl carbinol, hexone, n-amyl acetate and the like. The uranium values may be recovered from the organic phase by back extraction with water.

PETIs as High-Temperature Resin-Transfer-Molding Materials

NASA Technical Reports Server (NTRS)

Connell, John N.; Smith, Joseph G., Jr.; Hergenrother, Paul M.

2005-01-01

Compositions of, and processes for fabricating, high-temperature composite materials from phenylethynyl-terminated imide (PETI) oligomers by resin-transfer molding (RTM) and resin infusion have been developed. Composites having a combination of excellent mechanical properties and long-term high-temperature stability have been readily fabricated. These materials are particularly useful for the fabrication of high-temperature structures for jet-engine components, structural components on highspeed aircraft, spacecraft, and missiles. Phenylethynyl-terminated amide acid oligomers that are precursors of PETI oligomers are easily made through the reaction of a mixture of aromatic diamines with aromatic dianhydrides at high stoichiometric offsets and 4-phenylethynylphthalic anhydride (PEPA) as an end-capper in a polar solvent such as N-methylpyrrolidinone (NMP). These oligomers are subsequently cyclodehydrated -- for example, by heating the solution in the presence of toluene to remove the water by azeotropic distillation to form low-molecular-weight imide oligomers. More precisely, what is obtained is a mixture of PETI oligomeric species, spanning a range of molecular weights, that exhibits a stable melt viscosity of less than approximately 60 poise (and generally less than 10 poise) at a temperature below 300 deg C. After curing of the oligomers at a temperature of 371 deg C, the resulting polymer can have a glass-transition temperature (Tg) as high as 375 C, the exact value depending on the compositions.

Equilibrium disorders in workers exposed to mixed solvents.

PubMed

Giorgianni, Concetto; Tanzariello, Mariagiuseppina; De Pasquale, Domenico; Brecciaroli, Renato; Spatari, Giovanna

2018-02-06

Organic solvents cause diseases of the vestibular system. However, little is known regarding the correlation between vestibular damage and exposure to organic solvents below threshold limit values. The best measure by which to evaluate vestibular disorders is static and dynamic posturography. The aim of this study was to evaluate equilibrium disorders via static and dynamic posturography in workers without clear symptoms and exposed to low doses of mixed solvents. 200 subjects were selected. Using an Otometrics device (Madsen, Denmark), all subjects endured static and dynamic posturography testing with both eyes-open and eyes-closed conditions. Results were compared with a control group of unexposed individuals. Based on the obtained data, the following results can be drawn: (a) subjects exposed to mixtures of solvents show highly significant differences regarding all static and dynamic posturography parameters in comparison to the control group; (b) posturography testing has proven to be a valid means by which to detect subliminal equilibrium disorders in subjects exposed to solvents. We can confirm that refinery workers exposed to mixtures of solvents can present subliminal equilibrium disorders. Early diagnosis of the latter is made possible by static and dynamic posturography.

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

PubMed Central

Goossens, Spencer; Mehdizadeh Rahimi, Ali

2017-01-01

We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics (Gibbs free energies, entropies, and heat capacities) in numerous polar solvents. We are also able to predict ion solvation free energies in water–co-solvent mixtures over available concentration series. The first modification to the classical dielectric Poisson model is a perturbation of the macroscopic dielectric-flux interface condition at the solute–solvent interface: we add a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is including the microscopic interface potential (static potential) in our model. We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water–co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. These and previous tests of the SLIC model indicate that it is a promising dielectric continuum model for accurate predictions in a wide range of conditions.

Recovery of isopropyl alcohol from waste solvent of a semiconductor plant.

PubMed

Lin, Sheng H; Wang, Chuen S

2004-01-30

An important waste solvent generated in the semiconductor manufacturing process was characterized by high isopropyl alcohol (IPA) concentration over 65%, other organic pollutants and strong color. Because of these characteristics, IPA recovery was deemed as a logic choice for tackling this waste solvent. In the present work, an integrated method consisting of air stripping in conjunction with condensation and packed activated carbon fiber (ACF) adsorption for dealing with this waste solvent. The air stripping with proper stripping temperature control was employed to remove IPA from the waste solvent and the IPA vapor in the gas mixture was condensed out in a side condenser. The residual IPA remaining in the gas mixture exiting the side condenser was efficiently removed in a packed ACF column. The air stripping with condensation was able to recover up to 93% of total IPA in the initial waste solvent. The residual IPA in the gas mixture, representing less than 3% of the initial IPA, was efficiently captured in the packed ACF column. Experimental tests were conducted to examine the performances of each unit and to identify the optimum operating conditions. Theoretical modeling of the experimental IPA breakthrough curves was also undertaken using a macroscopic model. The verified breakthrough model significantly facilitates the adsorption column design. The recovered IPA was found to be of high purity and could be considered for reuse. Copyright 2003 Elsevier B.V.

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

NASA Astrophysics Data System (ADS)

Molavi Tabrizi, Amirhossein; Goossens, Spencer; Mehdizadeh Rahimi, Ali; Knepley, Matthew; Bardhan, Jaydeep P.

2017-03-01

We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics (Gibbs free energies, entropies, and heat capacities) in numerous polar solvents. We are also able to predict ion solvation free energies in water-co-solvent mixtures over available concentration series. The first modification to the classical dielectric Poisson model is a perturbation of the macroscopic dielectric-flux interface condition at the solute-solvent interface: we add a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is including the microscopic interface potential (static potential) in our model. We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water-co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. These and previous tests of the SLIC model indicate that it is a promising dielectric continuum model for accurate predictions in a wide range of conditions.

Green synthesis of Ni-Nb oxide catalysts for low-temperature oxidative dehydrogenation of ethane.

PubMed

Zhu, Haibo; Rosenfeld, Devon C; Anjum, Dalaver H; Caps, Valérie; Basset, Jean-Marie

2015-04-13

The straightforward solid-state grinding of a mixture of Ni nitrate and Nb oxalate crystals led to, after mild calcination (T<400 °C), nanostructured Ni-Nb oxide composites. These new materials efficiently catalyzed the oxidative dehydrogenation (ODH) of ethane to ethylene at a relatively low temperature (T<300 °C). These catalysts appear to be much more stable than the corresponding composites prepared by other chemical methods; more than 90 % of their original intrinsic activity was retained after 50 h with time on-stream. Furthermore, the stability was much less affected by the Nb content than in composites prepared by classical "wet" syntheses. These materials, obtained in a solvent-free way, are thus promising green and sustainable alternatives to the current Ni-Nb candidates for the low-temperature ODH of ethane. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ethanol/water pulps from sugar cane straw and their biobleaching with xylanase from Bacillus pumilus.

PubMed

Moriya, Regina Y; Gonçalves, Adilson R; Duarte, Marta C T

2007-04-01

The influence of independent variables (temperature and time) on the cooking of sugar cane straw with ethanol/water mixtures was studied to determine operating conditions that obtain pulp with high cellulose contents and a low lignin content. An experimental 2(2) design was applied for temperatures of 185 and 215 degrees C, and time of 1 and 2.5 h with the ethanol/water mixture concentration and constant straw-to-solvent ratio. The system was scaled-up at 200 degrees C cooking temperature for 2 h with 50% ethanol-water concentration, and 1:10 (w/v) straw-to-solvent ratio to obtain a pulp with 3.14 cP viscosity, 58.09 kappa-number, and the chemical composition of the pulps were 3.2% pentosan and 31.5% lignin. Xylanase from Bacillus pumilus was then applied at a loading of 5-150 IU/g dry pulp in the sugar cane straw ethanol/water pulp at 50 degrees C for 2 and 20 h. To ethanol/water pulps, the best enzyme dosage was found to be 20 IU/g dry pulp at 20 h, and a high enzyme dosage of 150 IU/g dry pulp did not decrease the kappa-number of the pulp.

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

NASA Astrophysics Data System (ADS)

Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh

2011-12-01

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

Extraction and Determination of Trace Amounts of p-Coumaric Acid in Vinegar, Carrot Juice, and Seed Extract from Silybum marianum (L.) Gaertn.

PubMed

Khani, Rouhollah; Rostami, Zeinab; Bagherzade, Ghodsieh; Khojeh, Vahid

2018-03-01

In this study, for the monitoring and quantification of p-coumaric acid (p-CA) in vinegar, carrot juice, and seed extract from the plant species Silybum marianum (L.) Gaertn, an efficient and low-cost analytical method has been applied. For this purpose, a dispersive liquid-liquid microextraction (DLLME) method, followed by UV-Vis spectrophotometric detection, was used. To form a cloudy solution, a binary mixture containing ethanol as a disperser solvent and chloroform as an extraction solvent was rapidly injected by syringe into a sample solution containing p-CA. After centrifugation, dilution of the obtained organic phase was done with the proper amount of ethanol, and the phase was transferred into a micro cell for subsequent measurement. Some effective parameters for the DLLME method, such as the volume of disperser solvent and extraction solvent, pH, and salt concentration were inspected by a 24 full factorial central composite design using design Export Software. Under the optimized conditions, linearity was between 10 and 150 ng/mL, and the LOD was 2.3 ng/mL. The results of the proposed method were similar to the obtained results using a GC with flame-ionization detection method.

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

NASA Astrophysics Data System (ADS)

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

2016-07-01

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

Effect of solvent quality on aggregate structures of common surfactants.

PubMed

Hollamby, Martin J; Tabor, Rico; Mutch, Kevin J; Trickett, Kieran; Eastoe, Julian; Heenan, Richard K; Grillo, Isabelle

2008-11-04

Aggregate structures of two model surfactants, AOT and C12E5 are studied in pure solvents D2O, dioxane-d8 (d-diox) and cyclohexane-d12 (C6D12) as well as in formulated D2O/d-diox and d-diox/C6D12 mixtures. As such these solvents and mixtures span a wide and continuous range of polarities. Small-angle neutron scattering (SANS) has been employed to follow an evolution of the preferred aggregate curvature, from normal micelles in high polarity solvents, through to reversed micelles in low polarity media. SANS has also been used to elucidate the micellar size, shape as well as to highlight intermicellar interactions. The results shed new light on the nature of aggregation structures in intermediate polarity solvents, and point to a region of solvent quality (as characterized by Hildebrand Solubility Parameter, Snyder polarity parameter or dielectric constant) in which aggregation is not favored. Finally these observed trends in aggregation as a function of solvent quality are successfully used to predict the self-assembly behavior of C12E5 in a different solvent, hexane-d14 (C6D14).

Method for generating a crystalline .sup.99 MoO.sub.3 product and the isolation .sup.99m Tc compositions therefrom

DOEpatents

Bennett, Ralph G.; Christian, Jerry D.; Kirkham, Robert J.; Tranter, Troy J.

1998-01-01

An improved method for producing .sup.99m Tc compositions. .sup.100 Mo metal is irradiated with photons in a particle (electron) accelerator to produce .sup.99 Mo metal which is dissolved in a solvent. A solvated .sup.99 Mo product is then dried to generate a supply of .sup.99 MoO.sub.3 crystals. The crystals are thereafter heated at a temperature which will sublimate the crystals and form a gaseous mixture containing vaporized .sup.99m TcO.sub.3 and vaporized .sup.99m TcO.sub.2 but will not cause the production of vaporized .sup.99 MoO.sub.3. The mixture is then combined with an oxidizing gas to generate a gaseous stream containing vaporized .sup.99m Tc.sub.2 O.sub.7. Next, the gaseous stream is cooled to a temperature sufficient to convert the vaporized .sup.99m Tc.sub.2 O.sub.7 into a condensed .sup.99m Tc-containing product. The product has high purity levels resulting from the use of reduced temperature conditions and ultrafine crystalline .sup.99 MoO.sub.3 starting materials with segregated .sup.99m Tc compositions therein which avoid the production of vaporized .sup.99 MoO.sub.3 contaminants.

Apparatus for diffusion-gap thermal desalination

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

Lowenstein, Andrew

A thermal distillation apparatus including evaporation surfaces that are wetted with a solution, and from which at least some of the volatile solvent contained in the solution evaporates, condensers having an external surface in close proximity to, but not touching, a corresponding one of the one or more evaporation surfaces, and on which vapors of the solvent condense, releasing thermal energy that heats a flow of the solution moving upward within the condensers, spacers that prevent contact between the evaporating surfaces and the condensers, wherein spaces between the evaporating surfaces and the condensers are filled with a gaseous mixture composedmore » of solvent vapor and one or more non-condensable gases, and except for diffusion of the solvent vapor relative to the non-condensable gases, the gaseous mixture is stationary.« less

Transparent ceramics and methods of preparation thereof

DOEpatents

Hollingsworth, Joel P [Oakland, CA; Kuntz, Joshua D [Livermore, CA; Seeley, Zachary M [Pullman, WA; Soules, Thomas F [Livermore, CA

2011-10-18

According to one embodiment, a method for forming a transparent ceramic preform includes forming a suspension of oxide particles in a solvent, adding the suspension to a mold of a desired shape, and uniformly curing the suspension in the mold for forming a preform. The suspension includes a dispersant but does not include a gelling agent. In another embodiment, a method includes creating a mixture without a gelling agent, the mixture including: inorganic particles, a solvent, and a dispersant. The inorganic particles have a mean diameter of less than about 2000 nm. The method also includes agitating the mixture, adding the mixture to a mold, and curing the mixture in the mold at a temperature of less than about 80.degree. C. for forming a preform. Other methods for forming a transparent ceramic preform are also described according to several embodiments.

Sol-gel type synthesis of Bi.sub.2 (Sr,Ta.sub.2)O.sub.9 using an acetate based system

DOEpatents

Boyle, Timothy J.

1997-01-01

A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen.

Sol-gel type synthesis of Bi{sub 2}(Sr,Ta{sub 2})O{sub 9} using an acetate based system

DOEpatents

Boyle, T.J.

1997-11-04

A method of forming a layered-perovskite bismuth-strontium-tantalum oxide (SBT) ferroelectric material is performed by dissolving a bismuth compound in a first solvent to form a first solution, mixing a strontium compound and a tantalum compound to form a binary mixture, dissolving the binary mixture in a second solvent to form a second solution, mixing the first solution with the second solution to form a SBT precursor solution, evaporating the first and second solvents to form a SBT precursor material and subsequently sintering said SBT precursor material in the presence of oxygen. 6 figs.

Palladium(II)-Catalysed Aminocarbonylation of Terminal Alkynes for the Synthesis of 2-Ynamides: Addressing the Challenges of Solvents and Gas Mixtures.

PubMed

Hughes, N Louise; Brown, Clare L; Irwin, Andrew A; Cao, Qun; Muldoon, Mark J

2017-02-22

2-Ynamides can be synthesised through Pd II catalysed oxidative carbonylation, utilising low catalyst loadings. A variety of alkynes and amines can be used to afford 2-ynamides in high yields, whilst overcoming the drawbacks associated with previous oxidative methods, which rely on dangerous solvents and gas mixtures. The use of [NBu 4 ]I allows the utilisation of the industrially recommended solvent ethyl acetate. O 2 can be used as the terminal oxidant, and the catalyst can operate under safer conditions with low O 2 concentrations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Technology upgrades and exposure to chemical agents: results of the PPTP study in the footwear industry].

PubMed

Gianoli, Enrica; Brusoni, Daniela; Cornaggia, Nicoletta; Saretto, Gianni

2012-01-01

In the present work the chemical compositions of the products used in shoes manufacturing are reported. The data were collected over the period 2004-2007 in 156 shoe factories in Vigevano area during a study aiming the evaluation of safety conditions and occupational exposure to hazardous chemicals of the employees. The study was part of a regional project for "Occupational cancer prevention in the footwear industry". In the first phase of the study an information form on production cycle, products used and their composition was filled during preliminary audit. In the second phase of the study an in depth qualitative/quantitative evaluation of professional exposure was conducted in 13 selected shoe factories. Data analysis showed the increase in use of water-based adhesives at expense of solvent-based adhesives, the reduction to less than 3.5 weight %, and up to 1 weight %, of n-hexane concentration in solvent mixtures, the increase in use of products containing less hazardous ketones, esters, cyclohexane and heptane. Only in very few cases, products containing from 4 to 12 weight% of toluene were used. These data attest a positive trend in workers risks prevention in shoes industry.

Combined application of mixture experimental design and artificial neural networks in the solid dispersion development.

PubMed

Medarević, Djordje P; Kleinebudde, Peter; Djuriš, Jelena; Djurić, Zorica; Ibrić, Svetlana

2016-01-01

This study for the first time demonstrates combined application of mixture experimental design and artificial neural networks (ANNs) in the solid dispersions (SDs) development. Ternary carbamazepine-Soluplus®-poloxamer 188 SDs were prepared by solvent casting method to improve carbamazepine dissolution rate. The influence of the composition of prepared SDs on carbamazepine dissolution rate was evaluated using d-optimal mixture experimental design and multilayer perceptron ANNs. Physicochemical characterization proved the presence of the most stable carbamazepine polymorph III within the SD matrix. Ternary carbamazepine-Soluplus®-poloxamer 188 SDs significantly improved carbamazepine dissolution rate compared to pure drug. Models developed by ANNs and mixture experimental design well described the relationship between proportions of SD components and percentage of carbamazepine released after 10 (Q10) and 20 (Q20) min, wherein ANN model exhibit better predictability on test data set. Proportions of carbamazepine and poloxamer 188 exhibited the highest influence on carbamazepine release rate. The highest carbamazepine release rate was observed for SDs with the lowest proportions of carbamazepine and the highest proportions of poloxamer 188. ANNs and mixture experimental design can be used as powerful data modeling tools in the systematic development of SDs. Taking into account advantages and disadvantages of both techniques, their combined application should be encouraged.

SEPARATION OF METAL VALUES FROM NUCLEAR REACTOR

DOEpatents

Campbell, D.O.; Cathers, G.I.

1962-06-19

A method is given for separating beryllium fluoride and an alkali metal fluoride from a mixture containing same and rare earth fluorides. The method comprises contacting said mixture with a liquid hydrogen fluoride solvent containing no more than about 30 per cent water by weight and saturated with a fluoride salt characterized by its solubility in anhydrous hydrogen fluoride for a period of time sufficient to dissolve said beryllium fluoride in said solvent. (AEC)

Semiconductor liquid crystal composition and methods for making the same

DOEpatents

Alivisatos, A. Paul; Li, Liang-shi

2005-04-26

Semiconductor liquid crystal compositions and methods for making such compositions are disclosed. One embodiment of the invention is directed to a liquid crystal composition including a solvent and semiconductor particles in the solvent. The solvent and the semiconductor particles are in an effective amount in the liquid crystal composition to form a liquid crystal phase.

Polymer collapse in miscible good solvents is a generic phenomenon driven by preferential adsorption

PubMed Central

Mukherji, Debashish; Marques, Carlos M.; Kremer, Kurt

2014-01-01

Water and alcohol, such as methanol or ethanol, are miscible and, individually, good solvents for poly(N-isopropylacrylamide) (PNIPAm), but this polymer precipitates in water–alcohol mixtures. The intriguing behaviour of solvent mixtures that cannot dissolve a given polymer or a given protein, while the same macromolecule dissolves well in each of the cosolvents, is called cononsolvency. It is a widespread phenomenon, relevant for many formulation steps in the physicochemical and pharmaceutical industry, that is usually explained by invoking specific chemical details of the mixtures: as such, it has so far eluded any generic explanation. Here, by using a combination of simulations and theory, we present a simple and universal treatment that requires only the preferential interaction of one of the cosolvents with the polymer. The results show striking quantitative agreement with experiments and chemically specific simulations, opening a new perspective towards an operational understanding of macromolecular solubility. PMID:25216245

Solubility of Naproxen in Polyethylene Glycol 200 + Water Mixtures at Various Temperatures

PubMed Central

Panahi-Azar, Vahid; Soltanpour, Shahla; Martinez, Fleming; Jouyban, Abolghasem

2015-01-01

The solubility of naproxen in binary mixtures of polyethylene glycol 200 (PEG 200) + water at the temperature range from 298.0 K to 318.0 K were reported. The combinations of Jouyban-Acree model + van’t Hoff and Jouyban-Acree model + partial solubility parameters were used to predict the solubility of naproxen in PEG 200 + water mixtures at different temperatures. Combination of Jouyban-Acree model with van’t Hoff equation can be used to predict solubility in PEG 200 + water with only four solubility data in mono-solvents. The obtained solubility calculation errors vary from ~ 17 % up to 35 % depend on the number of required input data. Non-linear enthalpy-entropy compensation was found for naproxen in the investigated solvent system and the Jouyban−Acree model provides reasonably accurate mathematical descriptions of the thermodynamic data of naproxen in the investigated binary solvent systems. PMID:26664370

Processable Conducting Polyaniline, Carbon Nanotubes, Graphene and Their Composites

NASA Astrophysics Data System (ADS)

Wang, Kan

Good processability is often required for applications of conducting materials like polyaniline (PANI), carbon nanotubes (CNTs) and graphene. This can be achieved by either physical stabilization or chemical functionalization. Functionalization usually expands the possible applications for the conducting materials depending on the properties of the functional groups. Processable conducting materials can also be combined with other co-dissolving materials to prepare composites with desired chemical and physical properties. Polyanilines (PANI) doped with dodecylbenzenesulfonic acid (DBSA) are soluble in many organic solvents such as chloroform and toluene. Single wall carbon nanotubes (SWCNTs) can be dispersed into PANI/DBSA to form homogeneous solutions. PANI/DBSA functions as a conducting surfactant for SWCNTs. The mixture can be combined with two-parts polyurethanes that co-dissolve in the organic solvent to produce conducting polymer composites. The composite mixtures can be applied onto various substrates by simple spray-on methods to obtain transparent and conducting coatings. Graphene, a single layer of graphite, has drawn intense interest for its unique properties. Processable graphene has been produced in N-methyl-2-pyrrolidone (NMP) by a one-step solvothermal reduction of graphite oxide without the aid of any reducing reagent and/or surfactant. The as-synthesized graphene disperses well in a variety of organic solvents such as dimethylsulfoxide (DMSO), ethanol and tetrahydrogenfuran (THF). The conductivity of solvothermal reduced graphite oxide is comparable to hydrazine reduced graphite oxide. Attempts were made to create intrinsically conducting glue comparable to mussel adhesive protiens using polyaniline and graphene. Mussels can attach to a variety of substrates under water. Catechol residue in 3,4-dihydroxyphenylalanine (L-DOPA) is the key to the wet adhesion. Tyrosine and phosphoserine with primary alkyl amine groups also participate in adhesion. A novel water soluble synthetic mussel adhesive containing both catechol and amine groups are synthesized in a simple approach. A polyallylamine backbone is used to take the place of the polyamide chain. Catechol is appended to the backbone as the key cross-linking group. Compared to polyallyamine, poly[N-(3,4- dihydroxybenzylidene)allylamine] exhibits good adhesion under alkaline water due to moderate cross-linking. When exposed to cross-linkers, this synthetic mussel adhesive can form a hydrogel at a very low concentration. Various methods were tried to attach catechol group onto polyaniline and graphene to make synthetic conductive mussel adhesive. Although the chemistry proved to be successful, the material doesn't show great adhesion to selected substrates probably due the nature of the backbone and difficulties associated with its processability

EPA's science blog: "It All Starts with Science"; Article title: "EPA's Solvent Substitution Software Tool, PARIS III"

EPA Science Inventory

EPA's solvent substitution software tool, PARIS III is provided by the EPA for free, and can be effective and efficiently used to help environmentally-conscious individuals find better and greener solvent mixtures for many different common industrial processes. People can downlo...

Phase behaviour, interactions, and structural studies of (amines+ionic liquids) binary mixtures.

PubMed

Jacquemin, Johan; Bendová, Magdalena; Sedláková, Zuzana; Blesic, Marijana; Holbrey, John D; Mullan, Claire L; Youngs, Tristan G A; Pison, Laure; Wagner, Zdeněk; Aim, Karel; Costa Gomes, Margarida F; Hardacre, Christopher

2012-05-14

We present a study on the phase equilibrium behaviour of binary mixtures containing two 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}imide-based ionic liquids, [C(n)mim] [NTf(2)] (n=2 and 4), mixed with diethylamine or triethylamine as a function of temperature and composition using different experimental techniques. Based on this work, two systems showing an LCST and one system with a possible hourglass shape are measured. Their phase behaviours are then correlated and predicted by using Flory-Huggins equations and the UNIQUAC method implemented in Aspen. The potential of the COSMO-RS methodology to predict the phase equilibria was also tested for the binary systems studied. However, this methodology is unable to predict the trends obtained experimentally, limiting its use for systems involving amines in ionic liquids. The liquid-state structure of the binary mixture ([C(2)mim] [NTf(2)]+diethylamine) is also investigated by molecular dynamics simulation and neutron diffraction. Finally, the absorption of gaseous ethane by the ([C(2)mim][NTf(2)]+diethylamine) binary mixture is determined and compared with that observed in the pure solvents. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mixtures of glyme and aprotic-protic ionic liquids as electrolytes for energy storage devices

NASA Astrophysics Data System (ADS)

Stettner, T.; Huang, P.; Goktas, M.; Adelhelm, P.; Balducci, A.

2018-05-01

Ionic liquids (ILs) have been proven to be promising electrolytes for electrochemical energy storage devices such as supercapacitors and lithium ion batteries. In the last years, due to deficiency in storage of lithium on earth, innovative systems, such as sodium-based devices, attracted considerable attention. IL-based electrolytes have been proposed also as electrolytes for these devices. Nevertheless, in the case of these systems, the advantages and limits of IL-based electrolytes need to be further investigated. In this work we report an investigation about the chemical-physical properties of mixtures containing bis(2-methoxyethyl)ether diglyme (2G), which is presently considered as one of the most interesting solvents for sodium-based devices, and the ionic liquids 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) and 1-butylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PyrH4TFSI). The conductivities, viscosities, and densities of several mixtures of 2G and these ILs have been investigated. Furthermore, their impact on the electrochemical behaviour of activated carbon composite electrodes has been considered. The results of this investigation indicate that these mixtures are promising electrolytes for the realization of advanced sodium-based devices.

Fundamental Insights into the Dissolution and Precipitation of Cellulosic Biomass from Ionic Liquid Mixtures

NASA Astrophysics Data System (ADS)

Minnick, David L.

Lignocellulose is the most abundant biopolymer on earth making it a promising feedstock for the production of renewable chemicals and fuels. However, utilization of biomass remains a challenge as recalcitrance of cellulose and hemicellulose hinder separation and conversion of these carbohydrates. For instance, the complex inter- and intra- molecular hydrogen bonding network of cellulose renders it insoluble in nearly all aqueous and organic solvents. Alternatively, select ionic liquids (ILs) dissolve significant quantities. Through an ionic liquid mediated dissolution and precipitation process cellulose crystallinity is significantly reduced consequently enhancing subsequent chemical and biochemical reaction processes. Therefore, understanding the thermodynamics of ionic liquid - cellulose mixtures is imperative to developing an IL based biomass processing system. This dissertation illustrates solid-liquid phase equilibrium results for the dissolution and precipitation of cellulose in various IL/cosolvent, IL/antisolvent, and IL/mixed solvent systems with the ionic liquid 1-ethyl-3-methylimidazolium diethyl phosphate ([EMIm][DEP]). Molecular interactions between the ionic liquid, organic solvents, and cellulose are assessed by spectroscopic techniques including Kamlet-Taft solvatochromic analysis, FTIR, and NMR. Additionally, this dissertation discusses how preferential solvation of the IL cation and anion by co- and anti-solvents impact the ability of IL ions to interact with cellulose thus affecting the cellulose dissolution capacity of the various IL-solvent mixtures.

Effect of Solvent Choice on the Self-Assembly Properties of a Diphenylalanine Amphiphile Stabilized by an Ion Pair.

PubMed

Mayans, Enric; Ballano, Gema; Sendros, Javier; Font-Bardia, Merçè; Campos, J Lourdes; Puiggalí, Jordi; Cativiela, Carlos; Alemán, Carlos

2017-07-19

A diphenylalanine (FF) amphiphile blocked at the C terminus with a benzyl ester (OBzl) and stabilized at the N terminus with a trifluoroacetate (TFA) anion was synthetized and characterized. Aggregation of peptide molecules was studied by considering a peptide solution in an organic solvent and adding pure water, a KCl solution, or another organic solvent as co-solvent. The choice of the organic solvent and co-solvent and the solvent/co-solvent ratio allowed the mixture to be tuned by modulating the polarity, the ionic strength, and the peptide concentration. Differences in the properties of the media used to dissolve the peptides resulted in the formation of different self-assembled microstructures (e.g. fibers, branched-like structures, plates, and spherulites). Furthermore, crystals of TFA⋅FF-OBzl were obtained from the aqueous peptide solutions for X-ray diffraction analysis. The results revealed a hydrophilic core constituted by carboxylate (from TFA), ester, and amide groups, and the core was found to be surrounded by a hydrophobic crown with ten aromatic rings. This segregated organization explains the assemblies observed in the different solvent mixtures as a function of the environmental polarity, ionic strength, and peptide concentration. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlling the size and morphology of precipitated calcite particles by the selection of solvent composition

NASA Astrophysics Data System (ADS)

Konopacka-Łyskawa, Donata; Kościelska, Barbara; Karczewski, Jakub

2017-11-01

Precipitated calcium carbonate is used as an additive in the manufacture of many products. Particles with specific characteristics can be obtained by the selection of precipitation conditions, including temperature and the composition of solvent. In this work, calcium carbonate particles were obtained in the reaction of calcium hydroxide with carbon dioxide at 65 °C. Initial Ca(OH)2 suspensions were prepared in pure water and aqueous solutions of ethylene glycol or glycerol of the concentration range up to 20% (vol.). The course of reaction was monitored by conductivity measurements. Precipitated solids were analyzed by FTIR, XRD, SEM and the particles size distribution was determined by a laser diffraction method. The adsorption of ethylene glycol or glycerol on the surface of scalenohedral and rhombohedral calcite was testes by a normal-phase high-performance liquid chromatography. The addition of organic solvents changed the viscosity of reaction mixtures, the rate of carbon dioxide absorption and the solubility of inorganic components and therefore influence calcium carbonate precipitation conditions. All synthesized calcium carbonate products were in a calcite form. Scalenohedral calcite crystals were produced when water was a liquid phase, whereas addition of organic solvents resulted in the formation of rhombo-scalenohedral particles. The increase in organic compounds concentration resulted in the decrease of mean particles size from 2.4 μm to 1.7 μm in ethylene glycol solutions and to 1.4 μm in glycerol solutions. On the basis of adsorption tests, it was confirm that calcite surface interact stronger with glycerol than ethylene glycol. The interaction between scalenohedral calcite and used organic additives was higher in comparison to the pure rhombohedral form applied as a stationary phase.

Advanced solvent based methods for molecular characterization of soil organic matter by high-resolution mass spectrometry.

PubMed

Tfaily, Malak M; Chu, Rosalie K; Tolić, Nikola; Roscioli, Kristyn M; Anderton, Christopher R; Paša-Tolić, Ljiljana; Robinson, Errol W; Hess, Nancy J

2015-01-01

Soil organic matter (SOM), a complex, heterogeneous mixture of above and belowground plant litter and animal and microbial residues at various degrees of decomposition, is a key reservoir for carbon (C) and nutrient biogeochemical cycling in soil based ecosystems. A limited understanding of the molecular composition of SOM limits the ability to routinely decipher chemical processes within soil and accurately predict how terrestrial carbon fluxes will respond to changing climatic conditions and land use. To elucidate the molecular-level structure of SOM, we selectively extracted a broad range of intact SOM compounds by a combination of different organic solvents from soils with a wide range of C content. Our use of electrospray ionization (ESI) coupled with Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) and a suite of solvents with varying polarity significantly expands the inventory of the types of organic molecules present in soils. Specifically, we found that hexane is selective for lipid-like compounds with very low O/C ratios (<0.1); water (H2O) was selective for carbohydrates with high O/C ratios; acetonitrile (ACN) preferentially extracts lignin, condensed structures, and tannin polyphenolic compounds with O/C > 0.5; methanol (MeOH) has higher selectivity toward compounds characterized with low O/C < 0.5; and hexane, MeOH, ACN, and H2O solvents increase the number and types of organic molecules extracted from soil for a broader range of chemically diverse soil types. Our study of SOM molecules by ESI FTICR MS revealed new insight into the molecular-level complexity of organics contained in soils. We present the first comparative study of the molecular composition of SOM from different ecosystems using ultra high-resolution mass spectrometry.

Quality improvement of melt extruded laminar systems using mixture design.

PubMed

Hasa, D; Perissutti, B; Campisi, B; Grassi, M; Grabnar, I; Golob, S; Mian, M; Voinovich, D

2015-07-30

This study investigates the application of melt extrusion for the development of an oral retard formulation with a precise drug release over time. Since adjusting the formulation appears to be of the utmost importance in achieving the desired drug release patterns, different formulations of laminar extrudates were prepared according to the principles of Experimental Design, using a design for mixtures to assess the influence of formulation composition on the in vitro drug release from the extrudates after 1h and after 8h. The effect of each component on the two response variables was also studied. Ternary mixtures of theophylline (model drug), monohydrate lactose and microcrystalline wax (as thermoplastic binder) were extruded in a lab scale vertical ram extruder in absence of solvents at a temperature below the melting point of the binder (so that the crystalline state of the drug could be maintained), through a rectangular die to obtain suitable laminar systems. Thanks to the desirability approach and a reliability study for ensuring the quality of the formulation, a very restricted optimal zone was defined within the experimental domain. Among the mixture components, the variation of microcrystalline wax content played the most significant role in overall influence on the in vitro drug release. The formulation theophylline:lactose:wax, 57:14:29 (by weight), selected based on the desirability zone, was subsequently used for in vivo studies. The plasma profile, obtained after oral administration of the laminar extruded system in hard gelatine capsules, revealed the typical trend of an oral retard formulation. The application of the mixture experimental design associated to a desirability function permitted to optimize the extruded system and to determine the composition space that ensures final product quality. Copyright © 2015 Elsevier B.V. All rights reserved.

Solvent effect on the synthesis of clarithromycin: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Duran, Dilek; Aviyente, Viktorya; Baysal, Canan

2004-02-01

Clarithromycin (6- O-methylerythromycin A) is a 14-membered macrolide antibiotic which is active in vitro against clinically important gram-positive and gram-negative bacteria. The selectivity of the methylation of the C-6 OH group is studied on erythromycin A derivatives. To understand the effect of the solvent on the methylation process, detailed molecular dynamics (MD) simulations are performed in pure DMSO, pure THF and DMSO:THF (1:1) mixture by using the anions at the C-6, C-11 and C-12 positions of 2',4''-[ O-bis(TMS)]erythromycin A 9-[ O-(dimethylthexylsilyl)oxime] under the assumption that the anions are stable on the sub-nanosecond time scale. The conformations of the anions are not affected by the presence of the solvent mixture. The radial distribution functions are computed for the distribution of different solvent molecules around the `O-' of the anions. At distances shorter than 5 Å, DMSO molecules are found to cluster around the C-11 anion, whereas the anion at the C-12 position is surrounded by the THF molecules. The anion at the C-6 position is not blocked by the solvent molecules. The results are consistent with the experimental finding that the methylation yield at the latter position is increased in the presence of a DMSO:THF (1:1) solvent mixture. Thus, the effect of the solvent in enhancing the yield during the synthesis is not by changing the conformational properties of the anions, but rather by creating a suitable environment for methylation at the C-6 position.

Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture

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

Kasai, Yukako; Yoshida, Norio, E-mail: noriwo@chem.kyushu-univ.jp; Nakano, Haruyuki

2015-05-28

The co-solvent effect on the proton transfer reaction of glycine in a water–acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water–acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is moremore » stable than the neutral form. The reaction free energy is −10.6 kcal mol{sup −1}. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol{sup −1}. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.« less

Sequential extraction protocol for organic matter from soils and sediments using high resolution mass spectrometry

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

Tfaily, Malak M.; Chu, Rosalie K.; Toyoda, Jason

A vast number of organic compounds are present in soil organic matter (SOM) and play an important role in the terrestrial carbon cycle, facilitate interactions between organisms, and represent a sink for atmospheric CO2. The diversity of different SOM compounds and their molecular characteristics is a function of the organic source material and biogeochemical history. By understanding how SOM composition changes with sources and the processes by which it is biogeochemically altered in different terrestrial ecosystems, it may be possible to predict nutrient and carbon cycling, response to system perturbations, and impact of climate change will have on SOM composition.more » In this study, a sequential chemical extraction procedure was developed to reveal the diversity of organic matter (OM) in different ecosystems and was compared to the previously published protocol using parallel solvent extraction (PSE). We compared six extraction methods using three sample types, peat soil, spruce forest soil and river sediment, so as to select the best method for extracting a representative fraction of organic matter from soils and sediments from a wide range of ecosystems. We estimated the extraction yield of dissolved organic carbon (DOC) by total organic carbon analysis, and measured the composition of extracted OM using high resolution mass spectrometry. This study showed that OM composition depends primarily on soil and sediment characteristics. Two sequential extraction protocols, progressing from polar to non-polar solvents, were found to provide the highest number and diversity of organic compounds extracted from the soil and sediments. Water (H2O) is the first solvent used for both protocols followed by either co-extraction with methanol-chloroform (MeOH-CHCl3) mixture, or acetonitrile (ACN) and CHCl3 sequentially. The sequential extraction protocol developed in this study offers improved sensitivity, and requires less sample compared to the PSE workflow where a new sample is used for each solvent type. Furthermore, a comparison of SOM composition from the different sample types revealed that our sequential protocol allows for ecosystem comparisons based on the diversity of compounds present, which in turn could provide new insights about source and processing of organic compounds in different soil and sediment types.« less

Sequential extraction protocol for organic matter from soils and sediments using high resolution mass spectrometry.

PubMed

Tfaily, Malak M; Chu, Rosalie K; Toyoda, Jason; Tolić, Nikola; Robinson, Errol W; Paša-Tolić, Ljiljana; Hess, Nancy J

2017-06-15

A vast number of organic compounds are present in soil organic matter (SOM) and play an important role in the terrestrial carbon cycle, facilitate interactions between organisms, and represent a sink for atmospheric CO 2 . The diversity of different SOM compounds and their molecular characteristics is a function of the organic source material and biogeochemical history. By understanding how SOM composition changes with sources and the processes by which it is biogeochemically altered in different terrestrial ecosystems, it may be possible to predict nutrient and carbon cycling, response to system perturbations, and impact of climate change will have on SOM composition. In this study, a sequential chemical extraction procedure was developed to reveal the diversity of organic matter (OM) in different ecosystems and was compared to the previously published protocol using parallel solvent extraction (PSE). We compared six extraction methods using three sample types, peat soil, spruce forest soil and river sediment, so as to select the best method for extracting a representative fraction of organic matter from soils and sediments from a wide range of ecosystems. We estimated the extraction yield of dissolved organic carbon (DOC) by total organic carbon analysis, and measured the composition of extracted OM using high resolution mass spectrometry. This study showed that OM composition depends primarily on soil and sediment characteristics. Two sequential extraction protocols, progressing from polar to non-polar solvents, were found to provide the highest number and diversity of organic compounds extracted from the soil and sediments. Water (H 2 O) is the first solvent used for both protocols followed by either co-extraction with methanol-chloroform (MeOH-CHCl 3 ) mixture, or acetonitrile (ACN) and CHCl 3 sequentially. The sequential extraction protocol developed in this study offers improved sensitivity, and requires less sample compared to the PSE workflow where a new sample is used for each solvent type. Furthermore, a comparison of SOM composition from the different sample types revealed that our sequential protocol allows for ecosystem comparisons based on the diversity of compounds present, which in turn could provide new insights about source and processing of organic compounds in different soil and sediment types. Copyright © 2017 Elsevier B.V. All rights reserved.

Stable Isotope-Assisted Evaluation of Different Extraction Solvents for Untargeted Metabolomics of Plants

PubMed Central

Doppler, Maria; Kluger, Bernhard; Bueschl, Christoph; Schneider, Christina; Krska, Rudolf; Delcambre, Sylvie; Hiller, Karsten; Lemmens, Marc; Schuhmacher, Rainer

2016-01-01

The evaluation of extraction protocols for untargeted metabolomics approaches is still difficult. We have applied a novel stable isotope-assisted workflow for untargeted LC-HRMS-based plant metabolomics , which allows for the first time every detected feature to be considered for method evaluation. The efficiency and complementarity of commonly used extraction solvents, namely 1 + 3 (v/v) mixtures of water and selected organic solvents (methanol, acetonitrile or methanol/acetonitrile 1 + 1 (v/v)), with and without the addition of 0.1% (v/v) formic acid were compared. Four different wheat organs were sampled, extracted and analysed by LC-HRMS. Data evaluation was performed with the in-house-developed MetExtract II software and R. With all tested solvents a total of 871 metabolites were extracted in ear, 785 in stem, 733 in leaf and 517 in root samples, respectively. Between 48% (stem) and 57% (ear) of the metabolites detected in a particular organ were found with all extraction mixtures, and 127 of 996 metabolites were consistently shared between all extraction agent/organ combinations. In aqueous methanol, acidification with formic acid led to pronounced pH dependency regarding the precision of metabolite abundance and the number of detectable metabolites, whereas extracts of acetonitrile-containing mixtures were less affected. Moreover, methanol and acetonitrile have been found to be complementary with respect to extraction efficiency. Interestingly, the beneficial properties of both solvents can be combined by the use of a water-methanol-acetonitrile mixture for global metabolite extraction instead of aqueous methanol or aqueous acetonitrile alone. PMID:27367667

Density, Viscosity and Surface Tension of Binary Mixtures of 1-Butyl-1-Methylpyrrolidinium Tricyanomethanide with Benzothiophene.

PubMed

Domańska, Urszula; Królikowska, Marta; Walczak, Klaudia

2014-01-01

The effects of temperature and composition on the density and viscosity of pure benzothiophene and ionic liquid (IL), and those of the binary mixtures containing the IL 1-butyl-1-methylpyrrolidynium tricyanomethanide ([BMPYR][TCM] + benzothiophene), are reported at six temperatures (308.15, 318.15, 328.15, 338.15, 348.15 and 358.15) K and ambient pressure. The temperature dependences of the density and viscosity were represented by an empirical second-order polynomial and by the Vogel-Fucher-Tammann equation, respectively. The density and viscosity variations with compositions were described by polynomials. Excess molar volumes and viscosity deviations were calculated and correlated by Redlich-Kister polynomial expansions. The surface tensions of benzothiophene, pure IL and binary mixtures of ([BMPYR][TCM] + benzothiophene) were measured at atmospheric pressure at four temperatures (308.15, 318.15, 328.15 and 338.15) K. The surface tension deviations were calculated and correlated by a Redlich-Kister polynomial expansion. The temperature dependence of the interfacial tension was used to evaluate the surface entropy, the surface enthalpy, the critical temperature, the surface energy and the parachor for pure IL. These measurements have been provided to complete information of the influence of temperature and composition on physicochemical properties for the selected IL, which was chosen as a possible new entrainer in the separation of sulfur compounds from fuels. A qualitative analysis on these quantities in terms of molecular interactions is reported. The obtained results indicate that IL interactions with benzothiophene are strongly dependent on packing effects and hydrogen bonding of this IL with the polar solvent.

Lipid and Lipid-Polymer Mixtures at an Interface

NASA Astrophysics Data System (ADS)

Kim, Joon Heon; Kim, Mahn Won

2000-03-01

The surface pressure (Π) and surface area/molecule (A) isotherms of a mixture of DMPC (DL-α-phosphatidylcholine,Dimyristoyl) and PEG-DMPE (1,2-Diacyl-sn-Glycero-3-Phosphoethanolamine-N-[Poly(ethylene glycol)5000]) system were measured at various compositions by the Langmuir surface balance technique at an air/water interface. In the range where the surface pressure is less than about 8 dynes/cm, a PEG polymer chain of PEG-DMPE molecules remains on the surface and the isotherm can be explained by the 2-D power law behavior of chains in a good solvent. In the range above 8 dynes/cm, a part of the PEG polymer segment is dissolved into the water phase, and the surface pressure can be explained as the sum of the 2-D component and 3-D component. Furthermore, the mixing energy is negative, which indicates an attractive interaction between DMPC and PEG-DMPE.

Lipid and lipid-polymer mixtures at an interface

NASA Astrophysics Data System (ADS)

Kim, Joon Heon; Kim, Mahn Won

2000-06-01

The surface pressure (Π) and surface area/molecule (A) isotherms of a mixture of DMPC (DL-α-phosphatidylcholine, Dimyristoyl) and PEG-DMPE (1,2-Diacyl-sn-Glycero-3-Phosphoethanolamine-N-[Poly(ethylene glycol)5000]) system were measured at various compositions by the Langmuir surface balance technique at an air/water interface. In the range where the surface pressure is less than about 8 dynes/cm, a PEG polymer chain of PEG-DMPE molecules remains on the surface and the isotherm can be explained by the 2-D power law behavior of chains in a good solvent. In the range above 8 dynes/cm, a part of the PEG polymer segment is dissolved into the water phase, and the surface pressure can be explained as the sum of the 2-D component and 3-D component. Furthermore, the mixing energy is negative, which indicates an attractive interaction between DMPC and PEG-DMPE. .

New hydrolytically stable solvent for Am/Eu separation in acidic media

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

Smirnov, I.V.; Babain, V.A.; Chirkov, A.V.

Americium and europium extraction by synergistic mixture of 2,6-bis(1-aryl-1H-tetrazol-5-yl)pyridines (ATP) - chlorinated cobalt dicarbollide (CCD) in polar diluent s from HNO{sub 3} media was studied. Meta-nitro-benzo-trifluoride, phenyl-tri-fluoro-methyl sulfone and 1,2-dichloroethane were used as diluents. The effect of diluent, composition of aqueous phase and substituent nature in aryl ring of ATPs on the extraction efficiency and selectivity of americium and europium separation was investigated. At the optimal ratio of nATP:CCD 1:1 the Am - Eu separation factor exceeded 90. Extraction of {sup 85}Sr, {sup 137}Cs and {sup 133}Ba was investigated and it was found that the mixture nATP-CCD provided the separationmore » of Sr /Ba pair with a factor of 35. High resistance of 2,6-bisaryltetrazolyl pyridines to the action of nitric acid was demonstrated. (authors)« less

Impact of solvent mixture on iron nanoparticles generated by laser ablation

NASA Astrophysics Data System (ADS)

Chakif, M.; Prymak, O.; Slota, M.; Heintze, E.; Gurevich, E. L.; Esen, C.; Bogani, L.; Epple, M.; Ostendorf, A.

2014-03-01

The present work reveals the structural and magnetic properties of iron oxide (FexOy) nanoparticles (NPs) prepared by femtosecond laser ablation. The FexOy-NPs were produced in solutions consisting of different ratios of water and acetone. Laser ablation in water yields agglomerates and that in acetone yields chain structures whereas that in water/acetone show a mixture of both. We observe significant fabrication dependent properties such as different crystallinities and magnetic behaviors. The structural characterization shows a change from iron (Fe) to a FexOy state of the NPs which depends on the solution composition. Furthermore, transmission electron microscopy measurements exhibit a broad particle size distribution in all samples but with significant differences in the mean sizes. Using magnetic measurements we show that nanoparticles fabricated in pure acetone have lower coercive fields which come along with a smaller mean particle size and therefore increasing superparamagnetic behavior.

Statistical Modeling of Zr/Hf Extraction using TBP-D2EHPA Mixtures

NASA Astrophysics Data System (ADS)

Rezaeinejhad Jirandehi, Vahid; Haghshenas Fatmehsari, Davoud; Firoozi, Sadegh; Taghizadeh, Mohammad; Keshavarz Alamdari, Eskandar

2012-12-01

In the present work, response surface methodology was employed for the study and prediction of Zr/Hf extraction curves in a solvent extraction system using D2EHPA-TBP mixtures. The effect of change in the levels of temperature, nitric acid concentration, and TBP/D2EHPA ratio (T/D) on the Zr/Hf extraction/separation was studied by the use of central composite design. The results showed a statistically significant effect of T/D, nitric acid concentration, and temperature on the extraction percentage of Zr and Hf. In the case of Zr, a statistically significant interaction was found between T/D and nitric acid, whereas for Hf, both interactive terms between temperature and T/D and nitric acid were significant. Additionally, the extraction curves were profitably predicted applying the developed statistical regression equations; this approach is faster and more economical compared with experimentally obtained curves.

Extraction processes and solvents for recovery of cesium, strontium, rare earth elements, technetium and actinides from liquid radioactive waste

DOEpatents

Zaitsev, Boris N.; Esimantovskiy, Vyacheslav M.; Lazarev, Leonard N.; Dzekun, Evgeniy G.; Romanovskiy, Valeriy N.; Todd, Terry A.; Brewer, Ken N.; Herbst, Ronald S.; Law, Jack D.

2001-01-01

Cesium and strontium are extracted from aqueous acidic radioactive waste containing rare earth elements, technetium and actinides, by contacting the waste with a composition of a complex organoboron compound and polyethylene glycol in an organofluorine diluent mixture. In a preferred embodiment the complex organoboron compound is chlorinated cobalt dicarbollide, the polyethylene glycol has the formula RC.sub.6 H.sub.4 (OCH.sub.2 CH.sub.2).sub.n OH, and the organofluorine diluent is a mixture of bis-tetrafluoropropyl ether of diethylene glycol with at least one of bis-tetrafluoropropyl ether of ethylene glycol and bis-tetrafluoropropyl formal. The rare earths, technetium and the actinides (especially uranium, plutonium and americium), are extracted from the aqueous phase using a phosphine oxide in a hydrocarbon diluent, and reextracted from the resulting organic phase into an aqueous phase by using a suitable strip reagent.

Method for selectively preparing evoglucosenone (LGO) and other anhydrosugars from biomass in polar aprotic solvents

DOEpatents

Huber, George W.; Cao, Fei; Dumesic, James A.; Schwartz, Thomas J.

2016-06-28

A method to produce 5-hydroxymethylfurfural (HMF) is described in which a reactant including cellulose, lignocellulose, or a combination thereof, in a reaction mixture of a polar, aprotic solvent and an acid is reacted for a time, at a temperature, and at a hydrogen ion concentration wherein at least a portion of the cellulose or lignocellulose present in the reactant is converted to HMF. The reaction mixture is initially substantially devoid of water. As the reaction proceeds, dehydration of intermediates causes the water concentration in the reaction mixture to rise to no more than about 2.0 wt % water.

Method for selectively preparing 5-hydroxymethylfurfual (HMF) from biomass in polar aprotic solvents

DOEpatents

Dumesic, James A.; Huber, George W.; Weingarten, Ronen

2016-01-26

A method to produce 5-hydroxymethylfurfural (HMF) is described in which a reactant including cellulose, lignocellulose, or a combination thereof, in a reaction mixture of a polar, aprotic solvent and an acid is reacted for a time, at a temperature, and at a hydrogen ion concentration wherein at least a portion of the cellulose or lignocellulose present in the reactant is converted to HMF. The reaction mixture is initially substantially devoid of water. As the reaction proceeds, dehydration of intermediates causes the water concentration in the reaction mixture to rise to no more than about 0.2 wt % water.

Preparation and mechanical properties of carbon fiber reinforced hydroxyapatite/polylactide biocomposites.

PubMed

Shen, Lie; Yang, Hui; Ying, Jia; Qiao, Fei; Peng, Mao

2009-11-01

A novel biocomposite of carbon fiber (CF) reinforced hydroxyapatite (HA)/polylactide (PLA) was prepared by hot pressing a prepreg which consisting of PLA, HA and CF. The prepreg was manufactured by solvent impregnation process. Polymer resin PLA dissolved with chloroform was mixed with HA. After reinforcement CF bundle was impregnated in the mixture, the solvent was dried completely and subsequently hot-pressed uniaxially under a pressure of 40 MPa at 170 degrees C for 20 min. A study was carried out to investigate change in mechanical properties of CF/HA/PLA composites before and after degradation in vitro. The composites have excellent mechanical properties. A peak showed in flexural strength, flexural modulus and shear strength aspects, reaching up 430 MPa, 22 GPa, 212 MPa, respectively, as the HA content increased. Degraded in vitro for 3 months, the flexural strength and flexural modulus of the CF/HA/PLA fell 13.2% and 5.4%, respectively, while the shear strength of the CF/HA/PLA composites remains at the 190 MPa level. The SEM photos showed that there were gaps between the PLA matrix and CF after degradation. Water uptake increased to 5%, but the mass loss rate was only 1.6%. The pH values of the PBS dropped less than 0.1. That's because the alkaline of HA neutralize the acid degrades from PLA, which can prevent the body from the acidity harm.

Improved solubility of DNA in recyclable and reusable bio-based deep eutectic solvents with long-term structural and chemical stability.

PubMed

Mondal, Dibyendu; Sharma, Mukesh; Mukesh, Chandrakant; Gupta, Vishal; Prasad, Kamalesh

2013-10-25

The solubility of DNA in bio-based deep eutectic solvents (DESs) consisting of mixtures of choline chloride with levulinic acid, glycerol, ethylene glycol, sorbitol and resorcinol was investigated. The macromolecule was found to be soluble and chemically and structurally stable in DESs consisting of mixtures containing glycerol and ethylene glycol. Furthermore recyclability of the DESs was demonstrated over three consecutive reuses in DNA dissolution.

Corrosion inhibiting organic coatings

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

Sasson, E.

1984-10-16

A corrosion inhibiting coating comprises a mixture of waxes, petroleum jelly, a hardener and a solvent. In particular, a corrosion inhibiting coating comprises candelilla wax, carnauba wax, microcrystalline waxes, white petrolatum, an oleoresin, lanolin and a solvent.

L-cysteine-derived ambidextrous gelators of aromatic solvents and ethanol/water mixtures.

PubMed

Pal, Amrita; Dey, Joykrishna

2013-02-19

A series of L-cysteine-derived double hydrocarbon chain amphiphilic gelators L-(3-alkyl-carbamoylsulfanyl)-2-(3-alkylurido)propionic acid with different hydrocarbon chain lengths (C6-C16) was designed and synthesized. These gelators efficiently gelate only aromatic solvents. The gelation ability increased with the increase of chain length up to C14, but then it dropped with further increase of chain length. The C12 and C14 derivatives also gelled ethanol/water mixtures. The gels were characterized by a number of methods, including FT-IR, NMR, and XRD spectroscopy, electron microscopy, and rheology. The amphiphiles were observed to form either flat lamellar or ribbonlike aggregates in aromatic solvents as well as in ethanol/water mixtures. The gelation in all the solvents employed was observed to be thermoreversible. The gel-to-sol transition temperature as well as mechanical strength of the organogels were observed to increase with the hydrocarbon chain length. Both types of gels of C8-C16 amphiphiles have gel-to-sol transition temperatures above the physiological temperature (310 K). FT-IR and variable temperature (1)H NMR measurements suggested that van der Waals interactions have major contribution in the gelation process. The gel-to-sol transition temperature and mechanical strength of the organogels in ethanol/water mixtures was observed to be higher than those of benzene organogel.

Preparation of B-trichloroborazine

NASA Technical Reports Server (NTRS)

Riccitiello, Salvatore R.; Hsu, Ming-Ta S.; Chen, Timothy S.

1987-01-01

The present invention relates to a method of preparing B-trichloroborazine. Generally, the method includes the combination of gaseous boron trichloride in an anhydrous aprotic organic solvent followed by addition of excess gaseous ammonia at ambient temperature or below. The reaction mixture is heated to about 100 to 140 C followed by cooling, removal of the solid ammonium chloride at ambient temperature, distillation of the solvent under vacuum if necessary at a temperature of up to about 112 C, and recovery of the B-trichloroborazine. Solvents include toluene, benzene, xylene, chlorinated hydrocarbons, chlorinated aromatic compounds, or mixtures thereof. Toluene is a preferred solvent. The process provides a convenient synthesis of a material which often decomposes on standing. B-trichloroborazine is useful in a number of chemical reactions, and particularly in the formation of high temperature inorganic polymers and polymer precursors.

Application of chiral critical clusters to assymetric synthesis

DOEpatents

Ferrieri, Richard A.

2002-01-01

Disclosed is a composition, a method of making and a method of using critical clusters for asymmetric synthesis using substantially optically-pure chiral solvent molecules in a supercritical fluid. The solvent molecules are capable of forming a multipoint hydrogen bonded solvate as they encage at least one solute molecule. The encaged solute molecule is capable of reacting to form an optically active chiral center. In another aspect, there is disclosed a method of directing the position of bonding between a solute molecule and a ligand involving encaging the solute molecule and the ligand with polar solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to change electric charge distribution in the solute molecule. In yet another aspect, disclosed is a method of making pharmaceutical compounds involving encaging a solute molecule, which is capable of forming a chiral center, and a ligand with polar solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to change electric charge distribution of the solute molecule. The solute molecule and ligand are then reacted whereby the ligand bonds to the solute molecule forming a chiral center. Also disclosed is a method for racemic resolution using critical clusters involving encaging racemic mixtures of solute molecules with substantially optically-pure chiral solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to form critical clusters. The solvent molecules are capable of multipoint hydrogen bonding with the solute molecules. The encaged solute molecules are then nonenzymatically reacted to enhance the optical purity of the solute molecules.

Morphometric approach to thermodynamic quantities of solvation of complex molecules: Extension to multicomponent solvent

NASA Astrophysics Data System (ADS)

Kodama, Ryota; Roth, Roland; Harano, Yuichi; Kinoshita, Masahiro

2011-07-01

The morphometric approach (MA) is a powerful tool for calculating a solvation free energy (SFE) and related quantities of solvation thermodynamics of complex molecules. Here, we extend it to a solvent consisting of m components. In the integral equation theories, the SFE is expressed as the sum of m terms each of which comprises solute-component j correlation functions (j = 1, …, m). The MA is applied to each term in a formally separate manner: The term is expressed as a linear combination of the four geometric measures, excluded volume, solvent-accessible surface area, and integrated mean and Gaussian curvatures of the accessible surface, which are calculated for component j. The total number of the geometric measures or the coefficients in the linear combinations is 4m. The coefficients are determined in simple geometries, i.e., for spherical solutes with various diameters in the same multicomponent solvent. The SFE of the spherical solutes are calculated using the radial-symmetric integral equation theory. The extended version of the MA is illustrated for a protein modeled as a set of fused hard spheres immersed in a binary mixture of hard spheres. Several mixtures of different molecular-diameter ratios and compositions and 30 structures of the protein with a variety of radii of gyration are considered for the illustration purpose. The SFE calculated by the MA is compared with that by the direct application of the three-dimensional integral equation theory (3D-IET) to the protein. The deviations of the MA values from the 3D-IET values are less than 1.5%. The computation time required is over four orders of magnitude shorter than that in the 3D-IET. The MA thus developed is expected to be best suited to analyses concerning the effects of cosolvents such as urea on the structural stability of a protein.

Solvent/Non-Solvent Sintering To Make Microsphere Scaffolds

NASA Technical Reports Server (NTRS)

Laurencin, Cato T.; Brown, Justin L.; Nair, Lakshmi

2011-01-01

A solvent/non-solvent sintering technique has been devised for joining polymeric microspheres to make porous matrices for use as drug-delivery devices or scaffolds that could be seeded with cells for growing tissues. Unlike traditional sintering at elevated temperature and pressure, this technique is practiced at room temperature and pressure and, therefore, does not cause thermal degradation of any drug, protein, or other biochemical with which the microspheres might be loaded to impart properties desired in a specific application. Also, properties of scaffolds made by this technique are more reproducible than are properties of comparable scaffolds made by traditional sintering. The technique involves the use of two miscible organic liquids: one that is and one that is not a solvent for the affected polymer. The polymeric microspheres are placed in a mold having the size and shape of the desired scaffold, then the solvent/non-solvent mixture is poured into the mold to fill the void volume between the microspheres, then the liquid mixture is allowed to evaporate. Some of the properties of the resulting scaffold can be tailored through choice of the proportions of the liquids and the diameter of the microspheres.

Optimization of an extraction protocol for organic matter from soils and sediments using high resolution mass spectrometry: selectivity and biases

NASA Astrophysics Data System (ADS)

Chu, R. K.; Tfaily, M. M.; Tolic, N.; Kyle, J. E.; Robinson, E. R.; Hess, N. J.; Paša-Tolić, L.

2015-12-01

Soil organic matter (SOM) is a complex mixture of above and belowground plant litter and microbial residues, and is a key reservoir for carbon (C) and nutrient biogeochemical cycling in different ecosystems. A limited understanding of the molecular composition of SOM prohibits the ability to routinely decipher chemical processes within soil and predict how terrestrial C fluxes will response to changing climatic conditions. Here, we present that the choice of solvent can be used to selectively extract different compositional fractions from SOM to either target a specific class of compounds or gain a better understanding of the entire composition of the soil sample using 12T Fourier transform ion cyclotron resonance mass spectrometry. Specifically, we found that hexane and chloroform were selective for lipid-like compounds with very low O:C ratios; water was selective for carbohydrates with high O:C ratios; acetonitrile preferentially extracts lignin, condensed structures, and tannin polyphenolic compounds with O:C > 0.5; methanol has higher selectivity towards lignin and lipid compounds characterized with relatively low O:C < 0.5. Hexane, chloroform, methanol, acetonitrile and water increase the number and types of organic molecules extracted from soil for a broader range of chemically diverse soil types. Since each solvent extracts a selective group of compounds, using a suite of solvents with varying polarity for analysis results in more comprehensive representation of the diversity of organic molecules present in soil and a better representation of the whole spectrum of available substrates for microorganisms. Moreover, we have developed a sequential extraction protocol that permits sampling diverse classes of organic compounds while minimizing ionization competition during ESI while increasing sample throughput and decreasing sample volume. This allowed us to hypothesize about possible chemical reactions relating classes of organic molecules that reflect abiotic and biotic processes impacting SOM composition.

Laser Raman spectroscopy of the effect of solvent on the low-frequency oscillations of organic molecules

NASA Astrophysics Data System (ADS)

Brandt, N. N.; Chikishev, A. Yu.; Dolgovskii, V. I.; Lebedenko, S. I.

2007-09-01

The effect of solvent on low-frequency oscillations is studied using an example of the 1,1,2,2-tetrachloroethane (TCE) and 1,1,2,2-tetrabromoethane (TBE) molecules, which exhibit torsional oscillations in the terahertz range. Dimethylsulfoxide (DMSO) and carbon tetrachloride (CTC) are used as solvents. It is demonstrated that a decrease in the concentration of the substance under study in the TBE/CTC, TCE/DMSO, and TCE/CTC mixtures leads to a frequency shift of the low-frequency oscillation. The shift is not observed in the TBE/DMSO mixture but a decrease in the TBE concentration causes significant broadening of the low-frequency line.

Physico-chemical properties of binary mixtures of aliphatic and aromatic solvents at 313 K on acoustical data

NASA Astrophysics Data System (ADS)

Dahire, S. L.; Morey, Y. C.; Agrawal, P. S.

2015-12-01

Density (ρ), viscosity (η), and ultrasonic velocity ( U) of binary mixtures of aliphatic solvents like dimethylformamide (DMF) and dimethylsulfoxide (DMSO) with aromatic solvents viz. chlorobenzene (CB), bromobenzene (BB), and nitrobenzene (NB) have been determined at 313 K. These parameters were used to calculate the adiabatic compressibility (β), intermolecular free length ( L f), molar volume ( V m), and acoustic impedance ( Z). From the experimental data excess molar volume ( V m E ), excess intermolecular free length ( L f E )), excess adiabatic compressibility (βE), and excess acoustic impedance ( Z E) have been computed. The excess values were correlated using Redlich-Kister polynomial equation to obtain their coefficients and standard deviations (σ).

Modelling of ceramide interactions with porous graphite carbon in non-aqueous liquid chromatography.

PubMed

West, C; Cilpa, G; Gaudin, K; Chaminade, P; Lesellier, E

2005-09-16

Interactions of solutes on porous graphitic carbon (PGC) with non-aqueous mobile phases are studied by the linear solvation energy relationship (LSER). Studies have been carried out with eight binary mixtures composed of a weak solvent (acetonitrile or methanol) and a strong solvent (tetrahydrofuran, n-butanol, CH2Cl2, 1,1,2-trichloro-2,2,1-trifluoroethane). The systematic analysis of a set of test compounds was performed for each solvent mixture in isocratic mode (50:50). The results were compared to those obtained on PGC with hydro-organic liquids and supercritical fluids. They were then correlated with the observed retention behaviour of lipid compounds, more particularly ceramides.

What information can frictional properties of polymer brushes tell us?

NASA Astrophysics Data System (ADS)

Zhang, Zhenyu; Moxey, Mark; Morse, Andrew; Armes, Steven; Lewis, Andrew; Geoghegan, Mark; Leggett, Graham

2013-03-01

We have used friction force microscopy (FFM) to quantitatively examine surface grown zwitterionic polymer brushes: poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC), and to establish the correlation between its frictional behaviour to other intrinsic properties. In a good solvent, it was found that the coefficient of friction (μ) decreased with increasing film thickness. We conclude that the amount of bound solvent increases as the brush length increases, causing the osmotic pressure to increase and yielding a reduced tendency for the brush layer to deform under applied load. When measured in a series of alcohol/water mixtures, a significant increase in μ was observed for ethanol/water mixtures at a volume fraction of 90%. This is attributed to brush collapse due to co-nonsolvency, leading to loss of hydration of the brush chains and hence substantially reduced lubrication. We show that single asperity contact mechanics is strongly dependent on solvent quality. Friction-load relationship was found linear in methanol (good solvent), but sub-linear in water and ethanol (moderate solvent).

Reliable Mechanochemistry: Protocols for Reproducible Outcomes of Neat and Liquid Assisted Ball-mill Grinding Experiments.

PubMed

Belenguer, Ana M; Lampronti, Giulio I; Sanders, Jeremy K M

2018-01-23

The equilibrium outcomes of ball mill grinding can dramatically change as a function of even tiny variations in the experimental conditions such as the presence of very small amounts of added solvent. To reproducibly and accurately capture this sensitivity, the experimentalist needs to carefully consider every single factor that can affect the ball mill grinding reaction under investigation, from ensuring the grinding jars are clean and dry before use, to accurately adding the stoichiometry of the starting materials, to validating that the delivery of solvent volume is accurate, to ensuring that the interaction between the solvent and the powder is well understood and, if necessary, a specific soaking time is added to the procedure. Preliminary kinetic studies are essential to determine the necessary milling time to achieve equilibrium. Only then can exquisite phase composition curves be obtained as a function of the solvent concentration under ball mill liquid assisted grinding (LAG). By using strict and careful procedures analogous to the ones here presented, such milling equilibrium curves can be obtained for virtually all milling systems. The system we use to demonstrate these procedures is a disulfide exchange reaction starting from the equimolar mixture of two homodimers to obtain at equilibrium quantitative heterodimer. The latter is formed by ball mill grinding as two different polymorphs, Form A and Form B. The ratio R = [Form B] / ([Form A] + [Form B]) at milling equilibrium depends on the nature and concentration of the solvent in the milling jar.

Electrolyte Suitable for Use in a Lithium Ion Cell or Battery

NASA Technical Reports Server (NTRS)

McDonald, Robert C. (Inventor)

2014-01-01

Electrolyte suitable for use in a lithium ion cell or battery. According to one embodiment, the electrolyte includes a fluorinated lithium ion salt and a solvent system that solvates lithium ions and that yields a high dielectric constant, a low viscosity and a high flashpoint. In one embodiment, the solvent system includes a mixture of an aprotic lithium ion solvating solvent and an aprotic fluorinated solvent.

Thermo-chemical extraction of fuel oil from waste lubricating grease.

PubMed

Pilusa, Tsietsi Jefrey; Muzenda, Edison; Shukla, Mukul

2013-06-01

This study investigated the recovery of oil from waste grease through the process of thermal degradation in an aqueous solution of potassium hydroxide (KOH) followed by solvent extraction. Waste high temperature metal bearing grease was dissolved in a 15 w/w% KOH solution at 80°C while being agitated at 2000 rpm using a shear action agitator for a period of 15 min. Two distinct layers were observed after 8 min of settling time. The top layer being of dark brown oil and the bottom layer was a heterogeneous mixture. The two layers were separated by decantation. The bottom layer was cooled down to 45°C followed by slow addition of toluene (C7H8) while agitating at 1200 rpm for 15 min to prevent solids settling and minimise rapid volatilisation of the organic compounds in the mixture. Two distinct layers were also formed, the top homogeneous mixture of light brown oil-toluene mixture and the bottom sludge layer. The solvent was recovered from the oil for re-use by fractional distillation of the homogenous mixture. It was observed that 15 w/w% potassium hydroxide solution can chemically degrade the soap matrix in the grease and extract up to 49 w/w% of the fuel oil when subjected to high shear stress at a temperature of 80°C. The 26 w/w% extraction of oil in the remaining sludge was obtained by solvent extraction process with mass ratios of sludge to solvent of 2:1. Solvent recovery of 88% by mass was obtained via fractional distillation method. The combined extraction processes brought an overall oil yield of 75 w/w% from the waste grease. The fuel oil obtained from this process has similar properties to paraffin oil and can be blended with other oils as an alternative energy source. Copyright © 2013 Elsevier Ltd. All rights reserved.

Electroplated Fe-Co-Ni films prepared from deep-eutectic-solvent-based plating baths

NASA Astrophysics Data System (ADS)

Yanai, Takeshi; Shiraishi, Kotaro; Akiyoshi, Toshiki; Azuma, Keita; Watanabe, Yoshimasa; Ohgai, Takeshi; Morimura, Takao; Nakano, Masaki; Fukunaga, Hirotoshi

2016-05-01

We fabricated soft magnetic films from DES-based plating baths, and investigated magnetic properties of the plated films. The plating baths were obtained by stirring the mixture of choline chloride, ethylene glycol, FeCl2 ṡ 4H2O, NiCl2 ṡ 6H2O and CoCl2 ṡ 6H2O. The composition of the electroplated film depended on the amount of the reagent in the plating bath, and we consequently obtained the films with various composition. The current efficiency of the plating process shows high values (> 88 %) in the wide composition range. The soft magnetic films with low coercivity were obtained at the Fe compositions of ≈ 30 at.% and > 80 at.%, and we found that low coercivity could be realized by the control of the film composition. We also found that the Fe-rich films prepared from DES-based plating bath have some advantages as a soft magnetic phase for a nanocomposite magnet due to their high saturation magnetization and very fine crystal structure.

Catalytic transformation of persistent contaminants using a new composite material based on nanosized zero-valent iron.

PubMed

Dror, Ishai; Jacov, Osnat Merom; Cortis, Andrea; Berkowitz, Brian

2012-07-25

A new composite material based on deposition of nanosized zerovalent iron (nZVI) particles and cyanocobalamine (vitamin B12) on a diatomite matrix is presented, for catalytic transformation of organic contaminants in water. Cyanocobalamine is known to be an effective electron mediator, having strong synergistic effects with nZVI for reductive dehalogenation reactions. This composite material also improves the reducing capacity of nZVI by preventing agglomeration of iron nanoparticles, thus increasing their active surface area. The porous structure of the diatomite matrix allows high hydraulic conductivity, which favors channeling of contaminated water to the reactive surface of the composite material resulting in faster rates of remediation. The composite material rapidly degrades or transforms completely a large spectrum of water contaminants, including halogenated solvents like TCE, PCE, and cis-DCE, pesticides like alachlor, atrazine and bromacyl, and common ions like nitrate, within minutes to hours. A field experiment where contaminated groundwater containing a mixture of industrial and agricultural persistent pollutants was conducted together with a set of laboratory experiments using individual contaminant solutions to analyze chemical transformations under controlled conditions.

DESIGNING GREENER SOLVENTS

EPA Science Inventory

Computer-aided design of chemicals and chemical mixtures provides a powerful tool to help engineers identify cleaner process designs and more-benign alternatives to toxic industrial solvents. Three software programs are discussed: (1) PARIS II (Program for Assisting the Replaceme...

Investigation on drug solubility enhancement using deep eutectic solvents and their derivatives.

PubMed

Li, Zheng; Lee, Ping I

2016-05-30

Deep eutectic solvent (DES) is a room temperature liquid typically formed by mixing two solid compounds, such as a quaternary ammonium salt (QAS) (e.g. choline chloride) and a hydrogen bond donor (HBD) (e.g. urea or a carboxylic acid) at their eutectic composition. Very often, a range of room temperature liquids can also be obtained near the eutectic composition. Hence, it is more convenient to introduce a more general term deep eutectic solvent derivatives (DESDs) to describe a wide range of DES-like derivatives including those derived from ternary mixtures. The melting point of the mixture is lowered because the hydrogen bonding between DESD components reduces the lattice energy of components of the eutectic system. Based on the analysis of available data for 22 such choline chloride-based DES pairs, we found that the observed melting point depression can be statistically correlated with the difference between the hydrogen bonding contribution (δh) and the polar contribution (δp) to the solubility parameter of the hydrogen bond donor (HBD) component. The correlation was validated with a new DESD based on glycolic acid and choline chloride, which form DESDs at a molar ratio between 1:1 and 1:4 with DES-like properties. As a room temperature liquid, this DESD exhibits a wide range of solubility enhancement on several weakly basic poorly water-soluble drugs. For example, the solubility of itraconazole, piroxicam, lidocaine, and posaconazole has been observed to increase by 6700, 430, 28, and 6400-fold, respectively as compared to their aqueous solubility at room temperature. Furthermore, another new ternary DESD based on choline chloride, glycolic acid, and oxalic acid at a molar ratio of 1:1.6:0.4 is shown to further increase the solubility of itraconazole to a remarkable level of 5.36mg/mL (a 53,600-fold increase!). Because the components of such DESDs can include those biodegradable ones that had previously been used in formulated human products, the potential applicability of suitable DESDs to drug delivery, especially in enhancing drug solubility for topical formulations could be very attractive. Copyright © 2016 Elsevier B.V. All rights reserved.

Three column intermittent simulated moving bed chromatography: 3. Cascade operation for center-cut separations.

PubMed

Jermann, Simon; Meijssen, Mattheus; Mazzotti, Marco

2015-01-23

A general design methodology for chromatographic three fraction separation by application of the three column intermittent simulated moving bed (3C-ISMB) cascade is proposed and experimentally validated by studying the purification of an intermediately retained stereoisomer of nadolol, from an equimolar mixture of its four stereoisomers. The theoretical part shows that the 3C-ISMB cascade can be easily designed by applying Triangle Theory. Moreover, a re-scaling approach for the second stage is proposed so as to account for the fact that the feed flow rates to stage 2 are generally higher as compared to stage 1 due to dilution in the latter. Scaling the columns of the second stage accordingly enables to run both stages under optimal conditions with respect to switching time and step ratio, which is an important advantage as compared to integrated ternary processes. The experimental part starts with studying the linear adsorption behavior of nadolol in heptane/ethanol/DEA on Chiralpak AD for varying ratios of heptane and ethanol. Based on that, a solvent composition of Hept/EtOH/DEA 30/70/0.3 (v/v/v) is selected and the competitive multi-component Langmuir isotherm of the quaternary mixture is determined by frontal analysis. The resulting isotherm parameters are used to design several first stage experiments aiming at removal of the most retained component. The resulting ternary intermediate product is reprocessed in several second stage experiments studying various configurations. Finally, the dilution of the intermediate product with Hept/DEA yielding a solvent composition of Hept/EtOH/DEA 60/40/0.3 (v/v/v) is examined showing that the resulting increase in retention is beneficial for final product purities. Moreover, the reduction in viscosity compensates for the dilution as it enables higher flow rates. Dilution of the intermediate product is hence the best option, yielding highest overall cascade productivity (2.10gl(-1)h(-1)) and highest product purity (97.8%) requiring a specific solvent consumption of 12l/g of product. Copyright © 2014 Elsevier B.V. All rights reserved.

Direct Immersion Annealing of Block Copolymer Thin Films

NASA Astrophysics Data System (ADS)

Karim, Alamgir

We demonstrate ordering of thin block copolymer (BCP) films via direct immersion annealing (DIA) at enhanced rate leading to stable morphologies. The BCP films are immersed in carefully selected mixtures of good and marginal solvents that can impart enhanced polymer mobility, while inhibiting film dissolution. DIA is compatible with roll-to-roll assembly manufacturing and has distinct advantages over conventional thermal annealing and batch processing solvent-vapor annealing methods. We identify three solvent composition-dependent BCP film ordering regimes in DIA for the weakly interacting polystyrene -poly(methyl methacrylate) (PS -PMMA) system: rapid short range order, optimal long-range order, and a film instability regime. Kinetic studies in the ``optimal long-range order'' processing regime as a function of temperature indicate a significant reduction of activation energy for BCP grain growth compared to oven annealing at conventional temperatures. An attractive feature of DIA is its robustness to ordering other BCP (e.g. PS-P2VP) and PS-PMMA systems exhibiting spherical, lamellar and cylindrical ordering. Inclusion of nanoparticles in these films at high concentrations and fast ordering kinetics study with neutron reflectivity and SANS will be discussed. This is (late) Contributed Talk Abstract for Dillon Medal Symposium at DPOLY - discussed with DPOLY Chair Dvora Perahia.

Progress on lipid extraction from wet algal biomass for biodiesel production.

PubMed

Ghasemi Naghdi, Forough; González González, Lina M; Chan, William; Schenk, Peer M

2016-11-01

Lipid recovery and purification from microalgal cells continues to be a significant bottleneck in biodiesel production due to high costs involved and a high energy demand. Therefore, there is a considerable necessity to develop an extraction method which meets the essential requirements of being safe, cost-effective, robust, efficient, selective, environmentally friendly, feasible for large-scale production and free of product contamination. The use of wet concentrated algal biomass as a feedstock for oil extraction is especially desirable as it would avoid the requirement for further concentration and/or drying. This would save considerable costs and circumvent at least two lengthy processes during algae-based oil production. This article provides an overview on recent progress that has been made on the extraction of lipids from wet algal biomass. The biggest contributing factors appear to be the composition of algal cell walls, pre-treatments of biomass and the use of solvents (e.g. a solvent mixture or solvent-free lipid extraction). We compare recently developed wet extraction processes for oleaginous microalgae and make recommendations towards future research to improve lipid extraction from wet algal biomass. © 2016 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.

Glycerol carbonate as green solvent for pretreatment of sugarcane bagasse

PubMed Central

2013-01-01

Background Pretreatment of lignocellulosic biomass is a prerequisite for effective saccharification to produce fermentable sugars. In this study, “green” solvent systems based on acidified mixtures of glycerol carbonate (GC) and glycerol were used to treat sugarcane bagasse and the roles of each solvent in deconstructing biomass were determined. Results Pretreatment of sugarcane bagasse at 90°C for only 30 min with acidified GC produced a solid residue having a glucan digestibility of 90% and a glucose yield of 80%, which were significantly higher than a glucan digestibility of 16% and a glucose yield of 15% obtained for bagasse pretreated with acidified ethylene carbonate (EC). Biomass compositional analyses showed that GC pretreatment removed more lignin than EC pretreatment (84% vs 54%). Scanning electron microscopy (SEM) showed that fluffy and size-reduced fibres were produced from GC pretreatment whereas EC pretreatment produced compact particles of reduced size. The maximal glucan digestibility and glucose yield of GC/glycerol systems were about 7% lower than those of EC/ethylene glycol (EG) systems. Replacing up to 50 wt% of GC with glycerol did not negatively affect glucan digestibility and glucose yield. The results from pretreatment of microcrystalline cellulose (MCC) showed that (1) pretreatment with acidified alkylene glycol (AG) alone increased enzymatic digestibility compared to pretreatments with acidified alkylene carbonate (AC) alone and acidified mixtures of AC and AG, (2) pretreatment with acidified GC alone slightly increased, but with acidified EC alone significantly decreased, enzymatic digestibility compared to untreated MCC, and (3) there was a good positive linear correlation of enzymatic digestibility of treated and untreated MCC samples with congo red (CR) adsorption capacity. Conclusions Acidified GC alone was a more effective solvent for pretreatment of sugarcane bagasse than acidified EC alone. The higher glucose yield obtained with GC-pretreated bagasse is possibly due to the presence of one hydroxyl group in the GC molecular structure, resulting in more significant biomass delignification and defibrillation, though both solvent pretreatments reduced bagasse particles to a similar extent. The maximum glucan digestibility of GC/glycerol systems was less than that of EC/EG systems, which is likely attributed to glycerol being less effective than EG in biomass delignification and defibrillation. Acidified AC/AG solvent systems were more effective for pretreatment of lignin-containing biomass than MCC. PMID:24156757

Development of Viscosity Model for Petroleum Industry Applications

NASA Astrophysics Data System (ADS)

Motahhari, Hamed reza

Heavy oil and bitumen are challenging to produce and process due to their very high viscosity, but their viscosity can be reduced either by heating or dilution with a solvent. Given the key role of viscosity, an accurate viscosity model suitable for use with reservoir and process simulators is essential. While there are several viscosity models for natural gases and conventional oils, a compositional model applicable to heavy petroleum and diluents is lacking. The objective of this thesis is to develop a general compositional viscosity model that is applicable to natural gas mixtures, conventional crudes oils, heavy petroleum fluids, and their mixtures with solvents and other crudes. The recently developed Expanded Fluid (EF) viscosity correlation was selected as a suitable compositional viscosity model for petroleum applications. The correlation relates the viscosity of the fluid to its density over a broad range of pressures and temperatures. The other inputs are pressure and the dilute gas viscosity. Each fluid is characterized for the correlation by a set of fluid-specific parameters which are tuned to fit data. First, the applicability of the EF correlation was extended to asymmetric mixtures and liquid mixtures containing dissolved gas components. A new set of mass-fraction based mixing rules was developed to calculate the fluid-specific parameters for mixtures. The EF correlation with the new set of mixing rules predicted the viscosity of over 100 mixtures of hydrocarbon compounds and carbon dioxide with overall average absolute relative deviations (AARD) of less than 10% either with measured densities or densities estimated by Advanced Peng-Robinson equation of state (APR EoS). To improve the viscosity predictions with APR EoS-estimated densities, general correlations were developed for non-zero viscosity binary interaction parameters. The EF correlation was extended to non-hydrocarbon compounds typically encountered in natural gas industry. It was demonstrated that the framework of the correlation is valid for these compounds, except for compounds with strong hydrogen bonding such as water. A temperature dependency was introduced into the correlation for strongly hydrogen bonding compounds. The EF correlation fit the viscosity data of pure non-hydrocarbon compounds with AARDs below 6% and predicted the viscosity of sour and sweet natural gases and aqueous solutions of organic alcohols with overall AARDs less than 9%. An internally consistent estimation method was also developed to calculate the fluid-specific parameters for hydrocarbons when no experimental viscosity data are available. The method correlates the fluid-specific parameters to the molecular weight and specific gravity. The method was evaluated against viscosity data of over 250 pure hydrocarbon compounds and petroleum distillations cuts. The EF correlation predictions were found to be within the same order of magnitude of the measurements with an overall AARD of 31%. A methodology was then proposed to apply the EF viscosity correlation to crude oils characterized as mixtures of the defined components and pseudo-components. The above estimation methods are used to calculate the fluid-specific parameters for pseudo-components. Guidelines are provided for tuning of the correlation to available viscosity data, calculating the dilute gas viscosities, and improving the densities calculated with the Peng-Robinson EoS. The viscosities of over 10 dead and live crude oils and bitumen were predicted within a factor of 3 of the measured values using the measured density of the oils as the input. It was shown that single parameter tuning of the model improved the viscosity prediction to within 30% of the measured values. Finally, the performance of the EF correlation was evaluated for diluted heavy oils and bitumens. The required density and viscosity data were collected for over 20 diluted dead and live bitumen mixtures using an in-house capillary viscometer also equipped with an in-line density-meter at temperatures and pressures up to 175 °C and 10 MPa. The predictions of the correlation were found within the same order of magnitude of the measured values with overall AARDs less than 20%. It was shown that the predictions of the correlation with generalized non-zero interaction parameters for the solvent-oil pairs were improved to overall AARDs less than 10%.

The influence of water mixtures on the dermal absorption of glycol ethers

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

Traynor, Matthew J.; Wilkinson, Simon C.; Williams, Faith M.

2007-01-15

Glycol ethers are solvents widely used alone and as mixtures in industrial and household products. Some glycol ethers have been shown to have a range of toxic effects in humans following absorption and metabolism to their aldehyde and acid metabolites. This study assessed the influence of water mixtures on the dermal absorption of butoxyethanol and ethoxyethanol in vitro through human skin. Butoxyethanol penetrated human skin up to sixfold more rapidly from aqueous solution (50%, 450 mg/ml) than from the neat solvent. Similarly penetration of ethoxyethanol was increased threefold in the presence of water (50%, 697 mg/ml). There was a correspondingmore » increase in apparent permeability coefficient as the glycol ether concentration in water decreased. The maximum penetration rate of water also increased in the presence of both glycol ethers. Absorption through a synthetic membrane obeyed Fick's Law and absorption through rat skin showed a similar profile to human skin but with a lesser effect. The mechanisms for this phenomenon involves disruption of the stratum corneum lipid bilayer by desiccation by neat glycol ether micelles, hydration with water mixtures and the physicochemical properties of the glycol ether-water mixtures. Full elucidation of the profile of absorption of glycol ethers from mixtures is required for risk assessment of dermal exposure. This work supports the view that risk assessments for dermal contact scenarios should ideally be based on absorption data obtained for the relevant formulation or mixture and exposure scenario and that absorption derived from permeability coefficients may be inappropriate for water-miscible solvents.« less

Benzene and cyclohexane separation using 1-butyl-3-methylimidazolium thiocyanate

NASA Astrophysics Data System (ADS)

Gonfa, Girma; Ismail, Marhaina; Bustam, Mohamad Azmi

2017-09-01

Cyclohexane is mainly produced by catalytic hydrogenation of benzene. Removal of unreacted benzene from the product stream is very important in this process. However, due to their close boiling points and azeotrope formation, it is very difficult to separate cyclohexane and benzene by conventional distillation. Currently, special separation processes such as processes extractive distillation is commercially used for this separation. However, this extractive distillation suffers from process complexity and higher energy consumption due to their low extractive selectivity of molecular entrainers used. The aim of the present work is to investigate the applicability of ionic liquids as entrainer in extractive distillation of benzene and cyclohexane mixture. In this study, we investigated 1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN]) ionic liquid for separation of benzene and cyclohexane by measuring the Vapor Liquid Equilibrium data of the two components in the presence of the ionic liquid. As green and potential environmentally friendly solvents, ionic liquids have attracted increasing attention as alternative conventional entrainers in extractive distillation. Isothermal Vapor Liquid Equilibrium for the benzene + cyclohexane + [BMIM][SCN] ternary system was obtained at 353.15 K using a Head Space Gas Chromatography. The addition of [BMIM][SCN] breaks the benzene-cyclohexane azeotrope and increased the relative volatility cyclohexane to benzene in the mixture. The effect of [BMIM][SCN] on the relative volatility cyclohexane to benzene was studied at various benzene and cyclohexane compositions and solvent to feed ratios. The performance of [BMIM][SCN] was compared with typical conventional solvents, dimethylformamide (DMF) and dimethylsulfoxide (DMSO). The results show that the relative volatility of cyclohexane to benzene in the presence of [BMIM][SCN] is higher compared that of DMSO and DMF.

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1995-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1995-10-03

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Solvent-modified ultrafast decay dynamics in conjugated polymer/dye labeled single stranded DNA

NASA Astrophysics Data System (ADS)

Kim, Inhong; Kang, Mijeong; Woo, Han Young; Oh, Jin-Woo; Kyhm, Kwangseuk

2015-07-01

We have investigated that organic solvent (DMSO, dimethyl sulfoxide) modifies energy transfer efficiency between conjugated polymers (donors) and fluorescein-labeled single stranded DNAs (acceptors). In a mixture of buffer and organic solvent, fluorescence of the acceptors is significantly enhanced compared to that of pure water solution. This result can be attributed to change of the donor-acceptor environment such as decreased hydrophobicity of polymers, screening effect of organic solvent molecules, resulting in an enhanced energy transfer efficiency. Time-resolved fluorescence decay of the donors and the acceptors was modelled by considering the competition between the energy harvesting Foerster resonance energy transfer and the energy-wasting quenching. This enables to quantity that the Foerster distance (R0 = 43.3 Å) and resonance energy transfer efficiency (EFRET = 58.7 %) of pure buffer solution become R0 = 38.6 Å and EFRET = 48.0 % when 80% DMSO/buffer mixture is added.

Protein dynamics in organic media at varying water activity studied by molecular dynamics simulation.

PubMed

Wedberg, Rasmus; Abildskov, Jens; Peters, Günther H

2012-03-01

In nonaqueous enzymology, control of enzyme hydration is commonly approached by fixing the thermodynamic water activity of the medium. In this work, we present a strategy for evaluating the water activity in molecular dynamics simulations of proteins in water/organic solvent mixtures. The method relies on determining the water content of the bulk phase and uses a combination of Kirkwood-Buff theory and free energy calculations to determine corresponding activity coefficients. We apply the method in a molecular dynamics study of Candida antarctica lipase B in pure water and the organic solvents methanol, tert-butyl alcohol, methyl tert-butyl ether, and hexane, each mixture at five different water activities. It is shown that similar water activity yields similar enzyme hydration in the different solvents. However, both solvent and water activity are shown to have profound effects on enzyme structure and flexibility.

Method of performing sugar dehydration and catalyst treatment

DOEpatents

Hu, Jianli [Kennewick, WA; Holladay, Johnathan E [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

2010-06-01

The invention includes a method of treating a solid acid catalyst. After exposing the catalyst to a mixture containing a sugar alcohol, the catalyst is washed with an organic solvent and is then exposed to a second reaction mixture. The invention includes a process for production of anhydrosugar alcohol. A solid acid catalyst is provided to convert sugar alcohol in a first sample to an anhydrosugar alcohol. The catalyst is then washed with an organic solvent and is subsequently utilized to expose a second sample. The invention includes a method for selective production of an anhydrosugar. A solid acid catalyst is provided within a reactor and anhydrosugar alcohol is formed by flowing a starting sugar alcohol into the reactor. The acid catalyst is then exposed to an organic solvent which allows a greater amount of additional anhydrosugar to be produced than would occur without exposing the acid catalyst to the organic solvent.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1996-02-13

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1996-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

THE RECOVERY OF URANIUM FROM GAS MIXTURE

DOEpatents

Jury, S.H.

1964-03-17

A method of separating uranium from a mixture of uranium hexafluoride and other gases is described that comprises bringing the mixture into contact with anhydrous calcium sulfate to preferentially absorb the uranium hexafluoride on the sulfate. The calcium sulfate is then leached with a selective solvent for the adsorbed uranium. (AEC)

Correlating the cold flow and melting properties of fatty acid methyl ester (FAME) mixtures

USDA-ARS?s Scientific Manuscript database

Fatty acid methyl ester (FAME) mixtures derived from plant oils or animal fats are used to make biodiesel, lubricants, surfactants, plasticizers, ink solvents, paint strippers and other products. Processing requires a precise knowledge of the physico-chemical properties of mixtures with diverse and ...

Separation processes using expulsion from dilute supercritical solutions

DOEpatents

Cochran, Jr., Henry D.

1993-01-01

A process for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

Spin-coating: A new approach for improving dispersion of cellulose nanocrystals and mechanical properties of poly (lactic acid) composites.

PubMed

Shojaeiarani, Jamileh; Bajwa, Dilpreet S; Stark, Nicole M

2018-06-15

This study systematically evaluated the influence of masterbatch preparation techniques, solvent casting and spin-coating methods, on composite properties. Composites were manufactured by combining CNCs masterbatches and PLA resin using twin screw extruder followed by injection molding. Different microscopy techniques were used to investigate the dispersion of CNCs in masterbatches and composites. Thermal, thermomechanical, and mechanical properties of composites were evaluated. Scanning electron microscopy (SEM) images showed superior dispersion of CNCs in spin-coated masterbatches compared to solvent cast masterbatches. At lower CNCs concentrations, both SEM and optical microscope images confirmed more uniform CNCs dispersion in spin-coated composites than solvent cast samples. Degree of crystallinity of PLA exhibited a major enhancement by 147% and 380% in solvent cast and spin-coated composites, respectively. Spin-coated composites with lower CNCs concentration exhibited a noticeable improvement in mechanical properties. However, lower thermal characteristics in spin-coated composites were observed, which could be attributed to the residual solvents in masterbatches. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sol-gel analogous aminolysis-ammonolysis of chlorosilanes to chlorine-free Si/(C)/N-materials.

PubMed

Wiltzsch, Conny; Wagler, Jörg; Roewer, Gerhard; Kroke, Edwin

2009-07-28

Large amounts of chlorosilanes, especially SiCl4 and CH3SiCl3, are produced as side-products of the industrial fabrication of solar or electronic grade silicon and the Müller-Rochow process. It was a goal of the present study to transform these compounds into useful chlorine-free precursors for Si/(C)/N ceramics via a sol-gel analogous liquid processing route. Chlorine substitution of the chlorosilanes (mixtures) with diethylamine did not yield chlorine-free products, complete reactions are only possible with lithium diethylamide. However, aminolyses with n-propylamine were successful. Transamination with ammonia was not possible with diethylaminosilanes but was with n-propylaminosilanes in various solvents. This result was attributed to steric reasons and polar interactions of the N-H groups. Colourless solid or liquid polysilazanes were obtained, depending on the silane (mixture) and the solvent. Transamination reactions of CH3Si(NH-n-Pr)3 in chloroform reproducibly yielded a cage-like oligosilazane of the composition (CH3)9Si9(NH)12N. Single crystal X-ray structure analysis revealed a seven-cyclic cluster containing four six- and three ten-membered silazane rings. This unique silazane cage as well as the other aminosilanes and the silazanes were comprehensively characterised using multi-nuclear solid state and solution NMR, elemental analyses and thermal gravimetry (TGA).

Structural and spectroscopic study of Al(III)-3-hydroxyflavone complex: determination of the stability constants in water-methanol mixtures.

PubMed

Davila, Y A; Sancho, M I; Almandoz, M C; Blanco, S E

2012-09-01

Stoichiometry and apparent stability constant (K(C)) of the complex formed between Al(III) and 3-hydroxyflavone were determined in methanol and water-methanol mixtures (% water w/w: 3.11; 6.15; 10.4; 15.2; 19.9 and 25.3) by UV-vis spectroscopy at 25.0°C and constant ionic strength (0.05 M, sodium chloride). Stoichiometry of the complex (1:2, metal:ligand) is not modified with an increase in water percentage in the analyzed interval. The value of K(C) in methanol is greater than in the binary solutions. The effects of changing solvent composition on K(C) data were explained by linear solvation free energy relationships using the solvatochromic parameter of Kamlet and Taft (α, β and π(*)). Multiple linear regression analysis indicates that the hydrogen bond donating ability (α) of the solvent and non-specific interactions (π(*)) play an important role in the degree of occurrence of the reaction. The effect of temperature on K(C) was also analyzed by assessing standard entropy and enthalpy variations of the reaction in methanol. Finally, the structure of the complex was investigated using FTIR spectroscopy and DFT calculations. The ligand exhibits small structural changes upon complexation, localized on the chelating site. The calculated vibrational frequencies of the complex were successfully compared against the experimental values. Copyright © 2012 Elsevier B.V. All rights reserved.

Dielectric Studies on Binary Mixtures of Diethyl Ether (DEE) in Polar Solvents

NASA Astrophysics Data System (ADS)

Pradhan, S. K.; Dash, S. K.; Swain, M. D.; Swain, B. B.

2011-11-01

Dielectric constant (ɛ) of diethylether (DEE) in binary mixtures with four polar solvents such as n-butanl, i-butanol, t-butanol and tolune has been measured at 455 kHz and at a temperature 303.15 K. The refractive indices were measured at a regulated temperature by Pulfrich refractometer at sodium D-line. The data is used to evaluate mutual correlation factor gab, excess molar polarization and excess free energy of mixing ΔGab by using Winkelmann-Quitzsch equation for binary mixtures to asses the suitability of the polar solvents as modifiers. The trend of variation for these parameters exhibit marked dependence on the nature of alcohols. Diethylether is one of the solvent extractant used for the extraction and separation of zirconium and hafnium in reactor technology. The extractant is blended with appropriate polar modifiers for greater dispersal and more rapid phase disengagement. This facilitates in the elimination of the third organo-aqueous phase containing some of the metal ions. As such the study of molecular interaction among the component molecules has been undertaken in these binary mixtures using the dielectric route. The interaction parameters such as mutual correlation factor gab is found to be less than one in all alcohols, while it is negative in toluene upto 0.7 DEE molefraction and thereafter becoming positive. The nature of variation of the excess miolar polarization ΔP and excess free energy of mixing Gab tends to support the assessment of gab to choose a suitable polar modifier.

Method for generating a crystalline {sup 99}MoO{sub 3} product and the isolation {sup 99m}Tc compositions therefrom

DOEpatents

Bennett, R.G.; Christian, J.D.; Kirkham, R.J.; Tranter, T.J.

1998-09-01

An improved method is described for producing {sup 99m}Tc compositions. {sup 100}Mo metal is irradiated with photons in a particle (electron) accelerator to produce {sup 99}Mo metal which is dissolved in a solvent. A solvated {sup 99}Mo product is then dried to generate a supply of {sup 99}MoO{sub 3} crystals. The crystals are thereafter heated at a temperature which will sublimate the crystals and form a gaseous mixture containing vaporized {sup 99m}TcO{sub 3} and vaporized {sup 99m}TcO{sub 2} but will not cause the production of vaporized {sup 99}MoO{sub 3}. The mixture is then combined with an oxidizing gas to generate a gaseous stream containing vaporized {sup 99m}Tc{sub 2}O{sub 7}. Next, the gaseous stream is cooled to a temperature sufficient to convert the vaporized {sup 99m}Tc{sub 2}O{sub 7} into a condensed {sup 99m}Tc-containing product. The product has high purity levels resulting from the use of reduced temperature conditions and ultrafine crystalline {sup 99}MoO{sub 3} starting materials with segregated {sup 99m}Tc compositions therein which avoid the production of vaporized {sup 99}MoO{sub 3} contaminants. 1 fig.

Hard-sphere mixture excess free energy at infinite size ratio

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

Tukur, N.M.; Hamad, E.Z.; Mansoori, G.A.

1999-02-01

This article presents the exact limiting value of the derivative of the excess Helmholtz energy, A{sup E}, with respect to molecular size at constant temperature, density and composition for a binary mixture of hard spheres with an infinite size ratio ({sigma}{sub 11}/{sigma}{sub 22}{r_arrow}{infinity}); i.e., lim{sub {sigma}{sub 22}{r_arrow}0}[({partial_derivative}A{sub hs}{sup E}/RT)/{partial_derivative}{sigma}{sub 22}]{sub T,{rho},x,{sigma}{sub 11}}=({pi}/2){rho}x{sub 1}x{sub 2}{sigma}{sub 11}{sup 2}/(1{minus}({pi}/6){rho}x{sub 1}{sigma}{sub 11}{sup 3}). This limiting value is compared with the Mansoori{endash}Carnahan{endash}Starling{endash}Leland (MCSL) and also used to test the limits of some commonly used models in estimating the excess free energy of solvents in mixtures or polymer solutions. The models evaluated include the van Laar,more » Wilson, Edmond{endash}Ogston, Flory{endash}Huggins, Lacome{endash}Sanchez, Scott{endash}Magat, and Chen {ital et al.} It is shown that while the MCSL equation of state produces the same limiting value as the exact value reported here the other mixture models deviate from the exact value. This expression may be utilized to correct the mixture theories at their infinite size ratio limits. {copyright} {ital 1999 American Institute of Physics.}« less

Development of Cellulose/PVDF-HFP Composite Membranes for Advanced Battery Separators

NASA Astrophysics Data System (ADS)

Castillo, Alejandro; Agubra, Victor; Alcoutlabi, Mataz; Mao, Yuanbing

Improvements in battery technology are necessary as Li-ion batteries transition from consumer electronic to vehicular and industrial uses. An important bottle-neck in battery efficiency and safety is the quality of the separators, which prevent electric short-circuits between cathode and anode, while allowing an easy flow of ions between them. In this study, cellulose acetate was dissolved in a mixed solvent with poly(vinylpyrrolidone) (PVP), and the mixture was forcespun in a peudo paper making process to yield nanofibrillated nonwoven mats. The mats were soaked in NaOH/Ethanol to strip PVP and regenerate cellulose from its acetate precursor. The cellulose mats were then dipped in poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP) to yield the cellulose/PVDF-HFP composte membranes. These membranes were characterized chemically through FTIR spectroscopy and solvent-stability tests, thermally through DSC, physically by stress/strain measurements along with weight-based electrolyte uptake, and electrically by AC-impedance spectroscopy combined with capacitative cycling.

Central composite design with the help of multivariate curve resolution in loadability optimization of RP-HPLC to scale-up a binary mixture.

PubMed

Taheri, Mohammadreza; Moazeni-Pourasil, Roudabeh Sadat; Sheikh-Olia-Lavasani, Majid; Karami, Ahmad; Ghassempour, Alireza

2016-03-01

Chromatographic method development for preparative targets is a time-consuming and subjective process. This can be particularly problematic because of the use of valuable samples for isolation and the large consumption of solvents in preparative scale. These processes could be improved by using statistical computations to save time, solvent and experimental efforts. Thus, contributed by ESI-MS, after applying DryLab software to gain an overview of the most effective parameters in separation of synthesized celecoxib and its co-eluted compounds, design of experiment software that relies on multivariate modeling as a chemometric approach was used to predict the optimized touching-band overloading conditions by objective functions according to the relationship between selectivity and stationary phase properties. The loadability of the method was investigated on the analytical and semi-preparative scales, and the performance of this chemometric approach was approved by peak shapes beside recovery and purity of products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel electrolytes for use in new and improved batteries: An NMR study

NASA Astrophysics Data System (ADS)

Berman, Marc B.

This thesis focuses on the use of nuclear magnetic resonance (NMR) spectroscopy in order to study materials for use as electrolytes in batteries. The details of four projects are described in this thesis as well as a brief theoretical background of NMR. Structural and dynamics properties were determined using several NMR techniques such as static, MAS, PFG diffusion, and relaxation to understand microscopic and macroscopic properties of the materials described within. Nuclei investigate were 1H, 2H, 7Li, 13C, 19F, 23Na, and 27Al. The first project focuses on an exciting new material to be used as a solid electrolyte membrane. T. The second project focuses on the dynamics of ionic liquid-solvent mixtures and their comparison to molecular dynamics computer simulations. The third project involves a solvent-free film containing NaTFSI salt mixed in to PEO for use in sodium-ion batteries. This final project focuses on a composite electrolyte consisting of a ceramic and solid: LiI:PEO:LiAlO2.

MICROEMULSION OF MIXED CHLORINATED SOLVENTS USING FOOD GRADE (EDIBLE) SURFACTANTS

EPA Science Inventory

Ground water contamination frequently consists of mixed chlorinated solvents [e.g., tetrachloroethylene (PCE), trichloroethylene (TCE), and trans-1,2- dichloroethylene (DCE)]. In this research, mixtures of the food grade (edible) surfactants bis(2-ethylhexyl) sodium sulfosuccinat...

Process for solvent refining of coal using a denitrogenated and dephenolated solvent

DOEpatents

Garg, Diwakar; Givens, Edwin N.; Schweighardt, Frank K.

1984-01-01

A process is disclosed for the solvent refining of non-anthracitic coal at elevated temperatures and pressure in a hydrogen atmosphere using a hydrocarbon solvent which before being recycled in the solvent refining process is subjected to chemical treatment to extract substantially all nitrogenous and phenolic constituents from the solvent so as to improve the conversion of coal and the production of oil in the solvent refining process. The solvent refining process can be either thermal or catalytic. The extraction of nitrogenous compounds can be performed by acid contact such as hydrogen chloride or fluoride treatment, while phenolic extraction can be performed by caustic contact or contact with a mixture of silica and alumina.

Ion Transport in Nanostructured Block Copolymer/Ionic Liquid Membranes

NASA Astrophysics Data System (ADS)

Hoarfrost, Megan Lane

Incorporating an ionic liquid into one block copolymer microphase provides a platform for combining the outstanding electrochemical properties of ionic liquids with a number of favorable attributes provided by block copolymers. In particular, block copolymers thermodynamically self-assemble into well-ordered nanostructures, which can be engineered to provide a durable mechanical scaffold and template the ionic liquid into continuous ion-conducting nanochannels. Understanding how the addition of an ionic liquid affects the thermodynamic self-assembly of block copolymers, and how the confinement of ionic liquids to block copolymer nanodomains affects their ion-conducting properties is essential for predictable structure-property control. The lyotropic phase behavior of block copolymer/ionic liquid mixtures is shown to be reminiscent of mixtures of block copolymers with selective molecular solvents. A variety of ordered microstructures corresponding to lamellae, hexagonally close-packed cylinders, body-centered cubic, and face-centered cubic oriented micelles are observed in a model system composed of mixtures of imidazolium bis(trifluoromethylsulfonyl)imide ([Im][TFSI]) and poly(styrene- b-2-vinyl pyridine) (PS-b-P2VP). In contrast to block copolymer/molecular solvent mixtures, the interfacial area occupied by each PS-b-P2VP chain decreases upon the addition of [Im][TFSI], indicating a considerable increase in the effective segregation strength of the PS-b-P2VP copolymer with ionic liquid addition. The relationship between membrane structure and ionic conductivity is illuminated through the development of scaling relationships that describe the ionic conductivity of block copolymer/ionic liquid mixtures as a function of membrane composition and temperature. It is shown that the dominant variable influencing conductivity is the overall volume fraction of ionic liquid in the mixture, which means there is incredible freedom in designing the block copolymer architecture in order to optimize the mechanical and other properties of the membrane without sacrificing conductivity. The derived scaling relationships are shown to be general for many block copolymer and ionic liquid chemistries. In certain cases, the mechanism of ion conduction in the ionic liquid is affected by block copolymer nanoconfinement. The introduction of excess neutral imidazole to [Im][TFSI] leads to enhanced proton conductivity as well as a high H+ transference number due to facilitated proton hopping between imidazole molecules. We show that there is increased proton hopping when the nonstoichiometric ionic liquid is confined to lamellar block copolymer nanodomains, which we hypothesize is due to changes in the hydrogen bond structure of the ionic liquid under confinement. This, in combination with unique ion aggregation behavior, leads to a lower activation energy for macroscopic ion transport compared to that in a corresponding homopolymer/ionic liquid mixture. Through this work, we further the understanding of the relationship between membrane composition, structure, and ion transport. The findings presented herein portend the rational design of nanostructured membranes having improved mechanical properties and conductivity.

Glove permeation by semiconductor processing mixtures containing glycol-ether derivatives.

PubMed

Zellers, E T; Ke, H Q; Smigiel, D; Sulewski, R; Patrash, S J; Han, M W; Zhang, G Z

1992-02-01

Results of permeation tests of several glove materials challenged with semiconductor processing formulations containing glycolether derivatives are described. Commercial glove samples of nitrile rubber (Edmont), natural rubber (Edmont and Baxter), butyl rubber (North), PVC Baxter), a natural rubber/neoprene/nitrile blend (Pioneer), and a natural rubber/neoprene blend (Playtex) were tested according to the ASTM F739-85 permeation test method (open-loop configuration). The liquid formulations examined included a positive photoresist thinner containing 2-ethoxyethyl acetate (2-EEA), n-butyl acetate, and xylene; a positive photoresist containing 2-EEA, n-butyl acetate, xylene, polymer resins, and photoactive compounds; a negative photoresist containing 2-methoxyethanol (2-ME), xylene, and cyclized poly(isoprene); and pure 2-methoxyethyl acetate (2-MEA), which is the solvent used in a commercial electron-beam resist. With the exception of the negative photoresist, butyl rubber provided the highest level of protection against the solvent mixtures tested, with no breakthrough observed after 4 hr of continuous exposure at 25 degrees C. Nitrile rubber provided the highest level of protection against the negative photoresist and reasonably good protection against initial exposure to the other solvent mixtures. Gloves consisting of natural rubber or natural rubber blends provided less protection against the mixtures than either nitrile or butyl rubber. For most of the glove samples, permeation of the glycol-ether derivatives contained in the mixtures was faster than that predicted from the permeation of the pure solvents. Increasing the exposure temperature from 25 to 37 degrees C did not significantly affect the performance of the butyl rubber glove. For the other gloves, however, exposures at 37 degrees C resulted in decreases in breakthrough times of 25-75% and increases in steady-state permeation rates of 80-457% relative to values obtained at 25 degrees C. Repeated exposure of nitrile rubber samples resulted in shorter breakthrough times for all mixture components. In fact, exposure for as little as one-half of the nominal breakthrough time followed by air drying overnight resulted in measurable quantities of one or more of the component solvents at the inner surface of the gloves at the beginning of the next exposure. This effect was not observed with the butyl rubber samples. With the exception of the negative photoresist, heating previously exposed nitrile rubber samples at 70 degrees C for 20 hr prior to retesting reduced or eliminated the effects of residual solvents, permitting reuse of the gloves. The use of thin PVC or natural rubber gloves adjacent to the nitrile gloves provided moderate increases in permeation resistance.(ABSTRACT TRUNCATED AT 400 WORDS)

Separation processes using expulsion from dilute supercritical solutions

DOEpatents

Cochran, H.D. Jr.

1993-04-20

A process is described for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

Chemical and biological characterisation of solvent extracts and essential oils from leaves and fruit of two Australian species of Pittosporum (Pittosporaceae) used in aboriginal medicinal practice.

PubMed

Sadgrove, Nicholas John; Jones, Graham Lloyd

2013-02-13

Although no known medicinal use for Pittosporum undulatum Vent. (Pittosporaceae) has been recorded, anecdotal evidence suggests that Australian Aboriginal people used Pittosporum angustifolium Lodd., G. Lodd. & W. Lodd. topically for eczema, pruritis or to induce lactation in mothers following child-birth and internally for coughs, colds or cramps. Essential oil composition and bioactivity as well as differential solvent extract antimicrobial activity from Pittosporum angustifolium are investigated here first, to partially describe the composition of volatiles released in traditional applications of Pittosporum angustifolium for colds or as a lactagogue, and second to investigate antibacterial activity related to topical applications. Essential oils were also investigated from Pittosporum undulatum Vent., first to enhance essential oil data produced in previous studies, and second as a comparison to Pittosporum angustifolium. Essential oils were hydrodistilled from fruit and leaves of both species using a modified approach to lessen the negative (frothing) effect of saponins. This was achieved by floating pumice or pearlite obsidian over the mixture to crush the suds formed while boiling. Essential oil extracts were analysed using GC-MS, quantified using GC-FID then screened for antimicrobial activity using a micro-titre plate broth dilution assay (MIC). Using dichloromethane, methanol, hexane and H(2)O as solvents, extracts were produced from leaves and fruit of Pittosporum angustifolium and screened for antimicrobial activity and qualitative phytochemical character. Although the essential oil from leaves and fruit of Pittosporum undulatum demonstrated some component variation, the essential oil from fruits of Pittosporum angustifolium had major constituents that strongly varied according to the geographical location of collection, suggesting the existence of at least two chemotypes; one with high abundance of acetic acid decyl ester. This chemotype had high antimicrobial activity whilst the other chemotype had only moderate antimicrobial activity against the three microbial species investigated here. This result may support the occurrence of geographical specificity with regard to ethnopharmacological use. Antimicrobial activity screening of the solvent extracts from Pittosporum angustifolium revealed the leaves to be superior to fruit, with water being the most suitable extraction solvent. To the best of our knowledge, this study constitutes the first time essential oils, and solvent extracts from the fruits of Pittosporum angustifolium, have been examined employing comprehensive chemical and biological analysis. The essential oil composition presented in this paper, includes components with structural similarity as chemosemiotic compounds involved in mother-infant identification, which may have significance with regard to traditional applications as a lactagogue. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

Molecular Dynamics Analysis of Lysozyme Protein in Ethanol- Water Mixed Solvent

DTIC Science & Technology

2012-01-01

molecular dynamics simulations of solvent effect on lysozyme protein, using water, ethanol, and different concentrations of water-ethanol mixtures as...understood. This work focuses on detailed molecular dynamics simulations of solvent effect on lysozyme protein, using water, ethanol, and different...using GROMACS molecular dynamics simulation (MD) code. Compared to water environment, the lysozyme structure showed remarkable changes in water

High-repetition-rate, narrow-band dye lasers with water as a solvent for dyes

NASA Astrophysics Data System (ADS)

Ray, Alok K.; Sinha, Sucharita; Kundu, Soumitra; Kumar, Sasi; Nair, Sivagiriyal Karunakaran Sreenivasan; Pal, Tamal; Dasgupta, Kamalesh

2002-03-01

The performance of a copper vapor laser-pumped narrow-band dye laser in oscillator-amplifier configuration with water-based binary mixture solvents is described. Although oscillator efficiency in water-surfactant (sodium lauryl sulfate) solvent was comparable with that that employed pure ethanolic solvent, amplifier efficiency was found to be lower. Experiments that were carried out with vertically polarized pump beams and either horizontally or vertically polarized signal beams show that, in case of both the pump and signal having orthogonal polarization (horizontal) and same polarization (vertical), the extraction efficiency for both ethanolic and water-micelle media increased substantially from 15.7% to 18.5% and from 10% to 12.5%, respectively. However, the relative difference remained nearly the same, indicating that a slower orientational diffusion of excited dye molecules in a micellar medium is not responsible for a decrease in amplifier efficiency. Amplifier efficiency comparable with that containing ethanolic dye solutions could be obtained with a binary solvent that comprises a mixture of water and about 30% n-propanol. The performances of two efficient dyes, Rhodamine-6G and Kiton Red S, using water-based solvents were studied.

Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy

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

Murugesan, Vijayakumar; Han, Kee Sung; Hu, Jianzhi

2017-03-19

Electrolytes help harness the energy from electrochemical processes by serving as solvents and transport media for redox-active ions. Molecular-level interactions between ionic solutes and solvent molecules – commonly referred to as solvation phenomena – give rise to many functional properties of electrolytes such as ionic conductivity, viscosity, and stability. It is critical to understand the evolution of solvation phenomena as a function of competing counterions and solvent mixtures to predict and design the optimal electrolyte for a target application. Probing oxygen environments is of great interest as oxygens are located at strategic molecular sites in battery solvents and are directlymore » involved in inter- and intramolecular solvation interactions. NMR signals from 17O nuclei in battery electrolytes offer nondestructive bulk measurements of isotropic shielding, electric field gradient tensors, and transverse and longitudinal relaxation rates, which are excellent means for probing structure, bonding, and dynamics of both solute and solvent molecules. This article describes the use of 17O NMR spectroscopy in probing the solvation structures of various electrolyte systems ranging from transition metal ions in aqueous solution to lithium cations in organic solvent mixtures.« less

Enzymatic temperature change indicator

DOEpatents

Klibanov, Alexander M.; Dordick, Jonathan S.

1989-01-21

A temperature change indicator is described which is composed of an enzyme and a substrate for that enzyme suspended in a solid organic solvent or mixture of solvents as a support medium. The organic solvent or solvents are chosen so as to melt at a specific temperature or in a specific temperature range. When the temperature of the indicator is elevated above the chosen, or critical temperature, the solid organic solvent support will melt, and the enzymatic reaction will occur, producing a visually detectable product which is stable to further temperature variation.

Thermoplastic composite matrices with improved solvent resistance

NASA Technical Reports Server (NTRS)

Hergenrother, P. M.; Jensen, B. J.; Havens, S. J.

1984-01-01

In order to improve solvent resistance of aromatic thermoplastic polymers, ethynyl-terminated aromatic sulfone polymers (ETS), sulfone/ester polymers (SEPE) containing pendent ethynyl groups, and phenoxy resin containing pendent ethynyl groups are synthesized. Cured polysulfones and phenoxy resins containing ethynyl groups on the ends or pendent on the molecules exhibited systematic behavior in solvent resistance, film flexibility, and toughness as a function of crosslink density. The film and composite properties of a cured solvent-resistant ETS were better than those of a commercially available solvent sensitive polysulfone. The study was part of a NASA program to better understand the trade-offs between solvent resistance, processability and mechanical properties which may be useful in designing composite structures for aerospace vehicles.

Method optimization for drug impurity profiling in supercritical fluid chromatography: Application to a pharmaceutical mixture.

PubMed

Muscat Galea, Charlene; Didion, David; Clicq, David; Mangelings, Debby; Vander Heyden, Yvan

2017-12-01

A supercritical chromatographic method for the separation of a drug and its impurities has been developed and optimized applying an experimental design approach and chromatogram simulations. Stationary phase screening was followed by optimization of the modifier and injection solvent composition. A design-of-experiment (DoE) approach was then used to optimize column temperature, back-pressure and the gradient slope simultaneously. Regression models for the retention times and peak widths of all mixture components were built. The factor levels for different grid points were then used to predict the retention times and peak widths of the mixture components using the regression models and the best separation for the worst separated peak pair in the experimental domain was identified. A plot of the minimal resolutions was used to help identifying the factor levels leading to the highest resolution between consecutive peaks. The effects of the DoE factors were visualized in a way that is familiar to the analytical chemist, i.e. by simulating the resulting chromatogram. The mixture of an active ingredient and seven impurities was separated in less than eight minutes. The approach discussed in this paper demonstrates how SFC methods can be developed and optimized efficiently using simple concepts and tools. Copyright © 2017 Elsevier B.V. All rights reserved.

Solvent and process for recovery of hydroxide from aqueous mixtures

DOEpatents

Moyer, Bruce A.; Chambliss, C. Kevin; Bonnesen, Peter V.; Keever, Tamara J.

2001-01-01

Hydroxide values and associated alkali metal may be recovered from alkaline aqueous solutions using classes of fluorinated alcohols in a water immiscible solvent. The alcohols are characterized by fluorine substituents which are proximal to the acidic alcohol protons and are located to adjust the acidity of the extractant and the solubility of the extractant in the solvent. A method for stripping the extractant and solvent to regenerate the extractant and purified aqueous hydroxide solution is described.

Organic solvent exposure and hearing loss in a cohort of aluminium workers.

PubMed

Rabinowitz, P M; Galusha, D; Slade, M D; Dixon-Ernst, C; O'Neill, A; Fiellin, M; Cullen, M R

2008-04-01

Organic solvent exposure has been shown to cause hearing loss in animals and humans. Less is known about the risk of hearing loss due to solvent exposures typically found in US industry. The authors performed a retrospective cohort study to examine the relationship between solvent exposure and hearing loss in US aluminium industry workers. A cohort of 1319 workers aged 35 years or less at inception was followed for 5 years. Linkage of employment, industrial hygiene and audiometric surveillance records allowed for estimation of noise and solvent exposures and hearing loss rates over the study period. Study subjects were classified as "solvent exposed" or not, on the basis of industrial hygiene records linked with individual job histories. High frequency hearing loss was modelled as both a continuous and a dichotomous outcome. Typical solvent exposures involved mixtures of xylene, toluene and/or methyl ethyl ketone (MEK). Recorded solvent exposure levels varied widely both within and between jobs. In a multivariate logistic model, risk factors for high frequency hearing loss included age (OR = 1.06, p = 0.004), hunting or shooting (OR = 1.35, p = 0.049), noisy hobbies (OR = 1.74, p = 0.01), baseline hearing level (OR = 1.04, p<0.001) and solvent exposure (OR = 1.87, p = 0.004). A multivariate linear regression analysis similarly found significant associations between high frequency hearing loss and age (p<0.001), hunting or shooting (p<0.001), noisy hobbies (p = 0.03), solvent exposure (p<0.001) and baseline hearing (p = 0.03). These results suggest that occupational exposure to organic solvent mixtures is a risk factor for high frequency hearing loss, although the data do not allow conclusions about dose-response relationships. Industries with solvent-exposed workers should include such workers in hearing conservation programs.

Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism.

PubMed

Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

2014-08-12

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism

NASA Astrophysics Data System (ADS)

Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

2014-08-01

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism

PubMed Central

Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

2014-01-01

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior. PMID:25113225

Non-aqueous liquid compositions comprising ion exchange polymers

DOEpatents

Kim, Yu Seung; Lee, Kwan-Soo; Rockward, Tommy Q. T.

2013-03-12

Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.

Non-aqueous liquid compositions comprising ion exchange polymers

DOEpatents

Kim, Yu Seung [Los Alamos, NM; Lee, Kwan-Soo [Blacksburg, VA; Rockward, Tommy Q. T. [Rio Rancho, NM

2011-07-19

Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.

Toxicity of DEDGN (Diethyleneglycol Dinitrate), Synthetic-HC Smoke Combustion Products, Solvent Yellow 33 and Solvent Green 3 to Freshwater Aquatic Organisms.

DTIC Science & Technology

1987-01-15

stock mixture of these components caused both an algistatic and algicidal effect on the alga. The rainbow trout and the water flea had 96-h and 48-h...stock mixture of these components caused both an algistatic and algicidal effect on the alga. LC50 values for the rainbow trout and the water flea...growth period, cell counts did not increase significantly from the initial inoculum level. 2. Algicidal concentration. This is the lowest concentration

Motor neuron disease and optic neuropathy after acute exposure to a methanol-containing solvent mixture.

PubMed

Chiò, Adriano; Herrero Hernandez, Elena; Mora, Gabriele; Valentini, Consuelo; Discalzi, Gianluigi; Pira, Enrico

2004-09-01

A 34-years-old floor-layer developed optic neuropathy and motor neuron disease after being accidentally exposed to a solvent mixture containing methanol and other substances. Optic neuropathy is a complication of methanol poisoning, but the onset of a motor neuron disorder resembling amyotrophic lateral sclerosis after the exposure to these substances has not been previously described. The temporal onset of the clinical symptoms, biological plausibility, young age of the patient and absence of neurological disorders in the family history raises suspicion of a possible causative relationship.

Dissolution of di-2-ethylhexyl phosphates of ree in an octane + octanol mixture under the influence of gaseous ammonia

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

Trifonov, Y.I.; Legin, E.K.; Suglobov, D.N.

1986-03-01

The authors find that the solubility of di-2-ethylhexyl phosphates rises considerably under the influence of gaseous ammonia on the solvent-LnA/sub 3/ system when a mixture of octane and octanol is used as solvent. The dissolving power of ammonia rises with alcohol concentration and attains the maximum at an alcohol content of ca 20 vol. %. An equation is presented that describes the dependence of the LnA/sub 3/ solubility on the partial amonia pressure.

Method to produce water-soluble sugars from biomass using solvents containing lactones

DOEpatents

Dumesic, James A.; Luterbacher, Jeremy S.

2015-06-02

A process to produce an aqueous solution of carbohydrates that contains C6-sugar-containing oligomers, C6 sugar monomers, C5-sugar-containing oligomers, C5 sugar monomers, or any combination thereof is presented. The process includes the steps of reacting biomass or a biomass-derived reactant with a solvent system including a lactone and water, and an acid catalyst. The reaction yields a product mixture containing water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof. A solute is added to the product mixture to cause partitioning of the product mixture into an aqueous layer containing the carbohydrates and a substantially immiscible organic layer containing the lactone.

Method to produce water-soluble sugars from biomass using solvents containing lactones

DOEpatents

Dumesic, James A.; Luterbacher, Jeremy S.

2017-08-08

A process to produce an aqueous solution of carbohydrates that contains C6-sugar-containing oligomers, C6 sugar monomers, C5-sugar-containing oligomers, C5 sugar monomers, or any combination thereof is presented. The process includes the steps of reacting biomass or a biomass-derived reactant with a solvent system including a lactone and water, and an acid catalyst. The reaction yields a product mixture containing water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof. A solute is added to the product mixture to cause partitioning of the product mixture into an aqueous layer containing the carbohydrates and a substantially immiscible organic layer containing the lactone.

A PROCESS FOR SEPARATING AZEOTROPIC MIXTURES BY EXTRACTIVE AND CONVECTIVE DISTILLATION

DOEpatents

Frazer, J.W.

1961-12-19

A method is described for separating an azeotrope of carbon tetrachloride and 1,1,2,2-tetrafluorodinitroethane boiling at 60 deg C. The ndethod comnprises, specifically, feeding azeotrope vapors admixed with a non- reactive gas into an extractive distillation column heated to a temperature preferably somewhat above the boiling point of the constant boiling mixture. A solvent, di-n-butylphthalate, is metered into the column above the gas inlet and permitted to flow downward, earrying with it the higher bomling fraction, while the constituent having the lower boiling point passes out of the top of the column with the non-reactive gas and is collected in a nitrogen cold trap. Other solvents which alter the vapor pressure relationship may be substituted. The method is generally applicable to azeotropic mixtures. A number of specific mixtures whicb may be separated are disclosed. (AEC)

Versatile solvent systems for the separation of betalains from processed Beta vulgaris L. juice using counter-current chromatography.

PubMed

Spórna-Kucab, Aneta; Ignatova, Svetlana; Garrard, Ian; Wybraniec, Sławomir

2013-12-15

Two mixtures of decarboxylated and dehydrogenated betacyanins from processed red beet roots (Beta vulgaris L.) juice were fractionated by high performance counter-current chromatography (HPCCC) producing a range of isolated components. Mixture 1 contained mainly betacyanins, 14,15-dehydro-betanin (neobetanin) and their decarboxylated derivatives while mixture 2 consisted of decarboxy- and dehydro-betacyanins. The products of mixture 1 arose during thermal degradation of betanin/isobetanin in mild conditions while the dehydro-betacyanins of mixture 2 appeared after longer heating of the juice from B. vulgaris L. Two solvent systems were found to be effective for the HPCCC. A highly polar, high salt concentration system of 1-PrOH-ACN-(NH4)2SO4 (satd. soln)-water (v/v/v/v, 1:0.5:1.2:1) (tail-to-head mode) enabled the purification of 2-decarboxy-betanin/-isobetanin, 2,17-bidecarboxy-betanin/-isobetanin and neobetanin (all from mixture 1) plus 17-decarboxy-neobetanin, 2,15,17-tridecarboxy-2,3-dehydro-neobetanin, 2-decarboxy-neobetanin and 2,15,17-tridecarboxy-neobetanin (from mixture 2). The other solvent system included heptafluorobutyric acid (HFBA) as ion-pair reagent and consisted of tert-butyl methyl ether (TBME)-1-BuOH-ACN-water (acidified with 0.7% HFBA) (2:2:1:5, v/v/v/v) (head-to-tail mode). This system enabled the HPCCC purification of 2,17-bidecarboxy-betanin/-isobetanin and neobetanin (from mixture 1) plus 2,15,17-tridecarboxy-2,3-dehydro-neobetanin, 2,17-bidecarboxy-2,3-dehydro-neobetanin and 2,15,17-tridecarboxy-neobetanin (mixture 2). The results of this research are crucial in finding effective isolation methods of betacyanins and their derivatives which are meaningful compounds due their colorant properties and potential health benefits regarding antioxidant and cancer prevention. The pigments were detected by LC-DAD and LC-MS/MS techniques. Copyright © 2013 Elsevier B.V. All rights reserved.

Method and apparatus for processing a test sample to concentrate an analyte in the sample from a solvent in the sample

DOEpatents

Turner, Terry D.; Beller, Laurence S.; Clark, Michael L.; Klingler, Kerry M.

1997-01-01

A method of processing a test sample to concentrate an analyte in the sample from a solvent in the sample includes: a) boiling the test sample containing the analyte and solvent in a boiling chamber to a temperature greater than or equal to the solvent boiling temperature and less than the analyte boiling temperature to form a rising sample vapor mixture; b) passing the sample vapor mixture from the boiling chamber to an elongated primary separation tube, the separation tube having internal sidewalls and a longitudinal axis, the longitudinal axis being angled between vertical and horizontal and thus having an upper region and a lower region; c) collecting the physically transported liquid analyte on the internal sidewalls of the separation tube; and d) flowing the collected analyte along the angled internal sidewalls of the separation tube to and pass the separation tube lower region. The invention also includes passing a turbulence inducing wave through a vapor mixture to separate physically transported liquid second material from vaporized first material. Apparatus are also disclosed for effecting separations. Further disclosed is a fluidically powered liquid test sample withdrawal apparatus for withdrawing a liquid test sample from a test sample container and for cleaning the test sample container.

Method and apparatus for processing a test sample to concentrate an analyte in the sample from a solvent in the sample

DOEpatents

Turner, T.D.; Beller, L.S.; Clark, M.L.; Klingler, K.M.

1997-10-14

A method of processing a test sample to concentrate an analyte in the sample from a solvent in the sample includes: (a) boiling the test sample containing the analyte and solvent in a boiling chamber to a temperature greater than or equal to the solvent boiling temperature and less than the analyte boiling temperature to form a rising sample vapor mixture; (b) passing the sample vapor mixture from the boiling chamber to an elongated primary separation tube, the separation tube having internal sidewalls and a longitudinal axis, the longitudinal axis being angled between vertical and horizontal and thus having an upper region and a lower region; (c) collecting the physically transported liquid analyte on the internal sidewalls of the separation tube; and (d) flowing the collected analyte along the angled internal sidewalls of the separation tube to and pass the separation tube lower region. The invention also includes passing a turbulence inducing wave through a vapor mixture to separate physically transported liquid second material from vaporized first material. Apparatus is also disclosed for effecting separations. Further disclosed is a fluidically powered liquid test sample withdrawal apparatus for withdrawing a liquid test sample from a test sample container and for cleaning the test sample container. 8 figs.

Pervaporation and Vapor Permeation Tutorial: Membrane Processes for the Selective Separation of Liquid and Vapor Mixtures

EPA Science Inventory

Pervaporation and vapor permeation are membrane-based processes proposed as alternatives to conventional separation technologies. Applications range from organic solvent removal from water, ethanol or butanol recovery from fermentation broths, solvent/biofuel dehydration to meet ...

Pervaporation & Vapor Permeation Membrane Processes for the Selective Separation of Liquid and Vapor Mixtures

EPA Science Inventory

Pervaporation and vapor permeation are membrane-based processes which have been proposed as alternatives to conventional separation technologies. Applications range from organic solvent removal from water, ethanol or butanol recovery from dilute fermentation broths, solvent/biofu...

Lithiated imines: solvent-dependent aggregate structures and mechanisms of alkylation.

PubMed

Zuend, Stephan J; Ramirez, Antonio; Lobkovsky, Emil; Collum, David B

2006-05-03

We describe efforts to understand the structure and reactivity of lithiated cyclohexanone N-cyclohexylimine. The lithioimine affords complex solvent-dependent distributions of monomers, dimers, and trimers in a number of ethereal solvents. Careful selection of solvent provides exclusively monosolvated dimers. Rate studies on the C-alkylations reveal chronic mixtures of monomer- and dimer-based pathways. We explore the factors influencing reactants and alkylation transition structures and the marked differences between lithioimines and isostructural lithium dialkylamides with the aid of density functional theory calculations.

Elementary kinematical model of thermal diffusion in liquids and gases.

PubMed

Brenner, Howard

2006-09-01

An elementary hydrodynamic and Brownian motion model of the thermal diffusivity D(T) of a restricted class of binary liquid mixtures, previously proposed by the author, is given a more transparent derivation than originally, exposing thereby the strictly kinematic-hydrodynamic nature of an important class of thermodiffusion separation phenomena. Moreover, it is argued that the solvent's thermometric diffusivity alpha appearing in that theory as one of the two fundamental parameters governing D(T) should be replaced by the solvent's (isothermal) self-diffusivity D(S). In addition, a corrective multiplier of O(1) is inserted to reflect the general physicochemical noninertness of the solute relative to the solvent, thus enhancing the applicability of the resulting formula D(T)=lambdaD(S)beta to "nonideal" solutions. Here, beta is the solvent's thermal expansivity and lambda is a term of O(1), insensitive to the physicochemical nature of the solute (thus rendering D(T) primarily dependent upon only the properties of the solvent). This formula is, on the basis of its derivation, presumably valid only under certain idealized, albeit well-defined, circumstances. This occurs when the solute molecules are: (i) large compared with those of the solvent; and (ii) present only in small proportions relative to those of the solvent. When the solute is physicochemically inert, it is expected that lambda=1. When these conditions are met, the resulting thermal diffusivity of the mixture is, in theory, independent of any and all properties of the solute. Moreover, because beta is algebraically signed, the thermal diffusivity can either by positive or negative, according as the solvent expands or contracts upon being heated. This formula for D(T) is compared with available experimental data for selected binary liquid mixtures. Reasonable agreement is found in almost all circumstances with lambda near unity, the more so the higher the temperature, especially when the solute-solvent mixture properties closely approximate those where agreement would be expected and conversely. Finally, it is pointed out that for the restricted circumstances described, the formula D(T)=lambdaD(S)beta is equally credible for gases. Here, based on gas-kinetic theory, it is possible to furnish the theoretical value of lambda. Overall, while spanning a range of about five orders of magnitude, the D(T) values given by this elementary formula are shown to apply with reasonable accuracy to: (i) liquids (including circumstances for which D(T) is negative) as well as gases; (ii) all combinations of solvents and solutes tested (the latter including, for example, polymer molecules and metallic colloidal particles); and (iii) all sizes of solute molecules, from angstroms to submicron.

Cold-development tool and technique for the ultimate resolution of ZEP520A to fabricate an EB master mold for nano-imprint lithography for 1Tbit/inch2 BPM development

NASA Astrophysics Data System (ADS)

Kobayashi, Hideo; Iyama, Hiromasa; Kagatsume, Takeshi; Watanabe, Tsuyoshi

2012-11-01

Cold-development is well-known for resolution enhancement on ZEP520A. Dipping a wafer in a developer solvent chilled by a freezer, such a typical method had been employed. But, it is obvious that the dip-development method has several inferiorities such as developer temperature instability, temperature inconsistency between developer and a wafer, water-condensation on drying. We then built a single wafer spin-develop tool, and established a process sequence, to solve those difficulties. And, we tried to see their effect down to -10degC over various developers. In specific, we tried to make hole patterns in hexagonal closest packing in 40nm, 35nm, 30nm, 25nm pitch, and examined holes pattern quality and resolution limit by varying setting temperature from room temperature to -10degC in the cold-development, as well as varying developer chemistry from the standard developer ZED N-50 (n-amyl acetate, 100%) to MiBK and IPA mixture which was a rinsing solvent mixture originally. We also examined the other developer (poor solvent mixture) we designed, N-50 and fluorocarbon (FC) mixture, MiBK and FC mixture, and IPA+FC mixture. This paper describes cold-development tool and technique, and its results down to minus (-) 10degC, for ZEP520A resolution enhancement to obtain 1Xnm bits (holes) in 25nm pitch to fabricate an EB master mold for Nano-Imprinting Lithography for 1Tbit/in2 bit patterned media (BPM) in HDD development and production.

Solution-Processed Solar Cells via Nanocrystal Inks and Molecular Solutions

NASA Astrophysics Data System (ADS)

Miskin, Caleb K.

On February 15, 2008 the National Academy of Engineering unveiled their fourteen grand challenges of engineering for the 21st century. At the top of the list and voted by the public as the most important challenge was the thrust to make solar energy economical. My research has been dedicated to solving this millennial challenge by developing routes to high-efficiency, solution-processed photovoltaics (PV) for low-cost and low-energy manufacturing. My research has primarily advanced two methods for solution processed PV. In one method, semiconducting nanocrystals are synthesized and then suspended in an appropriate solvent to form an ink. The ink is then applied to a substrate by a variety of high-throughput methods such as spray coating or doctor blading and then annealed to form a polycrystalline absorber layer for solar energy. I have applied this method with great success to Cu2ZnSnS 4, a promising earth-abundant, non-toxic semiconductor. A challenge with this material is its propensity to form binary and ternary undesired phases. Using advanced nano-characterization techniques, my colleagues and I have been able to determine the spatially resolved composition of these nanoparticles and have found them to be highly non-uniform. In addition, I developed synthesis techniques aimed at controlling the nucleation and growth of this material to improve nanocrystal compositional homogeneity. Though particles produced in this work still exhibit some non-uniformities, they are greatly improved. When combined with optimized fabrication techniques, I have been able to advance the efficiency of nanocrystal ink based solar cells of CZTS from 7.2 to 9.0 percent in our lab. Another promising route to solution-processed PV is by directly coating molecular precursor solutions (rather than first forming nanocrystals) and annealing the coating to form the polycrystalline solar absorber layer. Unfortunately, a major challenge is that many metals, metal salts, and chalcogens that would be useful precursors to such films have poor solubility in organic solvents compatible with roll-to-roll manufacturing techniques. Interestingly, we have found that mixtures of commonly available thiols and amines are able to dissolve at room temperature and pressure a host of metals and salts that are otherwise insoluble in either solvent by itself. In this work, I have primarily focused on CdTe--which has been by far the most successful technology in terms of production cost ($/peak watt) and energy payback time for thin-film solar cells. In this research thrust I demonstrate for the first time the fabrication of CdTe thin-films via a solution-processed molecular precursor approach by dissolving CdCl2 and Te in ethylenediamine and 1-propanethiol. The films are formed by spin-coating thin layers of the solution and then annealing each layer until a 1.5 mum thick film is achieved. I have achieved 0.5% efficient devices by this method. As thiol-amine mixtures have the potential to leave residual sulfur in these films, other novel solvent systems are presented as future work. While amine-thiol mixtures are excellent solvents for many materials, they do not dissolve lead chalcogenides with ease. I leverage this to develop room-temperature synthesis routes to PbS, PbSe, PbTe, and PbSxSe 1-x nanoparticles. This is achieved by mixing a lead salt dissolved in thiol-amine with a chalcogen dissolved in thiol-amine at room temperature. We find that when particles produced in this manner are pressed into pellets, they show comparable thermoelectric performance to more complicated and energy intensive synthesis techniques. Ultimately, we wish to enable the use of these particles in room-temperature fabricated quantum dot solar cells. This requires the synthesis of highly monodisperse, stable colloids and is the subject of future work using thiol-amine mixtures and related aqueous analogues.

Non-aqueous liquid compositions comprising ion exchange polymers reference to related application

DOEpatents

Kim,; Yu Seung, Lee [Los Alamos, NM; Kwan-Soo, Rockward [Los Alamos, NM; T, Tommy Q [Rio Rancho, NM

2012-08-07

Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.

Actinide extraction methods

DOEpatents

Peterman, Dean R [Idaho Falls, ID; Klaehn, John R [Idaho Falls, ID; Harrup, Mason K [Idaho Falls, ID; Tillotson, Richard D [Moore, ID; Law, Jack D [Pocatello, ID

2010-09-21

Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

Tunable integration of absorption-membrane-adsorption for efficiently separating low boiling gas mixtures near normal temperature

PubMed Central

Liu, Huang; Pan, Yong; Liu, Bei; Sun, Changyu; Guo, Ping; Gao, Xueteng; Yang, Lanying; Ma, Qinglan; Chen, Guangjin

2016-01-01

Separation of low boiling gas mixtures is widely concerned in process industries. Now their separations heavily rely upon energy-intensive cryogenic processes. Here, we report a pseudo-absorption process for separating low boiling gas mixtures near normal temperature. In this process, absorption-membrane-adsorption is integrated by suspending suitable porous ZIF material in suitable solvent and forming selectively permeable liquid membrane around ZIF particles. Green solvents like water and glycol were used to form ZIF-8 slurry and tune the permeability of liquid membrane surrounding ZIF-8 particles. We found glycol molecules form tighter membrane while water molecules form looser membrane because of the hydrophobicity of ZIF-8. When using mixing solvents composed of glycol and water, the permeability of liquid membrane becomes tunable. It is shown that ZIF-8/water slurry always manifests remarkable higher separation selectivity than solid ZIF-8 and it could be tuned to further enhance the capture of light hydrocarbons by adding suitable quantity of glycol to water. Because of its lower viscosity and higher sorption/desorption rate, tunable ZIF-8/water-glycol slurry could be readily used as liquid absorbent to separate different kinds of low boiling gas mixtures by applying a multistage separation process in one traditional absorption tower, especially for the capture of light hydrocarbons. PMID:26892255

Preparation of Water-Selective Polybutadiene Membranes and Their Use in Drying Alcohols by Pervaporation and Vapor Permeation Technologies

EPA Science Inventory

Separating azeotrope-forming solvent-water mixtures by conventional distillation poses technical, economic, and environmental challenges. Membrane technology using water-permselective membranes provides an efficient alternative for water removal from solvents. We present here a n...

Heat Effect of the Protonation of Glycine and the Enthalpies of Resolvation of Participating Chemical Species in Water-Dimethylsulfoxide Solvent Mixtures

NASA Astrophysics Data System (ADS)

Isaeva, V. A.; Sharnin, V. A.

2018-02-01

Enthalpies of the protonation of glycine in water‒dimethylsulfoxide (DMSO) mixed solvents are determined calorimetrically in the range of DMSO mole fractions of 0.0 to 0.9, at T = 298.15 K and an ionic strength μ = 0.3 (NaClO4). It is established that the protonation of glycine becomes more exothermic with an increasing mole fraction of DMSO, and the enthalpies of resolvation of glycine and glycinium ions in water‒DMSO solvent mixtures are calculated. It is shown that the small changes in the enthalpy of protonation observed at low mole fractions of DMSO are caused by the contributions from the solvation of proton and protonated glycine cancelling each other out. The enthalpy term of the Gibbs energy of the reaction leading to the formation of glycinium ion is estimated along with the enthalpy of resolvation of the reacting species in the water‒DMSO mixed solvent.

Phase equilibria in fullerene-containing systems as a basis for development of manufacture and application processes for nanocarbon materials

NASA Astrophysics Data System (ADS)

Semenov, K. N.; Charykov, N. A.; Postnov, V. N.; Sharoyko, V. V.; Murin, I. V.

2016-01-01

This review is the first attempt to integrate the available data on all types of phase equilibria (solubility, extraction and sorption) in systems containing light fullerenes (C60 and C70). In the case of solubility diagrams, the following types of phase equilibria are considered: individual fullerene (C60 or C70)-solvent under polythermal and polybaric conditions; C60-C70-solvent, individual fullerene-solvent(1)-solvent(2), as well as multicomponent systems comprising a single fullerene or an industrial mixture of fullerenes and vegetable oils, animal fats or essential oils under polythermal conditions. All published experimental data on the extraction equilibria in C60-C70-liquid phase(1)-liquid phase(2) systems are described systematically and the sorption characteristics of various materials towards light fullerenes are estimated. The possibility of application of these experimental data for development of pre-chromatographic and chromatographic methods for separation of fullerene mixtures and application of fullerenes as nanomodifiers are described. The bibliography includes 87 references.

Molecular dynamics of acetamide based ionic deep eutectic solvents

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Enhanced Mass Defect Filtering To Simplify and Classify Complex Mixtures of Lignin Degradation Products.

PubMed

Dier, Tobias K F; Egele, Kerstin; Fossog, Verlaine; Hempelmann, Rolf; Volmer, Dietrich A

2016-01-19

High resolution mass spectrometry was utilized to study the highly complex product mixtures resulting from electrochemical breakdown of lignin. As most of the chemical structures of the degradation products were unknown, enhanced mass defect filtering techniques were implemented to simplify the characterization of the mixtures. It was shown that the implemented ionization techniques had a major impact on the range of detectable breakdown products, with atmospheric pressure photoionization in negative ionization mode providing the widest coverage in our experiments. Different modified Kendrick mass plots were used as a basis for mass defect filtering, where Kendrick mass defect and the mass defect of the lignin-specific guaiacol (C7H7O2) monomeric unit were utilized, readily allowing class assignments independent of the oligomeric state of the product. The enhanced mass defect filtering strategy therefore provided rapid characterization of the sample composition. In addition, the structural similarities between the compounds within a degradation sequence were determined by comparison to a tentatively identified product of this compound series. In general, our analyses revealed that primarily breakdown products with low oxygen content were formed under electrochemical conditions using protic ionic liquids as solvent for lignin.

Effect of N-Methyl Substitution in the Glycine Molecule on the Enthalpy of Dissolution in Mixed Water-Alcohol Solvents at 298.15 K

NASA Astrophysics Data System (ADS)

Badelin, V. G.; Smirnov, V. I.

2018-07-01

The enthalpies of dissolution of N-methylglycine in water + ethanol, water + (1-propanol) and water + (2-propanol) are determined via calorimetry at an alcohol concentration of x 2 = 0-0.25 mole fraction. The standard values of enthalpies of dissolution (Δ_{sol}H°) and transfer (Δ_{tr}H°) of N-methylglycine from water to solution are calculated. The effect the structure and properties of N-methylglycine and the composition of a water-alcohol mixture have on N-methylglycine's enthalpy characteristics is examined. The enthalpy coefficients of pair interactions ( h xy ) between N-methylglycine and alcohol molecules are calculated. They have positive values and grow in the series ethanol (EtOH) < 1-propanol (1-PrOH), < 2-propanol (2-PrOH). A comparative analysis is performed of the enthalpy characteristics of dissolution and transfer of N-methylglycine and the analogous characteristics of glycine and DL-α-alanine in similar mixtures.

Behavior of soluble and immobilized acid phosphatase in hydro-organic media.

PubMed

Wan, H; Horvath, C

1975-11-20

The hydrolysis of p-nitrophenyl phosphate by wheat germ acid phosphatase (orthophosphoric monoester phosphohydrolase, EC 3.1.3.2) has been investigated in mixtures of aqueous buffers with acetone, dioxane and acetonitrile. The enzyme was either in free solution or immobilized on a pellicular support which consisted of a porous carbonaceous layer on solid glass beads. The highest enzyme activity was obtained in acetone and acetonitrile mixed with citrate buffer over a wide range of organic solvent concentration. In 50% (v/v) acetone both V and Km of the immobilized enzyme were about half of the values in the neat aqueous buffer, but the Ki for inorganic phosphate was unchanged. In 50% (v/v) mixtures of various solvents and citrate buffers of different pH, the enzymic activity was found to depend on the pH of the aqueous buffer component rather than the pH of the hydro-organic mixture as measured with the glass-calomel electrode. The relatively high rates of p-nitrophenol liberation in the presence of glucose even at high organic solvent concentrations suggest that transphosphorylation is facilitated at low water activity.

Competitive adsorption in model charged protein mixtures: Equilibrium isotherms and kinetics behavior

NASA Astrophysics Data System (ADS)

Fang, F.; Szleifer, I.

2003-07-01

The competitive adsorption of proteins of different sizes and charges is studied using a molecular theory. The theory enables the study of charged systems explicitly including the size, shape, and charge distributions in all the molecular species in the mixture. Thus, this approach goes beyond the commonly used Poisson-Boltzmann approximation. The adsorption isotherms of the protein mixtures are studied for mixtures of two proteins of different size and charge. The amount of proteins adsorbed and the fraction of each protein is calculated as a function of the bulk composition of the solution and the amount of salt in the system. It is found that the total amount of proteins adsorbed is a monotonically decreasing function of the fraction of large proteins on the bulk solution and for fixed protein composition of the salt concentration. However, the composition of the adsorbed layer is a complicated function of the bulk composition and solution ionic strength. The structure of the adsorb layer depends upon the bulk composition and salt concentration. In general, there are multilayers adsorbed due to the long-range character of the electrostatic interactions. When the composition of large proteins in bulk is in very large excess it is found that the structure of the adsorb multilayer is such that the layer in contact with the surface is composed by a mixture of large and small proteins. However, the second and third layers are almost exclusively composed of large proteins. The theory is also generalized to study the time-dependent adsorption. The approach is based on separation of time scales into fast modes for the ions from the salt and the solvent and slow for the proteins. The dynamic equations are written for the slow modes, while the fast ones are obtained from the condition of equilibrium constrained to the distribution of proteins given by the slow modes. Two different processes are presented: the adsorption from a homogeneous solution to a charged surface at low salt concentration, and large excess of the large proteins in bulk. The second process is the kinetics of structural and adsorption change by changing the salt concentration of the bulk solution from low to high. The first process shows a large overshoot of the large proteins on the surface due to their excess in solution, followed by a surface replacement by the smaller molecules. The second process shows a very fast desorption of the large proteins followed by adsorption at latter stages. This process is found to be driven by large electrostatic repulsions induced by the fast ions from the salt approaching the surface. The relevance of the theoretical predictions to experimental system and possible directions for improvements of the theory are discussed.

Effective recovery of poly-β-hydroxybutyrate (PHB) biopolymer from Cupriavidus necator using a novel and environmentally friendly solvent system.

PubMed

Fei, Tao; Cazeneuve, Stacy; Wen, Zhiyou; Wu, Lei; Wang, Tong

2016-05-01

This work demonstrates a significant advance in bioprocessing for a high-melting lipid polymer. A novel and environmental friendly solvent mixture, acetone/ethanol/propylene carbonate (A/E/P, 1:1:1 v/v/v) was identified for extracting poly-hydroxybutyrate (PHB), a high-value biopolymer, from Cupriavidus necator. A set of solubility curves of PHB in various solvents was established. PHB recovery of 85% and purity of 92% were obtained from defatted dry biomass (DDB) using A/E/P. This solvent mixture is compatible with water, and from non-defatted wet biomass, PHB recovery of 83% and purity of 90% were achieved. Water and hexane were evaluated as anti-solvents to assist PHB precipitation, and hexane improved recovery of PHB from biomass to 92% and the purity to 93%. A scale-up extraction and separation reactor was designed, built and successfully tested. Properties of PHB recovered were not significantly affected by the extraction solvent and conditions, as shown by average molecular weight (1.4 × 10(6) ) and melting point (175.2°C) not being different from PHB extracted using chloroform. Therefore, this biorenewable solvent system was effective and versatile for extracting PHB biopolymers. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:678-685, 2016. © 2016 American Institute of Chemical Engineers.

Improving nanoparticle dispersion and charge transfer in cadmium telluride tetrapod and conjugated polymer blends.

PubMed

Monson, Todd C; Hollars, Christopher W; Orme, Christine A; Huser, Thomas

2011-04-01

The dispersion of CdTe tetrapods in a conducting polymer and the resulting charge transfer is studied using a combination of confocal fluorescence microscopy and atomic force microscopy (AFM). The results of this work show that both the tetrapod dispersion and charge transfer between the CdTe and conducting polymer (P3HT) are greatly enhanced by exchanging the ligands on the surface of the CdTe and by choosing proper solvent mixtures. The ability to experimentally probe the relationship between particle dispersion and charge transfer through the combination of AFM and fluorescence microscopy provides another avenue to assess the performance of polymer/semiconductor nanoparticle composites. © 2011 American Chemical Society

Thermophysical properties of tri-n-butylphosphate-ionic liquid mixture

NASA Astrophysics Data System (ADS)

Rout, Alok; Mishra, Satyabrata; Venkatesan, K. A.; Antony, M. P.; Pandey, N. K.

2018-04-01

Thermophysical properties such as viscosity, density, energy of activation and coefficient of thermal expansion were measured for the solvent phase composed of tri-n-butylphosphate (TBP), 1-butyl-3-methylimidazolium bis(trifluoromethane-sulfonyl)imide ([C4mim][NTf2]) and 1.1 M TBP/[C4mim][NTf2]. The results were compared with that of nitric acid equilibrated [C4mim][NTf2] and 1.1M TBP/[C4mim][NTf2]. Thermal stability of the ionic liquid phase was assessed by using differential scanning calorimetric (DSC) technique. Other important physical properties such as refractive index and surface tension of the ionic liquid phase composition were evaluated before and after acid saturation.

Lattice model for water-solute mixtures.

PubMed

Furlan, A P; Almarza, N G; Barbosa, M C

2016-10-14

A lattice model for the study of mixtures of associating liquids is proposed. Solvent and solute are modeled by adapting the associating lattice gas (ALG) model. The nature of interaction of solute/solvent is controlled by tuning the energy interactions between the patches of ALG model. We have studied three set of parameters, resulting in, hydrophilic, inert, and hydrophobic interactions. Extensive Monte Carlo simulations were carried out, and the behavior of pure components and the excess properties of the mixtures have been studied. The pure components, water (solvent) and solute, have quite similar phase diagrams, presenting gas, low density liquid, and high density liquid phases. In the case of solute, the regions of coexistence are substantially reduced when compared with both the water and the standard ALG models. A numerical procedure has been developed in order to attain series of results at constant pressure from simulations of the lattice gas model in the grand canonical ensemble. The excess properties of the mixtures, volume and enthalpy as the function of the solute fraction, have been studied for different interaction parameters of the model. Our model is able to reproduce qualitatively well the excess volume and enthalpy for different aqueous solutions. For the hydrophilic case, we show that the model is able to reproduce the excess volume and enthalpy of mixtures of small alcohols and amines. The inert case reproduces the behavior of large alcohols such as propanol, butanol, and pentanol. For the last case (hydrophobic), the excess properties reproduce the behavior of ionic liquids in aqueous solution.

Fluoroester Co-Solvents for Low-Temperature Li+ Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar; Prakash, G. K. Surya; Smith, Kiah; Bhalla, Pooja

2009-01-01

Electrolytes comprising LiPF6 dissolved in alkyl carbonate/fluoroester mixtures have been found to afford improved low-temperature performance and greater high-temperature resilience in rechargeable lithium-ion electrochemical cells. These and other electrolytes comprising lithium salts dissolved mixtures of esters have been studied in continuing research directed toward extending the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. The purpose of the present focus on high-temperature resilience in addition to low-temperature performance is to address issues posed by the flammability of the esters and, at temperatures near the upper end (about 55 C) of their intended operating temperature range, by their high chemical reactivity. As used here, high-temperature resilience signifies, loosely, a desired combination of low flammability of an electrolyte mixture and the ability of a cell that contains the mixture to sustain a relatively small loss of reversible charge/discharge capacity during storage in the fully charged condition at high temperature. The selection of fluoroesters for study as candidate electrolyte solvent components to increase high-temperature resilience was prompted in part by the observation that like other halogenated compounds, fluoroesters have low flammability. The fluoroesters investigated in this study include trifluoroethyl butyrate (TFEB), ethyl trifluoroacetate (ETFA), trifluoroethyl acetate (TFEA), and methyl pentafluoropropionate (MPFP). Solvent mixtures were prepared by mixing these fluoroesters with two other esters: ethylene carbonate (EC) and ethyl methyl carbonate (EMC).

Preferential solvation bromophenol blue in water-alcohol binary mixture.

PubMed

Dangui, Anayana Z; Santos, Vanessa M S; Gomes, Benhur S; de Castilho, Taiane S; Nicolini, Keller P; Nicolini, Jaqueline

2018-05-29

In this study, the perichromic behavior of bromophenol blue (BPB) in various binary solvent mixtures was investigated. The binary mixtures considered were comprised of water and methanol (MeOH), ethanol (EtOH), n-propanol (n-PrOH), isopropanol (iso-PrOH) or t-butanol (t-BuOH). The investigation of a preferential solvation model that considers the addition of small quantities of alcohol to water in the presence of bromophenol blue (BPB) is described in this paper. The data obtained were employed to study the preferential solvation (PS) of the probe. It was observed that with increases in the molar fraction of water the spontaneity of the system decreases. This can be explained by the high solubility of BPB in ethanol, with ∆G>0 at higher wavelengths (region rich in water with violet solution) and ∆G<0 at lower wavelengths (region rich in alcohol with yellow solution). The pK of the binary mixture changed in all solvents and for all ratios, and the higher the water ratio is the lower the pK In will be. In binary mixture, an increase in the hydrogen bond acceptor (HBA) nature of the solvents tested resulted in a bathochromic effect on the absorption band of BPB (Δλ=12nm). All of the data obtained showed a good nonlinear fit with the mathematical model (SD≤6.6×10 -3 ), suggesting that BPB has other potential applications besides its use as a pH indicator. Copyright © 2017. Published by Elsevier B.V.

High shear mixing granulation of ibuprofen and beta-cyclodextrin: effects of process variables on ibuprofen dissolution.

PubMed

Ghorab, Mohamed K; Adeyeye, Moji Christianah

2007-10-19

The aims of the study were to evaluate the effect of high shear mixer (HSM) granulation process parameters and scale-up on wet mass consistency and granulation characteristics. A mixer torque rheometer (MTR) was employed to evaluate the granulating solvents used (water, isopropanol, and 1:1 vol/vol mixture of both) based on the wet mass consistency. Gral 25 and mini-HSM were used for the granulation. The MTR study showed that the water significantly enhanced the beta-cyclodextrin (beta CD) binding tendency and the strength of liquid bridges formed between the particles, whereas the isopropanol/water mixture yielded more suitable agglomerates. Mini-HSM granulation with the isopropanol/water mixture (1:1 vol/vol) showed a reduction in the extent of torque value rise by increasing the impeller speed as a result of more breakdown of agglomerates than coalescence. In contrast, increasing the impeller speed of the Gral 25 resulted in higher torque readings, larger granule size, and consequently, slower dissolution. This was due to a remarkable rise in temperature during Gral granulation that reduced the isopropanol/water ratio in the granulating solvent as a result of evaporation and consequently increased the beta CD binding strength. In general, the HSM granulation retarded ibuprofen dissolution compared with the physical mixture because of densification and agglomeration. However, a successful HSM granulation scale-up was not achieved due to the difference in the solvent mixture's effect from 1 scale to the other.

An evaporation-assisted dispersive liquid-liquid microextraction technique as a simple tool for high performance liquid chromatography tandem-mass spectrometry determination of insecticides in wine.

PubMed

Timofeeva, Irina; Kanashina, Daria; Moskvin, Leonid; Bulatov, Andrey

2017-08-25

A sample pre-treatment technique based on evaporation-assisted dispersive liquid-liquid microextraction (EVA-DLLME), followed by HPLC-MS/MS has been developed for the determination of organophosphate insecticides (malathion, diazinon, phosalone) in wine samples. The procedure includes the addition of mixture of organic solvents (with density higher than water), consisting of the extraction (low density) and volatile (high density) solvents, to aqueous sample followed by heating of the mixture obtained, what promotes the volatile solvent evaporation and moving extraction solvent droplets from down to top of the aqueous sample and, as a consequence, microextraction of target analytes. To initiate the evaporation process an initiator is required. It was established that hexanol (extraction solvent) and dichloromethane (volatile solvent) mixture (1:1, v/v) provides effective microextraction of the insecticides from wine samples with recovery from 92 to 103%. The conditions of insecticides' microextraction such as selection of extraction solvent, ratio of hexanol/dichloromethane and hexanol/sample, type and concentration of initiator, and effect of ethanol as one of the main components of wine have been studied. Under optimal experimental conditions the linear detection ranges were found to be 10 -7 -10 -3 gL -1 for malathion, 10 -9 -10 -4 gL -1 for diazinon, and 10 -6 -10 -2 gL -1 for phosalone. The LODs, calculated from a blank test, based on 3σ, found to be 3×10 -8 gL -1 for malathion, 3×10 -10 gL -1 for diazinon and 3×10 -7 gL -1 for phosalone. The advantages of EVA-DLLME are the rapidity, simplicity, high sample throughput and low cost. As an outcome, the analytical results agreed fairly well with the results obtained by a reference GC-MS method. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermodynamics of Dilute Solutions.

ERIC Educational Resources Information Center

Jancso, Gabor; Fenby, David V.

1983-01-01

Discusses principles and definitions related to the thermodynamics of dilute solutions. Topics considered include dilute solution, Gibbs-Duhem equation, reference systems (pure gases and gaseous mixtures, liquid mixtures, dilute solutions), real dilute solutions (focusing on solute and solvent), terminology, standard states, and reference systems.…

Surfactant for dye-penetrant inspection is insensitive to liquid oxygen

NASA Technical Reports Server (NTRS)

1966-01-01

LOX insensitive solvent is blended into a mixture of commercially available surfactants to clean metal surfaces which are to be investigated by the dye-penetrant method. The surfactant mixture is applied before and after application of the dye.

Effect of stirring on the safety of flammable liquid mixtures.

PubMed

Liaw, Horng-Jang; Gerbaud, Vincent; Chen, Chan-Cheng; Shu, Chi-Min

2010-05-15

Flash point is the most important variable employed to characterize fire and explosion hazard of liquids. The models developed for predicting the flash point of partially miscible mixtures in the literature to date are all based on the assumption of liquid-liquid equilibrium. In real-world environments, however, the liquid-liquid equilibrium assumption does not always hold, such as the collection or accumulation of waste solvents without stirring, where complete stirring for a period of time is usually used to ensure the liquid phases being in equilibrium. This study investigated the effect of stirring on the flash-point behavior of binary partially miscible mixtures. Two series of partially miscible binary mixtures were employed to elucidate the effect of stirring. The first series was aqueous-organic mixtures, including water+1-butanol, water+2-butanol, water+isobutanol, water+1-pentanol, and water+octane; the second series was the mixtures of two flammable solvents, which included methanol+decane, methanol+2,2,4-trimethylpentane, and methanol+octane. Results reveal that for binary aqueous-organic solutions the flash-point values of unstirred mixtures were located between those of the completely stirred mixtures and those of the flammable component. Therefore, risk assessment could be done based on the flammable component flash-point value. However, for the assurance of safety, it is suggested to completely stir those mixtures before handling to reduce the risk. Copyright (c) 2010 Elsevier B.V. All rights reserved.

From Solvent-Free to Dilute Electrolytes: Essential Components for a Continuum Theory.

PubMed

Gavish, Nir; Elad, Doron; Yochelis, Arik

2018-01-04

The increasing number of experimental observations on highly concentrated electrolytes and ionic liquids show qualitative features that are distinct from dilute or moderately concentrated electrolytes, such as self-assembly, multiple-time relaxation, and underscreening, which all impact the emergence of fluid/solid interfaces, and the transport in these systems. Because these phenomena are not captured by existing mean-field models of electrolytes, there is a paramount need for a continuum framework for highly concentrated electrolytes and ionic liquid mixtures. In this work, we present a self-consistent spatiotemporal framework for a ternary composition that comprises ions and solvent employing a free energy that consists of short- and long-range interactions, along with an energy dissipation mechanism obtained by Onsager's relations. We show that the model can describe multiple bulk and interfacial morphologies at steady-state. Thus, the dynamic processes in the emergence of distinct morphologies become equally as important as the interactions that are specified by the free energy. The model equations not only provide insights into transport mechanisms beyond the Stokes-Einstein-Smoluchowski relations but also enable qualitative recovery of three distinct regions in the full range of the nonmonotonic electrical screening length that has been recently observed in experiments in which organic solvent is used to dilute ionic liquids.

Vitrification of polymer solutions as a function of solvent quality, analyzed via vapor pressures

NASA Astrophysics Data System (ADS)

Bercea, Maria; Wolf, Bernhard A.

2006-05-01

Vapor pressures (headspace sampling in combination with gas chromatography) and glass transition temperatures [differential scanning calorimetry (DSC)] have been measured for solutions of polystyrene (PS) in either toluene (TL) (10-70°C) or cyclohexane (CH) (32-60°C) from moderately concentrated solutions up to the pure polymer. As long as the mixtures are liquid, the vapor pressure of TL (good solvent) is considerably lower than that of CH (theta solvent) under other identical conditions. These differences vanish upon the vitrification of the solutions. For TL the isothermal liquid-solid transition induced by an increase of polymer concentration takes place within a finite composition interval at constant vapor pressure; with CH this phenomenon is either absent or too insignificant to be detected. For PS solutions in TL the DSC traces look as usual, whereas these curves may become bimodal for solutions in CH. The implications of the vitrification of the polymer solutions for the determination of Flory-Huggins interaction parameters from vapor pressure data are discussed. A comparison of the results for TL/PS with recently published data on the same system demonstrates that the experimental method employed for the determination of vapor pressures plays an important role at high polymer concentrations and low temperatures.

Solvent-Polarity-Induced Active Layer Morphology Control in Crystalline Diketopyrrolopyrrole-Based Low Band Gap Polymer Photovoltaics

NASA Astrophysics Data System (ADS)

Ferdous, Sunzida; Liu, Feng; Wang, Dong; Russell, Thomas

2014-03-01

The effects of various processing solvents on the morphology of diketopyrrolopyrrole (DPP)-based low band gap polymer (PDPPBT) and phenyl-C71-butyric acid methyl ester (PC71BM) blends are studied. The quality of the processing solvents was varied systematically using a mixture of a non-aromatic polar primary solvent with high boiling point secondary solvents of increasing polarities. An unfavorable solvent-PC71BM interaction affects the growth process of polymer crystallites inside the blend. When non-aromatic polar solvent was used, large PC71BM aggregates were formed that increase in size with the addition of non-polar secondary solvents. When polar solvents were instead used as the secondary solvents, the size scales of the aggregates decrease markedly, creating a percolated fibrillar network. Power conversion efficiencies of 0.03% to 5% are obtained, depending on the solvent system used.

Supercritical solvent coal extraction

NASA Technical Reports Server (NTRS)

Compton, L. E. (Inventor)

1984-01-01

Yields of soluble organic extract are increased up to about 50% by the supercritical extraction of particulate coal at a temperature below the polymerization temperature for coal extract fragments (450 C.) and a pressure from 500 psig to 5,000 psig by the conjoint use of a solvent mixture containing a low volatility, high critical temperature coal dissolution catalyst such as phenanthrene and a high volatility, low critical temperature solvent such as toluene.

SOLVENT EXTRACTION OF RUTHENIUM

DOEpatents

Hyman, H.H.; Leader, G.R.

1959-07-14

The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

A simulated RTM process for fabricating polyimide (AMB-21) carbon fiber composites

NASA Technical Reports Server (NTRS)

Avva, V. Sarma; Sadler, Robert L.; Thomas, Shanon

1995-01-01

An experimental polyimide matrix, AMB-21 - supplied by NASA/LeRC, was especially formulated to be non-carcinogenic. It was also expected to be amenable to a Resin Transfer Molding Process (RTM). AMB-21 is a solid at room temperature and must be heated to a very high temperature to obtain a fluid state. However, even after heating it to a realistic high temperature, it was found to be too viscous for use in a RTM process. As a result, a promising approach was experimented leading to the introduction of the resin into a solvent solution in order to obtain a viscosity suitable for RTM. A mixture of methanol and tetrahydroferone was found to be a suitable solvent mixture. The matrix solution was introduced into carbon-fiber preform using two techniques: (1) injection of matrix into a Resin Transfer Mold after positioning the preform into the 'mold cavity', and (2) infiltration of matrix into the preform using the 'autoclave through-the-thickness transfer process'. After completing the resin transfer (infiltration) process, the 'filled' preform was heated to 300 F for one hour to reduce the solvent content. The temperature was then increased to 400 F under a vacuum to complete the solvent evaporation and to remove volatile products of the polyimide imidization. The impregnated preform was removed from the mold and press-cured at 200 psi and 600 FF for two hours. The resulting panel was found to be of reasonably good quality. This observation was based on the results obtained from short beam shear strength (700-8000 psi) tests and microscopic examination of the cross-section indicating a very low level of porosity. Further, the flash around the molded panels from the compression molding was free of porosity indicating the removal of volatiles, solvents, and other imidization products. Based on these studies, a new RTM mold containing a diaphragm capable of applying 200 psi at 600 F has been designed and constructed with the expectation that it will allow the incorporation of all of the above processing steps, including the consolidation with the preform in the mold cavity. Moreover, the new diaphragm design will enable to process larger preform panels. Processing studies with the diaphragm mold are being initiated.

Comparison of the free and bound phenolic profiles and cellular antioxidant activities of litchi pulp extracts from different solvents

PubMed Central

2014-01-01

Background The phenolic contents and antioxidant activities of fruits could be underestimated if the bound phenolic compounds are not considered. In the present study, the extraction efficiencies of various solvents were investigated in terms of the total content of the free and bound phenolic compounds, as well as the phenolic profiles and antioxidant activities of the extracts. Methods Five different solvent mixtures were used to extract the free phenolic compounds from litchi pulp. Alkaline and acidic hydrolysis methods were compared for the hydrolysis of bound phenolic compounds from litchi pulp residue. The phenolic compositions of the free and bound fractions from the litchi pulp were identified using HPLC-DAD. The antioxidant activities of the litchi pulp extracts were determined by oxygen radical absorbance capacity (ORAC) and cellular antioxidant activity (CAA) assays. Results Of the solvents tested, aqueous acetone extracted the largest amount of total free phenolic compounds (210.7 mg GAE/100 g FW) from litchi pulp, followed sequentially by aqueous mixtures of methanol, ethanol and ethyl acetate, and water itself. The acid hydrolysis method released twice as many bound phenolic compounds as the alkaline hydrolysis method. Nine phenolic compounds were detected in the aqueous acetone extract. In contrast, not all of these compounds were found in the other four extracts. The classification and content of the bound phenolic compounds released by the acid hydrolysis method were higher than those achieved by the alkaline hydrolysis. The aqueous acetone extract showing the highest ORAC value (3406.9 μmol TE/100 g FW) for the free phenolic extracts. For the CAA method, however, the aqueous acetone and methanol extracts (56.7 and 55.1 μmol QE/100 g FW) showed the highest levels of activity of the five extracts tested. The ORAC and CAA values of the bound phenolic compounds obtained by acid hydrolysis were 2.6- and 1.9-fold higher than those obtained using the alkaline hydrolysis method. Conclusions The free and bound phenolic contents and profiles and antioxidant activities of the extracts were found to be dependent on the extraction solvent used. Litchi exhibited good cellular antioxidant activity and could be a potentially useful natural source of antioxidants. PMID:24405977

Phenolic compounds containing/neutral fractions extract and products derived therefrom from fractionated fast-pyrolysis oils

DOEpatents

Chum, Helena L.; Black, Stuart K.; Diebold, James P.; Kreibich, Roland E.

1993-01-01

A process for preparing phenol-formaldehyde novolak resins and molding compositions in which portions of the phenol normally contained in said resins are replaced by a phenol/neutral fractions extract obtained from fractionating fast-pyrolysis oils. The fractionation consists of a neutralization stage which can be carried out with aqueous solutions of bases or appropriate bases in the dry state, followed by solvent extraction with an organic solvent having at least a moderate solubility parameter and good hydrogen bonding capacity. Phenolic compounds-containing/neutral fractions extracts obtained by fractionating fast-pyrolysis oils from a lignocellulosic material, is such that the oil is initially in the pH range of 2-4, being neutralized with an aqueous bicarbonate base, and extracted into a solvent having a solubility parameter of approximately 8.4-9.11 [cal/cm.sup.3 ].sup.1/2 with polar components in the 1.8-3.0 range and hydrogen bonding components in the 2-4.8 range and the recovery of the product extract from the solvent with no further purification being needed for use in adhesives and molding compounds. The product extract is characterized as being a mixture of very different compounds having a wide variety of chemical functionalities, including phenolic, carbonyl, aldehyde, methoxyl, vinyl and hydroxyl. The use of the product extract on phenol-formaldehyde thermosetting resins is shown to have advantages over the conventional phenol-formaldehyde resins.

Preparation and Characterization of Cabamazepine Cocrystal in Polymer Solution.

PubMed

Zhang, Hao; Zhu, Ying; Qiao, Ning; Chen, Yang; Gao, Linghuan

2017-12-01

In this study, we attempted to prepare carbamazepine (CBZ) cocrystal through the solution method in ethanol-water solvent mixture (volume ratio 1:1) and polyvinyl pyrrolidone (PVP) solution. Nicotinamide (NIC) and saccharin (SAC) were selected as cocrystal coformers. Cocrystal screening products were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), and Powder X-ray Diffraction (PXRD) techniques. Characterization results show that in ethanol-water solvent mixture, pure CBZ-NIC cocrystal can be prepared, while CBZ-SAC cocrystal cannot be obtained. The addition of PVP can inhibit CBZ-NIC cocrystal formation and facilitate CBZ-SAC cocrystal formation.

Preparation and Characterization of Carbamazepine Cocrystal in Polymer Solution

PubMed Central

Zhang, Hao; Zhu, Ying; Chen, Yang; Gao, Linghuan

2017-01-01

In this study, we attempted to prepare carbamazepine (CBZ) cocrystal through the solution method in ethanol-water solvent mixture (volume ratio 1:1) and polyvinyl pyrrolidone (PVP) solution. Nicotinamide (NIC) and saccharin (SAC) were selected as cocrystal coformers. Cocrystal screening products were characterized by Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), and Powder X-ray Diffraction (PXRD) techniques. Characterization results show that in ethanol-water solvent mixture, pure CBZ-NIC cocrystal can be prepared, while CBZ-SAC cocrystal cannot be obtained. The addition of PVP can inhibit CBZ-NIC cocrystal formation and facilitate CBZ-SAC cocrystal formation. PMID:29194387

Heat resistant substrates and battery separators made therefrom

NASA Technical Reports Server (NTRS)

Langer, Alois (Inventor); Scala, Luciano C. (Inventor); Ruffing, Charles R. (Inventor)

1976-01-01

A flexible substrate having a caustic resistant support and at least one membrane comprising a solid polymeric matrix containing a network of interconnected pores and interdispersed inorganic filler particles with a ratio of filler: polymer in the polymeric matrix of between about 1:1 to 5:1, is made by coating at least one side of the support with a filler:coating formulation mixture of inorganic filler particles and a caustic resistant, water insoluble polymer dissolved in an organic solvent, and removing the solvent from the mixture to provide a porous network within the polymeric matrix.

QUANTITATIVE RADIO-CHEMICAL ANALYSIS-SOLVENT EXTRACTION OF MOLYBDENUM-99

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

Wish, L.

1961-09-12

A method was developed for the rapid quantitative separation of Mo/sup 99/ from fission product mixtures. It is based on the extraction of Mo into a solution of alpha -benzoin oxime in chloroform. The main contaminants are Zr, Nb, and 1. The first two are eliminated by couple with fluoride and the third by volatilization or solvent extraction. About 5% of the Te/sup 99/ daughter is extracted with its parent, and it is necessary to wait 48 hrs for equilibrium of fission product mixtures by this method and a standard radiochemical gravimetric procedure showed agreement within 1 to 2%. (auth)

Dopant ink composition and method of fabricating a solar cell there from

DOEpatents

Loscutoff, Paul; Wu, Kahn; Molesa, Steven Edward

2017-10-25

Dopant ink compositions and methods of fabricating solar cells there from are described. A dopant ink composition may include a cross-linkable matrix precursor, a bound dopant species, and a solvent. A method of fabricating a solar cell may include delivering a dopant ink composition to a region above a substrate. The dopant ink composition includes a cross-linkable matrix precursor, a bound dopant species, and a solvent. The method also includes baking the dopant ink composition to remove a substantial portion of the solvent of the dopant ink composition, curing the baked dopant ink composition to cross-link a substantial portion of the cross-linkable matrix precursor of the dopant ink composition, and driving dopants from the cured dopant ink composition toward the substrate.

Dopant ink composition and method of fabricating a solar cell there from

DOEpatents

Loscutoff, Paul; Wu, Kahn; Molesa, Steven Edward

2015-03-31

Dopant ink compositions and methods of fabricating solar cells there from are described. A dopant ink composition may include a cross-linkable matrix precursor, a bound dopant species, and a solvent. A method of fabricating a solar cell may include delivering a dopant ink composition to a region above a substrate. The dopant ink composition includes a cross-linkable matrix precursor, a bound dopant species, and a solvent. The method also includes baking the dopant ink composition to remove a substantial portion of the solvent of the dopant ink composition, curing the baked dopant ink composition to cross-link a substantial portion of the cross-linkable matrix precursor of the dopant ink composition, and driving dopants from the cured dopant ink composition toward the substrate.

Ion conducting polymers and polymer blends for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

Solvent effects on infrared spectra of progesterone in CHCl 3/ cyclo-C 6H 12 binary solvent systems

NASA Astrophysics Data System (ADS)

Liu, Qing; Wang, Xiao-yan; Zhang, Hui

2007-01-01

The infrared spectroscopy studies of the C 3 and C 20 carbonyl stretching vibrations ( υ(C dbnd O)) of progesterone in CHCl 3/ cyclo-C 6H 12 binary solvent systems were undertaken to investigate the solute-solvent interactions. With the mole fraction of CHC1 3 in the binary solvent mixtures increase, three types of C 3 and C 20 carbonyl stretching vibration band of progesterone are observed, respectively. The assignments of υ(C dbnd O) of progesterone are discussed in detail. In the CHCl 3-rich binary solvent systems or pure CHCl 3 solvent, two kinds of solute-solvent hydrogen bonding interactions coexist for C 20 C dbnd O. Comparisons are drawn for the solvent sensitivities of υ(C dbnd O) for acetophenone and 5α-androstan-3,17-dione, respectively.

Feasibility of correlating separation of ternary mixtures of neutral analytes via thin layer chromatography with supercritical fluid chromatography in support of green flash separations.

PubMed

Ashraf-Khorassani, M; Yan, Q; Akin, A; Riley, F; Aurigemma, C; Taylor, L T

2015-10-30

Method development for normal phase flash liquid chromatography traditionally employs preliminary screening using thin layer chromatography (TLC) with conventional solvents on bare silica. Extension to green flash chromatography via correlation of TLC migration results, with conventional polar/nonpolar liquid mixtures, and packed column supercritical fluid chromatography (SFC) retention times, via gradient elution on bare silica with a suite of carbon dioxide mobile phase modifiers, is reported. Feasibility of TLC/SFC correlation is individually described for eight ternary mixtures for a total of 24 neutral analytes. The experimental criteria for TLC/SFC correlation was assumed to be as follows: SFC/UV/MS retention (tR) increases among each of the three resolved mixture components; while, TLC migration (Rf) decreases among the same resolved mixture components. Successful correlation of TLC to SFC was observed for most of the polar organic solvents tested, with the best results observed via SFC on bare silica with methanol as the CO2 modifier and TLC on bare silica with a methanol/dichloromethane mixture. Copyright © 2015 Elsevier B.V. All rights reserved.

Modeling and analysis of personal exposures to VOC mixtures using copulas

PubMed Central

Su, Feng-Chiao; Mukherjee, Bhramar; Batterman, Stuart

2014-01-01

Environmental exposures typically involve mixtures of pollutants, which must be understood to evaluate cumulative risks, that is, the likelihood of adverse health effects arising from two or more chemicals. This study uses several powerful techniques to characterize dependency structures of mixture components in personal exposure measurements of volatile organic compounds (VOCs) with aims of advancing the understanding of environmental mixtures, improving the ability to model mixture components in a statistically valid manner, and demonstrating broadly applicable techniques. We first describe characteristics of mixtures and introduce several terms, including the mixture fraction which represents a mixture component's share of the total concentration of the mixture. Next, using VOC exposure data collected in the Relationship of Indoor Outdoor and Personal Air (RIOPA) study, mixtures are identified using positive matrix factorization (PMF) and by toxicological mode of action. Dependency structures of mixture components are examined using mixture fractions and modeled using copulas, which address dependencies of multiple variables across the entire distribution. Five candidate copulas (Gaussian, t, Gumbel, Clayton, and Frank) are evaluated, and the performance of fitted models was evaluated using simulation and mixture fractions. Cumulative cancer risks are calculated for mixtures, and results from copulas and multivariate lognormal models are compared to risks calculated using the observed data. Results obtained using the RIOPA dataset showed four VOC mixtures, representing gasoline vapor, vehicle exhaust, chlorinated solvents and disinfection by-products, and cleaning products and odorants. Often, a single compound dominated the mixture, however, mixture fractions were generally heterogeneous in that the VOC composition of the mixture changed with concentration. Three mixtures were identified by mode of action, representing VOCs associated with hematopoietic, liver and renal tumors. Estimated lifetime cumulative cancer risks exceeded 10−3 for about 10% of RIOPA participants. Factors affecting the likelihood of high concentration mixtures included city, participant ethnicity, and house air exchange rates. The dependency structures of the VOC mixtures fitted Gumbel (two mixtures) and t (four mixtures) copulas, types that emphasize tail dependencies. Significantly, the copulas reproduced both risk predictions and exposure fractions with a high degree of accuracy, and performed better than multivariate lognormal distributions. Copulas may be the method of choice for VOC mixtures, particularly for the highest exposures or extreme events, cases that poorly fit lognormal distributions and that represent the greatest risks. PMID:24333991

The influence of natural deep eutectic solvents on bioactive natural products: studying interactions between a hydrogel model and Schisandra chinensis metabolites.

PubMed

Liu, Yang; Zhang, Yu; Chen, Shao-Nong; Friesen, J Brent; Nikolić, Dejan; Choules, Mary P; McAlpine, James B; Lankin, David C; Gemeinhart, Richard A; Pauli, Guido F

2018-06-01

Natural Deep Eutectic Solvent (NADES) species can exhibit unexpected solubilizing power for lipophilic molecules despite their simple composition: hydrophilic organic molecules and water. In the present study, the unique properties of NADES species were applied in combination with a model polymer system: a hydrophilic chitosan/alginate hydrogel. Briefly, NADES species (e.g., mannose-dimethylurea-water, 2:5:5, mole/mole) formed matrices to 1) dissolve lipophilic molecules (e.g., curcumin), 2) load lipophilic molecule(s) into the hydrogel, and 3) spontaneously vacate from the system. NADES species ubiquitously occur in natural sources, and a crude extract is a mixture of the NADES species and bioactive metabolites. Based on these ideas, we hypothesized that the crude extract may also allow the loading of natural bioactive molecules from a natural NADES species into (bio)hydrogel systems. To evaluate this hypothesis in vitro, Schisandra chinensis fruit extract was chosen as a representative mixture of lipophilic botanical molecules and hydrophilic NADES species. The results showed that the NADES matrix of S. chinensis was capable of loading at least three bioactive lignans (i.e., gomisin A, gomisin J, and angeloylgomisin H) into the polymer system. The lipophilic metabolites can subsequently be released from the hydrogel. The outcomes suggest that a unique drug delivery mechanism may exist in nature, thereby potentially improving the bioavailability of lipophilic metabolites through physicochemical interactions with the NADES. Copyright © 2018 Elsevier B.V. All rights reserved.

Toxicity profile of choline chloride-based deep eutectic solvents for fungi and Cyprinus carpio fish.

PubMed

Juneidi, Ibrahim; Hayyan, Maan; Mohd Ali, Ozair

2016-04-01

An investigation on the toxicological assessment of 10 choline chloride (ChCl)-based deep eutectic solvents (DESs) towards four fungi strains and Cyprinus carpio fish was conducted. ChCl was combined with materials from different chemical groups such as alcohols, sugars, acids and others to form DESs. The study was carried out on the individual DES components, their aqueous mixture before DES formation and their formed DESs. The agar disc diffusion method was followed to investigate their toxicity on four fungi strains selected as a model of eukaryotic microorganisms (Phanerochaete chrysosporium, Aspergillus niger, Lentinus tigrinus and Candida cylindracea). Among these DESs, ChCl:ZnCl2 exhibited the highest inhibition zone diameter towards the tested fungi growth in vitro, followed by the acidic group (malonic acid and p-toluenesulfonic acid). Another study was conducted to test the acute toxicity and determine the lethal concentration at 50 % (LC50) of the same DESs on C. carpio fish. The inhibition range and LC50 of DESs were found to be different from their individual components. DESs were found to be less toxic than their mixture or individual components. The LC50 of ChCl:MADES is much higher than that of ChCl:MAMix. Moreover, the DESs acidic group showed a lower inhibition zone on fungi growth. Thus, DESs should be considered as new components with different physicochemical properties and toxicological profiles, and not merely compositions of compounds.

Recovery of soluble chloride salts from the wastewater generated during the washing process of municipal solid wastes incineration fly ash.

PubMed

Tang, Hailong; Erzat, Aris; Liu, Yangsheng

2014-01-01

Water washing is widely used as the pretreatment method to treat municipal solid waste incineration fly ash, which facilitates the further solidification/stabilization treatment or resource recovery of the fly ash. The wastewater generated during the washing process is a kind of hydrosaline solution, usually containing high concentrations of alkali chlorides and sulphates, which cause serious pollution to environment. However, these salts can be recycled as resources instead of discharge. This paper explored an effective and practical recovery method to separate sodium chloride, potassium chloride, and calcium chloride salts individually from the hydrosaline water. In laboratory experiments, a simulating hydrosaline solution was prepared according to composition of the waste washing water. First, in the three-step evaporation-crystallization process, pure sodium chloride and solid mixture of sodium and potassium chlorides were obtained separately, and the remaining solution contained potassium and calcium chlorides (solution A). And then, the solid mixture was fully dissolved into water (solution B obtained). Finally, ethanol was added into solutions A and B to change the solubility of sodium, potassium, and calcium chlorides within the mixed solvent of water and ethanol. During the ethanol-adding precipitation process, each salt was separated individually, and the purity of the raw production in laboratory experiments reached about 90%. The ethanol can be recycled by distillation and reused as the solvent. Therefore, this technology may bring both environmental and economic benefits.

Analysis of Benzo[a]pyrene in Vegetable Oils Using Molecularly Imprinted Solid Phase Extraction (MISPE) Coupled with Enzyme-Linked Immunosorbent Assay (ELISA)

PubMed Central

Pschenitza, Michael; Hackenberg, Rudolf; Niessner, Reinhard; Knopp, Dietmar

2014-01-01

This paper describes the development of a molecularly imprinted polymer-based solid phase extraction (MISPE) method coupled with enzyme-linked immunosorbent assay (ELISA) for determination of the PAH benzo[a]pyrene (B[a]P) in vegetable oils. Different molecularly imprinted polymers (MIPs) were prepared using non-covalent 4-vinylpyridine/divinylbenzene co-polymerization at different ratios and dichloromethane as porogen. Imprinting was done with a template mixture of phenanthrene and pyrene yielding a broad-specific polymer for PAHs with a maximum binding capacity (Q) of ∼32 μg B[a]P per 50 mg of polymer. The vegetable oil/n-hexane mixture (1:1, (v/v)) was pre-extracted with acetonitrile, the solvent evaporated, the residue reconstituted in n-hexane and subjected to MISPE. The successive washing with n-hexane and isopropanol revealed most suitable to remove lipid matrix constituents. After elution of bound PAHs from MISPE column with dichloromethane, the solvent was evaporated, the residue reconstituted with dimethyl sulfoxide and diluted 100-fold with methanol/water (10:90, (v/v)) for analysis of B[a]P equivalents with an ELISA. The B[a]P recovery rates in spiked vegetable oil samples of different fatty acid composition were determined between 63% and 114%. The presence of multiple PAHs in the oil sample, because of MIP selectivity and cross-reactivity of the ELISA, could yield overestimated B[a]P values. PMID:24887045

Modeling of dielectric properties of aqueous salt solutions with an equation of state.

PubMed

Maribo-Mogensen, Bjørn; Kontogeorgis, Georgios M; Thomsen, Kaj

2013-09-12

The static permittivity is the most important physical property for thermodynamic models that account for the electrostatic interactions between ions. The measured static permittivity in mixtures containing electrolytes is reduced due to kinetic depolarization and reorientation of the dipoles in the electrical field surrounding ions. Kinetic depolarization may explain 25-75% of the observed decrease in the permittivity of solutions containing salts, but since this is a dynamic property, this effect should not be included in the thermodynamic modeling of electrolytes. Kinetic depolarization has, however, been ignored in relation to thermodynamic modeling, and authors have either neglected the effect of salts on permittivity or used empirical correlations fitted to the measured static permittivity, leading to an overestimation of the reduction in the thermodynamic static permittivity. We present a new methodology for obtaining the static permittivity over wide ranges of temperatures, pressures, and compositions for use within an equation of state for mixed solvents containing salts. The static permittivity is calculated from a new extension of the framework developed by Onsager, Kirkwood, and Fröhlich to associating mixtures. Wertheim's association model as formulated in the statistical associating fluid theory is used to account for hydrogen-bonding molecules and ion-solvent association. Finally, we compare the Debye-Hückel Helmholtz energy obtained using an empirical model with the new physical model and show that the empirical models may introduce unphysical behavior in the equation of state.

FINAL REPORT: Room Temperature Hydrogen Storage in Nano-Confined Liquids

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

VAJO, JOHN

2014-06-12

DOE continues to seek solid-state hydrogen storage materials with hydrogen densities of ≥6 wt% and ≥50 g/L that can deliver hydrogen and be recharged at room temperature and moderate pressures enabling widespread use in transportation applications. Meanwhile, development including vehicle engineering and delivery infrastructure continues for compressed-gas hydrogen storage systems. Although compressed gas storage avoids the materials-based issues associated with solid-state storage, achieving acceptable volumetric densities has been a persistent challenge. This project examined the possibility of developing storage materials that would be compatible with compressed gas storage technology based on enhanced hydrogen solubility in nano-confined liquid solvents. These materialsmore » would store hydrogen in molecular form eliminating many limitations of current solid-state materials while increasing the volumetric capacity of compressed hydrogen storage vessels. Experimental methods were developed to study hydrogen solubility in nano-confined liquids. These methods included 1) fabrication of composites comprised of volatile liquid solvents for hydrogen confined within the nano-sized pore volume of nanoporous scaffolds and 2) measuring the hydrogen uptake capacity of these composites without altering the composite composition. The hydrogen storage capacities of these nano-confined solvent/scaffold composites were compared with bulk solvents and with empty scaffolds. The solvents and scaffolds were varied to optimize the enhancement in hydrogen solubility that accompanies confinement of the solvent. In addition, computational simulations were performed to study the molecular-scale structure of liquid solvent when confined within an atomically realistic nano-sized pore of a model scaffold. Confined solvent was compared with similar simulations of bulk solvent. The results from the simulations were used to formulate a mechanism for the enhanced solubility and to guide the experiments. Overall, the combined experimental measurements and simulations indicate that hydrogen storage based on enhanced solubility in nano-confined liquids is unlikely to meet the storage densities required for practical use. Only low gravimetric capacities of < 0.5 wt% were achieved. More importantly, solvent filled scaffolds had lower volumetric capacities than corresponding empty scaffolds. Nevertheless, several of the composites measured did show significant (>~ 5x) enhanced hydrogen solubility relative to bulk solvent solubility, when the hydrogen capacity was attributed only to dissolution in the confined solvent. However, when the hydrogen capacity was compared to an empty scaffold that is known to store hydrogen by surface adsorption on the scaffold walls, including the solvent always reduced the hydrogen capacity. For the best composites, this reduction relative to an empty scaffold was ~30%; for the worst it was ~90%. The highest capacities were obtained with the largest solvent molecules and with scaffolds containing 3- dimensionally confined pore geometries. The simulations suggested that the capacity of the composites originated from hydrogen adsorption on the scaffold pore walls at sites not occupied by solvent molecules. Although liquid solvent filled the pores, not all of the adsorption sites on the pore walls were occupied due to restricted motion of the solvent molecules within the confined pore space.« less

Molecular insights into early stage aggregation of di-Fmoc-L-lysine in binary mixture of organic solvent and water

NASA Astrophysics Data System (ADS)

Huda, Md Masrul; Rai, Neeraj

Molecular gels are relatively new class of soft materials, which are formed by the supramolecular aggregation of low molecular weight gelators (LMWGs) in organic solvents and/or water. Hierarchical self-assembly of small gelator molecules lead to three-dimensional complex fibrillar networks, which restricts the flow of solvents and results in viscous solid like materials or gels. These gels have drawn significant attentions for their potential applications for drug delivery, tissue engineering, materials for sensors etc. As of now, self-assembly of gelator molecules into one-dimensional fibers is not well understood, although that is very important to design new gelators for desired applications. Here, we present molecular dynamics study that provides molecular level insight into early stage aggregation of selected gelator, di-Fmoc-L-lysine in binary mixture of organic solvent and water. We will present the role of different functional groups of gelator molecule such as aromatic ring, amide, and carboxylic group on aggregation. We will also present the effect of concentrations of gelator and solvent on self-assembly of gelators. This study has captured helical fiber growth and branching of fiber, which is in good agreement with experimental observations.

Properties of Polyvinylpyrrolidone in a Deep Eutectic Solvent

DOE PAGES

Sapir, Liel; Stanley, Christopher B.; Harries, Daniel

2016-03-10

Deep eutectic solvents (DES) are mixtures of two or more components with high melting temperatures, which form a liquid at room temperature. These DES hold great promise as green solvents for chemical processes, as they are inexpensive and environmentally friendly. Specifically, they present a unique solvating environment to polymers that is different from water. In this paper, we use small angle neutron scattering to study the polymer properties of the common, water-soluble, polyvinylpyrrolidone (PVP) in the prominent DES formed by a 1:2 molar mixture of choline chloride and urea. We find that the polymer adopts a slightly different structure inmore » DES than in water, so that at higher concentrations the polymer favors a more expanded conformation compared to the same concentration in water. Yet, the osmotic pressure of PVP solutions in DES is very similar to that in water, indicating that both solvents are of comparable quality and that the DES components interact favorably with PVP. Finally, the osmotic pressure measurements within this novel class of promising solvents should be of value toward future technological applications as well as for osmotic stress experiments in nonaqueous environments.« less

Properties of Polyvinylpyrrolidone in a Deep Eutectic Solvent

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

Sapir, Liel; Stanley, Christopher B.; Harries, Daniel

Deep eutectic solvents (DES) are mixtures of two or more components with high melting temperatures, which form a liquid at room temperature. These DES hold great promise as green solvents for chemical processes, as they are inexpensive and environmentally friendly. Specifically, they present a unique solvating environment to polymers that is different from water. In this paper, we use small angle neutron scattering to study the polymer properties of the common, water-soluble, polyvinylpyrrolidone (PVP) in the prominent DES formed by a 1:2 molar mixture of choline chloride and urea. We find that the polymer adopts a slightly different structure inmore » DES than in water, so that at higher concentrations the polymer favors a more expanded conformation compared to the same concentration in water. Yet, the osmotic pressure of PVP solutions in DES is very similar to that in water, indicating that both solvents are of comparable quality and that the DES components interact favorably with PVP. Finally, the osmotic pressure measurements within this novel class of promising solvents should be of value toward future technological applications as well as for osmotic stress experiments in nonaqueous environments.« less

Characterization of Microwave-Induced Electric Discharge Phenomena in Metal–Solvent Mixtures

PubMed Central

Chen, Wen; Gutmann, Bernhard; Kappe, C Oliver

2012-01-01

Electric discharge phenomena in metal–solvent mixtures are investigated utilizing a high field density, sealed-vessel, single-mode 2.45 GHz microwave reactor with a built-in camera. Particular emphasis is placed on studying the discharges exhibited by different metals (Mg, Zn, Cu, Fe, Ni) of varying particle sizes and morphologies in organic solvents (e.g., benzene) at different electric field strengths. Discharge phenomena for diamagnetic and paramagnetic metals (Mg, Zn, Cu) depend strongly on the size of the used particles. With small particles, short-lived corona discharges are observed that do not lead to a complete breakdown. Under high microwave power conditions or with large particles, however, bright sparks and arcs are experienced, often accompanied by solvent decomposition and formation of considerable amounts of graphitized material. Small ferromagnetic Fe and Ni powders (<40 μm) are heated very rapidly in benzene suspensions and start to glow in the microwave field, whereas larger particles exhibit extremely strong discharges. Electric discharges were also observed when Cu metal or other conductive materials such as silicon carbide were exposed to the microwave field in the absence of a solvent in an argon or nitrogen atmosphere. PMID:24551491

Characterization of microwave-induced electric discharge phenomena in metal-solvent mixtures.

PubMed

Chen, Wen; Gutmann, Bernhard; Kappe, C Oliver

2012-02-01

Electric discharge phenomena in metal-solvent mixtures are investigated utilizing a high field density, sealed-vessel, single-mode 2.45 GHz microwave reactor with a built-in camera. Particular emphasis is placed on studying the discharges exhibited by different metals (Mg, Zn, Cu, Fe, Ni) of varying particle sizes and morphologies in organic solvents (e.g., benzene) at different electric field strengths. Discharge phenomena for diamagnetic and paramagnetic metals (Mg, Zn, Cu) depend strongly on the size of the used particles. With small particles, short-lived corona discharges are observed that do not lead to a complete breakdown. Under high microwave power conditions or with large particles, however, bright sparks and arcs are experienced, often accompanied by solvent decomposition and formation of considerable amounts of graphitized material. Small ferromagnetic Fe and Ni powders (<40 μm) are heated very rapidly in benzene suspensions and start to glow in the microwave field, whereas larger particles exhibit extremely strong discharges. Electric discharges were also observed when Cu metal or other conductive materials such as silicon carbide were exposed to the microwave field in the absence of a solvent in an argon or nitrogen atmosphere.

Method to produce biomass-derived compounds using a co-solvent system containing gamma-valerolactone

DOEpatents

Dumesic, James A.; Motagamwala, Ali Hussain

2017-06-27

A method to produce an aqueous solution of carbohydrates containing C5- and/or C6-sugar-containing oligomers and/or C5- and/or C6-sugar monomers in which biomass or a biomass-derived reactant is reacted with a solvent system having an organic solvent, and organic co-solvent, and water, in the presence of an acid. The method produces the desired product, while a substantial portion of any lignin present in the reactant appears as a precipitate in the product mixture.

Search for liquids electrospraying the smallest possible nanodrops in vacuo

NASA Astrophysics Data System (ADS)

Alonso-Matilla, R.; Fernández-García, J.; Congdon, H.; Fernández de la Mora, J.

2014-12-01

Prior work with electrosprays in vacuum of mixtures of ionic liquids (ILs) and the moderately high boiling point (Tb) solvents formamide (FM) and propylene carbonate (PC) (Tb of 210 and 241 °C) has shown that the charged drops produced have reasonably narrow charge/mass distributions, controllable over a wide mass/charge range. This enables their use as propellants in electrical propulsion with specific impulse Isp varying from a few hundred to a few thousand seconds (10 kV beam energy) and with excellent propulsion efficiency. However, some limitations are imposed by the finite room temperature volatility of FM and PC. Here, we seek improved performance from propellants based on the polar but viscous solvent Sulfolane (SF; ɛ = 43.2, μ = 10.3 cP) and the low viscosity but less polar solvent tributyl phosphate (TBP; ɛ = 8.9, μ = 3.4 cP), both with Tb > 280 °C. Neither TBP nor its low viscosity mixtures with SF achieve the electrical conductivities needed to yield high Isp. Most ILs used in SF/IL mixtures tested were based on the 1-ethyl-3-methylimidazolium (EMI) or 1,3-dimethylimidazolium (DMI) cations, including EMI-BF4, EMI-N(CN)2, and DMI-N(CN)2. These combinations reach high conductivities, some approaching 3 S/m, but have limited propulsive performance because evaporation of ions directly from the electrified meniscus produces undesirable mixed beams of drops and ions. Exceptional characteristics are found in mixtures of SF with ethylammonium nitrate (EAN), where the small EA+ cation is strongly bound to the solvent, greatly delaying ion evaporation from the meniscus. Evidence on the formation of nano-jets with diameters as small as 1 nm is seen. Although unprecedented, this finding agrees with what would be expected if ion evaporation were suppressed. SF/EAN mixtures thus provide the best available sources to produce the smallest possible nanodrops, minimally polluted by ions.

Acute effects of an organic solvent mixture on the human central nervous system.

PubMed

Muttray, Axel; Martus, P; Schachtrup, S; Müller, E; Mayer-Popken, O; Konietzko, J

2005-09-12

At workplaces, organic solvents are often used as mixtures. Nevertheless, there is limited knowledge of their acute effects on human central nervous system. Here we report the effects of a toluene-acetone mixture. In a parallel design, subgroups of 12 healthy men each were exposed to a mixture containing 25 ppm acetone and 250 ppm toluene or to air (control) in an exposure chamber for 4.5 hours. Concentrations corresponded to the German TLV (TRGS 403). Concentrations of toluene and acetone in venous blood were measured by headspace gas chromatography. Subjects were sedentary. The following tests were performed before and at the end of exposure: Questionnaires, simple reaction time, vigilance, quantitative analysis of EEG with open and closed eyes and during the Color Word Stress test, and visual evoked potentials (VEP). Blood levels were 0.14 (+/- 0.04 SD) mg toluene/l and 5.43 (+/- 1.37 SD) mg acetone/l at the end of solvent exposure. Scores of neurotoxic and irritating symptoms were not elevated during solvent exposure. Exposed subjects performed as well as control subjects on the simple reaction time test and on the vigilance test, neither reaction time nor number of hits differed significantly. A general linear model on log transformed spectral power values showed insignificant changes in EEG. In the alpha subset2-band an average reduction to 86 % was observed in exposed as compared to non exposed subjects with closed eyes, a reduction to 88 % in the theta-band with open eyes, and a reduction to 92 % in the theta-band during the Color Word Stress test. VEP P 100 latencies and amplitudes did not change. The mixture consisting of toluene and acetone did not cause any adverse acute effect. With respect to EEG data, possible subclinical effects on central nervous system cannot be excluded.